CN105622857B - A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite - Google Patents
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite Download PDFInfo
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- CN105622857B CN105622857B CN201610203125.3A CN201610203125A CN105622857B CN 105622857 B CN105622857 B CN 105622857B CN 201610203125 A CN201610203125 A CN 201610203125A CN 105622857 B CN105622857 B CN 105622857B
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract
The present invention provides a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, comprises the following steps：1] polymer polyatomic alcohol and hydrophily function monomer vacuum dehydration processing；2] catalyst and diisocyanate are added to react at room temperature 0.5 2 hours, is warming up to 60 80 DEG C of insulation reactions 15 hours；3] 40 50 DEG C are cooled to, chain extender insulation reaction is added 24 hours；4] 60 70 DEG C are warming up to, reactive monomer end-blocking is added；5] 30 50 DEG C are cooled to, nertralizer regulation pH value is added.6] 60 DEG C are warming up to, deionized water, dispersed with stirring is added dropwise；7] 60 65 DEG C are warming up to, the aqueous solution of initiator is added dropwise and into nuclear monomer, temperature programming insulation reaction obtains a kind of aqueous polyurethane nano composite of inierpeneirating network structure.Advantages of the present invention：Efficiently solve VOC emission problem；The characteristics of nano composite material possesses core shell structure and inierpeneirating network structure so that it has good mechanical property；Using the synthesis technique of continuity method, be conducive to improving production efficiency.
Description
Technical field
The invention belongs to macromolecule field of new materials, and in particular to a kind of inierpeneirating network structure aqueous polyurethane nano is combined
The preparation method of material.
Background technology
World Environment pollution is very serious, and energy-saving and emission-reduction are very urgent while promoting economic development.Europe
The organic volatile of alliance and the U.S. to coating/ink（VOC）Discharge capacity has formulated harsh limit standard, and China was from 2015
The consumption tax is levied to solvent based coating, promotes industry to make the transition and upgrade.Therefore, the environment-friendlywater-based water-based paint with novel structure/
The design synthesis and the innovation of synthetic method of ink/adhesive and its resin all have great importance.
Aqueous polyurethane applies quite varied polymeric material as a class, so far the existing developing history of decades,
Also there are 30 years of researches and development and application history in China.But the aqueous polyurethane developed is more using acetone as solvent, between
Method of having a rest is synthesized, and synthesis finishes removed under reduced pressure acetone again, obtains aqueous polyurethane dispersion or emulsion.There are two nothings in this method
The shortcoming that method overcomes.First, acetone and water can be dissolved each other with any ratio, and can pass through decompression with water formation azeotropic mixture, post-synthesis phase
The method of removing acetone can not eliminate acetone；Furthermore, batch process is first to synthesize waterborne polyurethane resin, then by resin by reacting
Device is transferred to disperser and adds water scattered, if the scattered needs that finish are further modified, needs dispersion liquid returning to reaction dress
Put, so complicated technique brings great inconvenience to synthesis and production.
Based on above-mentioned background, a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite has been invented,
This method synthesizes waterborne polyurethane resin using organic solvent-free, efficiently solves the VOC emission problem caused by acetone method；
Meanwhile, the method for having invented continuity method synthesis or production aqueous polyurethane efficiently solves the complicated technology problem of batch process,
Improve production efficiency；The introducing of inierpeneirating network structure causes acrylate to be connected with polyurethane resin by chemical bond
Come, efficiently solve the compatibility and problems of stability in storage of two kinds of different resins, veritably realize two kinds of resins each
The organic unity of excellent properties so that material has more preferable film forming, film has well wear-resisting and scoring resistance and higher
Mechanical strength, improve the actual application value of material.A kind of inierpeneirating network structure aqueous polyurethane nano invented is answered
Condensation material can be applied in printing packagings such as food, medicine, tobacco and wine, books and periodicals as water varnish, water-based ink and water-based gloss oil
Field.
The content of the invention
It is an object of the invention to provide a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite,
It mainly solves the deficiency present in existing aqueous polyurethane coating/ink/adhesive：Solventless method synthesis is invented aqueous
Polyurethane resin, efficiently solve the VOC emission problem caused by acetone method, it is to avoid solvent borne polyurethane system is because a large amount of
Organic solvent pollution environment, it is unhealthful, cause the problem of production cost is high；Interpenetrating networks are introduced in terms of MOLECULE DESIGN
Structure so that material has more preferable film forming, film forming has good wear-resisting and scoring resistance and higher mechanical strength；Together
When, the method for having invented continuity method synthesis or production aqueous polyurethane efficiently solves the complicated technology problem of batch process, carried
High production efficiency；This invention also solves the temperature tolerance after existing aqueous polyurethane system film forming is poor, hardness is low, adhesive strength
Low problem.
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite of the present invention, is specifically included following
Step：
1] polymer polyatomic alcohol and hydrophily function monomer are added into reaction vessel, at 90-120 DEG C at vacuum dehydration
Reason 1-2 hours；
2] system temperature is down to room temperature, adds catalyst, be uniformly mixed；
3] add diisocyanate and reaction 0.5-2 hours is stirred at room temperature, be warming up to 60-80 DEG C of insulation reaction 1-5 small
When, obtain Waterborne Polyurethane Prepolymer；
4] system temperature is down to 40-50 DEG C, adds polyalcohol or polyamine conduct of the relative molecular mass below 500
Chain extender, chain extending reaction 2-4 hours；
5] 60-70 DEG C is warming up to, the reactive monomer of metering and the end group of Waterborne Polyurethane Prepolymer is added（-NCO）Hair
Give birth to end capping reaction, while adding methyl methacrylate diluted system viscosity, add polymerization inhibitor, be incubated at 60-70 DEG C anti-
Answer 3-5 hours；- NCO conversion ratio is titrated by n-Butylamine titration method, stops reaction after-NCO content reaches theoretical value, i.e.,
Obtain aqueous polyurethane acrylate resin；
6] 30-50 DEG C is cooled to, nertralizer neutralized aqueous polyurethane acrylate resin is added, regulation pH value is in 7-8.5
Between；
7] 60-70 DEG C is warming up to, deionized water is added dropwise, the dispersed with stirring when being added dropwise obtains aqueous polyurethane acrylate
Aqueous dispersion；
8] 60-65 DEG C is warming up to, the aqueous solution of initiator is added dropwise, while nuclear monomer is added dropwise into, time for adding is small no more than 1
When, insulation reaction 2-3 hours at 60-65 DEG C；70-75 DEG C is warming up to again, and insulation reaction 2-3 hours obtains a kind of IPN net
The aqueous polyurethane nano composite of network structure, the nano composite material is the emulsion with blue light.
