CN101880516A - Low free MDI monomer bicomponent solvent-free - Google Patents
Low free MDI monomer bicomponent solvent-free Download PDFInfo
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- CN101880516A CN101880516A CN 201010217392 CN201010217392A CN101880516A CN 101880516 A CN101880516 A CN 101880516A CN 201010217392 CN201010217392 CN 201010217392 CN 201010217392 A CN201010217392 A CN 201010217392A CN 101880516 A CN101880516 A CN 101880516A
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- acid
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- 239000000178 monomer Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 230000001070 adhesive effect Effects 0.000 claims abstract description 21
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 claims abstract description 18
- 239000004814 polyurethane Substances 0.000 claims abstract description 18
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 26
- 230000032050 esterification Effects 0.000 claims description 21
- 238000005886 esterification reaction Methods 0.000 claims description 21
- 238000010792 warming Methods 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920005906 polyester polyol Polymers 0.000 claims description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 8
- 239000010773 plant oil Substances 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000539 dimer Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- -1 poly-adipic acid diol ester Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- QFHGBZXWBRWAQV-UHFFFAOYSA-N dichloro-ethyl-phenylsilane Chemical compound CC[Si](Cl)(Cl)C1=CC=CC=C1 QFHGBZXWBRWAQV-UHFFFAOYSA-N 0.000 claims description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- CVAGYCLEIYGJQT-UHFFFAOYSA-N dichloro(dioctyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)CCCCCCCC CVAGYCLEIYGJQT-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 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 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000004800 polyvinyl chloride Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229920000915 polyvinyl chloride Polymers 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- 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
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
-
- 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
- C08G18/70—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of a low free MDI monomer bicomponent solvent-free weight regulator, raising the temperature to 70-80 DEG C for reacting until hydroxy in a system reacts sufficiently; and adding a trimerization catalyst for carrying out trimerization reaction until the trimerization reaction is complete, ending the reaction to obtain the component B. The method has simple process and low production cost; the prepared polyurethane adhesive has low MDI monomer free amount, high curing speed, high solvent resistance and hydrolysis resistance and excellent property; and the component A and the component B in a solvent free adhesive do not contain the solvent, accord with the requirements on environment protection and energy saving, have good storage stability, and are beneficial to transportation and use.
Description
Technical field
The present invention relates to a kind of polyurethane adhesive, particularly a kind of low free MDI monomer double component solvent-free polyurethane adhesive.
Background technology
Along with the raising of country to environmental requirement, to limit gradually the quantity discharged of solvent, the usage quantity of solvent-based adhesive will gradually reduce.
Solvent-free compounding technology meets efficiently fully, environmental protection, requirements of saving energy, it has technical process simple, occupation area of equipment is little, raw material is economized, power consumption is few, and maintenance cost is low, production rate high-technology advantage, and no solvent residue in the composite product, can the safety in utilization of product not caused damage.The risk of its production process presence of fire etc. reduces greatly, and is safer.The two-pack solventless adhesive is to be coated with under solvent-free situation, is not subjected to the solvent discharge quantitative limitation, adapts to country to environmental protection requirement, more and more is subjected to insider's attention and application.
Diphenylmethanediisocyanate is abbreviated as MDI, and replacing TDI to prepare polyurethane curing agent with MDI is the hot subject of urethane industry research in recent years.Advantages such as this at first is because MDI compares with TDI, and it is big to have a molecular weight, and volatility is little, and smell is little, and toxicity is little had both satisfied the requirement of current social enviroment protection, also helped workers'health.Secondly, MDI compares with TDI, and price is much lower, helps saving cost, improves competitiveness of product, and the solidifying agent of producing with MDI has better mechanical property in addition.
At present, be that the method for feedstock production solidifying agent is with MDI and polyol blends reaction with MDI, generate base polyurethane prepolymer for use as.But in the MDI molecule, because the conjugated structure of aromatic ring influence, make the carbon atom cloud density on the NCO descend, demonstrate better Electron Affinities, the easier attack that is subjected to nucleophilic reagent so the NCO group has bigger reactive behavior, very easily causes the big and skewness of prepolymerization reaction molecular weight of product, viscosity is big, with problems such as host mutual solubility differences.For addressing this problem, generally the method for Cai Yonging is to make MDI excessive greatly, as to control NCO:OH be 10:1, even it is higher, and adopt SA macromolecule polyester polyol or polyether glycol and MDI prepolymerization reaction, the reaction product that obtains like this contains the MDI free monomer of high level, its free MDI monomer content is up to 5 ~ 10%, too much dimerization reaction can take place in free MDI monomer, the generation insolubles is separated out, make the product muddiness, small molecule monomer causes degradation under the binding property to interfacial migration.Therefore, should reduce the monomeric residual quantity of MDI in the preparation process as far as possible.
