CN105461863A - Acrylate modified waterborne polyurethane emulsion and preparation method thereof - Google Patents
Acrylate modified waterborne polyurethane emulsion and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention discloses acrylate modified waterborne polyurethane emulsion and a preparation method thereof. The acrylate modified waterborne polyurethane emulsion is prepared from the following components in parts by weight: 20-30 parts of polyhydric alcohols, 10-20 parts of diisocyanate, 2-6 parts of hydrophilic chain-extending agent, 2-5 parts of organic base, 5-15 parts of cross-linking agent, 10-25 parts of acrylate monomer, 100-200 parts of deionized water, 0.01-0.1 part of dibutyltin dilaurate, 0.2-1 part of initiator and 10-30 parts of acetone. Acrylate is used to modify waterborne polyurethane, and a polyurethane material excellent in overall performance is obtained; the acrylate is used to participate in reaction, double bonds are introduced to a polyurethane main chain, then acrylate monomer polymerization is triggered, and a complex net structure can be formed; compared with traditional waterborne polyurethane, water resistance, heat resistance and mechanical property are obviously improved.
Description
Technical field
The present invention relates to field of macromolecular chemical material, particularly relate to a kind of acrylic ester modified water-soluble polyurethane emulsion and preparation method thereof.
Background technology
Urethane is a kind of multifunctional macromolecule material, and its raw material variety is various, and molecular structure is adjustable, is widely used in multiple fields such as porous plastics, elastomerics, sizing agent, coating.Current polyurethane material has solvent-borne type and water-soluble two class.In general, solvent borne polyurethane is formed by solution polymerization for primary solvent with acetone, butanone, toluene etc., and these solvents are all noxious solvents, therefore solvent borne polyurethane contaminate environment in production and use procedure.Safety coefficient is low, have very large harm to the healthy of people.Along with social progress and scientific and technical development, the environmental consciousness of people constantly strengthens, and development high quality, free of contamination environment-protecting polyurethane become development trend.
Aqueous polyurethane is using water to replace organic solvent as dispersion medium, has the advantages such as nontoxic, environmental protection, cheapness, is more and more subject to people's attention.Outside cold-resistant, the fundamental characteristics such as good springiness, gloss are high, soft or hard section temperature is adjustable that aqueous polyurethane not only has that solvent borne polyurethane has, also there is advantages such as not firing, nontoxic, pollution-free, but also there is the shortcomings such as solid content is low, physical and mechanical properties is poor, water tolerance, poor heat resistance, this have impact on the application of aqueous polyurethane to a great extent.Chinese patent (CN101429417A) discloses a kind of water-based polyurethane adhesive of the high adhesion adopting aliphatic isocyanates to synthesize, although solid content increases, keep away the poor mechanical property of unavoidable glued membrane and the lower feature of water tolerance; Chinese patent (CN101993677) discloses the aqueous polyurethane that a kind of butyleneglycol is chainextender, but its viscosity lower needs adds thickening material to adjust, and troublesome poeration is complicated.United States Patent (USP) (US4870129) discloses the aqueous polyurethane that a kind of solid content can reach 40% ~ 50%, hydrophilic reagent employs sulfonic acid two amine type, need in preparation process to add a large amount of solvents, consume energy during recovery Datong District time can cause the pollution of environment.
Acrylic resin has the advantages such as high, ageing-resistant, the anti-yellowing change of physical strength, water tolerance, but there is organic solvent resistance difference, poor heat resistance, the shortcoming such as wear no resistance.If the aqueous polyurethane of activity double key end-blocking can be had by synthesis, it can be used as seed emulsion emulsion acrylic monomer, and then by initiator initiating methacrylates monomer, prepare modified product.The performance of urethane and acrylate very large complementation be can be obtained like this, the water tolerance of aqueous polyurethane, thermotolerance and mechanical property both compounds can be improved.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the acrylic ester modified water-soluble polyurethane emulsion of a kind of water resistance, resistance toheat and good mechanical properties is provided.
