CN1784453A - 聚((聚硫烷基)酯),它们的应用及其衍生物 - Google Patents
聚((聚硫烷基)酯),它们的应用及其衍生物 Download PDFInfo
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- CN1784453A CN1784453A CN200480012203.7A CN200480012203A CN1784453A CN 1784453 A CN1784453 A CN 1784453A CN 200480012203 A CN200480012203 A CN 200480012203A CN 1784453 A CN1784453 A CN 1784453A
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- -1 coatings Substances 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 28
- 229920001021 polysulfide Polymers 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
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- 239000001384 succinic acid Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims 1
- 125000005313 fatty acid group Chemical group 0.000 claims 1
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- 238000006243 chemical reaction Methods 0.000 abstract description 18
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- 238000002360 preparation method Methods 0.000 description 10
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- 150000007520 diprotic acids Chemical class 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 125000000962 organic 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
- 239000010457 zeolite Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
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- 239000011593 sulfur Substances 0.000 description 3
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 3
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 2
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- 229920002732 Polyanhydride Polymers 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229920001079 Thiokol (polymer) Polymers 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
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- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical class O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 125000004990 dihydroxyalkyl group Chemical group 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- ZEMHQYNMVKDBFJ-UHFFFAOYSA-N n-(3-hydroxypropyl)prop-2-enamide Chemical compound OCCCNC(=O)C=C ZEMHQYNMVKDBFJ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 235000006408 oxalic acid Nutrition 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000010703 silicon Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- 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
