CN101747488A - Solvent-free curing agent diphenyl methane diisocyanate prepolymer and preparation method and application thereof - Google Patents
Solvent-free curing agent diphenyl methane diisocyanate prepolymer and preparation method and application thereof Download PDFInfo
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- CN101747488A CN101747488A CN200810236746A CN200810236746A CN101747488A CN 101747488 A CN101747488 A CN 101747488A CN 200810236746 A CN200810236746 A CN 200810236746A CN 200810236746 A CN200810236746 A CN 200810236746A CN 101747488 A CN101747488 A CN 101747488A
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- solvent
- mdi
- curing agent
- methane diisocyanate
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 62
- 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 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003607 modifier Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 150000002009 diols Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- XITBUIKSNALZPJ-UHFFFAOYSA-N N=C=O.N=C=O.C(C=C1)=CC=C1C1=CC=CC=C1.C Chemical compound N=C=O.N=C=O.C(C=C1)=CC=C1C1=CC=CC=C1.C XITBUIKSNALZPJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 150000003384 small molecules Chemical class 0.000 claims description 5
- HEBTZZBBPUFAFE-UHFFFAOYSA-N 2-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=CC=C1S(=O)(=O)N=C=O HEBTZZBBPUFAFE-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 239000011527 polyurethane coating Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- -1 trihydroxyethyl isocyanuric ester Chemical class 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GFMIDCCZJUXASS-UHFFFAOYSA-N hexane-1,1,6-triol Chemical compound OCCCCCC(O)O GFMIDCCZJUXASS-UHFFFAOYSA-N 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010998 test method Methods 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
- SGPMZDLPUCDQQQ-UHFFFAOYSA-N 1-isocyano-3-(2,2,2-trihydroxyethyl)-7,9-dihydropurine-2,6,8-trione Chemical class OC(CN1C(N(C(C=2NC(NC1=2)=O)=O)[N+]#[C-])=O)(O)O SGPMZDLPUCDQQQ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a solvent-free curing agent diphenyl methane diisocyanate prepolymer and a preparation method and application thereof. MDI is added into a reactor, when the temperature is increased to 60 DEG C, the MDI is melted to be mixed, dehydrate divalent alcohol is added to be reacted for 1 to 4 hours under the temperature of 50 to 100 DEG C so as to prepare an MDI modifier; and the temperature is reduced to 55 DEG C, trihydric alcohol is divided to be added and to be reacted for 1 to 6 hours under the temperature of 50 to 100 DEG C; and the temperature is reduced to 60 DEG C, a deicer is added to prepare the product. The divalent alcohol is used for modifying the MDI and then is blended and pre-polymerized with the trihydric alcohol, so the curing agent difficulty of the low-viscosity solvent-free MDI pre-polymer can be solved, different requirements on the solvent-free curing agent from the solvent-free main agent of coat, adhesive agent and the like of the polyurethane industry can be satisfied; moreover, the solvent-free curing agent diphenyl methane diisocyanate prepolymer has the advantages that no solvent pollutes the environment, the strength is high, the viscosity is low, the storage stability is good and the like.
Description
Technical field
The present invention relates to a kind of no-solvent polyurethane coating, adhesive solidification agent and preparation method thereof, is a kind of solvent-free biphenyl methane diisocyanate prepolymer and preparation method thereof specifically.
Background technology
People are medium with the organic solvent at coating and the tackiness agent that polyurethane field adopted for a long time, because of having many advantages, it has obtained using widely, but it in use will have a large amount of solvent discharges every year in atmosphere, cause serious environmental to pollute and the wasting of resources.In the last few years, along with improving constantly of people's environmental protection consciousness, National Environment Policy Act rule and the requirement of setting up conservation-minded society forced the urethane industry that solvent-free manufacturing technology is innovated.Because solvent-free curing agent does not contain solvent,, also developed the solvent-free product of some practicalities in recent years, but biphenyl methane diisocyanate prepolymer class solvent-free curing agent had not been appeared in the newspapers so have characteristics such as the solvent of saving and environmental protection.
