CN102617827B - Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof - Google Patents
Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
- C07C275/58—Y being a hetero atom
- C07C275/62—Y being a nitrogen atom, e.g. biuret
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
- C08G18/305—Water creating amino end groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Abstract
The invention relates to a polyurethane coating and an adhesive curing agent and preparation methods thereof, and concretely relates to curing agent modified HDI biuret and a preparation method thereof. The preparation method mainly solves problems low HDI conversion rate, and energy waste caused by multitime monomer recovery of known methods for preparing HDI biuret through reacting HDI with water. The curing agent of the invention is generated by reacting a dihydric alcohol, water and the HDI in an organic solvent, wherein the molar ratio of the dihydric alcohol to the HDI is 0.05-0.2:1, the molar ratio of water to the residual HDI is 1:3-4, and the weight ratio of the solvent to (reactants of the dihydric alcohol, water and the HDI) is 0-60:40-100. The curing agent modified HDI biuret which has a low viscosity and makes the one-time feeding conversion rate of HDI monomers reach 80-98% is mainly used as a curing agent for automobile and high grade car paints, and boil-resistant laminating adhesives, and has a nonyellowing characteristic at a high temperature under ultraviolet ray.
Description
Technical field
The present invention relates to a kind of polyurethane coating, adhesive solidification agent and preparation method thereof, is a kind of modification hexamethylene diisocyanate solidifying agent and preparation method thereof specifically.
Background technology
1, hexamethylene-diisocyanate (HDI) belongs to not flavescence aliphatic diisocyanate, it is the main raw material of high performance polyurethane coating and tackiness agent, be characterized in polyurethane products light, the Heat stability is good made, yellowing phenomenon can not occur under the uviolizing out of doors, the chemical reaction that aromatic isocyanate becomes carcinogenic aromatic amine can not occur under the high temperature steaming condition, be a kind of raw material very important in the vulcabond raw material.But the HDI monomer is larger because of its volatility, and toxicity is also large during construction, and general method all is with HDI and H in the world
2O reaction is made and is applied to other purposes after HDI biuret or HDI autohemagglutination become the HDI tripolymer again.
HDI and H
2It is as follows that O reacts the chemical equation of making biuret:
From the structure of HDI biuret (biuret triisocyanate), should be by the reaction of 3 moles of HDI and 1 mole of water and generate.Introduce the manufacture method of HDI biuret according to relevant urethane books, if by 3: the 1 moles of a large amount of oyster white dopes of meeting generation that feed intake, will can not get product, increase along with the HDI molar ratio, white depositions (polyureas) reduces gradually, evidence, mol ratio be 6: 1 more suitable.Prior art just allows HDI excessive more than one times when raw material feeds intake, and the transformation efficiency of HDI monomer is the highest in the reaction does not reach 50% yet, and excessive HDI monomer reclaims with thin-film evaporator, for again recycling.The production technique of prior art not only efficient is low, and repeatedly reclaims monomer and cause energy dissipation.
Patent documentation Chinese invention patent application prospectus CN101475680A is in the method for disclosed spray method synthesizing hexamethylene diisocyanate on July 8 (HDI) biuret in 2009, its patent No. is 200910003621.4, having introduced spray method can be evenly dispersed in water in the material to reduce the generation of polyureas, the mol ratio of HDI and water is 2～15, does not still solve the problem of HDI biuret low conversion rate.
Summary of the invention
The objective of the invention is in order to remedy the deficiencies in the prior art the transformation efficiency of HDI monomer to be brought up to 80～98%, and product without white depositions generate curing agent modified 1, the own isocyanic ester biuret of 6-.
Technical solution of the present invention is: at first with dibasic alcohol part HDI is carried out modification, to remain HDI and water by 3～4: 1 mol ratio feeds intake again, the circulating reaction technology of taking substep to add water, stepwise reaction is made modification HDI diisocyanate biuret curing agent, wherein HDI is the abbreviation of the own isocyanic ester biuret of 1,6-.
The present invention is the activity that changes part HDI with dibasic alcohol to the purpose that part HDI carries out modification, and the activity difference in the formation system between the differing molecular so that the reaction of follow-up generation biuret can be carried out in order, is avoided polymeric generation.
