CN102212182A - Curing agent methylene diphenyl diisocyanate tripolymer and method for preparing same - Google Patents
Curing agent methylene diphenyl diisocyanate tripolymer and method for preparing same Download PDFInfo
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- 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 title claims abstract description 112
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 150000003077 polyols Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000013638 trimer Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- -1 1,2-propylene glycol ester Chemical class 0.000 claims description 12
- 238000005070 sampling Methods 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- CVNPKVXQUCOSOI-UHFFFAOYSA-N 3-ethylheptane-2,3-diol Chemical compound CCCCC(O)(CC)C(C)O CVNPKVXQUCOSOI-UHFFFAOYSA-N 0.000 claims description 3
- BUUSNVSJZVGMFY-UHFFFAOYSA-N 4-ethylheptane-3,3-diol Chemical compound CCCC(CC)C(O)(O)CC BUUSNVSJZVGMFY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 159000000011 group IA salts Chemical class 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000011527 polyurethane coating Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 13
- 229920002554 vinyl polymer Polymers 0.000 description 13
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- FWVCSXWHVOOTFJ-UHFFFAOYSA-N 1-(2-chloroethylsulfanyl)-2-[2-(2-chloroethylsulfanyl)ethoxy]ethane Chemical compound ClCCSCCOCCSCCCl FWVCSXWHVOOTFJ-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a curing agent, namely a methylene diphenyl diisocyanate (MDI) tripolymer and a method for preparing the same. The method comprises the following steps of: adding the MDI and an organic solvent into a reaction kettle, raising the temperature, dissolving the MDI, stirring uniformly, adding dehydrated polyol, and reacting for 1 to 6 hours at the temperature of between 40 and 90 DEG C to obtain modified MDI; reducing the temperature to 40 DEG C, dripping mixed solution of a trimerization catalyst and an organic solvent, reacting at the temperature of between 30 and 80 DEG C, and adding a polymerization inhibitor when the percentage of isocyanate group (NCO) reaches a preset value; and reducing the temperature to obtain the MDI tripolymer curing agent. The invention provides the method for preparing the tripolymer curing agent by using the MDI. The process is simple, the requirements of equipment are low, the content of the tripolymer is high, and the curing agent is well soluble in resins and can substitute a tolylene diisocyanate (TDI) tripolymer with similar performance. The curing agent is mainly used for being matched with two-component polyurethane coatings and main agents of adhesives, and can also be used for other fields.
Description
Technical field
The present invention relates to a kind of polyurethane coating, adhesive solidification agent and preparation method thereof, is a kind of diphenylmethanediisocyanate trimer curing agent and preparation method thereof specifically.
Background technology
Diphenylmethanediisocyanate and homologue thereof (english abbreviation MDI) are a large amount of raw materials that use of polyurethane industrial, wherein account for 4 of main output, 4 '-MDI has performances such as excellent intensity, self-vulcanizing are fast, but its symmetry, regular, inflexible structure cause existing manufacturing technology can't be made into tripolymer and are applied to coating and tackiness agent, and the main application of MDI is still made polyurethane foam and Embedding Material.
Through consulting relevant patent documentation, also do not make 4 in the world at present, the patent report of 4 '-MDI tripolymer product only has some to prepare trimerical report with the MDI isomers in China national Department of Intellectual Property invention disclosed public announcement of a patent application specification sheets.Publication number CN101307126A " MDI trimerization solidifying agent and preparation method thereof ", disclosed manufacturing MDI tripolymer method has only introduced 2, and 4 '-MDI content must be greater than 50% MDI manufacture method, promptly 2,4 '-MDI content less than 50% MDI with this method be can not do trimerical.Publication number CN101239987A " contains silicone-modified polyisocyanate trimer curing agent of sulfydryl or hydroxyl and preparation method thereof ", introduced with silicone-modified MDI and prepared trimerical method, the isomers composition situation to MDI does not describe, and the MDI that explains in the example mixes MDI.Up to now, also do not contain more than 50% 4, the MDI of 4 '-MDI prepares trimerical bibliographical information, does not more have purely 4, and 4 '-MDI prepares trimerical report.Tracing it to its cause is 4,4 '-MDI specific molecule structure, and its two isocyano group activity are identical, and activity is very high, and chemical reaction velocity is wayward.In the present MDI raw material of producing, 4, the ratio that 4 '-MDI output accounts for is big, low price, and 2,4 '-MDI yields poorly, and the price height, mechanical property is also not as the former.How utilizing 4 more, it is to be stranded the technical barrier of scratching the polyurethane industrial development that big and MDI excellent performance of this amount of 4 '-MDI makes tripolymer always.
