CN101906204B - Performed polymer based on methyl diphenylene diisocyanate as polyurethane coating curing agent and preparation method thereof - Google Patents
Performed polymer based on methyl diphenylene diisocyanate as polyurethane coating curing agent and preparation method thereof Download PDFInfo
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- CN101906204B CN101906204B CN201010250479.6A CN201010250479A CN101906204B CN 101906204 B CN101906204 B CN 101906204B CN 201010250479 A CN201010250479 A CN 201010250479A CN 101906204 B CN101906204 B CN 101906204B
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- diphenylene diisocyanate
- methyl diphenylene
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- 0 CCC(C)(*)OC(Nc1ccc(Cc(cc2)ccc2N=C=O)cc1)=O Chemical compound CCC(C)(*)OC(Nc1ccc(Cc(cc2)ccc2N=C=O)cc1)=O 0.000 description 1
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Abstract
The present invention relates to a kind of performed polymer based on methyl diphenylene diisocyanate as polyurethane coating curing agent and preparation method thereof, described prepolymer comprises (a) and derives from the product (a) that excess methyl diphenylene diisocyanate is less than the ternary primary alconol of 200 with molecular weight；(b) product (b) that excess methyl diphenylene diisocyanate is less than the binary secondary alcohol of 200 with molecular weight is derived from, wherein, the mole ratio of described product (a) and described product (b) is in the range of 4/9～8/3: 1, and wherein, described methyl diphenylene diisocyanate comprises relative to the gross weight of described methyl diphenylene diisocyanate: the 4 of 40% to 100%, 4 '-methyl diphenylene diisocyanate；The 4 of 0% to 55%, 2 '-methyl diphenylene diisocyanate；With 0% to 5% 2,2 '-methyl diphenylene diisocyanate.
Description
The application is filing date December in 2008 17, Application No. 200810029535.6, invention entitled " as
Performed polymer based on methyl diphenylene diisocyanate of polyurethane coating curing agent and preparation method thereof " application for a patent for invention
Divisional application.
Technical field
The present invention relates to a kind of performed polymer based on methyl diphenylene diisocyanate as polyurethane coating curing agent
And preparation method thereof.
Background technology
At present, the production method of domestic the most frequently used polyurethane coating curing agent is to use trimethylolpropane and toluene two
Isocyanates reaction generates performed polymer.In performed polymer production process, there is the toluene di-isocyanate(TDI) residual failing to react, due to
The vapour pressure of monomer toluene di-isocyanate(TDI) is of a relatively high, and 2,4 toluene diisocyanate is 1.3*10 when 20 DEG C-2mbar；2,
6-toluene di-isocyanate(TDI) is 1.3*10 when 20 DEG C-2Mbar, and toluene diisocyanate vapor toxicity is bigger, it is necessary in pre-polymerization
It is removed after thing preparation.But, the step for of being generally not desirable to based on cost consideration, and free toluene in performed polymer
Diisocyanate is the most also difficult to completely remove, therefore toluene di-isocyanate(TDI) performed polymer in the market still contains a certain amount of
Free toluene diisocyanate.Then people begin attempt to the methyl diphenylene diisocyanate to force down based on steam, and they are 20 years old
DEG C time be 4.0*10-4The similar system substituent group of mbar is in the system of toluene di-isocyanate(TDI).
Methyl diphenylene diisocyanate is owing to degree of functionality is too low, its acetic ester solution bin stability is the best and and hydroxyl
Acrylic resin and the alkyd resin compatibility are the best, are not suitable for directly as polyurethane coating curing agent.
Poly methylene poly phenyl poly isocyanate is relatively deep due to color, is also not suitable for solidifying directly as polyurethane coating
Agent.
The synthetic method of methyl diphenylene diisocyanate performed polymer is the most widely reported, generally uses polyethers to diphenylmethyl
Alkane diisocyanate carries out addition, for example, see the one disclosed in Chinese patent literature CN1724576A is based on 2,4 '-MDI
Low-viscosity polyurethane prepolymers, a kind of disclosed in Chinese patent literature CN1232555C has low MDI monomer content
MDI base polyurethane prepolymer, the polyurethane prepolymer of a kind of stable storing disclosed in Chinese patent literature CN100372880C
Body and preparation method thereof, a kind of allophanate-modified stable liquid two disclosed in Chinese patent literature CN1878816A
Methylenebis phenyl isocyanate trimer and prepolymer thereof and their preparation method, Chinese patent literature CN100368454C
Disclosed in the polymerization allophanate of a kind of novel methyl diphenylene diisocyanate and prepolymer, and their preparation
Method, reactive polyurethane adhesion promotor of a kind of monomer-free disclosed in Chinese patent literature CN1256359C etc.,
These patent documentations not mentioned, whether whether these performed polymers can not mentioned yet testing as polyurethane coating curing agent
The base of the polyurethane coating curing agents such as the compatibility of its acetic ester solution bin stability and alkyd resin and acrylic resin
This performance.Under normal circumstances, firming agent and the compatibility of resin refer to after firming agent and mixed with resin are uniformly the most as clear as crystal, clearly
Clear transparent good for the compatibility, become turbid and can not pass through for the compatibility.Further, above Patents document does not all account for two
The application in polyurethane coating of the methylenebis phenyl isocyanate performed polymer.
