CN116410442A - Storage-stable polyisocyanate composition - Google Patents
Storage-stable polyisocyanate composition Download PDFInfo
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- CN116410442A CN116410442A CN202111662647.7A CN202111662647A CN116410442A CN 116410442 A CN116410442 A CN 116410442A CN 202111662647 A CN202111662647 A CN 202111662647A CN 116410442 A CN116410442 A CN 116410442A
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- Prior art keywords
- diisocyanate
- polyisocyanate
- polyisocyanate composition
- reaction
- composition
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- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 85
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000012948 isocyanate Substances 0.000 claims abstract description 27
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 53
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 53
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- -1 cyclohexylhexamethylene diisocyanate Chemical compound 0.000 claims description 3
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- WTHDANPEBBZWQC-UHFFFAOYSA-N benzyl(dimethyl)phosphane Chemical compound CP(C)CC1=CC=CC=C1 WTHDANPEBBZWQC-UHFFFAOYSA-N 0.000 claims description 2
- DTGZJGZYPXAZTG-UHFFFAOYSA-N bicyclo[2.2.1]heptane;1,2-diisocyanatoethane Chemical compound C1CC2CCC1C2.O=C=NCCN=C=O DTGZJGZYPXAZTG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 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
- 230000035484 reaction time Effects 0.000 claims description 2
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 claims description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 2
- FPZZZGJWXOHLDJ-UHFFFAOYSA-N trihexylphosphane Chemical compound CCCCCCP(CCCCCC)CCCCCC FPZZZGJWXOHLDJ-UHFFFAOYSA-N 0.000 claims description 2
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 claims description 2
- IWPNEBZUNGZQQQ-UHFFFAOYSA-N tripentylphosphane Chemical compound CCCCCP(CCCCC)CCCCC IWPNEBZUNGZQQQ-UHFFFAOYSA-N 0.000 claims description 2
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 claims description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 2
- OKMVYXTWPPPSIM-UHFFFAOYSA-N dicyclopentylphosphane Chemical compound C1CCCC1PC1CCCC1 OKMVYXTWPPPSIM-UHFFFAOYSA-N 0.000 claims 1
- 229960005082 etohexadiol Drugs 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 20
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 239000010409 thin film Substances 0.000 description 8
- SNAMIIGIIUQQSP-UHFFFAOYSA-N bis(6-methylheptyl) hydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(=O)OCCCCCC(C)C SNAMIIGIIUQQSP-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical class N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XGYWVPFXBQFLIT-UHFFFAOYSA-M C(CCC)O.[OH-].C[N+](C)(C)C Chemical compound C(CCC)O.[OH-].C[N+](C)(C)C XGYWVPFXBQFLIT-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 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 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- FXMRLRPICAHOGI-UHFFFAOYSA-N butyl(dicyclopentyl)phosphane Chemical compound C1CCCC1P(CCCC)C1CCCC1 FXMRLRPICAHOGI-UHFFFAOYSA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 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
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 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 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
The present invention provides a storage stable polyisocyanate composition. The composition is a polyisocyanate composition obtained from aliphatic diisocyanate or alicyclic diisocyanate and dihydric alcohol, wherein the integral area of the component peak with the weight average molecular weight of 550+/-80 accounts for 0.1-5% of the total peak area of GPC, the area of the peak of the component with the weight average molecular weight of 450+/-80 accounts for 10-70% of the total peak area of GPC, and the viscosity of the polyisocyanate composition is not more than 2000 mPa.s. The isocyanate composition has good storage stability, and the monomer content increases by less than or equal to 0.1 percent when stored for 30 days at 50 ℃ based on the quality of polyisocyanate products.
Description
Technical Field
The invention belongs to the field of polyisocyanates, and particularly relates to a polyisocyanate composition with storage stability.
Background
Isocyanate homopolymers containing uretdione groups have very low viscosities and therefore have excellent application properties as crosslinker component in waterborne, low-solvent, high-solids coating compositions, especially in place of solvents as diluents for curing agents.
At present, methods for preparing polyisocyanates containing uretdione groups from aromatic, aliphatic or cycloaliphatic diisocyanate monomers in the presence of catalysis are known, and the advantages and disadvantages of various dimerization catalysts or catalyst systems are discussed in detail in various documents.
