CN102432775B - Preparation method of waterborne polyurethane-polyacrylic ester composite emulsion - Google Patents
Preparation method of waterborne polyurethane-polyacrylic ester composite emulsion Download PDFInfo
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Abstract
The invention provides a preparation method of a waterborne polyurethane-polyacrylic ester composite emulsion. The preparation method comprises the following steps of: firstly, synthesizing ethenyl-terminated waterborne polyurethane as an emulsifying agent and a seed phase for polymerizing ethylene emulsions; and secondly, introducing a polyacrylic este molecular chain to a molecule of the waterborne polyurethane by an emulsion polymerization reaction through a chemical bond to obtain the waterborne polyurethane-polyacrylic ester composite emulsion with a core-shell structure. The method has the advantages of wide range for alternative polyacrylic ester monomers, low prices, simple synthetic reaction and easiness in preparation of a composite structure with two different polymeric chains.
Description
Technical field
The present invention proposes a kind of preparation method of waterborne polyurethane-polyacrylate compounded latex, and it is by aqueous polyurethane and two kinds of chemically composited forming of compositions process of water polyacrylic acid, relates to the synthesis technical field of polymkeric substance and material.
Technical background
For the needs to environment protection and Sustainable development and human health, aqueous polyurethane has been widely used in fields such as coating and paint.Can present excellent elasticity, rub resistance and lower temperature resistance after the aqueous polyurethane film forming, but its water tolerance and chemical resistance are relatively poor.For water tolerance and the chemical resistance that improves aqueous polyurethane, common way is that they are mixed with polyacrylic ester, and this is because polyacrylic ester has excellent weathering resistance, water tolerance and chemical resistant properties, and the price of polyacrylic ester is more cheap relatively simultaneously.But, because macroface occurring than missionary society, the consistency of these two kinds of polymkeric substance separates, simply these two kinds different polymer dispersion liquids are mixed the degradation that will cause film.Solving these two kinds of inconsistent methods of different polymkeric substance is that vinylformic acid or vinyl polymer are introduced or is grafted in the aqueous polyurethane chain, make these two kinds of different polymeric chains combine closely and form a kind of composite emulsion, can give full play to urethane and polyacrylic ester characteristic separately simultaneously.The route of synthesizing cross-linked type composite emulsion has a lot, such as the graft copolymerization on the polyacrylic ester chain of seeded emulsion polymerization, latex interpenetrating polymerization, cross-couplings and urethane.Seeded emulsion polymerization is the seed phase of the urethane of water-based as the acrylic monomer polymerization, by letex polymerization, polyacrylate grafting on polyurethane chain.The prerequisite of this synthetic route is that urethane can be emulsified into stable colloidal solid, and acrylic monomer can carry out the polymerization of the concurrent lactogenesis liquid of swelling in aqueous polyurethane then.Can access cross-linking type PUA composite emulsion at last by this way.With respect to other method, seed emulsion polymerization is easy and simple to handle and be widely used in the industrial production.Existing used for water color ink emulsion is that water-soluble is good inadequately on the one hand, on the other hand, a lot of emulsions add tensio-active agent emulsification, and the emulsion-stabilizing phase had only about half a year, and add tensio-active agent can not film forming (participation adhesive attraction), the sticking power and the moisture-proof that influence printing ink are wiped.
Summary of the invention
The objective of the invention is to, propose a kind of preparation method of waterborne polyurethane-polyacrylate compounded latex, it is that water-soluble is good inadequately on the one hand that the present invention is intended to solve existing used for water color ink emulsion; On the other hand, a lot of emulsions add tensio-active agent emulsification, and the emulsion-stabilizing phase had only about half a year, and add tensio-active agent can not film forming, influence sticking power and the moisture-proof wiping problem of printing ink.
