WO2023096492A1 - Surface covering - Google Patents
Surface covering Download PDFInfo
- Publication number
- WO2023096492A1 WO2023096492A1 PCT/NL2022/050684 NL2022050684W WO2023096492A1 WO 2023096492 A1 WO2023096492 A1 WO 2023096492A1 NL 2022050684 W NL2022050684 W NL 2022050684W WO 2023096492 A1 WO2023096492 A1 WO 2023096492A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- surface covering
- oil
- polyvinyl butyral
- organophosphorus
- covering according
- Prior art date
Links
- 239000003921 oil Substances 0.000 claims abstract description 100
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 235000019198 oils Nutrition 0.000 claims description 98
- -1 di-adipates Chemical class 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 26
- 239000004014 plasticizer Substances 0.000 claims description 22
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 22
- 239000008158 vegetable oil Substances 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000004359 castor oil Substances 0.000 claims description 19
- 235000019438 castor oil Nutrition 0.000 claims description 19
- 239000003063 flame retardant Substances 0.000 claims description 19
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000975 dye Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004040 coloring Methods 0.000 claims description 6
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical group C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 230000000670 limiting effect Effects 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002657 fibrous material Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229960004592 isopropanol Drugs 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 229940117958 vinyl acetate Drugs 0.000 claims description 4
- 239000004971 Cross linker Substances 0.000 claims description 3
- 239000004608 Heat Stabiliser Substances 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 229920006348 thermoplastic styrenic block copolymer Polymers 0.000 claims description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 2
- 244000226021 Anacardium occidentale Species 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 235000016401 Camelina Nutrition 0.000 claims description 2
- 244000197813 Camelina sativa Species 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 241000195493 Cryptophyta Species 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 241000221089 Jatropha Species 0.000 claims description 2
- 241000665629 Linum flavum Species 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 235000019485 Safflower oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- 235000019498 Walnut oil Nutrition 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 239000000828 canola oil Substances 0.000 claims description 2
- 235000019519 canola oil Nutrition 0.000 claims description 2
- 235000020226 cashew nut Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 235000005687 corn oil Nutrition 0.000 claims description 2
- 239000002285 corn oil Substances 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 239000008169 grapeseed oil Substances 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 claims description 2
- 229960003988 indigo carmine Drugs 0.000 claims description 2
- 239000004179 indigotine Substances 0.000 claims description 2
- 235000012738 indigotine Nutrition 0.000 claims description 2
- 229940074320 iso-sulfan blue Drugs 0.000 claims description 2
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010466 nut oil Substances 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 235000005713 safflower oil Nutrition 0.000 claims description 2
- 239000003813 safflower oil Substances 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- NLUFDZBOHMOBOE-UHFFFAOYSA-M sodium;2-[[4-(diethylamino)phenyl]-(4-diethylazaniumylidenecyclohexa-2,5-dien-1-ylidene)methyl]benzene-1,4-disulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC=C(C=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 NLUFDZBOHMOBOE-UHFFFAOYSA-M 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 239000008170 walnut oil Substances 0.000 claims description 2
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000007142 ring opening reaction Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000005336 safety glass Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002924 oxiranes Chemical group 0.000 description 3
- 125000000466 oxiranyl group Chemical group 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-Butylbenzenesulfonamide Natural products CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
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- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000001004 diazonium dye Substances 0.000 description 1
- YICSVBJRVMLQNS-UHFFFAOYSA-N dibutyl phenyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OC1=CC=CC=C1 YICSVBJRVMLQNS-UHFFFAOYSA-N 0.000 description 1
- RYSCVIAVOSESIU-UHFFFAOYSA-N didodecyl (4-methylphenyl) phosphate Chemical compound CCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCC)OC1=CC=C(C)C=C1 RYSCVIAVOSESIU-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- JSPBAVGTJNAVBJ-UHFFFAOYSA-N ethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCC)OC1=CC=CC=C1 JSPBAVGTJNAVBJ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000002949 hemolytic effect Effects 0.000 description 1
- 229910000515 huntite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010449 novaculite Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000011088 parchment paper Substances 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- YVURAEQQLUQPFO-UHFFFAOYSA-N phosphoric acid;styrene Chemical compound OP(O)(O)=O.C=CC1=CC=CC=C1 YVURAEQQLUQPFO-UHFFFAOYSA-N 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- WDRCVXGINNJWPH-UHFFFAOYSA-N tris(6-methylheptyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC(C)C)C(C(=O)OCCCCCC(C)C)=C1 WDRCVXGINNJWPH-UHFFFAOYSA-N 0.000 description 1
- FSLSJTZWDATVTK-UHFFFAOYSA-N tris(6-methylheptyl) phosphate Chemical compound CC(C)CCCCCOP(=O)(OCCCCCC(C)C)OCCCCCC(C)C FSLSJTZWDATVTK-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/06—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
Definitions
- the invention is directed to a surface covering, to a method for preparing said surface covering, and to a method for applying said surface covering.
- Watertight surface coverings are used in construction for waterproofing surfaces, such as roofs, facades, etc.
- Conventional materials used for such surface coverings are based, for instance, on bitumen, polyvinyl chloride, polychloroprene, or ethylene propylene diene monomer (EPDM).
- EPDM ethylene propylene diene monomer
- Another material suggested in the art to be advantageous for flashing material or roofing material is polyvinyl butyral.
- WO-A-2016/108686 discloses a lead alternative flashing material comprising a perforated sheet of metal attached to a thermoplastic layer that may comprise polyvinyl butyral.
- WO-A-2020/122727 discloses a synthetic flashing material comprising 75 wt.% or more of polymer, such as polyvinyl butyral, and less than 10 wt.% of metal.
- WO-A-2021/064634 discloses a construction material comprising polyvinyl butyral and an ammonium polyphosphate fire retardant.
- WO-A-2017/064260 discloses a decorative multi-layer surface covering comprising polyvinyl butyral.
- WO-A-2020/156740 discloses cellulose ester compositions for surface coverings.
- Polyvinyl butyral is an industrially important polymer widely used in laminated safety glass and surface treatments because it exhibits a very high adhesion to glass.
- polyvinyl butyral is a promising material for use in surface coverings.
- polyvinyl chloride is a hydrophobic material, and as a consequence impermeable to moisture. Additionally, polyvinyl chloride typically suffers from leaking plasticiser, which causes the polyvinyl chloride surface covering to become brittle over time.
- Polyvinyl butyral on the other hand can take up and release relatively large amounts of moisture. Although the material is not permeable to water in liquid form, it does allow permeation of vapour. Polyvinyl butyral further has limited capacity for oil uptake.
- polyvinyl butyral is a promising material for use in surface coverings
- the compounding of polyvinyl butyral with other components is challenging, in particular when the polyvinyl butyral used is recycled polyvinyl butyral that originates from various recycle sources.
- Processability problems arise when blending and extruding the polyvinyl butyral with other components. Addition of such other components, however, may be required for depending on the application of the product.
- Polyvinyl butyral is, for instance, typically heavily plasticised in order to improve mechanical and rheological properties.
- surface covering measures have to be taken in order to prevent the material from combusting.
- the invention aims at providing a surface covering comprising polyvinyl butyral that has excellent processability. Further objective of the invention is to provide a polyvinyl butyral based surface covering that can be easily compounded with other components.
- the invention is directed to a surface covering comprising - 60-90 % by total weight of the surface covering of polyvinyl butyral, and - 1-15 % by total weight of the surface covering of one or more organophosphorus oils and/or one or more organohalogen oils.
- the inventors found that the use of an organophosphorus oil and/or an organohalogen oil surprisingly improves the processability during compounding of the polyvinyl butyral based composition.
- the organophosphorus oil and/or the organohalogen oil further act both as plasticiser, so the currently used plasticiser content can be lowered, and it can act as flame retardant.
- the oil helps to disperse other flame retardants (inorganic) and therefore increases the effectiveness of the flame retardant action.
- the surface covering of the invention as a result requires overall less amount of plasticiser which makes that the resulting product can be better glued to another surface covering comprising polyvinyl butyral, preferably another surface covering of the invention.
- the oil may advantageously be based on vegetable oil.
- the organophosphorus oil may be a phosphorus containing vegetable oil based derivative and/or the organohalogen oil may be a halogen containing vegetable oil based derivative.
- Such vegetable oils are domestically abundant, cost-effective, and non-toxic.
- the surface covering of the invention is particularly suitable for covering the surface of a roof, a basement, a façade, a wall, a floor or a pool. In such applications, the surface covering serves as a waterproof membrane.
- polyvinyl butyral as used herein is meant to refer to a polyacetal prepared by reacting poly(vinyl alcohol) with butyraldehyde, after obtaining poly(vinyl alcohol) by means of transesterification of from poly(vinyl acetate) usually with methanol and base catalysis.
- Polyvinyl butyral is commercially available from Monsanto Company as Butvar ® .
- the conditions of the reaction between polyvinyl alcohol and butyraldehyde, and their relative concentrations are closely controlled to form polymers containing predetermined proportions of hydroxyl, acetate, and butyral groups.
- poly(vinyl butyrate) is in the art often interchangeably used with the term poly(vinyl butyral).
- poly(vinyl butyrate) is meant to refer to a polymer that comprises butyral groups. Since not all hydroxyl groups of the poly(vinyl alcohol) react with aldehyde, polyvinyl butyral invariably contains a certain percentage of hydroxyl groups. Moreover, a small group of the acetal groups always remain in the polymer chain from the upstream transesterification during which poly(vinyl acetate) is converted to poly(vinyl alcohol).
- the final product has the character of a terpolymer of vinyl butyral, vinyl alcohol, and vinyl acetate.
- the vinyl alcohol unit is polar and hydrophilic and the vinyl butyral unit is hydrophobic.
- the chemical structure of polyvinyl butyral is shown below.
- the vinyl alcohol content in commercial polyvinyl butyral can typically be in the range of 5-30 % by total weight of the polyvinyl butyral, such as from 10-25 %, whereas the vinyl acetate content may be in the range of 0-2.5 % by total weight of the polyvinyl butyral, such as 0-2 %.
- the polyvinyl butyral may be virgin polyvinyl butyral, but it is also possible to use polyvinyl butyral that originates from a recycle stream. Such polyvinyl butyral is referred herein as recycled polyvinyl butyral.
- the recycled polyvinyl butyral may originate from various sources, including laminated safety glass (such as from automobile windshields or from construction), photovoltaic modules, flexible packaging, etc.
- the polyvinyl butyral has a weight average molecular weight M w of 70000 g/mol or more, as determined by size exclusion chromatography using low angle laser light scattering, such as 100000 g/mol to 250000 g/mol, or 120000 g/mol to 200000 g/mol.
- the polyvinyl butyral has a melt flow index of 1-10 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 2-7 g/10 min, such as 3-6 g/10 min, or 4-5 g/10 min.
- the surface covering of the invention comprises polyvinyl butyral in an amount of 60-90 % by total weight of the surface covering.
- the surface covering comprises polyvinyl butyral in an amount of 62-88 % by total weight of the surface covering, such as 65-85 %, 68-82 %, or 70-80 %.