Our method as mentioned by patent documents above carries out the synthesis of methyl diphenylene diisocyanate performed polymer, sends out
The most all can not store with the form stable of 50% butyl acetate solution, major part performed polymer can not lead to the compatibility of alkyd resin
Crossing, wherein, alkyd resin is as a example by the AP572 of the quality preferably SAPICI company of Italy generally acknowledged the most in the industry；All pre-
Aggressiveness all can not pass through with the compatibility of Hydroxylated acrylic resin, and wherein, Hydroxylated acrylic resin is with the matter generally acknowledged the most in the industry
Measure preferable Bayer A.GAs a example by A 450BA/X.
It addition, Chinese patent literature CN1116327C discloses a kind of coating curing agent: trimethylolpropane and castor
Oleum Sesami carries out alcoholysis reaction, alcoholysis product and 4, and the reaction of 4 '-methyl diphenylene diisocyanate obtains coating curing agent.But due to
The color of Oleum Ricini adds high temperature alcoholysis, and products therefrom color and luster is deeper.Chinese patent literature CN1116328C discloses
A kind of by trimethylolpropane and 4,2 '-and 4, the polyurethane that the reaction of 4 '-mixtures of diisocyanates and diphenylmethane obtains is coated with
Material firming agent, wherein, 4, the consumption of 2 '-methyl diphenylene diisocyanate account for the percentage by weight of whole consumption be 40%～
60%.Its acetic ester solution bin stability is tested by these two patent documentations, it is also considered that cross the application in coating,
But, the test in life-span of constructing after all not carrying out joining paint in above Patents document.
It is uniform that the construction life-span is often referred to firming agent and mixed with resin, and after be transferred to be suitable for the viscosity of construction with solvent, viscosity
Usually rock field cup 12s, viscosity doubles the required time.We press Chinese patent literature CN1116327C and
The method that CN1116328C is provided carries out firming agent synthesis, the test construction life-span after mixing with alkyd resin, wherein, and alkyd tree
Fat is as a example by the AP572 of the quality preferably SAPICI company of Italy generally acknowledged the most in the industry, and the life-span of constructing when 25 DEG C is respectively 1
Hour and 70 minutes, when 30 DEG C construct the life-span be respectively 30 minutes and 35 minutes, after mixing with Hydroxylated acrylic resin test execute
In the work life-span, wherein, Hydroxylated acrylic resin is with the preferable Bayer A.G of quality the most generally acknowledgedAs a example by A 450BA/X, the life-span of constructing when 25 DEG C is respectively 40 minutes and 50 minutes, constructs the life-span when 30 DEG C
It is respectively 15 minutes and 25 minutes；But, the construction life-span of bicomponent polyurethane coating usually requires that more than 1 hour, best
More than 2 hours, this construction life-span mostly come from concrete Construction practices and sums up, " the spray polyurea of such as Huang Weibo chief editor
Elastomeric technology " page 109 the second nature section the 6th row the most once mentioned " substituted radicals by different ", polyaspartate
Sprayed on material mixed with HDI trimer " the construction life-span can extend to more than 2h from 5min ", and in the first paragragh
Second row is mentioned, before construction life " the preferable engineering time expected from people also has a certain distance ".More than in literary composition
The secondary benefit mentioning construction life: beneficially " sprayed protection equipment subtracts as page 96 the 7th row mentions engineering time prolongation
Blocking up the probability of rifle phenomenon and maintenance shut-downs less, efficiency of construction improves "；In page 113 application example (the second nature section the third line)
After mentioning engineering time prolongation " dual component material first mixes, rear roller coating technology is constructed to allow employing "；P113 page second certainly
System after so section the 6th row also mentions engineering time prolongation " uses conventional spray guns just can construct ".And two component polyurethane is coated with
Material main construction method be exactly dual component material first mix, after carry out conventional spray guns construction, client is to this coating application life-span
Usually require that more than 1 hour, more preferably greater than 2 hours.Wherein, " spray Polyurea Elastomer Technology " is by Chemical Industry Press
Materials Science and Engineering publishing centre is published, and Xinhua Bookstore's Beijing sale room sells, Beijing cloud great printing Co., Ltd because of
Element, in July, 2005 first edition, in July, 2005 Beijing the 1st time printing.
