CN116265504A - 改性异氰酸酯及其制备方法与应用 - Google Patents
改性异氰酸酯及其制备方法与应用 Download PDFInfo
- Publication number
- CN116265504A CN116265504A CN202111546306.3A CN202111546306A CN116265504A CN 116265504 A CN116265504 A CN 116265504A CN 202111546306 A CN202111546306 A CN 202111546306A CN 116265504 A CN116265504 A CN 116265504A
- Authority
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- China
- Prior art keywords
- parts
- isocyanate
- mass
- modified isocyanate
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012948 isocyanate Substances 0.000 title claims abstract description 88
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000003077 polyols Chemical class 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003112 inhibitor Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 12
- 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 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
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- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 2
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- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
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- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 14
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 11
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- 150000001718 carbodiimides Chemical class 0.000 abstract description 2
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
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- 238000000926 separation method Methods 0.000 description 3
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 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 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PGYPOBZJRVSMDS-UHFFFAOYSA-N loperamide hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)N(C)C)CCN(CC1)CCC1(O)C1=CC=C(Cl)C=C1 PGYPOBZJRVSMDS-UHFFFAOYSA-N 0.000 description 2
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- 229920000728 polyester Polymers 0.000 description 2
- -1 polyoxypropylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
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- 238000012797 qualification Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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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
- C08G18/28—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group 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
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
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- 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
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- 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
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
本发明涉及一种改性异氰酸酯及其制备方法与应用,主要解决现有技术中改性异氰酸酯的储存不稳定,流动性差,制备的聚氨酯泡沫拉伸强度低、撕裂性能差的问题,本发明通过采用一种改性异氰酸酯,以质量份数计包括有机异氰酸酯11.3~92.1份,小分子有机醇0.3~17.2份,聚醚多元醇3.3~67.7份,抗氧剂50~500ppm,阻聚剂10~130ppm;有机异氰酸酯以质量份数计包括10~60份2,4‑MDI,20~70份4,4'‑MDI,10~50份碳化二亚胺改性异氰酸酯,及5~35份多亚甲基多苯基异氰酸酯;聚醚多元醇的平均分子量为450~2450,官能度为1~2.5,EO含量为30~55%,PO含量为60~75%,伯羟基含量为30~60%及其制备方法的技术方案较好地解决了上述问题,可用于聚氨酯高回弹或自结皮产品的工业生产中。
Description
技术领域
本发明属于聚氨酯领域,特别涉及一种改性异氰酸酯及其制备方法与应用。
背景技术
作为聚氨酯领域的主要原材料,有机异氰酸酯在聚氨酯泡沫、弹性体、胶黏剂等行业大量应用;但传统的甲苯二异氰酸酯、二苯基甲烷二异氰酸酯等单体、单体混合物及聚合物在应用宽容度、制品性能、存储条件等方面存在局限性;同时对制品拉伸、撕裂等物理机械性能方面也有着重要影响。
针对制品的拉伸撕裂性能方面,现有技术的解决方案主要有如下三种:(1)选用不同的扩链剂、交联剂,改变微观结构构型,提升制品性能;(2)选用特定结构的聚醚、聚酯及其他特种多元醇,改变软段结构,提升制品性能;(3)有机异氰酸酯改性,主要采用氨基甲酸酯改性和碳化二亚胺改性,改变硬段结构,提升制品性能。在实际应用中,还需考虑配方宽容度大、操作简单可靠、低成本等因素,上述方法很难同时满足要求,并且制品拉伸撕裂性能方面的提升程度有限,因此,开发出一种能够较大程度地提高制品拉伸撕裂性能,同时能符合实际应用要求的改性异氰酸酯产品显得尤为重要。
中国专利CN101353413B公开了一种用于冷熟化高回弹泡沫塑料的改性MDI,包括异氰酸酯、聚醚多元醇、改性剂和阻聚剂,以异氰酸酯、聚醚多元醇和改性剂总质量为100%计,异氰酸酯75~84%、聚醚多元醇15~24%、改性剂0.5~1.9%,阻聚剂按原料总重量为10ppm,其中异氰酸酯为二苯基甲烷二异氰酸酯和多亚甲基多苯基异氰酸酯的混合物,二者质量比为0.8~1.2,聚醚多元醇为3官能度和数均分子量为5000~7000,伯羟基质量含量65~80%,用甘油为起始剂,用氧化乙烯封端的聚氧化丙烯三元醇,改性剂为数均分子量为2000~3000的硅氧烷改性聚醚多元醇;制得了一种手感较好、密度较低、开孔性好的高回弹泡沫,但其泡沫的力学性能一般、发泡物料流动性差。