- the surface covering can comprise an amount of polymer material of 60 % or more based on total weight of surface covering, such as 65 % or more, or 75 % or more.
- organophosphorus oil as used herein is meant to refer to any nonpolar chemical substance that comprises at least one phosphorus atom, is a viscous liquid at 20 °C, and is both hydrophobic and lipophilic.
- the organophosphorus oil may suitably be a phosphorus containing vegetable-oil based derivative, i.e. a vegetable oil that has been modified to comprise one or more phosphorus atoms.
- organohalogen oil as used herein is meant to refer to any nonpolar chemical substance that comprises at least one halogen atom, is a viscous liquid at 20 °C, and is both hydrophobic and lipophilic.
- the organohalogen oil may suitably be a halogen containing vegetable-oil based derivative, i.e. a vegetable oil that has been modified to comprise one or more halogen atoms.
- the surface covering of the invention at least comprises one or more organophosphorus oils, such as one or more phosphorus containing vegetable oil-based derivatives.
- the organophosphorus oil and/or organohalogen oil may be based on one or more vegetable oils.
- Examples thereof include castor oil, linseed oil, sunflower oil, corn oil, cotton oil, coconut oil, algae oil, jatropha oil, soybean oil, cashew nut oil, rapeseed oil, walnut oil, safflower oil, grapeseed oil, canola oil, sesame oil, peanut oil, olive oil, palm oil, camelina oil and the like.
- These vegetable oils may be treated in a variety of conventional ways that are commonly known to the person skilled in the art in order to produce derivatives that contain phosphorus and/or halogen.
- One possible way of obtaining a phosphorus containing vegetable oil-based derivative is by epoxidation.
- castor oil can be esterified at hydroxyl groups and then epoxidised at unsaturation producing epoxidised castor oil polyol ester, which can subsequently be treated with phosphorus oxychloride forming chlorophosphate ester of castor oil.
- Another example is to epoxidise castor oil at the double bond and then modifying the inserted oxirane ring with diethyl phosphate in the presence of triphenylphosphine, thereby producing a castor oil phosphate ester.
- Yet a further example is to epoxidise soybean oil followed by epoxide ring opening reaction with phosphoric acid, and treatment of the formed phosphorylated polyols with polymeric diphenyl methane diisocyanate to produce phosphorylated polyol polyurethanes.
- castor oil is epoxidised, and phosphaphenanthrene groups are inserted on epoxidised castor oil by oxirane ring opening reaction.
- hydroxyl groups of castor oil and hydroxyl groups formed during oxirane ring opening can then be esterified yielding a castor oil polyester with phosphaphenanthrene groups
- Another approach to obtain a phosphorus containing vegetable oil-based derivative is by glycerolysis.
- castor oil reacted with glycerol in the presence of sodium methoxide and triethanolamine thereby forming monoglyceride and diglyceride of castor oil.
- These can be further epoxidised at double bonds, and the epoxy ring opening reaction with diethyl phosphate to form a phosphorus containing polyol derivative of castor oil.
- glycerolysed products of castor oil, monoglyceride and diglyceride are epoxidised and phosphaphenanthrene groups are inserted in castor oil mono- and diglycerides by epoxide ring opening reaction.
- the hydroxyl groups of castor oil and those formed by epoxide ring opening are then further esterified to produce phosphaphenanthrene-containing castor oil polyols.
- the phosphorus may be introduced into the vegetable oil by means of functional groups including phosphaphenanthrene groups, diphenyl phosphine oxide groups, diethyl phosphate groups, chlorinated phosphate groups, phosphonate groups, phosphine groups, phosphine oxide groups, phosphinite groups, phosphonite groups, phosphinate groups, phosphate groups, any combinations thereof.
- the phosphorus containing vegetable oil-based derivative can comprise one or more phosphorus containing groups selected from the group consisting of phosphaphenanthrene groups, diphenyl phosphine oxide groups, diethyl phosphate groups, chlorinated phosphate groups, and phosphonate groups.
- organophosphorus oils such as tris(dichloropropyl) phosphate (available under the trademark FYROL ® FR-2 from ICL Industrial Products), neopentyl glycol bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate) (available under the trademark FYROLFLEX ® RDP from ICL Industrial Products), bisphenol A bis(diphenyl phosphate) (available under the trademark FYROLFLEX ® BDP from ICL Industrial Products), butylated triphenyl phosphate (available under the trademark PHOSFLEX ® 71B from ICL Industrial Products), and isopropylated triphenyl phosphate (available under the trademark PHOSFLEX ® 31L from ICL Industrial Products).
- organophosphorus oils such as tris(dichloropropyl) phosphate (available under the trademark FYROL ® FR-2 from ICL Industrial Products), neopentyl glycol bis(diphenyl phosphate
- the surface covering of the invention comprises resorcinol bis(diphenyl phosphate) and/or bisphenol A bis(diphenyl phosphate) as organophosphorus oil.
- the surface covering may, alternatively or in addition, include one or more organohalogen oils, preferably organobromine oils and/or organochlorine oils.
- organohalogen oils for example, include halogenated vegetable oils, such as halogenated castor oil, halogenated soybean oil, and halogenated ricinoleic esters.
- Such compounds can, for example, be synthesised by reacting epoxidized vegetable oil with hydrochloric or hydrobromic acid in a solvent.
- Other synthesis routes include, e.g.
- the total amount of organophosphorus oil and/or organohalogen oil in the surface covering is in the range of 1-15 % by total weight of the surface covering.
- the total amount of organophosphorus oil and/or organohalogen oil in the surface covering is in the range of 2-14 %, 2-13 %, 3-12 %, 4-12 %, 4-11 %, 3-11 %, 3-10 %, or 5-10 %.
- the surface covering of the invention comprises one or more organophosphorus oils containing diphenyl phosphate and/or triphenyl phosphate groups, such as neopentyl glycol bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), butylated triphenyl phosphate, isopropylated triphenyl phosphate, triphenyl phosphate, isodecyl diphenyl phosphate, and cresyl diphenyl phosphate.
- organophosphorus oils containing diphenyl phosphate and/or triphenyl phosphate groups such as neopentyl glycol bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), butylated triphenyl phosphate, isopropylated triphenyl phosphate, triphenyl
- organophosphorus oils may preferably be present in an amount of 1-15 % by total weight of the surface covering, such as 2-14 %, 2-13 %, 3-12 %, 4-12 %, 4-11 %, 3-11 %, 3-10 %, or 5-10 %.
- the organophosphorus oil and/or organohalogen oil has flame retarding properties, the presence of additional flame retardants that are not organophosphorus oil or organohalogen oil may be limited. Additional flame retardants that may be present in the surface covering of the invention include e.g.
- ammonium polyphosphate aluminium trihydrate, magnesium hydroxide, zinc stannate, antimony trioxide, zirconium phosphate, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, 2,4,6-triamino-1,3,5-triazine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, mixtures of piperazine pyrophosphate and melamine pyrophosphate, piperazine pyrophosphate, a phosphonitrilic chloride, a phosphorus ester amide, a phosphoric acid amide, a phosphonic acid amide, a phosphinic acid amide, piperizine polyphosphate, phenyl-bis(dodecyl) phosphate, phenyl-bis(neopentyl) phosphate, phenyl ethylene hydrogen phosphate,
- the surface covering comprises, next to the organophosphorus and/or organohalogen oil, as additional flame retardants one or more selected from ammonium polyphosphate and aluminium trihydrate, preferably both.
- the relatively expensive ammonium polyphosphate is used in limited amounts.
- the weight ratio between aluminium trihydrate and ammonium polyphosphate can accordingly be in the range of from 20 : 1 to 3 : 1, preferably from 15 : 1 to 5 : 1, more preferably from 12 : 1 to 8 : 1.
- the surface covering of the invention comprises 1-5 % by total weight of the surface covering of ammonium polyphosphate (such as 2-4 %) and 10-40 % by total weight of the surface covering of aluminium trihydrate (such as 15-35 %).
- the surface covering further comprises a crosslinker selected from the group consisting of pentaerythritol, stearyl alcohol and mannitol, preferably pentaerythritol.
- a crosslinker selected from the group consisting of pentaerythritol, stearyl alcohol and mannitol, preferably pentaerythritol.
- these compounds Upon heating, such as above 250 °C, these compounds cause cross-linking of the polyvinyl butyral material, thereby forming a thick carbon barrier.
- the organophosphorus oil and/or the organohalogen oil has plasticising properties, the presence of additional plasticisers that are not organophosphorus oil or organohalogen oil may be limited. Additional plasticisers that may be present in the surface covering of the invention include e.g.
- plasticisers that are not based on vegetable oil include, aromatic diesters, such as diisononyl phthalate, diisodecyl phthalate, linear dinonyl phthalate (L9P), dioctyl terephthalate, dibutyl phthalate, dioctyl phthalate, benzylbutylphthalate and dihexyl phthalate, aliphatic diesters, such as diisononyl adipate and diisodecyl adipate, aromatic sulphonamides, such as N-n-butylbenzenesulphonamide, aromatic phosphate esters, such as tricresyl phosphate and trixylyl phosphate, alkyl phosphate esters, such as tributyl phosphate and tri-iso-octyl phosphat
- plasticisers not being organophosphorus oil or organohalogen oil may, for instance, be present in amounts of 5 % or less by total weight of the surface covering, such as 4 % or less, 1 % or less, 0.5 % or less, or 0.1 % or less.
- the presence of the organophosphorus oil and/or organohalogen oil improves the processability of the polyvinyl butyral surprisingly well.
- melt flow index of the compound composition used for preparing the surface covering of the invention is suitably 10-50 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 12-40 g/10 min, such as 14-35 g/10 min, 15-30 g/10 min, or 15-25 g/10 min.
- the surface covering may comprise one or more colouring agent, in particular a white pigment. This may, for example, be advantageous in applications where the surface covering is exposed to ultraviolet radiation, such as by sunlight.
- Preferred colouring agents include titanium dioxide, and barium sulphate.
- the colouring agent may serve to increase reflection of ultraviolet radiation.
- the increased reflection has the effect that the surface covering will heat up less.
- the white pigment may serve as a blocker of ultraviolet radiation and slow down any degradation of organic material, such as the polyvinyl butyral and/or phosphorus containing vegetable oil-based derivative.
- the presence of a colouring agent, such as a white pigment is particularly advantageous in case the surface covering is a roof covering, or a façade covering.
- the amount of colouring agent in the surface covering may be in the range of 10 % or less by total weight of the surface covering, such as in the range of 0.1-10 %, 0.1-9 %, 0.2-8 %, 0.3-7 %, 0.5-5 %, or 1-3 %.
- the reflectance of the surface covering may also be expressed as in terms of Solar Reflectance Index (SRI).
- SRI is a measure of the solar reflectance and emissivity of materials that can be used as an indicator of how hot materials are likely to become when solar radiation is incident on the surface thereof. The lower the SRI, the hotter a material is likely to become in the sunshine. SRI can be measured in accordance with ASTM E 1980-01.
- the surface covering of the invention has a SRI of 20 or higher, such as 30 or higher, 40 or higher, or even 50 or higher.
- the surface covering of the invention may further comprise one or more additives.
