CN101235195A - Cation water polyurethane/acrylic ester composite emulsion and preparation method thereof - Google Patents
Cation water polyurethane/acrylic ester composite emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to cationic water-based polyurethane/acrylic ester composite emulsion and the preparation process, belonging to the chemical product and preparation technology field. Raw materials comprise diisocyanate mixture, polyhydric alcohol, organotin catalyst, chain extender, thinner, neutralizing agent and initiating agent. The preparation process comprises adding polyhydric alcohol into a reactor to dehydrate in vacuum, adding into diisocyanate mixture and organotin catalyst, conducting prepolymerization reaction to synthesize prepolymer with isocyanate-termi-nated, coldly adding thinner to dilute and to condense and reflow, adding chain extender to obtain mixture through chain extending reaction, cooling down, adding neutralizing agent to finish salt-forming reaction, regulating pH value, adding deionized water to conduct dispersed emulsification to obtain cationic water-based polyurethane elusion, and heating up and adding initiating agent to initiate free radical polymerization reaction to prepare composite elusion. The cationic water-based polyurethane/acrylic ester composite emulsion is synthesized through adopting non solvent process with low pollution and environment-friendly, increases solvent resistance, water resistance and tensile strength of glue film through introducing micro-cross-linked structure, increases hydrolytic stability of the glue film through introducing carbodiimide structure, and increases elongation at break and elasticity property through of glue film through introducing 2, 4-MDI.
Description
Technical field
The present invention relates to cation water polyurethane/acrylic ester composite emulsion and preparation method thereof, belong to Chemicals and preparation method thereof technical field.
Background technology
Aqueous polyurethane is for solvent borne polyurethane, and it is that polyurethane particles is dispersed in the binary colloidal system in the external phase (water).Aqueous polyurethane is medium with water, and execution conditions are good, produces and application safety, has the tangible value of environmental protection, and simultaneously, water cheaply is easy to get, thus can obviously reduce product cost, thereby more and more cause people's attention.
Mostly initial polyaminoester emulsion is with the organic solvent to be dispersion medium, and along with the establishment of various countries' environmental regulation and the enhancing of Environmental awareness, the discharging of the volatile organic compounds (VOC) in traditional solvent-borne type emulsion more and more is restricted.Therefore, the low water-based emulsion that pollutes environment-friendly type of exploitation has become the main direction of exploitation.In recent years, aqueous polyurethane is in commercial existing application, but since the drawbacks limit of performance its practical application, mainly be because aqueous polyurethane owing to introduced the hydrophilic radical of self-emulsifying, therefore there are shortcomings such as poor water resistance, physical strength are low in glued membrane, thereby has limited its practical performance.The water-and acrylate emulsion has advantages such as physical strength height, ageing-resistant, good weatherability and water-tolerant, but has the shortcoming of hot sticky cold crisp.Waterborne polyurethane resin and acrylic ester emulsion is compound, can overcome shortcoming separately, accomplish to maximize favourable factors and minimize unfavourable ones, film performance is significantly improved.
The isocyanic ester that is used to prepare aqueous polyurethane has aliphatic isocyanates and aromatic isocyanate, because the price of aliphatic isocyanates is higher, has improved the cost of aqueous polyurethane, thereby has limited the application of aqueous polyurethane.Aromatic isocyanate methylenediphenyl diisocyanates (MDI) and tolylene diisocyanate (TDI) output are bigger, can be used for the less demanding aqueous polyurethane Application Areas of xanthochromia, each isomer vapour pressure of MDI is lower, the normal temperature volatility is very little, TDI can be replaced, the main raw material of producing aqueous polyurethane can be developed into.
According to the position of substituting group NCO, MDI has three kinds of isomer, is respectively 2,4-MDI, 4,4-MDI and 2,2-MDI, common MDI-100 are 4, the MDI of 4-MDI content 98～100%, MDI-50 are 2,4-MDI/4, the MDI isomer mixture of 4-MDI mol ratio about 50/50.Liquefied mdi is the diphenylmethanediisocyanate of carbodiimide modification, it consists of 4,4-MDI, 2,4-MDI, carbodiimide, uretonimine, polymer, wherein requiring NCO content is between the 28.13%-29.35%, and two ring total amounts are between the 66.4%-70.5%, 2,4-MDI content is between the 0.68%-3.21%, and functionality is 2.05～2.15.Carbodiimide modification MDI crystallization drop out point point is 10～15 ℃, and normal temperature for liquid, can be stored and be used down at normal temperatures.Add a spot of liquefied mdi, crosslinking structure wherein makes the emulsion that makes have better stability, improves the anti-dissolubility and the water tolerance of glued membrane, and 2, the existence of 4-MDI also increases the snappiness of goods, improves elongation at break, makes sample have the good elasticity performance.
