CN117304676A - 高耐候的聚氨酯弹性体及其制备方法 - Google Patents
高耐候的聚氨酯弹性体及其制备方法 Download PDFInfo
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- CN117304676A CN117304676A CN202311257065.XA CN202311257065A CN117304676A CN 117304676 A CN117304676 A CN 117304676A CN 202311257065 A CN202311257065 A CN 202311257065A CN 117304676 A CN117304676 A CN 117304676A
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- Prior art keywords
- polyurethane elastomer
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- isocyanate prepolymer
- polyol
- polyisocyanate
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 34
- 239000012948 isocyanate Substances 0.000 claims abstract description 29
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 25
- 229920000570 polyether Polymers 0.000 claims abstract description 25
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 23
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 23
- -1 carbonate polyol Chemical class 0.000 claims abstract description 20
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000004611 light stabiliser Substances 0.000 claims abstract description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920005906 polyester polyol Polymers 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 6
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 4
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 claims description 4
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 241001112258 Moca Species 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims 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 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims 1
- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical compound CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 claims 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000032683 aging Effects 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004984 aromatic diamines Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- 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
-
- 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
-
- 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
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/48—Polyethers
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及一种高耐候的聚氨酯弹性体及其制备方法，主要解决现有技术中聚氨酯弹性体的耐候性差、耐水解性差的问题。本发明通过采用一种高耐候的聚氨酯弹性体，以重量份数计，包含异氰酸酯预聚物50～98份，扩链剂2～50份，抗氧剂0.1～1份，紫外线吸收剂0.1～1份，光稳定剂0.1～1份；其中，所述的异氰酸酯预聚物，以重量份数计，包含多元醇60～90份，多异氰酸酯10～40份，催化剂0.01～0.2份；所述的异氰酸酯预聚物中包含由聚醚碳酸酯多元醇与多异氰酸酯反应制得的预聚物及其制备方法的技术方案，较好地解决了该技术问题，可用于聚氨酯弹性体的工业生产中。
Description
技术领域
本发明涉及聚氨酯弹性体领域，尤其涉及一种高耐候的聚氨酯弹性体及其制备方法。
背景技术
聚氨酯弹性体，又称聚氨酯橡胶，是一类在分子链中含有较多的氨基甲酸酯(-NHCOO-)特性基团的弹性聚合物材料。它们通常由多异氰酸酯和多元醇反应生成异氰酸酯预聚物、及小分子多元醇或芳香族二胺扩链剂等制备而成。聚氨酯弹性体的性能范围很宽，是介于橡胶到塑料的一类高分子材料。应用上来讲，聚氨酯作为一种具有高强度、抗撕裂、耐磨等特性的高分子材料，在日常生活、工农业生产、医学等领域广泛应用，具体来说，聚氨酯弹性体可以用作滚筒、传送带、软管、汽车零件、鞋底、合成皮革、电线电缆和医用人工脏器等。
传统的聚醚多元醇在制备聚氨酯弹性体时，往往存在强度低、耐候性差的缺点；普通的聚酯多元醇在制备聚氨酯弹性体时，存在耐水解性能差的缺点；其他如端羟基聚丁二烯或聚己内酯多元醇制备的聚氨酯弹性体存在价格高、粘度大，弹性差等缺点。而以CO2、环氧丙烷等为原料，在DMC催化剂的作用下反应得到的聚醚碳酸酯多元醇，结构中同时含有醚键和碳酸酯键，能够兼具二者的优点，相比于普通的聚酯多元醇，碳酸酯键不易水解，使得制品的耐湿热性能得到了提高，在保证较高的强度的同时具有较好的弹性和耐水解性能，能极大的提升弹性体的耐候性。另一方面，聚醚碳酸酯多元醇的应用还可以实现CO2气体的再利用，符合国家经济社会发展所倡导的碳中和目标，具有重要的现实意义。
中国专利申请CN202210476773公开了一种面向表面防护应用的耐腐蚀、耐候聚氨酯弹性体，由脂肪族或脂环族二异氰酸酯、氢化端羟基聚丁二烯、二官能度仲胺化合物三类单体合成，该发明选用二官能度仲胺化合物作为扩链剂；制得的弹性体耐候性较好，但是强度较低，且脂肪族异氰酸酯和氢化端羟基聚丁二烯较为昂贵，难以满足实际应用的要求。
中国专利申请CN201310730287公开了一种酯醚共聚型热固性聚氨酯弹性体及其制备方法，包括：由聚醚多元醇、异氰酸酯和封端剂预聚反应生成A物质；由聚酯多元醇、交联剂和封端剂预聚反应生成B物质；由所述A物质、所述B物质、解封剂和催化剂在搅拌的条件下进行交联固化反应，得到共聚物；将制得的共聚物进行浇注，即制得酯醚共聚型热固性聚氨酯弹性体。但其聚酯多元醇和聚醚多元醇和多异氰酸酯是无规共聚，耐候性相对还是不高。
发明内容
本发明所要解决的技术问题之一是，现有技术中聚氨酯弹性体的耐候性差、耐水解性差的问题；提供一种高耐候的聚氨酯弹性体，该弹性体同时具有高强度、高弹性、高耐候性和耐水解性好的优点。
本发明所要解决的技术问题之二是提供一种与解决技术问题之一相对应的高耐候的聚氨酯弹性体的制备方法。
