CN116284716A - Polyester and preparation method and application thereof - Google Patents
Polyester and preparation method and application thereof Download PDFInfo
- Publication number
- CN116284716A CN116284716A CN202310303407.0A CN202310303407A CN116284716A CN 116284716 A CN116284716 A CN 116284716A CN 202310303407 A CN202310303407 A CN 202310303407A CN 116284716 A CN116284716 A CN 116284716A
- Authority
- CN
- China
- Prior art keywords
- polyester
- reaction
- catalyst
- polyol
- azide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- -1 alkynyl compound Chemical class 0.000 claims abstract description 52
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 238000010276 construction Methods 0.000 claims abstract description 6
- 150000001540 azides Chemical class 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 18
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 18
- 238000006068 polycondensation reaction Methods 0.000 claims description 17
- 229920005862 polyol Polymers 0.000 claims description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 150000003077 polyols Chemical class 0.000 claims description 16
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 9
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 150000007519 polyprotic acids Polymers 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- GKPOMITUDGXOSB-UHFFFAOYSA-N but-3-yn-2-ol Chemical compound CC(O)C#C GKPOMITUDGXOSB-UHFFFAOYSA-N 0.000 claims description 5
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 claims description 5
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 4
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- BOFLDKIFLIFLJA-UHFFFAOYSA-N 2-methylbut-1-en-3-yne Chemical group CC(=C)C#C BOFLDKIFLIFLJA-UHFFFAOYSA-N 0.000 claims description 3
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 3
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229940093476 ethylene glycol Drugs 0.000 claims description 3
- 229940100573 methylpropanediol Drugs 0.000 claims description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- 235000013772 propylene glycol Nutrition 0.000 claims description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 3
- QEMMTKPYWRKLME-UHFFFAOYSA-N 3-fluoroprop-1-yne Chemical compound FCC#C QEMMTKPYWRKLME-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000012948 isocyanate Substances 0.000 abstract description 5
- 150000002513 isocyanates Chemical class 0.000 abstract description 5
- 239000002360 explosive Substances 0.000 abstract description 4
- 238000005491 wire drawing Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- RTWCHRMHGXBETA-UHFFFAOYSA-N prop-1-yn-1-amine Chemical compound CC#CN RTWCHRMHGXBETA-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical group BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
- C08F299/0485—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
- C08G18/4623—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing primary or secondary terminal aminogroups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a polyester, a preparation method and application thereof, wherein the raw materials for preparing the polyester comprise the following components: polyester polyol, azide, reaction auxiliary agent, alkynyl compound and catalyst; the azide compound includes bis (p-nitrophenyl) azido phosphate. In the invention, the polyester has high conversion rate to hydroxyl groups (such as primary hydroxyl groups) of the polyester polyol, and the reaction selectivity of the polyester can be greatly improved and the application range of the polyester can be expanded on the basis of keeping the excellent performance of the polyester per se by introducing different functional groups into the terminal groups, for example, the reaction wire drawing time with isocyanate can be improved on the basis of not affecting the self-learning performance of the polyester, thereby being beneficial to expanding the production and construction operation range and being beneficial to manufacturing large-sized materials; and the raw materials for preparing the polyester are safe and not explosive, and are suitable for large-scale use in factories.
Description
Technical Field
The invention relates to the technical field of polyester, in particular to polyester and a preparation method and application thereof.
Background
Because polyester materials possess excellent materials and chemical properties, the polyester materials have been increasingly used in the construction industry, the automobile industry, the clothing industry, the household appliance industry and the like. However, due to the limitations of the raw materials and processes for preparing polyesters, the types of polyesters having further reactive groups are limited, and three types of polyesters which are produced on a relatively large scale are polyester polyols, unsaturated polyesters and polyester acrylates. The polyester polyol is a polyester having terminal hydroxyl groups, the unsaturated polyester is a polyester having double bonds in the backbone, and the polyester acrylate is a terminal acrylate group.
In the prior art, different functional groups are generally introduced in the polycondensation stage of polyester synthesis to increase the variety of polyester functional groups.