The method of tradition synthetic water based polyurethane adopts acetone or butanone method more, and the use of organic solvent be removed by distillation not only bad for environmental protection and need, and technology is loaded down with trivial details, consumes energy.Replace acetone or butanone as the thinner of system with acrylate, be again simultaneously the reaction monomers of preparation composite emulsion, thereby avoided in technology, steaming the complicated procedures that desolventizes.
Summary of the invention
The cation water polyurethane/acrylic ester composite emulsion that the object of the present invention is to provide a kind of mixing isocyanate component of the diphenylmethanediisocyanate that adopts methylenediphenyl diisocyanates and carbodiimide modification to make, and a kind of reduction emulsion particle is provided, improves glued membrane water tolerance and the low preparation method who pollutes the solvent-free cation water polyurethane/acrylic ester composite emulsion of environmental protection.
The objective of the invention is to realize by following measure:
Cation water polyurethane/acrylic ester composite emulsion of the present invention, its special character are that its material composition comprises:
1) mixture of the diphenylmethanediisocyanate isomer mixture of the different isomerization body burden of 10～32 mass parts and carbodiimide modified diphenylmethane diisocyanate;
2) polyvalent alcohol of 26～78 mass parts;
3) 0 ~ 1 mass parts organotin catalysts;
4) 1 ~ 14 mass parts small molecule chain extender composition wherein comprises 25% ~ 100% hydroxyl can be provided and contain the chainextender of halogens, tertiary amine at least;
5) thinner of 9～40 mass parts;
6) neutralizing agent of 1～10 mass parts;
7) initiator of 0.05～0.35 mass parts.
In order further to realize purpose of the present invention, described isocyanate mixture be 90 ~ 100% contain 98%4 at least, the diphenylmethanediisocyanate isomer mixture of 4-diphenylmethanediisocyanate and 0 ~ 10% carbodiimide modified diphenylmethane diisocyanate.Also can be 90 ~ 100% 2, the diphenylmethanediisocyanate isomer mixture of 4-diphenylmethanediisocyanate content 45 ~ 55% and 0 ~ 10% carbodiimide modified diphenylmethane diisocyanate.
In order further to realize purpose of the present invention, described polyvalent alcohol are how pure the many alcohol of the polyoxygenated ethylidene of molecular weight between 800 ~ 3000, the many alcohol of polyoxygenated propylidene, the many alcohol of polyoxygenated ethylene propylene copolyether, polytetrahydrofuran polyethers, polyester polyol, the many alcohol of polycaprolactone, polycarbonate are.
Described small molecule chain extender composition is made up of the chainextender that hydroxyl is provided and contains halogens, tertiary amine of 0 ~ 80% dibasic alcohol and 20 ~ 100%.Dibasic alcohol in the described small molecule chain extender can be ethylene glycol, propylene glycol, 1,4-butyleneglycol, pentanediol, hexylene glycol, glycol ether, neopentyl glycol.The hydrophilic chain extender that hydroxyl can be provided is the chainextender that contains halogens, tertiary amine, and commonly used have N methyldiethanol amine, N, N-dimethylethanolamine, thanomin, diethanolamine and a trolamine.Preferred N methyldiethanol amine.
Replacing the dispersion medium of the acetone/butanone in the traditional acetone method among the present invention is the esters of acrylic acid material: methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Octyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, Octyl acrylate.The esters of acrylic acid material can reduce the viscosity of system first, second Raolical polymerizable can take place.Make that the quaternary ammoniated neutralizing agent of tertiary amine is an inorganic acids in the chainextender, as: hydrochloric acid, nitric acid, and organic acid have acetate, propionic acid, monochloroacetic acid, oxyacetic acid, vinylformic acid, methacrylic acid.This patent preferably can participate in the vinylformic acid of Raolical polymerizable.