中国专利CN101597370B公开了一种水发泡自结皮聚氨酯组合物、其制备方法及应用,其中组分B是NCO含量为18~29%的改性异氰酸酯,按重量份数计包括20~50份的预聚体1#(4,4’-MDI与聚己内酯二元醇聚合得NCO含量为9~18%的预聚体);10~30份的预聚体2#(4,4’-MDI与高官能度聚醚多元醇聚合得NCO含量为20~29%的预聚体);5~10份的预聚体3#(2,4-MDI和4,4-MDI的混合物与二元醇聚合得NCO含量26~30%的预聚体);5~30份的2,4-MDI和4,4’-MDI的混合物;20~40份的4,4’-MDI;20~60份的碳化二亚胺改性MDI;3~30份的聚合MDI;制得了一种环保型自结皮聚氨酯组合物,但改性异氰酸酯组分中易残留粗MDI,相容性差,存储过程中易浑浊分层。
发明内容
本发明所要解决的技术问题之一是现有技术中改性异氰酸酯的储存不稳定,流动性差,制备的聚氨酯泡沫拉伸强度低、撕裂性能差的问题,提供一种改性异氰酸酯,该异氰酸酯具有储存稳定,流动性好,制备的聚氨酯泡沫拉伸强度高、撕裂性能好的优点。
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改性异氰酸酯的制备方法。
本发明所要解决的技术问题之三是提供一种与解决技术问题之一相对应的改性异氰酸酯的应用。
为解决上述技术问题之一,本发明提供的技术方案如下:一种改性异氰酸酯,以质量份数计包括:有机异氰酸酯11.3~92.1份,小分子有机醇0.3~17.2份,聚醚多元醇3.3~67.7份,抗氧剂按原料总质量为50~500ppm,阻聚剂按原料总质量为10~130ppm;其中,所述的有机异氰酸酯以质量份数计包括:10~60份的2,4-二苯基甲烷二异氰酸酯,20~70份的4,4'-二苯基甲烷二异氰酸酯,10~50份的碳化二亚胺改性异氰酸酯,以及5~35份的多亚甲基多苯基异氰酸酯;所述的小分子有机醇选自单醇或二醇中的至少一种;所述的聚醚多元醇的平均分子量为450~2450,官能度为1~2.5,EO质量百分含量为30~55%,PO质量百分含量为60~75%,伯羟基质量百分含量为30~60%;所述的抗氧剂选自受阻酚类抗氧剂、受阻胺类抗氧剂或亚磷酸酯类抗氧剂中的至少一种;所述的阻聚剂选自酰氯类或酸类中的至少一种。
上述技术方案中,优选地,所述的改性异氰酸酯的异氰酸根质量百分含量为16~32%。
上述技术方案中,优选地,所述的小分子有机醇的相对分子质量为32~400;所述的单醇选自乙醇、丙醇、异丙醇、正丁醇、异丁醇、仲丁醇或正戊醇中的至少一种;所述的二醇选自1,2-丁二醇、1,4-丁二醇、甲基丙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、二甘醇、一缩二丙二醇、二乙二醇单丁醚、二丙二醇单甲醚或二丙二醇单丁醚中的至少一种;所述的酰氯类选自苯甲酰氯、苯乙酰氯或己二酰氯中的至少一种;所述的酸类选自磷酸、多聚磷酸、己二酸、柠檬酸、酒石酸或对甲苯磺酸中的至少一种。
上述技术方案中,优选地,所述的聚醚多元醇的官能度为1.2~2.0,EO质量百分含量为34~45%,PO质量百分含量为66~73%,伯羟基质量百分含量为40~45%。
上述技术方案中,优选地,所述的有机异氰酸酯以质量份数计,包含12~23份的2,4-二苯基甲烷二异氰酸酯,20~40份的4,4'-二苯基甲烷二异氰酸酯,20~40份的碳化二亚胺改性异氰酸酯及7~19份的多亚甲基多苯基异氰酸酯。
上述技术方案中,优选地,所述的改性异氰酸酯以质量份数计包括:有机异氰酸酯85~91.5份,小分子有机醇1.5~3份,聚醚多元醇5~27份,抗氧剂按原料总质量为100~400ppm,阻聚剂按原料总质量为10~130ppm。
为解决上述技术问题之二,本发明提供的技术方案如下:一种改性异氰酸酯的制备方法,包括以下步骤:
(1)按以下的组分质量百分比准备原料:
