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CN103086991B - A kind of use 65/35 tolylene diisocyanate synthesizes the preparation method of 75% solid content, low free solidifying agent - Google Patents

A kind of use 65/35 tolylene diisocyanate synthesizes the preparation method of 75% solid content, low free solidifying agent Download PDF

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CN103086991B
CN103086991B CN201310000173.9A CN201310000173A CN103086991B CN 103086991 B CN103086991 B CN 103086991B CN 201310000173 A CN201310000173 A CN 201310000173A CN 103086991 B CN103086991 B CN 103086991B
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tolylene diisocyanate
warming
tmp
batch
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CN103086991A (en
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周玲
李晓明
强光明
付振波
陈玫君
蒙鸿飞
陶春霞
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Gansu Yinguang Juyin Chemical Industry Co Ltd
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Gansu Yinguang Juyin Chemical Industry Co Ltd
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Abstract

The present invention relates to the preparation method that a kind of use 65/35 tolylene diisocyanate synthesizes 75% solid content, low free solidifying agent, characterization step comprises: (1) tolylene diisocyanate and TriMethylolPropane(TMP) react and form prepolymer at 70 ± 5 DEG C in reaction solvent; (2) when the weight percentage of survey dissociateive NCO group is 15 ~ 16%, add a kind of catalyst for trimerization 2,4,6-tri-(dimethylaminomethylphenol), when the weight percentage surveying dissociateive NCO group is down to 14 ~ 15%, add trimerization stopper phosphoric acid stopped reaction; (3) after adding oxidation inhibitor 2,6 ditertiary butyl p cresol, when prepolymer cures agent becomes transparent liquid, the solvent commonly used with polyisocyanates is by the discharging of prepolymer latting drown, and the total overall reaction time is in 2.5 ~ 4 hours.Obtained low-free TDI, the environmental protection coating material solidifying agent of high solids content have the good characteristics such as gloss of film is good, good springiness, good toughness, greatly reduce toxicity and transportation cost.

Description

A kind of use 65/35 tolylene diisocyanate synthesizes the preparation method of 75% solid content, low free solidifying agent
Technical field
The present invention relates to the preparation method of solidifying agent in a kind of aromatic series polyurethane paint, be specifically related to the preparation method that a kind of use 65/35 tolylene diisocyanate synthesizes 75% solid content, Low Free-TDI Curing Agent.
Background technology
Solidifying agent is the important component part of double-component polyurethane coating, solidifying agent kind mainly can be divided into by amount of solid content difference: N-75 (75%), N-60, N-50 are several, solid content is higher, less to environmental hazard, the transportation cost of product is lower, and preparation technology and difficulty of processing are also larger.Solidifying agent is as the polymkeric substance of the TDI of property, be widely used in Polyester Paint, high-grade acrylic coating, polyurethane binder, have the good characteristics such as ultra fastcuring, heat-resisting, UV resistant, yellowing resistance, free TDI content are low, especially its low volatility decreases the murder by poisoning to workman.What market generally used has 50 types and 75 type two series products, as the intermediate of coating, not only can improve the physicals of coating, simultaneously, in solidifying agent, TDI free monomer is all between 0.5 ~ 1.0%, and this just greatly reduces the toxicity of TDI, brings great convenience to construction.Solidifying agent, not only for the preparation of various sharp paint, varnish, also can replace a small amount of isocyanic ester to prepare polyurethane coating in polyurethane industrial.Like this, not only do not affect its use properties, but also reduce cost, shorten set time, widened range of application.Compensate for the vacancy that can not use polyurethane paint because isocyanic ester is expensive.Polyurethane coating Common Curing Agents can be divided into by type: TDI+TMP affixture, the affixture of TDI+ hydroxyl material, TDI tripolymer.TMP-TDI affixture is the important member of polyurethane coating industry, there is because of it good characteristics such as gloss of film is good, good springiness, good toughness, become the main flow of Coating Market, be widely used in Polyester Paint, high-grade acrylic coating, polyurethane binder, therefore competitively carry out this research both at home and abroad.Environment-friendly type fixed agent is the coating curing agent of low-free TDI, high solids content, has both greatly reduced toxicity and has additionally reduced transportation cost.At present, domestic most manufacturer is because of by the restriction of state of the art, and the solid content of TMP-TDI affixture, free TDI content and external product also exist certain gap.TMP-TDI solidifying agent is mainly derived from two aspects to the impact that environment produces: contained organic solvent in first solidifying agent, and it two is free TDIs in TMP-TDI solidifying agent.Standard GB/T 18581-2001 specifies, after solidifying agent is used for joining paint, the content of free TDI