Being fit to organotin catalysts of the present invention is dibutyl tin laurate, stannous octoate, triethylamine, two inferior ethene triamines.Preferred dibutyl tin laurate.Initiator is in oiliness initiator Diisopropyl azodicarboxylate, water-based initiator potassium persulfate, the ammonium persulphate or two kinds of mixed initiators of oiliness/water-based.
The preparation method of above-mentioned cation water polyurethane/acrylic ester composite emulsion comprises the steps:
Proportioning at first as required adds reactor with polyhydric alcohol composition and vacuumizes dehydration more than one hour at 100-120 ℃, then the diphenylmethanediisocyanate of different isomerization body burden and the mixture and the organotin catalysts of carbodiimide modified diphenylmethane diisocyanate are added in the reactor, prepolymerization reaction 1～2.5 hour (preferred 1.5～2 hours) under 75～90 ℃ of (preferred 75～80 ℃) nitrogen protections, synthetic performed polymer with isocyanate terminated base;
Above-mentioned reaction product is cooled to 40～55 ℃, it is 50～80% (preferred 70%) that the adding thinner is diluted to solid content, condensing reflux, add small molecule chain extender and hydrophilic chain extender, chain extending reaction obtained mixture in 0.5 ~ 1.5 hour under 60 ~ 90 ℃ of nitrogen protections, temperature of reaction is 55～70 ℃, 0.5～1.5 hour reaction times (preferred 1 hour);
Reaction product is cooled to below 45 ℃, neutralizing agent is added in the reactor, neutralise mixt is finished salt-forming reaction, after adjusting mixture pH value is 5～7 (preferred 5 ~ 5.6), in stir speed (S.S.) is at the uniform velocity to add the deionized water dispersion and emulsion under the stirrer of 500～10000r/m (preferred 2000r/m) stirs, and makes cation aqueous polyurethane emulsion;
With the cation aqueous polyurethane emulsion that makes above, intensification is 60～90 ℃ (preferred 60～70 ℃), at N
2Under the protection and reflux condensation mode of gas, add initiator initiating methacrylates class monomer and vinylformic acid generation Raolical polymerizable, react 1.5～3 hours (preferred 1.5～2.5 hours), make the cation water polyurethane/acrylic ester composite emulsion emulsion.
Advantage of the present invention is to adopt the low no-solvent process synthesizing cationic water-based composite emulsion of environmental protection, the diphenylmethanediisocyanate that adopts the different isomerization body burden and the mixture of carbodiimide modified diphenylmethane diisocyanate of polluting, introduce the solvent resistance that little crosslinking structure has improved glued membrane, water tolerance and tensile strength, introduce the stability to hydrolysis that the carbodiimide structure has improved glued membrane, introduce 2,4-MDI has improved the elongation at break and the elastic performance of glued membrane.
Cation water polyurethane/acrylic ester composite emulsion of the present invention can be used as coating-forming agent, tackiness agent etc. and is applied to industries such as weaving, leather, coating, tackiness agent, wood working, building, printing and dyeing.
Embodiment
Substantive features that the present invention gives prominence to and progress can be able to further embodiment from following embodiment.Should point out that they do not impose any restrictions the present invention.
Embodiment 1
Is 0.09MPa dehydration 1h with 41.34g polytetrahydrofuran (Mn=2000) 110～120 ℃ of vacuum tightnesss, adds then and is furnished with in the there-necked flask of thermometer, stirring rod, reflux condensing tube, logical N
2Protection; constant temperature to 70 ℃ adds the diphenylmethanediisocyanate of 12.13g solid MDI (4,4-MDI content is 98%) and the modification of 1.34g carbodiimide; add the 0.10g dibutyltin dilaurate after half hour; 80 ℃ of reaction 2h are cooled to 55 ℃, and adding an amount of methyl methacrylate, to be diluted to solid content be 70%; condensing reflux; add 2.40gN-methyldiethanolamine (N-MDEA is with a small amount of butanone dissolving), reaction 1h.The temperature of reactor is reduced to below 45 ℃, add the 0.86g methacrylic acid, react 0.5h, add 5% dilute hydrochloric acid adjusting PH=5 ~ 6 simultaneously.This prepolymer is cooled to room temperature, at the uniform velocity add deionized water 250g, in stir speed (S.S.) is to make solid content under the 2000r/m to be approximately 20% aqueous polyurethane emulsion, add 0.18g Diisopropyl azodicarboxylate (AIBN, be dissolved in micro-MMA), 70 ℃ of reaction 2.5h make solid content and are approximately 30% water polyurethane/acrylic ester composite emulsion.