The circulating reaction technology that substep of the present invention adds water, stepwise reaction has formed the excessive local environment of HDI relative in the system, and the direction that is conducive to react towards generating biuret carries out.
The present invention is take organic solvent as solvent, generates described two by dibasic alcohol, water and HDI reaction
Unit's alcohol is 0.05～0.2: 1 with the mol ratio of HDI, described water is 1: 3～4 with the mol ratio of residue HDI, the OH base of the water that namely feeds intake and the structure proportion of the mol ratio of the NCO base of HDI near the biuret triisocyanate, the weight ratio of the consumption that described solvent load and reactant dibasic alcohol, water and HDI add up to is 0～60: 40～100.
The HDI of the present invention transformation efficiency that feeds intake is 80～98%, generates without white depositions, and product viscosity is low,
Only have 2000～4000 mpa.s(25 ℃).
Preparation method of the present invention, its step is as follows:
A, add HDI and organic solvent in reactor, the rear adding that stirs is warming up to 60 ℃ through the dibasic alcohol of dehydration, 60～90 ℃ of reactions 1～6 hour, makes the HDI modifier;
B, be cooled to below 70 ℃, add first part's water, react and be warmed up to 75～100 ℃ of reactions 1～3 hour after 0.5～1.5 hour, be warmed up to again 120～140 ℃ and reacted 1～3 hour; Be cooled to below 70 ℃, add second section water, repeat above-mentioned technological process, until add the water of whole meterings, react be warmed up to after 0.5～1.5 hour 75～100 ℃ the reaction 1～3 hour, be warmed up to again 120～140 ℃ the reaction 1～5 hour, at this moment between, the degree of being undertaken by the content monitoring reaction that detects NCO to reactant sampling is when the content of NCO tends towards stability, is during near theoretical value reaction end;
C, sampling detect solid content, viscosity, NCO percentage composition and the transformation efficiency of product;
D, the distillation under vacuum with conventional, film evaporation method or solvent extration are extracted solvent and a small amount of residual HDI in the product out, are cooled to below 70 ℃ to add organic solvent by the requirement of product solid content, stir, and discharging gets modification HDI diisocyanate biuret curing agent.
Dibasic alcohol described in the technical solution of the present invention is polyester diol, polyether Glycols, other dibasic alcohol or small molecules dibasic alcohol, wherein any one or two or more mixtures.
Polyester diol described in the technical solution of the present invention is poly-hexanodioic acid-ethylene glycol and 1,2-propylene glycol ester dibasic alcohol, poly-hexanodioic acid-butanediol ester dibasic alcohol, poly-sebacic acid-hexanodioic acid-ethylene glycol-DOPCP dibasic alcohol, poly-m-phthalic acid-hexanodioic acid-neopentyl glycol-glycol ether ester dibasic alcohol, polycarbonate diol or polycaprolactone dibasic alcohol.
Polyether Glycols described in the technical solution of the present invention is Polyoxypropylene diol, polyoxyethylene-propylene dibasic alcohol or polytetrahydrofuran dibasic alcohol.
Other dibasic alcohol described in the technical solution of the present invention is terminal hydroxy group acrylic resin or terminal hydroxy group Synolac.
Small molecules dibasic alcohol described in the technical solution of the present invention is the 3-methyl isophthalic acid, the 5-pentanediol, neopentyl glycol, ethylene glycol, glycol ether, cyclohexanediol, methyl propanediol, TCD three ring glycol, 1, ammediol, 1, the 4-hydroxymethyl-cyclohexane, 1, the 4-butyleneglycol, 1, the 3-butyleneglycol, 1, the 5-pentanediol, the diethyl pentanediol, 1, the 2-propylene glycol, glycol ether, erythritan, 1, the 6-hexylene glycol, neopentyl glycol, the butyl ethyl propylene glycol, 2,2-two (4-hydroxy phenyl) propane, hydroxypivalyl hydroxypivalate neopentyl alcohol ester, Resorcinol double hydroxyethyl ether, two (2-hydroxyethyl) ethers of quinhydrones, Resorcinol bis-hydroxypropyl ether, Resorcinol bis-hydroxypropyl ethyl ether, 2,5-ditert-butylhydro quinone, dipropylene glycol, tripropylene glycol or Rutgers 612.
Water described in the technical solution of the present invention is deionized water or distilled water.