Free MDI monomer needs to be removed by the aftertreatment technology of complexity, as wiped film evaporator, and solvent-assisted distillation/condistillation, molecular sieve, solvent extraction etc.Existing MDI removal method, adopt the distillatory method to remove as the residual monomer of the patent (CN02105524.6) of U.S. gas chemicals company reaction, though also can prepare the base polyurethane prepolymer for use as of free MDI monomer mass percent less than 2.5% low free MDI monomer content.But the NCO mass percent has only 0.5 ~ 8% in this patent, and lower NCO content can cause sizing agent shortcomings such as curing speed is slow, viscosity is excessive, levelling property difference to occur in use.
Summary of the invention
The object of the present invention is to provide the preparation method of the solvent-free dual-component polyurethane adhesive of a kind of low free MDI monomer.
The technical solution used in the present invention is:
The preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer, comprise the preparation of A component end OH polyvalent alcohol and the preparation of B component end NCO base polyurethane prepolymer for use as, the A component is obtained by esterification by dibasic alcohol and long carbochain aliphatic dibasic acid and/or aromatic acid, the B component by MDI monomer, plant oil modified polyvalent alcohol and/or polyester polyol by NCO/OH=3~5.5:1(mol ratio) reaction make, the preparation of B component may further comprise the steps:
1) plant oil modified polyvalent alcohol, the first at the most pure content of water in system of polyester polyols dehydration of alcohols (mass percent) are lower than 0.05%, add MDI monomer, molecular weight regulator, being warming up to 70~80 ℃, to react to the system hydroxyl reaction complete;
2) add catalyst for trimerization continuation insulation and react, trimerization reaction is the back termination reaction fully, obtains the B component.
The preparation of A component may further comprise the steps:
1) dibasic alcohol is mixed with long carbochain aliphatic dibasic acid and/or aromatic acid, carries out esterification at 130~160 ℃, when the system aquifer yield reach the esterification theory go out water number 60~80% the time, be warming up to 200~220 ℃ and continue to react;
2) reduce to below the 15mgKOH/g when acid number, decompression esterification is to acid number<1.0mgKOH/g, and cooling discharge obtains the A component.
Functional group's mol ratio of dibasic alcohol and long carbochain aliphatic dibasic acid, aromatic acid is OH/COOH=1.4~1.7/1.0.
Dibasic alcohol is preferably glycol ether, 1,4-butyleneglycol, neopentyl glycol.
Long carbochain aliphatic dibasic acid is preferably nonane diacid, sebacic acid, dimer (fatty acid) yl; Aromatic acid comprises m-phthalic acid, terephthalic acid, phthalic anhydride.
Polyester polyol is preferably poly-adipic acid diol ester, polycarbonate polyol, pla-pcl polyvalent alcohol.
Molecular weight regulator is preferably diphenyl dichlorosilane, ethylphenyl dichlorosilane, di-n-octyl dichlorosilane.
Catalyst for trimerization is organic amine catalyzer or organic phosphine class catalyzer.
Stopper is preferably phosphoric acid, Benzoyl chloride, triphenyl phosphite.
The inventive method preparation technology is simple, greatly reduces production cost.The polyurethane adhesive that makes, the MDI monomer free amount is low, and curing speed is fast, solvent resistance and anti-hydrolytic performance height, superior performance; A, B component all do not contain solvent in the solvent-free sizing agent, meet environmental protection, energy-conservation requirement; Stability in storage is good, helps transportation and use.
Embodiment
The preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer, comprise the preparation of A component end OH polyvalent alcohol and the preparation of B component end NCO base polyurethane prepolymer for use as, it is characterized in that: the A component is obtained by esterification by dibasic alcohol and long carbochain aliphatic dibasic acid and/or aromatic acid, the B component by MDI monomer, plant oil modified polyvalent alcohol and/or polyester polyol by NCO/OH=3~5.5:1(mol ratio) reaction make, the preparation of B component may further comprise the steps:
1) plant oil modified polyvalent alcohol, the first at the most pure content of water in system of polyester polyols dehydration of alcohols (mass percent) are lower than 0.05%, add MDI monomer, molecular weight regulator, being warming up to 70~80 ℃, to react to the system hydroxyl reaction complete;
2) add catalyst for trimerization continuation insulation and react, trimerization reaction is the back termination reaction fully, obtains the B component.