The present invention has adopted following technical scheme:
A kind of preparation method of waterborne polyurethane-polyacrylate compounded latex, it may further comprise the steps: steps A: synthesis of vinyl end-sealed type aqueous polyurethane; Step B: utilize ethenyl blocking type aqueous polyurethane to synthesize the waterborne polyurethane-polyacrylate composite emulsion,
Wherein, described steps A specifically comprises:
Steps A 1: end hydroxy polyether, dimethylol propionic acid and 1,4-butyleneglycol mixed and be dissolved in and form mixing solutions in the organic solvent;
Steps A 2: under 40 ~ 65 ℃, catalyzer, diisocyanate cpd and acetone are splashed in the mixing solutions;
Steps A 3: be warmed up to 65 ℃～95 ℃ after dropwising, and under this temperature, reacted 3 hours～5 hours, make diisocyanate terminated type polyurethane;
Steps A 4: in diisocyanate terminated type polyurethane, add vinyl monomer, under 60～80 ℃, proceed to react 1.5 hours～2.5 hours, obtain the ethenyl blocking type polyurethane;
Steps A 5: under 30～50 ℃, with triethylamine neutralization of ethylene base end-sealed type urethane, be reflected at 15 minutes～finish in 30 minutes;
Steps A 6: add a certain amount of distilled water in the ethenyl blocking type polyurethane that is neutralized, at room temperature high speed dispersion obtained ethenyl blocking type aqueous polyurethane in 30 minutes～60 minutes.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, described step B specifically comprises:
Step B1: adopt the semi-continuous emulsion polymerizing method, ethenyl blocking type aqueous polyurethane is mixed with the load weighted acrylic ester monomer of calculating and stir and carry out pre-emulsification and obtain pre-emulsification;
Step B2: get 8%～10 % of the pre-emulsification weight part that obtains among the step B1 and the initiator of 8%～10 % weight part and join in the reactor, logical N
2Protection, 60 ℃～85 ℃ down reactions 15 minutes～30 minutes, described initiator is Potassium Persulphate, the total consumption of initiator is 1%～3% of the weight of the monomer of all participation polyreactions;
Step B3: remaining pre-emulsification and Potassium Persulphate were added in the reactor reaction respectively 3 hours～5 hours, obtain the waterborne polyurethane-polyacrylate compounded latex.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, described end hydroxy polyether is cetomacrogol 1000, polypropylene glycol 1000 or PTMG 1000.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, described organic solvent is polar solvent, selects acetone, N for use, N-diformamide or N-Methyl pyrrolidone, consumption of organic solvent for the weight that adds whole raw materials used before the organic solvent and 10%～15%.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, described catalyzer is butyl (tetra) titanate, dibutyl tin laurate or titanium isopropylate, catalyst consumption is 0.5%～1% of vulcabond weight.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, described diisocyanate cpd is tolylene diisocyanate or isophorone diisocyanate.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, described vinyl monomer is vinylbenzene, methyl methacrylate, methacrylic acid second fat, methyl acrylate or butyl acrylate.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, the addition of described triethylamine is so that the pH value of neutralization back system is standard for 6-7.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, the structural formula of described ethenyl blocking type polyurethane is as follows:
In the formula, R
1For
Or
R
2Be cetomacrogol 1000 and polypropylene glycol 1000 and PTMG 1000.
The preparation method of described waterborne polyurethane-polyacrylate compounded latex, wherein, described waterborne polyurethane-polyacrylate compounded latex is the core/shell type structure, and the chitin of composite colloidal particle is urethane, examines to be polyacrylic ester.
Compared with prior art, the present invention has following unusual effect:
Its utilizes synthetic aqueous polyurethane carries out letex polymerization as acrylic ester monomer emulsifying agent and seed mutually, be incorporated into the polyacrylic ester molecular chain in the molecular structure of aqueous polyurethane by chemical bond, prepare the waterborne polyurethane-polyacrylate compounded latex of nucleocapsid structure, the alternative acrylic ester monomer scope of this method is big, cheap, building-up reactions is simple, be easy to prepare the composite structure of two kinds of polymkeric substance.
Embodiment
For making purpose of the present invention, technical scheme and advantage clearer, clear and definite, below the present invention is described in more detail with reference to embodiment.