为解决上述技术问题之一，本发明采用的技术方案如下：一种高耐候的聚氨酯弹性体，以重量份数计，包含异氰酸酯预聚物50～98份，扩链剂2～50份，抗氧剂0.1～1份，紫外线吸收剂0.1～1份，光稳定剂0.1～1份；其中，所述的异氰酸酯预聚物，以重量份数计，包含多元醇60～90份，多异氰酸酯10～40份，催化剂0.01～0.2份；所述的异氰酸酯预聚物中包含由聚醚碳酸酯多元醇与多异氰酸酯反应制得的预聚物。
上述技术方案中，优选地，所述的聚醚碳酸酯多元醇的官能度为2～4，数均分子量为1000～5000，CO2质量百分含量为5～35％。
上述技术方案中，优选地，所述的异氰酸酯预聚物中还包含由聚醚多元醇或聚酯多元醇与多异氰酸酯反应制得的预聚物。
上述技术方案中，优选地，所述的多异氰酸酯选自甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、4，4'-二环己基甲烷二异氰酸酯(HMDI)、六次甲基二异氰酸酯(HDI)、对苯基二异氰酸酯(PPDI)或1,5-奈二异氰酸酯(NDI)中的至少一种。
上述技术方案中，优选地，所述的催化剂选自二月桂酸二丁基锡、新癸酸铋或三乙烯二胺中的至少一种。
上述技术方案中，优选地，所述的光稳定剂选自苯并三唑类、二苯酮类、三嗪类或受阻胺类中的至少一种。
上述技术方案中，优选地，所述的扩链剂选自1，4-丁二醇(BDO)、丙二醇(PG)、乙二醇(EG)、l，6-己二醇(HDO)、氢醌-双(β-羟乙基)醚(HQEE)、二乙基甲苯二胺(DETDA)、二甲硫基甲苯二胺(DMTDA)、4，4’-亚甲基双(3-氯-2，6-二乙基苯胺)(MCDEA)或3,3’-二氯-4,4’-二苯基甲烷二(MOCA)中的至少一种。
上述技术方案中，优选地，所述的紫外线吸收剂选自2'-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯苯并三唑(UV-326)、2-(2'-羟基-3',5'-二叔丁基苯基)-5-氯代苯并三唑(UV-327)或2-羟基-4-正辛氧基二苯甲酮(UV-531)中的至少一种。
为解决上述技术问题之二，本发明采用的技术方案如下：一种高耐候的聚氨酯弹性体的制备方法，包括以下步骤：
步骤一：以重量份数计，将多元醇60～90份、多异氰酸酯10～40份和催化剂0.01～0.2份进行预聚反应，生成异氰酸酯预聚物，得到物料Ⅰ，其中，所述的异氰酸酯预聚物中包含由聚醚碳酸酯多元醇与多异氰酸酯反应制得的预聚物；
步骤二：以重量份数计，将步骤一得到的异氰酸酯预聚物50～98份，和抗氧剂0.1～1份、紫外线吸收剂0.1～1份、光稳定剂0.1～1份进行混合抽真空脱泡，得到物料Ⅱ；
步骤三：以重量份数计，将步骤二得到的物料Ⅱ和2～50份的扩链剂在搅拌的条件下进行交联固化反应，得到共聚物，即物料Ⅲ；
步骤四：将步骤三制得的共聚物进行浇注，制得高耐候的聚氨酯弹性体。
上述技术方案中，优选地，所述的异氰酸酯预聚物的制备方法为，将多元醇加入反应釜中，升温至110～130℃真空脱水1～2h，降温至70～80℃，加入多异氰酸酯，在80～85℃氮气保护条件下反应2～3h，得到异氰酸酯预聚物。
本发明提供一种高耐候的聚氨酯弹性体，通过引入含键能较高和不易水解的碳酸酯键的聚醚碳酸酯多元醇来制备弹性体，聚醚碳酸酯多元醇结构中除了含有内聚力较大的碳酸酯键外，还含有大量柔性较好的醚键，制备的弹性体既有较好的弹性又有良好抗水解性，再加上与扩链剂、抗氧剂、紫外线吸收剂、光稳定剂和催化剂等物料的协同配合，使得最终制得的聚氨酯弹性体在经过热老化、紫外老化、浸水老化后仍能保持较高的强度和弹性(如实施例2中弹性体的初始拉伸强度为21.31MPa、断裂伸长率为733.2％，热老化后拉伸强度为20.58MPa、断裂伸长率为710.6％，紫外老化后拉伸强度为16.78MPa、断裂伸长率为665.3％，浸水老化后拉伸强度为19.86MPa、断裂伸长率为690.8％)，同时具有高耐候性、高耐水解性的优点，取得了较好的技术效果。
具体实施方式
下面通过实施例对本发明作进一步的阐述，有必要在此指出的是以下实施例只是对本发明的进一步解释说明，不能理解为对本发明保护范围的限制，该领域的技术人员可以根据本发明的内容作一些非本质的改进和调整，均落入本发明的保护范围内。
表1原料清单