Organic solvent described in the technical solution of the present invention is the ester class of vinyl acetic monomer, N-BUTYL ACETATE, ethylene glycol ether acetate, propylene glycol monomethyl ether acetate, methylcarbonate, diethyl carbonate, diphenyl carbonate, the ketone of acetone, butanone, cyclohexanone, toluene, dimethylbenzene aromatic hydrocarbons, dioxane, tetrahydrofuran (THF), N, dinethylformamide reaches wherein two or more mixture.
Among preparation method's step a of the present invention, from the symmetrical structure of HDI, two NCO groups active identical be that the gordian technique of making biuret is started with, at first react first with dibasic alcohol and part HDI, generate a kind of HDI modifier, this so that in the system activity between the molecule, between the NCO group formed difference.The principle of the invention is that follow-up generation biuret reaction has been created condition.
Among preparation method's step b of the present invention, the moisture that measures being become some parts, add several times, is for the relatively excessive local environment of HDI in the formation system, is conducive to reaction and progressively generates biuret.After adding first part water, first 75～100 ℃ of reactions of low temperature 1～3 hour, this stage is HDI and water reaction, generates first primary amine and carbonic acid gas, and primary amine is very fast to generate the urea groups vulcabond with the HDI reaction; Be warmed up to 120～140 ℃ of reactions 1～3 hour, this stage is that urea groups vulcabond and HDI reaction generate biuret again.Be cooled to below 70 ℃, add the second part water again, the above-mentioned technological process that circulates until add the water of whole meterings, has been carried out above-mentioned technological process.In each stage of above-mentioned reaction, because each molecular activity exists difference, gradation adds the technique of water, gradation low temperature and pyroreaction, be conducive between the differing molecular, the reaction between the different activities group can carry out by speed in order, be conducive to the generation of unit molecule biuret, avoid and reduced the generation of " polyureas ", also namely do not have white depositions.
Reaction end of the present invention is after adding last water, and NCO content determines to react whether this end in the sampling detecting reactant, when the content of NCO no longer descends, tends towards stability, is during near the Design Theory value reaction end.Distillation under vacuum, film evaporation method or the solvent extration that can quote relevant patent and the introduction of urethane books to the processing of a small amount of residual HDI monomer carry out.
The HDI of the product of the present invention monomer conversion that once feeds intake is 80～98%, and the height of its transformation efficiency is relevant with dibasic alcohol kind and the consumption of selection, and generalized case can both reach more than 90%.The present invention is comparing below 50% with the monomer conversion that once feeds intake of the HDI biuret of domestic and international prior art manufacturing, has improved nearly one times.
The molecular characterization of product of the present invention is to contain simultaneously dibasic alcohol modification HDI structure and biuret structure, dibasic alcohol modification HDI structure represents in above-mentioned chemical equation (A), biuret structure characterizes 2245cm-with the biuret structure charateristic avsorption band of the infrared spectrogram of laboratory sample of the present invention
1The place is-the NCO absorption peak 2935cm-
1The place is the absorption peak of methyl and methylene radical, 3305cm-
1The place is-NH-absorption peak 1735cm-
1For-CO-absorption peak, therefore think that product of the present invention has biuret structure.
The present invention also aims to provide a kind of dibasic alcohol modification HDI diisocyanate biuret curing agent series product, the introducing of dibasic alcohol has changed the performance of HDI diisocyanate biuret curing agent, can design some property by customer requirements, such as the snappiness that increases solidifying agent and give goods, rigidity, wear resistance, flexibility and with the consistency of resin etc., select different dibasic alcohol can produce a series of modification HDI diisocyanate biuret curing agents, satisfy the needs of polyurethane coating, tackiness agent various uses.
Modification HDI diisocyanate biuret curing agent of the present invention and supporting Synolac, acrylic resin etc. have good intermiscibility.
The present invention will have now and make HDI diisocyanate biuret curing agent technology and reach a new high, and improve the production efficiency of product, reduced the HDI monomer the Distillation recovery number of times, increased plant factor, reduced energy consumption and made the HDI product diversification.
Product of the present invention has not flavescence characteristic under ultraviolet ray and the high temperature mainly as the solidifying agent of automobile, high-grade car coating and the compound film adhesive of anti-the boiling.