Summary of the invention
The purpose of the present invention aims to provide that a kind of lighter color, toxicity is low, excellent storage stability and alkyd resin and acrylic acid
Resin compatible good and join life-span length of constructing after paint, construction effect good as polyurethane coating curing agent based on diphenyl
Performed polymer of methane diisocyanate and preparation method thereof, to overcome weak point of the prior art.
A kind of based on methyl diphenylene diisocyanate pre-as polyurethane coating curing agent designed by this purpose
Aggressiveness, is characterized in that with acetates as solvent, and by the molecular weight little molecule ternary primary alconol less than 200, molecular weight is less than 200
Little molecule binary secondary alcohol, reacts with substance A and generates,
Ternary primary alconol refers to that three hydroxyls are all the trihydroxylic alcohol of primary hydroxyl, and binary secondary alcohol refers to that two hydroxyls are all secondary hydroxyl
Dihydroxylic alcohols,
Described little molecule ternary primary alconol, the equivalent proportion of little molecule binary secondary alcohol and substance A is little molecule ternary primary alconol: little
Molecule binary secondary alcohol: substance A is 0.4～0.8: 0.2～0.6: 2.1,
As solvent acetates consumption with as the little molecule ternary primary alconol of reactant, little molecule binary secondary alcohol and
The weight ratio of the consumption of the total of substance A is 30～60: 40～70,
Wherein, substance A contains: (1) 40%～the 4 of 100%, 4 '-methyl diphenylene diisocyanate, (2) 0%～55%
4,2 '-methyl diphenylene diisocyanate, and (3) 0%～the 2 of 5%, 2 '-methyl diphenylene diisocyanate, with weight hundred
Proportion by subtraction meter.
Described little molecule ternary primary alconol is 1,1,1-trimethylolpropane and/or 1,1,1-trimethylolethane.
Described little molecule binary secondary alcohol is 2,4-pentanediol, 2,5-hexanediol, dipropylene glycol, any one in tripropylene glycol
Kind or more than one mixture.
The solvent of described acetates is ethyl acetate, butyl acetate, ethylene glycol ether acetate, propylene glycol monomethyl ether acetic acid
Any one or more than one mixture in ester.
A kind of preparation method of the performed polymer based on methyl diphenylene diisocyanate as polyurethane coating curing agent,
It is characterized in that by little molecule ternary primary alconol, little molecule binary secondary alcohol respectively at 105～115 DEG C, vacuum dehydration 2～treat for 4 hours
With, it is ensured that its moisture is less than 0.04%, under nitrogen protection, the solvent of substance A and acetates is first put into reaction and holds
In device and stir, maintain temperature at 50～70 DEG C, less molecule ternary primary alconol is slowly dropped in reactor, dripped
Cheng Zhong, is kept stirring for so that material is uniform in reactor, drip and complete follow-up continuing react 1 under stirring at 50～75 DEG C
～5 hours, then little molecule binary secondary alcohol is slowly dropped in reactor, during dropping, be kept stirring in reactor with
Make material uniform, drip and react 1～5 hour at 50～75 DEG C under stirring complete follow-up continuing, be cooled to less than 40 DEG C
Or room temperature discharging.
The time for adding of described little molecule ternary primary alconol is 0.5 hour to 4 hours.
The time for adding of described little molecule ternary primary alconol is 1 hour to 2 hours.
The time for adding of described little molecule binary secondary alcohol is 1 hour to 4 hours.
The time for adding of described little molecule binary secondary alcohol is 2 hours to 3 hours.
The polyurethane coating curing agent second day sample analysis after cooling discharge as above: with standard GB/T/
The method that T3143-1982 specifies measures the color and luster of firming agent；Measure with the method that standard GB/T/T12009.3-1989 specifies
Firming agent viscosity at 25 DEG C, the method specified with GB/T12009.4-1989 measures the NCO content of firming agent, samples simultaneously
Sealed type storage is observed in the calorstat of 5 DEG C, 25 DEG C and 50 DEG C respectively.
Firming agent compatibility test: firming agent sample with resin by NCO: OH=1: 1 mixs homogeneously, and transparent liquid is phase
Capacitive is good, if muddiness, can not pass through for the compatibility.Resin is respectively Hydroxylated acrylic resin and alkyd resin, hydroxy
Acid resin chooses Bayer A.GA 450BA/X, alkyd resin chooses SAPICI company of Italy
AP572。
Construction life test: firming agent sample with resin by NCO: OH=1: 1 mixs homogeneously, add n-butyl acetate tune viscosity
To rock field cup 12s, viscosity doubles, and the time of i.e. 24 seconds is the construction life-span.