must control below 0.7%.Therefore, polyurethane curing agent product dominates the market, the important performance indexes of winning the market, and depends on the height of free TDI content.This just requires in solidifying agent product development process, does everything possible and reduces the content of free TDI.Environment-friendly type TMP-TDI solidifying agent is the coating curing agent of low-free TDI, high solids content (75%), it is the main development direction of solidifying agent, N-75 solidifying agent be comply with the exploitation of paint development direction there is large arch dam, low free environmental type solidifying agent, it is free obtained that to be TMP-TDI affixture fallen by later stage chemical method.There is production cost low, be suitable for the feature of China's national situation, processing parameter and the independent research of proportioning raw materials system, and solvent is not containing triphen, has the outstanding feature of environmental protection.TMP-TDI affixture has the good characteristics such as gloss of film is good, good springiness, good toughness because of it, has become the main flow of Coating Market.Because system amount of solid content is high, synthesis difficulty is large, at present, the producer of domestic this state of the art of grasp is few, and substantially rests on the lab scale stage, and after indivedual large enterprises realize industrialization, production cost is very high, there is no profit margin, and process operations is loaded down with trivial details, therefore, the basic dependence on import of this product.So-called environment-friendly type 75 solidifying agent that domestic market produces, much by MDI modification, can not mention in the same breath with TMP-TDI type N-75 solidifying agent in environmental protection and paint film property.The solidifying agent used in polyurethane coating is the prepolymer that is obtained by reacting under certain conditions of vulcabond (as TDI, MDI, HDI etc.) and multicomponent alcoholics compound (as alkane, water etc. in trishydroxymethyl) or the vulcabond polymkeric substance that autohemagglutination is formed under catalyst action mainly.
Reaction mechanism: 3 molecule TDI and 1 molecule TriMethylolPropane(TMP) (TMP) addition reaction.
Tolylene diisocyanate is owing to being subject to methyl steric influence, the specific activity 2 of the NCO base of 4 and the NCO base activity of 6 high, so specific activity 2,6 body high 7.9 times of 2,4 bodies during normal temperature, but along with the rising of temperature of reaction, the poor activity of two kinds of isomer is apart from reducing gradually.According to this characteristic, we are in solidifying agent is produced, during lesser temps, the NCO base of 4 is preferential to react with containing-OH substrate, and the NCO base of 2 or 6 reacts again, form-OH radical reaction the film forming containing the active substance of NCO base and polyethers, polyester components. like this when manufacturing solidifying agent, just can control level of response makes the molecular weight distribution of solidifying agent narrower, and snappiness is better, and viscosity is lower, intermiscibility is better, and shelf stability is better.Depositing of solidifying agent should be under neutrality to solutions of weak acidity.If there is alkaline matter in system, then produce catalytic effect, very easy gelling.For reducing affixture free monomers, add catalyzer in the production process back segment of affixture, then the NCO base preferential three on 4 of free TDI contained by is polymerized to involatile matter, thus reaches the effect reducing free TDI:
Application number is 03113570.6 Chinese invention patent " a kind of preparation method of low free toluene diisocyanate solidifying agent ", the characterization step disclosed comprises: (1) tolylene diisocyanate and polyvalent alcohol react and form prepolymer at 50 ~ 80 DEG C in reaction media, wherein the consumption of reactant tolylene diisocyanate and polyvalent alcohol meets the mol ratio of NCO/OH is 2 ~ 3, and reaction media is selected from sulfurous gas, gamma-butyrolactone, dimethyl sulfoxide (DMSO), carboxylic acid dimethyl; (2) when the weight percentage of survey dissociateive NCO group is 15 ~ 16%, add a kind of polyisocyanates catalyst for trimerization, its total consumption walks 0.02 ~ 0.15% of gained prepolymer cures agent gross weight before being, reaction is continued at 50 ~ 70 DEG C, when the weight percentage surveying dissociateive NCO group is down to 14 ~ 15%, add polyisocyanates trimerization stopper stopped reaction; (3) extraction agent is added, repeatedly extract, extraction agent is aliphatic hydrocarbon or cyclic aliphatic hydrocarbon or their mixture, total consumption of extraction agent is 5 ~ 6 times of front step gained prepolymer cures agent gross weight, extraction agent major part is removed by stratification, remaining extraction agent is by distillation removing, and when prepolymer cures agent becomes transparent liquid, the solvent commonly used with polyisocyanates is by the discharging of prepolymer latting drown.Described polyvalent alcohol is selected from ethylene glycol, propylene glycol, Diethylene Glycol, neopentyl glycol, dipropylene glycol, butyleneglycol, trihydroxybutane, TriMethylolPropane(TMP), tetramethylolmethane or their mixture.