CN1334264a discloses a method for improving the storage stability of uretdione polyisocyanates, wherein "substituted urea or substituted amide is added during the reaction" is used to improve the storage stability of the product. Other problems still occur during storage, such as: the viscosity of the product rises rapidly, and when the molecular weight of the added substituted urea is smaller, a small amount of the substituted urea enters a light component condenser along with the separation process in the separation process, so that the recycling of the monomer is affected.
CN110305294a discloses that controlling the acid content in the terminator to be less than or equal to 300ppm in terms of hydrogen chloride, the monomer content of the prepared polyisocyanate increases by less than or equal to 0.1wt% when stored below 40 ℃ for 6 months, however, when the storage temperature increases to 50 ℃, the rate of monomer increase is significantly accelerated.
CN1511858A discloses a storage-stable process for preparing uretdione, which can make the monomer content of high-content uretdione product stored at 50 ℃ for 6 months less than 0.5%, but the reaction temperature needs to be controlled below 40 ℃, resulting in a substantial reduction in the reaction efficiency.
The main defects of the uretdione polyisocyanate prepared by the prior art are that the uretdione polyisocyanate is re-cracked into isocyanate monomers in the storage process, so that the free isocyanate monomers are higher, the application performance of downstream products is affected, and the use of the uretdione polyisocyanate curing agent is seriously affected due to the harm to operators and the environment in the construction process. In practical use, after the storage stability temperature of the uretdione-containing polyisocyanate is raised to 50 ℃, the product storage and downstream construction are facilitated.
Disclosure of Invention
The object of the present invention is to provide a polyisocyanate composition which gives a product which, during storage at 50 ℃, has a small increase in free monomer content and which meets the demands of practical downstream applications and occupational health and safety.
In order to achieve the above object, the present invention provides a polyisocyanate composition according to the following technical scheme:
a polyisocyanate composition which is a polyisocyanate composition obtained from an aliphatic diisocyanate and/or a cycloaliphatic diisocyanate and a diol having a carbon number of 20 or less, said composition comprising:
a. the integral area of the component peaks having a weight average molecular weight of 550.+ -. 80 accounts for 0.1-5%, preferably 0.2-3% of the total peak area;
b. the integrated area of the peaks of the component having a weight average molecular weight of 450.+ -. 80 accounts for 10-70%, preferably 20-60% of the total peak area.
In the present invention, the above-mentioned different molecular weight component peaks are obtained by characterization by gel chromatography (GPC).
In the present invention, the viscosity of the polyisocyanate composition is 2000 mPas or less, preferably 1000 mPas or less.
In the present invention, the aliphatic diisocyanate and/or alicyclic diisocyanate is an organic diisocyanate having 4 to 20 carbon atoms in addition to NCO groups in the carbon skeleton, preferably the isocyanate is selected from one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexylhexamethylene diisocyanate (HMDI), dicyclohexylmethane diisocyanate (HXDI), norbornane dimethylene diisocyanate (NBDI), cyclohexyldiisocyanate (CHDI) and 2, 4-trimethylhexamethylene diisocyanate (TMHDI), more preferably hexamethylene diisocyanate.
In the invention, the dihydric alcohol is dihydric alcohol with carbon atom less than or equal to 10, preferably one or more of ethylene glycol, propylene glycol, butanediol, hexanediol and octanediol.
In a preferred embodiment, the diol is used in an amount of 0 to 5%, preferably 0.1 to 5%, more preferably 0.5 to 3% by weight of the starting isocyanate used.
In the present invention, the composition has a free isocyanate monomer content increase of less than or equal to 0.1wt% based on the total mass of the polyisocyanate composition when stored at 50℃for 30 days.
It is another object of the present invention to provide a process for preparing a polyisocyanate composition.
A process for preparing the polyisocyanate composition described above, which is process a or process B.
In the invention, the preparation method A comprises the following steps:
s1-1: reacting excessive organic isocyanate with dihydric alcohol to obtain a prepolymerization reaction liquid;
s1-2: adding a catalyst into the prepolymerization reaction liquid, and adding a terminator to terminate the reaction after the reaction reaches a set conversion rate;
s1-3: removing unreacted organic isocyanate monomer to obtain the product of polyisocyanate.
In the invention, the preparation method B comprises the following steps:
s2-1: reacting excessive organic isocyanate with dihydric alcohol to obtain a prepolymerization reaction solution, and removing unreacted organic isocyanate monomers;
s2-2: adding a catalyst into the organic isocyanate, and after the reaction reaches a set conversion rate, adding a terminator to terminate the reaction to remove unreacted organic isocyanate monomers;
s2-3: blending the S2-1 product with the S2-1 product to obtain the product of the polyisocyanate.