- additives may suitably be selected from the group consisting of ultraviolet blocking agents, blowing agents, antioxidants, processing aids, pigments, dyes, fillers, antibacterial agents, release agents, heat stabilisers, light stabilisers, compatibilisers, inorganic material additives, surfactants, coupling agents, impact-reinforcing agents, lubricants, weather-resistant agents, adhesion aids, adhesives, and any combination thereof.
- suitable ultraviolet blocking agents include titanium dioxide, carbon black, and combinations thereof.
- blowing agents examples include azodicarbonamide, expandable microspheres, p-p'-oxy-bis(benzenesulphonylhydrazide), p-toluene sulphonyl semicarbizide, sodium bicarbonate, citric acid, and any combination thereof. If present, the amount of the blowing agents can be 5 % or less by total weight of the surface covering, preferably in the range of 0.01-4 %, more preferably in the range of 0.05-3 %.
- suitable processing aids include metal salts of carboxylic acids, such as zinc stearate or calcium stearate, fatty acids, such as stearic acid, oleic acid or erucic acid, fatty amides, such as stearamide, oleamide, erucamide or N,N'-ethylene bis-stearamide, polyethylene wax, oxidised polyethylene wax, polymers of ethylene oxide, copolymers of ethylene oxide and propylene oxide, vegetable waxes, petroleum waxes, non-ionic surfactants, fluoropolymers, such as polytetrafluoroethylene and the like, and polysiloxanes.
- carboxylic acids such as zinc stearate or calcium stearate
- fatty acids such as stearic acid, oleic acid or erucic acid
- fatty amides such as stearamide, oleamide, erucamide or N,N'-ethylene bis-stearamide
- polyethylene wax oxidised polyethylene
- the amount of the processing aids can be 5 % or less by total weight of the surface covering, preferably in the range of 0.05-5 %, more preferably in the range of 0.1-3 %.
- suitable pigments include carbon black, titanium dioxide, barium sulphate, and any combination thereof.
- the amount of the pigments can be 10 % or less by total weight of the surface covering, preferably in the range of 0.5-10 %, more preferably in the range of 1-5 %.
- suitable dyes include organic dyes, such as coumarins, lanthanide complexes, hydrocarbon and substituted hydrocarbon dyes, polycyclic aromatic hydrocarbons, scintillation dyes (preferably oxazoles and oxadiazoles), aryl- or heteroaryl-substituted poly(C 2-8 olefins), carbocyanine dyes, phthalocyanine dyes and pigments, oxazine dyes, carbostyryl dyes, porphyrin dyes, acridine dyes, anthraquinone dyes, arylmethane dyes, azo dyes, diazonium dyes, nitro dyes, quinone imine dyes, tetrazolium dyes, thiazole dyes, perylene dyes, perinone dyes, bis-benzoxazolylthiophene, xanthene dyes, and any combination thereof.
- organic dyes such as coumarins, lanthanide complex
- the amount of the dyes can be 5 % or less by total weight of the surface covering, such as 0.1-5 %, 0.2-4 %, 0.3-3 %, or 0.5-2 %.
- suitable fillers include carbon black, wollastonite, solid microspheres, hollow microspheres, kaolin, clay-based minerals, bauxite, calcium carbonate, feldspar, barium sulphate, titanium dioxide, talc, pyrophyllite, quartz, natural silica, such as crystalline silica and microcrystalline silica, synthetic silicates, such as calcium silicate, zirconium silicate and aluminium silicate, including mullite, sillimanite, cyanite, andalusite and synthetic alkali metal aluminosilicates, microcrystalline novaculite, diatomaceous silica, perlite, synthetic silica, such as fumed silica and precipitated silica, antimony oxide, bentonite, mica, vermiculite, zeolite, and
- the amount of fillers is 10 % or less by total weight of the surface covering, such as 1-8 %, or 2-5 %.
- suitable antioxidants include hindered phenols, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, bis[( ⁇ -(3,5-di-tert-butyl-4-hydroxybenzyl)-methylcarboxyethyl)] sulphide, 4,4'-thio-bis(2-methyl-6-tert-butylphenol), 4,4'-thio-bis(2-tert-butyl-5-methylphenol), 2,2'-thio-bis(4-methyl-6-tert-butylphenol), thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate, phosphites and phosphonites, such as tris(2,4-di-tert-
- Primary antioxidants function as radical catchers and particularly remove peroxyl radicals (ROO•) and, to a lesser extent, alkoxy radicals (RO•), hydroxyl radicals (HO•), and alkyl radicals (R•). Oxidation begins with the formation of alkyl radicals, which react rapidly with molecular oxygen and thus form peroxyl radicals.
- Secondary antioxidants particularly remove organic hydroperoxides (ROOH) formed by the effect of primary oxidants. Hydroperoxides are less reactive than radicals, but undergo hemolytic bonding and break new radicals.
- the amount of the antioxidants can be 5 % or less by total weight of the surface covering, preferably in the range of 0.1-5 %, more preferably in the range of 0.2-3 %.
- the weather-resistance agents include benzophenone-type weather resistance agents, amine-type weather resistance agents, and combinations thereof.
- the total amount of additives is preferably 10 % or less by total weight of the surface covering, such as 0.1-10 %, 0.2-8 %, 0.3-5 %, or 0.5-3 %.
- the surface covering can comprise a support carrier. Such a support carrier may further improve the mechanical properties of the surface covering. Suitable support carriers may be selected from the group consisting of glass fibre, carbon fibre, basalt fibre, natural fibres (e.g.
- the support carrier comprises glass fibre.
- the support may have the form of a laminate.
- the surface covering is self-supporting.
- the surface covering may have a fibrous material content of 1 % or less based on total weight of the surface covering, such as 0.5 % or less, or 0.1 % or less.
- the surface covering is free from fibrous material in these embodiments.
- the surface covering may comprise one or more additional polymers.
- thermoplastic polyurethanes polyisobutenes, polychloroprene, polycaprolactones, polyesters, thermoplastic polyolefins, polyolefins, silicones, siloxanes, thermoplastic elastomers, including vulcanised thermoplastic elastomers and styrenic block copolymers, polyvinyl chlorides, styrene butadiene copolymers including poly(styrene-butadiene-styrene), poly(styrene-ethylene/butadiene-styrene) and poly(styrene-ethylene/propylene-styrene), copolymers of ethylene and vinylacetate.
- the additional polymers can comprise one or more selected from the group consisting of polyisobutenes, polycaprolactones, polyesters, silicones, thermoplastic elastomers, such as vulcanised thermoplastic elastomers and styrenic block copolymers, thermoplastic polyolefins, and thermoplastic polyurethanes.
- the surface covering of the invention comprises - polyvinyl butyral, preferably in an amount of 50-90 % by total weight of the surface covering, such as 60-90 %, 60-80 %, or 60-70 %; - one or more organophosphorus oils and/or one or more organohalogen oils, preferably in an amount of 1-15 % by total weight of the surface covering, such as 2-12 % or 3-10 %; - ammonium polyphosphate, preferably in an amount of 1-5 % by total weight of the surface covering, such as 2-4 %; and - aluminium trihydrate, preferably in an amount of 10-40 % by total weight of the surface covering, such as 15-35 %, or 20-30 %.
- a surface covering comprising - polyvinyl butyral, preferably in an amount of 50-90 % by total weight of the surface covering, such as 60-90 %, 60-80 %, or 60-70 %; - organophosphorus oil comprising one or more biphenyl phosphate and/or triphenyl phosphate groups, preferably in an amount of 1-15 % by total weight of the surface covering, such as 2-12 % or 3-10 %; - ammonium polyphosphate, preferably in an amount of 1-5 % by total weight of the surface covering, such as 2-4 %; and - aluminium trihydrate, preferably in an amount of 10-40 % by total weight of the surface covering, such as 15-35 %, or 20-30 %.
- Different components of the surface covering described herein may be present in a single layer (i.e. two or more selected from polyvinyl butyral, one or more organophosphorus oils and/or one or more organohalogen oils, additional flame retardant, crosslinker, additional plasticiser, colouring agent, ultraviolet blocking agents, blowing agents, antioxidants, processing aids, pigments, dyes, fillers, antibacterial agents, release agents, heat stabilisers, light stabilisers, compatibilisers, inorganic material additives, surfactants, coupling agents, impact-reinforcing agents, lubricants, weather-resistant agents, adhesion aids, adhesives).
- a single layer i.e. two or more selected from polyvinyl butyral, one or more organophosphorus oils and/or one or more organohalogen oils, additional flame retardant, crosslinker, additional plasticiser, colouring agent, ultraviolet blocking agents, blowing agents, antioxidants, processing aids, pigments, dyes, fillers, antibacterial agents, release agents, heat stabili
- the polyvinyl butyral and the one or more organophosphorus oils and/or one or more organohalogen oils are present in the same layer of the surface covering.
- the surface covering is a single layer surface covering.
- the surface covering of the invention may suitably have a thickness in the range of 0.3-5 mm, such as 0.5-4 mm, 0.8-3 mm, or 1-2 mm.
- the surface covering may optionally comprise at least one release sheet for storage. The presence of such release sheet may provide protection to the synthetic flashing material when stored, such as on a roll.
- the release sheet may suitably be removed from the surface covering by peeling off before, during and/or after applying the surface covering to a surface, such as the surface of a construction.
- the release sheet may be present on the top and/or bottom of the surface covering.
- the release sheet may comprise one or more materials selected from the group consisting of polytetrafluoroethylene, silicones, waxed paper, parchment paper, plastic sheets, such as bubble wrap, and other release sheets known in the art.
- the surface covering of the invention can reach UL 94 V-2 flammability rating at a thickness of 1.5 mm, preferably UL 94 V-1, more preferably UL 94 V-0. The ratings refer to Underwriters-Laboratories standard UL 94. In the UL 94 test, a specimen is exposed vertically to a flame for 10 seconds. The specimen is ignited at the bottom and burns up.
- Flaming droplets are allowed to fall on cotton located below the sample. If the average burning time is less than 5 seconds (per application of flame) and the droplets do not ignite the cotton, the material is classified as UL 94 V-0. If the average of burning time is less than 25 seconds and the droplets do not ignite the cotton, the material is classified as UL 94 V-1. If the average burning time is less than 25 seconds but the droplets ignite the cotton, the material is classified as UL 94 V-2. Another way of determining flame retardancy is by performing a limiting oxygen index (LOI) measurement according to ISO 4589.
- LOI limiting oxygen index
- the surface covering of the invention can reach a LOI value of 21.0 % or more, more preferably 22.0 % or more.
- the inventors surprisingly found that a surface covering of the invention including the organophosphorus oil and/or organohalogen oil has improved rigidness, as compared to a surface covering lacking said component.
- the invention is directed to a method for preparing a surface covering as described herein, comprising a) providing a feed stream of recycled polyvinyl butyral, b) optionally, pre-treating the feed stream of recycled polyvinyl butyral to remove one or more components therefrom, preferably said one or more components comprise volatile plasticisers, c) compounding the feed stream of recycled polyvinyl butyral from step a) or the pre-treated feed stream of recycled polyvinyl butyral from step b) with one or more organophosphorus oils and/or one or more organohalogen oils, and d) forming the compounded material into a layer to produce the surface covering.