CN108285524a discloses a slip-resistant polyurethane elastomer stock solution, and a preparation method and application thereof, wherein the slip-resistant polyurethane elastomer stock solution comprises a polyurethane stock solution a component and a polyurethane stock solution B component; the polyurethane stock solution A component contains polyether ester dihydric alcohol and polyester polyol; the polyurethane stock solution B component contains hydroxyl-terminated liquid rubber modified polyester polyol. The polyester polyol disclosed by the method is prepared by esterification polycondensation reaction of adipic acid, micromolecular dihydric alcohol, hydroxyl-terminated polybutadiene liquid rubber and the like, so that a polyester product with double bonds is obtained.
CN103087304a discloses a process for producing polyester polyol, which comprises modifying natural oil with maleic anhydride, and reacting with small molecule polyol, dicarboxylic acid or carboxylic ester to obtain high cyclopentane-soluble polyester polyol product. The maleic anhydride is used for modifying natural oil and then reacts with micromolecular polyalcohol, dicarboxylic acid or carboxylic ester to obtain a polyester polyalcohol product with high cyclopentane solubility.
In the prior art, how to introduce different functional groups into the terminal groups can greatly improve the reaction selectivity of the polyester and expand the application range of the polyester on the basis of keeping the excellent performance of the polyester.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide polyester, a preparation method and application thereof, wherein the polyester has high conversion rate to hydroxyl groups of polyester polyol, different functional groups are introduced into terminal groups, so that the reaction selectivity of the polyester can be greatly improved and the application range of the polyester can be greatly expanded on the basis of keeping the excellent performance of the polyester, for example, the reaction wire drawing time with isocyanate can be improved on the basis of not influencing the self-chemical performance of the polyester, the expansion of the production construction operation range is facilitated, and the manufacture of large-size materials is facilitated; and the raw materials for preparing the polyester are safe and not explosive, and are suitable for large-scale use in factories.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polyester, the polyester comprising the following components: polyester polyol, azide, reaction auxiliary agent, alkynyl compound and catalyst;
the azide compound includes bis (p-nitrophenyl) azido phosphate.
According to the invention, bis (p-nitrophenyl) azido phosphate is introduced into the raw materials for preparing the polyester, so that the conversion rate of hydroxyl groups of polyester polyol can be improved, and the polyester is further matched with alkynyl compounds to obtain polyesters with different end group functional groups, so that the reaction selectivity of the polyester is greatly improved and the application range of the polyester is greatly expanded on the basis of keeping the excellent performance of the polyester.
Preferably, the reaction auxiliary comprises an alkenyl compound.
Preferably, the reaction auxiliary comprises 1, 8-diazabicyclo [5,4,0] undec-7-ene.
In the invention, the reason that the reaction auxiliary agent is preferably 1, 8-diazabicyclo [5,4,0] undec-7-ene is that the reaction auxiliary agent can be used together with the azide compound, improves the conversion rate of hydroxyl groups of polyester polyol, greatly improves the reaction selectivity of the polyester and expands the application range of the polyester on the basis of keeping the excellent performance of the polyester.
Preferably, the polyester polyol has terminal hydroxyl groups.
Preferably, the polyester polyol is prepared from a raw material comprising a polyol monomer and a polybasic acid.
Preferably, the polyol monomers include any one or a combination of at least two of ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, diethylene glycol, triethylene glycol, methylpropanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, glycerol, trimethylolpropane, polyethylene glycol, or polytetramethylene glycol, wherein typical but non-limiting combinations include: ethylene glycol, a combination of 1, 3-propanediol and 1, 2-propanediol, a combination of 1, 4-butanediol, diethylene glycol and triethylene glycol, a combination of methylpropanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, glycerol and trimethylolpropane, a combination of 1, 6-hexanediol, glycerol, trimethylolpropane, polyethylene glycol and polytetramethylene glycol, and the like.
Preferably, the polyacid comprises any one or a combination of at least two of succinic acid, adipic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, or trimellitic anhydride, wherein typical but non-limiting combinations include: combinations of succinic acid and adipic acid, combinations of sebacic acid, terephthalic acid and phthalic anhydride, combinations of sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid and trimellitic anhydride, and the like.