Another object of the present invention is to provide the preparation method of above-mentioned cheapness, the simple acrylic ester modified water-soluble polyurethane emulsion of technique.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of acrylic ester modified water-soluble polyurethane emulsion, be made up of the component of following parts by weight: polyvalent alcohol 20 ~ 30 parts, vulcabond 10 ~ 20 parts, hydrophilic chain extender 2 ~ 6 parts, organic bases 2 ~ 5 parts, linking agent 5-15 part, acrylate monomer 10 ~ 25 parts, deionized water 100 ~ 200 parts, dibutyl tin laurate 0.01 ~ 0.1 part, initiator 0.2 ~ 1 part, 10 ~ 30 parts, acetone.
As preferably, in aforesaid propylene acid esters modified aqueous polyurethane emulsion, described polyvalent alcohol is following one or more: poly adipate succinic acid ester dibasic alcohol, PCDL or polycaprolactone diols, molecular weight is 1000 ~ 3000.
As preferably, in aforesaid propylene acid esters modified aqueous polyurethane emulsion, described vulcabond is following one or more: isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate or diphenylmethanediisocyanate.
As preferably, in aforesaid propylene acid esters modified aqueous polyurethane emulsion, described hydrophilic chain extender is dihydroxypropionic acid or dihydroxyl butyric acid.
As preferably, in aforesaid propylene acid esters modified aqueous polyurethane emulsion, described linking agent is following one: Propylene glycol monoacrylate, pentaerythritol triacrylate or pentaerythritol diacrylate.
As preferably, in aforesaid propylene acid esters modified aqueous polyurethane emulsion, described acrylate monomer be following one or more: methyl acrylate, methyl methacrylate, ethyl propenoate or butyl acrylate.
As preferably, in aforesaid propylene acid esters modified aqueous polyurethane emulsion, described organic bases be following one or more: triethylamine, diethylamine, diisopropylamine, DIPEA.
As preferably, in aforesaid propylene acid esters modified aqueous polyurethane emulsion, described initiator is azo-bis-isobutyl cyanide or Potassium Persulphate.
The preparation method of aforesaid propylene acid esters modified aqueous polyurethane emulsion, comprises the steps:
(1) polyvalent alcohol is put into dry reactor, heating makes the polyvalent alcohol melting in reactor, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 70 ~ 80 DEG C subsequently and add vulcabond and dibutyl tin laurate, react after 2 ~ 3 hours under nitrogen protection, then add hydrophilic chain extender reaction and obtain performed polymer in 2 ~ 3 hours;
(2) at 70 ~ 80 DEG C, add linking agent subsequently and carry out end capping 2 ~ 3 hours, obtain base polyurethane prepolymer for use as main chain being introduced activity double key;
(3) after reaction terminates, add acrylate monomer and reduce viscosity and be cooled to after 30 ~ 50 DEG C, add in organic bases and stir, finally adding deionized water and carry out high speed dispersion emulsification, obtain aqueous polyurethane emulsion main chain being introduced activity double key;
(4) initiator is dissolved in acetone, at 70 ~ 90 DEG C, slowly drop in emulsion, after dropwising, at 70 ~ 90 DEG C, continue reaction 3 ~ 4 hours; Solvent removed by vacuum, namely obtains high solids content, high viscosity, acrylic ester modified water-soluble polyurethane emulsion that thermotolerance is high.
Compared with prior art, the present invention has following beneficial effect:
1. preparation method's technique is simple, and reaction conditions is gentle, and product characteristics is stablized, and production cost is low, is conducive to large-scale industrial production application, thus has broad application prospects.
2. the acrylic ester modified water-soluble polyurethane of the present invention's synthesis has the advantage such as simple economy, environmental protection, thus has the social value theory of environmental protection.
3. the present invention utilizes acrylate to carry out modification to aqueous polyurethane, obtain the polyurethane material of excellent combination property, utilize acrylate to participate in reaction and double bond is incorporated into polyurethane backbone, cause the polymerization of Acrylic Acid Monomer subsequently, complicated reticulated structure can be formed, compare traditional waterborne polyurethane, water tolerance, thermotolerance, mechanical property are significantly improved.
Accompanying drawing explanation
Fig. 1 is the thermal multigraph of acrylic ester modified water-soluble polyurethane; X-coordinate is temperature T/ DEG C, and ordinate zou is rate of weight loss TG/%.