- the feed stream of recycled polyvinyl butyral in step a) has a melt flow index of 1-10 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 2-7 g/10 min, such as 3-6 g/10 min, or 4-5 g/10 min.
- the optional pre-treatment in step b) is highly advantageous since recycled polyvinyl butyral typically originates from various sources with varying plasticiser content.
- the optional pre-treatment in step b) allows for removing undesirable components (such as relatively volatile components including plasticisers) from the recycled polyvinyl butyral, resulting in a polymer product having more constant properties, such as melt flow index.
- said pre-treating step b) comprises feeding the feed stream of recycled polyvinyl butyral to an extruder, melting said feed stream in the extruder to produce polymer melt and passing said polymer melt through one or more degassing zones connected to a vacuum pump, and measuring the melt flow index of the polymer product, wherein the vacuum pump is operated at a pressure that is controlled by the measured melt flow index of the polymer product.
- a vacuum pump is operated at a pressure that is controlled by the measured melt flow index of the polymer product.
- step c) the feed stream of recycled polyvinyl butyral from step a) or the pre-treated feed stream of recycled polyvinyl butyral from step b) is compounded together with one or more organophosphorus oils and/or organohalogen oils and, optionally, any other components that are used in the surface covering.
- the melt flow index of the compound composition with the organophosphorus oil and/or organohalogen oil in step c) that is used for forming the surface covering in step d) is suitably 10-50 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 12-40 g/10 min, such as 14-35 g/10 min, 15-30 g/10 min, or 15-25 g/10 min. Then, the compounded material may be formed into a layer to produce the surface covering.
- step c) and/or step d) of the method for preparing the surface covering of the invention are performed at a temperature of 190 °C or less, more preferably at a temperature of 180 °C, such as at a temperature of 175 °C or less.
- a temperature of 190 °C or less is then preferably supplied on a roll for storage and transport, optionally using a release sheet as described herein.
- a roll may have a width of typically 0.5-5 m, such as 1-4 m, or 1.5-3 m.
- the lengths of the roll may be 5-200 m, such as 10-150 m, 12-100 m or 15-80 m.
- the invention is directed to a method for applying a surface covering as described herein onto a surface, comprising i) applying strips of surface covering on a surface, whereby adjacent strips of surface covering have overlapping regions; and ii) bonding the overlapping regions of the strips of surface covering using an alcohol solvent.
- the surface covering can thus readily be applied on a surface, thereby allowing for a waterproof seam.
- the alcohol solvent preferably comprises one or more selected from the group of methanol, ethanol, iso-propyl alcohol, n-propyl alcohol, tert-butyl alcohol, n-butanol, and iso-butyl alcohol. More preferably, the alcohol solvent comprises or is iso-propyl alcohol.
- the alcohol solvent is provided with a colour indicator.
- a colour indicator Some suitable but non-limiting examples thereof include methylene blue, methyl viologen, isosulfan blue and indigo carmine.
- the alcohol solvent comprises methylene blue.
- the colour indicator will be uncovered, which can advantageously serve as an identifier for the origin of the strips of surface covering.
- small pieces of surface covering are fixed on the surface, such as by screwing, at regular intervals.
- the strips of surface covering can thereafter be bonded to these fixed small pieces using alcohol solvent. This allows easy recovery of the strips of surface covering at the end of its service life. New strips of surface covering can then be applied on the remaining fixed small pieces.
- Table 1 The results are shown in Table 1 below.
- Table 1 Examples D and E which include the resorcinol bis(diphenyl phosphate) showed a surprising increase in limiting oxygen index, as compared to Examples A and C, which have about the same total amount of fire retardant as Example D and E, respectively.
- tensile test specimens type 1A according to ISO 527-2 were cut from a surface covering and analysed using dynamic mechanical analysis (DMA). The storage modulus and loss modulus of the samples was determined at room temperature. The sample was clamped in a single cantilever clamp and oscillated at different frequencies (1 to 100 Hz) and an amplitude of 0.1 % strain.
- DMA dynamic mechanical analysis
- the storage modulus represents the strength of the material and the loss modulus represents the ability to absorb and dissipate energy.
- the results of three different samples are shown in Figure 1.
- Samples 1 and 3 are samples with 70 wt.% PVB, 27.27 wt.% of ATH and 2.73 wt.% of APP.
- Sample 2 is a sample with 70.9 wt.% PVB, 18.2 wt.% of ATH, 1.82 wt.% of APP, and 9.09 wt.% of RDP oil.
- Both samples without the resorcinol bis(diphenyl phosphate) oil (Samples 1 and 3) have comparable strength values.
- the sample with resorcinol bis(diphenyl phosphate) oil (Sample 2) is surprisingly more rigid than the other samples.
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Abstract
The invention is directed to a surface covering, to a method for preparing said surface covering, and to a method for applying said surface covering. The surface covering of the invention comprises - 60-90 % by total weight of the surface covering of polyvinyl butyral, and - 1-15 % by total weight of the surface covering of one or more organophosphorus oils and/or one or more organohalogen oils.
Description
Title: SURFACE COVERING The invention is directed to a surface covering, to a method for preparing said surface covering, and to a method for applying said surface covering. Watertight surface coverings are used in construction for waterproofing surfaces, such as roofs, facades, etc. Conventional materials used for such surface coverings are based, for instance, on bitumen, polyvinyl chloride, polychloroprene, or ethylene propylene diene monomer (EPDM). Another material suggested in the art to be advantageous for flashing material or roofing material is polyvinyl butyral. For example, WO-A-2016/108686 discloses a lead alternative flashing material comprising a perforated sheet of metal attached to a thermoplastic layer that may comprise polyvinyl butyral. WO-A-2020/122727 discloses a synthetic flashing material comprising 75 wt.% or more of polymer, such as polyvinyl butyral, and less than 10 wt.% of metal. WO-A-2021/064634 discloses a construction material comprising polyvinyl butyral and an ammonium polyphosphate fire retardant. WO-A-2017/064260 discloses a decorative multi-layer surface covering comprising polyvinyl butyral. WO-A-2020/156740 discloses cellulose ester compositions for surface coverings. Polyvinyl butyral is an industrially important polymer widely used in laminated safety glass and surface treatments because it exhibits a very high adhesion to glass. The primary use of polyvinyl butyral is in safety glass laminates, particularly in automotive and architectural glass. A layer of polyvinyl butyral is compressed between two sheets of glass under heat and pressure. The resulting glass sandwich looks like any other normal sheet of glass. Although laminated glass can break, the pieces of glass remain intact, adhering to the protective polyvinyl butyral layer. Laminated
glass has numerous benefits as a result of its safety properties (no injuries caused by flying shards of glass) and its sound insulation properties. Recycling safety glass and extracting the polyvinyl butyral therefore provides an easily accessible and widely available source of polyvinyl butyral. Like polyvinyl chloride, polyvinyl butyral is a promising material for use in surface coverings. However both materials behave fundamentally different, because polyvinyl chloride is a hydrophobic material, and as a consequence impermeable to moisture. Additionally, polyvinyl chloride typically suffers from leaking plasticiser, which causes the polyvinyl chloride surface covering to become brittle over time. Polyvinyl butyral on the other hand can take up and release relatively large amounts of moisture. Although the material is not permeable to water in liquid form, it does allow permeation of vapour. Polyvinyl butyral further has limited capacity for oil uptake. While polyvinyl butyral is a promising material for use in surface coverings, the compounding of polyvinyl butyral with other components is challenging, in particular when the polyvinyl butyral used is recycled polyvinyl butyral that originates from various recycle sources. Processability problems arise when blending and extruding the polyvinyl butyral with other components. Addition of such other components, however, may be required for depending on the application of the product. Polyvinyl butyral is, for instance, typically heavily plasticised in order to improve mechanical and rheological properties. Furthermore, when used as surface covering measures have to be taken in order to prevent the material from combusting. When exposed to fire, polymers (being mainly made up of carbon and hydrogen) generally burn rapidly, releasing a lot of heat and smoke, and potentially causing great damage. The use of flame retardants has therefore become essential from the viewpoint of safety and environment. Flame retardants stop or
inhibit the polymer combustion process, acting physically or chemically, by interfering with heating, pyrolysis, ignition, and/or thermal degradation. Many flame retardants, however, are still based on petroleum resources. Flame retardants from bio-based resources would be a desirable alternative. The invention aims at providing a surface covering comprising polyvinyl butyral that has excellent processability. Further objective of the invention is to provide a polyvinyl butyral based surface covering that can be easily compounded with other components. Another objective of the invention is to provide a polyvinyl butyral based surface covering having limited amount of plasticiser. Yet a further objective of the invention is to provide a polyvinyl butyral based surface covering comprising a bio-based flame retardant. Yet another objective of the invention is to provide a surface covering that can be easily glued together with good adhesion strength. The inventors found that one or more of these objectives can be met, at least in part, by a surface covering comprising a specific combination of polyvinyl butyral and a phosphorus containing oil that simultaneously acts as plasticiser and flame retardant. Accordingly, in one aspect the invention is directed to a surface covering comprising - 60-90 % by total weight of the surface covering of polyvinyl butyral, and - 1-15 % by total weight of the surface covering of one or more organophosphorus oils and/or one or more organohalogen oils. The inventors found that the use of an organophosphorus oil and/or an organohalogen oil surprisingly improves the processability during compounding of the polyvinyl butyral based composition. The organophosphorus oil and/or the organohalogen oil further act both as plasticiser, so the currently used plasticiser content can be lowered, and it can act as flame retardant. Furthermore the oil helps to disperse other
flame retardants (inorganic) and therefore increases the effectiveness of the flame retardant action. The surface covering of the invention as a result requires overall less amount of plasticiser which makes that the resulting product can be better glued to another surface covering comprising polyvinyl butyral, preferably another surface covering of the invention. As will be described herein, the oil may advantageously be based on vegetable oil. Accordingly, the organophosphorus oil may be a phosphorus containing vegetable oil based derivative and/or the organohalogen oil may be a halogen containing vegetable oil based derivative. Such vegetable oils are domestically abundant, cost-effective, and non-toxic. In addition, they possess functional moieties such as double bonds, hydroxyl groups and ester groups which can readily undergo derivatisation reactions such as epoxidation, esterification, urethanation, alcoholysis, etc. which can then be easily modified e.g. by phosphorylation to introduce phosphorus and/or by halogenation to introduce halogen. The surface covering of the invention is particularly suitable for covering the surface of a roof, a basement, a façade, a wall, a floor or a pool. In such applications, the surface covering serves as a waterproof membrane. The term “polyvinyl butyral” as used herein is meant to refer to a polyacetal prepared by reacting poly(vinyl alcohol) with butyraldehyde, after obtaining poly(vinyl alcohol) by means of transesterification of from poly(vinyl acetate) usually with methanol and base catalysis. Polyvinyl butyral is commercially available from Monsanto Company as Butvar®. The conditions of the reaction between polyvinyl alcohol and butyraldehyde, and their relative concentrations are closely controlled to form polymers containing predetermined proportions of hydroxyl, acetate, and butyral groups. Although chemically not entirely correct, the term poly(vinyl butyrate) is in the art often interchangeably used with the term poly(vinyl butyral). As used in this application, the term “poly(vinyl butyrate)” is meant to refer to a polymer that comprises butyral groups. Since not all
hydroxyl groups of the poly(vinyl alcohol) react with aldehyde, polyvinyl butyral invariably contains a certain percentage of hydroxyl groups. Moreover, a small group of the acetal groups always remain in the polymer chain from the upstream transesterification during which poly(vinyl acetate) is converted to poly(vinyl alcohol). Therefore, the final product has the character of a terpolymer of vinyl butyral, vinyl alcohol, and vinyl acetate. The vinyl alcohol unit is polar and hydrophilic and the vinyl butyral unit is hydrophobic. The chemical structure of polyvinyl butyral is shown below.