Preferably, the catalyst comprises an addition catalyst.
Preferably, the catalyst further comprises a polycondensation catalyst.
Preferably, the addition catalyst comprises any one or a combination of at least two of cuprous bromide, cuprous iodide, triethylamine or pentamethyldiethylenetriamine, wherein typical but non-limiting combinations include: combinations of cuprous bromide and cuprous iodide, combinations of cuprous iodide, triethylamine and pentamethyldiethylenetriamine, combinations of cuprous bromide, cuprous iodide, triethylamine and pentamethyldiethylenetriamine, and the like.
Preferably, the polycondensation catalyst comprises any one or a combination of at least two of stannous octoate, tetrabutyl titanate, or tetraisopropyl titanate, wherein typical but non-limiting combinations include: a combination of stannous octoate and tetrabutyl titanate, a combination of tetrabutyl titanate and tetraisopropyl titanate, a combination of stannous octoate, tetrabutyl titanate and tetraisopropyl titanate, and the like.
Preferably, the alkynyl compound comprises any one or a combination of at least two of propargylamine, 4-ethynylaniline, vinylacetylene, isopropenylacetylene, 3-butyn-2-ol, 3-bromopropyne, 3-chloropropylene, 3-fluoropropyne, propyne-maleimide, propynylamide, trimethylsilylacetylene, alkyne-terminated ethoxy compounds, or alkyne-terminated propoxy compounds, wherein typical but non-limiting combinations include: combinations of propargylamine, 4-ethynylaniline and vinylacetylene, combinations of isopropenylacetylene, 3-butyn-2-ol, 3-bromopropylene and 3-chloropropylene, 3-fluoropropylene, propyne-maleimide, propynylamide and trimethylsilylacetylene, and the like.
Preferably, the raw materials for preparing the polyester comprise the following components in parts by weight:
in the invention, the preparation raw materials are matched and used in specific parts by weight, and specifically, the addition amounts of the azide and the reaction auxiliary agent can be designed according to the addition amounts of the polyalcohol monomer and the polybasic acid to obtain the polyester with excellent performance.
In the present invention, the polyol monomer is 30 to 70 parts by weight, for example, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, etc.
The polyacid is 30-70 parts by weight, for example 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, etc.
The azide compound is 0.1 to 40 parts by weight, for example, 0.5 parts, 1 part, 2 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, etc.
The reaction auxiliary agent is 0.01-15 parts by weight, for example 0.05 parts, 0.1 parts, 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts and the like.
The alkynyl compound is 0 to 100 parts by weight and is not equal to 0 parts, for example, 5 parts, 10 parts, 20 parts, 40 parts, 60 parts, 80 parts, etc.
The catalyst is 0 to 0.3 parts by weight and is not equal to 0 parts, for example 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, etc.
Preferably, the molar ratio of the azide compound to the hydroxyl terminated groups of the polyester polyol is (1 to 1.2): 1, wherein 1-1.2 may be 1.05, 1.1, 1.15, etc.
Preferably, the molar ratio of the reaction auxiliary to the azide is (0.8-1.2): 1, wherein 0.8-1.2 may be 0.85, 0.9, 0.95, etc., further preferably 1:1.
Preferably, the molar ratio of the alkynyl compound to the azide compound is (0.8-1.2): 1, wherein 0.8-1.2 may be 0.85, 0.9, 0.95, etc., and further preferably 1:1.
Preferably, in the catalyst, the weight part of the polycondensation catalyst is 0 to 0.1 part, and is not equal to 0 part, for example, 0.02 part, 0.04 part, 0.06 part, 0.08 part, and the like.
Preferably, in the catalyst, the weight parts of the addition catalyst are 0.01-0.2 parts, for example 0.02 parts, 0.04 parts, 0.06 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.14 parts, 0.16 parts, 0.18 parts, etc.