Embodiment
Embodiment 1:
(1) PCDL being 2000 by 25 parts of molecular weight adds in dry reactor, after heating makes the PCDL melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 80 DEG C subsequently, the dibutyl tin laurate of 10 parts of isophorone diisocyanates, 0.1% mass parts is added in reaction flask, react 2 hours under 80 DEG C of nitrogen protections, the dihydroxypropionic acid then adding 2 parts again reacts and obtains performed polymer in 2 hours;
(2) reaction is dropped to 70 DEG C, add 5 parts of Propylene glycol monoacrylates and carry out end capping 2 hours, obtain base polyurethane prepolymer for use as main chain being introduced activity double key;
(3), after reaction terminates, temperature is down to 40 DEG C and is added the methyl acrylate of 15 parts altogether and the viscosity of methyl methacrylate reduction performed polymer, then adds the triethylamine neutralization reaction half hour of 2 parts.Add deionized water dispersion and emulsion under last high speed shear, obtain aqueous polyurethane emulsion main chain being introduced activity double key;
(4) azo-bis-isobutyl cyanide is dissolved in the acetone of 10 parts, slowly drops in emulsion at 80 DEG C, within 3 hours, drip off.At 80 DEG C, continue reaction 3 hours after dropwising, vacuum removal acetone, namely obtain acrylic ester modified water-soluble polyurethane emulsion.The thermal multigraph of gained acrylic ester modified water-soluble polyurethane emulsion as shown in Figure 1.
Embodiment 2:
(1) the poly adipate succinic acid ester dibasic alcohol being 2000 by 25 parts of molecular weight adds in dry reactor, after heating makes the PCDL melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 80 DEG C subsequently, the dibutyl tin laurate of 10 parts of isophorone diisocyanates, 0.1% mass parts is added in reaction flask, react 2 hours under 80 DEG C of nitrogen protections, the dihydroxypropionic acid then adding 3 parts again reacts and obtains performed polymer in 2 hours;
(2) under 80 DEG C of nitrogen protections, add 6 parts of Propylene glycol monoacrylates and carry out end capping 2 hours, obtain base polyurethane prepolymer for use as main chain being introduced activity double key;
(3), after reaction terminates, temperature is down to 40 DEG C and is added the methyl acrylate of 15 parts altogether and the viscosity of methyl methacrylate reduction performed polymer, then adds the triethylamine neutralization reaction half hour of 2 parts.Add deionized water dispersion and emulsion under last high speed shear, obtain aqueous polyurethane emulsion main chain being introduced activity double key;
(4) azo-bis-isobutyl cyanide is dissolved in the acetone of 10 parts, slowly drops in emulsion at 80 DEG C, within 3 hours, drip off.At 80 DEG C, reaction 3 hours is continued, vacuum removal acetone after dropwising.Namely acrylic ester modified water-soluble polyurethane emulsion is obtained.
Embodiment 3:
(1) PCDL being 2000 by 20 parts of molecular weight adds in dry reactor, after heating makes the PCDL melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 80 DEG C subsequently, the dibutyl tin laurate of 10 parts of hexamethylene diisocyanates, 0.1% mass parts is added in reaction flask, react 2 hours under 80 DEG C of nitrogen protections, the dihydroxyl butyric acid then adding 2 parts again reacts and obtains performed polymer in 2 hours;
(2) reaction is dropped to 70 DEG C, add 5 parts of pentaerythritol diacrylates and carry out end capping 2 hours, obtain base polyurethane prepolymer for use as main chain being introduced activity double key;
(3), after reaction terminates, temperature is down to 40 DEG C and is added the ethyl propenoate of 20 parts altogether and the viscosity of methyl methacrylate reduction performed polymer, then adds the triethylamine neutralization reaction half hour of 2 parts.Add deionized water dispersion and emulsion under last high speed shear, obtain aqueous polyurethane emulsion main chain being introduced activity double key;
(4) azo Potassium Persulphate is dissolved in the deionized water of 10 parts, slowly drops in emulsion at 80 DEG C, within 3 hours, drip off.At 80 DEG C, reaction 3 hours is continued, vacuum removal acetone after dropwising.Namely acrylic ester modified water-soluble polyurethane emulsion is obtained.