Diphenylmethanediisocyanate mainly contains two kinds of isomerss, 4,2 '-MDI and 4,4 '-MDI.Sometimes also contain in the industrialization product a spot of 2,2 '-MDI isomer, its poor-performing, general less use.4 of diphenylmethanediisocyanate, 2 '-MDI isomer, structure is asymmetric, active high several times of 2 NCO groups of 4 NCO group specific activitys, its chemical reaction velocity can finely be controlled; 4, the symmetrical configuration of 4 '-MDI isomer, also exist inductive effect between two NCO groups, promptly the active size of two NCO groups is identical, and all than higher, this makes them be easy to participate in simultaneously reaction, especially under the situation of solvent-free reaction, understand chain-react, viscosity is increased fast, even form gel, promptly its chemical reaction velocity is difficult to control; These two kinds of isomer respectively give goods certain characteristic, 4,4 '-MDI is than 4,2 '-MDI gives the higher intensity of goods, hardness, wear resistance, thermotolerance, curing speed faster, 4,2 '-MDI gives the better snappiness of goods, elasticity, and how these two kinds of isomer being processed into serial solvent-free prepolymer cures agent with various proportionings is the problem that the present invention will solve.
Summary of the invention
The purpose of this invention is to provide a kind of solvent-free curing agent diphenyl methane diisocyanate prepolymer and its production and application.It is pure 4 that the present invention adopts, 4 '-diphenylmethanediisocyanate, or with 4,2 '-and 4,4 '-diphenylmethanediisocyanate mixes with any proportioning, makes a series of MDI prepolymer solvent-free curing agents.
Product of the present invention is a kind of mixed prepolymer, and its signal modular construction formula is:
In the formula: R is alkyl, the phenyl or derivatives thereof of dibasic alcohol, R
1Alkyl, phenyl or derivatives thereof for trivalent alcohol.
The product index of mixed prepolymer of the present invention following (following content all is weight percentage):
(1) outward appearance; Light yellow transparent liquid;
(2) viscosity: 1000～15000mpa.s (25 ℃);
(3) NCO content: 6～22%;
(4) storage period: half a year.
Preparation method of the present invention and step thereof comprise:
A, in reactor, add diphenylmethanediisocyanate, be warming up to about 60 ℃ its fusing is stirred evenly, add dibasic alcohol,, make the MDI modifier 50～100 ℃ of reactions 1～4 hour down through dehydration;
B, be cooled to about 50 ℃, add trivalent alcohol, added in 1～4 hour, at 50～100 ℃, insulation reaction 1～6 hour is cooled to 60 ℃; C, adding water-removal agent fully stir, and discharging gets solvent-free biphenyl methane diisocyanate prepolymer solidifying agent;
Wherein each reactant consumption is as follows by weight percentage:
Diphenylmethanediisocyanate 50～86%
Dibasic alcohol 5～45%
Trivalent alcohol 4～15%
Water-removal agent 0～5%
Among the step a, design raw material feed ratio NCO/OH＞2, under the excessive greatly situation of NCO, the diphenylmethanediisocyanate in the reactor is existing 4,4 '-MDI, have 4 again, 2 '-MDI, and two NCO groups of 4,4 '-MDI is active high, it at first generates a kind of novel substance 4,4 '-MDI modifier with diol reaction.
4,4 '-MDI and diol reaction make 4, and the chemical equation of 4 '-MDI modifier is:
In the formula: R is alkyl, the phenyl or derivatives thereof of dibasic alcohol.
Among the step b, 4,4 '-MDI modifier, 4,2 '-and 4, the chemical equation that 4 '-MDI mixture and trivalent alcohol reaction make the MDI mixed prepolymer is:
In the formula: R is alkyl, the phenyl or derivatives thereof of dibasic alcohol, R
1Alkyl, phenyl or derivatives thereof for trivalent alcohol.
From (B) formula as can be seen the present invention prepolymer, introduced dibasic alcohol and trivalent alcohol structure, primary product is (B-1) formula, (B-2) formula and (B-3) formula, and 4,2 '-MDI and 4,4 '-MDI is the mixed structure of arrangement alternately.If do not have 4 in the raw material, 2 '-MDI has only 4, and 4 '-MDI then also has only 4 in the structural formula, and 4 '-MDI occurs.The present invention by introduce different dibasic alcohol can make different 4,4 '-MDI modifier, in conjunction with 4,2 '-MDI and 4, proportioning that 4 '-MDI is different and different trivalent alcohols can make a series of MDI prepolymer solvent-free curing agents.