In a second aspect, the present invention provides a process for producing the polyester of the first aspect, comprising the steps of:
and reacting polyester polyol, an azide compound, a reaction auxiliary agent and an alkynyl compound under the action of a catalyst to obtain the polyester.
Preferably, the reaction comprises the steps of firstly reacting polyester polyol, azide compound and reaction auxiliary agent for the first time to obtain polyester with the terminal azide group, and then reacting the polyester with the terminal azide group for the second time to obtain the polyester.
Preferably, the temperature of the first reaction is 60-130 ℃, e.g., 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, etc.
Preferably, the time of the first reaction is 6-24h, e.g., 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, etc.
Preferably, the temperature of the second reaction is 60-100deg.C, such as 65deg.C, 70deg.C, 75deg.C, 80deg.C, 85deg.C, 90deg.C, 95deg.C, etc.
Preferably, the time of the second reaction is 4-20h, e.g., 6h, 8h, 10h, 12h, 14h, 16h, 18h, etc.
Preferably, the preparation method of the polyester polyol comprises the following steps:
and (3) carrying out polycondensation reaction on a polyol monomer and polybasic acid under the action of a catalyst to obtain the polyester polyol.
Preferably, the temperature of the polycondensation reaction is 200-250 ℃, e.g., 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, etc.
Preferably, the polycondensation reaction is carried out for a period of time ranging from 4 to 18 hours (e.g., 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, etc.) to an acid value of less than 3mgKOH/g (e.g., 2.5mgKOH/g, 2.0mgKOH/g, 1.5mgKOH/g, 1.0mgKOH/g, 0.5mgKOH/g, etc.), and a hydroxyl value ranging from 20mgKOH/g to 400mgKOH/g (e.g., 50mgKOH/g, 100mgKOH/g, 150mgKOH/g, 200mgKOH/g, 250mgKOH/g, 300mgKOH/g, 350mgKOH/g, etc.).
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Carrying out polycondensation reaction on a polyol monomer and polybasic acid under the action of a polycondensation catalyst at 200-250 ℃ to obtain the polyester polyol;
(2) The polyester polyol, the azide compound and the reaction auxiliary agent are reacted for the first time under the action of a catalyst at 60-130 ℃ to obtain the polyester with the terminal azide group, and then the polyester with the terminal azide group and the alkynyl compound are reacted for the second time under the action of an addition catalyst at 60-100 ℃ to obtain the polyester.
In a third aspect, the present invention provides the use of a polyester according to the first aspect in a building, automobile, clothing or household appliance.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, the polyester has high conversion rate to hydroxyl groups (such as primary hydroxyl groups) of the polyester polyol, and the reaction selectivity of the polyester can be greatly improved and the application range of the polyester can be expanded on the basis of keeping the excellent performance of the polyester per se by introducing different functional groups into the terminal groups, for example, the reaction wire drawing time with isocyanate can be improved on the basis of not affecting the self-learning performance of the polyester, thereby being beneficial to expanding the production and construction operation range and being beneficial to manufacturing large-sized materials; and the raw materials for preparing the polyester are safe and not explosive, and are suitable for large-scale use in factories.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a polyester, wherein the polyester is amine-terminated polyester, and the raw materials for preparing the polyester comprise the following components: the preparation method of the polyester comprises the following steps of:
(1) Adding the mixture into a reaction kettle according to the mol ratio of diethylene glycol/phthalic anhydride/tetrabutyl titanate of 1.4/1/0.0001, heating to 220 ℃ under the protection of nitrogen, maintaining the temperature for reaction for 16 hours, and separating and removing the produced condensed water and micromolecular polyol through a fractionating tower connected with the reaction kettle in the reaction process, wherein the acid value is lower than 3mgKOH/g, and stopping the reaction to obtain the polyester polyol.