In the invention, the reaction temperature of the S1-1 and the S2-1 is 80-120 ℃, preferably 100-110 ℃; the reaction time is 0.5 to 4 hours, preferably 1 to 2 hours.
In the present invention, the catalyst of S1-2 and S2-2 is one or more of tertiary phosphine, preferably trimethyl phosphine, triethyl phosphine, tripropyl phosphine, triisopropyl phosphine, tri-n-butyl phosphine, tri-tertiary butyl phosphine, dicyclopentyl butyl phosphine, tripentyl phosphine, tricyclopentyl phosphine, trihexyl phosphine, triphenyl phosphine, tribenzyl phosphine, benzyl dimethyl phosphine, tricyclohexyl phosphine, tri-n-octyl phosphine, more preferably tributyl phosphine and/or tri-n-octyl phosphine.
The inventors have surprisingly found that, when the component structure analysis is performed on the reaction liquid of the polyisocyanate composition by a high performance gel chromatography apparatus, the peak of the component having a weight average molecular weight of 550.+ -. 80 and the peak of the component having a weight average molecular weight of 450.+ -. 80 significantly affect the storage stability of the product.
Wherein, the content of the peak of the related components with the weight average molecular weight of 550+/-80 is mainly determined by the prepolymerization process and the activity of dihydric alcohol. When the integral area of the component peak with the weight average molecular weight of 550+/-80 accounts for 0.1-5% of the total peak area, the storage stability of the product can be obviously improved. The content thereof can be carried out by controlling the process of the prepolymerization reaction, or the separated product can be added into the product by separating the prepolymerization reaction liquid. The ratio of the peak area of the component peak with the weight average molecular weight of 550+/-80 to the total peak area is less than 0.1%, the increase of the monomer content during storage at 50 ℃ cannot be restrained, and white floccules appear during storage after the ratio is more than 5%, so that the downstream product application is influenced.
In the preparation of the polyisocyanate composition, the peak of the weight average molecular weight of 450+/-80 correspondingly contains a large amount of uretdione structures, the viscosity of the product and the content of monomers in the system can be influenced by the structure, and the high-content uretdione structures are prepared, and a tertiary phosphine catalyst is preferably selected and has the following structure:
wherein R is 1 、R 2 、R 3 Independently of each other selected from aliphatic substituents or aromatic substituents. The catalyst is generally used in an amount of from 0.01 to 1% by weight, preferably from 0.05 to 0.5% by weight, based on the amount of starting diisocyanate used.
In the invention, the tertiary phosphine catalyst is a nucleophilic reagent which is easily oxidized by oxygen in the air, and is strictly deoxidized when in use, and meanwhile, the tertiary phosphine catalyst is protected by inert gas, for example, trioctylphosphine can undergo a severe oxidation reaction when exposed to the air, so that trioctylphosphine oxide is generated.
In the method of the invention, the area of the peak of the component with the weight average molecular weight of 450+/-80 can be regulated by regulating the conversion rate in the system, when the residual mass of isocyanate in the system accounts for 10% -80%, preferably 30% -70% of the total mass of isocyanate monomers in the system, a terminator is added to stop the reaction, the content of the separated polyisocyanate can be controlled to be 10% -70%, preferably 20% -60%, the used catalyst poison is dimethyl sulfate, methyl p-toluenesulfonate, phosphate, acyl chloride, sulfur or peroxide, and the like, the amount of the catalyst poison required for stopping the reaction depends on the amount of the catalyst in the system, and the amount of the terminator is 80% -120% of the mole number of the catalyst used in the reaction.
After the reaction is finished, unreacted monomers can be separated by one or more of a flash evaporator, a falling film evaporator, a thin film evaporator and a short path evaporator, so that isocyanate monomers in the system are removed. The unreacted isocyanate monomer content in the polyisocyanate composition is preferably 0.5% by weight or less, more preferably 0.3% by weight or less. Since uretdione polyisocyanates are easily decomposed at high temperatures, the separation temperature is controlled to 120-150℃and the residence time of the material at high temperatures is less than or equal to 30 minutes, preferably less than or equal to 20 minutes, in order to reduce the decomposition of uretdione polyisocyanates.