- C08G18/08—Processes
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
基于含聚硫化物的二醇与二元酸的反应产物,制备了化合物和这些化合物的聚合物,方便地将酸催化剂使用于该反应中。通过对摩尔比的适当选择,所形成的化合物可以具有一个羟基和一个羧基、两个羟基或两个羧基作为端基。这些化合物能够被改性,是通过加入增大基团(augmenting group)以便改变端基或单体的性质。发现这些聚合物具有优异的用途,可以用作胶粘剂、密封剂、涂料、油漆、弹性体、塑料制品(plastic formulations)、纤维、薄膜和模制物品。
Description
背景
技术领域
本发明的领域是含聚硫的聚酯合成物(polysulfur-containingpolymeric ester compositions)和它们的聚合物。
发明的背景
尽管聚合物领域发展成熟,但仍然有许多机会,以创造出具有新颖性质和用途的聚合物。聚合物(polymers)可以被划分成加成聚合物(addition polymers)和缩合聚合物(condensation polymers)。在缩合聚合物中,有聚酯(polyesters)、聚醚(polyethers)、聚氨酯(polyurethanes)、聚酰胺(polyamines)和聚酐(polyanhydrides)。这些聚合物广泛应用于模制产品、润滑剂、密封剂、涂料、油漆、弹性体(elastamers)、薄膜、纤维、高弹体(elastamers)以及其它制剂的领域中。它们的性质可以广泛地予以变化,是取决于所应用的官能基团,同时涉及本性及多样性;主链骨架单元;主链的官能度;这些聚合物分子的分子量和在分子量范围上的均一性;和类似因素。由于聚合物性质的巨大多样性,就聚合物而言,可能存在数量巨大的特定用途;在此情况下,聚合物的性质被按规格改制,用于一个特殊需求。
含有聚硫烷基基团的聚合物(polymers containing polythioalkylgroups)还未被大量应用于聚合物领域,除了Thiokol聚合物之外;因为环境因素,Thiokol聚合物目前未被广泛地使用。但是,硫存在于聚合物中能够具有期望的性质。已有报道,一些含有多硫键的聚合物产品(polymeric products containing polysulfide linkages)被用于多种多样的目的,例如在聚合物主链上具有二硫化物和醚基团;二硫化物和氨基甲酸酯基团;以及二硫化物和乙缩醛基团的聚合物。也有报道其他聚合物组合物,其中二硫化物是在聚合物的侧链中,例如在丙烯酸树脂的加成聚合物中。虽然在文献中公开了具有硫化物的具体化合物,其中硫化物具有一个以上的硫,但是,对大部分而言,它们并未作为实验工作范例予以描述。特别地,还没有报道:在主链中应用具有聚硫化物官能性的单体单元、并由含有聚硫化物的二醇和二元酸之间的结合作用形成而来的聚合物。
相关文献
在美国专利号US 2,582,605中,报道了二(羟乙基)硫化物和-二硫化物的酯。在美国专利号US 3,386,963中,报道了具有羟基端位并与聚氨酯进一步反应的烷基二硫化物聚合物。在美国专利号US 4,124,645中,在报道的聚合物中,聚合的硫二甘醇经反应提供卤素端基,其然后再进一步与聚硫化钠反应,形成一种乳胶分散体。在美国专利号US 4,764,299中,报道了末端为硫醇的聚合硫化物和聚硫乙二醇的聚合物。美国专利号US 6,383,324报道了“二烯基乙二硫醇的无规共聚聚缩醛”与聚异氰酸的聚合。在美国专利号US 4,131,716和US 6,114,485中,报道了硫取代的丙烯酸聚合物(sulfur substituted acrylic polymers)。
发明内容
提供了合成物(组合物(compositions)),其包括缩合产物(condensationproduct),缩合产物缩合自如下两种化合物:二元酸或其酸酐和二(羟基取代的有机基团)聚硫化物,其中所述合成物具有由该两种化合物的结合物所组成的一个或多个单元。所述合成物,是通过在选择的酸性条件下、和在一定摩尔比的条件下结合所述化合物而形成,以提供期望的产物。在不存在反应物之一的大量过量(large excess)的情况下,由此反应形成而来的合成物通常为混合物,除非采用阻止低聚反应的特定条件。视两种反应物的比例情况,组合物中大多数分子可以具有一个羟基和一个羧基作为端基(terminating groups),或具有两个羟基或两个羧基作为端基。所有这些化合物可以与多种多样的多官能化合物反应,以便生成具有适用于特定最终用途之性质的产物。
具体实施方式的描述