By weight, each component content is for the raw material respectively reacted and auxiliary dosage：
Diisocyanate： 37.5-70
Polymer polyatomic alcohol： 37.5-72.5
Hydrophily function monomer： 2.5-5
Methyl methacrylate： 7.5-10
Into nuclear monomer： 82.5-87.5
Reactive monomer： 7.5-10
Chain extender： 2.25-7
Catalyst： 0.5-0.55
Polymerization inhibitor： 0.25-0.5
Nertralizer： 4-5
Initiator： 0.5-0.75
Deionized water： 265-275.
The polymer polyatomic alcohol is PPG, including PolyTHF ethoxylated polyhydric alcohol（PTMEG）, polyethylene glycol oxide
Polyalcohol（PEG）, polyoxypropylene polyol（PPG）, one kind or many in polyethylene glycol oxide propylene-based block copolymer polyalcohol
The mixture of PPG is planted, number-average molecular weight is in 1000-2000, and PPG has preferable water resistance, synthesized
Aqueous polyurethane acrylate in aqueous phase stable not facile hydrolysis.
The step 1], by one or more addition reaction vessels in the PPG, while adding hydrophily
Function monomer, and progressively it is warming up to 90 DEG C ~ 120 DEG C, vacuum is slowly risen to 0.098-0.1MPa, dewater treatment 1 ~ 2 is small
When.
The hydrophily function monomer is one kind in the compound containing carboxyl, amino, hydroxyl or sulfonate radical in molecule
Or a variety of mixtures.
The hydrophily function monomer is dihydromethyl propionic acid（DMPA）, dimethylolpropionic acid (DMBA), pyromellitic acid two
Acid anhydride (BPDA), 1,2- propane diols -3- sodium sulfonates, 1,4- butanediol -2- sodium sulfonates, 2- [(2- amino-ethyls) amino] ethyl sulfonic acid sodium
One or more mixtures in salt.
The catalyst is mainly triethylenediamine, double（Dimethylaminoethyl）Ether, 2-（2- Dimethylamino-ethoxies）
The mixture of one or both of ethanol, organo-tin compound, organomercurial compound and organo-lead compound.
The chain extender is ethylene glycol, 1,4- butanediols, 1,2- propane diols, 1,3- propane diols, diglycol, 1,6-
Hexylene glycol, glycerine, trimethylolpropane, ethylenediamine, 1,6- hexamethylene diamines, hydrazine hydrate, monoethanolamine, diethanol amine and triethanolamine
In one or more mixtures.
The polymerization inhibitor is hydroquinones, 2,6- di-t-butyl -4- sylvans, alkylation aniline and phosphorous acid esters chemical combination
One or more mixtures in thing.
The reactive monomer is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, acrylic acid
One kind in hydroxypropyl acrylate, pentaerythritol triacrylate and epoxy modification acrylate, end that can be with Waterborne Polyurethane Prepolymer
Base（-NCO）Generation hair is answered, and obtains the aqueous polyurethane acrylate resin of acrylate ended.
The diisocyanate is aromatic series and/or aliphatic diisocyanate, mainly including 2,4- toluene diisocynates
Ester（TDI）, 4,4 '-'-diphenylmethane diisocyanate（MDI）, 4,4 '-hydrogenated diphenyl methane diisocyanate（HMDI）, different Fo Er
Ketone diisocyanate（IPDI）And hexamethylene diisocyanate（HDI）One or both of mixture.
The isocyanato（-NCO）Conversion ratio, be foundation《It is different in HG-T 2409-1992 base polyurethane prepolymer for use as
The measure of cyanic acid ester group content》Method is titrated, and is illustrated that prepolymerization reaction terminates when-NCO content reaches theoretical value, that is, is obtained aqueous
Polyurethane acrylic resin.
The step 3], add diisocyanate and reaction 1 hour is stirred at room temperature, be warming up to 60-80 DEG C of insulation reaction
1-5 hours, obtain Waterborne Polyurethane Prepolymer.
The nertralizer is trimethylamine compound, ammoniacal liquor, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, by metering
It is added drop-wise in aqueous polyurethane acrylate resin, is stirred when being added dropwise, neutralization reaction 1 hour at 30 ~ 50 DEG C obtains solvable
In the carboxylic acid type aqueous polyurethane acrylate of water, pH value is controlled between 7 ~ 8.5.
System temperature is risen to 60 DEG C, deionized water is added dropwise into the aqueous polyurethane acrylate resin after neutralization,
Stir, 1 hour completion of dropping, be stirred for scattered 1 hour when being added dropwise；Occur mutually to overturn in the process, i.e., hydrophilic carboxylic acid
The outside ordered arrangement of salt groups, urethane acrylate main chain inward curl is agglomerating, forms oil-in-water（O/W）Spherical micelle knot
Structure, i.e. aqueous urethane acrylate dispersoid.
Initiator used is azo-bis-isobutyl cyanide, the different cyanogen in heptan of azo two, ammonium persulfate or potassium peroxydisulfate；Initiator is added to draw
Acrylate mixture copolymerization is sent out, while triggering aqueous polyurethane acrylate to crosslink reaction.
It is described into the mixture that nuclear monomer is styrene and acrylate, due to being oily matter into nuclear monomer, thus into
Nuclear monomer enters inside aqueous polyurethane micella, as oil phase.
The acrylate is methacrylic acid, methyl methacrylate, methyl acrylate, butyl methacrylate, third
Olefin(e) acid butyl ester, hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate, metering system
One or more in sour isobornyl thiocyanoacetate, isobornyl acrylate, pentaerythritol triacrylate and epoxy modification acrylate.