The preparation of A component may further comprise the steps:
1) dibasic alcohol is mixed with long carbochain aliphatic dibasic acid and/or aromatic acid, carries out esterification at 130~160 ℃, when the system aquifer yield reach the esterification theory go out water number 60~80% the time, be warming up to 200~220 ℃ and continue to react;
2) reduce to below the 15mgKOH/g when acid number, decompression esterification is to acid number<1.0mgKOH/g, and cooling discharge obtains the A component.
Functional group's mol ratio of dibasic alcohol and long carbochain aliphatic dibasic acid, aromatic acid is OH/COOH=1.4~1.7/1.0.
Dibasic alcohol is preferably glycol ether, 1,4-butyleneglycol, neopentyl glycol, and dibasic alcohol both can be used alone, but also also mix together.
Long carbochain aliphatic dibasic acid is preferably nonane diacid, sebacic acid, dimer (fatty acid) yl, and long carbochain aliphatic dibasic acid both can be used alone, but also also mix together; Dimer (fatty acid) yl is a kind of mixture of complicated component, and its main component contains two hydroxy-acid groups, is made by cycloaddition reaction by unsaturated fatty acids.
Aromatic acid comprises m-phthalic acid, terephthalic acid, phthalic anhydride, and aromatic acid both can be used alone, but also also mix together.
Plant oil modified polyvalent alcohol is preferably epoxy soybean oil, plam oil, Oleum Cocois, castor oil modified polyvalent alcohol, and plant oil modified polyvalent alcohol both can be used alone, but also also mix together.
Polyester polyol is preferably poly-adipic acid diol ester, polycarbonate polyol, pla-pcl polyvalent alcohol, and polyester polyol both can be used alone, but also also mix together.
Molecular weight regulator is preferably diphenyl dichlorosilane, the ethylphenyl dichlorosilane, and the di-n-octyl dichlorosilane both can be used alone, but also also mix together.The preferred addition of molecular weight regulator is 0.5~1.2% of a MDI quality.
Catalyst for trimerization is organic amine catalyzer or organic phosphine class catalyzer, comprises the Sanya ethylene diamine, N, and the N dimethyl benzylamine, tributylphosphine, its consumption are preferably 0.01 of MDI quality~0.05 ‰.
Stopper can be stoppers commonly used such as phosphoric acid, Benzoyl chloride, triphenyl phosphite, and its consumption is preferably 0.1 of MDI quality~0.3 ‰.
The A component can also be added with the curing conditioning agent, solidify conditioning agent for containing the organic acid or the organic acid salt of 2 ~ 8 carbon atoms, be preferably the carboxylate salt of citric acid, maleic acid and organic zinc, organotin, adding the curing conditioning agent of different amounts according to concrete needs, is those skilled in the art's basic general knowledge.
Below in conjunction with embodiment, further specify the present invention.
Employed various raw materials in the embodiment of the invention are conventional commercially available kind.
Embodiment 1
The preparation of A component:
1) get 106.1g glycol ether, 177.05g neopentyl glycol, 153.2g1,4-butyleneglycol (containing 4.4 moles of OH altogether) adds in the reactor, is heated to 80~100 ℃, and dibasic alcohol is dissolved fully;
2) add 43.2g dimer (fatty acid) yl, 263.0g adipic acid, 232.5g terephthalic acid (containing 3.1 moles of COOH altogether), faint logical nitrogen protection, be warming up to 130~160 ℃ and carry out esterification, when the system aquifer yield reach the esterification theory go out water number 60~80% after, be warming up to 200~220 ℃ and continue reaction;
3) reduce to below the 15mgKOH/g when acid number, stop logical nitrogen, being evacuated to vacuum tightness is 0.266kPa, carries out decompression esterification to acid number<1.0mgKOH/g, and cooling discharge obtains the A component.
Viscosity under 25 ℃ of the A components that obtains is 1180mPas, and hydroxyl value is 146mgKOH/g.
The preparation of B component:
1) gets poly-adipic acid 1,4 butanediol ester 120g, castor oil modified polyvalent alcohol 80g(contain 0.16 mole of OH altogether) dewatering under 120 ℃ to content of water in system is less than 0.05%, add 129.9gMDI monomer, 0.65g molecular weight regulator diphenyl dichlorosilane according to NCO/OH=3:1, be warming up to 70~80 ℃, stirring reaction hydroxyl reaction to the system is complete;
2) add 0.05g catalyst for trimerization N, the N dimethyl benzylamine is proceeded to react in 70~80 ℃, after total NCO content reduces to 14.5%, and trimerization reaction is complete, is cooled to 40 ℃, adds 0.0129g terminator Benzoyl chloride termination reaction, obtains the B component.