Paint film property is tested: firming agent sample and Hydroxylated acrylic resin, and it is public that Hydroxylated acrylic resin chooses Bayer Bitterfeld GmbH
DepartmentA 450BA/X, by NCO: OH=1: 1 mix homogeneously, by GB 1727-79 spraying process at tinplate
Upper painting film, as coating surface has shrinkage cavity, bubble, pinprick, can add a small amount of auxiliary agent and control.When being dried by GB/T 1728-79 test
Between, surface drying uses fingers-touch method, does solid work employing pressure filter paper method；Paint film property is tested: by GB/T 1720-79 test paint after 48 hours
Film adhesive force；Paint film flexibility is tested by GB/T 1731-93；Paint film resistance to impact is tested by GB/T 1732-93；By GB/T
6739-2006 tests hardness of paint film.
The clear appearance of the polyurethane coating curing agent prepared by the present invention is transparent, and color and luster is not more than No. 20 platinum cobalt colors, NCO
Content according to the difference of non-volatile part between 5.5～11.5；After storing 30 days at 5 DEG C, outward appearance is the most as clear as crystal, and color and luster is less than
No. 20 platinum cobalt colors；50 DEG C storage 30 days after outward appearance the most as clear as crystal, color and luster be less than No. 50 platinum cobalt colors, NCO content decline 0.4%
Within, viscosity build is within 20%；25 DEG C storage 1 year after outward appearance the most as clear as crystal, color and luster be less than No. 50 platinum cobalt colors, NCO contains
Amount declines within 0.3%, and viscosity build is within 15%.
The polyurethane coating curing agent that the present invention prepares is equal with the compatibility of Hydroxylated acrylic resin and alcohol alcohol resin respectively
Well；The construction life-span: 1) 25 DEG C time the construction life-span: be 3～3.5 hours after mixing with Hydroxylated acrylic resin, with alkyd resin
Be 3.5～4 hours after mixing, 2) 30 DEG C time the construction life-span: be 100～120 minutes after mixing with Hydroxylated acrylic resin, with alcohol
It it is 2～2.5 hours after acid resin mixing.
The firming agent paint film property test that the present invention prepares is as follows: surface drying time is 25～30 minutes；The time of doing solid work is 24
Hour；Paint film adhesion is 1～2 grade；Paint film flexibility 1mm；Paint film resistance to impact 50cm；Hardness of paint film H～2H.
The present invention compares polyurethane coating curing agent based on toluene diisocynate, has the advantages that product toxicity is low, by
Using 4 in the present invention, 4 '-methyl diphenylene diisocyanate prepares firming agent as raw material, at normal temperatures diphenyl methane two
The vapor pres-sure of isocyanates is low more than toluene di-isocyanate(TDI), and performed polymer toxicity the most of the present invention is relatively low.
The present invention is on the premise of taking into full account firming agent applicable cases, by rationally selecting and optimizing the kind of alcohol and join
Ratio, and optimum synthesis technique, use the technique that trihydroxylic alcohol, dihydroxylic alcohols successively drip respectively so that the polyurethane that the present invention prepares
Coating curing agent has a relatively low color and luster, preferable shelf characteric, 25 DEG C of sealed type storages after 1 year outward appearance the most as clear as crystal, color and luster
Less than No. 50 platinum cobalt colors, NCO content declines within 0.3%, and viscosity build is within 15%.
By alcohol and the optimization of synthesis technique, the polyurethane based on methyl diphenylene diisocyanate that the present invention prepares is coated with
Material firming agent is good with Hydroxylated acrylic resin and the alkyd resin compatibility, and has obtained the longer construction life-span.
The present invention uses 4,4 '-methyl diphenylene diisocyanate, or 4,4 '-and 4,2 '-diphenylmethane diisocyanate
The mixture of ester makees raw material synthesis of polyurethane coating curing agent, and this raw material sources is extensive, wherein, 4,4 '-diphenyl methane
Diisocyanate price relatively 4,2 '-methyl diphenylene diisocyanate and 4, the mixture of 4 '-methyl diphenylene diisocyanate
For low, the former apparent availability is also sufficient more than the latter.
The present invention uses the trihydroxylic alcohol of molecular weight and dihydroxylic alcohols to methyl diphenylene diisocyanate addition, it is to avoid make
By the bigger polyethers of molecular weight, polyester, oils, when making the lacquering of firming agent of synthesis, rate of drying is very fast, and hardness is higher.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
First embodiment
By the 1 of 26.8kg, 1,1-trimethylolpropane is true at 105 DEG C～115 DEG C respectively with the dipropylene glycol of 26.8kg
Empty dehydration 2～4 hours is stand-by,
Now, the equivalent proportion of 1,1,1-trimethylolpropane and dipropylene glycol is 6: 4,
Ensure that its moisture is less than 0.04%.Under nitrogen protection, by the methyl diphenylene diisocyanate of 262.5kg
And the butyl acetate of 316.1kg puts in reaction vessel and stirs, maintain temperature at 60 DEG C,
Again by 1,1,1-trimethylolpropane is slowly dropped in reactor, be kept stirring in reactor during dropping with
Making material mixing and reaction all uniform, time for adding is 90 minutes, drip complete follow-up continue under stirring anti-at 60 DEG C
Answer 4 hours；After dipropylene glycol is slowly dropped in reactor, be kept stirring in reactor during dropping so that material mixing
All uniform with reaction, time for adding is 2 hours, drips and reacts 4 hours at 60 DEG C under stirring complete follow-up continuing, cooling
To 40 DEG C of dischargings.