The step 8], while the aqueous solution of initiator is added dropwise and remaining into nuclear monomer, dripped within 1 hour at 65 DEG C
Finish, insulation reaction 2 ~ 3 hours at 65 DEG C, insulation reaction 2 ~ 3 hours at 75 DEG C；In the presence of initiator, into nuclear monomer mixing
Thing is copolymerized inside spherical micelle, while crosslinking reaction with the acrylate of end-blocking, forms interpenetrating networks knot
Structure.
Acrylate modified aqueous polyurethane acrylate composite is a kind of compound with inierpeneirating network structure
Material；Water-soluble polyurethane acrylic resin has self-emulsifying function, when adding water scattered occur hydrophilic and oleophilic structure upset and
O/W stable dispersion phase is formed, the acrylate mixture being added dropwise is internally formed oil phase into micella, is copolymerized into
Core, the acrylate blocked with aqueous polyurethane crosslinks reaction, forms inierpeneirating network structure；Obtain using polyacrylate as
Core, aqueous polyurethane are the core shell structure of shell.
The inierpeneirating network structure aqueous polyurethane nano composite that a kind of utilization above method of the present invention is prepared,
The particle diameter of the nano composite material is between 30 ~ 50nm, the nano composite material has core shell structure.
The nano composite material is a kind of translucent emulsion with blue light.
The inierpeneirating network structure aqueous polyurethane nano composite that a kind of utilization above method of the present invention is prepared
Purposes, the nano composite material can be used as water paint matrix resin, water-based ink binder and Aqueous Adhesives main body tree
Fat is applied to building materials, furniture, leather, fabric and printing packaging industry.
Advantages of the present invention is mainly reflected in：
The preparation method of the inierpeneirating network structure aqueous polyurethane nano composite of the present invention, wherein, without using acetone
Make solvent, efficiently controlled VOC emission problem, reduce the pollution to environment and healthhazard；
The preparation method of the inierpeneirating network structure aqueous polyurethane nano composite of the present invention, wherein, this is nano combined
Material possesses core shell structure feature with acrylic ester modified water-soluble polyurethane；
The preparation method of the inierpeneirating network structure aqueous polyurethane nano composite of the present invention, wherein, this is nano combined
Material introduces inierpeneirating network structure, and material has good mechanical property, wear-resisting and scoring resistance energy；
The preparation method of the inierpeneirating network structure aqueous polyurethane nano composite of the present invention, wherein, synthesis or production
Replace traditional batch process in technique with continuity method, be conducive to improving production efficiency；
The preparation method of the inierpeneirating network structure aqueous polyurethane nano composite of the present invention, wherein, this is nano combined
Material can be applied to require very strict food, medicine, cigarette to VOC emission as water varnish, water-based ink and water-based gloss oil
The printing packaging such as wine, books and periodicals field.
Brief description of the drawings
The synthetic reaction equation and schematic arrangement of Fig. 1 embodiments 1；
The dynamic light scattering method of Fig. 2 embodiments 1 tests the grain size distribution of dispersion；
The dynamic light scattering method of Fig. 3 embodiments 1 tests the grain size distribution of nano composite material；
The aqueous polyurethane nano composite scanning electron microscope (SEM) photograph of Fig. 4 embodiments 1（SEM）；
The aqueous polyurethane nano composite transmission electron microscope picture of Fig. 5 embodiments 1（TEM）.
Embodiment
For the present invention is furture elucidated technology, it is described in detail with reference to specific embodiment, the present invention is included but not
It is limited to following examples.
Embodiment 1
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, wherein, each component is by weight
Meter：
2,4 toluene diisocyanate（TDI）： 37.5
PolyTHF ethoxylated polyhydric alcohol (PTMEG2000)： 72.5
Dihydromethyl propionic acid (DMPA)： 2.5
Methyl methacrylate (MMA)： 65
Styrene (St)： 32.5
Hydroxy propyl methacrylate（HPA）： 7.5
1,4- butanediols (BDO)： 2
Trimethylolpropane (TMP)： 0.25
Triethylenediamine (TEDA)： 0.25
Dibutyl tin laurate (DBTL)： 0.3
2,6 di tert butyl 4 methyl phenol (antioxidant 264)： 0.25
Triethylamine (TEA)： 4
Ammonium persulfate (APS)： 0.5
Deionized water (H2O)： 275
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, its preparation process is as follows：To be many
First alcohol PTMEG（Polymer polyatomic alcohol）And DMPA（Hydrophily function monomer）Dewater treatment is carried out at 90 ~ 120 DEG C 1-2 hours,
It is cooled to after room temperature and adds catalyst TEDA and DBTL, is uniformly mixed, adds TDI（Diisocyanate）At room temperature
Stirring reaction 1 hour, then it is warming up to 60-80 DEG C, insulation reaction 2 ~ 4 hours is cooled to 40 ~ 50 DEG C, BDO is added into system
（Chain extender）、TMP（Chain extender）And MMA（It is cross-linking into nuclear monomer）, chain extending reaction 2 hours, chain extending reaction terminate after again to body
System adds the HPA of metering（It is cross-linking into nuclear monomer/reactive monomer）And antioxidant 264, after being reacted 3-5 hours at 60 DEG C,
The content of isocyanate groups is titrated, when reaching the theoretical extent of reaction, stops reaction, cools to less than 40 DEG C, add TEA
（Nertralizer）Urethane acrylate is neutralized, regulation pH value is warming up to 60 DEG C between 7 ~ 8.5, deionized water is added dropwise, strongly stirs
Mix scattered 1 hour, obtain the translucent aqueous urethane acrylate dispersoid of blue light, then MMA is added dropwise simultaneously（It is cross-linking into
Nuclear monomer）With St（It is cross-linking into nuclear monomer）Mixture and APS（Initiator）The aqueous solution, be warming up to 65 DEG C, insulation reaction
2 ~ 3 hours, then it is warming up to 75 DEG C, insulation reaction 2 ~ 3 hours obtains inierpeneirating network structure aqueous polyurethane nano composite.
Wherein, viscosity is in 600mPa.S when the equal relative molecular mass of the number of polyalcohol is 2000,25 DEG C.
