GB1602063A - Polymer beads - Google Patents
Polymer beads Download PDFInfo
- Publication number
- GB1602063A GB1602063A GB19793/78A GB1979378A GB1602063A GB 1602063 A GB1602063 A GB 1602063A GB 19793/78 A GB19793/78 A GB 19793/78A GB 1979378 A GB1979378 A GB 1979378A GB 1602063 A GB1602063 A GB 1602063A
- Authority
- GB
- United Kingdom
- Prior art keywords
- monomer
- mole
- modifier
- ion exchange
- units
- 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.)
- Expired
Links
- 239000011324 bead Substances 0.000 title claims description 35
- 229920000642 polymer Polymers 0.000 title description 10
- 239000000178 monomer Substances 0.000 claims description 40
- 229920001577 copolymer Polymers 0.000 claims description 34
- 239000003607 modifier Substances 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 21
- 239000003456 ion exchange resin Substances 0.000 claims description 21
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- -1 hydroxyalkyl ammonium Chemical compound 0.000 claims description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 claims description 10
- 230000000052 comparative effect Effects 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 239000004971 Cross linker Substances 0.000 claims description 7
- 125000000746 allylic group Chemical group 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 4
- 125000004954 trialkylamino group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 claims description 3
- 230000003204 osmotic effect Effects 0.000 claims description 3
- 230000035939 shock Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 150000003456 sulfonamides Chemical class 0.000 claims description 3
- 238000005349 anion exchange Methods 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 2
- 229920002554 vinyl polymer Polymers 0.000 description 9
- IYQYZZHQSZMZIG-UHFFFAOYSA-N tricyclo[5.2.1.0(2.6)]deca-3,8-diene, 4.9-dimethyl Chemical compound C1C2C3C=C(C)CC3C1C=C2C IYQYZZHQSZMZIG-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229920006163 vinyl copolymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- CRDAMVZIKSXKFV-FBXUGWQNSA-N (2-cis,6-cis)-farnesol Chemical compound CC(C)=CCC\C(C)=C/CC\C(C)=C/CO CRDAMVZIKSXKFV-FBXUGWQNSA-N 0.000 description 1
- 239000000260 (2E,6E)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol Substances 0.000 description 1
- NCIGMZODLBFTKN-BSWSSELBSA-N (4E,6E)-2-methylnona-2,4,6-triene Chemical compound CC\C=C\C=C\C=C(C)C NCIGMZODLBFTKN-BSWSSELBSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- QMFJIJFIHIDENY-UHFFFAOYSA-N 1-Methyl-1,3-cyclohexadiene Chemical group CC1=CC=CCC1 QMFJIJFIHIDENY-UHFFFAOYSA-N 0.000 description 1
- IROFMMHLTOVXFS-UHFFFAOYSA-N 1-chloro-2,3-bis(ethenyl)benzene Chemical compound ClC1=CC=CC(C=C)=C1C=C IROFMMHLTOVXFS-UHFFFAOYSA-N 0.000 description 1
- KAJRUHJCBCZULP-UHFFFAOYSA-N 1-cyclohepta-1,3-dien-1-ylcyclohepta-1,3-diene Chemical compound C1CCC=CC=C1C1=CC=CCCC1 KAJRUHJCBCZULP-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- FCMUPMSEVHVOSE-UHFFFAOYSA-N 2,3-bis(ethenyl)pyridine Chemical compound C=CC1=CC=CN=C1C=C FCMUPMSEVHVOSE-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- LBQJCDLKJGOHEA-UHFFFAOYSA-N 2-ethenylbut-3-enylbenzene Chemical compound C=CC(C=C)CC1=CC=CC=C1 LBQJCDLKJGOHEA-UHFFFAOYSA-N 0.000 description 1
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 1
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical group ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- KHAHWKLZGBIAKT-UHFFFAOYSA-N 4-(4-methylpyrimidin-2-yl)benzaldehyde Chemical compound CC1=CC=NC(C=2C=CC(C=O)=CC=2)=N1 KHAHWKLZGBIAKT-UHFFFAOYSA-N 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- IAWYWVVBKGWUEP-UHFFFAOYSA-N benzyl phenylmethoxycarbonyloxy carbonate Chemical compound C=1C=CC=CC=1COC(=O)OOC(=O)OCC1=CC=CC=C1 IAWYWVVBKGWUEP-UHFFFAOYSA-N 0.000 description 1