The clear appearance of the firming agent of synthesis is transparent, and color and luster is No. 20 platinum cobalt colors, and NCO content is 7.3%, gluing when 25 DEG C
Degree is 120mPas；
After storing 30 days at 5 DEG C, outward appearance is the most as clear as crystal, and color and luster is less than No. 20 platinum cobalt colors；
50 DEG C storage 30 days after outward appearance the most as clear as crystal, color and luster be less than No. 50 platinum cobalt colors, NCO content is 7%, 25 DEG C of viscosity
For 140mPas；
25 DEG C storage 1 year after outward appearance the most as clear as crystal, color and luster be less than No. 50 platinum cobalt colors, NCO content is 7.1%, when 25 DEG C
Viscosity be 135mPas.
Compatibility test: the firming agent 57.5g prepared in first embodiment is mixed all with Hydroxylated acrylic resin 170g
Obtaining mixed liquor after even, Hydroxylated acrylic resin selects Bayer A.GA 450BA/X, lower same, mixed
Conjunction liquid is as clear as crystal；Mixed after the firming agent 57.5g prepared in first embodiment is mixed homogeneously with alkyd resin 63.7g
Liquid, the AP572 of the Italian SAPICI company of alkyd resin selection, lower same, mixed liquor is as clear as crystal.Therefore what first embodiment prepared
Firming agent is the best with hydroxy acrylic acid and the alkyd resin compatibility.
Construction life test: the firming agent 57.5g that first embodiment prepares is mixed all with Hydroxylated acrylic resin 170g
Obtain mixed liquor after even, with n-butyl acetate, this mixture viscosity is adjusted to rock field cup 12s, at 30 DEG C after 2 hours, this mixture
Rock field cup viscosity be 24s, i.e. construction the life-span be 2 hours；
Then, mixed after the firming agent 57.5g that first embodiment prepares being mixed homogeneously with alkyd resin 63.7g
Liquid, is adjusted to rock field cup 12s with n-butyl acetate by this mixture viscosity, and at 30 DEG C after 150 minutes, the rock field cup of this mixture glues
Degree is 24s, and i.e. the construction life-span is 150 minutes；
Firming agent 57.5g and the 170g Hydroxylated acrylic resin that first embodiment prepares is mixed homogeneously, prepares coating lacquer
Film, the performance of this coating paint film is as follows: surface drying time 25 minutes；Do solid work the time 24 hours；Paint film adhesion 1 grade；Paint film is pliable and tough
Property 1mm；Paint film resistance to impact 50cm；Hardness of paint film 2H.
Second embodiment
By the 1 of 24kg, 1,1-trimethylolethane and the tripropylene glycol vacuum at 105 DEG C～115 DEG C respectively of 38.4kg
Be dehydrated 2～4 hours stand-by,
Now, the equivalent proportion of 1,1,1-trimethylolethane and tripropylene glycol is 6: 4,
Ensure that its moisture is less than 0.04%.Under nitrogen protection, by 262.5kg methyl diphenylene diisocyanate and
216.6kg butyl acetate is put in reaction vessel and stirs, maintain temperature at 60 DEG C,
Again by 1,1,1-trimethylolethane is slowly dropped in reactor, be kept stirring in reactor during dropping with
Making material mixing and reaction all uniform, time for adding is 90 minutes, drip complete follow-up continue under stirring anti-at 60 DEG C
Answer 4 hours, after tripropylene glycol is slowly dropped in reactor, be kept stirring in reactor during dropping so that material mixing
All uniform with reaction, time for adding is 2 hours, drips and reacts 4 hours at 60 DEG C under stirring complete follow-up continuing, cooling
To 40 DEG C with bottom discharge.
The clear appearance of the firming agent of synthesis is transparent, and color and luster is No. 20 platinum cobalt colors, and NCO content is 8.5%, and 25 DEG C of viscosity are
250mPas；
After storing 30 days at 5 DEG C, outward appearance is the most as clear as crystal, and color and luster is less than No. 20 platinum cobalt colors；
50 DEG C storage 30 days after outward appearance the most as clear as crystal, color and luster be less than No. 50 platinum cobalt colors, NCO content is 8.3%, 25 DEG C glue
Degree is 280mPas；
25 DEG C storage 1 year after outward appearance the most as clear as crystal, color and luster be less than No. 50 platinum cobalt colors, NCO content is 8.3%, 25 viscosity
For 280mPas.