Embodiment 4:
(1) polycaprolactone diols being 2000 by 30 parts of molecular weight adds in dry reactor, after heating makes the polycaprolactone diols melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 80 DEG C subsequently, isophorone diisocyanate and the hexamethylene diisocyanate of 10 parts will be had altogether, wherein the ratio of the amount of IPDI and HDI is 2:1, the dibutyl tin laurate of 0.1% mass parts adds in reaction flask, react 2 hours under 80 DEG C of nitrogen protections, the dihydroxypropionic acid then adding 2 parts again reacts and obtains performed polymer in 2 hours;
(2) reaction is dropped to 70 DEG C, add 5 parts of pentaerythritol diacrylates and carry out end capping 2 hours, obtain base polyurethane prepolymer for use as main chain being introduced activity double key;
(3), after reaction terminates, temperature is down to 30 DEG C and is added the butyl acrylate of 15 parts altogether and the viscosity of methyl methacrylate reduction performed polymer, then adds the diisopropylamine neutralization reaction half hour of 2 parts.Add deionized water dispersion and emulsion under last high speed shear, obtain aqueous polyurethane emulsion main chain being introduced activity double key;
(4) azo-bis-isobutyl cyanide is dissolved in the acetone of 10 parts, slowly drops in emulsion at 80 DEG C, within 2 hours, drip off.At 80 DEG C, reaction 4 hours is continued, vacuum removal acetone after dropwising.Namely acrylic ester modified water-soluble polyurethane emulsion is obtained.
Embodiment 5:
(1) the poly adipate succinic acid ester dibasic alcohol being 2000 by 25 parts of molecular weight adds in dry reactor, after heating makes the poly adipate succinic acid ester dibasic alcohol melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 80 DEG C subsequently, the dibutyl tin laurate of 10 parts of isophorone diisocyanates, 0.1% mass parts is added in reaction flask, react 2 hours under 80 DEG C of nitrogen protections, the dihydroxypropionic acid then adding 2 parts again reacts and obtains performed polymer in 2 hours;
(2) reaction is under 80 DEG C of nitrogen protections, adds 5 parts of pentaerythritol triacrylates and carries out end capping 2 hours, obtain base polyurethane prepolymer for use as main chain being introduced activity double key;
(3), after reaction terminates, temperature is down to 30 DEG C and is added the butyl acrylate of 15 parts altogether and the viscosity of methyl methacrylate reduction performed polymer, then adds the triethylamine neutralization reaction half hour of 2 parts.Add deionized water dispersion and emulsion under last high speed shear, obtain aqueous polyurethane emulsion main chain being introduced activity double key;
(4) azo-bis-isobutyl cyanide is dissolved in the acetone of 10 parts, slowly drops in emulsion at 80 DEG C, within 3 hours, drip off.At 80 DEG C, reaction 3 hours is continued, vacuum removal acetone after dropwising.Namely acrylic ester modified water-soluble polyurethane emulsion is obtained.Accompanying drawing is shown in the test of its infrared detection, thermogravimetric.
Embodiment 6:
(1) the poly adipate succinic acid ester dibasic alcohol being 2000 by 25 parts of molecular weight adds in dry reactor, after heating makes the poly adipate succinic acid ester dibasic alcohol melting in reaction flask, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 80 DEG C subsequently, the dibutyl tin laurate of 10 parts of tolylene diisocyanates, 0.1% mass parts is added in reaction flask, react 2 hours under 80 DEG C of nitrogen protections, the dihydroxypropionic acid then adding 2 parts again reacts and obtains performed polymer in 2 hours;
(2) reaction is dropped to 70 DEG C, add 5 parts of pentaerythritol triacrylates and carry out end capping 2 hours, obtain base polyurethane prepolymer for use as main chain being introduced activity double key;
(3), after reaction terminates, temperature is down to 40 DEG C and is added the butyl acrylate of 15 parts altogether and the viscosity of methyl methacrylate reduction performed polymer, then adds the triethylamine neutralization reaction half hour of 2 parts.Add deionized water dispersion and emulsion under last high speed shear, obtain aqueous polyurethane emulsion main chain being introduced activity double key;
(4) azo-bis-isobutyl cyanide is dissolved in the acetone of 10 parts, slowly drops in emulsion at 80 DEG C, within 2 hours, drip off.At 80 DEG C, reaction 3 hours is continued, vacuum removal acetone after dropwising.Namely acrylic ester modified water-soluble polyurethane emulsion is obtained.