- 230000001851 biosynthetic effect Effects 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- VPPSHXIFIAJKMX-UHFFFAOYSA-N bis(prop-2-enyl) 2,3-dihydroxybutanedioate Chemical compound C=CCOC(=O)C(O)C(O)C(=O)OCC=C VPPSHXIFIAJKMX-UHFFFAOYSA-N 0.000 description 1
- HABAXTXIECRCKH-UHFFFAOYSA-N bis(prop-2-enyl) butanedioate Chemical compound C=CCOC(=O)CCC(=O)OCC=C HABAXTXIECRCKH-UHFFFAOYSA-N 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- FPODCVUTIPDRTE-UHFFFAOYSA-N bis(prop-2-enyl) hexanedioate Chemical compound C=CCOC(=O)CCCCC(=O)OCC=C FPODCVUTIPDRTE-UHFFFAOYSA-N 0.000 description 1
- BKXRKRANFLFTFU-UHFFFAOYSA-N bis(prop-2-enyl) oxalate Chemical compound C=CCOC(=O)C(=O)OCC=C BKXRKRANFLFTFU-UHFFFAOYSA-N 0.000 description 1
- AOESAXAWXYJFNC-UHFFFAOYSA-N bis(prop-2-enyl) propanedioate Chemical compound C=CCOC(=O)CC(=O)OCC=C AOESAXAWXYJFNC-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- 229930006739 camphene Natural products 0.000 description 1
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexediene Natural products C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229940043259 farnesol Drugs 0.000 description 1
- 229930002886 farnesol Natural products 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010338 mechanical breakdown Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- AYGYHGXUJBFUJU-UHFFFAOYSA-N n-[2-(prop-2-enoylamino)ethyl]prop-2-enamide Chemical compound C=CC(=O)NCCNC(=O)C=C AYGYHGXUJBFUJU-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 1
- PLCFYBDYBCOLSP-UHFFFAOYSA-N tris(prop-2-enyl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound C=CCOC(=O)CC(O)(CC(=O)OCC=C)C(=O)OCC=C PLCFYBDYBCOLSP-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
(54) POLYMER BEADS
(71) We, ROHM AND HAAS COMPANY, a corporation organized under the State of Delaware, United States of America, of Independence Mall
West, Philadelphia, Pennsylvania 19015, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the following statement:- This invention is concerned with the preparation of crosslinked vinyl copolymers as discrete copolymer beads in aqueous dispersions, with the beads themselves and with ion exchange resins for which the beads constitute the base polymer matrix.
The techniques of preparing crosslinked vinyl copolymers in bead form (as precursors for conversion into ion exchange resins) by free-radical catalyzed polymerization of the monomer mixture in aqueous dispersion are well known. The term "crosslinked vinyl copolymer" in this specification means crosslinked, insoluble, infusible copolymers of 50 to 99.5 mole percent preferably 80 to 99% units of vinyl non-allylic aromatic monomer containing a single vinyl group e.g., styrene, vinyl toluene, vinyl naphthalene, ethyl vinyl benzene, vinyl chlorobenzene and chloromethyl styrene units, with 0.5 to 50 mole percent, preferably I to 20%, of units of crosslinker monomer compound having at least two active non-allylic vinyl groups, for example, divinyl benzene, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, divinyl toluene, trivinyl benzene, divinyl chlorobenzene, divinylpyridine, divinylnaphthalene, ethylene glycol diacrylate, neopentyl glycol dimethacrylate, diethylene glycol divinylether, bisphenol - A - dimethacrylate, pentaerythritol tetra- and trimethacrylates, divinylxylene, divinylethylbenzene, divinyl sulfone, divinyl ketone, divinyl sulfide, N,N' - methylene - diacrylamide,
N,N' - methylene - dimethacrylamide, N,N' - ethylene - diacrylamide, trivinyl naphthalene, polyvinyl anthracenes and the polyvinyl ethers of glycol, glycerol, pentaerythritol, resorcinol and the monothio and dithio derivatives of glycols. The copolymer may include units of up to 5 mole percent of other vinyl monomers which do not fundamentally affect the nature of the resin matrix, for example, acrylonitrile and butadiene units and others as known in the art.