Embodiment 2
Is 0.09MPa dehydration 1h with 77.65g polytetrahydrofuran (Mn=4000) 110～120 ℃ of vacuum tightnesss, adds then and is furnished with in the there-necked flask of thermometer, stirring rod, reflux condensing tube, logical N
2Protection; constant temperature to 70 ℃ adds the diphenylmethanediisocyanate of 11.21g solid MDI (2,4-MDI content is 47%) and the modification of 1.00g carbodiimide; add the 0.10g dibutyltin dilaurate after half hour; 80 ℃ of reaction 2h are cooled to 55 ℃, and adding an amount of methyl methacrylate, to be diluted to solid content be 75%; condensing reflux; add 2.58gN-methyldiethanolamine (N-MDEA is with a small amount of butanone dissolving), reaction 1h.The temperature of reactor is reduced to below 45 ℃, add the 1.25g methacrylic acid, react 0.5h, add 5% dilute hydrochloric acid adjusting PH=5 ~ 6 simultaneously.This prepolymer is cooled to room temperature, at the uniform velocity add deionized water 450g, in stir speed (S.S.) is to make solid content under the 2000r/m to be approximately 20% aqueous polyurethane emulsion, add 0.22g Diisopropyl azodicarboxylate (AIBN, be dissolved in micro-MMA), 70 ℃ of reaction 2.5h make solid content and are approximately 30% water polyurethane/acrylic ester composite emulsion.
Embodiment 3
Is 0.09MPa dehydration 1h with 40.00g polyoxyethylene glycol (Mn=1000) 110～120 ℃ of vacuum tightnesss, adds then and is furnished with in the there-necked flask of thermometer, stirring rod, reflux condensing tube, logical N
2Protection; constant temperature to 70 ℃ adds the diphenylmethanediisocyanate of 15.88g solid MDI (4,4-MDI content is 98%) and the modification of 1.38g carbodiimide; add the 0.10g dibutyltin dilaurate after half hour; 80 ℃ of reaction 2h are cooled to 55 ℃, and adding an amount of methyl methacrylate, to be diluted to solid content be 70%; condensing reflux; add 2.65gN-methyldiethanolamine (N-MDEA is with a small amount of butanone dissolving) and 0.90g 1.4-butyleneglycol, reaction 1h.The temperature of reactor is reduced to below 45 ℃, add the 0.86g methacrylic acid, react 0.5h, add 5% dilute hydrochloric acid adjusting PH=5 ~ 6 simultaneously.This prepolymer is cooled to room temperature, at the uniform velocity add deionized water 300g, in stir speed (S.S.) is to make solid content under the 2000r/m to be approximately 20% aqueous polyurethane emulsion, add 0.19g Diisopropyl azodicarboxylate (AIBN, be dissolved in micro-MMA), 70 ℃ of reaction 2.5h make solid content and are approximately 30% water polyurethane/acrylic ester composite emulsion.
Embodiment 4
Is 0.09MPa dehydration 1h with 25.36g polyoxyethylene glycol (Mn=1000) 110～120 ℃ of vacuum tightnesss, adds then and is furnished with in the there-necked flask of thermometer, stirring rod, reflux condensing tube, logical N
2Protection; constant temperature to 70 ℃ adds the diphenylmethanediisocyanate of 10.59g solid MDI (2,4-MDI content is 47%) and the modification of 1.00g carbodiimide; add the 0.10g dibutyltin dilaurate after half hour; 80 ℃ of reaction 2h are cooled to 55 ℃, and adding an amount of methyl methacrylate, to be diluted to solid content be 75%; condensing reflux; add 3.12gN-methyldiethanolamine (N-MDEA is with a small amount of butanone dissolving), reaction 1h.The temperature of reactor is reduced to below 45 ℃, add the 1.09g methacrylic acid, react 0.5h, add 5% dilute hydrochloric acid adjusting PH=5 ~ 6 simultaneously.This prepolymer is cooled to room temperature, at the uniform velocity add deionized water 200g, in stir speed (S.S.) is to make solid content under the 2000r/m to be approximately 20% aqueous polyurethane emulsion, add 0.09g Diisopropyl azodicarboxylate (AIBN, be dissolved in micro-MMA), 70 ℃ of reaction 2.5h make solid content and are approximately 30% water polyurethane/acrylic ester composite emulsion.