(2) Cooling to 80 ℃, adding bis (p-nitrophenyl) azido phosphate and 1, 8-diazabicyclo [5,4,0] undec-7-ene respectively according to the mol ratio of 1.1/1 with hydroxyl groups of polyester polyol, maintaining the temperature for reaction for 18 hours, adding propargylamine, cuprous bromide and pentamethyldiethylenetriamine when the hydroxyl value is lower than 5mg KOH/g, and reacting for 16 hours at 80 ℃ to obtain the polyester, wherein the mol ratio of propargylamine, cuprous bromide and pentamethyldiethylenetriamine with the azido groups is 1/0.001/0.001, and reacting with isocyanate to produce polyurea products.
Example 2
The embodiment provides a polyester, wherein the polyester is vinyl-terminated polyester, and the raw materials for preparing the polyester comprise the following components: the preparation method of the polyester comprises the following steps of:
(1) Adding the mixture into a reaction kettle according to the mol ratio of diethylene glycol to adipic acid to tetrabutyl titanate of 1.3 to 1 to 0.0001, heating to 220 ℃ under the protection of nitrogen, maintaining the temperature for reaction for 14 hours, and separating and removing the produced condensed water and micromolecular polyol through a fractionating tower connected with the reaction kettle in the reaction process, wherein the acid value is lower than 3mg KOH/g, and stopping the reaction to obtain the polyester polyol.
(2) Cooling to 80 ℃, adding bis (p-nitrophenyl) azido phosphate and 1, 8-diazabicyclo [5,4,0] undec-7-ene respectively according to the mol ratio of 1.1/1 with hydroxyl groups of polyester polyol, maintaining the temperature for reaction for 18 hours, adding vinylacetylene, cuprous bromide and pentamethyldiethylenetriamine when the hydroxyl value is lower than 5mg KOH/g, and reacting for 16 hours at 80 ℃ to obtain the polyester, wherein the mol ratio of vinylacetylene, cuprous bromide and pentamethyldiethylenetriamine to the azido groups is 1/0.001/0.001, and the thermosetting plastic product can be produced through double bond crosslinking.
Example 3
The embodiment provides a polyester, wherein the polyester is secondary hydroxyl crystalline polyester, and the raw materials for preparing the polyester comprise the following components: the preparation method of the polyester comprises the following steps of:
(1) Adding the mixture into a reaction kettle according to the mol ratio of 1, 4-butanediol/adipic acid/tetrabutyl titanate of 1.1/1/0.0001, heating to 220 ℃ under the protection of nitrogen, maintaining the temperature for reaction for 18 hours, separating and removing the produced condensed water and micromolecular polyol through a fractionating tower connected with the reaction kettle in the reaction process, and stopping the reaction when the acid value is lower than 3mg KOH/g, thus obtaining the polyester polyol.
(2) Cooling to 80 ℃, adding bis (p-nitrophenyl) azido phosphate and 1, 8-diazabicyclo [5,4,0] undec-7-ene respectively according to the mol ratio of 1.1/1 with hydroxyl groups of polyester polyol, maintaining the temperature for reaction for 18 hours, adding 3-butyn-2-ol, cuprous bromide and pentamethyldiethylenetriamine when the hydroxyl value is lower than 5mgKOH/g, and maintaining the mol ratio of the 3-butyn-2-ol, cuprous bromide and pentamethyldiethylenetriamine to the azido groups for reaction for 16 hours at 80 ℃ to obtain the polyester which still has part of alcoholic hydroxyl groups and can produce a crystalline polyurethane product of a slow reaction system.
Example 4
The embodiment provides a polyester, wherein the polyester is a bromine-terminated polyester, and the raw materials for preparing the polyester comprise the following components: the preparation method of the polyester comprises the following steps of:
(1) Adding the mixture into a reaction kettle according to the mol ratio of glycol to adipic acid to tetrabutyl titanate of 1.2 to 1 to 0.0001, heating to 220 ℃ under the protection of nitrogen, maintaining the temperature for reaction for 14 hours, and separating and removing the produced condensed water and micromolecular polyol through a fractionating tower connected with the reaction kettle in the reaction process, wherein the acid value is lower than 3mg KOH/g, and stopping the reaction to obtain the polyester polyol.