Compatibility test: the firming agent 49.4g that the second embodiment prepares is mixed homogeneously with Hydroxylated acrylic resin 170g
After obtain mixed liquor, mixed liquor is as clear as crystal；The firming agent 49.4g that second embodiment prepares is mixed with alkyd resin 63.7g
Obtaining mixed liquor after Jun Yun, mixed liquor is as clear as crystal.Therefore firming agent and hydroxy acrylic acid and alkyd tree that the second embodiment prepares
The fat compatibility is the best.
Construction life test: the firming agent 49.4g that the second embodiment prepares is mixed all with Hydroxylated acrylic resin 170g
Obtain mixed liquor after even, with n-butyl acetate, mixture viscosity is adjusted to rock field cup 12s, at 25 DEG C after 3.5 hours, mixed liquor
Rock field cup viscosity is 24s, and i.e. the construction life-span is 3.5 hours；The firming agent 49.4g that second embodiment is prepared and alkyd resin
Obtain mixed liquor after 63.7g mix homogeneously, with n-butyl acetate, mixture viscosity is adjusted to rock field cup 12s, at 25 DEG C 4 hours
After, the rock field cup viscosity of mixed liquor is 24s, and i.e. the construction life-span is 4 hours；
The firming agent 49.4g that second embodiment prepares is mixed homogeneously with Hydroxylated acrylic resin 170g, prepares coating lacquer
Film, the performance of this coating paint film is as follows: surface drying time 25 minutes；Do solid work the time 24 hours；Paint film adhesion 1 grade；Paint film is pliable and tough
Property 1mm；Paint film resistance to impact 50cm；Hardness of paint film 2H.
The 3rd following embodiment～sixth embodiment are comparative example
3rd embodiment
By the 1 of 26.8kg, 1,1-trimethylolpropane is true at 105 DEG C～115 DEG C respectively with the dipropylene glycol of 26.8kg
Empty dehydration 2～4 hours is stand-by, it is ensured that its moisture is less than 0.04%.Under nitrogen protection, by the diphenylmethyl of 262.5kg
The butyl acetate of alkane diisocyanate and 316.1kg puts into mixing and stirring in reaction vessel, and maintain temperature at 60 DEG C, then
By 1, after 1,1-trimethylolpropane and dipropylene glycol are sufficiently mixed, it is slowly dropped in reactor, reactor during dropping
Inside being kept stirring for so that material is uniform, time for adding is 90 minutes, drip complete follow-up continue under stirring anti-at 60 DEG C
Answer 4 hours, be cooled to 40 DEG C with bottom discharge.
The firming agent that 3rd embodiment prepares becomes turbid after storing 5 days at 25 DEG C, occurs layering after 10 days.
The present embodiment does not use the first dropping ternary primary alconol that the present invention describes in the preparation of polyurethane coating curing agent,
Then the dropping mode of dropping binary secondary alcohol, but the mode of dropping, result system after using ternary primary alconol to mix with binary secondary alcohol
The firming agent obtained becomes turbid in storage process.
4th embodiment
By the 1 of 26.8kg, 1,1-trimethylolpropane is true at 105 DEG C～115 DEG C respectively with the dipropylene glycol of 26.8kg
Empty dehydration 2～4 hours is stand-by, it is ensured that its moisture is less than 0.04%.Under nitrogen protection, by the diphenylmethyl of 262.5kg
The butyl acetate of alkane diisocyanate and 316.1kg puts into mixing and stirring in reaction vessel, and maintain temperature at 60 DEG C, then
Dipropylene glycol is slowly dropped in reactor, is kept stirring for so that material is uniform during dropping in reactor, time for adding
Be 90 minutes, drip and react 4 hours at 60 DEG C complete follow-up continue under stirring, after by 1,1,1-trimethylolpropane delays
Slowly being added drop-wise in reactor, be kept stirring for so that material is uniform during dropping in reactor, time for adding is 2 hours, dropping
After continue under stirring to react 4 hours at 60 DEG C, be cooled to 40 DEG C with bottom discharge.
The firming agent that 4th embodiment prepares becomes turbid after storing 3 days at 25 DEG C, occurs layering after 8 days.
The present embodiment does not use the first dropping ternary primary alconol that the present invention describes in prepared by firming agent, then drips binary
The dropping mode of secondary alcohol, but use first dropping binary secondary alcohol, then drip the dropping mode of ternary primary alconol, what result prepared consolidates
Agent is quickly become turbid and lamination in storage process.
Additionally, it is well known that, owing to time prepared by polyurethane curing agent, NCO functional group is excessive relative to OH functional group, close
Methyl diphenylene diisocyanate is instilled by one-tenth in alcohol be clearly the most not all right, due to dropping process gradually by OH functional group mistake
Amount is transitioned into NCO functional group excess, it will cause the sharp increase even gel of molecular weight.NCO functional group phase in the present invention
Also it is excessive (NCO: OH equivalent proportion is 2: 1) to OH functional group, it is apparent that can not use diphenyl methane two isocyanide
Acid esters instills the technology mode in alcohol.