In this specification "vinyl" includes "vinylidene", when used generically.
The conventional conditions of polymerization used heretofore lead to crosslinked vinyl copolymers, which, when converted to ion exchange resins by attachment of functional groups thereto, have certain operational deficiencies resulting from physical weaknesses.
The present invention may be used to yield ion exchange resins in which the polymer beads have greater mechanical strength and increased resistance to those swelling pressures which are produced within a bead during acid/base cycling (i.e., osmotic shock). Greater mechanical strength manifests itself in improved resistance to physical breakdown from external forces such as weight of the resin column bed, high fluid flows and backwashing. Thus, the physically strong ion exchange resins of this invention are especially useful in treating fluid streams at high flow rates, for example in condensate polishing applications in which resins of lesser quality are prone to mechanical breakdown and short life spans.
In the past, it has generally been the practice to exclude reaction modifiers in the preparation of crosslinked vinyl polymers used as the base matrix copolymer for ion exchange resins because they have been regarded as detrimental to the properties of these copolymers. U.S. 2,241,770 teaches that styrene is stabilized for storage by treatment with a representative modifier, phenylacetylene, with the admonition to remove the phenylacetylene from the monomer prior to its polymerization. While polymerization of styrene in conjunction with phenylacetylene at temperatures between 100 C and 225"C to produce a linear, uncrosslinked polymer is described in U.S. 2,290,547, there is no suggestion in the art that crosslinked copolymers useful for conversion into greatly improved ion exchange resins could be derived from polymerization systems incorporating modifiers such as phenyl-acetylene. British patent 1,261,427 teaches that the gel effect in the polymerization of acrylonitrile, acrylates and methacrylates or copolymerization thereof with styrene or vinyl acetate can be reduced or eliminated by the use of cyclic compounds such as 1,4-cyclohexadiene and terpinolene. Again, there is no suggestion in this art that such modifiers are useful in preparing improved crosslinked copolymers. U.S. Patent No. 3,976,629 discloses the use of various aliphatic compounds containing at least two polymerizable bonds, such as isoprene and cyclopentadiene, as crosslinkers in aliphatic monomer mixtures. Combinations of aromatic and polyunsaturated aliphatic crosslinker including compounds used herein as rate modifiers, are also known in the prior ion exchange art (see, e.g., U.S. Patent 3,674,728). These polyunsaturated aliphatic materials have been employed previously at much higher levels than herein for different purposes and under different polymerization conditions.
In accordance with this invention, vinyl monomer, crosslinking monomer, and other optional monomer are polymerized in aqueous dispersion in the presence of free-radical initiator and from 0.01 to 10 millimoles, per mole of monomer, of organic acetylenically or allylically unsaturated compound, said compound being capable of moderating rate of polymerization by "allylically unsaturated" we mean that the compound has a -CH < group attached to an aliphatic > CH=CH < group. Representative modifiers are phenyl-acetylene, terpinolene, bicycloheptadiene, dimethyloctatriene, dimer of cyclopentadiene, dimer of methylcyclopentadiene, terpenes, a-methyl styrene, methyl styrene dimer, limonene, cyclohexadiene, methyl cyclohexadiene, camphene, geraniol, farnesol, 2-norbornene, cyclododecatriene, cyclooctadiene, cyclododecene, allyl benzene and 4 - vinyl - 1 - cyclohexene
Other allylically unsaturated monomers useful as modifiers include allyl acrylate, diallyl mareate, diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate, diallyl tartrate.
diallyl silicate, triallyl tricarballylate, triallyl aconitrate, triallyl citrate, triallyl phosphate and the polyallyl ethers of glycol, glycerol, pentaerythritol and resorcinol.
A preferred amount of modifier is 0.1 to 10 millimoles per mole of monomer, more preferably 0.2 to 5 millimoles per mole of monomer.