The unconverted diisocyanate obtained by separation can be returned to the reaction kettle again to participate in the reaction, or can be distilled or rectified to participate in the reaction, and in the method, the unconverted diisocyanate is preferably returned to the reaction kettle again directly to participate in the reaction without distillation or rectification.
Furthermore, stabilizers and additives, which are conventional in the polyisocyanate art, may be added to the process of the present invention wherever desired. Comprises the following steps: antioxidants, hindered phenols (e.g., 2, 6-di-t-butyl-4-methylphenol, octadecyl 3, 5-di-t-butyl-4-hydroxyphenyl propionate, etc.), phosphites (e.g., tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, etc.), ultraviolet absorbers (e.g., benzotriazoles, salicylates, benzophenones, etc.), hindered amine light stabilizers (e.g., 2, 6-tetramethylpiperidine), etc.
The polyisocyanate products prepared by the process of the present invention are useful in the preparation of single and multi-component polyurethane coatings or adhesives and may be used with prior art prepared di-or polyisocyanate products such as mixtures of di-or polyisocyanates containing biurets, carbamates, allophanates, isocyanurates and iminooxadiazinediones.
The invention also relates to polyurethane coatings and polyurethane adhesives prepared from the polyisocyanates prepared by the method of the invention. In addition, the polyisocyanate prepared by the method can be used for preparing polyurethane coating, polyurethane adhesive and other related products after being blocked by the blocking agent.
Compared with the prior art, the invention has the following positive effects:
the content of the integral area of the peaks of the components with the weight average molecular weight of 550+/-80 and the weight average molecular weight of 450+/-80 in the polyisocyanate is controlled, so that the storage stability of the product at 50 ℃ is greatly improved, and the content of the free isocyanate monomer of the obtained uretdione polyisocyanate product is increased by less than or equal to 0.1 weight percent (calculated based on the polyisocyanate product) after the product is stored below 50 ℃ for 30 days.
Drawings
FIG. 1 is a gel chromatogram of example 1, peak 5 is a peak having a weight average molecular weight of 550.+ -. 80, and peak 6 is a peak having a weight average molecular weight of 450.+ -. 80.
Detailed Description
The following examples further illustrate the method provided by the present invention, but the invention is not limited to the examples listed and includes any other known modifications within the scope of the claims of the present invention, the specific application of the present invention is not limited to the applications described in the examples, and the simple modifications to the present invention that can be made by those skilled in the art using the concepts of the present invention are within the scope of the claimed invention.
The following test method is adopted in the embodiment of the invention:
(1) The area of the component peak with the weight average molecular weight of 550+/-80 and the peak area with the weight average molecular weight of 450+/-80 are measured by using a Gel chromatography technology (LC-20 AD/RID-10A, a chromatographic column is MZ-Gel SD plus10E3A,5 μm (8.0 x 300 mm), MZ-Gel SDplus 500A 5 μm (8.0 x 300 mm), MZ-Gel SDplus 100A5 μm (8.0 x 300 mm), island body fluid is connected in series, polystyrene is used for standard sample, a mobile phase is tetrahydrofuran, the flow rate is 1.0mL/min, the analysis time is 40min, the chromatographic column temperature is 35 ℃), the analysis is performed by using a differential detector, the quantification of isocyanate raw materials is performed, the areas of polymers and monomers in the system are measured by an area normalization method, and the reaction conversion rate is=S (peak area of monomers)/S (sum of peak areas of each component peak) is 100%.
(2) High performance liquid chromatography equipped with ultraviolet detector or diode array detector, instrument model recommended use island jin 20AT, chromatogram column: waters XSelect T3 (4.6 x 250mm,5 um), mobile phase a (water), mobile phase B (methanol), flow rate: 1ml/min, analysis time: 50min, column temperature: analysis was performed using a 258nm uv detector at 40 ℃;
gradient elution conditions:
sample configuration: 500mg of the sample is taken and placed in a 10ml volumetric flask, the derivative solution (100 g of benzyl alcohol is dissolved in the 1000ml volumetric flask, 3g of dibutyltin dilaurate is added, the volume is fixed to 1000ml by methylene dichloride), the mixture is added to a scale mark, the mixture is uniformly shaken and sealed, the mixture is placed in a 50 ℃ oven for reaction for 3 hours, and the sample analysis is carried out after cooling.