5th embodiment
By the 1 of 44.67kg, 1,1-trimethylolpropane at 105 DEG C～115 DEG C vacuum dehydration 2～4 hours stand-by, protect
Demonstrate,prove its moisture less than 0.04%.Under nitrogen protection, by methyl diphenylene diisocyanate and the 307.17kg of 262.5kg
Butyl acetate put into mixing and stirring in reaction vessel, and maintain temperature at 60 DEG C, then by 1,1,1-trimethylolpropane
Being slowly dropped in reactor, be kept stirring for so that material is uniform during dropping in reactor, time for adding is 90 minutes, drips
Adding and react 4 hours at 60 DEG C under stirring complete follow-up continuing, material gradually becomes muddy and viscosity is high, last gel.
Use ternary primary alconol that the present embodiment is described by the present invention in prepared by firming agent and binary secondary alcohol, but only
Using ternary primary alconol, result is gel in preparation process.
Sixth embodiment
By the 1 of 26.8kg, 1,1-trimethylolpropane and the propylene glycol vacuum at 105 DEG C～115 DEG C respectively of 15.2kg
Be dehydrated 2～4 hours stand-by, it is ensured that its moisture be less than 0.04%.Under nitrogen protection, by the diphenyl methane of 262.5kg
The butyl acetate of diisocyanate and 304.5kg puts into mixing and stirring in reaction vessel, and maintain temperature at 60 DEG C, then will
1,1,1-trimethylolpropane is slowly dropped in reactor, is kept stirring for so that material is uniform during dropping in reactor,
Time for adding is 90 minutes, drips and reacts 4 hours at 60 DEG C complete follow-up continue under stirring, after propylene glycol is slowly dripped
Being added in reactor, be kept stirring for so that material is uniform during dropping in reactor, time for adding is 2 hours, drips complete
Rear continuation is reacted 4 hours under stirring at 60 DEG C, cooling discharge.
The firming agent of contrast sixth embodiment becomes turbid after storing 30 days at 25 DEG C.
The scheme that the present embodiment is not provided by the present invention in prepared by firming agent, uses ternary primary alconol and binary secondary alcohol,
But using ternary primary alconol and binary primary-secondary alcohol, result is become turbid in storage process, and binary primary-secondary alcohol therein is one
Hydroxyl is primary hydroxyl, and another hydroxyl is the dihydroxylic alcohols of secondary hydroxyl.
Claims (13)
1. a polyurethane coating curing agent, it is prepolymer based on methyl diphenylene diisocyanate, and is included in vinegar
In esters of gallic acid solvent,
A) product (a) that excess methyl diphenylene diisocyanate is less than the ternary primary alconol of 200 with molecular weight is derived from；With
B) product (b) that excess methyl diphenylene diisocyanate is less than the binary secondary alcohol of 200 with molecular weight is derived from,
Wherein, the consumption of described acetates solvent and described ternary primary alconol, described binary secondary alcohol and described diphenyl methane two
The weight ratio of the total amount of isocyanates is 30～60:40～70,
Described ternary primary alconol, the equivalent proportion of described binary secondary alcohol and described methyl diphenylene diisocyanate is 0.4～0.8:0.2
～0.6:2.1, and
Wherein, described methyl diphenylene diisocyanate comprises relative to the gross weight of described methyl diphenylene diisocyanate:
The 4,4 ' of 40% to 100%-methyl diphenylene diisocyanate；The 2,4 ' of 0% to 55%-methyl diphenylene diisocyanate；
With 0% to 5% 2,2 '-methyl diphenylene diisocyanate,
Wherein, after described firming agent is stored 1 year at 25 DEG C, outward appearance is the most as clear as crystal, and color and luster is less than No. 50 platinum cobalt colors, and NCO contains
Amount declines within 0.3%, and viscosity build is within 15%.
2. firming agent as claimed in claim 1, wherein,
Described product (a) is the compound of following structure formula (I),
Described product (b) is the compound of following structure formula (II):
Wherein, n is 3, and R is the trivalent residue derived from described ternary primary alconol；M is 2, R ' it is two derived from described binary secondary alcohol
Valency residue, and
RepresentAnd
Represent
3. firming agent as claimed in claim 1 or 2, wherein,
Described product (a) is the compound of following structure formula (III)
Described product (b) is the compound of following structure formula (IV)
Wherein, n is 3, and R is the trivalent residue derived from described ternary primary alconol；M is 2, R ' it is two derived from described binary secondary alcohol
Valency residue.
Firming agent the most according to claim 1 and 2, wherein, described ternary primary alconol be 1,1,1-trimethylolpropane and/or
1,1,1-trimethylolethane.
Firming agent the most according to claim 1 and 2, wherein, described binary secondary alcohol is 2,4-pentanediol, 2,5-hexanediol,
Any one or more than one mixture in dipropylene glycol, tripropylene glycol.