Claims (9)
1. an acrylic ester modified water-soluble polyurethane emulsion, it is characterized in that being made up of the component of following parts by weight: polyvalent alcohol 20 ~ 30 parts, vulcabond 10 ~ 20 parts, hydrophilic chain extender 2 ~ 6 parts, organic bases 2 ~ 5 parts, linking agent 5-15 part, acrylate monomer 10 ~ 25 parts, deionized water 100 ~ 200 parts, 0.01 ~ 0.1 part, tin dilaurate base tin, initiator 0.2 ~ 1 part, 10 ~ 30 parts, acetone.
2. acrylic ester modified water-soluble polyurethane emulsion according to claim 1, it is characterized in that, described polyvalent alcohol is following one or more: poly adipate succinic acid ester dibasic alcohol, PCDL or polycaprolactone diols, molecular weight is 1000 ~ 3000.
3. acrylic ester modified water-soluble polyurethane emulsion according to claim 1, it is characterized in that, described vulcabond is following one or more: isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate or diphenylmethanediisocyanate.
4. acrylic ester modified water-soluble polyurethane emulsion according to claim 1, is characterized in that, described hydrophilic chain extender is dihydroxypropionic acid or dihydroxyl butyric acid.
5. acrylic ester modified water-soluble polyurethane emulsion according to claim 1, is characterized in that, described linking agent is following one: Propylene glycol monoacrylate, pentaerythritol triacrylate or pentaerythritol diacrylate.
6. acrylic ester modified water-soluble polyurethane emulsion according to claim 1, is characterized in that, described acrylate monomer be following one or more: methyl acrylate, methyl methacrylate, ethyl propenoate or butyl acrylate.
7. acrylic ester modified water-soluble polyurethane emulsion according to claim 1, is characterized in that, described organic bases be following one or more: triethylamine, diethylamine, diisopropylamine, DIPEA.
8. acrylic ester modified water-soluble polyurethane emulsion according to claim 1, is characterized in that, described initiator is azo-bis-isobutyl cyanide or Potassium Persulphate.
9. the preparation method of acrylic ester modified water-soluble polyurethane emulsion described in claim 1, is characterized in that comprising the steps:
(1) polyvalent alcohol is put into dry reactor, heating makes the polyvalent alcohol melting in reactor, the 1h that dewaters is vacuumized at 120 DEG C, be cooled to 70 ~ 80 DEG C subsequently and add vulcabond and dibutyl tin laurate, react after 2 ~ 3 hours under nitrogen protection, then add hydrophilic chain extender reaction and obtain performed polymer in 2 ~ 3 hours;
(2) at 70 ~ 80 DEG C, add linking agent subsequently and carry out end capping 2 ~ 3 hours, obtain base polyurethane prepolymer for use as main chain being introduced activity double key;
(3) after reaction terminates, add acrylate monomer and reduce viscosity and be cooled to after 30 ~ 50 DEG C, add in organic bases and stir, finally adding deionized water and carry out high speed dispersion emulsification, obtain aqueous polyurethane emulsion main chain being introduced activity double key;
(4) initiator is dissolved in acetone, at 70 ~ 90 DEG C, slowly drop in emulsion, after dropwising, at 70 ~ 90 DEG C, continue reaction 3 ~ 4 hours; Solvent removed by vacuum, namely obtains acrylic ester modified water-soluble polyurethane emulsion.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510973379.9A CN105461863A (en) | 2015-12-23 | 2015-12-23 | Acrylate modified waterborne polyurethane emulsion and preparation method thereof |
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| CN201510973379.9A CN105461863A (en) | 2015-12-23 | 2015-12-23 | Acrylate modified waterborne polyurethane emulsion and preparation method thereof |