根据本主题发明,组合物是通过使用含聚硫化物的二醇(polysulfide-containing diol)与二元羧酸(dibasic carboxylic acid)的结合作用而产生的。产物在它们的主链上具有聚硫化物键和酯键。每个分子将具有至少一个单元,单元包括一个含氧基团(oxy group)、一个羰基基团、一个有机酯基团、一个聚硫基团;以及每个分子将具有至少5个,通常为至少6个碳原子,更通常为至少8个碳原子,并且不大于约80个碳原子,通常不大于约60个碳原子,更通常不大于约46个碳原子。硫原子距离氧原子至少为约2个碳原子。
包括这些单元的产物可通过两种反应物的结合而制得,理想地,在酸的存在下,在升温以及除去形成的水的条件下进行。根据这些条件的不同,产物的制备可采用大约1∶1摩尔比的反应物,以及在端位优势地具有羟基和羧基基团,其中所述产物为均聚物或低聚物,其通常具有多于约2个单元,以及具有的分子量为5000dal(道尔顿)或以上;或者采用在大于1∶1到1∶2之间的摩尔比,以及具有优势地端位的羟基基团或羧基基团。如上所表明的那样,通过采用特定的条件或反应物中之一种的大过量,可以获得更均一的组合物,其中反应物的摩尔比为1∶2,而且具有确定的组成。
在谈及一种均聚物或者复数个均聚物时,意指一种二(羟基取代有机基团)与一种二元酸(dibaic acid)的结合作用形成重复单元、而且这些分子将会既具有羟基又具有羧基末端。“伸长单体(extendedmonomeric)”单元会具有在大于1∶1直到1∶2之间的两种反应物的摩尔比,以致存在大多数具有相同官能性的末端基团,其中伸长单体单元分子可以作为单体予以应用。具体对共聚物而言,伸长单体(extendedmonomer)更适合对应于具有多个相同官能性的单体。
每个产品都包括具有下述式子所示的单体单元(monomer unit):
-ORSnR1OAO-或-OAOR1SnRO-
其中:
O和S具有它们的标准意义,即氧(oxygen)和硫(sulfur);
n至少为2且不大于约8,通常不大于约4,一般为在2-4的范围内变化,更通常为2-3;
R和R1是相同的或不同的;为有机二价基;通常为脂肪族的,更通常为烃;饱和的或不饱和的,直链的或支链的链;一般地,R和R1具有2个到20个、更通常为2个到12个碳原子,其中R和R1中碳原子的总数目将在约4个到40个的范围中,通常为4个到24个碳原子;及
A为有机二元羧酸(organic dibasic carboxylic acid)的残基(缺少两个羟基氧,在通式中已经阐明),其具有至少1个碳原子到不大于约60个碳原子,一般为从约2个到60个,更通常为约2个到40个,经常为约2个到12个;以及,对不是由两个一元羧酸的二聚形成的酸而言,其碳原子简便地为约2个到6个,对脂肪酸二聚体而言,碳原子为从约24个到40个。
当组合物由反应物形成,且在以它的反应物的摩尔比为约1∶1直到2∶1,包括2∶1或更大摩尔比时,并且组合物具有的分子量低于约5000道尔顿(dal)时,它被称为“伸长单体”;伸长单体(extended monomer)具有下面通式之一:
(a)MFmRSnR1OM1;或
(b)MZAORSnR1F1 mAZ1M1,
其中:
O和S具有氧(oxygen)和硫(sulfur)的标准涵义;
n为至少2且不大于约8,通常为在约2到4的范围中,更通常为在2到3的范围中;
F具有通式-ORSnR1OAO-;
F1具有通式-OAOR1SnRO-;
m至少为1;
Z和Z1为含氧基(oxy)或氨基;
M和M1是相同的或不同的;都为氢,当只有二元酸与二(羟基取代有机基团)聚硫化物进行反应时;或者,为有机取代基,如果适当则与氧结合形成醚或酯,或与氮结合形成取代的氨基或酰胺基;当带有单个基团(single group)时,它被称作“增大伸长单体(augmented extendedmonomer)”。
剩余符号是如同在前所定义的那样。
伸长单体(extended monomer)和增大单体(augmented monomers)可被用于形成均聚物或共聚物(在伸长单体中,只有端羟基伸长单体可用于形成均聚物)。
R和R1可为亚乙基、亚丙基、亚异丙基、亚丁基、亚己基、亚己烯基(hexenylene)、亚丁烯基(butynylene)、等等。
优选的聚硫二醇化合物(polysulfide diol compounds)为脂肪族的,其中R和R1为具有2-12个、通常为2个到6个碳原子的二烯基,特别是聚亚甲基或者是甲基或乙基取代的聚亚甲基。优选地,羟基基团距离聚硫化物基团是2到3个碳原子。
A的例子包括羰基二醇(碳酸;尤其在与二醇的摩尔比为1∶2之时)、草酸二醇、丙二酸二醇、丁二酸二醇、庚二酸二醇、己二酸二醇、癸二酸二醇、马来酸二醇、邻苯二甲酸二醇、对苯二甲酸二醇、脂肪酸二聚物(尤其是16到18个碳原子的脂肪酸)、氧(双-乙酰基)(oxy(bis-acetyl))、N-甲基氨基(双-丙酰基)(N-methyl amino(bis-propionyl))、1,4-二乙酰基环己烷、等等。优选的A基团为脂肪族的;可为饱和的或不饱和的,直链或支链的;可以含有0到2个杂原子,如氧、氮和硫。
Z和Z1是相同的或不同的。在大多数情况下,为含氧基(oxy-)或-NH-;但也可以为取代氨基,具有1到6个、通常为1到2个碳原子的烷基基团。