Wherein, PPG and DMPA pass through vacuum in dewater treatment, reaction bulb before diisocyanate is added
It is slow to rise in 0.1MPa, control reaction vessel that temperature is between 90-120 DEG C, vacuum dehydration 1 ~ 2 hour.
Wherein described foundation《The measure of isocyanate group content in HG-T 2409-1992 base polyurethane prepolymer for use as》Method,
The content of isocyanate groups is titrated, the extent of reaction is determined, reaction is represented when isocyanate content reaches theoretical value
Complete, obtain waterborne polyurethane prepolymer.
The great advantage of the nano composite material is:Raw materials of the present invention are not related to organic solvent, strict control
Product VOC content, is different from the method that traditional acetone method synthesizes aqueous polyurethane；Synthesis technique uses continuity method, favorably
Synthesized and production efficiency in improving, hence it is evident that better than traditional batch process synthesis technique.
The material properties test result of embodiment 1：
| Test event | Method of testing | Test result |
| Outward appearance | Observation | It is translucent to have blue light liquid |
| Solid content（%） | GB1725-79 2004 | 30±2 |
| PH values | GB/T23769-2009 | 7.5 |
| Adhesive force | GB/T 1720-1979(89) | ≤1 |
| Hardness | GB/T 1720-1979(89) | ≥H |
| Viscosity | （When applying 4 glasss 25 DEG C） | 25 ± 2 seconds |
| Particle diameter | Dynamic light scattering method | 30-50nm |
| Pattern | ESEM method（SEM） | It is spherical |
Embodiment 2
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, wherein, each component is by weight：
IPDI（IPDI）： 62.5
PolyTHF ethoxylated polyhydric alcohol (PTMEG1000)： 37.5
Dimethylolpropionic acid (DMBA)： 5
Methyl methacrylate (MMA)： 40
Butyl acrylate（BA） 25
Styrene (St)： 30
Hydroxy-ethyl acrylate（HEA）： 10
Ethylene glycol (ED)： 2.5
Trimethylolpropane (TMP)： 0.5
It is double（Dimethylaminoethyl）Ether： 0.25
Dibutyl tin laurate (DBTL)： 0.3
Hydroquinones： 0.5
Ammoniacal liquor： 5
Potassium peroxydisulfate： 0.75
Deionized water (H2O)： 275
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, its preparation process is as follows：To be many
First alcohol PTMEG and DMBA carries out dewater treatment 1-2 hours at 120 DEG C, be cooled to after room temperature add catalyst TEDA and
DBTL, is well mixed at room temperature, adds IPDI and reaction 0.5 hour is stirred at room temperature, then is reacted 4 hours at 60-80 DEG C,
50 DEG C are cooled to, ED, TMP and MMA are added into system, chain extending reaction adds the HEA and antioxygen of metering to system again after 3 hours
Agent is double（Dimethylaminoethyl）Ether, after reacting 4 hours, titrates the content of isocyanate groups, when reaching the theoretical extent of reaction,
Stop reaction, cool to less than 40 DEG C, add TEA, regulation pH value is between 7 ~ 8.5, then is warming up to 65 DEG C, dropwise addition deionization
Water, scattered 1 hour of strong stirring obtains the translucent dispersion of blue light, then be added dropwise simultaneously MMA, St and BA mixture and
The APS aqueous solution, at 2 hours, 75 DEG C insulation reaction 2 hours for insulation reaction at 65 DEG C, obtain the aqueous poly- ammonia of inierpeneirating network structure
Ester nano composite material.
Wherein, viscosity is in 500mPa.S when the equal relative molecular mass of the number of polyalcohol is 1000,25 DEG C.
Wherein, to pass through vacuum in dewater treatment, reactor before IPDI is added slow by PPG and DMBA
0.1MPa is risen to, controls temperature to be no more than 2 hours for 120 DEG C.
Wherein described foundation《The measure of isocyanate group content in HG-T 2409-1992 base polyurethane prepolymer for use as》Method,
The content of isocyanate groups is titrated, the extent of reaction is determined, reaction is represented when isocyanate content reaches theoretical value
Complete, obtain waterborne polyurethane prepolymer.
The great advantage of the nano composite material is:Raw materials of the present invention are not related to organic solvent, strict control
Product VOC content, is different from the method that traditional acetone method synthesizes aqueous polyurethane；Synthesis technique uses continuity method, favorably
Synthesized and production efficiency in improving, hence it is evident that better than traditional batch process synthesis technique；Synthesized acrylic ester modified water-soluble gathers
Urethane acrylate nano composite material has excellent anti-yellowing property.
The material properties test result of embodiment 2：
| Test event | Method of testing | Test result |
| Outward appearance | Observation | It is translucent to have blue light liquid |
| Solid content（%） | GB1725-79 2004 | 30±2 |
| PH values | GB/T23769-2009 | 7 |
| Adhesive force | GB/T 1720-1979(89) | ≤1 |
| Hardness | GB/T 1720-1979(89) | ≥H |
| Viscosity | （When applying 4 glasss 25 DEG C） | 26 seconds |
| Particle diameter | Dynamic light scattering method | 30-40nm |
| Pattern | ESEM method（SEM） | It is spherical |
Embodiment 3
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, wherein, each group is by weight：
'-diphenylmethane diisocyanate（MDI）： 70
Polyoxyethylated polyols (PEG1000)： 40
Dimethylolpropionic acid (DMBA)： 5
Methyl methacrylate (MMA)： 35
Methacrylic acid（AA） 10
Butyl acrylate（BA） 25
Styrene (St)： 25
Hydroxy-ethyl acrylate（HEA）： 10
1,6- hexamethylene diamines (HMD)： 2.5
Trimethylolpropane (TMP)： 0.5
Dibutyl tin laurate (DBTL)： 0.5
2-（2- Dimethylamino-ethoxies）Ethanol 0.2
Phosphite ester： 0.5
Sodium hydroxide： 6
Ammonium persulfate (APS)： 0.75
Deionized water (H2O)： 275
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, its preparation process is as follows：To be many
First alcohol PEG and DMBA carries out dewater treatment 1-2 hours at 120 DEG C, is cooled to after room temperature and adds DBTL and make catalyst, room temperature
It is lower well mixed, add MDI and reaction 2 hours is stirred at room temperature, then reacted 2 hours at 60 DEG C, it is cooled to 50 DEG C, Xiang Ti
HMD, TMP and MMA are added in system, chain extending reaction adds the HEA and antioxidant phosphite ester of metering to system after 2.5 hours, then
60 DEG C are warming up to, insulation reaction 4 hours titrates the content of isocyanate groups, when reaching the theoretical extent of reaction, stopped anti-
Should, less than 40 DEG C are cooled to, TEA is added, regulation pH value is warming up to 60 DEG C of dropwise addition deionized waters, strong stirring point 7.5 or so
Dissipate 1 hour, obtain the transparent or semitransparent dispersion of blue light, then MMA, AA, St and BA mixture and APS is simultaneously added dropwise
The aqueous solution, insulation reaction 2 hours at 60 DEG C, insulation reaction 2 hours at 70 DEG C finally obtain the aqueous poly- ammonia of inierpeneirating network structure
Ester nano composite material.