Application number is 200510101144.7 Chinese invention patents " preparation methods of the tolylene diisocyanate addition that a kind of intermiscibility is good and trimerization mixed type solidifying agent ", the characterization step disclosed and raw material and consumption are: the mixture of (A) a kind of tolylene diisocyanate or two kinds of tolylene diisocyanates, 40 ~ 65 parts, (B) the ester class of boiling point 200 DEG C or varsol, 25 ~ 50 parts, (C) aliphatic dihydroxy alcohol, 11 ~ 15 parts, (D) isocyanate trimerization catalyst, 0.005 ~ 0.015 part, (F) isocyanate trimerization stopper, the equivalents added is 2 times of isocyanate trimerization catalyst, above number all refers to weight part, preparation process is: first raw material A, B are dropped into reactor, stirs logical N 2protective reaction, under the condition of 30 ~ 80 DEG C, adds the reaction of C material, add once every half an hour, divide and add for four times, continue insulation reaction 3 hours at 70 ~ 80 DEG C, then D is added at twice, interval half an hour once, continue 70 ~ 80 DEG C of insulation reaction, detected the weight percentage of dissociateive NCO group later every 1 hour, when relatively admittedly containing 50%, the weight percentage of NCO be 7.2 ~ 8.2% time, add F immediately, be cooled to 40 DEG C with bottom discharge.
Application number is 200610141852.8 Chinese invention patents " a kind of preparation methods of low free toluene diisocyanate polyurethane curing agent ", the characterization step disclosed comprises: tolylene diisocyanate, solvent S and catalyst A are dropped into reaction vessel by (1), add oxidation inhibitor and long-chain alcohol, stir in reaction vessel, carry out heating and/or being incubated, detect nco value simultaneously; (2) when nco value reaches 20 ~ 40%, Phase transfer solvent X is added; (3) add catalyst B, in reaction process, detect nco value; (4) if nco value is higher than 15%, repeating step (3), until nco value reaches 10 ~ 15%; (5) stopper stopped reaction is added; (6) optionally, supplement add solvent S; (7) underpressure distillation, removing Phase transfer solvent X.The solid content adjusting polyurethane curing agent with solvent S is 40 ~ 50%, then filters and packages.Described solvent S be selected from N-BUTYL ACETATE, vinyl acetic monomer, and composition thereof, described catalyst A is selected from acetic acid, KOH, NaOH, tributyl phosphorus, triethylenediamine and any mixture thereof, described oxidation inhibitor is selected from phosphoric acid, triphenyl phosphite and BHT, and described long-chain alcohol is selected from orange osmanthus alcohol, octadecanol, 16 carbon alcohol and any mixture thereof.Described Phase transfer solvent X is selected from sherwood oil, methylcarbonate, normal hexane, hexanaphthene or its any mixture.Described catalyst B be selected from acetic acid, KOH, NaOH, tributyl phosphorus, triethylenediamine,
The object of the invention is to solve the too much defect of too long in flow, raw material that technique scheme exists and the new technical scheme that proposes.
Summary of the invention
Raw materials comprises:
1, tolylene diisocyanate (TDI), molecular formula: C 9h 6n 2o 2, molecular weight: 174.
Two kinds of isomer: 2,4 bodies, 2,6 bodies;
TDI specification: T-100T-80T-65
Zero pour: >=21 DEG C of 12.5-14.5 DEG C of 4.0-6.0 DEG C
T-65 is T-80 reacting balance comparatively, controlled, and system side reaction is few.The present invention T-65 used is that 2,4 bodies account for 65 ± 1%, 2, and 6 bodies account for the mixture of 35 ± 1%.
2, TriMethylolPropane(TMP) (TMP)
Molecular formula: CH 3cH 2c (CH 2oH) 3, molecular weight: 134.2, fusing point: the easy moisture absorption of 57-58 DEG C, TMP, avoid in carrying damaging packaging, clout must seal.
3, catalyzer is 2,4,6-tri-(dimethylaminomethylphenol), purity > 95%.
4, reaction solvent is vinyl acetic monomer or N-BUTYL ACETATE.
5, oxidation inhibitor is 2,6 ditertiary butyl p cresol.
6, stopper is phosphoric acid.