当M和M1不是氢,即,定义为“增大伸长单体”时,则
M被定义为W1R2-,及
M1被定义为W2R3-,
其中:
R2和R3是相同的或不同的;为有机二价基(organic divalent radicals);通常以碳原子终止,具有碳原子数为1个到20个,通常为2个到12个碳原子数,它们可以为脂肪族的、脂环族的、芳香族的、杂环族的(通常具有1-3个,更通常具有1-2个环杂原子,它们是氧、氮和硫)或其组合;通常为脂肪族,取代的或不取代的,直链的或支链的链;脂肪饱和或不饱和的,通常具有不多于3个、更通常不多于2个的脂肪不饱和位如双键或三键,共轭的或不共轭的;其中不参与形成增大单体的反应的取代基对增大单体的制备反应将为惰性的,并且对聚合反应为惰性的,可以是无机或有机取代,包含杂原子如氧、氮、硫、磷、硅、硼等,包括基团如含氧基(醚)、硫基(通常为醚)、氰基、氨基和取代氨基I°、II°、III°及IV°、卤基、偶氮基等、含氧羰基(酮、醛)、非含氧羰基(羧酸、酯和酰胺)、磷酰基、膦酰基(phosphonyl)、甲硅烷基、硼基(boronyl)等,杂取代基通常不多于约4个,更通常不多于约2个杂取代基,一般具有2到12个碳原子,更通常为2到6个碳原子,以及具有0到8个、更通常为0到6个、一般为0到4个杂原子;一般为具有2到6个碳原子的脂肪族,特别是聚亚甲基或者是甲基或乙基取代的聚亚甲基;及
W和W1是相同的或不同的,通常是相同的;为氨基,包括具有约1到6个、通常为约1到4个碳原子的伯氨基和仲氨基,为羟基、羧基、异硫氰酸酯、异氰酸酯、含氧羰基、非含氧羰基、硅氧烷、硅烷、环碳酸酯(cyclocarbonate),为活性烯烃例如烯丙酰基、异丁烯酰基、烯丙基,为乙烯基如乙烯醚、活性卤基和类似物。
可用于对伸长单体的尺寸进行进一步增大的化合物,包括二元胺如丙邻二胺、N-甲基亚丁基二胺、N-氨乙基哌嗪、1,1-二甲基-1,4-二氨基丁烷、三甲基六亚甲基二胺、2-甲基五亚甲基二胺、氮丙啶、环氧乙烷、缩水甘油醇,二醇如二甘醇、三丙二醇,苯磷二酚、对苯二酚、各种二羟烷基聚硫化物、羟基乙酸,丙烯酸和甲基丙烯酸,丙烯酸羟乙基酯和甲基丙烯酸酯,N-羟丙基丙烯酰胺、二(羟丁基)二乙基硅氧烷、烯丙基醇、碳酸甘油、氯乙酸、丙烯酸、二羟基丙酮、4,4-二(羟甲基)丁酸,等等。
伸长单体,以及含有聚硫化物二醇和二元酸的基本单元的聚合物,可以通过以合适摩尔比将两种反应物结合而制得,这依赖于期望哪种单体和是否期望端羟基或端羧基基团。聚硫化物二醇(polysulfide diol)和二酸(diacid)或酸酐被以合适比例组合,便利地,在不存在溶剂下、在酸催化剂存在下,加热至升高温度为约90℃以上,一般为在约100到180℃的范围中,同时从反应混合物中除去水。水可方便地通过轻微真空除去,约1-20mmHg(毫米汞柱)。可以使用任何便利的酸催化剂(acid catalyst),虽然发现对一些结合作用,一种催化剂比另一种优越。在大多数情况下,采用磺酸催化剂,尤其是甲磺酸,尽管可以采用对甲苯磺酸。其它催化剂包括沸石(zeolites)、路易斯酸(Lewis acids)、酸性硅藻土(adidicdiatomaceous earths)、等等。催化剂的量一般在反应物的约0.01到2wt%的范围中。在一些情况下,采用二醇的混合物,其中聚硫化物可为具有不同硫数目的聚硫化物的混合物。例如,商业可得的DiHEDs(ChevronPhillips Chemicals LP,普通级)包括95-97%二(羟乙基)二硫化物和3-5%的高级聚硫化物,主要是三硫化物。
高分子量的聚(硫酯)具有以下通式:
XfmX1
其中:
f为基团-ORSnR1OAO-;
X为H或HOA-;
X1为H或-RSnR1OH;
m的范围为约2到100,通常在约2到60的范围中,更通常为在约4到50的范围中;及
其余符号如前文所定义。
在二元酸与二(羟基取代有机基团)聚硫化物之间的摩尔比接近1∶1或等于1∶1时,可以生成这些聚合物。
本主题单体可以与具有相同或不同的官能性(functionalities)的双官能化合物反应,其中在单体通常具有约2个到12个、更通常为2个到6个碳原子时,所述双功能化合物一般具有至少2个碳原子,而且通常只有两个反应性官能团,虽然如果希望发生交联,也会有多达4个的反应性官能团;或者当期望预聚物时,具有1000或更多个碳原子,通常不多于约500个碳原子。常用的试剂包括羟基乙酸,其中端羟基可与羧基官能团交换或者端羧基官能团能被延伸而保留羧基官能团。因此,通过合适的挑选,可根据期望用于共聚过程的共聚单体,改变末端官能团。用于与单体反应的官能团可包括活性卤素、羟基和羧基,而端基官能团可包括活性卤素、不含氧和含氧羰基、羟基、氨基如伯氨和仲氨、甲硅烷基、硅氧烷基、等等。至于交联,可采用羟基、羧基、氨基等官能团的结合,具有至少约3个和不多于约5个的反应性官能团。
伸长单体和增大单体的聚合物一般可用下面通式描述:
T(ED)rT1
其中:
T和T1是相同的或不同的,为来源于共聚单体之一的聚合物的端基;
E和D中的之一为本主题的延伸和/或增大单体单元,另一个为共聚单体;及