(2) Cooling to 80 ℃, adding bis (p-nitrophenyl) azido phosphate and 1, 8-diazabicyclo [5,4,0] undec-7-ene respectively according to the mol ratio of 1.1/1 with hydroxyl groups of polyester polyol, maintaining the temperature for reaction for 18 hours, adding 3-bromopropyne, cuprous bromide and pentamethyldiethylenetriamine when the hydroxyl value is lower than 5mg KOH/g, and maintaining the mol ratio of the 3-bromopropyne, the cuprous bromide and the pentamethyldiethylenetriamine to the azido groups to be 1/0.001/0.001, and reacting for 16 hours at the 80 ℃ to obtain the polyester, wherein a block copolymer product can be formed through controllable free radical polymerization.
Example 5
The embodiment provides a polyester, wherein the polyester is maleimide-based polyester, and the raw materials for preparing the polyester comprise the following components: the preparation method of the polyester comprises the following steps of:
(1) Adding the mixture into a reaction kettle according to the mol ratio of triethylene glycol/sebacic acid/tetrabutyl titanate of 1.5/1/0.0001, heating to 220 ℃ under the protection of nitrogen, maintaining the temperature for reaction for 18 hours, separating and removing the produced condensed water and micromolecular polyol through a fractionating tower connected with the reaction kettle in the reaction process, and stopping the reaction when the acid value is lower than 3mgKOH/g, thus obtaining the polyester polyol.
(2) Cooling to 80 ℃, adding bis (p-nitrophenyl) azido phosphate and 1, 8-diazabicyclo [5,4,0] undec-7-ene respectively according to the mol ratio of 1.1/1 with hydroxyl groups of polyester polyol, maintaining the temperature for reaction for 18 hours, adding propyne-maleimide, cuprous bromide and pentamethyldiethylenetriamine when the hydroxyl value is lower than 5mgKOH/g, and maintaining the mol ratio of the propyne-maleimide, the cuprous bromide and the pentamethyldiethylenetriamine to the azido groups to be 1/0.001/0.001, and maintaining the temperature for reaction for 16 hours to obtain the polyester, wherein the bovine serum albumin can be combined through sulfhydryl coupling.
Example 6
The embodiment provides a polyester, wherein the polyester is silicon-based polyester, and the raw materials for preparing the polyester comprise the following components: the preparation method of the polyester comprises the following steps of:
(1) Adding the mixture into a reaction kettle according to the mol ratio of diethylene glycol/terephthalic acid/phthalic anhydride/tetrabutyl titanate of 3/1/1/0.0002, heating to 220 ℃ under the protection of nitrogen, maintaining the temperature for reaction for 18 hours, separating and removing the produced condensed water and micromolecular polyol through a fractionating tower connected with the reaction kettle in the reaction process, and stopping the reaction when the acid value is lower than 3mg KOH/g, thus obtaining the polyester polyol.
(2) Cooling to 80 ℃, adding bis (p-nitrophenyl) azido phosphate and 1, 8-diazabicyclo [5,4,0] undec-7-ene respectively according to the mol ratio of 1.1/1 with the hydroxyl groups of the polyester polyol, maintaining the temperature for reaction for 18 hours, adding trimethylsilylacetylene, cuprous bromide and pentamethyldiethylenetriamine when the hydroxyl value is lower than 5mgKOH/g, and maintaining the mol ratio of the trimethylsilylacetylene, cuprous bromide and pentamethyldiethylenetriamine to the azido groups for reaction for 16 hours at 80 ℃ to obtain the polyester.
Example 7
The embodiment provides a polyester, wherein the polyester is a polyester polyether block copolymer, and the raw materials for preparing the polyester comprise the following components: the preparation method of the polyester comprises the following steps of:
(1) Adding the mixture into a reaction kettle according to the mol ratio of glycol to adipic acid to tetrabutyl titanate of 1.3 to 1 to 0.0001, heating to 220 ℃ under the protection of nitrogen, maintaining the temperature for reaction for 14 hours, and separating and removing the produced condensed water and micromolecular polyol through a fractionating tower connected with the reaction kettle in the reaction process, wherein the acid value is lower than 3mgKOH/g, and stopping the reaction to obtain the polyester polyol.