The polymerization is normally carried out at a temperature from 30 to 950C, preferably 45 to 850 C, and more preferably from 50 to 75"C. It is desirable to employ lower temperatures of reaction in the earlier stages of the polymerization, for example until at least about 50% of the monomers in the dispersion are reacted, preferably 75% or more. The free radical initiator used in the process of the invention is one capable of catalyzing polymerization at the aforesaid temperatures, which are in general somewhat lower, e.g., from 15 to 350C lower, than those normally used in suspension polymerization for similar products.
Suitable initiators include di(4- t- butycyclohexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, di - (sec - butyl) - peroxydicarbonate, di - (2 ethylhexyl) peroxy dicarbonate, dibenzyl peroxydicarbonate, diisopropyl peroxydicarbonate, azobis (isobutyronitrile), azobis (2,4 - dimethylvaleronitrile), tbutyl peroxypivalate, lauroyl peroxide, benzoyl peroxide, t-butyl peroctoate and tbutyl peroxyisobutyrate. The amount of initiator is normally from about 0.1 to 2 percent, based on monomer weight, preferably 0.3 to 1%. It also may be advantageous when using catalysts which are active at relatively low temperatures, such as 30dO"C, to employ a second so-called "chaser catalyst" which is active at higher temperature, e.g., 75--1000C., in order to achieve higher yields of crosslinked vinyl polymer, for example, from about 0.05 to 0.1 ó based on monomer weight of such initiators as benzoyl peroxide, t-butyl peroctoate and tbutyl peroxyisobutyrate.
The aqueous medium in which the polymerization is conducted in dispersion form will usually contain minor amounts of the conventional suspension additives, that is, dispersants such as xanthan gum (biosynthetic polysaccharide), poly(diallyl dimethyl ammonium chloride), polyacrylic acid (and salts), polyacrylamide, magnesium silicate, and hydrolyzed poly(styrene-maleic anhydride); protective colloids such as carboxymethyl cellulose, hydroxyalkyl cellulose, methyl cellulose, polyvinyl alcohol, gelatin, and alginates; buffering aids such as phosphate and borate salts; and pH control chemicals such as sodium hydroxide and sodium carbonate.
The crosslinked, high-molecular weight copolymers may be recovered from the reactor as hard, discrete beads of particle size within the range of 0.02 to 2 mm, average particle size being 0.2 to 1 mm. These copolymers may be converted to ion exchange resins by attachment of functional groups thereto by conventional means, suitable functional groups including sulfonamide, trialkylamino, tetraalkyl ammonium, carboxyl, carboxylate, sulfonic, sulfonate, hydroxyalkyl ammonium, iminodiacetate, amine oxide, phosphonate, and others known in the art.
Functionalizing reactions which may be performed on vinyl aromatic copolymers to produce ion exchange resins are exemplified by sulfonation with concentrated sulfuric acid, chlorosulfonation with chlorosulfonic acid followed by amination, reaction with sulfuryl chloride or thionyl chloride followed by amination, and chloromethylation followed by amination. Typical functionalizing reactions on (vinyl) acrylic copolymers include hydrolysis to acrylic acid resins, amidolysis, transesterification, and the like. Ion exchange resins may be further delineated by the types: strong acid cation, i.e., containing the groupings sulfonic (-SO3H) or sulfonate (-SO3M), where M is usually an alkali metal ion); weak acid cation, i.e., containing the groupings carboxyl (-CO2ll) or carboxylate (CO2M, where M is usually an alkali metal ion); strong base anion, i.e., containing the tetraalkyl ammonium groupings: -NR3X, where R is an alkyl or hydroxy alkyl group and X is usually chloride or hydroxide; and weak base anion, i.e., containing a trialkylamino group, -NR2, where R is an alkyl or hydroxyalkyl group.
The improvements in the properties of polymers when they are produced according to this invention are evident when the crosslinked copolymers are converted to ion exchange resins by the attachment of the aforesaid functional groups. The enhanced physical strength of these latter resins is apparent from their resistance to crushing which is conveniently measured on the Chatillon instrument, as well as by visual inspection before and after use in ion exchange applications.