The vinyl alcohol content in commercial polyvinyl butyral can typically be in the range of 5-30 % by total weight of the polyvinyl butyral, such as from 10-25 %, whereas the vinyl acetate content may be in the range of 0-2.5 % by total weight of the polyvinyl butyral, such as 0-2 %. The polyvinyl butyral may be virgin polyvinyl butyral, but it is also possible to use polyvinyl butyral that originates from a recycle stream. Such polyvinyl butyral is referred herein as recycled polyvinyl butyral. The recycled polyvinyl butyral may originate from various sources, including laminated safety glass (such as from automobile windshields or from construction), photovoltaic modules, flexible packaging, etc. Typically, the polyvinyl butyral has a weight average molecular weight Mw of 70000 g/mol or more, as determined by size exclusion
chromatography using low angle laser light scattering, such as 100000 g/mol to 250000 g/mol, or 120000 g/mol to 200000 g/mol. Suitably, the polyvinyl butyral has a melt flow index of 1-10 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 2-7 g/10 min, such as 3-6 g/10 min, or 4-5 g/10 min. The surface covering of the invention comprises polyvinyl butyral in an amount of 60-90 % by total weight of the surface covering. Preferably, the surface covering comprises polyvinyl butyral in an amount of 62-88 % by total weight of the surface covering, such as 65-85 %, 68-82 %, or 70-80 %. Suitably, the surface covering can comprise an amount of polymer material of 60 % or more based on total weight of surface covering, such as 65 % or more, or 75 % or more. The term “organophosphorus oil” as used herein is meant to refer to any nonpolar chemical substance that comprises at least one phosphorus atom, is a viscous liquid at 20 °C, and is both hydrophobic and lipophilic. The organophosphorus oil may suitably be a phosphorus containing vegetable-oil based derivative, i.e. a vegetable oil that has been modified to comprise one or more phosphorus atoms. The term “organohalogen oil” as used herein is meant to refer to any nonpolar chemical substance that comprises at least one halogen atom, is a viscous liquid at 20 °C, and is both hydrophobic and lipophilic. The organohalogen oil may suitably be a halogen containing vegetable-oil based derivative, i.e. a vegetable oil that has been modified to comprise one or more halogen atoms. Preferably, the surface covering of the invention at least comprises one or more organophosphorus oils, such as one or more phosphorus containing vegetable oil-based derivatives. The organophosphorus oil and/or organohalogen oil may be based on one or more vegetable oils. Examples thereof include castor oil, linseed
oil, sunflower oil, corn oil, cotton oil, coconut oil, algae oil, jatropha oil, soybean oil, cashew nut oil, rapeseed oil, walnut oil, safflower oil, grapeseed oil, canola oil, sesame oil, peanut oil, olive oil, palm oil, camelina oil and the like. These vegetable oils may be treated in a variety of conventional ways that are commonly known to the person skilled in the art in order to produce derivatives that contain phosphorus and/or halogen. One possible way of obtaining a phosphorus containing vegetable oil-based derivative is by epoxidation. By way of example, castor oil can be esterified at hydroxyl groups and then epoxidised at unsaturation producing epoxidised castor oil polyol ester, which can subsequently be treated with phosphorus oxychloride forming chlorophosphate ester of castor oil. Another example is to epoxidise castor oil at the double bond and then modifying the inserted oxirane ring with diethyl phosphate in the presence of triphenylphosphine, thereby producing a castor oil phosphate ester. Yet a further example is to epoxidise soybean oil followed by epoxide ring opening reaction with phosphoric acid, and treatment of the formed phosphorylated polyols with polymeric diphenyl methane diisocyanate to produce phosphorylated polyol polyurethanes. In another example, castor oil is epoxidised, and phosphaphenanthrene groups are inserted on epoxidised castor oil by oxirane ring opening reaction. The hydroxyl groups of castor oil and hydroxyl groups formed during oxirane ring opening can then be esterified yielding a castor oil polyester with phosphaphenanthrene groups Another approach to obtain a phosphorus containing vegetable oil-based derivative is by glycerolysis. For example, castor oil reacted with glycerol in the presence of sodium methoxide and triethanolamine thereby forming monoglyceride and diglyceride of castor oil. These can be further epoxidised at double bonds, and the epoxy ring opening reaction with diethyl phosphate to form a phosphorus containing polyol derivative of castor oil. According to another example, glycerolysed products of castor oil, monoglyceride and diglyceride, are epoxidised and phosphaphenanthrene
groups are inserted in castor oil mono- and diglycerides by epoxide ring opening reaction. The hydroxyl groups of castor oil and those formed by epoxide ring opening are then further esterified to produce phosphaphenanthrene-containing castor oil polyols. Many other possible synthesis routes exist and are readily available to the person skilled in the art. The phosphorus may be introduced into the vegetable oil by means of functional groups including phosphaphenanthrene groups, diphenyl phosphine oxide groups, diethyl phosphate groups, chlorinated phosphate groups, phosphonate groups, phosphine groups, phosphine oxide groups, phosphinite groups, phosphonite groups, phosphinate groups, phosphate groups, any combinations thereof. The phosphorus containing vegetable oil-based derivative can comprise one or more phosphorus containing groups selected from the group consisting of phosphaphenanthrene groups, diphenyl phosphine oxide groups, diethyl phosphate groups, chlorinated phosphate groups, and phosphonate groups. Apart from using vegetable oils, it is also possible to use other organophosphorus oils, such as tris(dichloropropyl) phosphate (available under the trademark FYROL® FR-2 from ICL Industrial Products), neopentyl glycol bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate) (available under the trademark FYROLFLEX® RDP from ICL Industrial Products), bisphenol A bis(diphenyl phosphate) (available under the trademark FYROLFLEX® BDP from ICL Industrial Products), butylated triphenyl phosphate (available under the trademark PHOSFLEX® 71B from ICL Industrial Products), and isopropylated triphenyl phosphate (available under the trademark PHOSFLEX® 31L from ICL Industrial Products). Preferably, the surface covering of the invention comprises resorcinol bis(diphenyl phosphate) and/or bisphenol A bis(diphenyl phosphate) as organophosphorus oil.
According to the invention, the surface covering may, alternatively or in addition, include one or more organohalogen oils, preferably organobromine oils and/or organochlorine oils. Suitably organohalogen oils, for example, include halogenated vegetable oils, such as halogenated castor oil, halogenated soybean oil, and halogenated ricinoleic esters. Such compounds can, for example, be synthesised by reacting epoxidized vegetable oil with hydrochloric or hydrobromic acid in a solvent. Other synthesis routes include, e.g. providing hydroxylated natural oil, and contacting the hydroxylated natural oil with halogenated reactive material such as halogenated anhydride or organic acid and alkyl esters or halogenated anhydrides or organic esters to halogenise the natural oil. The total amount of organophosphorus oil and/or organohalogen oil in the surface covering is in the range of 1-15 % by total weight of the surface covering. Preferably the total amount of organophosphorus oil and/or organohalogen oil in the surface covering is in the range of 2-14 %, 2-13 %, 3-12 %, 4-12 %, 4-11 %, 3-11 %, 3-10 %, or 5-10 %. Such amounts allow for excellent flame retardancy properties, while at the same time providing desirable processability. In a preferred embodiment, the surface covering of the invention comprises one or more organophosphorus oils containing diphenyl phosphate and/or triphenyl phosphate groups, such as neopentyl glycol bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), butylated triphenyl phosphate, isopropylated triphenyl phosphate, triphenyl phosphate, isodecyl diphenyl phosphate, and cresyl diphenyl phosphate. Such organophosphorus oils may preferably be present in an amount of 1-15 % by total weight of the surface covering, such as 2-14 %, 2-13 %, 3-12 %, 4-12 %, 4-11 %, 3-11 %, 3-10 %, or 5-10 %. As the organophosphorus oil and/or organohalogen oil has flame retarding properties, the presence of additional flame retardants that are
not organophosphorus oil or organohalogen oil may be limited. Additional flame retardants that may be present in the surface covering of the invention include e.g. one or more selected from the group consisting of ammonium polyphosphate, aluminium trihydrate, magnesium hydroxide, zinc stannate, antimony trioxide, zirconium phosphate, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, 2,4,6-triamino-1,3,5-triazine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, mixtures of piperazine pyrophosphate and melamine pyrophosphate, piperazine pyrophosphate, a phosphonitrilic chloride, a phosphorus ester amide, a phosphoric acid amide, a phosphonic acid amide, a phosphinic acid amide, piperizine polyphosphate, phenyl-bis(dodecyl) phosphate, phenyl-bis(neopentyl) phosphate, phenyl ethylene hydrogen phosphate, phenyl-bis(3,5,5'-trimethylhexyl phosphate), ethyldiphenyl phosphate, 2-ethylhexyl di(p-tolyl)phosphate, diphenyl hydrogen phosphate, bis(2-ethylhexyl) p-tolylphosphate, tritolyl phosphate, bis(2-ethylhexyl)-phenyl phosphate, tri(nonylphenyl) phosphate, phenylmethyl hydrogen phosphate, di(dodecyl) p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, diphenyl hydrogen phosphate, resorcinol diphenyl phosphate, bisphenol A polyphosphate, bisphenol A diphenyl phosphate, bisphenol A diphosphate, (2,6-dimethylphenol)-1,3-phenylene bisphosphate, magnesium hydroxide, aluminium trihydrate (Al2O3·H2O), aluminium hydroxide Al(OH)3, huntite, hydromagnesite, antimony trioxide, potassium hydroxide, and other flame retardants, such as aluminium anhydrate, molybdenum disulphide, clay, diatomite, kaolinite, montmorillonite, hydrotalcite, talc, silica (e.g. precipitated silica and silicates, fumed silica, etc.), white carbon, celite, asbestos, ground minerals, lithopone, and any combination thereof.