MDI also has an outstanding advantage in the vulcabond series raw material, be exactly that the room temperature steam forces down, volatility is little, the room temperature vapour pressure of MDI is less than the thousandth of TDI (tolylene diisocyanate) (below 25 ℃, vapour pressure＜0.001Pa of MDI, and the vapour pressure of TDI is 3Pa), therefore, MDI has the noresidue monomer than TDI and poisons problem.Do not have MDI tripolymer product in the market, what the insider used is the TDI tripolymer.The trimerical disadvantage of TDI is residual more free monomer, remove difficulty, need with technologies such as big, the expensive thin film evaporation of technical difficulty, solvent extractions, production efficiency is low, energy consumption is big, and domestic most of enterprise does not all carry out this road clearing process.Free TDI pollutes environment, infringement production operation personnel health, and this is that National Environment Policy Act does not fill perhaps.Aspect strength property, MDI is more superior than TDI, and self-vulcanizing speed is faster, and production efficiency is higher, if can make the MDI tripolymer, will replace the TDI tripolymer undoubtedly, becomes the very promising self-vulcanizing environmentally friendly machine of polyurethane industrial.
If can solve 4,4 '-MDI trimerization problem, then the trimerization problem of its isomer and arbitrary proportion mixing MDI thereof just can be readily solved.
Summary of the invention
The object of the present invention is to provide a kind of curing agent diphenyl methane diisocyanate tripolymer that is applicable to coating and tackiness agent.
The present invention also aims to provide above-mentioned curing agent diphenyl methane diisocyanate trimer preparation method, solve 4 of symmetrical configuration, 4 '-MDI content is made trimerical technical barrier greater than 50% MDI, with a kind of convenience, be suitable for, economic method carries out trimerization again with behind MDI and the different polyol reaction, produces a series of MDI trimer curing agents that are applicable to coating and tackiness agent.
Innovative point of the present invention is that MDI is carried out modification, by introducing polyvalent alcohol and part MDI reaction earlier, generating portion modification MDI; The activity of modification MDI descends, unmodified MDI activity is constant, this has just constituted in the system active enough big difference between the molecule, after adding catalyst for trimerization, the speed of response of each molecule is inequality, active reaction earlier high, that no steric hindrance hinders, active afterreaction low, that have steric hindrance to hinder, this speed in order reaction helps the generation of single tripolymer molecule, avoids and has reduced the polymeric generation of dimer, the tetramer and macromole.The principle of the invention has innovated existing document and ordinary method is made the tripolymer technology.
Product of the present invention is a kind of mixture, and its signal modular construction formula is:
Wherein: M is
R is alkyl, phenyl or the ethers of polyvalent alcohol, the compound of ester class.
Product index of the present invention following (following content is weight percentage):
(1) outward appearance: colourless to light yellow transparent liquid;
(2) solid content: 50～75%;
(3) NCO content: 10～16%, in total solids.
(4) storage period: half a year.