Waterborne polyurethane-polyacrylate compounded latex preparation method provided by the invention carries out according to the following steps:
Steps A: synthesis of vinyl end-sealed type aqueous polyurethane, its concrete grammar is:
Steps A 1: end hydroxy polyether, dimethylol propionic acid and 1,4-butyleneglycol mixed and be dissolved in and form mixing solutions in the organic solvent;
Wherein, the amount of described end hydroxy polyether, dimethylol propionic acid and 1,4-butyleneglycol is to determine according to the molecular weight real-time measuring data of end hydroxy polyether.Described end hydroxy polyether is cetomacrogol 1000 or polypropylene glycol 1000, PTMG 1000.Described organic solvent is polar solvent, selects acetone or N for use, N-diformamide, N-Methyl pyrrolidone, consumption of organic solvent for the weight that adds whole raw materials used before the organic solvent and 10%～15%.
Steps A 2: under 40 ~ 65 ℃, catalyzer, diisocyanate cpd and acetone are splashed in the mixing solutions;
Wherein, the solubleness in acetone determines the amount of described catalyzer, diisocyanate cpd and acetone in real time according to catalyzer and vulcabond, and its speed that splashes into mixing solutions wants slow, observes while drip.Described catalyzer is butyl (tetra) titanate, dibutyl tin laurate, titanium isopropylate, and catalyst consumption is 0.5%～1% of vulcabond weight.Described diisocyanate cpd is tolylene diisocyanate (TDI) or isophorone diisocyanate (IPDI).
Steps A 3: be warmed up to 65 ℃～95 ℃ after dropwising, and under this temperature, reacted 3 hours～5 hours, make diisocyanate terminated type polyurethane;
Steps A 4: in diisocyanate terminated type polyurethane, add vinyl monomer, under 60～80 ℃, proceed to react 1.5 hours～2.5 hours, obtain the ethenyl blocking type polyurethane;
Wherein, described vinyl monomer is vinylbenzene, methyl methacrylate, methacrylic acid second fat, methyl acrylate or butyl acrylate, methacrylic acid-beta-hydroxy ethyl ester.According to the addition that molecular weight requirement and the film forming adhesion property of emulsion are adjusted methacrylic acid-beta-hydroxy ethyl ester.
Steps A 5: under 30～50 ℃, with triethylamine neutralization of ethylene base end-sealed type urethane, be reflected at 15 minutes～finish in 30 minutes;
Wherein, the addition of described triethylamine is so that the pH value of neutralization back system is standard for 6-7.
Steps A 6: add a certain amount of distilled water in the ethenyl blocking type polyurethane that is neutralized, at room temperature high speed dispersion obtained ethenyl blocking type aqueous polyurethane in 30 minutes～60 minutes.
Wherein, the amount of the distilled water of interpolation is to calculate amount of water according to 40%～50% of the emulsion concentration of setting.Described emulsion concentration refers to the desired emulsion solid content of current production batch (abbreviation concentration).
Step B: utilize ethenyl blocking type aqueous polyurethane to synthesize the waterborne polyurethane-polyacrylate composite emulsion, its concrete grammar is:
Step B1: adopt the semi-continuous emulsion polymerizing method, ethenyl blocking type aqueous polyurethane is mixed with the load weighted acrylic ester monomer of calculating and stir and carry out pre-emulsification and obtain pre-emulsification;
Step B2: get 8%～10 % of the pre-emulsification weight part that obtains among the step B1 and the initiator of 8%～10 % weight part and join in the reactor, logical N
2Protection was reacted 15 minutes～30 minutes down at 60 ℃～85 ℃, and described initiator is Potassium Persulphate, and the total consumption of initiator is 1%～3% of monomer weight; All monomers of participating in polyreaction comprise esters of acrylic acid, end hydroxy polyether, dimethylol propionic acid, vulcabond etc.
Step B3: remaining pre-emulsification and Potassium Persulphate were added in the reactor reaction respectively 3 hours～5 hours, obtain milky stable composite emulsion, i.e. the waterborne polyurethane-polyacrylate compounded latex.