Viscosity under 25 ℃ of the B components that obtains is 2950mPas, and NCO%=8.3%, the content of free MDI monomer are 1.8%.
By the mol ratio NCO/OH=1.6:1 of functional group, take by weighing after A, B component mix, carry out multiple film, being about to tackiness agent is uniformly coated between polyvinyl chloride (PVC)/two-layer base material of the natural vulcanized rubber of PVC, PVC/ (RB), after composite base material at room temperature placed 3 days, the T stripping strength that records PVC/PVC was 4.5N/mm; The T stripping strength of PVC/RB is 5.09N/mm.
Embodiment 2
The preparation of A component:
1) gets 69.12g dimer (fatty acid) yl, 319.6g nonane diacid, 124.59g m-phthalic acid, (containing 2.8 moles of COOH altogether) 99.75g glycol ether, 186.95g neopentyl glycol, 151.40g1,4-butyleneglycol (containing 4.5 moles of OH altogether) adds in the reactor, faint logical nitrogen protection, be warming up to 130~160 ℃ and carry out esterification, when the system aquifer yield reach the esterification theory go out water number 70~80% after, be warming up to 200~220 ℃ and continue reaction;
2) reduce to below the 15mgKOH/g when acid number, stop logical nitrogen, being evacuated to vacuum tightness is 0.266kPa, carries out decompression esterification to acid number<1.0mgKOH/g, and cooling discharge obtains the A component.
Viscosity under 25 ℃ of the A components that obtains is 1050mPas, and hydroxyl value is 164mgKOH/g.
The preparation of B component:
1) getting water content, to be less than 0.05% molecular weight be that 1000 pla-pcl glycol 120g, epoxy soybean oil modified polyalcohol 60g(contain 0.14 mole of OH altogether), add MDI monomer 145.04g, 1.16g molecular weight regulator ethylphenyl dichlorosilane according to NCO/OH=4:1, being warming up to 70~80 ℃, to react to the system hydroxyl reaction complete;
2) add 0.072g catalyst for trimerization tributylphosphine and proceed to react in 70~80 ℃, when NCO base content≤13.4%, after trimerization reaction is complete, be cooled to 40 ℃, add 0.03g terminator Benzoyl chloride termination reaction, discharging obtains the B component.
Viscosity under 25 ℃ of the B components that obtains is 3580mPas, and NCO%=10.34%, the content of free MDI monomer are 2.0%.
By the mol ratio NCO/OH=1.7 of functional group, take by weighing after A, B component mix, carry out multiple film, place that the T stripping strength of PVC/PVC is 5.88N/mm after 3 days; The T stripping strength of PVC/RB is 6.02N/mm.
Embodiment 3
The preparation of A component:
1) gets 0.12g dimer (fatty acid) yl, 343.82g hexanodioic acid, 93.02g m-phthalic acid (containing 2.56 moles of COOH altogether), 127.34g glycol ether, 151.02g neopentyl glycol, 160.48g1,4-butyleneglycol (containing 4.35 moles of OH altogether) joins in the reactor, faint logical nitrogen protection, be warming up to 130~160 ℃ and carry out esterification, when the system aquifer yield reach the esterification theory go out water number 70~80% after, be warming up to 200~220 ℃ and continue reaction;
2) reduce to below the 15mgKOH/g when acid number, stop logical nitrogen, being evacuated to vacuum tightness is 0.266kPa, carries out decompression esterification to acid number<1.0mgKOH/g, and cooling discharge obtains the A component.
Viscosity under 25 ℃ of the A components that obtains is 850mPas, and hydroxyl value is 182mgKOH/g.
The preparation of B component:
1) getting water content, to be less than 0.05% molecular weight be that 2000 polycarbonate diol 120g, epoxy soybean oil modified polyalcohol 60g(contain 0.12 mole of OH altogether), add the molecular weight regulator ethylphenyl dichlorosilane of MDI monomer 175.4g, 2.15g according to NCO/OH=5.5:1, being warming up to 70~80 ℃, to react to the system hydroxyl reaction complete;
2) add 0.018g catalyst for trimerization tributylphosphine and proceed to react,, after trimerization reaction is complete, be cooled to 40 ℃, add 0.052g terminator Benzoyl chloride termination reaction, obtain the B component when NCO base content≤14.3% in 70~80 ℃.
Viscosity under 25 ℃ of the B components is 3200mPas, and NCO%=12.83%, the content of free MDI monomer are 2.3%.
By the mol ratio NCO/OH=1.6 of functional group, take by weighing after A, B component mix, carry out multiple film, place that the T stripping strength of PVC/PVC is 4.89N/mm after 3 days; The T stripping strength of PVC/RB is 5.23N/mm.