Firming agent the most according to claim 1 and 2, wherein, described acetates solvent be ethyl acetate, butyl acetate,
Any one or more than one mixture in ethylene glycol ether acetate, propylene glycol methyl ether acetate.
7. a polyurethane coating curing agent, it is prepared by a method comprising the following steps:
A) under nitrogen protection, methyl diphenylene diisocyanate and acetates solvent put in reactor and stir all
Even, maintenance temperature is at 50 to 70 DEG C, then is slowly dropped to by the water content molecular weight less than the 0.04% ternary primary alconol less than 200
In reactor, during dropping, it is kept stirring for so that material is uniform in reactor, drips complete follow-up continue under stirring
React 1～5 hour at 50 to 75 DEG C；Then
B) by water content less than 0.04% molecular weight less than 200 binary secondary alcohol be slowly dropped in described reactor, dropping
During, be kept stirring for so that material is uniform in reactor, drip complete follow-up continue under stirring anti-at 50 to 75 DEG C
Answer 1～5 hour, be cooled to 40 DEG C with bottom discharge,
Wherein, the consumption of described acetates solvent and described ternary primary alconol, described binary secondary alcohol and described diphenyl methane two
The weight ratio of the total amount of isocyanates is 30～60:40～70；And
Wherein, described ternary primary alconol, the equivalent proportion of described binary secondary alcohol and described methyl diphenylene diisocyanate be 0.4～
0.8:0.2～0.6:2.1；And
Wherein, described methyl diphenylene diisocyanate comprises relative to the gross weight of described methyl diphenylene diisocyanate:
The 4,4 ' of 40% to 100%-methyl diphenylene diisocyanate；The 2,4 ' of 0% to 55%-methyl diphenylene diisocyanate；
With 0% to 5% 2,2 '-methyl diphenylene diisocyanate.
Firming agent the most according to claim 7, wherein, described ternary primary alconol is 1,1,1-trimethylolpropane and/or 1,
1,1-trimethylolethane.
Firming agent the most according to claim 7, wherein, described binary secondary alcohol is 2,4-pentanediol, 2,5-hexanediol, dipropyl
Any one or more than one mixture in glycol, tripropylene glycol.
10. firming agent as claimed in claim 7, wherein, the time for adding of described ternary primary alconol is 0.5 hour to 4 hours.
11. firming agent as claimed in claim 7, wherein, the time for adding of described ternary primary alconol is 1 hour to 2 hours.
12. firming agent as claimed in claim 7, wherein, the time for adding of described binary secondary alcohol is 1 hour to 4 hours.
13. firming agent as claimed in claim 7, wherein, the time for adding of described binary secondary alcohol is 2 hours to 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010250479.6A CN101906204B (en) | 2008-07-17 | 2008-07-17 | Performed polymer based on methyl diphenylene diisocyanate as polyurethane coating curing agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010250479.6A CN101906204B (en) | 2008-07-17 | 2008-07-17 | Performed polymer based on methyl diphenylene diisocyanate as polyurethane coating curing agent and preparation method thereof |
| CN2008100295356A CN101323660B (en) | 2008-07-17 | 2008-07-17 | Prepolymer used as polyurethane coating curing agent and based on methyl diphenylene diisocyanate, and preparation thereof |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100295356A Division CN101323660B (en) | 2008-07-17 | 2008-07-17 | Prepolymer used as polyurethane coating curing agent and based on methyl diphenylene diisocyanate, and preparation thereof |
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| CN101906204B true CN101906204B (en) | 2016-08-10 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4490302A (en) * | 1983-11-25 | 1984-12-25 | Mobay Chemical Corporation | Liquid diphenylmethane diisocyanate compositions |
| CN1357558A (en) * | 2000-12-05 | 2002-07-10 | 上海市涂料研究所 | Paint curing agent 4,4'-diphenyl methane diisocyanate prepolymer and its prepn |
| CN1869092A (en) * | 2006-06-08 | 2006-11-29 | 北京科聚化工新材料有限公司 | Polyurethane prepolymerized body having stable storagibility and its preparation method |
-
2008
- 2008-07-17 CN CN201010250479.6A patent/CN101906204B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4490302A (en) * | 1983-11-25 | 1984-12-25 | Mobay Chemical Corporation | Liquid diphenylmethane diisocyanate compositions |
| CN1357558A (en) * | 2000-12-05 | 2002-07-10 | 上海市涂料研究所 | Paint curing agent 4,4'-diphenyl methane diisocyanate prepolymer and its prepn |
| CN1869092A (en) * | 2006-06-08 | 2006-11-29 | 北京科聚化工新材料有限公司 | Polyurethane prepolymerized body having stable storagibility and its preparation method |
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| CN101906204A (en) | 2010-12-08 |
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