(3) Viscosity measurements dynamic mechanical viscosity was measured using a Brookfield DV-I Prime viscometer using an S21 spindle at 25 ℃.
In the following examples, the following raw material information was used:
hexamethylene diisocyanate (HDI for short): wanhua chemistry, purity > 99%;
2-ethyl-1, 3-hexanediol: ala Ding Shiji, purity > 99%;
tri-n-octylphosphine: sigma reagent, purity > 95%;
diisooctyl phosphate: ala Ding Shiji, purity > 98.5%;
n-butanol: alatine with purity of 99%;
tetramethyl ammonium hydroxide: sigma reagent with purity not less than 95%, crystal;
1, 3-butanediol: ala Ding Shiji, purity > 99.5%;
tributylphosphine: ala Ding Shiji, purity > 95%;
dibutyl phosphate: ala Ding Shiji with purity > 95%.
The following examples and comparative examples were conducted under the protection of dry nitrogen until the catalyst was added and during the entire reaction, without any particular explanation. All percentages are by mass unless otherwise indicated, and the pressures are absolute.
Example 1
The preparation method A is adopted.
S1-1: the total mass M is 1000g of hexamethylene diisocyanate, 15g of 2-ethyl-1, 3-hexanediol is added under stirring at 100 ℃ for reaction for 1 hour;
s1-2: cooling to 60 ℃, adding 2.5g of trioctylphosphine, and quantitatively monitoring the proportion of the residual mass M1 of the HDI in the reaction system to the total mass M of the added HDI through gel chromatography; when the residual mass M1 of the HDI in the system accounts for 50% of the total mass M of the added HDI, diisooctyl phosphate (molar ratio of diisooctyl phosphate to trioctylphosphine 1:1) is added and heated to 80 ℃ for 2 hours to terminate the reaction;
s1-3: unreacted HDI in the reaction system was distilled off by a two-stage thin film evaporator at a temperature of 140℃and a pressure of 0.3mbar to give a polyisocyanate composition 1 containing uretdione groups.
Example 2
Preparation method B was used.
S2-1: the total mass M is 1000g of hexamethylene diisocyanate, 30g of 2-ethyl-1, 3-hexanediol is added under stirring at 100 ℃ to react for 4 hours to obtain a pre-polymerization reaction liquid, and the reaction liquid is subjected to two-stage thin film evaporator distillation at 140 ℃ and a pressure of 0.3mbar to remove unreacted HDI in the reaction system, so as to obtain the polyisocyanate composition with the monomer content of less than 0.5%.
S2-2: weighing 1000g of total mass of HDI, heating to 60 ℃, adding 2.5g of trioctylphosphine, and quantitatively monitoring the proportion of the residual mass M1 of the HDI in the reaction system to the total mass M of the added HDI through gel chromatography; when the residual mass M1 of HDI in the system is 50% of the total mass M of HDI added, diisooctyl phosphate (molar ratio to trioctylphosphine 1:1) is added and heated to 80℃for 2 hours to terminate the reaction, and the unreacted HDI in the reaction system is distilled off by a two-stage thin film evaporator at 140℃and a pressure of 0.3mbar to obtain a polyisocyanate composition containing uretdione groups.
S2-3: the polyisocyanate of S2-1 was blended into the polyisocyanate product containing uretdione groups of S2-2 at a mixing mass ratio of the former to the latter of 5:95, to give polyisocyanate composition 2.
Example 3
The procedure was as in example 1, except that the addition of diisooctyl phosphate (molar ratio to trioctylphosphine: 1) was terminated when the residual mass M1 of HDI in the system was 30% of the total mass M of HDI added, and the separation was carried out to obtain a polyisocyanate composition 3 containing uretdione groups.
Example 4
S1-1: the total mass M is 1000g of hexamethylene diisocyanate (HDI for short), 10g of 1, 3-butanediol is added in sequence under stirring at 80 ℃ for reaction for 1 hour;
s1-2: then cooling to 60 ℃, adding 3g of tributylphosphine, and quantitatively monitoring the proportion of the residual mass M1 of the HDI in the reaction system to the total mass M of the added HDI through gel chromatography; when the residual mass M1 of the HDI in the system accounts for 50% of the total mass M of the added HDI, dibutyl phosphate (molar ratio of dibutyl phosphate to tributyl phosphine 1:1) is added and heated to 80 ℃ for 2 hours to terminate the reaction;
s1-3: unreacted HDI in the reaction system was distilled off by a two-stage thin film evaporator at a temperature of 140℃and a pressure of 0.3mbar to give a polyisocyanate composition 4 containing uretdione groups.