Among the step a, described diphenylmethanediisocyanate can be pure 4,4 '-diphenylmethanediisocyanate, or 2,2 ', 4,2 '-and 4,4 '-diphenylmethanediisocyanate is with the mixture of any weight percent.
Described dibasic alcohol is a polyester diol, polyether Glycols, other dibasic alcohol, the oligopolymer and the small molecules dibasic alcohol that contain two active hydrogens, as poly-hexanodioic acid-1,4-butanediol ester glycol, polycaprolactone glycol, polycarbonate diol, polyoxypropyleneglycol, polytetrahydrofuran diol, the Synolac glycol, polybutadiene diol, Polybutadiene-acrylonitrile copolymerization glycol, the 3-methyl isophthalic acid, 5-pentanediol micromolecular dibasic alcohol, the modified vegetable oil dibasic alcohol, and two or more contains the mixture of dihydroxylic material, they can be with 4,4 '-MDI reaction makes 4,4 '-MDI modifier.
Reaction formula (A), 4,4 '-diphenylmethanediisocyanate and diol reaction make series 4, and the effect of 4 '-MDI modifier is to reduce by 4, the activity of 4 '-MDI two ends NCO group.Because of 4,4 '-MDI symmetrical configuration, two NCO groups active identical, the inductive effect that produces mutually between them makes activity very high, promptly two NCO groups are easy to participate in fast simultaneously reaction, form chain reaction, and viscosity is sharply increased, even the generation gel.The present invention by dibasic alcohol 4,4 '-MDI changes system into 4,4 '-MDI modifier, because the existence of R base, the inductive effect between two NCO groups disappears active decline, when one of them-NCO continue with trivalent alcohol-during the OH reaction, the resistance that R base produces and the activity of reduction all will hinder another-and NCO participates in reaction, thus this group can be remained, avoided the chain reaction generation.
From reaction formula (B) as can be seen, 4,4 '-MDI modifier molecular ratio is bigger, activity is difficulty relatively, there be mixed and disorderly, the state of disarray that produces in big and small molecule in the system in addition, when an end-NCO and trivalent alcohol-the OH reaction after, can hinder another-NCO and-reaction of OH; 4, two NCO group activity of 2 '-MDI differ several times, active high one-NCO earlier with trivalent alcohol-OH reaction after, by CONTROL PROCESS can with another-NCO remains; Dibasic alcohol and trivalent alcohol structure that the present invention introduces, upset the regularly arranged of MDI mixed prepolymer molecule, make it become unformed character, so can produce the serial MDI prepolymer cures agent of the solvent-free low viscosity (25C is about 1000～15000mpa.s) among the step c.
Among the step b, be cooled to about 55 ℃, the effect that gradation adds trivalent alcohol is to slow down heat release.Described trivalent alcohol is the small molecules polyvalent alcohol with three hydroxyls, as TriMethylolPropane(TMP), trimethylolethane, glycerol, 1,2, and 6-hexanetriol, trihydroxyethyl isocyanuric ester, and two or more contains the mixture of trihydroxylic material.
Among the step c, add water-removal agent, continue reaction more than 10 minutes, discharging.
Among the step c, the effect that adds water-removal agent is the moisture of removing in the reaction product, improves storage property, reaches the blushing that ambient moisture causes too greatly when preventing to use.
The said water-removal agent of the present invention comprise to Methyl benzenesulfonyl isocyanate, triethyl orthoformate, Benzoyl chloride, molecular sieve powder any, two or more mixture.
Biphenyl methane diisocyanate prepolymer of the present invention can be mixed with double-component polyurethane coating, tackiness agent etc. with solvent-free component such as the polyester that contains reactive hydrogen, polyethers, alkyd, vinylformic acid, silicone resin, also can be used as other purposes, can also add organic solvent and make the solvent-borne type solidifying agent at the isocyanate group and the moisture content generation curing reaction of solidifying agent under the wet environment.