Wherein, the adding method of described pre-emulsification and Potassium Persulphate is for becoming to drip in shape or the fine rule stream shape adding reactor.The final dispersion medium of described waterborne polyurethane-polyacrylate compounded latex is deionized water, and dilutable water is regulated concentration (viscosity).
The structural formula of described ethenyl blocking type polyurethane is as follows:
In the formula, R
1For
Or
R
2Be cetomacrogol 1000 and polypropylene glycol 1000 and PTMG 1000.
Described waterborne polyurethane-polyacrylate compounded latex is the core/shell type structure, and the chitin of composite colloidal particle is urethane, examines to be polyacrylic ester.
Below be further explained by 9 the present invention of embodiment, but the present invention is not limited to these technical parameter of giving an example and processes.
, ethenyl blocking type aqueous polyurethane (VLWPU) preparation embodiment
Table 1 preparation ethenyl blocking type aqueous polyurethane raw material (weight part)
Preparation process is as follows:
Embodiment 1: ethenyl blocking type aqueous polyurethane (
VLWPU) the typical case synthesize in the 250 mL four-hole boiling flasks that thermometer, mechanical stirrer and prolong (top is connected with drying tube) be housed and carry out.
At first at room temperature
PPG1000(9.05 g),
DMPA(0.68 g) and 1,4-
BD(0.35 g) joins in the flask.Add subsequently
NMP(1.8 g) stirs until obtaining homogeneous system.Be warmed up to 60～90 ℃, in 30～60 min, dropwise add then
IPDI(4.65 g),
DBTDLThe mixed solution that (3～5) and acetone (5.0 g) are formed, sustained reaction 3～5 h, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).Again to wherein adding
HEMA(0.81 g) keeps being reflected at 60～80 ℃ and continuing down reaction 1.5～2.5 h, obtain the ethenyl blocking type polyurethane (
VLPU).Be cooled to subsequently under 30～50 ℃, use
TEA(0.56 g) neutralization
VLPU, be reflected in 15～30 min and finish.At last, slowly add distilled water (50 g) in the urethane that is neutralized, at room temperature to obtain carboxyl-content be 5% ethenyl blocking type aqueous polyurethane to high speed dispersion 30～60 min.
The above-mentioned formulation of foundation
VLWPUBe translucent blueing light emulsion, latex particle size is less and viscosity is little.Test through IR (KBr): ν=3330,2958,2847,2268,1727,1650,1110cm
-1
Embodiment 2: at room temperature
PPG1000(10.07 g),
DMPA(0.45 g) and 1,4-
BD(0.33 g) joins in the flask.Add subsequently
NMP(1.8g) stir until obtaining a homogeneous system.At this moment temperature is risen to 60～90 ℃, in 30～60 min, dropwise add then
IPDI(4. 5 g),
DBTDLThe mixed solution of (3～5) and acetone (5.0 g) is reflected at and carries out 3～5 h under the oil bath agitation condition, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).At this moment, add
HEMA(0.65 g) is reflected at and proceeds 1.5～2.5 h under 60～80 ℃, obtained the ethenyl blocking type polyurethane (
VLPU).Secondly, under 30～50 ℃, use
TEA(0.42 g) neutralization
VLPU, be reflected in 15～30 min and finish.At last, slowly add distilled water (50 g) in the urethane that is neutralized, at room temperature high speed dispersion 30～60 min obtain carboxyl-content be 3% ethenyl blocking type aqueous polyurethane (
VLWPU).Embodiment 2 is prepared
VLWPUBe milky emulsion, latex particle size is big and precipitation is unstable easily.
Embodiment 3: following of normal temperature
PPG1000(9 g),
DMPA(0.55 g) and 1,4-
BD(0.28g) join in the flask.Add subsequently
NMP(1.8g) stir until obtaining a homogeneous system.At this moment temperature is risen to 60～90 ℃, in 30～60 min, dropwise add then
IPDI(4. 52 g),
DBTDLThe mixed solution of (3～5) and acetone (5.0 g) is reflected at and carries out 3～5 h under the oil bath agitation condition, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).At this moment, add
HEMA(0.7 g) is reflected at and proceeds 1.5～2.5 h under 60～80 ℃, obtained the ethenyl blocking type polyurethane (
VLPU).Secondly, under 30～50 ℃, use
TEA(0.48 g) neutralization
VLPU, be reflected in 15～30 min and finish.At last, slowly add distilled water (50 g) in the urethane that is neutralized, at room temperature high speed dispersion 30～60 min obtain carboxyl-content be 4% ethenyl blocking type aqueous polyurethane (
VLWPU).Obtain thus
VLWPUBe oyster white blueing light emulsion a little, latex particle size is bigger.