The low free N-75 type solidifying agent quality index of finished product
Index name Index
Viscosity (painting cup)≤ 30min
Solid content (%) 75±1
Free TDI (%)≤ 0.5
-NCO content (%) 13.0±0.5
Colourity≤ 20
Appearance toughness (%) >= 140
Add TDI (T-65) and solvent in a kettle. in proportion, then add oxidation inhibitor, UV light absorber is warmed up to 60 DEG C.TriMethylolPropane(TMP) is divided into 4 parts to add successively, question response temperature not when raising, then adds next batch.After last batch of reaction to be added terminates, be warming up to 70 DEG C and be incubated half an hour, then add catalyzer insulation 2-3 hour.When analysis indexes is suitable, add terminator and remaining solvent.TDI and solvent first drop in container by the preparation technology of TDI-TMP affixture, add solid TMP in batches.This technique effectively improves the colourity situation of product, is beneficial to again the steady control of temperature of reaction, simultaneously, according to the difference of reaction severe degree, inventory is finally defined as adding successively from less to more by we, is convenient to the effective control to reaction process, and product is desirable.The effect of post-processed: make free TDI generate tripolymer non-volatile matter, reduce free TDI content, after catalysis completes, its activity ends must be made.The method stopped adds stopper, and this step directly affects the package stability of product.Along with the increase of the mol ratio of TDI and TMP in synthesis, the viscosity of product reduces, NCO massfraction increases, mean that the molecular weight of product is low, even molecular weight distribution, better with the compatibility of other resins, package stability is better, when mol ratio is more higher than theoretical value, in product, containing more free TDI, environmental protection can be unfavorable for; If ratio is lower than theoretical value, then the molar ratio of NCO and OH is less than 2, thus generates the higher affixture of molecular weight, and the viscosity of product is higher, solidifies even completely, and exists and the inconsistent problem of multiple hydroxy resin component.Therefore, mol ratio is selected more satisfactory in 3: 1 ~ 3.01: 1 scope.
Due to the feature of environmental protection requirement of N-75 solidifying agent, so can not contain triphen in solvent, desirable solvent should be vinyl acetic monomer and N-BUTYL ACETATE.Also will consider Cost Problems when selective solvent, under the prerequisite that can meet quality index, use cost is more low better, in addition, and also should in limit of consideration to the treatment process of used solvent.Esters solvent, except moisture, also must reduce free acid and the content of alcohol as far as possible, so as not to NCO radical reaction, therefore, must select " ammonia ester level solvent ".
Within the same reaction time, at differential responses temperature, have viscosity with temperature raise and increase, NCO% downward trend thereupon, product colourity with temperature raise and deepen, especially at comparatively high temps, NCO% decline, viscosity may increase sharply and even produce gel.Therefore, high temperature will be avoided aborning.And under same reaction temperature, along with the prolongation in reaction times, NCO% reduces, its change tends towards stability to a certain extent.But long-time heating can cause the xanthochromia of material.So, when viscosity and NCO% reach requirement, should termination reaction in time.From the viewpoint of speed of response and product colourity two, it is comparatively reasonable that temperature of reaction controls below 80 DEG C, and the reaction times is between 3 hours.
The feature of environmental protection of N-75 solidifying agent is except solvent environmental protection, most important performance is embodied in free TDI content lower than 0.7%, add suitable catalyzer in the later stage of solidifying agent synthesis, utilize chemical process that free TDI in solidifying agent is reduced, add terminator and catalyst reaction again, thus reach the object reducing free TDI.During synthesizing isocyanate tripolymer, select suitable catalyzer most important, the kind of catalyzer not only affects the NCO content in product, and affect preparation condition and production technique, the reducing effect of different catalyzer to the content of free TDI differs, and what have even occurs that viscosity rises soon, the situation of color depth.Experiment is screened from the activity of catalyzer and functional two aspects of catalyzer catalyzer.
Optimised process
The mol ratio of TDI and TMP is: between 3: 1 ~ 3.01: 1
Reaction times: 2.5 ~ 4 hours
Temperature of reaction: 75 ± 5 DEG C
Reaction solvent is: vinyl acetic monomer or N-BUTYL ACETATE
Oxidation inhibitor is: 2,6 ditertiary butyl p cresol (BHT);
Catalyzer is: 2,4,6-tri-(dimethylaminomethylphenol) (DMP);
Stopper is: phosphoric acid (H 3pO 4);
UV light absorber: 2-(2 '-hydroxyl-3 ' 5 '-di-t-butyl) the chloro-benzotriazole of-5-
TMP divides 4 times and adds successively from less to more, and after TMP adds, apparent viscosity change adds solvent.The N-75 solidifying agent synthesized under this technique, quality index reaches Standard.Low Free-TDI Curing Agent be TDI content lower than 0.7% solidifying agent.Three hydroxyl solidifying agent of modification belong to low free solidifying agent, are the resultants of TriMethylolPropane(TMP), properties-correcting agent and TDI addition reaction.By properties-correcting agent and TDI-2,6 precursor reactants reduce the content of free TDIs, and after adding properties-correcting agent, the better performances of paint film, again safety and environmental protection, belong to middle-grade solidifying agent, large relative to its alloytype hardener dose, applied widely and by seasonal limitation.