Preparation method of the present invention and step thereof comprise:
A, in reactor, add diphenylmethanediisocyanate and organic solvent, be warming up to 60 ℃ its dissolving stirred evenly, be cooled to 40～60 ℃, add polyvalent alcohol through dehydration, 40～90 ℃ of reactions 1～6 hour, make the diphenylmethanediisocyanate modifier; B, be cooled to 30～50 ℃, drip the mixed solution that catalyzer and organic solvent are formed,, detect the NCO weight percentage, when reaching set(ting)value, add stopper termination trimerization reaction, be cooled to 50 ℃ every sampling in 0.5～1 hour 30～80 ℃ of reactions; C, add organic solvent, stir by the requirement of product solid content, discharging, the MDI trimer curing agent;
Wherein each reactant consumption is as follows by weight percentage:
MDI 55～96％
Polyvalent alcohol 4～45%
The weight ratio of consumption of organic solvent and reactant consumption is 2.5～5: 5～7.5.
NCO weight percentage set(ting)value is for removing the part MDI with polyol reaction, remains MDI and carries out trimerization to the percent 90 NCO weight percentage in system when above.
In its preparation method step b can also for: in another reactor, add organic solvent and catalyzer, be warming up to 30～50 ℃, again the diphenylmethanediisocyanate modifier that makes among the step a is added several times, temperature is even in the reinforced process of control, rise slowly, added material in 1～5 hour, 30～80 ℃ of reactions, detect the NCO weight percentage every sampling in 0.5～1 hour, when NCO content reaches set(ting)value, add stopper and stop trimerization reaction, be cooled to 50 ℃.
Diphenylmethanediisocyanate described in the step a is 4 of a symmetrical configuration, 4 '-MDI, isomer 2, and 4 '-MDI, 2, at least a among 2 '-MDI, the composition content of three kinds of isomerss can be any weight ratio.
Polyvalent alcohol described in the step a is polyester polyol, polyether glycol, contain the polyvalent alcohol and the small molecules polyvalent alcohol of two and two above hydroxyls, wherein at least a.
Described polyester polyol is poly-hexanodioic acid-ethylene glycol and 1,2-propylene glycol ester dibasic alcohol, poly-hexanodioic acid-butanediol ester dibasic alcohol, poly-sebacic acid-hexanodioic acid-ethylene glycol-DOPCP dibasic alcohol, poly-m-phthalic acid-hexanodioic acid-neopentyl glycol-glycol ether ester dibasic alcohol, polycarbonate diol, the polycaprolactone polyol that contains two and two above hydroxyls.
Polyether glycol is polyoxytrimethylene polyvalent alcohol, polyoxyethylene-propylene polyvalent alcohol, the polytetrahydrofuran dibasic alcohol that contains two and two above hydroxyls.
The polyvalent alcohol that contains two and two above hydroxyls is Synolac polyvalent alcohol, polybutadiene diol, castor oil polyhydric alcohol, soybean oil polyvalent alcohol.
The small molecules polyvalent alcohol is the 3-methyl isophthalic acid, 5-pentanediol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,5-pentanediol, diethyl pentanediol, 1,2-propylene glycol, glycol ether, 1,6-hexylene glycol, neopentyl glycol, neopentyl glycol, butyl ethyl propylene glycol, dipropylene glycol, tripropylene glycol, Rutgers 612.
MDI and polyol reaction make the chemical equation of MDI modifier and are among the step a:
MDI modifier, MDI trimerization reaction under catalyst action makes trimerical chemical equation and is among the step b:
Wherein: M is
R is alkyl, phenyl or the ethers of polyvalent alcohol, the compound of ester class.
From above-mentioned chemical equation (A) as can be seen: MDI elder generation and polyol reaction, the modification MDI of generation termination band NCO group, it has changed the activity of MDI.The polyvalent alcohol difference that adds, the active degree that descends of the modification MDI of generation is also different.
From chemical equation (B) as can be seen: the R base makes the NCO group activity of modification MDI descend, the molecule activity resistance increases, do not change with the MDI of polyol reaction is active, formed active bigger difference between the molecule, like this between the molecule, just inequality with the chemical reaction velocity between the molecule different N CO, under catalyst action, active high, there is not sterically hindered NCO reaction earlier, active low, sterically hindered NCO afterreaction has living space, this speed reaction in order helps single tripolymer molecule generation, avoid and reduced dimer, the tetramer and macromole polymer generate, therefore, the present invention can prepare low viscous colourless or light yellow transparent MDI tripolymer product.The trimerization reaction terminal point is that the slippage by NCO in the continuous detection reaction system is determined, when the trimerization degree reaches 90% when above, promptly reaches NCO weight percentage set(ting)value, adding stopper termination reaction.Product exists with three kinds of structure formations in the system: modification MDI molecule is not participated in trimeric and is existed with (B-1) formula, and the MDI molecule carries out trimeric and generates (B-2) formula, and modification MDI molecule and MDI molecule carry out trimeric jointly and generate (B-3) formula.