For example, strongly acidic styrene-type resins frequently exhibit Chatillon values in the range of about 1000 to about 5000 gm, force per bead, in contrast to resins derived from copolymers prepared by prior art polymerization methods which have
Chatillon values of 50 to 500 gm/bead. Similarly, strong base sytrene-type resins of the invention frequently exhibit Chatillon values of about 500 to 1500 in contrast with resins derived from copolymers prepared by prior art methods which have
Chatillon values of 25 to 400.
Some preferred embodiments of this invention will now be described, for illustration only, in the following Examples, which also include information on prior art techniques for comparative purposes only.
Examples 1-3 A. Polymer beads are made in a polymerization reactor which is a two-liter, three neck, round bottom flask equipped with a two-blade paddle stirrer, thermometer, condenser, heating mantle with temperature controller, and provision for sweeping in a blanket of inert gas. Into this reactor is charged a monomer mixture consisting of 491.7 g. styrene, 85.5 g. divinylbenzene, 8.8 g.
methyl acrylate, 0.293 g. methylcyclopentadiene dimer, 2.64 g. di - (4 - t butylcyclohexyl)peroxydicarbonate, and 0.293 g. t-butyl peroctoate. The head space is swept with 8% O2 in nitrogen for 30 minutes at 50 cc./min. Then an aqueous phase is added consisting of 510 g. water, 20.1 g. poly-(diallyl dimethyl ammonium chloride) dispersant ("Padmac A"), 1.6 g. gelatin protective colloid ("Pharmagel"), 0.88 g. boric acid, 0.59 g. sodium nitrite, and sufficient 50% sodium hydroxide solution to maintain pH between 10 and 10.5. The stirrer is started and the gas sweep is changed to all nitrogen. The reaction mixture is heated from room temperature to 55+20C over 45 minutes and held at this temperature for 7 hours.
The polymerization is finished off by holding at 750C for one hour and 95"C for another hour. The copolymer beads are washed and excess water is removed by vacuum filtration on a Buchner funnel.
B. In another polymer bead production carried out in like manner, except for the omission of the oxygen-nitrogen sweep, 500.5 g. styrene, 85.5 g. divinylbenzene, 0.586 g. methylcyclopentadiene dimer, and 2.2 g. benzoyl peroxide are mixed with an aqueous phase composed of 510 g. water, 20.1 g. "Padmac A" dispersant, 1.6 g.
"Pharmagel" colloid, 0.88 g. boric acid, 0.59 g. sodium nitrite, and sufficient 50"" sodium hydroxide solution to maintain pH between 10 and 10.5. The reaction mixture is heated from room temperature to 75"C over a 45 min. period and held at 73--77"C for four hours. The polymerization is finished off at a temperature of 95"C. maintained for one hour. The copolymer beads are washed and prepared for functionalization.
Ion exchange resins are then made from the above polymer beads using the technique which follows.
A portion of wet polymer beads as prepared above (110 gms.) is added to 600 grams of 95% H2SO4 in a one liter flask equipped with stirrer, condenser, dropping funnel, thermometer, caustic scrubber and heating means. Thirty nine grams of ethylene dichloride (bead swelling agent) are added, and the suspension is heated from 30"C to 120"C over a 3 hour period. This is followed by a hydration procedure in which water is added to quench the product. The polymer beads are transferred to a backwash tower and backwashed to remove residual acid.
Ion exchange resin products prepared by functionalizing (by sulfonation as above) the copolymer from polymerization method B are characterized in Table 1.
Other exemplary modifiers, instead of methylcyclopentadiene dimer (MCPD) were utilized to yield improvements in bead appearance. Also the polymerization processes were repeated omitting the polymerization modifier to give comparative resins.
TABLE 1 Appearance
(Perfect/ Modifier Chatillon Cracked
Example (mmole/mole monomer) (g/bead) Fragmented)
1 MCPD (0.6) 520 89/10/1
2 Terpinolene (0.7) 780 82/15/3
3 Phenylacetylene (1.0) 670 89/4/7
Comparative None 400 53/45/2
Comparative None 440 55/41/4
An even greater improvement in bead quality is observed with ion exchange resin on the basis of copolymer from polymerization method A. The sulfonated resin derived therefrom is characterized by the following properties.