r将会至少为2,一般平均至少约5,通常不大于约1000,更通常不大于约500,一般不大于约100。
制备的聚合物将会具有至少一个延伸和/或增大单体单元(extendedand/or augmented monomeric unit),一般至少为两个这样的单元,并且可以具有500个或更多这样的单元,这与聚合物的本性有关。特别感兴趣的一组聚合物是具有约2个到100个、更通常为约5个到50个的总单体单元的聚合物,来源于本主题的伸长单体和共聚单体(comonomers)。可使用相同或不同的本主题伸长单体,聚合物可包括嵌段共聚物、交替共聚物、交联共聚物等。共聚单体可为约500道尔顿(dal)以下的小分子量双官能团或高级官能团分子,可为2个或更多单元、通常不多于约100个单元的低聚物,或单体的任何其它组织,以便提供共聚体的第二节(secondmember)。如上所表明的,可以得到缩合聚合物,其中本主题单体在聚合物的主链中;或者本主题单体可以被连接到可经历加成聚合的单体上,其中本主题单体将是聚合物的侧链或交联接头(cross-linker)。
多种多样的第二单体可被用于获得本发明的聚合产物。一组重要的化合物是聚异氰酸酯,以形成聚氨酯。示例性的聚异氰酸酯包括2,4-及2,6-甲苯二异氰酸酯、异佛乐酮二异氰酸酯、三甲基六亚甲基异氰酸酯、3,3’-二甲氧基-4,4’-亚联苯基二异氰酸酯、亚萘基-1,5-二异氰酸酯、六亚甲基二异氰酸酯、1,4-亚苯基二异氰酸酯、等等。有关二异氰酸酯的示例性专利是美国专利号US 4,032,468,US 5,043,398和US 5,098,788及其中所引用的文献,这里特别引入作为参考,这只是有关聚异氰酸酯用途的大量专利文献的示例说明,与许多广泛的共聚单体一起可用于各种不同组的应用中。
聚氨酯可由羟基封端的伸长单体制得,经由它们与聚异氰酸酯的反应而进行;以及由异氰酸酯增大的伸长单体制备而来,经由与传统的多羟基化合物和多胺增链剂(chain extenders)和交联剂的反应而进行,根据上面引用的参考文献中和存在于文献资料中的其它参考文献所述的传统方法进行。一般地,在异氰酸酯反应的典型催化剂的存在下,反应在约20到150℃的温度范围中发生,这为本领域普通技术人员所知。NCO与OH的比例应予以选择,根据所产生物质的目标性质而定:如果目的是产生硬聚氨酯塑料或聚氨酯弹性体,NCO/OH比应当接近1∶1。如果目的是产生可固化的反应性树脂或预聚物,则该比例应高一些。反应时间根据反应物的种类而改变,一般不超过几小时。
端羧基和端羟基的伸长单体和增大单体通过聚醚化、聚酯化和聚酰胺化反应聚合而生成的产物也是重要的,其中单体的羟基基团和羧基基团可以与多功能共反应物的胺或羟基基团反应,形成具有酰胺、醚和酯连接的聚合物。按此方式,可制得具有多种物理和化学性质的聚合物。这些反应中的共聚单体是聚胺、聚醚或其组合,其中共聚单体可为二级或更高级,为脂肪族、脂环族、芳香族或其组合,可以是取代的或未取代的,取代基通常在聚合反应中为惰性的,例如醚、酯、酰胺、氰、稳定的卤素如与芳环上碳结合的卤素等,或者为杂环丙烷即氮丙啶、环氧乙烷及其取代衍生物,其中取代基通常为烃基(alkyl)。由此,共聚单体可示例性地为乙二醇、丙二醇、聚乙二醇、二(羟乙基)胺、二(氨乙基)醚、N-甲基二(氨乙基)醚、二(羟乙基)硫化物或二硫化物、对苯二酚(氢醌,hydroquinone)、邻苯二酚(catechol)、1,4-二氨基环己烷、1,4-苯二胺等。共聚单体具有约2到20个、通常为约2到12个碳原子,具有2到7个、通常为2到5个杂原子,大多数情况下杂原子为N、S和O。
代替上述缩合聚合物(condesation polymers),本主题单体可被改性用于加成聚合物(addition polymers)。通过改变羟基或羧基,加入可加成聚合的烯烃基团(olefinic group),可得到如下产物,这些产物能够用作可加成聚合单体,其中只有一个烯烃基团被加入;或者用作交联剂时,两个烯烃基团被加入。在后一种情况下,通过与不同的可加成聚合单体进行的共聚,可得到可逆地交联的聚合物。通过减少二硫化物键,使交联断裂,而通过氧化,二硫化物可被恢复,交联则被重新建立。
可使用任何便利的可加成聚合化合物,其与本主题伸长单体的羟基或羧基进行反应,以及与本主题增大单体的相同官能团和氨基基团进行反应。因此,可采用任何具有可用于反应的羟基、羧基或氨基的活性亚乙基。例如,丙烯酸、羟基取代活性亚乙基如羟乙氧基乙烯、氨基乙氧基乙烯、丙烯酸氨乙基酯、羟乙基丙烯酰胺、等等。
用作共聚单体的常规可加成聚合单体包括:丙烯酸类如丙烯酸、甲基丙烯酸、-氯丙烯酸、丙烯酸乙酯、丙烯酰胺等,乙烯基化合物如羟乙基乙烯醚、羧乙基乙烯醚、乙烯基乙醇酸酯、烯丙醇等,以及多烯如2-羟甲基丁二烯、羧甲基丁二烯、对-羧基苯乙烯等。
可采用传统的方法配制聚合物。常用的添加剂包括增塑剂、增充剂(extender)、UV吸收剂、稳定剂、释放剂(release agent)等。这些添加剂的使用基于聚合物的性质,使用的量根据本主题单体所提供的性质而为传统量或减小量。