Add TDI and solvent in a kettle., then add oxidation inhibitor, UV light absorber is warmed up to 65 DEG C.TriMethylolPropane(TMP) is divided into 4 parts by amount from less to more, adds successively in this order.Question response temperature when raising, does not add next batch.When adding last batch of, be incubated half an hour at 70 DEG C, then add catalyzer insulation 2-3 hour.After analysis indexes is suitable, add terminator and remaining solvent.
Accompanying drawing explanation
Fig. 1 65/35 tolylene diisocyanate synthesizes the process flow diagram of 75% solid content, Low Free-TDI Curing Agent.
Embodiment
The present invention is further described below in conjunction with specific embodiment.
Embodiment 1
(1) first add solvent butyl acetate 70kg, then add 65/35 tolylene diisocyanate (T-65) 400kg and mix, be heated to 50 DEG C;
(2) add the chloro-benzotriazole 0.2kg of oxidation inhibitor 2,6 ditertiary butyl p cresol (BHT) 0.3kg, UV light absorber 2-(2 '-hydroxyl-3 ' 5 '-di-t-butyl)-5-successively, said mixture is warming up to 60 DEG C;
(3) TriMethylolPropane(TMP) (TMP) 103kg is divided into four parts, adds after first TMP20kg mixes and be warming up to 62 DEG C;
(4) add after second batch TMP23kg mixes and be warming up to 65 DEG C;
(5) after adding the 3rd batch of TMP27kg mixing again, temperature is risen to 68 DEG C;
(6) after adding the 4th batch of TMP33kg mixing again, temperature is risen to 70 DEG C;
(7) after temperature rise terminates, be incubated half an hour, add catalyzer 2,4,6-tri-(dimethylaminomethylphenol) (DMP) 0.24kg, insulation 2-3 hour;
(8) when viscosity and NCO% reach requirement, should termination reaction in time, to add after stopper phosphoric acid (H3PO4) 0.16g insulation 30 minutes;
(9) apparent viscosity change adds residual solvent N-BUTYL ACETATE 60kg, cools to room temperature.
Embodiment 2
(1) first add solvent acetic acid ethyl ester 80kg, then add 65/35 tolylene diisocyanate (T-65) 400kg and mix, be heated to 50 DEG C;
(2) add the chloro-benzotriazole 0.2kg of oxidation inhibitor 2,6 ditertiary butyl p cresol (BHT) 0.3kg, UV light absorber 2-(2 '-hydroxyl-3 ' 5 '-di-t-butyl)-5-successively, said mixture is warming up to 60 DEG C;
(3) TriMethylolPropane(TMP) (TMP) 103kg is divided into four parts, first adds after first TMP20kg mixes and be warming up to 65 DEG C;
(4) add after second batch TMP23kg mixes and be warming up to 68 DEG C;
(5) 70 DEG C are warming up to after adding the 3rd batch of TMP27kg mixing again;
(6) 75 DEG C are warming up to after adding the 4th batch of TMP33kg mixing again;
(7) apparent viscosity change adds solvent residue vinyl acetic monomer 50kg;
(8) after temperature rise terminates, be incubated half an hour, add catalyzer 2,4,6-tri-(dimethylaminomethylphenol) (DMP) 0.24kg, insulation 2-3 hour;
(9) when viscosity and NCO% reach requirement, should termination reaction in time, to add after stopper phosphoric acid (H3PO4) 0.16kg insulation 30 minutes, cool to room temperature.
Embodiment 3
Difference: 1, the colourity of Multistep feeding goods is low is better than the goods colourity of traditional dropping technique; 2, reinforced viscosity is on the low side from less to more, is beneficial to the steady control of temperature, and the controllability of reaction process is better, and by product is few.