Whole beads 100% Cracked beads 3%
Fractured beads 0% Perfect beads 97% Friability: Chatillon value, g/bead 1880
Solids, H+ form 47.0 ,Ó Salt Splitting Cation capacity, meq./g dry 5.06
Examples 4--6 Further crosslinked styrene copolymers are prepared as above in polymerization A with variations in the concentration of the modifier, MCPD, then sulfonated as described above to yield ion exchange resins. The properties of these
resins are compared to commercial sulfonated resins made from copolymers prepared without modifier addition and with the properties of a sulfonated resin
made on the basis of copolymer prepared by polymerization A with modifier
omitted. The results are given in Table 2.
TABLE 2
Modifier Conc., mmole per Chatillon, Microcycling Stability*
Example Mole Monomer g/bead Before** After
4 0.15 1870 98/2/0 96/4/0
5 0.3 1700 98/2/0 - 6 0.3 1880 97/3/0 93/7/0
Comparative
Commercial
Resin 300 72/26/2 49/46/5
Commercial
Resin 510 98.5/1.5/0 55/42/3
Comparative None 1170 82/16/2 Notes: *100 cycles with IN Hcl and 0.5N NaOH solutions.
**Perfect/Cracked/Fragmented.
Examples 7 and 8
Other crosslinked styrene copolymers are prepared in accordance with this invention using a representative reaction modifier, then chloromethylated and aminated in conventional manner to form strong base, anion exchange resins, the properties of which are compared to commercial resins having the same functional groups and made from copolymers prepared without modifier addition. The results are given in Table 3.
TABLE 3
MCPD Modifier Anion Exchange Microcycling
Conc., (mmole/mole Chatillon Capacity, Stability* Example monomer) (g/bead) meq/gm % Solids Before** After
7 0.3 372 4.22 45.5 99/1/0 95/5/0
8 0.6 278 4.30 45.2 98/2/0 90/9/1
Commercial
Resin X - 140 4.20 46.0 94/6/0 72/28/0
Commercial
Resin Y - 400 4.40 42.5 97/3/0 90/9/0
*100 cycles with hot (50"C) lNNaOH and 0.25 NHCl-0.25 NH2SO4 solutions.
**Perfect/Cracked/Fragmented
In like manner, ion exchange resins derived from crosslinked styrene copolymers prepared employing other polymerization modifiers mentioned earlier herein exhibit comparable properties of high mechanical strength and resistance to osmotic shock.
WHAT WE CLAIM IS:
1. A process for preparing beads of crosslinked copolymer containing (a) 50 to 99.5 mole % units of non-allylic, aromatic monomer containing a single vinyl group and (b) 0.5 to 50 mole % units of crosslinker monomer having at least two active non-allylic vinyl groups, by free radical polymerization in aqueous dispersion wherein the polymerization reaction is carried out in the presence of from 0.01 to 10 millimoles per mole of monomer of reaction moderating modifier which comprises one or more acetylenically or allylically unsaturated organic compounds admixed with the monomer.
2. A process as claimed in Claim 1 wherein the monomer (a) comprises styrene and the monomer (b) comprises divinylbenzene.
3. A process as claimed in any preceding claim wherein the modifier comprises one or more of: phenylacetylene, terpinolene and the dimer of methylcyclopentadiene.