Preparation MDI trimerical catalyzer is the alkaline salt of lithium acetate, potassium acetate, the tertiary phosphine class of tri-n-butyl phosphine, triethyl phosphine, and trivinyl diamines, N, the tertiary amines of N-dimethyl benzylamine, wherein at least a, add-on is 0.01～0.5% of a MDI weight.
The stopper that stops trimerization reaction is at least a in Benzoyl chloride, phosphoric acid, methyl tosylate, the methyl-sulfate, and add-on is 0.005～0.3% of a MDI weight.
The used organic solvent of the present invention is the ester class of vinyl acetic monomer, N-BUTYL ACETATE, propylene glycol monomethyl ether acetate, the ketone of acetone, butanone, pimelinketone, toluene, dimethylbenzene aromatic hydrocarbons, dioxane, tetrahydrofuran (THF), N, dinethylformamide reaches wherein two or more mixture.
The difference that disclosed MDI prepares the tripolymer method among the present invention and Chinese invention patent ublic specification of application CN101307126A, the CN101239987A is: introduced polyvalent alcohol part MDI molecule is carried out modification, formed between each molecule actively, can control trimerization reaction effectively and normally carry out than big-difference.
The introducing of polyvalent alcohol of the present invention has changed the performance of MDI, make tripolymer have more snappiness, wideer with consistency increase, the self-vulcanizing velocity range of resin, can also design some property by customer requirements, therefore can produce the various serial MDI trimer curing agent of kind, satisfy the needs of polyurethane coating, tackiness agent various uses.
Innovative point of the present invention is to have solved 4, and 4 '-MDI content is greater than 50% MDI and pure 4, and 4 '-MDI can not a trimeric difficult problem.
The present invention is a kind of can control texture symmetric 4, and 4 '-MDI carries out the method for orderly chemical reaction, adopts common equipment just can produce the MDI tripolymer easily, present method is equally applicable to 4,4 '-MDI and 2,4 '-MDI and 2, the mixture of 2 '-MDI prepares tripolymer.MDI tripolymer product of the present invention and supporting Synolac, acrylic resin etc. have good intermiscibility.
The present invention compared with prior art has following advantage: one, the present invention has changed the method for traditional manufacturing diisocyanate trimer.The polyalcohol modified MDI technology that the present invention introduces makes the isometry physical efficiency of MDI prepare the tripolymer product with any weight proportion.Two, toxicity is low.The MDI tripolymer that the present invention produces does not have TDI tripolymer residual monomer environmental pollution problem.Three, cost performance is higher.The MDI tripolymer has higher intensity than TDI tripolymer, self-vulcanizing speed faster, and raw material sources are abundant, low price.Four, technology advanced person.Whole chemical reaction of the present invention carries out under 100 ℃ of water-baths, and energy consumption is low, and technology is simple, production efficiency height, three-waste free discharge.Five, excellent storage stability.The MDI trimerization physical efficiency that the present invention makes was stored more than half a year.Six, solid content height.Viscosity of the present invention is low, and solid content is up to 75%.Seven, applied widely.Select different polyvalent alcohols and different constituent proportionings, can be made into a series of MDI trimer curing agents, the kind of diversification can satisfy the various demands of supporting double-component polyurethane coating, tackiness agent host.
In order to implement the present invention better, the present invention is further illustrated now to enumerate following embodiment.