表1中，聚醚碳酸酯多元醇A、B均为实验室自制，聚醚碳酸酯多元醇A的制备方法按照中国专利CN 110922577B中的实施例4进行；聚醚碳酸酯多元醇B的制备方法参照中国专利CN 110922577B中的实施例4，区别在于制备过程中起始剂低分子量聚醚多元醇A4的用量为480g，第二部分环氧丙烷(Ⅱ)的用量为469g，第二部分环氧乙烷(Ⅱ)的用量为201g，低分子量聚醚多元醇与氧化烯烃的质量比为1∶1.5。
异氰酸酯预聚物的制备方法如下：
Prep-1：将78.97份聚醚碳酸酯多元醇A在115℃下减压脱水2h，降温至75℃，依次投入21份多异氰酸酯MDI-100和0.03份催化剂A-33，在85℃氮气保护条件下反应2h制备而成。
Prep-2：将78.97份聚醚碳酸酯多元醇cardyon在115℃下减压脱水2h，降温至80℃，依次投入21份多异氰酸酯MDI-100和0.03份催化剂A-33，在80℃氮气保护条件下反应2h制备而成。
Prep-3：将78.97份聚醚多元醇DL-2000D在110℃下减压脱水2h，降温至80℃，依次投入21份多异氰酸酯MDI-100和0.03份催化剂A-33，在82℃氮气保护条件下反应2h制备而成。
Prep-4：将78.97份聚酯多元醇PE-1156在120℃下减压脱水2h，降温至70℃，依次投入21份多异氰酸酯MDI-100和0.03份催化剂A-33，在80℃氮气保护条件下反应2h制备而成。
Prep-5：将65.37份聚醚碳酸酯多元醇B在115℃下减压脱水2h，降温至80℃，依次投入34.6份多异氰酸酯MDI-100和0.03份催化剂A-33，在80℃氮气保护条件下反应2h制备而成。
【实施例1】
一种高耐候的聚氨酯弹性体的制备方法，包括以下步骤：
(1)按表2中的物料组分配方称取异氰酸酯预聚物，升温至100℃，在真空度为-0.1MPa下抽真空25分钟；
(2)然后将温度降至70℃，加入抗氧剂、紫外线吸收剂、光稳定剂，均匀搅拌15分钟，再次在真空度为-0.1MPa下抽真空20分钟；
(3)将扩链剂加入到步骤(2)的混合物中，搅拌10分钟，再次抽真空5分钟后，倒入预先涂好脱模剂的模具中，放入105℃的鼓风烘箱中，硫化35分钟，脱模；
(4)脱模后，将制品继续在105℃的烘箱中硫化23小时，即得高耐候的聚氨酯弹性体，其性能数据见表3所示。
【实施例2～7】
实施例2～7按照实施例1的各个步骤进行，区别在于反应原料和原料配比不同，具体见表2所示；制得的高耐候的聚氨酯弹性体的性能数据见表3所示。
表2实施例1～7及对比例1～2中各组分的原料重量份数
【对比例1】
按照实施例1的制备方法制备聚氨酯弹性体，不同的是将异氰酸酯预聚物Prep-1全部替换为Prep-3，具体见表2所示；制得的聚氨酯弹性体的性能数据见表3所示。
【对比例2】
按照实施例1的制备方法制备聚氨酯弹性体，不同的是将异氰酸酯预聚物Prep-1全部替换为Prep-4，具体见表2所示；制得的聚氨酯弹性体的性能数据见表3所示。
表3实施例1～7和对比例1～2制备得到的聚氨酯弹性体的性能数据
表3中，拉伸强度、断裂伸长率的测试均按照标准GB/T 528-2009的要求进行，测试前试样先在25±2℃，50±5％RH的温湿度环境下放置24h进行状态调节后再测试；老化测试中，将试样放置于不同的老化环境下，老化结束后再次测试试样的拉伸强度、断裂伸长率，通过热老化、人工气候老化的结果综合评估试样的耐候性能，通过浸水老化后结果评估试样的耐水解性能。
其中，热老化是将试样置于100℃的高温条件下进行热老化28天，老化完成后按照GB/T 2941-2006的规定进行环境调节，再按照国标GB/T 528-2009的要求测试拉伸强度和断裂伸长率，通过拉伸强度、断裂伸长率的变化来表征弹性体试样的耐热老化性能。
人工气候老化的测试条件按照标准GB/T 16585-1996的要求进行，具体为采用UVA紫外光源，对试样进行光照4h接着冷凝4h的循环老化28天，老化完成后按照GB/T 2941-2006的规定进行状态调节，再按照标准GB/T 528-2009的要求测试其拉伸强度和断裂伸长率，通过拉伸强度、断裂伸长率的变化来表征聚氨酯弹性体试样的耐紫外老化性能。
浸水老化是将试样置于60±2℃的去离子水中浸泡28天进行水解老化，老化完成后按照GB/T 2941-2006的规定进行环境调节，再依标准GB/T 528-2009的要求测试其拉伸强度和断裂伸长率，通过拉伸强度、断裂伸长率的变化来表征聚氨酯弹性体试样的耐水解性能。