Comparative example 1
Polyisocyanates were prepared which contained no components having a weight average molecular weight of 550.+ -.80.
Weighing 1000g of total mass of HDI, heating to 60 ℃, adding 2.5g of trioctylphosphine, and quantitatively monitoring the proportion of the residual mass M1 of the HDI in the reaction system to the total mass M of the added HDI through gel chromatography; when the residual mass M1 of HDI in the system was 50% of the total mass M of HDI added, diisooctyl phosphate (molar ratio to trioctylphosphine 1:1) was added and heated to 80℃for 2 hours to terminate the reaction, and the unreacted HDI in the reaction system was distilled off by a two-stage thin film evaporator at a temperature of 140℃and a pressure of 0.3mbar to give a polyisocyanate composition 5 containing uretdione groups.
Comparative example 2
To control the content of the weight average molecular weight 550.+ -. 80, the polyisocyanate composition having a higher content of the weight average molecular weight 550.+ -. 80 was prepared by adjusting the content of the polyisocyanate of S2-1 in example 2, and 40g of the polyisocyanate composition of step 1 in example 2 and 160g of the composition of comparative example 1 were uniformly mixed in a mixing ratio of 20:80 to obtain a polyisocyanate composition 6.
Comparative example 3
Polyisocyanate compositions having a low weight average molecular weight of 450.+ -.80 were prepared.
The catalyst was diluted, 0.4g of tetramethylammonium hydroxide was taken, 9.6g of n-butanol was added, and the mixture was uniformly mixed to prepare a catalyst solvent of 4%.
The total mass M is 1000g of hexamethylene diisocyanate (HDI for short), 15g of n-butanol is added under stirring at 60 ℃ to react for 1 hour, then the temperature is increased to 90 ℃, 0.6g of tetramethylammonium hydroxide-butanol is added, and the proportion of the consumption mass M1 of the HDI in the reaction system to the total mass M of the added HDI is quantitatively monitored through gel chromatography; when the consumed mass M1 of HDI in the system was 50% of the total mass M of HDI added, dibutyl phosphate (molar ratio to tetramethylammonium hydroxide 1:1) was added to terminate the reaction. Unreacted HDI in the reaction system was distilled off by a two-stage thin film evaporator at a temperature of 160℃and a pressure of 0.3mbar to give a polyisocyanate composition having a weight average molecular weight of 450.+ -. 80 and a peak content of about 0.5%.
The above composition was added with 10% of polyisocyanate composition-5 and mixed uniformly to obtain polyisocyanate composition 7.
Comparative example 4
Polyisocyanate compositions having a high weight average molecular weight of 450.+ -.80 were prepared.
The total mass M is 1000g of hexamethylene diisocyanate (HDI for short), 15g of 2-ethyl-1, 3-hexanediol is sequentially added under stirring at 100 ℃ to react for 1 hour, then the temperature is reduced to 60 ℃, 2.5g of trioctylphosphine is added, and the proportion of the residual mass M1 of the HDI in the reaction system to the total mass M of the added HDI is quantitatively monitored through gel chromatography; when the residual mass M1 of HDI in the system was 90% of the total mass M of HDI added, diisooctyl phosphate (molar ratio to trioctylphosphine 1:1) was added and heated to 80℃for 2 hours to terminate the reaction, and the unreacted HDI in the reaction system was distilled off by a two-stage thin film evaporator at 140℃and a pressure of 0.3mbar to give a polyisocyanate composition 8 containing uretdione groups.