Embodiment
Embodiment 1
A, in reactor, add 200 gram MDI-50 (promptly 4,2 '-MDI weight is 50%, 4,4 '-MDI weight is 50% mixture) liquid and 60 gram N-BUTYL ACETATEs, be warming up to 60 ℃ its dissolving stirred evenly, be cooled to 50 ℃, add 52 gram Synolac polyvalent alcohols, 60～70 ℃ of reactions 2 hours, 80～90 ℃ were reacted 2 hours; B, be cooled to 30 ℃, drip the mixed solution that 0.1 gram tri-n-butyl phosphine and 20 gram vinyl acetic monomers are formed, 35～40 ℃ of reactions 1 hour, be warmed up to 50～55 ℃ of reactions again, detect the NCO percentage composition, when NCO content reduces to 11.0%, (set when MDI trimerization degree reaches 95% every sampling in 1 hour, the theoretical NCO% of system is 11.1%), add the mixed solution that 0.03 gram Benzoyl chloride and 4 gram vinyl acetic monomers are formed, be warmed up to 70 ℃ of insulations 0.5 hour, be cooled to 50 ℃ again; C, discharging, 336 gram solid contents are 75% light yellow transparent MDI trimer curing agent.The NCO percentage composition of this solidifying agent is 10.5% after testing.
Annotate:
1, detect the mensuration of solid content by National Standard GB/T 2793-1995 tackiness agent non-volatile content " carry out.
2, detecting NCO content is undertaken by the Ministry of Chemical Industry's standard " isocyanate group Determination on content in the HG/T2409-92 base polyurethane prepolymer for use as ".
Embodiment 2
A, in reactor, add 200 gram MDI-50 liquid and 170 gram N-BUTYL ACETATEs, be warming up to 40 ℃, add 18.3 gram Rutgers 612s, 40～50 ℃ of reactions 1.5 hours, 60～75 ℃ of reactions 2 hours through dehydration; B, be cooled to 45 ℃, drip the mixed solution that 0.3 gram Lithium Acetate and 30 gram vinyl acetic monomers are formed, 45～55 ℃ of reactions 1 hour, be warming up to 60～70 ℃ of reactions again, detect the NCO percentage composition, when NCO content reduces to 8.4%, (set when MDI trimerization degree reaches 98% every sampling in 1 hour, solid content is that 52% theoretical NCO% is 8.2%), add the mixed solution that 0.04 gram phosphoric acid and 19 gram vinyl acetic monomers are formed, be warmed up to 80 ℃ of insulations 1 hour, be cooled to 50 ℃; C, discharging, 437 gram solid contents are 50% MDI trimer curing agent.The NCO percentage composition of this solidifying agent is 7.6% after testing.(0.6 gram of gross weight may be thought of as volatilization loss for solvent 219 grams, reactant 218.6 grams.)
Embodiment 3
A, the MDI-100 that add 100 gram fusings in No. 1 reactor (are pure 4,4 '-MDI) and 100 gram MDI-50 liquid and 100 gram N-BUTYL ACETATEs, being warming up to 60 ℃ stirs evenly its dissolving, be cooled to 40 ℃, adding is through the 5 gram neopentyl glycol and the 6 gram butyl ethyl propylene glycol of dehydration, 50～60 ℃ of reactions 1 hour, 70～80 ℃ were reacted 1 hour, got MDI modifier solution; B, in No. 2 reactors, add the mixing solutions that 100 gram vinyl acetic monomers and 0.1 gram tri-n-butyl phosphine are formed, be warming up to 40 ℃, again the MDI modifier solution of making in No. 1 still is divided in No. 2 stills of five addings, temperature is even in the reinforced process of control, rise slowly, added material in 3 hours, 40～45 ℃ of reactions 1 hour, be warmed up to 50～55 ℃ of reactions again, detect the NCO percentage composition every sampling in 1 hour, when NCO content drops to 8.4%, add the mixed solution that 0.04 gram Benzoyl chloride and 11 gram N-BUTYL ACETATEs are formed, be warmed up to 70 ℃ of insulations 1 hour, be cooled to 50 ℃ again; C, discharging, 422 gram solid contents are 50% MDI trimer curing agent.