Embodiment 4: identical with the program of the several embodiment in front, at first at room temperature
PPG1000(8 g),
DMPA(0.78 g) and 1,4-
BD(0.3g) join in the flask.Add subsequently
NMP(1.8g) stir until obtaining a homogeneous system.At this moment temperature is risen to 60～90 ℃, in 30～60 min, dropwise add then
IPDI(4. 52 g),
DBTDLThe mixed solution of (3～5) and acetone (5.0 g) is reflected at and carries out 3～5 h under the oil bath agitation condition, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).At this moment, add
HEMA(0.8 g) is reflected at and proceeds 1.5～2.5 h under 60～80 ℃, obtained the ethenyl blocking type polyurethane (
VLPU).Secondly, under 30～50 ℃, use
TEA(0.6 g) neutralization
VLPU, be reflected in 15～30 min and finish.At last, slowly add distilled water (50 g) in the urethane that is neutralized, at room temperature high speed dispersion 30～60 min obtain carboxyl-content be 6% ethenyl blocking type aqueous polyurethane (
VLWPU).Obtain thus
VLWPUBe translucent blueing light emulsion, latex particle size is less, but viscosity is big slightly.
Embodiment 5: synthesizer and operating process are the same,
At firstAt room temperature
PPG1000(7.65 g),
DMPA(0.78 g) and 1,4-
BD(0.25g) join in the flask.Add subsequently
NMP(1.8g) stir until obtaining a homogeneous system.At this moment temperature is risen to 60～90 ℃, in 30～60 min, dropwise add then
IPDI(4. 52 g),
DBTDLThe mixed solution of (3～5) and acetone (5.0 g) is reflected at and carries out 3～5 h under the oil bath agitation condition, obtain isocyanate-terminated polyurethane prepolymer (
NCO-PU).At this moment, add
HEMA(0.77 g) is reflected at and proceeds 1.5～2.5 h under 60～80 ℃, obtained the ethenyl blocking type polyurethane (
VLPU).Secondly, under 30～50 ℃, use
TEA(0.68 g) neutralization
VLPU, be reflected in 15～30 min and finish.At last, slowly add distilled water (50 g) in the urethane that is neutralized, at room temperature high speed dispersion 30～60 min obtain carboxyl-content be 7% ethenyl blocking type aqueous polyurethane (
VLWPU).By example 5 described formulation
VLWPUFor translucent and blue light phenomenon clearly, latex particle size is little, but system viscosity is bigger.
, the waterborne polyurethane-polyacrylate compounded latex preparation:
Table 2 preparation waterborne polyurethane-polyacrylate compounded latex raw material (weight part)
Concrete preparation process is as follows:
Embodiment 6: semicontinuous emulsifier-free emulsion polymerization method is adopted in the preparation of waterborne polyurethane-polyacrylate compounded latex, at first is any one carboxyl-content of preparation among the embodiment 1 ~ 5 5% ethenyl blocking type aqueous polyurethane
VLWPU(30 g) mixes with vinylbenzene (5 g) and butyl acrylate (5 g), and carries out pre-emulsification under suitable stirring velocity.Then earlier the pre-emulsification of 10 % and 10 %
KPS(amount of initiator is 1 % of amount of monomer) joins in the 250 mL four-hole boiling flasks, logical N
2Protection, 60～80 ℃ are reacted 15～30 min down.Then remaining pre-emulsification and
KPSBe added dropwise to speed slowly respectively and react 3～5 h in the flask.Obtain the stable composite emulsion of oyster white blueing light at last.With transmission electron microscope (
TEM) observe its pattern.Described waterborne polyurethane-polyacrylate compounded latex is the core/shell type structure, and the chitin of composite colloidal particle is urethane, examines to be polyacrylic ester.