Such additional flame retardants that are not organophosphorus oil or organohalogen oil (in particular the flame retardants as mentioned in the list above) may be present in the surface covering in amounts of 15 % or less by total weight of the surface covering, such as 10 % or less, 5 % or less, 1 % or less, 0.5 % or less, or 0.1 % or less. In a preferred embodiment, the surface covering comprises, next to the organophosphorus and/or organohalogen oil, as additional flame retardants one or more selected from ammonium polyphosphate and aluminium trihydrate, preferably both. In view of costs, the relatively expensive ammonium polyphosphate is used in limited amounts. The weight ratio between aluminium trihydrate and ammonium polyphosphate can accordingly be in the range of from 20 : 1 to 3 : 1, preferably from 15 : 1 to 5 : 1, more preferably from 12 : 1 to 8 : 1. Preferably, the surface covering of the invention comprises 1-5 % by total weight of the surface covering of ammonium polyphosphate (such as 2-4 %) and 10-40 % by total weight of the surface covering of aluminium trihydrate (such as 15-35 %). In a special embodiment, the surface covering further comprises a crosslinker selected from the group consisting of pentaerythritol, stearyl alcohol and mannitol, preferably pentaerythritol. Upon heating, such as above 250 °C, these compounds cause cross-linking of the polyvinyl butyral material, thereby forming a thick carbon barrier. As the organophosphorus oil and/or the organohalogen oil has plasticising properties, the presence of additional plasticisers that are not organophosphorus oil or organohalogen oil may be limited. Additional plasticisers that may be present in the surface covering of the invention include e.g. one or more selected from the group consisting of adipates, di-adipates, maleates, glycols, and citrates. Particular plasticisers that are not based on vegetable oil include, aromatic diesters, such as diisononyl phthalate, diisodecyl phthalate, linear dinonyl phthalate (L9P), dioctyl terephthalate, dibutyl phthalate, dioctyl phthalate, benzylbutylphthalate
and dihexyl phthalate, aliphatic diesters, such as diisononyl adipate and diisodecyl adipate, aromatic sulphonamides, such as N-n-butylbenzenesulphonamide, aromatic phosphate esters, such as tricresyl phosphate and trixylyl phosphate, alkyl phosphate esters, such as tributyl phosphate and tri-iso-octyl phosphate, dialkylether aromatic esters, such as dibutoxyethyl phthalate, dialkylether diesters, tricarboxylic esters, polymeric polyester plasticisers, polyglycol diesters, alkyl alkylether diesters, such as dibutoxyethyl glutarate, di-(2-butoxyethyl) adipate, di-(butylethoxyethyl)glutarate and di-(butoxyethoxyethyl)adipate, aromatic trimesters, such as trioctyl trimellitate and triisooctyl trimellitate, epoxodised esters, chlorinated hydrocarbons or paraffins, aromatic oils, alkylether monoesters, naphthenic oils, alkylmonoesters, glyceride oils, paraffinic oils, silicone oils, citrate plasticisers, such as tributyl citrate, and sebacate plasticisers, such as dibutyl sebacate. It is preferred that the amount of such additional plasticisers that are not organophosphorus oil or organohalogen oil in the surface covering of the invention is low. Such plasticisers not being organophosphorus oil or organohalogen oil (in particular plasticisers as mentioned in the list above) may, for instance, be present in amounts of 5 % or less by total weight of the surface covering, such as 4 % or less, 1 % or less, 0.5 % or less, or 0.1 % or less. The presence of the organophosphorus oil and/or organohalogen oil improves the processability of the polyvinyl butyral surprisingly well. This may be illustrated by the change in melt flow index of the compound composition used for preparing the surface covering of the invention as compared to the melt flow index of the polyvinyl butyral alone. The melt flow index of the compound composition used for preparing the surface covering is suitably 10-50 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 12-40 g/10 min, such as 14-35 g/10 min, 15-30 g/10 min, or 15-25 g/10 min.
In certain embodiments, the surface covering may comprise one or more colouring agent, in particular a white pigment. This may, for example, be advantageous in applications where the surface covering is exposed to ultraviolet radiation, such as by sunlight. Preferred colouring agents, for example, include titanium dioxide, and barium sulphate. In such applications, the colouring agent may serve to increase reflection of ultraviolet radiation. As a further advantage, the increased reflection has the effect that the surface covering will heat up less. Additionally, the white pigment may serve as a blocker of ultraviolet radiation and slow down any degradation of organic material, such as the polyvinyl butyral and/or phosphorus containing vegetable oil-based derivative. The presence of a colouring agent, such as a white pigment, is particularly advantageous in case the surface covering is a roof covering, or a façade covering. The amount of colouring agent in the surface covering may be in the range of 10 % or less by total weight of the surface covering, such as in the range of 0.1-10 %, 0.1-9 %, 0.2-8 %, 0.3-7 %, 0.5-5 %, or 1-3 %. The reflectance of the surface covering may also be expressed as in terms of Solar Reflectance Index (SRI). The SRI is a measure of the solar reflectance and emissivity of materials that can be used as an indicator of how hot materials are likely to become when solar radiation is incident on the surface thereof. The lower the SRI, the hotter a material is likely to become in the sunshine. SRI can be measured in accordance with ASTM E 1980-01. Preferably, the surface covering of the invention has a SRI of 20 or higher, such as 30 or higher, 40 or higher, or even 50 or higher. The surface covering of the invention may further comprise one or more additives. Such additives may suitably be selected from the group consisting of ultraviolet blocking agents, blowing agents, antioxidants, processing aids, pigments, dyes, fillers, antibacterial agents, release agents, heat stabilisers, light stabilisers, compatibilisers, inorganic material additives, surfactants, coupling agents, impact-reinforcing agents,
lubricants, weather-resistant agents, adhesion aids, adhesives, and any combination thereof. Examples of suitable ultraviolet blocking agents include titanium dioxide, carbon black, and combinations thereof. Examples of suitable blowing agents include azodicarbonamide, expandable microspheres, p-p'-oxy-bis(benzenesulphonylhydrazide), p-toluene sulphonyl semicarbizide, sodium bicarbonate, citric acid, and any combination thereof. If present, the amount of the blowing agents can be 5 % or less by total weight of the surface covering, preferably in the range of 0.01-4 %, more preferably in the range of 0.05-3 %. Examples of suitable processing aids include metal salts of carboxylic acids, such as zinc stearate or calcium stearate, fatty acids, such as stearic acid, oleic acid or erucic acid, fatty amides, such as stearamide, oleamide, erucamide or N,N'-ethylene bis-stearamide, polyethylene wax, oxidised polyethylene wax, polymers of ethylene oxide, copolymers of ethylene oxide and propylene oxide, vegetable waxes, petroleum waxes, non-ionic surfactants, fluoropolymers, such as polytetrafluoroethylene and the like, and polysiloxanes. The amount of the processing aids can be 5 % or less by total weight of the surface covering, preferably in the range of 0.05-5 %, more preferably in the range of 0.1-3 %. Examples of suitable pigments include carbon black, titanium dioxide, barium sulphate, and any combination thereof. The amount of the pigments can be 10 % or less by total weight of the surface covering, preferably in the range of 0.5-10 %, more preferably in the range of 1-5 %. Examples of suitable dyes include organic dyes, such as coumarins, lanthanide complexes, hydrocarbon and substituted hydrocarbon dyes, polycyclic aromatic hydrocarbons, scintillation dyes (preferably
oxazoles and oxadiazoles), aryl- or heteroaryl-substituted poly(C2-8 olefins), carbocyanine dyes, phthalocyanine dyes and pigments, oxazine dyes, carbostyryl dyes, porphyrin dyes, acridine dyes, anthraquinone dyes, arylmethane dyes, azo dyes, diazonium dyes, nitro dyes, quinone imine dyes, tetrazolium dyes, thiazole dyes, perylene dyes, perinone dyes, bis-benzoxazolylthiophene, xanthene dyes, and any combination thereof. The amount of the dyes can be 5 % or less by total weight of the surface covering, such as 0.1-5 %, 0.2-4 %, 0.3-3 %, or 0.5-2 %. Examples of suitable fillers include carbon black, wollastonite, solid microspheres, hollow microspheres, kaolin, clay-based minerals, bauxite, calcium carbonate, feldspar, barium sulphate, titanium dioxide, talc, pyrophyllite, quartz, natural silica, such as crystalline silica and microcrystalline silica, synthetic silicates, such as calcium silicate, zirconium silicate and aluminium silicate, including mullite, sillimanite, cyanite, andalusite and synthetic alkali metal aluminosilicates, microcrystalline novaculite, diatomaceous silica, perlite, synthetic silica, such as fumed silica and precipitated silica, antimony oxide, bentonite, mica, vermiculite, zeolite, and combinations of metals with various salts, such as calcium, magnesium, zinc, barium, aluminium combined with oxide, sulphate, borate, phosphate, carbonate, hydroxide and the like, and any combination thereof. It is preferred that the amount of fillers (such as carbon black) is 10 % or less by total weight of the surface covering, such as 1-8 %, or 2-5 %. Examples of suitable antioxidants include hindered phenols, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, bis[(β-(3,5-di-tert-butyl-4-hydroxybenzyl)-methylcarboxyethyl)] sulphide, 4,4'-thio-bis(2-methyl-6-tert-butylphenol), 4,4'-thio-bis(2-tert-butyl-5-methylphenol), 2,2'-thio-bis(4-methyl-6-tert-butylphenol), thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate, phosphites and
phosphonites, such as tris(2,4-di-tert-butylphenyl)phosphite and di-tert-butylphenyl-phosphonite, thio compounds, such as dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate, various siloxanes, polymerised 2,2,4-trimethyl-1,2-dihydroquinoline, N,N'-bis(1,4-dimethylpentyl-p-phenylenediamine), alkylated diphenylamines, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamines and other hindered amine antidegradants or stabilisers, and or any combination thereof. Both primary and secondary antioxidants may be applied. Primary antioxidants function as radical catchers and particularly remove peroxyl radicals (ROO•) and, to a lesser extent, alkoxy radicals (RO•), hydroxyl radicals (HO•), and alkyl radicals (R•). Oxidation begins with the formation of alkyl radicals, which react rapidly with molecular oxygen and thus form peroxyl radicals. Secondary antioxidants particularly remove organic hydroperoxides (ROOH) formed by the effect of primary oxidants. Hydroperoxides are less reactive than radicals, but undergo hemolytic bonding and break new radicals. The amount of the antioxidants can be 5 % or less by total weight of the surface covering, preferably in the range of 0.1-5 %, more preferably in the range of 0.2-3 %. Examples of the weather-resistance agents include benzophenone-type weather resistance agents, amine-type weather resistance agents, and combinations thereof. The total amount of additives is preferably 10 % or less by total weight of the surface covering, such as 0.1-10 %, 0.2-8 %, 0.3-5 %, or 0.5-3 %. In certain applications, the surface covering can comprise a support carrier. Such a support carrier may further improve the mechanical properties of the surface covering. Suitable support carriers may be selected from the group consisting of glass fibre, carbon fibre, basalt fibre, natural
fibres (e.g. flax fibre, and hemp fibre), aramid fibre, polyester fibre, polyethylene fibre (including e.g. Dyneema® fibre), and any combination thereof. More preferably said support carrier comprises glass fibre. The support may have the form of a laminate. In other embodiments, the surface covering is self-supporting. In such embodiments, the surface covering may have a fibrous material content of 1 % or less based on total weight of the surface covering, such as 0.5 % or less, or 0.1 % or less. Preferably, the surface covering is free from fibrous material in these embodiments. Apart from polyvinyl butyral, the surface covering may comprise one or more additional polymers. These can, for instance, be selected from the group consisting of thermoplastic polyurethanes, polyisobutenes, polychloroprene, polycaprolactones, polyesters, thermoplastic polyolefins, polyolefins, silicones, siloxanes, thermoplastic elastomers, including vulcanised thermoplastic elastomers and styrenic block copolymers, polyvinyl chlorides, styrene butadiene copolymers including poly(styrene-butadiene-styrene), poly(styrene-ethylene/butadiene-styrene) and poly(styrene-ethylene/propylene-styrene), copolymers of ethylene and vinylacetate. Preferably, the additional polymers can comprise one or more selected from the group consisting of polyisobutenes, polycaprolactones, polyesters, silicones, thermoplastic elastomers, such as vulcanised thermoplastic elastomers and styrenic block copolymers, thermoplastic polyolefins, and thermoplastic polyurethanes. In a preferred embodiment the surface covering of the invention comprises - polyvinyl butyral, preferably in an amount of 50-90 % by total weight of the surface covering, such as 60-90 %, 60-80 %, or 60-70 %; - one or more organophosphorus oils and/or one or more organohalogen oils, preferably in an amount of 1-15 % by total weight of the surface covering, such as 2-12 % or 3-10 %;
- ammonium polyphosphate, preferably in an amount of 1-5 % by total weight of the surface covering, such as 2-4 %; and - aluminium trihydrate, preferably in an amount of 10-40 % by total weight of the surface covering, such as 15-35 %, or 20-30 %. Even more preferred is a surface covering comprising - polyvinyl butyral, preferably in an amount of 50-90 % by total weight of the surface covering, such as 60-90 %, 60-80 %, or 60-70 %; - organophosphorus oil comprising one or more biphenyl phosphate and/or triphenyl phosphate groups, preferably in an amount of 1-15 % by total weight of the surface covering, such as 2-12 % or 3-10 %; - ammonium polyphosphate, preferably in an amount of 1-5 % by total weight of the surface covering, such as 2-4 %; and - aluminium trihydrate, preferably in an amount of 10-40 % by total weight of the surface covering, such as 15-35 %, or 20-30 %. Different components of the surface covering described herein may be present in a single layer (i.e. two or more selected from polyvinyl butyral, one or more organophosphorus oils and/or one or more organohalogen oils, additional flame retardant, crosslinker, additional plasticiser, colouring agent, ultraviolet blocking agents, blowing agents, antioxidants, processing aids, pigments, dyes, fillers, antibacterial agents, release agents, heat stabilisers, light stabilisers, compatibilisers, inorganic material additives, surfactants, coupling agents, impact-reinforcing agents, lubricants, weather-resistant agents, adhesion aids, adhesives). In particular, it is preferred that the polyvinyl butyral and the one or more organophosphorus oils and/or one or more organohalogen oils are present in the same layer of the surface covering. More preferably, the surface covering is a single layer surface covering. The surface covering of the invention may suitably have a thickness in the range of 0.3-5 mm, such as 0.5-4 mm, 0.8-3 mm, or 1-2 mm.