4. A process as claimed in any preceding claim which is carried out at a temperature of 30 to 950 C.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (14)
- **WARNING** start of CLMS field may overlap end of DESC **.TABLE 2 Modifier Conc., mmole per Chatillon, Microcycling Stability* Example Mole Monomer g/bead Before** After4 0.15 1870 98/2/0 96/4/05 0.3 1700 98/2/0 -6 0.3 1880 97/3/0 93/7/0 Comparative Commercial Resin 300 72/26/2 49/46/5 Commercial Resin 510 98.5/1.5/0 55/42/3 Comparative None 1170 82/16/2 Notes: *100 cycles with IN Hcl and 0.5N NaOH solutions.**Perfect/Cracked/Fragmented.Examples 7 and 8 Other crosslinked styrene copolymers are prepared in accordance with this invention using a representative reaction modifier, then chloromethylated and aminated in conventional manner to form strong base, anion exchange resins, the properties of which are compared to commercial resins having the same functional groups and made from copolymers prepared without modifier addition. The results are given in Table 3.TABLE 3 MCPD Modifier Anion Exchange Microcycling Conc., (mmole/mole Chatillon Capacity, Stability* Example monomer) (g/bead) meq/gm % Solids Before** After7 0.3 372 4.22 45.5 99/1/0 95/5/08 0.6 278 4.30 45.2 98/2/0 90/9/1 Commercial Resin X - 140 4.20 46.0 94/6/0 72/28/0 Commercial Resin Y - 400 4.40 42.5 97/3/0 90/9/0 *100 cycles with hot (50"C) lNNaOH and 0.25 NHCl-0.25 NH2SO4 solutions.**Perfect/Cracked/Fragmented In like manner, ion exchange resins derived from crosslinked styrene copolymers prepared employing other polymerization modifiers mentioned earlier herein exhibit comparable properties of high mechanical strength and resistance to osmotic shock.WHAT WE CLAIM IS: 1. A process for preparing beads of crosslinked copolymer containing (a) 50 to 99.5 mole % units of non-allylic, aromatic monomer containing a single vinyl group and (b) 0.5 to 50 mole % units of crosslinker monomer having at least two active non-allylic vinyl groups, by free radical polymerization in aqueous dispersion wherein the polymerization reaction is carried out in the presence of from 0.01 to 10 millimoles per mole of monomer of reaction moderating modifier which comprises one or more acetylenically or allylically unsaturated organic compounds admixed with the monomer.
- 2. A process as claimed in Claim 1 wherein the monomer (a) comprises styrene and the monomer (b) comprises divinylbenzene.
- 3. A process as claimed in any preceding claim wherein the modifier comprises one or more of: phenylacetylene, terpinolene and the dimer of methylcyclopentadiene.
- 4. A process as claimed in any preceding claim which is carried out at a temperature of 30 to 950 C.
- 5. A process as claimed in any preceding claim wherein the concentration ofmodifier is 0.1 to 10 millimoles per mole of monomer.
- 6. A process as claimed in any preceding claim wherein the concentration of modifier is from 0.2 to 5 millimoles per mole of monomer.
- 7. A process as claimed in any preceding claim which is carried out at a temperature of 45 to 85"C.
- 8. A process as claimed in Claim 1 substantially as described in any one of the foregoing Examples.
- 9. Beads of crosslinked copolymer containing (a) 50 to 99.5 mole 'í) units of non-allylic aromatic monomer containing a single vinyl group and (b) 0.5 to 50 mole % units of crosslinker monomer containing at least two active non-allylic vinyl groups, whenever prepared by a process as claimed in any one of Claims I to 5.
- 10. Beads of crosslinked copolymer containing (a) 50 to 99.5 mole , units of non-allylic aromatic monomer containing a single vinyl group and (b) 0.5 to 50 mole % units of crosslinker monomer containing at least two active non-allylic vinyl groups, whenever prepared by a process as claimed in any one of Claims 6 to 8.
- 11. A process for producing ion exchange resin which comprises adding ion exchange functional groups to copolymer product as claimed in Claim 9.
- 12. A process for producing ion exchange resin which comprises adding ion exchange functional groups to copolymer product as claimed in Claim 10.
- 13. An ion exchange resin obtained by attaching sulfonamide, sulfonic, sulfonate, carboxyl, carboxylate, trialkylamino, tetraalkyl ammonium, hydroxyalkyl ammonium, iminodiacetate, amine oxide, and/or phosphonate functional groups to copolymer product as claimed in Claim 11.