Embodiment 7: primary process is with embodiment 6, is the carboxyl-content of preparation 5% earlier
VLWPU(30 g) mixes with vinylbenzene (3 g) and butyl acrylate (7 g), and carries out pre-emulsification under suitable stirring velocity.Then earlier 10 %'s of the pre-emulsification of 10 % and initiator total amount
KPSJoin in the 250 mL four-hole boiling flasks logical N
2Protection, 60～80 ℃ are reacted 15～30 min down.Then remaining pre-emulsification and KPS are added dropwise to speed slowly respectively and react 3～5 h in the flask.Obtain the composite emulsion of oyster white blueing light at last.
Embodiment 8: according to the program of embodiment 6, be carboxyl-content 5% earlier
VLWPU(30 g) and vinylbenzene (
Styrene, 7 g) and butyl acrylate (3 g) mixing, carry out pre-emulsification.Then earlier the pre-emulsification of 10 % and 10 %
KPS(amount of initiator is 1 % of amount of monomer) joins in the 250 mL four-hole boiling flasks, logical N
2Protection, 60～80 ℃ are reacted 15～30 min down.Then remaining pre-emulsification and KPS are added dropwise to speed slowly respectively and react 3～5 h in the flask.Obtain milky composite emulsion at last.
Embodiment 9: adopt semicontinuous emulsifier-free emulsion polymerization legal system to be equipped with the waterborne polyurethane-polyacrylate compounded latex equally.Be carboxyl-content 5%
VLWPU(30 g) mixes with vinylbenzene (10 g) and carries out pre-emulsification.Then earlier the pre-emulsification of 10 % and 10 %
KPS(amount of initiator is 1 % of amount of monomer) joins in the 250 ml four-hole boiling flasks, logical N
2Protection, 60～80 ℃ are reacted 15～30 min down.Then remaining pre-emulsification and
KPSBe added dropwise to speed slowly respectively and react 3～5 h in the flask.Obtain milky composite emulsion at last, emulsion is very unstable, is easy to sedimentation.
The waterborne polyurethane-polyacrylate compounded latex of above-mentioned steps B gained is filmed at tinplate, at room temperature dry 24 h, dry 24 h in 30～50 ℃ of thermostat containers then.Testing standard is that hardness of film adopts GB/T 6739-1996; Film adhesive adopts GB 1720-79 (89) to measure; The snappiness of filming adopts GB/T 1731-93 to measure; The coating film gloss degree adopts GB 1743-79 (89) to measure; Water-resistance property of coating adopts GB/T 1733-93 to measure; The water-intake rate of filming is measured by HG 2-1612-85.Draw the following table data:
The performance of table 3 waterborne polyurethane-polyacrylate compounded latex
Waterborne polyurethane-polyacrylate composite emulsion of the present invention is through infrared spectra, and methods such as gel permeation chromatography and TEM characterize, and has confirmed composite emulsion structure, molecular weight, particle diameter and pattern.
The waterborne polyurethane-polyacrylate compounded latex that the present invention makes, the material choice scope is bigger, and cost is lower; Has the self-emulsifying function, the emulsion stable storing; Deionized water with or the inexpensive solvent that has no side effect such as ethanol in can disperse well, " green " environmental protection is easy to adjust concentration and viscosity when subsequent applications; Film forming properties is good, and tint retention is good, and is good to the color developing of pigment, the glossiness height.