The present invention produces a series of MDI prepolymer solvent-free curing agents with MDI, dibasic alcohol, trivalent alcohol, not only solved a process for machining and manufacturing difficult problem, but also can utilize enterprise to have the equipment of producing the TDI solidifying agent now, and need not to drop into new installation, be convenient to enterprise and change the line of production to solvent-free MDI solidifying agent.The present invention is mixed with double-component polyurethane coating, tackiness agent etc. with the polyester that contains solvent-free hydroxyl component, polyethers, alkyd, vinylformic acid, silicone resin etc., can not only satisfy the different curing process requirements of user, but also give performances such as goods intensity preferably, hardness, wear-resisting, heatproof, range of application is very extensive.
The present invention compared with prior art has following advantage: one, toxicity is low.The present invention's 100% solid solventless has solved the solvent discharge environmental pollution problem, has saved the production cost of solvent simultaneously.Two, excellent storage stability.MDI of the present invention and dibasic alcohol and trivalent alcohol react, and generate macromolecular structure, have avoided the dimerization of MDI isocyanic ester in depositing process and solidifying agent gluing or the spoilage problems that trimerization reaction brings.Three, structure design innovation.The present invention reacts with trivalent alcohol with the modification MDI of dibasic alcohol elder generation again, and innovative design goes out the method that a cover is made serial MDI prepolymer molecular structure, has solved MDI and has made a solvent-free curing agent difficult problem.Four, technology advanced person.Whole technological process temperature of reaction is all below 100 ℃, and enterprise can utilize the equipment of the existing TDI of production solidifying agent, need not to drop into new installation, is convenient to enterprise and produces in batches.Five, use good manufacturability.Serial MDI solvent-free curing agent of the present invention can with the supporting use of solvent-free host of the paint that contains reactive hydrogen, coating etc., have coating viscosity low characteristics.Six, applied range.4, the add-on of 4 '-MDI can increase and decrease arbitrarily, and it gives the strength ratio 4 of goods, 2 '-MDI height, but 4, and it is better that 2 '-MDI gives the elasticity of goods, so the present invention gives the broader mechanical property of goods, higher temperature tolerance and better wear resistance.
In order to implement the present invention better, the present invention is further illustrated now to enumerate following embodiment.
Embodiment
Embodiment 1
A, add 380 gram MDI-100 in reactor, be warming up to about 65 ℃ its fusing is stirred evenly, add through vacuumizing 50 gram polytetrahydrofuran diols of dehydration, 50～60 ℃ of reactions 1 hour down, 70～80 ℃ of reactions 1 hour down make the MDI modifier; B, be cooled to 60 ℃, divide the 46 gram TriMethylolPropane(TMP)s that add fusing for 3 times, add in 3 hours, 50～60 ℃ of reactions 1 hour, 70～80 ℃ of reactions 1 hour, 80～90 ℃ of reactions 1.5 hours are cooled to 60 ℃; C, add 2 gram Benzoyl chloride water-removal agents, continue to stir 15 minutes, discharging, 478 gram viscosity are the solvent-free MDI prepolymer cures agent of 4500mpa.s (25 ℃), the NCO content of this solidifying agent is 16.5% after testing.
Annotate: 1, detect NCO content and 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 ".
2, detect the mensuration of viscosity by National Standard GB/T2794-1995 tackiness agent viscosity " carry out.
3, MDI-100 be 100% 4,4 '-MDI, MDI-50 are 4,2 '-MDI and 4,4 '-MDI respectively account for 50%.
Embodiment 2
A, add 150 gram MDI-50 in reactor, be warming up to about 55 ℃ it is stirred evenly, add through vacuumizing 100 gram polycaprolactone glycols of dehydration, 50～60 ℃ of reactions 1.5 hours down, 70～80 ℃ of reactions 1 hour make the MDI modifier; B, be cooled to below 50 ℃, divide to add 11.8 gram solid trimethylolethanes for 2 times, added in 2 hours, 50～60 ℃ of reactions 2 hours, 70～80 ℃ of reactions 1 hour 80～90 ℃ of reactions 1.5 hours, were cooled to 60 ℃; C, add 1.5 grams, continue to stir 10 minutes the Methyl benzenesulfonyl isocyanate water-removal agent, discharging, 263.3 gram viscosity are the solvent-free MDI prepolymer cures agent of 12500mpa.s (25 ℃), the NCO content of this solidifying agent is 10.2% after testing.