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| CN105461863A true CN105461863A (en) | 2016-04-06 |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860085A (en) * | 2016-06-24 | 2016-08-17 | 安徽省思维新型建材有限公司 | Method for preparing modified polyurethane |
| CN106008988A (en) * | 2016-06-24 | 2016-10-12 | 安徽省思维新型建材有限公司 | Preparation method of polypropylene-based modified polyurethane composite material |
| CN106117451A (en) * | 2016-07-29 | 2016-11-16 | 同光（江苏）新材料科技有限公司 | A kind of preparation method of acrylic ester grafted modified aqueous polyurethane resin |
| CN106832174A (en) * | 2017-03-23 | 2017-06-13 | 江苏耐斯数码科技股份有限公司 | A kind of autofluorescence brightens acrylic acid modified polyurethane emulsion and preparation method thereof |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN107603400A (en) * | 2017-09-18 | 2018-01-19 | 广州冠志新材料科技有限公司 | Waterborne polyurethane modified acrylic acid ester emulsion and preparation method thereof and water-borne wood coating |
| CN107629541A (en) * | 2017-09-26 | 2018-01-26 | 句容市后白镇迎瑞印花厂 | A kind of water-based UV ink and preparation method thereof |
| CN108219076A (en) * | 2017-12-26 | 2018-06-29 | 万华化学（宁波）有限公司 | The preparation method of water-based hydroxyl polyurethane-acrylate and its application in anti-graffiti coating |
| CN108264630A (en) * | 2017-12-29 | 2018-07-10 | 广东博海化工科技有限公司 | Cured modified waterborne, polycarbonate polyaminoester emulsion and preparation method thereof after a kind of UV |
| CN109438626A (en) * | 2018-10-24 | 2019-03-08 | 三棵树涂料股份有限公司 | A kind of preparation method of acrylic ester modified water-soluble polyurethane composite dispersion |
| CN110317558A (en) * | 2019-08-05 | 2019-10-11 | 陕西科技大学 | A kind of poly-dopamine acrylic adhesive for polyurethane and preparation method thereof |
| CN111732693A (en) * | 2020-06-29 | 2020-10-02 | 合肥小陀螺新材料科技有限公司 | Polyacrylate modified polyurethane material for mud pump piston and preparation method thereof |
| CN111995719A (en) * | 2020-07-10 | 2020-11-27 | 重庆中科烯维科技有限公司 | High-performance aqueous polyurethane acrylate composite emulsion and preparation method thereof |
| CN112029341A (en) * | 2020-09-15 | 2020-12-04 | 浙江华宝油墨有限公司 | Environment-friendly acrylate modified waterborne polyurethane printing ink and preparation method thereof |
| CN112279971A (en) * | 2020-11-04 | 2021-01-29 | 湖南中泰特种装备有限责任公司 | Hydroxyl functionalized waterborne polyurethane emulsion and preparation method thereof |
| CN112898893A (en) * | 2019-12-04 | 2021-06-04 | 洛阳尖端技术研究院 | Waterborne polyurethane emulsion, waterborne polyurethane wave-absorbing coating, preparation method of waterborne polyurethane wave-absorbing coating and wave-absorbing honeycomb |
| CN114539505A (en) * | 2022-01-18 | 2022-05-27 | 威斯坦(厦门)实业有限公司 | Amino acid modified waterborne polyurethane acrylate and preparation method thereof |
| CN114805696A (en) * | 2022-04-22 | 2022-07-29 | 台州学院 | Polymerizable polyurethane/acrylate composite emulsion, preparation method and application |
| CN115595036A (en) * | 2022-11-04 | 2023-01-13 | 广州立诺新材料科技有限公司（Cn） | Acrylic acid modified polyurethane dispersion for plastic-replacing gloss oil and preparation method thereof |
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Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106008988A (en) * | 2016-06-24 | 2016-10-12 | 安徽省思维新型建材有限公司 | Preparation method of polypropylene-based modified polyurethane composite material |
| CN105860085A (en) * | 2016-06-24 | 2016-08-17 | 安徽省思维新型建材有限公司 | Method for preparing modified polyurethane |
| CN106117451A (en) * | 2016-07-29 | 2016-11-16 | 同光（江苏）新材料科技有限公司 | A kind of preparation method of acrylic ester grafted modified aqueous polyurethane resin |