(1) 65/35 tolylene diisocyanate (T-65) 1200kg is heated to 50 DEG C;
(2) add the chloro-benzotriazole 0.6kg of oxidation inhibitor 2,6 ditertiary butyl p cresol (BHT) 0.9kg, UV light absorber 2-(2 '-hydroxyl-3 ' 5 '-di-t-butyl)-5-successively, said mixture is warming up to 60 DEG C;
(3) TriMethylolPropane(TMP) (TMP) 309kg is divided into four parts, first adds after first TMP45kg mixes and be warming up to 65 DEG C;
(4) add second batch TMP55kg to mix;
(5) 68 DEG C are warming up to after adding the 3rd batch of TMP85kg mixing again;
(6) 70 DEG C are warming up to after adding the 4th batch of TMP124kg mixing again;
(7) add solvent acetic acid ethyl ester 70kg, be incubated half an hour, add catalyzer 2,4,6-tri-(dimethylaminomethylphenol) (DMP) 0.72kg, insulation 2-3 hour;
(8) when viscosity and NCO% reach requirement, should termination reaction in time, to add after stopper phosphoric acid (H3PO4) 0.48kg insulation 30 minutes;
(9) apparent viscosity change adds residual solvent N-BUTYL ACETATE 60kg, cools to room temperature.
Embodiment 4
Difference: the content of the catalyzer of employing is higher, effectively can reduce the content of free TDI in specific time, and meanwhile, the molecular weight distribution of guarantee system is more even.
(1) 65/35 tolylene diisocyanate (T-65) 200kg is heated to 50 DEG C;
(2) add the chloro-benzotriazole 0.1kg of oxidation inhibitor 2,6 ditertiary butyl p cresol (BHT) 0.15kg, UV light absorber 2-(2 '-hydroxyl-3 ' 5 '-di-t-butyl)-5-successively, said mixture is warming up to 60 DEG C;
(3) TriMethylolPropane(TMP) (TMP) 52kg is divided into four parts, first adds after first TMP10kg mixes and be warming up to 65 DEG C;
(4) second batch TMP11kg is added;
(5) 68 DEG C are warming up to after adding the 3rd batch of TMP14kg mixing again;
(6) 70 DEG C are warming up to after adding the 4th batch of TMP17kg mixing again;
(7) add solvent acetic acid ethyl ester 35kg, be incubated half an hour, add catalyzer 2,4,6-tri-(dimethylaminomethylphenol) (DMP) 0.2kg, insulation 2-3 hour;
(8) when viscosity and NCO% reach requirement, should termination reaction in time, to add after stopper phosphoric acid (H3PO4) 0.16kg insulation 30 minutes;
(9) apparent viscosity change adds residual solvent N-BUTYL ACETATE 30kg; Cool to room temperature.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to structure of the present invention.Every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong in the scope of technical scheme of the present invention.

Claims (5)

1. synthesize a preparation method for 75% solidifying agent with 65/35 tolylene diisocyanate, its characterization step comprises:
(1) tolylene diisocyanate and TriMethylolPropane(TMP) react and form prepolymer at 70 ± 5 DEG C in reaction solvent, reaction solvent is selected from vinyl acetic monomer, N-BUTYL ACETATE or the two mixture, wherein the consumption of reactant tolylene diisocyanate and TriMethylolPropane(TMP) meets mol ratio is between 3:1 ~ 3.01:1, described tolylene diisocyanate is 2,4-tolylene diisocyanate account for 65 ± 1% and 2,6-tolylene diisocyanate account for the mixture of two kinds of tolylene diisocyanates of 35 ± 1%;
(2) when the weight percentage of survey dissociateive NCO group is 15 ~ 16%, add a kind of catalyst for trimerization 2,4,6-tri-(dimethylaminomethylphenol), described catalyst for trimerization 2,4, the purity > 95% of 6-tri-(dimethylaminomethylphenol), its total consumption walks 0.02 ~ 0.15% of gained prepolymer cures agent gross weight before being, reaction is continued at 70 ± 5 DEG C, when the weight percentage surveying dissociateive NCO group is down to 14 ~ 15%, add trimerization stopper phosphoric acid stopped reaction;
(3) after adding oxidation inhibitor 2,6 ditertiary butyl p cresol, when prepolymer cures agent becomes transparent liquid, the solvent commonly used with polyisocyanates is by the discharging of prepolymer latting drown, and the total overall reaction time is in 2.5 ~ 4 hours.