(2) Cooling to 80 ℃, adding bis (p-nitrophenyl) azido phosphate and 1, 8-diazabicyclo [5,4,0] undec-7-ene respectively according to the mol ratio of 1.1/1 with the hydroxyl groups of the polyester polyol, maintaining the temperature for reaction for 18 hours, adding alkyne- (PEG) 400 (alkyne-terminated ethoxy compound), cuprous bromide and pentamethyldiethylenetriamine when the hydroxyl value is lower than 5mgKOH/g, and maintaining the mol ratio of the cuprous bromide and pentamethyldiethylenetriamine to the azido groups for reaction for 16 hours, thereby obtaining the polyester which can be used as a surfactant.
Example 8
This example differs from example 3 in that the 1, 8-diazabicyclo [5,4,0] undec-7-ene was replaced with an equimolar amount of 7-methyl-1, 5, 7-triazabicyclo [4, 0] dec-5-ene, the remainder being the same as in example 3.
Comparative example 1
This comparative example differs from example 3 in that the bis (p-nitrophenyl) azido phosphate was replaced with an equimolar amount of sodium azide, the remainder being the same as example 3.
Comparative example 2
This comparative example differs from example 3 in that the bis (p-nitrophenyl) azido phosphate was replaced with an equimolar amount of sodium azide and the 1, 8-diazabicyclo [5,4,0] undec-7-ene was replaced with an equimolar amount of ammonia chloride, all the remainder being identical to example 3.
Performance testing
The polyesters described in examples 3, 8 and comparative examples 1-2 were tested as follows:
(1) Conversion of primary hydroxyl groups of the polyester polyol: the following hydrogen contents were detected separately by nuclear magnetic resonance hydrogen spectroscopy: hydroxyl-terminated polyester polyol-CH 2 2H of methylene in OH, conversion of primary hydroxyl to azide group followed by-CH 2 -N 3 2H of the medium methylene group, and H in the 1,2, 3-triazole group after cycloaddition reaction.
(2) Reactivity (gel time): the polyester, 1, 4-butanediol and diphenylmethane diisocyanate are mixed according to the mole ratio of 1:2:3 reaction was carried out at 80℃and gel time was measured.
(3) Mechanical properties (hardness, tensile strength): the polyester, toluene diisocyanate and 3,3 '-dichloro-4, 4' -diaminodiphenyl methane are mixed according to the mole ratio of 1:2:1 polyurethane elastomers were prepared and tested for hardness according to the standard of GB/T531-1999 and tensile strength according to the standard of GB/T528-2009.
The test results are summarized in table 1.
TABLE 1
As can be seen from an analysis of the data in Table 1, in the preferable range (taking example 3 as an example), the conversion rate of the polyester of the present invention to the primary hydroxyl groups of the polyester polyol is 83% or more and the gel time is 156s or more; the hardness of the prepared elastomer is 92-95Shore A, the tensile strength is 52-55MPa, and the mechanical properties are not greatly different, because the main structure of the polyester polyol is not changed, but the chemical functional groups of the end groups are changed. The preparation raw materials of the polyester are safe, the polyester is suitable for large-scale use in factories, the conversion rate of the polyester to the primary hydroxyl of the polyester polyol is high, different functional groups are introduced into the terminal group, the reaction selectivity of the polyester can be greatly improved, the application range of the polyester is expanded on the basis of keeping the excellent performance of the polyester, for example, the reaction gel time with isocyanate can be improved on the basis of not affecting the self-learning performance of the polyester, the expansion of the production construction operation range is facilitated, and the preparation of large-size materials is facilitated.
Analysis of comparative examples 1-2 and example 3 shows that comparative examples 1-2 do not perform as well as example 3, demonstrating that the polyesters of the invention perform better. The conversion rate of comparative examples 1-2 reaches more than 50%, but sodium azide is an explosive and is not suitable for large-scale use in factories.