Embodiment 5
Is 0.09MPa dehydration 1h with 20.00g polyoxyethylene glycol (Mn=2000) 110～120 ℃ of vacuum tightnesss with 20.00g polytetrahydrofuran (Mn=2000), adds then and is furnished with in the there-necked flask of thermometer, stirring rod, reflux condensing tube, logical N
2Protection; constant temperature to 70 ℃ adds the diphenylmethanediisocyanate of 13.27g solid MDI (4,4-MDI content is 98%) and the modification of 1.35g carbodiimide; add the 0.10g dibutyltin dilaurate after half hour; 80 ℃ of reaction 2h are cooled to 55 ℃, and adding an amount of butyl methacrylate, to be diluted to solid content be 65%; condensing reflux; add 2.83gN-methyldiethanolamine (N-MDEA is with a small amount of butanone dissolving), reaction 1h.The temperature of reactor is reduced to below 45 ℃, add the 1.10g methacrylic acid, react 0.5h, add 5% dilute hydrochloric acid adjusting PH=5 ~ 6 simultaneously.This prepolymer is cooled to room temperature, at the uniform velocity add deionized water 300g, in stir speed (S.S.) is to make solid content under the 2000r/m to be approximately 20% aqueous polyurethane emulsion, add 0.12g Diisopropyl azodicarboxylate (AIBN, be dissolved in micro-MMA), 70 ℃ of reaction 2.5h make solid content and are approximately 30% water polyurethane/acrylic ester composite emulsion.
Embodiment 6
Is 0.09MPa dehydration 1h with 21.26g polyoxyethylene glycol (Mn=2000) 110～120 ℃ of vacuum tightnesss with 23.25g polytetrahydrofuran (Mn=2000), adds then and is furnished with in the there-necked flask of thermometer, stirring rod, reflux condensing tube, logical N
2Protection; constant temperature to 70 ℃ adds the diphenylmethanediisocyanate of 17.43g solid MDI (2,4-MDI content is 47%) and the modification of 1.55g carbodiimide; add the 0.10g dibutyltin dilaurate after half hour; 80 ℃ of reaction 2h are cooled to 55 ℃, and adding an amount of methyl methacrylate, to be diluted to solid content be 70%; condensing reflux; add 4.76gN-methyldiethanolamine (N-MDEA is with a small amount of butanone dissolving), reaction 1h.The temperature of reactor is reduced to below 45 ℃, add the 1.72g methacrylic acid, react 0.5h, add 5% dilute hydrochloric acid adjusting PH=5 ~ 6 simultaneously.This prepolymer is cooled to room temperature, at the uniform velocity add deionized water 300g, in stir speed (S.S.) is to make solid content under the 2000r/m to be approximately 20% aqueous polyurethane emulsion, add 0.15g Diisopropyl azodicarboxylate (AIBN, be dissolved in micro-MMA), 70 ℃ of reaction 2.5h make solid content and are approximately 30% water polyurethane/acrylic ester composite emulsion.
Embodiment 7
Is 0.09MPa dehydration 1h with 44.26g polyoxyethylene glycol (Mn=2000) 110～120 ℃ of vacuum tightnesss, adds then and is furnished with in the there-necked flask of thermometer, stirring rod, reflux condensing tube, logical N
2Protection; constant temperature to 70 ℃ adds the diphenylmethanediisocyanate of 15.46g solid MDI (2,4-MDI content is 47%) and the modification of 1.50g carbodiimide; add the 0.10g dibutyltin dilaurate after half hour; 80 ℃ of reaction 2h are cooled to 55 ℃, and adding an amount of methyl methacrylate, to be diluted to solid content be 70%; condensing reflux; add 4.98gN-methyldiethanolamine (N-MDEA is with a small amount of butanone dissolving), reaction 1h.The temperature of reactor is reduced to below 45 ℃, add the 1.79g methacrylic acid, react 0.5h, add 5% dilute hydrochloric acid adjusting PH=5 ~ 6 simultaneously.This prepolymer is cooled to room temperature, at the uniform velocity add deionized water 300g, in stir speed (S.S.) is to make solid content under the 2000r/m to be approximately 20% aqueous polyurethane emulsion, add 0.35gKPS (being dissolved in the minor amount of water), 60 ℃ of reaction 2.5h make solid content and are approximately 30% water polyurethane/acrylic ester composite emulsion.