根据传统的方法,将会制备这些化合物,其中醚类可用碳二亚胺、混合酸酐或酸等、以合适的反应物比例进行结合而制得;合适地除去水,和类似因素;在温和反应条件下。加成聚合物可以在与聚硫化物的存在条件相容的条件下进行聚合。可采用酸、金属离子或光化辐射,任选联合使用光敏引发剂,可以发现催化作用的用处。例如,参见美国专利号US 4,131,716。
虽然上述聚合物为最常用的聚合物,但本主题单体也可用于聚合物如聚缩醛、多磷酸酯、醇酸树脂聚合物、聚二烯、聚脂肪酸和类似物。
本主题单体可将许多优异性质赋予采用该单体的聚合物。本主题单体可增强柔韧性、低温性质、疏水性、耐非极性有机溶剂性、对金属表面甚至生锈金属表面的亲和性、耐气候性,包括抗臭氧性、不透气性、抗紫外光辐射性、机械性质以及耐磨性,尤其是在与聚异氰酸酯共聚单体相结合的情况下。
由于本主题单体的相容性,本主题单体可用在聚合物中,用作粘合剂、密封剂、涂料、弹性体、塑料制品、模制产品、纤维、热熔胶粘剂的,作为添加剂和改性剂以及独立地作为其它反应性化合物的前驱体(precursors)。采用本主题聚合物本身或与其它相容聚合物结合使用,从聚合物可制得具有各种不同特征和性质的多种物体。
下面用实施例进行例示性方式说明,但不是限制。
实施例
实施例1
从二(羟乙基)二硫化物和脂肪酸二聚物制备端羧基聚(硫酯)。
将27g的二(羟乙基)二硫化物(DiHEDS,由Chevron Phillips ChemicalsLP生产,普通级)和200g二聚体的脂肪酸二聚物(CAS#61788-89-4,Pripol-1013,来自Uniqema,ICI Company)组合起来,放于夹套式反应容器中,进行搅拌混合。组分的摩尔比为1∶2。用0.2g(原料总重量的0.05%)、纯度为98%的一水合对甲苯磺酸(CAS号6192-52-5,得自Sigma-Aldrich)作为催化剂。
醚化反应在125-130℃(260-270°F)下进行3-4小时,同时不断进行搅拌。为了促使水份从反应混合物中排除,施加10mm Hg的真空。
为在该阶段进行工艺控制,对羧基基团的浓度进行监控(ASTM D465)。
当酸的浓度接近端羧基聚(二硫酯)的计算酸值时,过程结束,不再有蒸馏物形成。所生成物质的酸值等于83.6mg KOH/g,而预计的酸值为83.58。所生成的物质为黑褐色液体,粘度为6000cps。
实施例2
从二(羟乙基)二硫化物和丁二酸酐制备端羟基聚(硫酯)。
将308g二(羟乙基)二硫化物(DiHEDS,CPChem L.L.C.,无水级)和100g的丁二酸酐(Sigma-Aldrich#108-30-5)(摩尔比为1∶2)放于反应容器中混合,加热至120℃,然后加入4g催化剂,即甲磺酸(CAS号75-75-2,Sigma-Aldrich)。该体系在10mmHg的真空下混合1小时,在120℃下继续混合,直至不再有水从反应混合物中蒸馏出来。
为进行工艺控制,采用ASTM D465对羧基的浓度进行监控。在过程结束时,羧基的剩余浓度可以忽略。生成的物质为透明黄色粘稠液体(2000cPs),其之后结晶成为白色似蜡硬质物质。
实施例3
从二(羟乙基)二硫化物和脂肪酸制备端羟基聚(硫酯)。
将600g二(羟乙基)二硫化物(DiHEDS,CPChem L.L.C.,无水级)和474g的脂肪酸酐(Adipure,由DuPont产,CAS#124-04-9)(摩尔比为6∶5)放入反应容器中混合,并加入3.13g的甲磺酸(CAS号75-75-2,Sigma-Aldrich)。将混合物加热到120℃,在10mm Hg真空下混合1小时,然后在120℃维持反应,直至不再有水从反应混合物中蒸馏出来。
为进行工艺控制,采用ASTM D465对羧基的浓度进行监控。在过程结束时,羧基的剩余浓度可以忽略。
生成的物质为透明黄色粘稠液体(~3000cPs),之后结晶成为白色似蜡硬质物质。
实施例4
从二(羟乙基)二硫化物、脂肪酸和二羟甲基丙酸制备端羟基聚(硫酯)。
将300g二(羟乙基)二硫化物(DiHEDS,CP Chem L.L.C.,无水级)和426g的脂肪酸酐以及196g的DMPA(GEO Specialty Chemicals,CAS#4767-03-7)(摩尔比为4∶6∶3)进行混合,在160℃下加热,在10mmHg真空下混合2.5小时。升温到180℃,在180℃下继续搅拌,直至不再有水从反应混合物中蒸馏出来。
采用ASTM D465对羧基的浓度进行监控。在过程结束时,羧基的剩余浓度等于DMPA羧基的浓度。
生成的物质为琥珀色高粘质液体(200000cPs)。
实施例5
从端羧基聚(硫酯)制备含聚硫化物的酰氨胺(amidoamine)。
在未分离或未冷却时,向来自实施例1的产物中加入N-氨基乙基哌嗪(AEP,CAS号140-31-8,Huntsman Corp.或Air Products and Chemicals,Inc),加入量为每1摩尔羧基加入1.05mol AEP。假设在第一阶段达到83.58mg KOH/g的目标酸值,该比例为每100份生成的聚酯对应20.4份AEP。
典型的第二阶段反应时间为2-3小时,温度为155-160℃,压力为大气压。达到目标胺值后,对该产物而言目标胺值为71.2mg KOH/g;将反应器压力降低到至少10mm Hg,以蒸馏出第二阶段所产生的水份。在真空期间,温度保持在155-160℃。