As can be seen from an analysis of example 8 and example 3, example 8 is inferior in performance to example 3, demonstrating that the polyester formed by using 1, 8-diazabicyclo [5,4,0] undec-7-ene as a reaction auxiliary is better in performance.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The polyester is characterized by comprising the following raw materials: polyester polyol, azide, reaction auxiliary agent, alkynyl compound and catalyst;
the azide compound includes bis (p-nitrophenyl) azido phosphate.
2. The polyester of claim 1, wherein the reaction promoter comprises an alkenyl compound;
preferably, the reaction auxiliary comprises 1, 8-diazabicyclo [5,4,0] undec-7-ene.
3. The polyester according to claim 1 or 2, wherein the polyester polyol has terminal hydroxyl groups;
preferably, the polyester polyol is prepared from a raw material comprising a polyol monomer and a polybasic acid;
preferably, the polyol monomers include any one or a combination of at least two of ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, diethylene glycol, triethylene glycol, methylpropanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, glycerol, trimethylolpropane, polyethylene glycol, or polytetramethylene glycol;
preferably, the polyacid comprises any one or a combination of at least two of succinic acid, adipic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid or trimellitic anhydride.
4. A polyester according to any of claims 1 to 3, wherein the catalyst comprises an addition catalyst;
preferably, the catalyst further comprises a polycondensation catalyst;
preferably, the addition catalyst comprises any one or a combination of at least two of cuprous bromide, cuprous iodide, triethylamine or pentamethyldiethylenetriamine;
preferably, the polycondensation catalyst comprises any one or a combination of at least two of stannous octoate, tetrabutyl titanate, or tetraisopropyl titanate.
5. The polyester of any of claims 1-4, wherein the alkynyl compound comprises any one or a combination of at least two of propargylamine, 4-ethynylaniline, vinylacetylene, isopropenylacetylene, 3-butyn-2-ol, 3-bromopropyne, 3-chloropropionylene, 3-fluoropropyne, propyne-maleimide, propyne amide, trimethylsilylacetylene, alkyne-terminated ethoxy compounds, or alkyne-terminated propoxy compounds.
6. The polyester according to any one of claims 1 to 5, wherein the raw materials for preparing the polyester comprise the following components in parts by weight:
preferably, in the catalyst, the weight part of the polycondensation catalyst is 0-0.1 part and is not equal to 0 part;
preferably, in the catalyst, the weight part of the addition catalyst is 0.01-0.2 part.
7. A process for the preparation of a polyester as claimed in any one of claims 1 to 6, comprising the steps of:
and reacting polyester polyol, an azide compound, a reaction auxiliary agent and an alkynyl compound under the action of a catalyst to obtain the polyester.
8. The method for preparing polyester according to claim 7, wherein the reaction comprises a first reaction of a polyester polyol, an azide compound and a reaction auxiliary agent to obtain a polyester having an azide group at the end, and a second reaction of the polyester having an azide group at the end with an alkyne compound to obtain the polyester;
preferably, the temperature of the first reaction is 60-130 ℃;
preferably, the temperature of the second reaction is 60-100 ℃;
preferably, the preparation method of the polyester polyol comprises the following steps:
carrying out polycondensation reaction on a polyol monomer and polybasic acid under the action of a catalyst to obtain the polyester polyol;
preferably, the temperature of the polycondensation reaction is 200-250 ℃.
9. The preparation method according to claim 7 or 8, characterized in that the preparation method comprises the steps of:
(1) Carrying out polycondensation reaction on a polyol monomer and polybasic acid under the action of a polycondensation catalyst at 200-250 ℃ to obtain the polyester polyol;
(2) The polyester polyol, the azide compound and the reaction auxiliary agent are reacted for the first time under the action of a catalyst at 60-130 ℃ to obtain the polyester with the terminal azide group, and then the polyester with the terminal azide group and the alkynyl compound are reacted for the second time under the action of an addition catalyst at 60-100 ℃ to obtain the polyester.
10. Use of the polyester of any one of claims 1 to 6 in construction, automotive, apparel or household appliances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310303407.0A CN116284716A (en) | 2023-03-27 | 2023-03-27 | Polyester and preparation method and application thereof |
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