Wherein, diisocyanate is 4,4 '-'-diphenylmethane diisocyanate（MDI）, relative molecular mass is 250.
Wherein, polyalcohol is polyoxyethylene glycol, and viscosity exists when the equal relative molecular mass of number is 1000,25 DEG C
500mPa.S。
Wherein, PPG and DMBA pass through vacuum in dewater treatment, reactor before MDI is added and slowly risen
To 0.1MPa, control in temperature for 100-120 DEG C or so 2 hours.
Wherein described foundation《The measure of isocyanate group content in HG-T 2409-1992 base polyurethane prepolymer for use as》Method,
The content of isocyanate groups is titrated, the extent of reaction is determined, reaction is represented when isocyanate content reaches theoretical value
Complete, obtain waterborne polyurethane prepolymer.
The great advantage of the nano composite material is:Raw materials of the present invention are not related to organic solvent, strict control
Product VOC content, is different from the method that traditional acetone method synthesizes aqueous polyurethane；Synthesis technique uses continuity method, favorably
Synthesized and production efficiency in improving, hence it is evident that better than traditional batch process；Synthesized acrylic ester modified water-soluble polyurethane propylene
Acid esters nano composite material has excellent resiliency energy and higher elongation at break.
The material properties test result of embodiment 3：
| Test event | Method of testing | Test result |
| Outward appearance | Observation | It is translucent to have blue light liquid |
| Solid content（%） | GB1725-79 2004 | 30 |
| PH values | GB/T23769-2009 | 7.5 |
| Adhesive force | GB/T 1720-1979(89) | ≤1 |
| Hardness | GB/T 1720-1979(89) | ≥H |
| Viscosity | （When applying 4 glasss 25 DEG C） | 27 seconds |
| Particle diameter | Dynamic light scattering method | 40-50nm |
| Pattern | ESEM method（SEM） | It is spherical |
Embodiment 4
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, wherein, each component content is by weight
Measure part meter：
4,4'- dicyclohexyl methyl hydride diisocyanates（HMDI）： 70
Polyoxyethylated polyols (PEG2000)： 40
Dimethylolpropionic acid (DMBA)： 5
Methyl methacrylate (MMA)： 35
Methacrylic acid（AA） 10
Butyl acrylate（BA） 25
Styrene (St)： 25
Hydroxy-ethyl acrylate（HEA）： 10
1,6- hexamethylene diamines (HMD)： 2.5
Trimethylolpropane (TMP)： 0.5
Dibutyl tin laurate (DBTL)： 0.5
Organic mercury 0.2
Alkyl benzene amine： 0.5
Potassium hydroxide： 5.5
The different cyanogen in heptan of azo two： 0.75
Deionized water (H2O)： 275
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, its preparation process is as follows：To be many
First alcohol PEG and DMBA carries out dewater treatment 1-2 hours at 120 DEG C, is cooled to after room temperature and adds DBTL and make catalyst, room temperature
Lower well mixed, add HMDI reacts 1 hour at room temperature, then is warming up to reaction 2 hours at 60 DEG C, is then cooled to 40 DEG C,
HMD, TMP and MMA are added into system, chain extending reaction adds the HEA and antioxidant alkylbenzene of metering to system again after 2.5 hours
Amine, is warming up to 70 DEG C and reacts 3-5 hours, titrate the content of isocyanate groups, when reaching the theoretical extent of reaction, stops anti-
Should, less than 40 DEG C are cooled to, TEA is added, deionized water is added dropwise 7 ~ 8 or so in regulation pH value, and strong stirring is scattered 1 hour, obtains
To the transparent or semitransparent WPUA dispersions for having blue light, then simultaneously be added dropwise MMA, AA, St and BA mixture and APS it is water-soluble
Liquid, at 2 hours, 70 DEG C insulation reaction 2 hours for insulation reaction at 65 DEG C, stop reaction, obtain the aqueous poly- ammonia of inierpeneirating network structure
Ester nano composite material.
Wherein, diisocyanate is 4,4'- dicyclohexyl methyl hydride diisocyanates, and relative molecular mass is 262, is abbreviated as
HMDI。
Wherein, polyalcohol is PEG, and viscosity is in 550mPa.S when the equal relative molecular mass of number is 2000,25 DEG C.
Wherein, PPG and DMBA pass through vacuum in dewater treatment, reactor before MDI is added and slowly risen
To 0.1MPa, temperature in reaction vessel is controlled to be dehydrated 2 hours for 120 DEG C.
Wherein described foundation《The measure of isocyanate group content in HG-T 2409-1992 base polyurethane prepolymer for use as》Method,
The content of isocyanate groups is titrated, the extent of reaction is determined, reaction is represented when isocyanate content reaches theoretical value
Complete, obtain waterborne polyurethane prepolymer.