以质量份数计包括:有机异氰酸酯11.3~92.1份,小分子有机醇0.3~17.2份,聚醚多元醇3.3~67.7份,抗氧剂按原料总质量为50~500ppm,阻聚剂按原料总质量为10~130ppm;其中,所述的有机异氰酸酯以质量份数计包括:10~60份的2,4-二苯基甲烷二异氰酸酯,20~70份的4,4'-二苯基甲烷二异氰酸酯,10~50份的碳化二亚胺改性异氰酸酯,以及5~35份的多亚甲基多苯基异氰酸酯;所述的小分子有机醇选自单醇或二醇中的至少一种;所述的聚醚多元醇的平均分子量为450~2450,官能度为1~2.5,EO质量百分含量为30~55%,PO质量百分含量为60~75%,伯羟基质量百分含量为30~60%;所述的抗氧剂选自受阻酚类抗氧剂、受阻胺类抗氧剂或亚磷酸酯类抗氧剂中的至少一种;所述的阻聚剂选自酰氯类或酸类中的至少一种;
(2)在与原料呈惰性的气体的保护下,将异氰酸酯单体、抗氧剂、小分子有机醇、聚醚多元醇混合,得到物料Ⅰ;
(3)物料Ⅰ在55~90℃下进行氨基甲酸酯改性反应,得到物料Ⅱ;
(4)对物料Ⅱ进行取样,利用红外光谱仪进行异氰酸根基团的定量测试,当测得异氰酸根质量百分含量达到16~32%时,加入阻聚剂,抑制异氰酸酯与氨基甲酸酯、脲的反应,以及异氰酸酯自聚反应,得到物料Ⅲ;
(5)将物料Ⅲ的温度降至40~70℃,搅拌2~4小时,结束反应,得到改性异氰酸酯。
上述技术方案中,优选地,所述的氨基甲酸酯改性反应的温度为75~85℃;当物料Ⅱ中异氰酸根的质量百分含量达到16~19%时,加入阻聚剂;物料Ⅲ的温度降至55~65℃,搅拌2~4小时,结束反应。
为解决上述技术问题之三,本发明提供的技术方案如下:将改性异氰酸酯用于聚氨酯高回弹或自结皮产品的发泡应用中。
对于聚醚型聚氨酯,其硬段的亚氨基基团不仅可以与其本身的羰基基团形成氢键,也可以与软段的醚键形成氢键;对于聚酯型聚氨酯,亚氨基基团还可以与软段中的羰基形成氢键;前者代表微相分离,后者代表微相混合,氢键含量的多少直接影响到体系的微相分离程度。而且,交联和硬段含量对氢键化程度有显著影响,交联的形成可降低氢键化程度;聚醚型聚氨酯中硬段含量的增加,使羰基的氢键化程度提高,亚氨基与醚键的氢键化程度则逐渐降低,微相分离程度随之提高。所以,氢键作为一种强静电力,影响相分离程度,进而影响聚氨酯的力学性能与聚集态结构。
本发明的改性异氰酸酯通过对有机异氰酸酯、小分子有机醇、聚醚多元醇、亚磷酸酯类辅助抗氧剂与受阻酚类主抗氧剂的种类和比例进行筛选,使得不同组分之间协同配合,得到的改性异氰酸酯具有适中的反应速率与良好的流动性,可缩短制品生产周期、提高产品合格率;同时有效降低了产品的结晶温度,使其具有优异的高低温存储性能,-15℃储存3个月不结晶,常温下存储3个月不结晶、不鼓桶,60℃存储72小时不结晶,在常规天气条件下可存储6个月以上,改性异氰酸酯产品的储存稳定性好;选配的聚醚多元醇具有特殊的链段结构与构型,使得改性异氰酸酯形成合理的基团分布构型与分布密度,用于聚氨酯发泡后得到的聚氨酯泡沫制品的相分离程度更充分,提高了聚氨酯泡沫制品的拉伸强度、断裂伸长率、撕裂强度等力学性能,使得泡沫的拉伸强度高达785kPa,断裂伸长率达275%,撕裂强度达13.6N/cm;所以,本发明的改性异氰酸酯具有反应速率适中、流动性好、储存稳定,制备的聚氨酯泡沫制品的拉伸性能、撕裂性能优异的优点,取得了好的技术效果。
本发明中改性异氰酸酯的储存稳定性评价方法如下:
将改性异氰酸酯样品密封于500mL铁瓶中,在常温下存储3个月,观察其结晶状态、是否鼓桶情况;
将改性异氰酸酯样品密封于500mL铁瓶中,在-15℃下存储3个月,观察其结晶状态;
将改性异氰酸酯样品密封于500mL铁瓶中,在60℃下存储72小时,观察是否鼓桶情况。
本发明中改性异氰酸酯发泡物料的流动性评价方法如下:
采用中国实用新型专利CN 202023181312.7中的流动性评价模具,将100g的模塑泡配方料倒入反应槽,温度为45℃,熟化2min,打开模具取出环形样块,测量环形样块的长度,得到流动周长,以评估流动性。
本发明中模塑泡制品的性能检测方法如下:
拉伸强度(kPa):GB/T 6344-2008;
断裂伸长率(%):GB/T 6344-2008;
撕裂强度(N/cm):GB/T 10808-2006。
具体实施方式
下面通过实施例对本发明作进一步的阐述,但不仅限于本实施例。
表1原料清单
【实施例1】
一种改性异氰酸酯,其制备方法包括以下步骤:
(1)在氮气的保护下,将750g Lupranate MS、750g Lupranate MIPS、360gLupranate M20S、1140g Cosmonate LL加入至5L的玻璃反应釜中,加热至75℃,搅拌至完全融化;