Embodiment 4
A, the MDI-100 that add 200 gram fusings in reactor and 80 gram N-BUTYL ACETATEs are warming up to 60 ℃ its dissolving are stirred evenly, and are cooled to 40 ℃, add 8 gram diethyl pentanediols through dehydration, 50～60 ℃ of reactions 1 hour, 70～80 ℃ of reactions 1.5 hours; Be cooled to 50 ℃, add 90 gram polyoxytrimethylene polyethers through dehydration again, 60～70 ℃ were reacted 2 hours, and 80～90 ℃ were reacted 1 hour; B, be cooled to 35 ℃, drip the mixed solution that 0.2 gram triethyl phosphine and 18 gram vinyl acetic monomers are formed, 40～45 ℃ of reactions 1 hour, be warming up to 55～65 ℃ of reactions again, detect the NCO percentage composition every sampling in 1 hour, when NCO content drops to 10.5%, add the mixed solution that 0.04 gram Benzoyl chloride and 2 gram vinyl acetic monomers are formed, be warmed up to 75 ℃ of insulations 0.5 hour, be cooled to 50 ℃; C, discharging, 398 gram solid contents are 75% water white transparency MDI trimer curing agent.
Embodiment 5
A, the MDI-100 that in reactor, adds 200 gram fusings and 200 gram N-BUTYL ACETATEs and 60 gram vinyl acetic monomers, be warming up to 60 ℃ its dissolving stirred evenly, be cooled to 50 ℃, add 120 gram poly-epsilon-caprolactone glycol through dehydration, 50～60 ℃ were reacted 2.5 hours, and 75～85 ℃ were reacted 2 hours; B, be cooled to 45 ℃, drip the mixed solution that 0.2 gram Lithium Acetate and 35 gram vinyl acetic monomers are formed, 45～50 ℃ of reactions 2 hours, be warmed up to 60～70 ℃ of reactions again, detect the NCO percentage composition every sampling in 1 hour, when NCO content drops to 7.3%, add the mixed solution that 0.04 gram Benzoyl chloride and 5 gram vinyl acetic monomers are formed, be warmed up to 80 ℃ of insulations 0.5 hour, be cooled to 50 ℃; C, add 20 gram propylene glycol monomethyl ether acetate and stir, discharging, 640 gram solid contents are 50% MDI trimer curing agent.
Embodiment 6
A, the MDI-100 that add 120 gram fusings in reactor and 70 gram vinyl acetic monomers are warming up to 60 ℃ its dissolving are stirred evenly, and are cooled to 40 ℃, add 5 gram dipropylene glycol through dehydration, 50～60 ℃ of reactions 1 hour, 70～80 ℃ of reactions 1.5 hours; Add 80 gram MDI-50 liquid again, be cooled to 50 ℃ after stirring; Adding is through the poly-hexanodioic acid of 80 grams-ethylene glycol and 1,2-propylene glycol esterdiol of dehydration, and 50～60 ℃ were reacted 1.5 hours, and 75～85 ℃ were reacted 2 hours; B, be cooled to 40 ℃, drip the mixed solution that 0.2 gram Lithium Acetate and 20 gram vinyl acetic monomers are formed, 45～50 ℃ of reactions 1.5 hours, be warmed up to 65～70 ℃ of reactions again, detect the NCO percentage composition every sampling in 1 hour, when NCO content drops to 11%, add the mixed solution that 0.04 gram Benzoyl chloride and 5 gram vinyl acetic monomers are formed, be warmed up to 75 ℃ of insulations 1 hour, be cooled to 50 ℃; C, discharging, 380 gram solid contents are 75% MDI trimer curing agent.
Application Example 1
Product 40 grams of embodiment 1 and the hydroxyl component of 100 gram phthalic resin coatings mix, and the coating lacquer film properties that makes is as follows: dryness: 25 ℃, surface drying time 40 minutes is done solid work 12 hours time; Test performance after 2 days: gloss (60 °): 〉=95%; Hardness: Shao Shi D40; Shock strength: 428N.cm; Sticking power: 1 grade; Snappiness: 1mm.