The great advantage of the nano composite material is:Raw materials of the present invention are not related to organic solvent, strict control
Product VOC content, is different from the method that traditional acetone method synthesizes aqueous polyurethane；Synthesis technique uses continuity method, favorably
Synthesized and production efficiency in improving, hence it is evident that better than traditional batch process synthesis technique；Synthesized acrylic ester modified water-soluble gathers
The performances such as urethane acrylate nano composite material has good color inhibition, anti-aging and higher modulus of elasticity.
The material properties test result of embodiment 4：
| Test event | Method of testing | Test result |
| Outward appearance | Observation | It is translucent to have blue light liquid |
| Solid content（%） | GB1725-79 2004 | 32 |
| PH values | GB/T23769-2009 | 8 |
| Adhesive force | GB/T 1720-1979(89) | ≤1 |
| Hardness | GB/T 1720-1979(89) | ≥H |
| Viscosity | （When applying 4 glasss 25 DEG C） | 24 seconds |
| Particle diameter | Dynamic light scattering method | 50nm |
| Pattern | ESEM method（SEM） | It is spherical |
Embodiment 5
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, wherein, each component content is by weight
Measure part meter：
Toluene di-isocyanate(TDI)（TDI）： 60
Polyoxypropylene polyol (PPG2000)： 40
Dimethylolpropionic acid (DMBA)： 5
Methyl methacrylate (MMA)： 35
Methacrylic acid（AA） 10
Butyl acrylate（BA） 25
Styrene (St)： 25
Hydroxy-ethyl acrylate（HEA）： 10
Ethylenediamine (EDA)： 0.25
Trimethylolpropane (TMP)： 0.5
Dibutyl tin laurate (DBTL)： 0.5
Organic mercury 0.2
2,6 di tert butyl 4 methyl phenol (antioxidant 264)： 0.5
Triethylamine (TEA)： 5
Azo-bis-isobutyl cyanide： 0.75
Deionized water (H2O)： 275
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, its preparation process is as follows：To be many
First alcohol PEG and DMBA carries out dewater treatment 2 hours at 120 DEG C, is cooled to after room temperature and adds DBTL and make catalyst, at room temperature
It is well mixed, add TDI and react 1 hour, then reacted 2 hours at 70 DEG C, be cooled to 40 DEG C, added into system EDA,
TMP and MMA, chain extending reaction adds the HEA and antioxidant 264 of metering to system again after 4 hours, be warming up to 70 DEG C and react 4 hours,
The content of isocyanate groups is titrated, when reaching the theoretical extent of reaction, stops reaction, cools to less than 40 DEG C, add in TEA
And water-soluble polyurethane acrylic resin, regulation pH value is between 7 ~ 8, and dropwise addition deionized water, strong stirring is scattered 1 hour, obtains
There are the transparent or semitransparent WPUA dispersions of blue light, then dropwise addition MMA, AA, St and BA mixture and the APS aqueous solution simultaneously,
Insulation reaction 2 hours at 60 DEG C, insulation reaction 2 hours, obtains inierpeneirating network structure aqueous polyurethane nano composite wood at 75 DEG C
Material.
Wherein, diisocyanate is 4,4'- dicyclohexyl methyl hydride diisocyanates, and relative molecular mass is 262, is abbreviated as
HMDI。
Wherein, polyalcohol is PPG, and viscosity is in 550mPa.S when the equal relative molecular mass of number is 2000,25 DEG C.
Wherein, to pass through vacuum in dewater treatment, reactor before HMDI is added slow by PPG and DMBA
0.1MPa is risen to, controls interior temperature to be dehydrated 2 hours for 100 DEG C or so.
Wherein described foundation《The measure of isocyanate group content in HG-T 2409-1992 base polyurethane prepolymer for use as》Method,
The content of isocyanate groups is titrated, the extent of reaction is determined, reaction is represented when isocyanate content reaches theoretical value
Complete, obtain waterborne polyurethane prepolymer.
The great advantage of the nano composite material is:Raw materials of the present invention are not related to organic solvent, strict control
Product VOC content, is different from the method that traditional acetone method synthesizes aqueous polyurethane；Synthesis technique uses continuity method, favorably
Synthesized and production efficiency in improving, hence it is evident that better than traditional batch process synthesis technique；Synthesized acrylic ester modified water-soluble gathers
Urethane acrylate nano composite material has the performances such as good color inhibition, anti-aging, higher modulus of elasticity and mechanical strength.
The material properties test result of embodiment 5：
| Test event | Method of testing | Test result |
| Outward appearance | Observation | It is translucent to have blue light liquid |
| Solid content（%） | GB1725-79 2004 | 31.5 |
| PH values | GB/T23769-2009 | 7.5 |
| Adhesive force | GB/T 1720-1979(89) | ≤1 |
| Hardness | GB/T 1720-1979(89) | ≥H |
| Viscosity | （When applying 4 glasss 25 DEG C） | 26 seconds |
| Particle diameter | Dynamic light scattering method | 30-35nm |
| Pattern | ESEM method（SEM） | It is spherical |
Embodiment 6
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, wherein, each component content is by weight
Measure part meter：
Toluene di-isocyanate(TDI)（TDI）： 60
Polyethylene glycol oxide/propylene polyalcohol (PEG/PPG2000)： 40
Dihydromethyl propionic acid (DMPA)： 5
Methyl methacrylate (MMA)： 50
Methacrylic acid（AA） 20
Styrene (St)： 25
Hydroxy-ethyl acrylate（HEA）： 10
BDO (BDO)： 2.5
Trimethylolpropane (TMP)： 1
Dibutyl tin laurate (DBTL)： 0.5
2,6 di tert butyl 4 methyl phenol (antioxidant 264)： 0.5
Triethylamine (TEA)： 5
Ammonium persulfate (APS)： 0.75
Deionized water (H2O)： 265
Hydrazine hydrate 50
A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, its preparation process is as follows：To be many
First alcohol PEG and DMBA carries out dewater treatment 2 hours at 120 DEG C, is cooled to after room temperature and adds DBTL and make catalyst, at room temperature
It is well mixed, add TDI and react at room temperature 1 hour, then reacted 2 hours at 60 DEG C, 50 DEG C are cooled to, is added into system
BDO, TMP and MMA, chain extending reaction add the HEA and antioxidant 264 of metering to system again after 2 hours, then are warming up to 65 DEG C of reactions
4 hours, the content of isocyanate groups is titrated, when reaching the theoretical extent of reaction, stops reaction, cools to less than 40 DEG C, plus
Enter TEA, regulation pH value is warming up to 60 DEG C 7 ~ 8 or so, and deionized water is added dropwise, and strong stirring is scattered 1 hour, has obtained blue light
Transparent or semitransparent WPUA dispersions, then be added dropwise MMA, AA and St mixture simultaneously, hydrazine hydrate and the APS aqueous solution,
Insulation reaction 2 hours at 65 DEG C, then insulation reaction 2 hours at 75 DEG C, stop reaction, obtain the aqueous poly- ammonia of inierpeneirating network structure
Ester nano composite material.