(2)将0.34g 2,6-二叔丁基-4-甲基苯酚和0.34g二亚磷酸季戊四醇酯二异葵酯加入至小分子有机醇中,均匀混合后加入至反应釜中,搅拌均匀;
(3)将反应釜加热至80℃,加入238.2g聚醚A,搅拌反应2小时;
(4)将0.17g苯乙酰氯加入至反应釜中,升温至85℃,反应1小时;
(5)将反应釜中物料降温至60℃,搅拌2小时,得到改性异氰酸酯;对该改性异氰酸酯进行性能评估,结果数据见表4所示;
将制得的改性异氰酸酯按表3的发泡配方进行配料,采用中国实用新型专利CN202023181312.7中的流动性评价模具,将100g的模塑泡配方料倒入反应槽,温度为45℃,熟化2min,打开模具取出环形样块,测量环形样块的长度,得到流动周长,结果数据见表4所示;
将余下的模塑泡配方料全部倒入发泡模具中进行发泡制样,模温50℃,脱模时间2min,整体密度80kg/m3,制得的聚氨酯泡沫熟化48小时后进行性能检测,其结果数据见表4所示。
【实施例2~5】
实施例2~5中改性异氰酸酯的制备方法按照实施例1中的各个步骤进行,区别为反应原料、原料配比不同,具体见表2所示,制得的改性异氰酸酯的储存稳定性数据见表4所示;将制得的改性异氰酸酯按表3的发泡配方进行配料,取100g进行流动性评价,余下的配方料进行发泡,流动性结果数据及聚氨酯泡沫的性能数据见表4所示。
表2实施例1~5中各组分原料的质量(g)
原料名称 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
Lupranate MS | 750 | 750 | 750 | 1050 | 750 |
Lupranate MIPS | 750 | 750 | 750 | 450 | 750 |
Lupranate M20S | 360 | 360 | 360 | 360 | 360 |
Cosmonate LL | 1140 | 1140 | 1140 | 1140 | 1140 |
聚醚A | 238.2 | / | / | 238.2 | 235.8 |
聚醚B | / | 220.2 | / | / | / |
聚醚C | / | / | 164.6 | / | / |
乙二醇 | 59.1 | / | / | / | 59.1 |
一缩二乙二醇 | 90 | 90 | 90 | 90 | / |
苯乙酰氯 | 0.17 | 0.17 | 0.17 | 0.17 | 0.17 |
2,6-二叔丁基-4-甲基苯酚 | 0.34 | 0.34 | 0.34 | 0.34 | 0.34 |
二亚磷酸季戊四醇酯二异葵酯 | 0.34 | 0.34 | 0.34 | 0.34 | 0.34 |
表3实施例1~5及比较例1~2中模塑泡发泡配方各组分质量份数
原料名称 | 质量份数 |
CHE-1Q59 | 80 |
CHP-H45 | 20 |
二乙醇胺 | 1.2 |
CHK-9701 | 0.9 |
DABCO BL-11 | 0.2 |
DABCO MP 608 | 1.1 |
B-8734 | 1.0 |
水 | 2.3 |
指数 | 85 |
改性异氰酸酯 | 51.2 |
【比较例1】
比较例1中改性异氰酸酯采用市售的Suprasec 2412,其储存稳定性数据见表4所示;将该改性异氰酸酯按表3的发泡配方进行配料,取100g进行流动性评价,余下的配方料进行发泡,流动性结果数据及聚氨酯泡沫的性能数据见表4所示。
【比较例2】
比较例1中改性异氰酸酯采用市售的Suprasec 2082,其储存稳定性数据见表4所示;将该改性异氰酸酯按表3的发泡配方进行配料,取100g进行流动性评价,余下的配方料进行发泡,流动性结果数据及聚氨酯泡沫的性能数据见表4所示。
表4实施例1~5及比较例1~2的性能结果数据
由表4可知,实施例1~5中改性异氰酸酯在-15℃储存3个月不结晶,常温下存储3个月不结晶、不鼓桶,60℃存储72小时不结晶,高低温存储性能优于比较例1~2;流动性评估实验中,实施例1~5的流动周长为67.3~71.3cm,流动性好;按模塑泡配方发泡制得的聚氨酯泡沫的拉伸强度在730 kPa以上,断裂伸长率在250%以上,撕裂强度在12 N/cm以上,拉伸、撕裂性能远优于比较例1~2。
可见,本发明的改性异氰酸酯具有储存稳定、流动性好、制得的聚氨酯泡沫拉伸性能、撕裂性能优异的优点,取得了好的技术效果,可用于聚氨酯高回弹或自结皮产品的工业应用中。