The surface covering may optionally comprise at least one release sheet for storage. The presence of such release sheet may provide protection to the synthetic flashing material when stored, such as on a roll. The release sheet may suitably be removed from the surface covering by peeling off before, during and/or after applying the surface covering to a surface, such as the surface of a construction. The release sheet may be present on the top and/or bottom of the surface covering. The release sheet may comprise one or more materials selected from the group consisting of polytetrafluoroethylene, silicones, waxed paper, parchment paper, plastic sheets, such as bubble wrap, and other release sheets known in the art. The surface covering of the invention can reach UL 94 V-2 flammability rating at a thickness of 1.5 mm, preferably UL 94 V-1, more preferably UL 94 V-0. The ratings refer to Underwriters-Laboratories standard UL 94. In the UL 94 test, a specimen is exposed vertically to a flame for 10 seconds. The specimen is ignited at the bottom and burns up. If the specimen self-extinguishes within 30 seconds, another 10 seconds application is made. Flaming droplets are allowed to fall on cotton located below the sample. If the average burning time is less than 5 seconds (per application of flame) and the droplets do not ignite the cotton, the material is classified as UL 94 V-0. If the average of burning time is less than 25 seconds and the droplets do not ignite the cotton, the material is classified as UL 94 V-1. If the average burning time is less than 25 seconds but the droplets ignite the cotton, the material is classified as UL 94 V-2. Another way of determining flame retardancy is by performing a limiting oxygen index (LOI) measurement according to ISO 4589. Preferably, the surface covering of the invention can reach a LOI value of 21.0 % or more, more preferably 22.0 % or more. The inventors surprisingly found that the presence of the organophosphorus oil and/or organohalogen oil (preferably those comprising one or more diphenyl phosphate and/or triphenyl phosphate groups) in the
surface covering of the invention yields remarkably good fire retardancy. In addition, the inventors surprisingly found that a surface covering of the invention including the organophosphorus oil and/or organohalogen oil has improved rigidness, as compared to a surface covering lacking said component. In a further aspect, the invention is directed to a method for preparing a surface covering as described herein, comprising a) providing a feed stream of recycled polyvinyl butyral, b) optionally, pre-treating the feed stream of recycled polyvinyl butyral to remove one or more components therefrom, preferably said one or more components comprise volatile plasticisers, c) compounding the feed stream of recycled polyvinyl butyral from step a) or the pre-treated feed stream of recycled polyvinyl butyral from step b) with one or more organophosphorus oils and/or one or more organohalogen oils, and d) forming the compounded material into a layer to produce the surface covering. Suitably, the feed stream of recycled polyvinyl butyral in step a) has a melt flow index of 1-10 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 2-7 g/10 min, such as 3-6 g/10 min, or 4-5 g/10 min. The optional pre-treatment in step b) is highly advantageous since recycled polyvinyl butyral typically originates from various sources with varying plasticiser content. The optional pre-treatment in step b) allows for removing undesirable components (such as relatively volatile components including plasticisers) from the recycled polyvinyl butyral, resulting in a polymer product having more constant properties, such as melt flow index. Preferably, said pre-treating step b) comprises feeding the feed stream of recycled polyvinyl butyral to an extruder, melting said feed
stream in the extruder to produce polymer melt and passing said polymer melt through one or more degassing zones connected to a vacuum pump, and measuring the melt flow index of the polymer product, wherein the vacuum pump is operated at a pressure that is controlled by the measured melt flow index of the polymer product. Such pre-treatment is described in more detail in WO-A-2022/098237. In step c), the feed stream of recycled polyvinyl butyral from step a) or the pre-treated feed stream of recycled polyvinyl butyral from step b) is compounded together with one or more organophosphorus oils and/or organohalogen oils and, optionally, any other components that are used in the surface covering. The melt flow index of the compound composition with the organophosphorus oil and/or organohalogen oil in step c) that is used for forming the surface covering in step d) is suitably 10-50 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 12-40 g/10 min, such as 14-35 g/10 min, 15-30 g/10 min, or 15-25 g/10 min. Then, the compounded material may be formed into a layer to produce the surface covering. Preferably, step c) and/or step d) of the method for preparing the surface covering of the invention are performed at a temperature of 190 °C or less, more preferably at a temperature of 180 °C, such as at a temperature of 175 °C or less. At temperatures above 190 °C, both flame retardancy properties and mechanical properties are reduced, due to degradation of components. For practical processability, the surface covering is then preferably supplied on a roll for storage and transport, optionally using a release sheet as described herein. Such a roll may have a width of typically 0.5-5 m, such as 1-4 m, or 1.5-3 m. The lengths of the roll may be 5-200 m, such as 10-150 m, 12-100 m or 15-80 m.
In yet a further aspect, the invention is directed to a method for applying a surface covering as described herein onto a surface, comprising i) applying strips of surface covering on a surface, whereby adjacent strips of surface covering have overlapping regions; and ii) bonding the overlapping regions of the strips of surface covering using an alcohol solvent. The surface covering can thus readily be applied on a surface, thereby allowing for a waterproof seam. The alcohol solvent preferably comprises one or more selected from the group of methanol, ethanol, iso-propyl alcohol, n-propyl alcohol, tert-butyl alcohol, n-butanol, and iso-butyl alcohol. More preferably, the alcohol solvent comprises or is iso-propyl alcohol. Preferably, the alcohol solvent is provided with a colour indicator. Some suitable but non-limiting examples thereof include methylene blue, methyl viologen, isosulfan blue and indigo carmine. Preferably, the alcohol solvent comprises methylene blue. These colour indicators allow visualising which parts have treated with the alcohol solvent. As such, the operator is able to check whether he has not missed any spots. When the surface covering is applied on a surface that is exposed to UV radiation, such as on a roof, then any colour indicator exposed to UV radiation will degrade. However, colour indicator that is present between the overlapping parts of the strips of surface covering is not exposed to the UV radiation and will accordingly not degrade (or to a much less extent). Upon recycling the surface covering, the strips of surface covering are separated and collected. In the overlapping regions, the colour indicator will be uncovered, which can advantageously serve as an identifier for the origin of the strips of surface covering. In a special embodiment, small pieces of surface covering are fixed on the surface, such as by screwing, at regular intervals. The strips of surface covering can thereafter be bonded to these fixed small pieces using
alcohol solvent. This allows easy recovery of the strips of surface covering at the end of its service life. New strips of surface covering can then be applied on the remaining fixed small pieces. All references cited herein are hereby completely incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein. The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising”, “having”, “including” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention. Preferred embodiments of this invention are described herein. Variation of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject-matter recited in the claims
appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. The claims are to be construed to include alternative embodiments to the extent permitted by the prior art. For the purpose of clarity and a concise description features are described herein as part of the same or separate embodiments, however, it will be appreciated that the scope of the invention may include embodiments having combinations of all or some of the features described. The invention will now be further illustrated by means of the following examples. Examples Different extrusion compound examples were prepared as shown in Table 1 below, wherein PVB is polyvinyl butyral, ATH is aluminium trihydrate, APP is ammonium polyphosphate, and RDP is resorcinol bis(diphenyl phosphate). The samples were injection moulding into tensile test bars for limiting oxygen index (LOI) measurements according to ISO 4589 on a FTT LOI apparatus. In a controlled oxygen percentage (O2/N2 mixture) atmosphere a specimen was ignited by a flame and the fire behaviour and burning time was recorded. When the sample extinguished the oxygen percentage was increased and when the sample did not extinguish the oxygen percentage was decreased. The lowest oxygen percentage at which the specimen extinguished was the recorded LOI value. The results are shown in Table 1 below.