Wherein, diisocyanate TDI, relative molecular mass is 174.
Wherein, polyalcohol is the block copolymer of oxirane and expoxy propane, and the equal relative molecular mass of number is 2000,25
DEG C when viscosity in 600mPa.S or so.
Wherein, PPG and DMPA pass through vacuum in dewater treatment, reactor before TDI is added and slowly risen
To 0.1MPa, control temperature in the kettle for 100 ~ 120 DEG C or so 2 hours.
Wherein described foundation《The measure of isocyanate group content in HG-T 2409-1992 base polyurethane prepolymer for use as》Method,
The content of isocyanate groups is titrated, the extent of reaction is determined, reaction is represented when isocyanate content reaches theoretical value
Complete, obtain waterborne polyurethane prepolymer.
The great advantage of the nano composite material is:Raw materials of the present invention are not related to organic solvent, strict control
Product VOC content, is different from the method that traditional acetone method synthesizes aqueous polyurethane；Synthesis technique uses continuity method, favorably
Synthesized and production efficiency in improving, hence it is evident that better than traditional batch process synthesis technique；Synthesized acrylic ester modified water-soluble gathers
Urethane acrylate nano composite material has higher mechanical strength.
The material properties test result of embodiment 6：
| Test event | Method of testing | Test result |
| Outward appearance | Observation | It is translucent to have blue light liquid |
| Solid content（%） | GB1725-79 2004 | 31 |
| PH values | GB/T23769-2009 | 7.5 |
| Adhesive force | GB/T 1720-1979(89) | ≤1 |
| Hardness | GB/T 1720-1979(89) | ≥H |
| Viscosity | （When applying 4 glasss 25 DEG C） | 23 seconds |
| Particle diameter | Dynamic light scattering method | 40-50nm |
| Pattern | ESEM method（SEM） | It is spherical |
Claims (12)
1. a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite, it is characterised in that specifically include with
Lower step：
1] polymer polyatomic alcohol and hydrophily function monomer are added into reaction vessel, vacuum dehydration handles 1- at 90-120 DEG C
2 hours；
2] system temperature is down to room temperature, adds catalyst, be uniformly mixed；
3] add diisocyanate and reaction 0.5-2 hours is stirred at room temperature, be warming up to 60-80 DEG C of insulation reaction 1-5 hours, obtain
To Waterborne Polyurethane Prepolymer；
4] system temperature is down to 40-50 DEG C, adds polyalcohol or polyamine of the relative molecular mass below 500 and be used as chain extension
Agent, chain extending reaction 2-4 hours；
5] 60-70 DEG C is warming up to, the end group-NCO of the reactive monomer and Waterborne Polyurethane Prepolymer that add metering is blocked
React, while adding methyl methacrylate diluted system viscosity, add polymerization inhibitor, insulation reaction 3-5 is small at 60-70 DEG C
When；- NCO conversion ratio is titrated by n-Butylamine titration method, stops reaction after-NCO content reaches theoretical value, that is, obtains aqueous
Polyurethane acrylate resin；
6] 30-50 DEG C is cooled to, nertralizer neutralized aqueous polyurethane acrylate resin is added, regulation pH value is between 7-8.5；
7] 60-70 DEG C is warming up to, deionized water is added dropwise, the dispersed with stirring when being added dropwise obtains the water of aqueous polyurethane acrylate
Dispersion；
8] 60-65 DEG C is warming up to, the aqueous solution of initiator is added dropwise, while nuclear monomer is added dropwise into, time for adding is no more than 1 hour,
Insulation reaction 2-3 hours at 60-65 DEG C；70-75 DEG C is warming up to again, and insulation reaction 2-3 hours obtains a kind of interpenetrating networks knot
The aqueous polyurethane nano composite of structure, the nano composite material is the emulsion with blue light.
2. the preparation method of the aqueous polyurethane nano composite of a kind of inierpeneirating network structure according to claim 1, its
It is characterised by：By weight, each component content is for the raw material respectively reacted and auxiliary dosage：
3. a kind of preparation method of the aqueous polyurethane nano composite of inierpeneirating network structure according to claim 1 or claim 2,
It is characterized in that：The polymer polyatomic alcohol is PPG, including PolyTHF ethoxylated polyhydric alcohol, polyethylene glycol oxide be polynary
Alcohol, polyoxypropylene polyol, one or more PPGs in polyethylene glycol oxide propylene-based block copolymer polyalcohol
Mixture, number-average molecular weight is in 1000-2000, and PPG has preferable water resistance, synthesized aqueous polyurethane third
Olefin(e) acid ester stable not facile hydrolysis in aqueous phase；The step 1], one or more add in the PPG is reacted
Container, while adding hydrophily function monomer, and is progressively warming up to 90 DEG C~120 DEG C, vacuum is slowly risen to 0.098-
0.1MPa, dewater treatment 1~2 hour.