为在该阶段进行工艺控制,采用ASTM D2073对胺值进行监控。当胺值接近目标胺值且不再有水份在真空下被除去时,过程结束。
生成的物质为褐色半固态物质,其熔点范围为40-50℃,其可溶于常规的酰氨胺和苯烷基胺。
实施例6
从端羟基聚(硫酯)制备具有末端异氰酸酯基的含聚硫化物异氰酸酯预聚物
将400g的来自实施例2的聚(硫酯)于60℃熔化,与15g 3ST ZeochemPurmol沸石粉末(由Zeochem,Louisville,KY生产)混合,以除去痕量水。然后将该混合物与234g的异佛乐酮二异氰酸酯(VestanatIPDI,Degussa Corp.,CAS#4098-71-9)在反应容器中组合(摩尔比为1∶2.05)。将反应混合物加热到90℃,并在氩气流下搅拌3小时。
采用ASTM D2572-97监控异氰酸酯基的浓度。在过程结束时,异氰酸酯基的浓度为2.4N,等于异氰酸酯基的初始浓度的一半。
生成的材料为白色不透明高粘性液体(150000cPs)。
实施例7
从端羟基聚(硫酯)制备含聚硫化物的异氰酸酯预聚物。
将445g的来自实施例3的聚(硫酯)于60℃熔化,与15g 3ST ZeochemPurmol沸石粉末(由Zeochem,Louisville,KY产)混合,以除去痕量水。然后将生成的混合物与372g的亚甲基-双(4-环己基异氰酸酯)(Desmodur,Bayer Corp.,CAS#5124-30-1)在反应容器中混合,加热到90℃,并在氩气流下搅动1小时。将95.2g的二羟甲基丙酸(DMPA,GEO Specialty Chemicals,CAS#4767-03-7)、200g的N-甲基吡咯烷酮(NMP,BASF,CAS#872-50-4)和36g的三乙胺(TEA,JT Baker,CAS#121-44-8)加入到反应混合物中。温度降至70℃,反应混合物在此温度下、在氩气中混合1小时。
采用ASTM D2572-97监控异氰酸酯基的浓度。过程结束时,异氰酸酯基的浓度为0.68N,刚好等于产生的预聚物中端位异氰酸酯基的计算浓度,由于三乙胺参与反应,该预聚物的侧位羧基受到抑制。
生成的材料为发白的粘性液体,其粘度约为70000cPs。
从上述结果显见,本主题化合物容易制备,产率好,条件简易。本主题单体提供给许多产品以期望的性质,增强了传统单体制得的产品的性质。通过替换在制备缩合聚合物中所采用的全部或部分的二醇或二元酸,所得到的产品具有改进的物理和化学性质。通过用可加成聚合的单体改性本主题单体,所形成的聚合物产品的性质可得到类似的提高。
这里全部引入通篇说明书所述的参考文献、文章、专利申请和专利作为参考,如同其全部内容在这里完整公开一样。
本发明已全部描述,对本领域的普通技术人员而言,在不偏离本发明在此所阐述的精神或范畴的情况下,对其进行诸多改变和修正是显而易见的。
Claims (22)
1.一种化合物,其特征在于具有由聚硫化物二醇和有机二元羧酸或其酸酐形成的单元,其中羟基与所述聚硫化物相离至少2个碳原子,具有总碳原子数至少为约5个,所述聚硫化物具有2个到8个硫原子。
2.如权利要求1所述的化合物,其中所述二元羧酸是具有至少约2个碳原子的有机二羧酸或酸酐,以及所述聚硫化物二醇为具有4个到40个碳原子的脂肪族。
3.如权利要求2所述的化合物,其中所述聚硫化物具有2个到4个硫原子。
4.如权利要求1所述的化合物,其中所述化合物是缩合共聚物。
5.如权利要求1所述的化合物,其中所述化合物是加成聚合物。
6.一种化合物,具有至少一个下述通式所示的单元:
-ORSnR1OAO-或-OAOR1SnRO-
其中:
O和S具有氧和硫的标准意义;
n至少为2且不大于约8;
R和R1是相同的或不同的,是有机二价基,每个具有2到20个碳原子;及
A为具有1到40个碳原子的二元羧酸的残基。
7.下述通式的组合物:
(a)MFmRSnR1OM1;或
(b)MZAORSnR1F1 mAZ1M1,
其中
O和S具有氧和硫的标准意义;
n为至少2且不大于约8;
F具有通式-ORSnR1OAO-;
F1具有通式-OAORSnR1O-;
m至少为1;
Z和Z1是相同的或不同的,为含氧基或氨基;
M和M1是相同的或不同的,为氢或有机取代基;
R和R1是相同的或不同的,为有机二价基,每个具有2到20个碳原子;及
A为具有2到40个碳原子的二羧酸的残基。
8.如权利要求7所述的组合物,其中M和M1为氢,A具有2到12个碳原子,以及R和R1为脂肪族。
9.如权利要求7所述的组合物,其中A为脂肪酸二聚物残基,以及R和R1为脂肪族。
10.如权利要求7所述的组合物,其中:
M定义为W1R2-:及
M1定义为W2R3-,其中:
R2和R3是相同的或不同的,为有机二价基,具有2到12个碳原子;及
W和W1是相同的或不同的,为氨基和具有约1到6个碳原子的取代氨基、羟基、羧基、异硫氰酸酯、异氰酸酯、含氧羰基、非含氧羰基、硅氧烷、硅烷、环碳酸酯、活性烯烃或活性卤基。
11.包括作为单体的如权利要求7所述组合物的共聚物,其中:
所述有机取代基M定义为W1R2-和M1定义为W2R3-;
R2和R3是相同的或不同的,为有机二价基,具有2到12个碳原子;及