Embodiment 3
A, in reactor, add 160 gram MDI-100 and 100 gram MDI-50, being warming up to 60 ℃ stirs evenly its fusing, adding is through vacuumizing 22 gram 3-methyl isophthalic acids of dehydration, the 5-pentanediol, reacted 2 hours down at 50～60 ℃, 70～80 ℃ were reacted 1 hour, and 80～90 ℃ were reacted 0.5 hour down, make the MDI modifier; B, be cooled to below 45 ℃, divide to add 20 grams 1,2 for 3 times, 6-hexanetriol liquid added in 3 hours, and 45～55 ℃ of reactions 1.5 hours, 65～75 ℃ of reactions 2 hours 85～95 ℃ of reactions 1 hour, were cooled to 60 ℃; C, add 2.5 gram triethyl orthoformate water-removal agents, continue to stir 12 minutes, discharging, 304.5 gram viscosity are the solvent-free MDI prepolymer cures agent of 1200mpa.s (25 ℃).
Embodiment 4
A, in reactor, add 150 gram MDI-100 and 220 gram MDI-50, be warming up to 50 ℃ its fusing stirred evenly, add through vacuumizing 38 gram phthalic anhydride glycol of dehydration, reacted 1 hour down at 45～55 ℃, 65～75 ℃ were reacted 1.5 hours, and 80～90 ℃ were reacted 1 hour down, make the MDI modifier; B, be cooled to 50 ℃, divide to add 24 gram glycerol liquid for 3 times, add in 2.5 hours,,, be cooled to 60 ℃ 70～80 ℃ of reactions 1 hour 50～60 ℃ of reactions 2 hours; C, discharging, getting 432 gram viscosity is the solvent-free MDI prepolymer cures agent of 4500mpa.s (25 ℃), the NCO content of this solidifying agent is 18.5% after testing.
Embodiment 5
A, in reactor, add 180 gram MDI-100 and 150 gram MDI-50, being warming up to 65 ℃ stirs evenly its fusing, 80 gram polyoxypropyleneglycols and the 70 gram polycaprolactone glycols of adding through vacuumizing dehydration, reacted 2 hours down at 55～65 ℃, 70～80 ℃ were reacted 1 hour, 80～90 ℃ were reacted 0.5 hour down, make the MDI modifier; B, be cooled to 60 ℃, divide and add 10 gram solid trihydroxyethyl isocyanuric esters for 2 times, react after 1 hour, divide again and add 26 gram solid TriMethylolPropane(TMP)s for three times, add in 2 hours, 55～65 ℃ of reactions 1.5 hours, 70～80 ℃ were reacted 1.5 hours, 85～95 ℃ of reactions 1 hour, be cooled to 60 ℃; C, add 2.8 grams, continue to stir 15 minutes Methyl benzenesulfonyl isocyanate and 1.2g Benzoyl chloride water-removal agent, discharging, 520 gram viscosity are the solvent-free MDI prepolymer cures agent of 6200mpa.s (25 ℃).
Application Example 1
Product 35 grams of embodiment 2 and hydroxyl component 100 grams of PU coating mix, and the coating lacquer film properties that makes is as follows: dryness: 25 ℃, surface drying time 30 minutes is done solid work 4 hours time; Test performance after 2 days: hardness: Shao Shi D62; Shock strength: 45KJ/m2 (being undertaken) by GB/T 2571-1995; Sticking power, the 1-2 level.
Application Example 2
Product 40 grams of embodiment 3 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 24 hours after, carry out T type peeling strength test by/T 2791-1995 " tackiness agent T peeling strength test method flexible material is to flexible material ", stripping strength is 1150g/15mm, and the laminated film behind cooking test does not find that film has separation phenomenon.
Application Example 3
Product 30 grams of embodiment 5 and package compound are mixed with hydroxyl component 100 grams of polyurethane adhesive, be used for the compound of PET aluminium plating film and CPP film, the performance that makes composite membrane is as follows: solidify under 25 ℃ of room temperatures 8 hours can the branch sanction, in 50 ℃ solidify 24 hours after, press GB/T 2790-1995 " 180 ° of peeling strength test methods of tackiness agent, flexible material is to rigid material " carry out 180 ° of peeling strength tests, the PET aluminium plating film is torn.