The present invention compared with prior art has following advantage: one, structural diversification.The present invention has introduced the dibasic alcohol structure in HDI biuret molecular structure, make modification HDI diisocyanate biuret curing agent structural diversification, is conducive to the expansion of end-use.Two, production efficiency is high.The present invention can be enhanced about more than once the production efficiency of prior art, and product generates without white depositions.Three, technique is advanced.Gradation of the present invention adds water, gradation and has changed the processing method of traditional manufacturing HDI biuret at the circulating reaction technology of low temperature and pyroreaction, and technique is simple, and plant factor is high.Four, energy consumption is low.Technique of the present invention has reduced the energy consumption that a large amount of residual monomers repeatedly reclaim, recycle.Five, product viscosity is low.Viscosity of the present invention is low, and solid content has reduced consumption of organic solvent up to more than 90%.Six, product index of the present invention following (following content is weight percentage):
(1) outward appearance: colourless to light yellow transparent liquid;
(2) solid content: 40～90%;
(3) NCO content: 16～23.5%, in total solids;
(4) storage period: 1 year.
Description of drawings
Fig. 1 is the infrared spectrogram that laboratory sample of the present invention detects with infrared spectrometer.
Embodiment
A, add 168 gram HDI and 22 gram N-BUTYL ACETATEs in reactor, the rear adding that stirs is warming up to 60 ℃ through 19.6 gram TCD of dehydration, three ring glycol, 60～70 ℃ of reactions 1 hour, is raised to 70～80 ℃ of reactions 1 hour again, makes the HDI modifier; B, be cooled to below 70 ℃, add 2.4 gram water for the first time, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 1 hour, be warmed up to again 120～130 ℃ and reacted 1 hour; Be cooled to below 70 ℃, add for the second time 1.2 gram water, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to again 120～130 ℃ and reacted 1 hour; Be cooled to below 70 ℃, add for the third time 1.2 gram water, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Again be warmed up to 125～135 ℃ of reactions, in this section period, detect the NCO percentage composition every sampling in 0.5 hour, when being worth 19.6% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 90%, and viscosity is 2800mpa.s(25 ℃), NCO content is 19.3%, transformation efficiency is that 96%(is in total solids); D, extract N-BUTYL ACETATE and a small amount of residual HDI in the product out with distillation under vacuum, be cooled to and add 22 gram N-BUTYL ACETATEs below 70 ℃, stir, discharging gets 214 gram solid contents and is 90% modification HDI diisocyanate biuret curing agent.The residual HDI content of this solidifying agent is 0.42% after testing.
Embodiment 2
A, in reactor, add 168 gram HDI and 81 gram N-BUTYL ACETATEs, the rear adding that stirs gathers sebacic acid-hexanodioic acid-ethylene glycol-DOPCP dibasic alcohol (molecular weight is 1000) through 70 grams of dehydration, be warming up to 60 ℃, 60～70 ℃ of reactions 1.5 hours, be raised to again 70～80 ℃ of reactions 2 hours, make the HDI modifier; B, be cooled to below 70 ℃, add 2.5 gram water for the first time, react and be warmed up to 75～85 ℃ of reactions 1.5 hours after 1.5 hours, be warmed up to again 120～130 ℃ and reacted 1.5 hours; Be cooled to below 70 ℃, add for the second time 1.3 gram water, react and be warmed up to 75～85 ℃ of reactions 1 hour after 1 hour, be warmed up to again 120～130 ℃ and reacted 1 hour; Be cooled to below 70 ℃, add for the third time 0.8 gram water, react and be warmed up to 75～85 ℃ of reactions 1 hour after 0.5 hour, be warmed up to again 120～130 ℃ and reacted 1 hour; Be cooled to below 70 ℃, the 4th adding 0.56 restrains water, reacts to be warmed up to 75～85 ℃ of reactions 1 hour after 0.5 hour, is warmed up to 120～130 ℃ of reactions 1 hour again; Again be warmed up to 125～135 ℃ of reactions, in this section period, detect the NCO percentage composition every sampling in 0.5 hour, when being worth 13% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 3100mpa.s(25 ℃), NCO content is 12.7%, transformation efficiency is that 91%(is in total solids); D, extract N-BUTYL ACETATE and a small amount of residual HDI in the product out with distillation under vacuum, be cooled to and add 50 gram N-BUTYL ACETATEs and 31 gram vinyl acetic monomers below 70 ℃, stir, discharging gets 324 gram solid contents and is 75% modification HDI diisocyanate biuret curing agent.The residual HDI content of this solidifying agent is 0.35% after testing.