Table 1
Examples D and E, which include the resorcinol bis(diphenyl phosphate) showed a surprising increase in limiting oxygen index, as compared to Examples A and C, which have about the same total amount of fire retardant as Example D and E, respectively. Additionally, tensile test specimens type 1A according to ISO 527-2 were cut from a surface covering and analysed using dynamic mechanical analysis (DMA). The storage modulus and loss modulus of the samples was determined at room temperature. The sample was clamped in a single cantilever clamp and oscillated at different frequencies (1 to 100 Hz) and an amplitude of 0.1 % strain. The storage modulus represents the strength of the material and the loss modulus represents the ability to absorb and dissipate energy. The results of three different samples are shown in Figure 1. Samples 1 and 3 are samples with 70 wt.% PVB, 27.27 wt.% of ATH and 2.73 wt.% of APP. Sample 2 is a sample with 70.9 wt.% PVB, 18.2 wt.% of ATH, 1.82 wt.% of APP, and 9.09 wt.% of RDP oil. Both samples without the resorcinol bis(diphenyl phosphate) oil (Samples 1 and 3) have comparable strength values. The sample with resorcinol bis(diphenyl phosphate) oil (Sample 2) is surprisingly more rigid than the other samples.
Claims
Claims 1. Surface covering comprising - 60-90 % by total weight of the surface covering of polyvinyl butyral, and - 1-15 % by total weight of the surface covering of one or more organophosphorus oils and/or one or more organohalogen oils.
2. Surface covering according to claim 1, wherein said surface covering comprises polyvinyl butyral in an amount of 65-85 % by total weight of the surface covering, such as 70-80 %.
3. Surface covering according to claim 1 or 2, wherein the organophosphorus oil comprises one or more phosphorus containing groups selected from the group consisting of diphenyl phosphate and triphenyl phosphate.
4. Surface covering according to claim 1 or 2, wherein the organophosphorus oil and/or the organohalogen oil is based on a vegetable oil.
5. Surface covering according to claim 4, wherein the vegetable oil is selected from the group consisting of castor oil, linseed oil, sunflower oil, corn oil, cotton oil, coconut oil, algae oil, jatropha oil, soybean oil, cashew nut oil, rapeseed oil, walnut oil, safflower oil, grapeseed oil, canola oil, sesame oil, peanut oil, olive oil, palm oil, and camelina oil.
6. Surface covering according to any one of claims 1-5, wherein said surface covering comprises organophosphorus oil and/or organohalogen oil in an amount of 2-13 % by total weight of the surface covering, such as 3-10 %.
7. Surface covering according to any one of claims 1-6, further comprising a flame retardant that is not organophosphorus oil or organohalogen oil, such as one or more selected from the group consisting of ammonium polyphosphate, aluminium trihydrate, magnesium hydroxide, zinc stannate, antimony trioxide, zirconium phosphate, melamine cyanurate, melamine polyphosphate, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide
8. Surface covering according to any one of claims 1-7, wherein said surface covering comprises ammonium polyphosphate and aluminium trihydrate.
9. Surface covering according to claim 7 or 8, wherein said surface covering comprises ammonium polyphosphate in an amount of 1-5 % by total weight of the surface covering, such as 2-4 %.
10. Surface covering according to claim 7-9, wherein said surface covering comprises aluminium trihydrate in an amount of 10-40 % by total weight of the surface covering, such as 15-35 %, or 20-30 %.
11. Surface covering according to any one of claims 1-10, further comprising a plasticiser that is not organophosphorus oil or organohalogen oil, such as one or more selected from the group consisting of adipates, di-adipates, maleates, glycols, and citrates.
12. Surface covering according to any one of claims 1-11, comprising plasticiser that is not organophosphorus oil or organohalogen oil in an amount of 5 % or less by total weight of the surface covering, such as 1 % or less, 0.5 % or less, or 0.1 % or less.
13. Surface covering according to any one of claims 1-12, further comprising a crosslinker selected from the group consisting of pentaerythritol, stearyl alcohol and mannitol, preferably pentaerythritol.
14. Surface covering according to any one of claims 1-13, further comprising a colouring agent, preferably selected from the group consisting of titanium dioxide, and barium sulphate.
15. Surface covering according to any one of claims 1-14, further comprising one or more additives selected from the group consisting of ultraviolet blocking agents, antioxidants, blowing agents, processing aids, pigments, dyes, fillers, antibacterial agents, release agents, heat stabilisers, light stabilisers, compatibilisers, inorganic material additives, surfactants, coupling agents, impact-reinforcing agents, lubricants, weather-resistant agents, adhesion aids, adhesives, and any combination thereof. 16. Surface covering according to any one of claims 1-15, wherein the polyvinyl butyral has a melt flow index of 1-10 g/10 min, as determined by ISO 1133 at a load of 2.
16 kg and at a temperature of 190 °C, preferably 2-7 g/10 min, such as 3-6 g/10 min, or 4-5 g/10 min.
17. Surface covering according to any one of claims 1-16, prepared from a compound composition having a melt flow index of 10-50 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 12-40 g/10 min, such as 14-35 g/10 min, 15-30 g/10 min, or 15-25 g/10 min.
18. Surface covering according to any one of claims 1-17, further comprising a support carrier, said support carrier preferably comprising one or more selected from the group consisting of glass fibre, carbon fibre, basalt fibre, natural fibres (e.g. flax fibre, and hemp fibre), aramid fibre, polyester
fibre, polyethylene fibre, more preferably said support carrier comprises glass fibre.
19. Surface covering according to any one of claims 1-18, wherein said surface covering is a self-supporting and has a fibrous material content of 1 % or less based on total weight of the surface covering, such as 0.5 % or less, or 0.1 % or less, preferably the surface covering is free from fibrous material.
20. Surface covering according to any one of claims 1-19, further comprising one or more additional polymers selected from the group consisting of thermoplastic polyurethanes, polyisobutenes, polycaprolactones, polyesters, thermoplastic olefins, polyolefins, silicones, siloxanes, thermoplastic elastomers, including vulcanised thermoplastic elastomers and styrenic block copolymers, poly(vinyl chloride), styrene butadiene copolymers including poly(styrene-butadiene-styrene), poly(styrene-ethylene/butadiene-styrene) and poly(styrene-ethylene/propylene-styrene), copolymers of ethylene and vinylacetate.
21. Surface covering according to any one of claims 1-20, having a Solar Reflectance Index (SRI) of 20 or higher, preferably 40 or higher.
22. Surface covering according to any one of claims 1-21, complying with UL 94 V-2 flammability rating at a thickness of 1.5 mm, preferably complying with UL 94 V-1 flammability rating, more preferably complying with UL 94 V-0 flammability rating.
23. Surface covering according to any one of claims 1-22, exhibiting a limiting oxygen index (LOI) as measured according to ISO 4589. Preferably,
the surface covering of the invention can reach a LOI value of 21.0 % or more, more preferably 22.0 % or more.
24. Surface covering according to any one of claims 1-23, having an average thickness of 0.3-5 mm, such as 0.5-4 mm, 0.8-3 mm, or 1-2 mm.
25. Method for preparing a surface covering according to any one of claims 1-24, comprising a) providing a feed stream of recycled polyvinyl butyral, b) optionally, pre-treating the feed stream of recycled polyvinyl butyral to remove one or more components therefrom, preferably said one or more components comprise volatile plasticisers, c) compounding the feed stream of recycled polyvinyl butyral from step a) or the pre-treated feed stream of recycled polyvinyl butyral from step b) with one or more organophosphorus oils and/or one or more organohalogen oils, and d) forming the compounded material into a layer to produce the surface covering.
26. Method according to claim 25, wherein said pre-treating comprises feeding the feed stream of recycled polyvinyl butyral to an extruder, melting said feed stream in the extruder to produce polymer melt and passing said polymer melt through one or more degassing zones connected to a vacuum pump, and measuring the melt flow index of the polymer product, wherein the vacuum pump is operated at a pressure that is controlled by the measured melt flow index of the polymer product.
27. Method according to claim 25 or 26, wherein the feed stream of recycled polyvinyl butyral in step a) has a melt flow index of 1-10 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 2-7 g/10 min, such as 3-6 g/10 min, or 4-5 g/10 min.
28. Method according to any one of claims 25-27, wherein the compound composition with the organophosphorus oil and/or organohalogen oil in step c) that is used for forming the surface covering in step d) has a melt flow index of 10-50 g/10 min, as determined by ISO 1133 at a load of 2.16 kg and at a temperature of 190 °C, preferably 12-40 g/10 min, such as 14-35 g/10 min, 15-30 g/10 min, or 15-25 g/10 min.
29. Method according to any one of claims 25-28, wherein step c) and/or step d) are performed at a temperature of 190 °C or less, such as 180 °C or less, or 175 °C or less.
30. Method for applying a surface covering according to any one of claims 1-24 on a surface, comprising i) applying strips of surface covering on a surface, whereby adjacent strips of surface covering have overlapping regions; and ii) bonding the overlapping regions of the strips of surface covering using an alcohol solvent.
31. Method according to claim 30, wherein said surface is the surface of a roof, a basement, a facade, a wall, a floor, or a pool.
32. Method according to claim 30 or 31, wherein the alcohol solvent comprises one or more selected from the group of methanol, ethanol, iso-propyl alcohol, n-propyl alcohol, tert-butyl alcohol, n-butanol, and iso-butyl alcohol, preferably, the alcohol solvent comprises or is iso-propyl alcohol.
33. Method according to claim 32, wherein said alcohol solvent further comprises a colour indicator, preferably one or more selected from the group consisting of methylene blue, methyl viologen, isosulfan blue and
indigo carmine, more preferably the alcohol solvent comprises methylene blue.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016108686A1 (en) | 2014-12-29 | 2016-07-07 | Redeahold Apeldoorn B.V. | Construction material |
WO2017064260A1 (en) | 2015-10-16 | 2017-04-20 | Tarkett Gdl | Decorative multi-layer surface covering comprising polyvinyl butyral |
WO2020122727A1 (en) | 2018-12-13 | 2020-06-18 | Redeahold Apeldoorn B.V. | Synthetic flashing material |
WO2020156740A1 (en) | 2019-01-29 | 2020-08-06 | Tarkett Gdl | Cellulose ester compositions for surface coverings |
WO2021064634A1 (en) | 2019-10-01 | 2021-04-08 | Redeahold Apeldoorn B.V. | Construction material |
WO2022098237A1 (en) | 2020-11-04 | 2022-05-12 | Redeahold Apeldoorn B.V. | Upgrading recycled polyvinyl butyral |
-
2021
- 2021-11-25 NL NL2029905A patent/NL2029905B1/en active
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2022
- 2022-11-25 WO PCT/NL2022/050684 patent/WO2023096492A1/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016108686A1 (en) | 2014-12-29 | 2016-07-07 | Redeahold Apeldoorn B.V. | Construction material |
WO2017064260A1 (en) | 2015-10-16 | 2017-04-20 | Tarkett Gdl | Decorative multi-layer surface covering comprising polyvinyl butyral |
WO2020122727A1 (en) | 2018-12-13 | 2020-06-18 | Redeahold Apeldoorn B.V. | Synthetic flashing material |
WO2020156740A1 (en) | 2019-01-29 | 2020-08-06 | Tarkett Gdl | Cellulose ester compositions for surface coverings |
WO2021064634A1 (en) | 2019-10-01 | 2021-04-08 | Redeahold Apeldoorn B.V. | Construction material |
WO2022098237A1 (en) | 2020-11-04 | 2022-05-12 | Redeahold Apeldoorn B.V. | Upgrading recycled polyvinyl butyral |
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