Embodiment 8
Is 0.09MPa dehydration 1h with 54.26g polycaprolactone polyol (Mn=1000) 110～120 ℃ of vacuum tightnesss, adds then and is furnished with in the there-necked flask of thermometer, stirring rod, reflux condensing tube, logical N
2Protection; constant temperature to 70 ℃ adds the diphenylmethanediisocyanate of 21.35g solid MDI (2,4--MDI content is 47%) and the modification of 2.15g carbodiimide; add the 0.10g dibutyltin dilaurate after half hour; 80 ℃ of reaction 2h are cooled to 55 ℃, and adding an amount of methyl methacrylate, to be diluted to solid content be 70%; condensing reflux; add 3.38gN-methyldiethanolamine (N-MDEA is with a small amount of butanone dissolving) and 0.90g1.4-butyleneglycol, reaction 1h.The temperature of reactor is reduced to below 45 ℃, add the 1.26g methacrylic acid, react 0.5h, add 5% dilute hydrochloric acid adjusting PH=5 ~ 6 simultaneously.This prepolymer is cooled to room temperature, at the uniform velocity add deionized water 400g, in stir speed (S.S.) is to make solid content under the 2000r/m to be approximately 20% aqueous polyurethane emulsion, add 0.23g Diisopropyl azodicarboxylate (AIBN, be dissolved in micro-MMA), 70 ℃ of reaction 2.5h make solid content and are approximately 30% water polyurethane/acrylic ester composite emulsion.
Embodiment 9
Is 0.09MPa dehydration 1h with 50.34g polycaprolactone polyol (Mn=2000) 110～120 ℃ of vacuum tightnesss, adds then and is furnished with in the there-necked flask of thermometer, stirring rod, reflux condensing tube, logical N
2Protection; constant temperature to 70 ℃ adds the diphenylmethanediisocyanate of 18.32g solid MDI (4,4-MDI content is 98%) and the modification of 1.22g carbodiimide; add the 0.10g dibutyltin dilaurate after half hour; 80 ℃ of reaction 2h are cooled to 55 ℃, and adding an amount of methyl methacrylate, to be diluted to solid content be 70%; condensing reflux; add 4.15gN-methyldiethanolamine (N-MDEA is with a small amount of butanone dissolving) and 2.13g propylene glycol, reaction 1h.The temperature of reactor is reduced to below 45 ℃, add the 1.38g methacrylic acid, react 0.5h, add 5% dilute hydrochloric acid adjusting PH=5 ~ 6 simultaneously.This prepolymer is cooled to room temperature, at the uniform velocity add deionized water 350g, in stir speed (S.S.) is to make solid content under the 2000r/m to be approximately 20% aqueous polyurethane emulsion, add 0.13g Diisopropyl azodicarboxylate (AIBN, be dissolved in micro-MMA), 70 ℃ of reaction 2.5h make solid content and are approximately 30% water polyurethane/acrylic ester composite emulsion.
Claims (10)
1. cation water polyurethane/acrylic ester composite emulsion is characterized in that its material composition comprises:
1) mixture of the diphenylmethanediisocyanate isomer mixture of the different isomerization body burden of 10～32 mass parts and carbodiimide modified diphenylmethane diisocyanate;
2) polyvalent alcohol of 26～78 mass parts;
3) 0 ~ 1 mass parts organotin catalysts;
4) 1 ~ 14 mass parts small molecule chain extender composition wherein comprises 25% ~ 100% hydroxyl can be provided and contain the chainextender of halogens, tertiary amine at least;
5) thinner of 9～40 mass parts;
6) neutralizing agent of 1～10 mass parts;
7) initiator of 0.05～0.35 mass parts.
2. cation water polyurethane/acrylic ester composite emulsion according to claim 1, it is characterized in that described isocyanate mixture be 90 ~ 100% contain 98%4 at least, the diphenylmethanediisocyanate isomer mixture of 4-diphenylmethanediisocyanate and 0 ~ 10% carbodiimide modified diphenylmethane diisocyanate.
3. cation water polyurethane/acrylic ester composite emulsion according to claim 1, it is characterized in that described isocyanate-based mixture be 90 ~ 100% 2, the diphenylmethanediisocyanate isomer mixture of 4-diphenylmethanediisocyanate content 45 ~ 55% and 0 ~ 10% carbodiimide modified diphenylmethane diisocyanate.