Should be understood that application of the present invention is not limited to above-mentioned giving an example, for those of ordinary skills, can be improved according to the above description or conversion that all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (9)
1. the preparation method of a waterborne polyurethane-polyacrylate compounded latex, it may further comprise the steps: steps A: synthesis of vinyl end-sealed type aqueous polyurethane;
Step B: utilize ethenyl blocking type aqueous polyurethane to synthesize the waterborne polyurethane-polyacrylate composite emulsion,
Wherein, described steps A specifically comprises:
Steps A 1: end hydroxy polyether, dimethylol propionic acid and 1,4-butyleneglycol mixed and be dissolved in and form mixing solutions in the organic solvent;
Steps A 2: under 40 ~ 65 ℃, catalyzer, diisocyanate cpd and acetone are splashed in the mixing solutions;
Steps A 3: be warmed up to 65 ℃～95 ℃ after dropwising, and under this temperature, reacted 3 hours～5 hours, make diisocyanate terminated type polyurethane;
Steps A 4: in diisocyanate terminated type polyurethane, add vinyl monomer, under 60～80 ℃, proceed to react 1.5 hours～2.5 hours, obtain the ethenyl blocking type polyurethane;
Steps A 5: under 30～50 ℃, with triethylamine neutralization of ethylene base end-sealed type urethane, be reflected at 15 minutes～finish in 30 minutes;
Steps A 6: add a certain amount of distilled water in the ethenyl blocking type polyurethane that is neutralized, at room temperature high speed dispersion obtained ethenyl blocking type aqueous polyurethane in 30 minutes～60 minutes;
Described step B specifically comprises:
Step B1: adopt the semi-continuous emulsion polymerizing method, ethenyl blocking type aqueous polyurethane is mixed with acrylic ester monomer and stir and carry out pre-emulsification and obtain pre-emulsification;
Step B2: get 8%～10 % of the pre-emulsification weight part that obtains among the step B1 and the initiator of 8%～10 % weight part and join in the reactor, logical N
2Protection, 60 ℃～85 ℃ down reactions 15 minutes～30 minutes, described initiator is Potassium Persulphate, the total consumption of initiator is 1%～3% of the monomer weight of all participation polyreactions;
Step B3: remaining pre-emulsification and Potassium Persulphate were added in the reactor reaction respectively 3 hours～5 hours, obtain the waterborne polyurethane-polyacrylate compounded latex.
2. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, described end hydroxy polyether is cetomacrogol 1000, polypropylene glycol 1000 or PTMG 1000.
3. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1, it is characterized in that, described organic solvent is polar solvent, select acetone, N for use, N-diformamide or N-Methyl pyrrolidone, consumption of organic solvent for the weight that adds whole raw materials used before the organic solvent and 10%～15%.
4. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1, it is characterized in that, described catalyzer is butyl (tetra) titanate, dibutyl tin laurate or titanium isopropylate, and catalyst consumption is 0.5%～1% of vulcabond weight.
5. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, described diisocyanate cpd is tolylene diisocyanate or isophorone diisocyanate.
6. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, described vinyl monomer is methacrylic acid-beta-hydroxy ethyl ester.
7. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, the addition of described triethylamine is so that the pH value of neutralization back system is standard for 6-7.
8. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, the structural formula of described ethenyl blocking type polyurethane is as follows:
9. the preparation method of waterborne polyurethane-polyacrylate compounded latex according to claim 1 is characterized in that, described waterborne polyurethane-polyacrylate compounded latex is the core/shell type structure, and the chitin of composite colloidal particle is urethane, examines to be polyacrylic ester.
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| CN102786651B (en) * | 2012-08-23 | 2013-12-11 | 深圳市科彩印务有限公司 | Waterborne polyurethane binder, waterborne polyurethane composite binder and preparation method of waterborne polyurethane binder and waterborne polyurethane composite binder |
| CN106749940A (en) * | 2016-12-03 | 2017-05-31 | 范进 | A kind of preparation method of high-toughness polypropylene yogurt glue |
| CN109096446B (en) * | 2018-07-18 | 2021-05-28 | 江苏景宏新材料科技有限公司 | Modified acrylate and preparation method thereof, printing ink and application thereof |
| CN110483698A (en) * | 2019-08-26 | 2019-11-22 | 广东工业大学 | A kind of aqueous polyurethane multiple emulsion and preparation method thereof |
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| CN101875711B (en) * | 2010-07-22 | 2012-06-27 | 武汉工程大学 | Preparation method of hydroxyl aqueous polyurethane-acrylate resin hybridized body |
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