2. synthesize a preparation method for 75% solidifying agent with 65/35 tolylene diisocyanate, its characterization step comprises:
(1) first add solvent butyl acetate 70kg, then add 65/35 tolylene diisocyanate (T-65) 400kg and mix, be heated to 50 DEG C; Described tolylene diisocyanate be 2,4 toluene diisocyanate account for 65 ± 1% and 2,6-tolylene diisocyanate account for the mixture of two kinds of tolylene diisocyanates of 35 ± 1%;
(2) add the chloro-benzotriazole 0.2kg of oxidation inhibitor 2,6 ditertiary butyl p cresol (BHT) 0.3kg, UV light absorber 2-(2 '-hydroxyl-3 ' 5 '-di-t-butyl)-5-successively, said mixture is warming up to 60 DEG C;
(3) TriMethylolPropane(TMP) (TMP) 103kg is divided into four parts, adds after first TMP20kg mixes and be warming up to 62 DEG C;
(4) add after second batch TMP23kg mixes and be warming up to 65 DEG C;
(5) after adding the 3rd batch of TMP27kg mixing again, temperature is risen to 68 DEG C;
(6) after adding the 4th batch of TMP33kg mixing again, temperature is risen to 70 DEG C;
(7) after temperature rise terminates, be incubated half an hour, add catalyzer 2,4,6-tri-(dimethylaminomethylphenol) (DMP) 0.24kg, insulation 2-3 hour; The purity > 95% of described catalyst for trimerization 2,4,6-tri-(dimethylaminomethylphenol);
(8) when viscosity and NCO% reach requirement, should termination reaction in time, add stopper phosphoric acid (H 3pO 4) insulation 30 minutes after 0.16g;
(9) apparent viscosity change adds residual solvent N-BUTYL ACETATE 60kg, cools to room temperature.
3. synthesize a preparation method for 75% solidifying agent with 65/35 tolylene diisocyanate, its characterization step comprises:
(1) first add solvent acetic acid ethyl ester 80kg, then add 65/35 tolylene diisocyanate (T-65) 400kg and mix, be heated to 50 DEG C; Described tolylene diisocyanate be 2,4 toluene diisocyanate account for 65 ± 1% and 2,6-tolylene diisocyanate account for the mixture of two kinds of tolylene diisocyanates of 35 ± 1%;
(2) add the chloro-benzotriazole 0.2kg of oxidation inhibitor 2,6 ditertiary butyl p cresol (BHT) 0.3kg, UV light absorber 2-(2 '-hydroxyl-3 ' 5 '-di-t-butyl)-5-successively, said mixture is warming up to 60 DEG C;
(3) TriMethylolPropane(TMP) (TMP) 103kg is divided into four parts, first adds after first TMP20kg mixes and be warming up to 65 DEG C;
(4) add after second batch TMP23kg mixes and be warming up to 68 DEG C;
(5) 70 DEG C are warming up to after adding the 3rd batch of TMP27kg mixing again;
(6) 75 DEG C are warming up to after adding the 4th batch of TMP33kg mixing again;
(7) apparent viscosity change adds solvent residue vinyl acetic monomer 50kg;
(8) after temperature rise terminates, be incubated half an hour, add catalyzer 2,4,6-tri-(dimethylaminomethylphenol) (DMP) 0.24kg, insulation 2-3 hour; The purity > 95% of described catalyst for trimerization 2,4,6-tri-(dimethylaminomethylphenol);
(9) when viscosity and NCO% reach requirement, should termination reaction in time, add stopper phosphoric acid (H 3pO 4) insulation 30 minutes after 0.16kg, cool to room temperature.
4. synthesize a preparation method for 75% solidifying agent with 65/35 tolylene diisocyanate, its characterization step comprises:
(1) 65/35 tolylene diisocyanate (T-65) 1200kg is heated to 50 DEG C; Described tolylene diisocyanate be 2,4 toluene diisocyanate account for 65 ± 1% and 2,6-tolylene diisocyanate account for the mixture of two kinds of tolylene diisocyanates of 35 ± 1%;
(2) add the chloro-benzotriazole 0.6kg of oxidation inhibitor 2,6 ditertiary butyl p cresol (BHT) 0.9kg, UV light absorber 2-(2 '-hydroxyl-3 ' 5 '-di-t-butyl)-5-successively, said mixture is warming up to 60 DEG C;
(3) TriMethylolPropane(TMP) (TMP) 309kg is divided into four parts, first adds after first TMP45kg mixes and be warming up to 65 DEG C;
(4) add second batch TMP55kg to mix;
(5) 68 DEG C are warming up to after adding the 3rd batch of TMP85kg mixing again;
(6) 70 DEG C are warming up to after adding the 4th batch of TMP124kg mixing again;
(7) add solvent acetic acid ethyl ester 70kg, be incubated half an hour, add catalyzer 2,4,6-tri-(dimethylaminomethylphenol) (DMP) 0.72kg, insulation 2-3 hour; The purity > 95% of described catalyst for trimerization 2,4,6-tri-(dimethylaminomethylphenol);
(8) when viscosity and NCO% reach requirement, should termination reaction in time, add stopper phosphoric acid (H 3pO 4) insulation 30 minutes after 0.48kg;
(9) apparent viscosity change adds residual solvent N-BUTYL ACETATE 60kg, cools to room temperature.