4. a kind of preparation method of the aqueous polyurethane nano composite of inierpeneirating network structure according to claim 1 or claim 2,
It is characterized in that：The hydrophily function monomer is the compound containing carboxyl, amino, hydroxyl or sulfonate radical in molecule, mainly
For dihydromethyl propionic acid (DMPA), dimethylolpropionic acid (DMBA), pyromellitic acid dianhydride, 1,2- propane diols -3- sodium sulfonates, 1,4-
One or more mixtures in butanediol -2- sodium sulfonates, 2- [(2- amino-ethyls) amino] b sodium salt；The catalysis
Agent is mainly triethylenediamine, double (dimethylaminoethyl) ethers, 2- (2- Dimethylamino-ethoxies) ethanol, organotin chemical combination
The mixture of one or both of thing, organomercurial compound and organo-lead compound；The chain extender is ethylene glycol, 1,4-
Butanediol, 1,2- propane diols, 1,3- propane diols, diglycol, 1,6-HD, glycerine, trimethylolpropane, second two
One or more mixtures in amine, 1,6- hexamethylene diamines, hydrazine hydrate, monoethanolamine, diethanol amine and triethanolamine；The inhibition
Agent is the one or more in hydroquinones, 2,6- di-t-butyl -4- sylvans, alkylation aniline and phosphite ester compound
Mixture；The reactive monomer is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, propylene
One kind in sour hydroxypropyl acrylate, pentaerythritol triacrylate and epoxy modification acrylate, can be with Waterborne Polyurethane Prepolymer
End group (- NCO) occurs hair and answered, and obtains the aqueous polyurethane acrylate resin of acrylate ended；The diisocyanate is
Aromatic series and/or aliphatic diisocyanate, mainly including 2,4- toluene di-isocyanate(TDI)s (TDI), 4,4 '-diphenyl-methane two is different
Cyanate (MDI), 4,4 '-hydrogenated diphenyl methane diisocyanate (HMDI), IPDI (IPDI) and six are sub-
The mixture of one or both of methyl diisocyanate (HDI)；The conversion ratio of the isocyanato-NCO, is foundation
《The measure of isocyanate group content in HG-T 2409-1992 base polyurethane prepolymer for use as》Method is titrated, when-NCO content reaches theory
Illustrate that prepolymerization reaction terminates, that is, obtains water-soluble polyurethane acrylic resin during value.
5. a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite according to claim 1 or claim 2, its
It is characterised by：The step 3], add diisocyanate and reaction 1 hour is stirred at room temperature, be warming up to 60-80 DEG C of insulation reaction
1-5 hours, obtain Waterborne Polyurethane Prepolymer；The nertralizer be trimethylamine compound, ammoniacal liquor, sodium hydrate aqueous solution,
Potassium hydroxide aqueous solution, by metered application into aqueous polyurethane acrylate resin, is stirred, at 30~50 DEG C when being added dropwise
Neutralization reaction 1 hour, obtains water-soluble carboxylic acid type aqueous polyurethane acrylate, and pH value is controlled between 7~8.5.
6. a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite according to claim 1 or claim 2, its
It is characterised by：System temperature is risen to 60 DEG C, deionized water is added dropwise into the aqueous polyurethane acrylate resin after neutralization,
Stir, 1 hour completion of dropping, be stirred for scattered 1 hour when being added dropwise；Occur mutually to overturn in the process, i.e., hydrophilic carboxylic acid
The outside ordered arrangement of salt groups, urethane acrylate main chain inward curl is agglomerating, forms the spherical micelle knot of oil-in-water (O/W)
Structure, i.e. aqueous urethane acrylate dispersoid.
7. a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite according to claim 1 or claim 2, its
It is characterised by：Initiator used is azo-bis-isobutyl cyanide, the different cyanogen in heptan of azo two, ammonium persulfate or potassium peroxydisulfate；Add initiator
Trigger acrylate mixture copolymerization, while triggering aqueous polyurethane acrylate to crosslink reaction.
8. a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite according to claim 1 or claim 2, its
It is characterised by：It is described into the mixture that nuclear monomer is styrene and acrylate, due to being oily matter into nuclear monomer, thus into
Nuclear monomer enters inside aqueous polyurethane micella, as oil phase.
9. a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite according to claim 1 or claim 2, its
It is characterised by：It is described into the mixture that nuclear monomer is styrene and methacrylic acid, due to being oily matter into nuclear monomer, so
Enter into nuclear monomer inside aqueous polyurethane micella, as oil phase.
10. a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite according to claim 8, it is special
Levy and be：The acrylate is methyl methacrylate, methyl acrylate, butyl methacrylate, butyl acrylate, methyl
Hydroxy-ethyl acrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate, isobornyl methacrylate, third
One or more in olefin(e) acid isobornyl thiocyanoacetate, pentaerythritol triacrylate and epoxy modification acrylate.
11. a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite according to claim 1 or claim 2,
It is characterized in that：The step 8], while the aqueous solution of initiator is added dropwise and remaining into nuclear monomer, it is added dropwise within 1 hour at 65 DEG C
Finish, insulation reaction 2~3 hours at 65 DEG C, insulation reaction 2~3 hours at 75 DEG C；In the presence of initiator, into nuclear monomer
Mixture is copolymerized inside spherical micelle, while crosslinking reaction with the acrylate of end-blocking, forms IPN net
Network structure.
12. a kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite according to claim 1 or claim 2,
It is characterized in that：Acrylate modified aqueous polyurethane acrylate composite is a kind of answering with inierpeneirating network structure
Condensation material；Water-soluble polyurethane acrylic resin has self-emulsifying function, the upset that hydrophilic and oleophilic structure occurs when adding water scattered
And O/W stable dispersion phase is formed, the acrylate mixture being added dropwise is internally formed oil phase into micella, is copolymerized
Nucleation, the acrylate blocked with aqueous polyurethane crosslinks reaction, forms inierpeneirating network structure；Obtain with polyacrylate
For the core shell structure that core, aqueous polyurethane are shell；The nano composite material is that a kind of translucent emulsion particle diameter with blue light is
Between 30~50nm, it can be applied to as water paint matrix resin, water-based ink binder and Aqueous Adhesives matrix resin
Building materials, furniture, leather, fabric and printing packaging industry.
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| CN103396753B (en) * | 2013-08-15 | 2015-02-25 | 西安大天新材料有限公司 | Preparation method of hot-melt polyurethane resin for bonding material |
| CN104017169B (en) * | 2014-06-05 | 2016-09-07 | 武汉长盈通光电技术有限公司 | A kind of preparation method of the core-shell type aqueous polyurethane emulsion containing crosslinking and hybrid structure |
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