A, add 168 gram HDI and 73 gram N-BUTYL ACETATEs in reactor, the rear adding that stirs is warming up to 60 ℃ through 9.4 gram 1,5-PDs of dehydration, 60～70 ℃ of reactions 1 hour, is raised to 70～80 ℃ of reactions 1 hour again; Add 35 gram terminal hydroxy group acrylic resins (molecular weight is 1000) through dehydration, 70～80 ℃ of reactions 1 hour, 80～90 ℃ were reacted 1 hour, and made the HDI modifier again; B, be cooled to below 70 ℃, add 2.3 gram water for the first time, react and be warmed up to 75～85 ℃ of reactions 1.5 hours after 1 hour, be warmed up to again 120～130 ℃ and reacted 1.5 hours; Be cooled to below 70 ℃, add for the second time 1.1 gram water, react and be warmed up to 75～85 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to again 120～130 ℃ and reacted 1.5 hours; Be cooled to below 70 ℃, add for the third time 1.1 gram water, react and be warmed up to 75～85 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Again be warmed up to 125～135 ℃ of reactions, in this section period, detect the NCO percentage composition every sampling in 0.5 hour, when being worth 14.5% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 2100mpa.s(25 ℃), NCO content is 14.2%, transformation efficiency is that 90%(is in total solids); D, extract N-BUTYL ACETATE and a small amount of residual HDI in the product out with distillation under vacuum, be cooled to and add 50 gram N-BUTYL ACETATEs and 23 gram propylene glycol monomethyl ether acetate below 70 ℃, stir, discharging gets 290 gram solid contents and is 75% modification HDI diisocyanate biuret curing agent.
Embodiment 4
A, in reactor, add 168 gram HDI and 69 gram N-BUTYL ACETATEs, the rear adding that stirs restrains two (hydroxyethyl) ethers of Resorcinols through 34.7 of dehydration, is warming up to 60 ℃, 60～70 ℃ of reactions 1 hour, be raised to again 70～80 ℃ of reactions 1 hour, make the HDI modifier; B, be cooled to below 70 ℃, add 2.0 gram water for the first time, react and be warmed up to 80～90 ℃ of reactions 1 hour after 0.5 hour, be warmed up to again 120～130 ℃ and reacted 1 hour; Be cooled to below 70 ℃, add for the second time 1.0 gram water, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to again 120～130 ℃ and reacted 1 hour; Be cooled to below 70 ℃, add for the third time 0.9 gram water, react and be warmed up to 80～90 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Again be warmed up to 125～135 ℃ of reactions, in this section period, detect the NCO percentage composition every sampling in 0.5 hour, when being worth 15.2% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 1600mpa.s(25 ℃), NCO content is 15.0%, transformation efficiency is that 94%(is in total solids); D, extract N-BUTYL ACETATE and a small amount of residual HDI in the product out with distillation under vacuum, be cooled to and add 69 gram N-BUTYL ACETATEs below 70 ℃, stir, discharging gets 275.5 gram solid contents and is 75% modification HDI diisocyanate biuret curing agent.
Embodiment 5
A, in reactor, add 168 gram HDI and 84 gram N-BUTYL ACETATEs, the rear adding that stirs restrained polytetrahydrofuran diols (molecular weight is 1000) through 80 of dehydration, is warming up to 60 ℃, 60～70 ℃ of reactions 3 hours, be raised to again 70～80 ℃ of reactions 2.5 hours, make the HDI modifier; B, be cooled to below 70 ℃, add 2.5 gram water for the first time, react and be warmed up to 75～85 ℃ of reactions 2.5 hours after 1.5 hours, be warmed up to again 120～130 ℃ and reacted 2.5 hours; Be cooled to below 70 ℃, add for the second time 1.3 gram water, react and be warmed up to 75～85 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to again 120～130 ℃ and reacted 1.5 hours; Be cooled to below 70 ℃, add for the third time 1.2 gram water, react and be warmed up to 75～85 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Again be warmed up to 125～135 ℃ of reactions, in this section period, detect the NCO percentage composition every sampling in 0.5 hour, when being worth 12.5% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 2100mpa.s(25 ℃), NCO content is 12.2%, transformation efficiency is that 92%(is in total solids); D, extract N-BUTYL ACETATE and a small amount of residual HDI in the product out with distillation under vacuum, be cooled to and add 50 gram N-BUTYL ACETATEs and 34 gram ethylene glycol ether acetates below 70 ℃, stir, discharging gets 337 gram solid contents and is 75% modification HDI diisocyanate biuret curing agent.