5. synthesize a preparation method for 75% solidifying agent with 65/35 tolylene diisocyanate, its characterization step comprises:
(1) 65/35 tolylene diisocyanate (T-65) 200kg is heated to 50 DEG C; Described tolylene diisocyanate be 2,4 toluene diisocyanate account for 65 ± 1% and 2,6-tolylene diisocyanate account for the mixture of two kinds of tolylene diisocyanates of 35 ± 1%;
(2) add the chloro-benzotriazole 0.1kg of oxidation inhibitor 2,6 ditertiary butyl p cresol (BHT) 0.15kg, UV light absorber 2-(2 '-hydroxyl-3 ' 5 '-di-t-butyl)-5-successively, said mixture is warming up to 60 DEG C;
(3) TriMethylolPropane(TMP) (TMP) 52kg is divided into four parts, first adds after first TMP10kg mixes and be warming up to 65 DEG C;
(4) second batch TMP11kg is added;
(5) 68 DEG C are warming up to after adding the 3rd batch of TMP14kg mixing again;
(6) 70 DEG C are warming up to after adding the 4th batch of TMP17kg mixing again;
(7) add solvent acetic acid ethyl ester 35kg, be incubated half an hour, add catalyzer 2,4,6-tri-(dimethylaminomethylphenol) (DMP) 0.2kg, insulation 2-3 hour; The purity > 95% of described catalyst for trimerization 2,4,6-tri-(dimethylaminomethylphenol);
(8) when viscosity and NCO% reach requirement, should termination reaction in time, add stopper phosphoric acid (H 3pO 4) insulation 30 minutes after 0.16kg;
(9) apparent viscosity change adds residual solvent N-BUTYL ACETATE 30kg; Cool to room temperature.
CN201310000173.9A 2013-01-04 2013-01-04 A kind of use 65/35 tolylene diisocyanate synthesizes the preparation method of 75% solid content, low free solidifying agent Expired - Fee Related CN103086991B (en)

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CN104403085A (en) * 2014-11-26 2015-03-11 广东东旭化学工业制造有限公司 European standard-reached low free matte trimer curing agent and preparation method thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1121503A (en) * 1997-07-04 1999-01-26 Hitachi Chem Co Ltd Modified cyanate ester resin vanish for printed circuit board and preparation of prepreg for laminate and metal-clad laminate using same
CN1425702A (en) * 2003-01-13 2003-06-25 深圳市飞扬实业有限公司 Process for preparing low free toluene diisocyanate curing agent
CN1958652A (en) * 2005-11-04 2007-05-09 深圳市飞扬实业有限公司 Method for preparing good mutual resolvable addition of toluene diisocynate and trimerization mixed type solidifying agent
CN102050935A (en) * 2010-12-08 2011-05-11 肇庆千江高新材料科技有限公司 Water-soluble polyurethane curing agent and preparation method thereof
CN102827346A (en) * 2012-09-17 2012-12-19 上海富臣化工有限公司 Low-free toluene diisocyanate polyurethane curing agent and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5585329B2 (en) * 2010-09-13 2014-09-10 横浜ゴム株式会社 Primer composition and laminate using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1121503A (en) * 1997-07-04 1999-01-26 Hitachi Chem Co Ltd Modified cyanate ester resin vanish for printed circuit board and preparation of prepreg for laminate and metal-clad laminate using same
CN1425702A (en) * 2003-01-13 2003-06-25 深圳市飞扬实业有限公司 Process for preparing low free toluene diisocyanate curing agent
CN1958652A (en) * 2005-11-04 2007-05-09 深圳市飞扬实业有限公司 Method for preparing good mutual resolvable addition of toluene diisocynate and trimerization mixed type solidifying agent
CN102050935A (en) * 2010-12-08 2011-05-11 肇庆千江高新材料科技有限公司 Water-soluble polyurethane curing agent and preparation method thereof
CN102827346A (en) * 2012-09-17 2012-12-19 上海富臣化工有限公司 Low-free toluene diisocyanate polyurethane curing agent and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
低游离甲苯二异氰酸酯的聚氨酯固化剂合成研究;杨斯伦等;《化学工程师》;20121231(第11期);72-75 *
降低聚氨酯固化剂中游离TDI含量的方法研究;张燕红等;《高校化学过程学报》;20091030;第23卷(第5期);807-812 *

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