In the preparation process of B component end NCO base polyurethane prepolymer for use as of the present invention, the ratio maximum of NCO/OH only is 5.5, and in the traditional preparation process method of solvent-free sizing agent end NCO base polyurethane prepolymer for use as, the ratio of NCO/OH is at least 10, in the preparation process of end NCO base polyurethane prepolymer for use as of the present invention, the monomeric addition of MDI is much smaller than traditional method.By the detected result of above 3 embodiment as can be known, in the reacted end NCO base polyurethane prepolymer for use as, need not further processing, the MDI monomer free amount is only up to 2.3%, less than ordinary method half.
Polyurethane adhesive of the present invention, the MDI monomer free amount is low, and adhesive property is good, and curing speed is fast, solvent resistance and anti-hydrolytic performance height, superior performance; All do not contain solvent in sizing agent A, the B component, meet environmental protection, energy-conservation requirement; Stability in storage is good, helps transportation and use.
Claims (10)
1. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer, comprise the preparation of A component end OH polyvalent alcohol and the preparation of B component end NCO base polyurethane prepolymer for use as, it is characterized in that: the A component is obtained by esterification by dibasic alcohol and long carbochain aliphatic dibasic acid and/or aromatic acid, the B component by MDI monomer, plant oil modified polyvalent alcohol and/or polyester polyol by NCO/OH=3~5.5:1(mol ratio) reaction make, the preparation of B component may further comprise the steps:
Water content (mass percent) in plant oil modified polyvalent alcohol, the first at the most pure system of polyester polyols dehydration of alcohols is lower than 0.05%, adds MDI monomer, molecular weight regulator, being warming up to 70~80 ℃, to react to the system hydroxyl reaction complete;
Add catalyst for trimerization continuation insulation and react, trimerization reaction is the back termination reaction fully, obtains the B component.
2. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer according to claim 1 is characterized in that: polyester polyol comprises poly-adipic acid diol ester, polycarbonate polyol, pla-pcl polyvalent alcohol.
3. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer according to claim 1 is characterized in that: the consumption of molecular weight regulator is 0.5~1.2% of a MDI quality.
4. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer according to claim 1 is characterized in that: molecular weight regulator comprises diphenyl dichlorosilane, ethylphenyl dichlorosilane, di-n-octyl dichlorosilane.
5. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer according to claim 1 is characterized in that: catalyst for trimerization is organic amine or organic phosphine.
6. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer according to claim 1 is characterized in that: functional group's mol ratio of dibasic alcohol and long carbochain aliphatic dibasic acid, aromatic acid is OH/COOH=1.4~1.7/1.0.
7. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer according to claim 1 is characterized in that: dibasic alcohol comprises glycol ether, 1,4-butyleneglycol, neopentyl glycol.
8. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer according to claim 1 is characterized in that: long carbochain aliphatic dibasic acid comprises nonane diacid, sebacic acid, dimer (fatty acid) yl.
9. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer according to claim 1 is characterized in that: aromatic acid comprises m-phthalic acid, terephthalic acid, phthalic anhydride.
10. the preparation method of the solvent-free dual-component polyurethane adhesive of low free MDI monomer according to claim 1, it is characterized in that: the preparation of A component may further comprise the steps: dibasic alcohol is mixed with long carbochain aliphatic dibasic acid and/or aromatic acid, carry out esterification at 130~160 ℃, when the system aquifer yield reach the esterification theory go out water number 60~80% the time, be warming up to 200~220 ℃ and continue reaction; When acid number is reduced to below the 15mgKOH/g, decompression esterification is to acid number<1.0mgKOH/g, and cooling discharge obtains the A component.
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CN 201010217392 CN101880516B (en) | 2010-07-05 | 2010-07-05 | Low free MDI monomer bicomponent solvent-free |
PCT/CN2010/075461 WO2012003648A1 (en) | 2010-07-05 | 2010-07-26 | Method of producing solvent-free two-component polyurethane adhesive having low content of free diphenylmethane diisocyanate |
RU2012101834/05A RU2510411C2 (en) | 2010-07-05 | 2010-07-26 | Two-component solvent-free polyurethane adhesive with low content of free mdi monomer |
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CN 201010217392 CN101880516B (en) | 2010-07-05 | 2010-07-05 | Low free MDI monomer bicomponent solvent-free |
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RU2510411C2 (en) | 2014-03-27 |
RU2012101834A (en) | 2013-07-27 |
CN101880516B (en) | 2013-01-30 |
WO2012003648A1 (en) | 2012-01-12 |
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