由实施例1～7和对比例1～2的性能数据表3可知，本发明制备的聚氨酯弹性体的初始拉伸强度和断裂伸长率均较高，即具有高强度、高弹性的特点；在耐热老化性能方面与对比例相当，但对比例1在进行人工气候老化后试样被破坏，对比例2进行浸水老化后试样强度、弹性均下降了50％以上，本发明的耐紫外老化性能优于对比例1，耐水解性能优于对比例2；可见，本发明制备的聚氨酯弹性体在热老化、紫外老化、水解老化后仍能保持较高的拉伸强度和弹性，同时具有高耐候性和高耐水解性的优点，取得了较好的技术效果，可用于聚氨酯弹性体的工业生产中。
Claims (10)
1.一种高耐候的聚氨酯弹性体，其特征在于，以重量份数计，包含异氰酸酯预聚物50～98份，扩链剂2～50份，抗氧剂0.1～1份，紫外线吸收剂0.1～1份，光稳定剂0.1～1份；其中，所述的异氰酸酯预聚物，以重量份数计，包含多元醇60～90份，多异氰酸酯10～40份，催化剂0.01～0.2份；所述的异氰酸酯预聚物中包含由聚醚碳酸酯多元醇与多异氰酸酯反应制得的预聚物。
2.根据权利要求1所述的高耐候的聚氨酯弹性体，其特征在于，所述的聚醚碳酸酯多元醇的官能度为2～4，数均分子量为1000～5000，CO2质量百分含量为5～35％。
3.根据权利要求1所述的高耐候的聚氨酯弹性体，其特征在于，所述的异氰酸酯预聚物中还包含由聚醚多元醇或聚酯多元醇与多异氰酸酯反应制得的预聚物。
4.根据权利要求1所述的高耐候的聚氨酯弹性体，其特征在于，所述的多异氰酸酯选自甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、4，4'-二环己基甲烷二异氰酸酯(HMDI)、六次甲基二异氰酸酯(HDI)、对苯基二异氰酸酯(PPDI)或1,5-奈二异氰酸酯(NDI)中的至少一种。
5.根据权利要求1所述的高耐候的聚氨酯弹性体，其特征在于，所述的催化剂选自二月桂酸二丁基锡、新癸酸铋或三乙烯二胺中的至少一种；所述的光稳定剂选自苯并三唑类、二苯酮类、三嗪类或受阻胺类中的至少一种。
6.根据权利要求1所述的高耐候的聚氨酯弹性体，其特征在于，所述的扩链剂选自1，4-丁二醇(BDO)、丙二醇(PG)、乙二醇(EG)、l，6-己二醇(HDO)、氢醌-双(β-羟乙基)醚(HQEE)、二乙基甲苯二胺(DETDA)、二甲硫基甲苯二胺(DMTDA)、4，4’-亚甲基双(3-氯-2，6-二乙基苯胺)(MCDEA)或3,3’-二氯-4,4’-二苯基甲烷二(MOCA)中的至少一种。
7.根据权利要求1所述的高耐候的聚氨酯弹性体，其特征在于，所述的紫外线吸收剂选自2'-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯苯并三唑(UV-326)、2-(2'-羟基-3',5'-二叔丁基苯基)-5-氯代苯并三唑(UV-327)或2-羟基-4-正辛氧基二苯甲酮(UV-531)中的至少一种。
8.根据权利要求1所述的高耐候的聚氨酯弹性体，其特征在于，所述的抗氧剂选自2,6-二叔丁基-4-甲基苯酚、亚磷酸三(2,4-二叔丁基苯基)酯、抗氧剂1010、抗氧剂1035、抗氧剂1076或抗氧剂1135中的至少一种。
9.权利要求1所述的高耐候的聚氨酯弹性体的制备方法，包括以下步骤：
步骤一：以重量份数计，将多元醇60～90份、多异氰酸酯10～40份和催化剂0.01～0.2份进行预聚反应，生成异氰酸酯预聚物，得到物料Ⅰ，其中，所述的异氰酸酯预聚物中包含由聚醚碳酸酯多元醇与多异氰酸酯反应制得的预聚物；
步骤二：以重量份数计，将步骤一得到的异氰酸酯预聚物50～98份，和抗氧剂0.1～1份、紫外线吸收剂0.1～1份、光稳定剂0.1～1份进行混合抽真空脱泡，得到物料Ⅱ；
步骤三：以重量份数计，将步骤二得到的物料Ⅱ和2～50份的扩链剂在搅拌的条件下进行交联固化反应，得到共聚物，即物料Ⅲ；
步骤四：将步骤三制得的共聚物进行浇注，制得高耐候的聚氨酯弹性体。
10.权利要求9所述的高耐候的聚氨酯弹性体的制备方法，其特征在于，所述的异氰酸酯预聚物的制备方法为，将多元醇加入反应釜中，升温至110～130℃真空脱水1～2h，降温至70～80℃，加入多异氰酸酯，在80～85℃氮气保护条件下反应2～3h，得到异氰酸酯预聚物。
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