Claims (9)
1.一种改性异氰酸酯,以质量份数计包括:有机异氰酸酯11.3~92.1份,小分子有机醇0.3~17.2份,聚醚多元醇3.3~67.7份,抗氧剂按原料总质量为50~500ppm,阻聚剂按原料总质量为10~130ppm;其中,所述的有机异氰酸酯以质量份数计包括:10~60份的2,4-二苯基甲烷二异氰酸酯,20~70份的4,4'-二苯基甲烷二异氰酸酯,10~50份的碳化二亚胺改性异氰酸酯,及5~35份的多亚甲基多苯基异氰酸酯;所述的小分子有机醇选自单醇或二醇中的至少一种;所述的聚醚多元醇的平均分子量为450~2450,官能度为1~2.5,EO质量百分含量为30~55%,PO质量百分含量为60~75%,伯羟基质量百分含量为30~60%;所述的抗氧剂选自受阻酚类抗氧剂、受阻胺类抗氧剂或亚磷酸酯类抗氧剂中的至少一种;所述的阻聚剂选自酰氯类或酸类中的至少一种。
2.根据权利要求1所述的改性异氰酸酯,其特征在于,所述的改性异氰酸酯的异氰酸根质量百分含量为16~32%。
3.根据权利要求1所述的改性异氰酸酯,其特征在于,所述的小分子有机醇的相对分子质量为32~400,所述的单醇选自乙醇、丙醇、异丙醇、正丁醇、异丁醇、仲丁醇或正戊醇中的至少一种;所述的二醇选自1,2-丁二醇、1,4-丁二醇、甲基丙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、二甘醇、一缩二丙二醇、二乙二醇单丁醚、二丙二醇单甲醚或二丙二醇单丁醚中的至少一种;所述的酰氯类选自苯甲酰氯、苯乙酰氯或己二酰氯中的至少一种;所述的酸类选自磷酸、多聚磷酸、己二酸、柠檬酸、酒石酸或对甲苯磺酸中的至少一种。
4.根据权利要求1所述的改性异氰酸酯,其特征在于,所述的聚醚多元醇的官能度为1.2~2.0,EO质量百分含量为34~45%,PO质量百分含量为66~73%,伯羟基质量百分含量为40~45%。
5.根据权利要求1~4中任一项所述的改性异氰酸酯,其特征在于,所述的有机异氰酸酯以质量份数计,包含12~23份的2,4-二苯基甲烷二异氰酸酯,20~40份的4,4'-二苯基甲烷二异氰酸酯,20~40份的碳化二亚胺改性异氰酸酯,以及7~19份的多亚甲基多苯基异氰酸酯。
6.根据权利要求1~4中任一项所述的改性异氰酸酯,其特征在于,所述的改性异氰酸酯以质量份数计包括:有机异氰酸酯85~91.5份,小分子有机醇1.5~3份,聚醚多元醇5~27份,抗氧剂按原料总质量为100~400ppm,阻聚剂按原料总质量为10~130ppm。
7.权利要求1所述的改性异氰酸酯的制备方法,包括以下步骤:
(1)按以下的组分质量百分比准备原料:
以质量份数计包括:有机异氰酸酯11.3~92.1份,小分子有机醇0.3~17.2份,聚醚多元醇3.3~67.7份,抗氧剂按原料总质量为50~500ppm,阻聚剂按原料总质量为10~130ppm;其中,所述的有机异氰酸酯以质量份数计包括:10~60份的2,4-二苯基甲烷二异氰酸酯,20~70份的4,4'-二苯基甲烷二异氰酸酯,10~50份的碳化二亚胺改性异氰酸酯,以及5~35份的多亚甲基多苯基异氰酸酯;所述的小分子有机醇选自单醇或二醇中的至少一种;所述的聚醚多元醇的平均分子量为450~2450,官能度为1~2.5,EO质量百分含量为30~55%,PO质量百分含量为60~75%,伯羟基质量百分含量为30~60%;所述的抗氧剂选自受阻酚类抗氧剂、受阻胺类抗氧剂或亚磷酸酯类抗氧剂中的至少一种;所述的阻聚剂选自酰氯类或酸类中的至少一种;
(2)在与原料呈惰性的气体的保护下,将异氰酸酯单体、抗氧剂、小分子有机醇、聚醚多元醇混合,得到物料Ⅰ;
(3)物料Ⅰ在55~90℃下进行氨基甲酸酯改性反应,得到物料Ⅱ;
(4)对物料Ⅱ进行取样测试,当其异氰酸根质量百分含量达到16~32%时,加入阻聚剂,抑制异氰酸酯与氨基甲酸酯、脲的反应,以及异氰酸酯自聚反应,得到物料Ⅲ;
(5)将物料Ⅲ的温度降至40~70℃,搅拌2~4小时,结束反应,得到改性异氰酸酯。
8.根据权利要求7所述的改性异氰酸酯的制备方法,其特征在于,所述的氨基甲酸酯改性反应的温度为75~85℃;当物料Ⅱ中异氰酸根的质量百分含量达到16~19%时,加入阻聚剂;物料Ⅲ的温度降至55~65℃,搅拌2~4小时,结束反应。
9.权利要求1所述的改性异氰酸酯在聚氨酯高回弹或自结皮产品中的应用。
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