Embodiment 6
A, add 168 gram HDI and 61 gram N-BUTYL ACETATEs in reactor, the rear adding that stirs is warming up to 60 ℃ through 10.4 gram neopentyl glycol of dehydration, 60～70 ℃ of reactions 1 hour, is raised to 70～80 ℃ of reactions 1 hour again, makes the HDI modifier; B, be cooled to below 70 ℃, add 1.8 gram water for the first time, react and be warmed up to 80～90 ℃ of reactions 1 hour after 0.5 hour, be warmed up to again 120～130 ℃ and reacted 1 hour; Be cooled to below 70 ℃, add for the second time 0.9 gram water, react and be warmed up to 80～90 ℃ of reactions 1.5 hours after 0.5 hour, be warmed up to again 120～130 ℃ and reacted 1 hour; Be cooled to below 70 ℃, add for the third time 0.9 gram water, react and be warmed up to 80～90 ℃ of reactions 1 hour after 0.5 hour, be warmed up to 120～130 ℃ and reacted 1 hour; Again be warmed up to 125～135 ℃ of reactions, in this section period, detect the NCO percentage composition every sampling in 0.5 hour, when being worth 20.7% near Design Theory, the termination reaction of lowering the temperature immediately; C, sampling detect, and the solid content of product is 75%, and viscosity is 3100mpa.s(25 ℃), NCO content is 20.4%, transformation efficiency is that 80%(is in total solids); D, extract N-BUTYL ACETATE and a small amount of residual HDI in the product out with distillation under vacuum, be cooled to and add 61 gram N-BUTYL ACETATEs below 70 ℃, stir, discharging gets 242 gram solid contents and is 75% modification HDI diisocyanate biuret curing agent.
Application Example 1
Product 30 grams of embodiment 1 and the hydroxyl component of 100 gram phthalic resin coatings mix, and the coating lacquer film properties that makes is as follows: dryness: 25 ℃, surface drying time 50 minutes is done solid work 12 hours time; Test performance after 3 days: gloss (60 °): 〉=95%; Hardness: Shao Shi D50; Shock strength: 428N.cm; Sticking power: 1 grade; Snappiness: 1mm.
The method of inspection: gloss is pressed GB9754-88, hardness and is pressed GB1730-79, shock strength and press that GB1732-93, sticking power press GB1720-89, snappiness is pressed the GB1731-79 standard.
Application Example 2
Product 40 gram of embodiment 3 and 100 gram Hydroxylated acrylic resin solution mixing, the coating lacquer film properties that makes is as follows: dryness: 25 ℃, surface drying time 50 minutes, when doing solid work 12 hours; Test performance after 3 days: gloss (60 °): 〉=95%; Hardness 〉=Shao Shi D60; Shock strength: 480N.cm; Sticking power: 1 grade; Snappiness: 1mm.
Application Example 3
Product 35 grams of embodiment 2 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 72 hours after, carry out T-shaped peeling strength test by GB/T 2791-1995 " tackiness agent T peeling strength test method flexible material is to flexible material ", stripping strength is 1030g/15mm, and the laminated film behind cooking test does not find that film has separation phenomenon.
Reference:
1, the Li Shaoxiong of Chemical Industry Press's " polyurethane adhesive ", Liu Yijun write, the 3rd printing in January, 2000 Beijing.
2, the 38th in October, 2008 volume the 10th phase of coatings industry " HDI biuret polyurethane curing agent synthetic with the separating of remaining HDI ".
3, Chinese invention patent application number: 200910003621.4, title: the method for spray method synthesizing hexamethylene diisocyanate (HDI) biuret.