W和W1是相同的或不同的,为氨基和具有约1到6个碳原子的取代氨基、羟基、羧基、异硫氰酸酯、异氰酸酯、含氧羰基、非含氧羰基、硅氧烷、硅烷、环碳酸酯、活性烯烃或活性卤基。
12.如权利要求11所述的化合物,其中所述聚合物为聚氨酯。
13.如权利要求11所述的化合物,其中所述聚合物为聚醚。
14.如权利要求11所述的化合物,其中所述聚合物为聚酯。
15.如权利要求11所述的化合物,其中所述聚合物为加成聚合物。
16.如权利要求11所述的共聚物,其中所述A为具有2到8个碳原子的二羧酸残基,n为2到4。
17.如权利要求15所述的化合物,其中W和W1中至少一个为羟基。
18.如权利要求15所述的化合物,其中W和W1中至少一个为羧基。
19.如权利要求15所述的化合物,其中W和W1中至少一个为胺。
20.下述通式的化合物:
(a)MFmRSnR1OM1;或
(b)MF1 mAOM1,
其中:
F具有通式-ORSNR1OAO-;
F1具有通式-OAORSnR1O-;
m至少为1;
n为2到4;
R和R1为亚乙基;
A为具有2到40个碳原子的脂肪族二羧酸的残基;及
M和M1为氢。
21.由反应物二(羟乙基)二硫化物、丁二酸或脂肪酸和二羟甲基丙酸以及酸催化剂进行反应而获得的合成物。
22.包括如权利要求1所述化合物的聚合物的物体。
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CNB2004800122037A Expired - Fee Related CN100379793C (zh) | 2003-04-17 | 2004-04-16 | 聚((聚硫烷基)酯),它们的应用及其衍生物 |
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CN102498146A (zh) * | 2009-06-29 | 2012-06-13 | 波利莫莱特股份有限公司 | 聚合物组合物及其制备和应用方法 |
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US8158726B2 (en) | 2003-04-17 | 2012-04-17 | Polymeright, Inc. | Poly(thioesters), their applications and derivatives |
US20130288933A1 (en) | 2012-04-30 | 2013-10-31 | Chevron Phillips Chemical Company Lp | Rheology Modifiers |
SE539314C2 (en) * | 2016-01-28 | 2017-06-27 | Perstorp Ab | Radiation curing composition |
CN110139884B (zh) | 2016-12-15 | 2022-05-31 | 陶氏环球技术有限责任公司 | 具有含硫聚酯多元醇的聚氨酯产品 |
CN107353386A (zh) * | 2017-07-14 | 2017-11-17 | 合肥思敬齐化工材料有限责任公司 | 自修复低模高强水性聚氨酯及其制备方法 |
CN109705969B (zh) * | 2019-01-23 | 2021-07-09 | 河南省核力科技发展有限公司 | 一种液压支架浓缩物专用润滑剂的制备方法 |
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CN102498146A (zh) * | 2009-06-29 | 2012-06-13 | 波利莫莱特股份有限公司 | 聚合物组合物及其制备和应用方法 |
US8889802B2 (en) | 2009-06-29 | 2014-11-18 | Polymeright, Inc. | Polymer compositions and methods of making and using same |
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US20040230030A1 (en) | 2004-11-18 |
EP2420523A1 (en) | 2012-02-22 |
EP1620490A2 (en) | 2006-02-01 |
WO2004094522A2 (en) | 2004-11-04 |
CN101270183A (zh) | 2008-09-24 |
WO2004094522A3 (en) | 2005-06-02 |
CN101270183B (zh) | 2012-05-23 |
BRPI0409461A (pt) | 2006-05-02 |
EP1620490A4 (en) | 2009-05-27 |
EP1620490B1 (en) | 2012-07-04 |
US20050143557A1 (en) | 2005-06-30 |
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