4. cation water polyurethane/acrylic ester composite emulsion according to claim 1 is characterized in that described polyhydric alcohol composition is many pure one or more of the many alcohol of the polyoxygenated ethylidene of molecular weight between 800 ~ 3000, the many alcohol of polyoxygenated propylidene, the many alcohol of polyoxygenated ethylene propylene copolyether, polytetrahydrofuran polyethers, polyester polyol, the many alcohol of polycaprolactone, polycarbonate.
5. cation water polyurethane/acrylic ester composite emulsion according to claim 1 is characterized in that described small molecule chain extender composition is made up of the chainextender that hydroxyl is provided and contains halogens, tertiary amine of 0 ~ 80% dibasic alcohol and 20 ~ 100%.
6. cation water polyurethane/acrylic ester composite emulsion according to claim 5, it is characterized in that described dibasic alcohol is ethylene glycol, propylene glycol, 1, one or more of 4-butyleneglycol, pentanediol, hexylene glycol, glycol ether, neopentyl glycol, it is N methyldiethanol amine, N that the chainextender of hydroxyl and halogen-containing element, tertiary amine is provided, a kind of in N-dimethylethanolamine, thanomin, diethanolamine and the trolamine.
7. cation water polyurethane/acrylic ester composite emulsion according to claim 1, it is characterized in that thinner is to issue living free radical polymeric material in the condition that initiator exists, and is the esters of acrylic acid material: one or more in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Octyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, the Octyl acrylate.
8. cation water polyurethane/acrylic ester composite emulsion according to claim 1, it is characterized in that making that the quaternary ammoniated neutralizing agent of tertiary amine is an inorganic acids in the chainextender: hydrochloric acid, nitric acid, and organic acid: a kind of in acetate, propionic acid, monochloroacetic acid, oxyacetic acid, vinylformic acid, the methacrylic acid, this neutralizing agent can participate in Raolical polymerizable in the presence of initiator.
9. cation water polyurethane/acrylic ester composite emulsion according to claim 1, it is characterized in that described organotin catalysts is dibutyl tin laurate, stannous octoate, triethylamine, two inferior ethene triamines, initiator is: the two kinds of mixed initiators of a kind of or oiliness/water-based in oiliness initiator Diisopropyl azodicarboxylate, water-based initiator potassium persulfate, the ammonium persulphate.
10. the preparation method of the described cation water polyurethane/acrylic ester composite emulsion of arbitrary claim among the right 1-9 is characterized in that comprising the steps:
Proportioning at first as required adds reactor with polyhydric alcohol composition and vacuumizes dehydration more than one hour at 100-120 ℃, then the diphenylmethanediisocyanate of different isomerization body burden and the mixture and the organotin catalysts of carbodiimide modified diphenylmethane diisocyanate are added in the reactor, prepolymerization reaction is 1～2.5 hour under 75～90 ℃ of nitrogen protections, synthetic performed polymer with isocyanate terminated base;
Above-mentioned reaction product is cooled to 40～55 ℃, and it is 50～80% that the adding thinner is diluted to solid content, condensing reflux, add small molecule chain extender, chain extending reaction obtained mixture in 0.5 ~ 1.5 hour under 60 ~ 90 ℃ of nitrogen protections, and temperature of reaction is 55～70 ℃, 0.5～1.5 hour reaction times;
Reaction product is cooled to below 45 ℃, neutralizing agent is added in the reactor, and neutralise mixt is finished reactant salt, after adjusting mixture pH value is 5～7, in stir speed (S.S.) is at the uniform velocity to add the deionized water dispersion and emulsion under the stirrer of 500～10000r/m stirs, and makes cation aqueous polyurethane emulsion;
With the cation aqueous polyurethane emulsion that makes above, intensification is 60～90 ℃, at N
2Under the protection and reflux condensation mode of gas, add initiator initiating methacrylates class monomer and vinylformic acid generation Raolical polymerizable, reacted 1.5～3 hours, make the cation water polyurethane/acrylic ester composite emulsion emulsion.
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| CN2008100146686A CN101235195B (en) | 2008-02-27 | 2008-02-27 | Cation water polyurethane/acrylic ester composite emulsion and preparation method thereof |
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