Claims (9)
1. solvent-free curing agent diphenyl methane diisocyanate prepolymer is characterized in that: its signal modular construction formula comprises:
With
With
Wherein R is alkyl, the phenyl or derivatives thereof of dibasic alcohol, R
1Alkyl, phenyl or derivatives thereof for trivalent alcohol;
The product index of this prepolymer is as follows, and following content all is weight percentage:
(1) outward appearance: light yellow transparent liquid;
(2) viscosity: 1000～15000mpa.s (25 ℃);
(3) NCO content: 6～22%.
2. the preparation method of a solvent-free curing agent diphenyl methane diisocyanate prepolymer, its step comprises:
A, in reactor, add diphenylmethanediisocyanate, be warming up to about 60 ℃ its fusing is stirred evenly, add dibasic alcohol,, make the MDI modifier 50～100 ℃ of reactions 1～4 hour down through dehydration;
B, be cooled to about 50 ℃, add trivalent alcohol, added in 1～4 hour, at 50～100 ℃, insulation reaction 1～6 hour is cooled to 60 ℃;
C, discharging get solvent-free biphenyl methane diisocyanate prepolymer solidifying agent;
Wherein each reactant consumption is as follows by weight percentage:
Diphenylmethanediisocyanate 50～86%
Dibasic alcohol 5～45%
Trivalent alcohol 4～15%
Water-removal agent 0～5%.
3. the preparation method of a kind of solvent-free curing agent diphenyl methane diisocyanate prepolymer according to claim 2, it is characterized in that: among the step a, described diphenylmethanediisocyanate can be pure 4,4 '-diphenylmethanediisocyanate, or 2,2 ', 4,2 '-and 4,4 '-diphenylmethanediisocyanate is with the mixture of any weight percent.
4. the preparation method of a kind of solvent-free curing agent diphenyl methane diisocyanate prepolymer according to claim 2, it is characterized in that: among the step a, described dibasic alcohol is a polyester diol, polyether Glycols, other dibasic alcohol, the oligopolymer and the small molecules dibasic alcohol that contain two active hydrogens, as poly-hexanodioic acid-1,4-butanediol ester glycol, polycaprolactone glycol, polycarbonate diol, polyoxypropyleneglycol, polytetrahydrofuran diol, the Synolac glycol, polybutadiene diol, Polybutadiene-acrylonitrile copolymerization glycol, the 3-methyl isophthalic acid, 5-pentanediol micromolecular dibasic alcohol, the modified vegetable oil dibasic alcohol, and two or more contains the mixture of dihydroxylic material.
5. the preparation method of a kind of solvent-free curing agent diphenyl methane diisocyanate prepolymer according to claim 2, it is characterized in that: among the step b, the method that adds trivalent alcohol is that gradation adds, and the trivalent alcohol of adding is liquid, fusing or solid trivalent alcohol.
6. the preparation method of a kind of solvent-free curing agent diphenyl methane diisocyanate prepolymer according to claim 2, it is characterized in that: among the step b, described trivalent alcohol is the small molecules polyvalent alcohol with three hydroxyls, as TriMethylolPropane(TMP), trimethylolethane, glycerol, 1,2,6-hexanetriol, trihydroxyethyl isocyanuric ester, and two or more contains the mixture of trihydroxylic material.
7. the preparation method of a kind of solvent-free curing agent diphenyl methane diisocyanate prepolymer according to claim 2 is characterized in that: among the step c, before the discharging, add water-removal agent, stir, continue reaction more than 10 minutes.
8. according to the preparation method of claim 2 or 7 described a kind of solvent-free curing agent diphenyl methane diisocyanate prepolymers, it is characterized in that: among the step c, described water-removal agent comprise to Methyl benzenesulfonyl isocyanate, triethyl orthoformate, Benzoyl chloride, molecular sieve powder any, two or more mixture.
9. the application of a solvent-free curing agent diphenyl methane diisocyanate prepolymer, it is characterized in that: biphenyl methane diisocyanate prepolymer of the present invention can be mixed with double-component polyurethane coating, tackiness agent with the polyester that contains reactive hydrogen, polyethers, alkyd, vinylformic acid, the solvent-free component of silicone resin, also can be used as other purposes, can also add solvent and make the solvent-borne type solidifying agent in isocyanate group under the wet environment and moisture content generation curing reaction.
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