- 14. An ion exchange resin obtained by attaching sulfonamide, sulfonic, sulfonate, carboxyl, carboxylate, trialkylamino, tetraalkyl ammonium, hydroxyalkyl ammonium, iminodiacetate, amine oxide, and/or phosphonate functional groups to copolymer product as claimed in Claim 12.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US79771677A | 1977-05-17 | 1977-05-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1602063A true GB1602063A (en) | 1981-11-04 |
Family
ID=25171614
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB19793/78A Expired GB1602063A (en) | 1977-05-17 | 1978-05-16 | Polymer beads |
Country Status (13)
Country | Link |
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JP (1) | JPS53141389A (en) |
AR (1) | AR221700A1 (en) |
AU (1) | AU516299B2 (en) |
BE (1) | BE867104A (en) |
BR (1) | BR7803065A (en) |
DE (1) | DE2820947A1 (en) |
ES (1) | ES469929A1 (en) |
FR (1) | FR2391233A1 (en) |
GB (1) | GB1602063A (en) |
IN (1) | IN148471B (en) |
IT (1) | IT1198295B (en) |
MX (1) | MX148905A (en) |
ZA (1) | ZA782707B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001030495A1 (en) * | 1999-10-27 | 2001-05-03 | Basf Aktiengesellschaft | Ion exchange resins and methods of making the same |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR7800684A (en) * | 1977-02-07 | 1978-10-10 | Rohm & Haas | PERFECTED ION EXCHANGE RESIN BILLS, PROCESS TO PREPARE HARD, GRINDED, INDIVIDUALIZED COPOLIMER ACCOUNTS, AND PROCESS TO PRODUCE AN ION EXCHANGE RESIN |
JP6677974B2 (en) * | 2015-03-26 | 2020-04-08 | 株式会社カネカ | Method for producing expandable styrene resin particles |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1181912B (en) * | 1961-09-09 | 1964-11-19 | Basf Ag | Process for the production of polystyrene and styrene copolymers with predominant proportions of polymerized styrene with improved mechanical properties |
NL137053C (en) * | 1967-01-30 | |||
CH586726A5 (en) * | 1972-08-02 | 1977-04-15 | Basf Ag |
-
1978
- 1978-05-03 MX MX173323A patent/MX148905A/en unknown
- 1978-05-11 ZA ZA00782707A patent/ZA782707B/en unknown
- 1978-05-12 IN IN362/DEL/78A patent/IN148471B/en unknown
- 1978-05-12 DE DE19782820947 patent/DE2820947A1/en active Granted
- 1978-05-15 AU AU36115/78A patent/AU516299B2/en not_active Expired
- 1978-05-16 BR BR787803065A patent/BR7803065A/en unknown
- 1978-05-16 GB GB19793/78A patent/GB1602063A/en not_active Expired
- 1978-05-16 IT IT68122/78A patent/IT1198295B/en active
- 1978-05-16 BE BE187720A patent/BE867104A/en not_active IP Right Cessation
- 1978-05-16 JP JP5723978A patent/JPS53141389A/en active Granted
- 1978-05-17 AR AR272218A patent/AR221700A1/en active
- 1978-05-17 FR FR7814588A patent/FR2391233A1/en active Granted
- 1978-05-17 ES ES469929A patent/ES469929A1/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001030495A1 (en) * | 1999-10-27 | 2001-05-03 | Basf Aktiengesellschaft | Ion exchange resins and methods of making the same |
US6569910B1 (en) | 1999-10-27 | 2003-05-27 | Basf Aktiengesellschaft | Ion exchange resins and methods of making the same |
Also Published As
Publication number | Publication date |
---|---|
ZA782707B (en) | 1979-06-27 |
AR221700A1 (en) | 1981-03-13 |
FR2391233B1 (en) | 1981-09-04 |
JPS625923B2 (en) | 1987-02-07 |
DE2820947C2 (en) | 1992-07-30 |
ES469929A1 (en) | 1979-09-16 |
JPS53141389A (en) | 1978-12-09 |
BE867104A (en) | 1978-11-16 |
IN148471B (en) | 1981-03-07 |
BR7803065A (en) | 1979-01-16 |
MX148905A (en) | 1983-06-30 |
DE2820947A1 (en) | 1978-11-30 |
IT1198295B (en) | 1988-12-21 |
AU3611578A (en) | 1979-11-22 |
FR2391233A1 (en) | 1978-12-15 |
AU516299B2 (en) | 1981-05-28 |
IT7868122A0 (en) | 1978-05-16 |
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Legal Events
Date | Code | Title | Description |
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PS | Patent sealed [section 19, patents act 1949] | ||
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19950516 |