The method of inspection: gloss is pressed GB9754-88, hardness and is pressed GB1730-79, shock strength and press that GB1732-93, sticking power press GB1720-89, snappiness is pressed the GB1731-79 standard.
Application Example 2
Product 40 grams of embodiment 3 and 100 gram Hydroxylated acrylic resin solution mix, and the coating lacquer film properties that makes is as follows: dryness: 25 ℃, surface drying time 50 minutes is done solid work 8 hours time; Test performance after 3 days: gloss (60 °): 〉=95%; Hardness 〉=Shao Shi D60; Shock strength: 540N.cm; Sticking power: 1 grade; Snappiness: 1mm.
Application Example 3
Product 35 grams of embodiment 6 and package compound are mixed with hydroxyl component 100 grams of polyurethane adhesive, be used for the compound of pure aluminum foil and CPP film, in 50 ℃ solidify 48 hours after, carry out T type peeling strength test by GB/T 2791-1995 " tackiness agent T peeling strength test method flexible material is to flexible material ", stripping strength is 1230g/15mm, and the laminated film behind cooking test does not find that film has separation phenomenon.
Claims (9)
1. curing agent diphenyl methane diisocyanate tripolymer is characterized in that:
Its signal modular construction formula is:
Wherein: M is
R is alkyl, phenyl or the ethers of polyvalent alcohol, the compound of ester class.
Product index of the present invention following (following content is weight percentage):
(1) outward appearance: colourless to light yellow transparent liquid;
(2) solid content: 50～75%;
(3) NCO content: 10～16%, in total solids.
2. described curing agent diphenyl methane diisocyanate trimer preparation method of claim 1, its step comprises:
A, in reactor, add diphenylmethanediisocyanate and organic solvent, be warming up to 60 ℃ its dissolving stirred evenly, be cooled to 40～60 ℃, add polyvalent alcohol through dehydration, 40～90 ℃ of reactions 1～6 hour, make the diphenylmethanediisocyanate modifier;
B, be cooled to 30～50 ℃, drip the mixed solution that catalyzer and organic solvent are formed,, detect the NCO weight percentage, when reaching set(ting)value, add stopper termination trimerization reaction, be cooled to 50 ℃ every sampling in 0.5～1 hour 30～80 ℃ of reactions;
C, add organic solvent, stir by the requirement of product solid content, discharging, the MDI trimer curing agent;
Wherein each reactant consumption is as follows by weight percentage:
MDI 55～96％
Polyvalent alcohol 4～45%
The weight ratio of consumption of organic solvent and reactant consumption is 2.5～5: 5～7.5;
NCO weight percentage set(ting)value is for removing the part MDI with polyol reaction, remains MDI and carries out trimerization to the percent 90 NCO weight percentage in system when above.
3. curing agent diphenyl methane diisocyanate trimer preparation method according to claim 2, it is characterized in that: its step b can also for: in another reactor, add organic solvent and catalyzer, be warming up to 30～50 ℃, again the diphenylmethanediisocyanate modifier that makes among the step a is added several times, temperature is even in the reinforced process of control, rise slowly, added material in 1～5 hour, 30～80 ℃ of reactions, detect the NCO weight percentage every sampling in 0.5～1 hour, when NCO content reaches set(ting)value, add stopper and stop trimerization reaction, be cooled to 50 ℃.
4. curing agent diphenyl methane diisocyanate trimer preparation method according to claim 2, it is characterized in that: the diphenylmethanediisocyanate described in the step a is 4 of a symmetrical configuration, 4 '-MDI, isomer 2,4 ' MDI, 2, at least a among 2 '-MDI.
5. curing agent diphenyl methane diisocyanate trimer preparation method according to claim 2, it is characterized in that: the polyvalent alcohol described in the step a is polyester polyol, polyether glycol, contain the polyvalent alcohol and the small molecules polyvalent alcohol of two and two above hydroxyls, wherein at least a.