| CN106832174A (en) * | 2017-03-23 | 2017-06-13 | 江苏耐斯数码科技股份有限公司 | A kind of autofluorescence brightens acrylic acid modified polyurethane emulsion and preparation method thereof |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN107603400B (en) * | 2017-09-18 | 2020-03-20 | 广州冠志新材料科技有限公司 | Waterborne polyurethane modified acrylate emulsion, preparation method thereof and waterborne wood coating |
| CN107603400A (en) * | 2017-09-18 | 2018-01-19 | 广州冠志新材料科技有限公司 | Waterborne polyurethane modified acrylic acid ester emulsion and preparation method thereof and water-borne wood coating |
| CN107629541A (en) * | 2017-09-26 | 2018-01-26 | 句容市后白镇迎瑞印花厂 | A kind of water-based UV ink and preparation method thereof |
| CN108219076B (en) * | 2017-12-26 | 2020-07-28 | 万华化学（宁波）有限公司 | Preparation method of water-based hydroxyl polyurethane-acrylate resin and application of water-based hydroxyl polyurethane-acrylate resin in anti-graffiti coating |
| CN108219076A (en) * | 2017-12-26 | 2018-06-29 | 万华化学（宁波）有限公司 | The preparation method of water-based hydroxyl polyurethane-acrylate and its application in anti-graffiti coating |
| CN108264630A (en) * | 2017-12-29 | 2018-07-10 | 广东博海化工科技有限公司 | Cured modified waterborne, polycarbonate polyaminoester emulsion and preparation method thereof after a kind of UV |
| CN109438626A (en) * | 2018-10-24 | 2019-03-08 | 三棵树涂料股份有限公司 | A kind of preparation method of acrylic ester modified water-soluble polyurethane composite dispersion |
| CN109438626B (en) * | 2018-10-24 | 2021-08-03 | 三棵树涂料股份有限公司 | Preparation method of acrylate modified waterborne polyurethane composite dispersion |
| CN110317558A (en) * | 2019-08-05 | 2019-10-11 | 陕西科技大学 | A kind of poly-dopamine acrylic adhesive for polyurethane and preparation method thereof |
| CN112898893A (en) * | 2019-12-04 | 2021-06-04 | 洛阳尖端技术研究院 | Waterborne polyurethane emulsion, waterborne polyurethane wave-absorbing coating, preparation method of waterborne polyurethane wave-absorbing coating and wave-absorbing honeycomb |
| CN111732693A (en) * | 2020-06-29 | 2020-10-02 | 合肥小陀螺新材料科技有限公司 | Polyacrylate modified polyurethane material for mud pump piston and preparation method thereof |
| CN111995719A (en) * | 2020-07-10 | 2020-11-27 | 重庆中科烯维科技有限公司 | High-performance aqueous polyurethane acrylate composite emulsion and preparation method thereof |
| CN112029341A (en) * | 2020-09-15 | 2020-12-04 | 浙江华宝油墨有限公司 | Environment-friendly acrylate modified waterborne polyurethane printing ink and preparation method thereof |
| CN112029341B (en) * | 2020-09-15 | 2021-06-25 | 浙江华宝油墨有限公司 | Environment-friendly acrylate modified waterborne polyurethane printing ink and preparation method thereof |
| CN112279971A (en) * | 2020-11-04 | 2021-01-29 | 湖南中泰特种装备有限责任公司 | Hydroxyl functionalized waterborne polyurethane emulsion and preparation method thereof |
| CN114539505A (en) * | 2022-01-18 | 2022-05-27 | 威斯坦(厦门)实业有限公司 | Amino acid modified waterborne polyurethane acrylate and preparation method thereof |
| CN114539505B (en) * | 2022-01-18 | 2023-11-03 | 威斯坦(厦门)实业有限公司 | Amino acid modified waterborne polyurethane acrylate and preparation method thereof |
| CN114805696A (en) * | 2022-04-22 | 2022-07-29 | 台州学院 | Polymerizable polyurethane/acrylate composite emulsion, preparation method and application |
| CN114805696B (en) * | 2022-04-22 | 2024-01-30 | 台州学院 | Polymerizable polyurethane/acrylic ester composite emulsion, preparation method and application |
| CN115595036A (en) * | 2022-11-04 | 2023-01-13 | 广州立诺新材料科技有限公司（Cn） | Acrylic acid modified polyurethane dispersion for plastic-replacing gloss oil and preparation method thereof |
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Application publication date: 20160406 |