Claims (8)
1. curing agent modified hexamethylene diisocyanate biuret, it is characterized in that: containing dibasic alcohol modification HDI structure and biuret structure in this solidifying agent, is take organic solvent as solvent, by dibasic alcohol, water and HDI reaction and generate; The mol ratio of described dibasic alcohol and HDI is 0.05～0.2: 1, described water is 1: 3～4 with the mol ratio of residue HDI, the weight ratio of the consumption that described solvent load and reactant dibasic alcohol, water and HDI add up to is 0～60: 40～100, wherein HDI is the abbreviation of hexamethylene diisocyanate; Described curing agent modified hexamethylene diisocyanate (HDI) biuret is made by following steps:
A, add HDI and organic solvent in reactor, the rear adding that stirs is warming up to 60 ℃ through the dibasic alcohol of dehydration, 60～90 ℃ of reactions 1～6 hour, makes the HDI modifier;
B, be cooled to below 70 ℃, add first part's water, react and be warmed up to 75～100 ℃ of reactions 1～3 hour after 0.5～1.5 hour, be warmed up to again 120～140 ℃ and reacted 1～3 hour; Be cooled to below 70 ℃, add second section water, repeat above-mentioned technological process, until add the water of whole meterings, react be warmed up to after 0.5～1.5 hour 75～100 ℃ the reaction 1～3 hour, be warmed up to again 120～140 ℃ the reaction 1～5 hour, at this moment between, the degree of being undertaken by the content monitoring reaction that detects NCO to reactant sampling is when the content of NCO tends towards stability, is during near theoretical value reaction end;
C, sampling detect solid content, viscosity, NCO percentage composition and the transformation efficiency of product;
D, the distillation under vacuum with conventional, film evaporation method or solvent extration are extracted solvent and a small amount of residual HDI in the product out, are cooled to below 70 ℃ to add organic solvent by the requirement of product solid content, stir, and discharging gets modification HDI diisocyanate biuret curing agent.
2. the preparation method of a curing agent modified hexamethylene diisocyanate biuret as claimed in claim 1, it is characterized in that: preparation process is as follows:
A, add HDI and organic solvent in reactor, the rear adding that stirs is warming up to 60 ℃ through the dibasic alcohol of dehydration, 60～90 ℃ of reactions 1～6 hour, makes the HDI modifier;
B, be cooled to below 70 ℃, add first part's water, react and be warmed up to 75～100 ℃ of reactions 1～3 hour after 0.5～1.5 hour, be warmed up to again 120～140 ℃ and reacted 1～3 hour; Be cooled to below 70 ℃, add second section water, repeat above-mentioned technological process, until add the water of whole meterings, react be warmed up to after 0.5～1.5 hour 75～100 ℃ the reaction 1～3 hour, be warmed up to again 120～140 ℃ the reaction 1～5 hour, at this moment between, the degree of being undertaken by the content monitoring reaction that detects NCO to reactant sampling is when the content of NCO tends towards stability, is during near theoretical value reaction end;
C, sampling detect solid content, viscosity, NCO percentage composition and the transformation efficiency of product;
D, the distillation under vacuum with conventional, film evaporation method or solvent extration are extracted solvent and a small amount of residual HDI in the product out, are cooled to below 70 ℃ to add organic solvent by the requirement of product solid content, stir, and discharging gets modification HDI diisocyanate biuret curing agent.
3. according to claim 1 a kind of curing agent modified 1, the hexamethylene-diisocyanate biuret, it is characterized in that: described dibasic alcohol is polyester diol, polyether Glycols, terminal hydroxy group acrylic resin, terminal hydroxy group Synolac or small molecules dibasic alcohol, wherein any one or two or more mixtures.
4. according to claim 3 a kind of curing agent modified 1, the hexamethylene-diisocyanate biuret is characterized in that: described polyester diol is poly-hexanodioic acid-ethylene glycol and 1,2-propylene glycol ester dibasic alcohol, poly-hexanodioic acid-butanediol ester dibasic alcohol, poly-sebacic acid-hexanodioic acid-ethylene glycol-DOPCP dibasic alcohol, poly-m-phthalic acid-hexanodioic acid-neopentyl glycol-glycol ether ester dibasic alcohol, polycarbonate diol or polycaprolactone dibasic alcohol.