6. according to the curing agent diphenyl methane diisocyanate trimer preparation method described in the claim 5, it is characterized in that: said polyester polyol is poly-hexanodioic acid-ethylene glycol and 1,2-propylene glycol ester dibasic alcohol, poly-hexanodioic acid-butanediol ester dibasic alcohol, poly-sebacic acid-hexanodioic acid-ethylene glycol-DOPCP dibasic alcohol, poly-m-phthalic acid-hexanodioic acid-neopentyl glycol-glycol ether ester dibasic alcohol, polycarbonate diol, polycaprolactone polyol;
Said polyether glycol is polyoxytrimethylene polyvalent alcohol, polyoxyethylene-propylene polyvalent alcohol, polytetrahydrofuran dibasic alcohol;
The said polyvalent alcohol that contains two and two above hydroxyls is Synolac polyvalent alcohol, polybutadiene diol, castor oil polyhydric alcohol, soybean oil polyvalent alcohol.
Said small molecules polyvalent alcohol is the 3-methyl isophthalic acid, 5-pentanediol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,5-pentanediol, diethyl pentanediol, 1,2-propylene glycol, glycol ether, 1,6-hexylene glycol, neopentyl glycol, neopentyl glycol, butyl ethyl propylene glycol, dipropylene glycol, tripropylene glycol, Rutgers 612.
7. curing agent diphenyl methane diisocyanate trimer preparation method according to claim 2, it is characterized in that: the catalyzer described in the step b is the alkaline salt of lithium acetate, potassium acetate, the tertiary phosphine class of tri-n-butyl phosphine, triethyl phosphine, trivinyl diamines, N, the tertiary amines of N-dimethyl benzylamine, wherein at least a, add-on is 0.01～0.5% of a MDI weight.
8. curing agent diphenyl methane diisocyanate trimer preparation method according to claim 2, it is characterized in that: the stopper described in the step b is at least a in Benzoyl chloride, phosphoric acid, methyl tosylate, the methyl-sulfate, and add-on is 0.005～0.3% of a MDI weight.
9. curing agent diphenyl methane diisocyanate trimer preparation method according to claim 2, it is characterized in that: described organic solvent is the ester class of vinyl acetic monomer, N-BUTYL ACETATE, propylene glycol monomethyl ether acetate, the ketone of acetone, butanone, pimelinketone, toluene, dimethylbenzene aromatic hydrocarbons, dioxane, tetrahydrofuran (THF), N, dinethylformamide reaches wherein two or more mixture.
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| CN102517410A (en) * | 2011-11-01 | 2012-06-27 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of novel flame-retardant polyurethane type PU (Polyurethane) tanning agent |
| CN102718724A (en) * | 2012-03-14 | 2012-10-10 | 江苏天竹化工科技有限公司 | Preparation method of environment-friendly and light resistant isocyanate trimer curing agent |
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| CN102517410A (en) * | 2011-11-01 | 2012-06-27 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of novel flame-retardant polyurethane type PU (Polyurethane) tanning agent |
| CN102718724A (en) * | 2012-03-14 | 2012-10-10 | 江苏天竹化工科技有限公司 | Preparation method of environment-friendly and light resistant isocyanate trimer curing agent |
| CN103224605A (en) * | 2013-03-01 | 2013-07-31 | 湖北乾兴化工有限公司 | Polyurethane curing agent with low free isocyanate monomer and preparation method thereof |
| CN104497946A (en) * | 2015-01-26 | 2015-04-08 | 温州泓呈祥科技有限公司 | Adhesive resistant to water and deformation |
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| CN106317373B (en) * | 2015-07-10 | 2021-06-25 | 万华化学（北京）有限公司 | Isocyanate prepolymer and preparation method thereof |
| CN106317373A (en) * | 2015-07-10 | 2017-01-11 | 万华化学（北京）有限公司 | Isocyanate prepolymer and preparation method thereof |
| CN107118328A (en) * | 2017-05-31 | 2017-09-01 | 佛山市高明区首邦化工有限公司 | A kind of light curing agent of low free monomer content and preparation method thereof |
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