The results of characterization of polyisocyanate compositions 1-8 are shown in the following table:
the polyisocyanate compositions 1 to 8 were placed in an oven at 50℃and stored for 30 days, and subjected to a storage stability test, the results of which are shown in the following table:
| examples/comparative examples | Initial monomer content/% | 50 ℃,30 days monomer content/% | Monomer content increase/% | Sample |
| Polyisocyanate component | ||||
| 1 | 0.1 | 0.18 | 0.08 | Clarifying |
| |
0.1 | 0.19 | 0.09 | Clarifying |
| |
0.1 | 0.2 | 0.1 | Clarifying |
| |
0.1 | 0.18 | 0.08 | Clarifying |
| |
0.1 | 0.75 | 0.65 | Clarifying |
| |
0.1 | 0.18 | 0.08 | Cloudiness |
| |
0.08 | 0.13 | 0.05 | Clarifying |
| Comparative polyisocyanate component 8 | 0.2 | 0.55 | 0.30 | Clarifying |
Component peaks with a weight average molecular weight of 450.+ -.80 affect the storage stability of the polyisocyanate and at higher levels tend to result in higher levels of system monomer, as shown in comparative polyisocyanate composition 5, with faster rates of increase in monomer levels and at lower levels do not result in significant increases in system monomer levels, as shown in polyisocyanate composition 7. When the peak content of the component with the weight average molecular weight of 450+/-80 is 10-70%, the monomer content in the system can be regulated in the storage process with the weight average molecular weight of 550+/-80, but when the content is higher, the compatibility of the system is poorer, and as shown by the result of comparing polyisocyanate 6, the turbidity phenomenon occurs in the storage process.
Claims (8)
1. A polyisocyanate composition characterized in that the composition is a polyisocyanate composition obtained from an aliphatic diisocyanate and/or a cycloaliphatic diisocyanate and a diol having a carbon number of 20 or less, the composition being:
a. the integral area of the component peaks having a weight average molecular weight of 550.+ -. 80 accounts for 0.1-5%, preferably 0.2-3% of the total peak area;
b. the integrated area of the peaks of the component having a weight average molecular weight of 450.+ -. 80 accounts for 10-70%, preferably 20-60% of the total peak area.
2. Polyisocyanate composition according to claim 1, characterized in that the viscosity of the polyisocyanate composition is equal to or less than 2000 mpa.s, preferably equal to or less than 1000mpa.s.
3. Polyisocyanate composition according to claim 1 or 2, characterized in that the aliphatic and/or cycloaliphatic diisocyanate is one or more of an organic diisocyanate having a carbon skeleton containing 4 to 20 carbon atoms in addition to NCO groups, preferably the isocyanate is selected from Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexylhexamethylene diisocyanate (HMDI), dicyclohexylmethane diisocyanate (HXDI), norbornane-dimethylene diisocyanate (NBDI), cyclohexyldiisocyanate (CHDI) and 2, 4-trimethylhexamethylene diisocyanate (TMHDI), more preferably hexamethylene diisocyanate.
4. A polyisocyanate composition according to any one of claims 1 to 3 wherein the diol is a diol having a carbon atom of 10 or less, preferably one or more of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol.
5. The polyisocyanate composition according to any one of claims 1 to 4 wherein the composition has a free isocyanate monomer content increase of 0.1% by weight or less based on the total mass of the polyisocyanate composition when stored at 50℃for 30 days.
6. A process for preparing the polyisocyanate composition of any one of claims 1 to 5, wherein the process is preparation a or preparation B;
and/or, the preparation method A comprises the following steps:
s1-1: reacting excessive organic isocyanate with dihydric alcohol to obtain a prepolymerization reaction liquid;
s1-2: adding a catalyst into the prepolymerization reaction liquid, and adding a terminator to terminate the reaction after the reaction reaches a set conversion rate;
s1-3: removing unreacted organic isocyanate monomer to obtain a polyisocyanate product;
and/or, the preparation method B comprises the following steps:
s2-1: reacting excessive organic isocyanate with dihydric alcohol to obtain a prepolymerization reaction solution, and removing unreacted organic isocyanate monomers;
s2-2: adding a catalyst into the organic isocyanate, and after the reaction reaches a set conversion rate, adding a terminator to terminate the reaction to remove unreacted organic isocyanate monomers;
s2-3: blending the S2-1 product with the S2-1 product to obtain the product of the polyisocyanate.
7. The method according to claim 6, wherein the reaction temperature of S1-1 and S2-1 is 80-120 ℃, preferably 100-110 ℃; the reaction time is 0.5 to 4 hours, preferably 1 to 2 hours.
8. The process according to claim 6 or 7, wherein the catalyst of S1-2 and S2-2 is a tertiary phosphine, preferably one or more of trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, dicyclopentylphosphine, tripentylphosphine, tricyclopentylphosphine, trihexylphosphine, triphenylphosphine, tribenzylphosphine, benzyldimethylphosphine, tricyclohexylphosphine, tri-n-octylphosphine, more preferably tributylphosphine and/or tri-n-octylphosphine.
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