5. a kind of curing agent modified hexamethylene diisocyanate biuret according to claim 3, it is characterized in that: described polyether glycol is Polyoxypropylene diol, polyoxyethylene-propylene dibasic alcohol or polytetrahydrofuran dibasic alcohol.
6. according to claim 3 a kind of curing agent modified 1, the hexamethylene-diisocyanate biuret, it is characterized in that: described small molecules dibasic alcohol is the 3-methyl isophthalic acid, the 5-pentanediol, neopentyl glycol, ethylene glycol, glycol ether, cyclohexanediol, methyl propanediol, TCD three ring glycol, 1, ammediol, 1, the 4-hydroxymethyl-cyclohexane, 1, the 4-butyleneglycol, 1, the 3-butyleneglycol, 1, the 5-pentanediol, the diethyl pentanediol, 1, the 2-propylene glycol, glycol ether, erythritan, 1, the 6-hexylene glycol, neopentyl glycol, the butyl ethyl propylene glycol, 2,2-two (4-hydroxy phenyl) propane, hydroxypivalyl hydroxypivalate neopentyl alcohol ester, Resorcinol double hydroxyethyl ether, two (2-hydroxyethyl) ethers of quinhydrones, Resorcinol bis-hydroxypropyl ether, Resorcinol bis-hydroxypropyl ethyl ether, 2,5-ditert-butylhydro quinone, dipropylene glycol, tripropylene glycol or Rutgers 612.
7. a kind of curing agent modified hexamethylene diisocyanate biuret according to claim 1, it is characterized in that: described water is deionized water or distilled water.
8. according to claim 1 a kind of curing agent modified 1, the hexamethylene-diisocyanate biuret, it is characterized in that: described organic solvent is the ester class of vinyl acetic monomer, N-BUTYL ACETATE, ethylene glycol ether acetate, propylene glycol monomethyl ether acetate, methylcarbonate, diethyl carbonate, diphenyl carbonate, the ketone of acetone, butanone, pimelinketone, toluene, dimethylbenzene aromatic hydrocarbons, dioxane, tetrahydrofuran (THF), DMF reach wherein two or more mixture.
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|---|---|---|---|
| CN 201110028404 CN102617827B (en) | 2011-01-27 | 2011-01-27 | Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof |
| DE112011101335.3T DE112011101335B4 (en) | 2011-01-27 | 2011-08-26 | Modified 1,6-hexamethylene diisocyanate biuret curing agent and a method of producing the same |
| PCT/CN2011/078973 WO2012100532A1 (en) | 2011-01-27 | 2011-08-26 | Modified 1,6-hexamethylene diisocyanate biuret curing agent and preparation method therefor |
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| CN 201110028404 CN102617827B (en) | 2011-01-27 | 2011-01-27 | Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof |
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| JP5761460B2 (en) * | 2012-12-20 | 2015-08-12 | Dic株式会社 | Resin composition for water vapor barrier adhesive and laminate |
| CN105820302B (en) * | 2016-04-30 | 2018-09-14 | 华南理工大学 | A kind of nonionic and the mixed and modified water-based polyurethane curing agent of anion and preparation method thereof |
| CN107793909B (en) * | 2017-10-21 | 2019-10-08 | 中海油常州涂料化工研究院有限公司 | A kind of aviation aircraft exterior skin Lacquer finish coating and preparation method thereof |
| CN107674553B (en) * | 2017-11-13 | 2020-01-21 | 中国海洋石油集团有限公司 | Coating system for outer skin of aviation aircraft and preparation method thereof |
| CN111592635B (en) * | 2020-05-08 | 2022-04-19 | 深圳市前海博扬研究院有限公司 | Water-based polyurea curing agent and preparation method and application thereof |
| CN114853742B (en) * | 2022-05-13 | 2023-07-14 | 万华化学集团股份有限公司 | Preparation method and application of modified HDI uretdione curing agent |
| CN116041224B (en) * | 2023-01-31 | 2024-02-13 | 美瑞新材料股份有限公司 | Preparation method of hexamethylene diisocyanate biuret curing agent |
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| DE112011101335T5 (en) | 2013-04-04 |
| DE112011101335B4 (en) | 2016-10-27 |
| WO2012100532A1 (en) | 2012-08-02 |
| CN102617827A (en) | 2012-08-01 |
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