CN105175642A - Self-crosslinking polyurethane-acrylate composite emulsion and preparation method thereof - Google Patents
Self-crosslinking polyurethane-acrylate composite emulsion and preparation method thereof Download PDFInfo
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- CN105175642A CN105175642A CN201510622498.XA CN201510622498A CN105175642A CN 105175642 A CN105175642 A CN 105175642A CN 201510622498 A CN201510622498 A CN 201510622498A CN 105175642 A CN105175642 A CN 105175642A
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000004945 emulsification Methods 0.000 title claims description 26
- 238000004132 cross linking Methods 0.000 title abstract description 15
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- 229920005906 polyester polyol Polymers 0.000 claims abstract description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 56
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- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 37
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 24
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- 230000003472 neutralizing effect Effects 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 9
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 9
- 235000005513 chalcones Nutrition 0.000 claims description 9
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 238000004448 titration Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- -1 acrylic ester Chemical class 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 11
- 239000003995 emulsifying agent Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 abstract description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract 2
- 239000002313 adhesive film Substances 0.000 abstract 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012975 dibutyltin dilaurate Substances 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 abstract 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
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- 239000004816 latex Substances 0.000 description 5
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- 239000011248 coating agent Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
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- 238000007334 copolymerization reaction Methods 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229920006222 acrylic ester polymer Polymers 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a self-crosslinking polyurethane-acrylate composite emulsion and a preparation method thereof. The self-crosslinking polyurethane-acrylate composite emulsion is prepared from polyester polyol, isophorone diisocyanate, diacetone acrylamide, reactive diluent, a hydrophilic chain extender, trimethylolpropane, dihydric alcohol, dibutyltin dilaurate, a neutralizer, water, ethylenediamine, adipic dihydrazide, an initiating agent and an initiating agent diluting solvent. The self-crosslinking polyurethane-acrylate composite emulsion has the advantages that the problem that water resistance is lowered due to addition of an emulsifying agent is avoided, pollution caused by an organic solvent and tediousness of the process of extracting the organic solvent in later period are avoided, and the hardness and resistance of an adhesive film can be improved.
Description
Technical field
The present invention relates to technical field of aqueous paint, be specifically related to a kind of self-crosslinkable polyurethane-acrylate composite emulsion and preparation method thereof.
Background technology
In recent years, along with the fast development of global economy, industry, a large amount of volatile organic matter of generation, produces serious pollution to air.And coating is after the organic substance generated and discharge in use only comes automobile, be air pollution source serious in city.Therefore the technician of current almost whole coating circle is at the content paying close attention to solvent, the research and development of solventless coatings.Water-borne coatings as a kind of coating taking water as solvent, already be familiar with by people.Various water-borne coatings is also come out one after another and is accepted by market soon.
The advantages such as urethane has that film-forming temperature is low, wear resistance good, chemical resistance is excellent, pliable and tough, strong adhesion, are described as the resin that best performance is different.At present, on market, polyurethane industries among others is still based on solvent based product, and in product, free toluene diisocyanate (TDI) content is higher, and containing volatile organic solvent, the health of harmful to human.Up to now, water-borne wood latex is on the market mainly based on ACRYLIC EMULSION and aqueous polyurethane emulsion.ACRYLIC EMULSION cost is lower, has excellent mechanical property, but its low-temperature performance, snappiness, chemicals-resistant corrodes, and the performances such as wear resistance are bad, are therefore difficult to obtain high performance coating in application process.Aqueous polyurethane emulsion has fabulous low-temperature performance and wear resistance, chemicals-resistant corrodibility, and performance also has many weak points compared with solvent borne polyurethane, and as low in solid content, poor water resistance, stability are bad.
In order to effectively promote the fast development of Polyurethane Industry, promoting high-performance, the environmental protection of urethane resin, the technical problems such as aqueous polyurethane solid content is low, poor water resistance, poor solvent resistance, stability are bad must be solved.For solving the problem, modification must be carried out to it.At present acrylic acid modified, organic-silicon-modified and epoxy resin modification etc. are mainly contained for waterborne polyurethane modified method.Acrylic ester polymer has excellent mechanical property, and ageing-resistant and yellowing resistance good, luster performance is excellent.The characteristic of urethane and acrylic ester polymer has certain complementarity, and therefore for realizing the diversification of performance, letex polymerization also changes from the unicity of component to compound direction.By forming the means such as nucleocapsid structure or interpenetrating(polymer)networks, acrylate being incorporated in polyurethane structural, forming Acrylic-PU Composition Latex, thus give the performance of resin excellence.
Summary of the invention
The invention provides self-crosslinkable polyurethane-acrylate composite emulsion and preparation method thereof, it solve aqueous polyurethane can not have that film-forming temperature is low, wear resistance good concurrently and excellent sticking power, water tolerance, solvent resistance, satisfactory mechanical property technical problem, the present invention solves further and with an organic solvent causes polluting and the later stage extracts the loaded down with trivial details technical problem of organic solvent technique out.The present invention, using intermediate product urethane as self-emulsifier, avoids the water tolerance decline problem that additional emulsifying agent causes; Take acrylate monomer as the thinner of urethane, avoid pollution that organic solvent causes and the later stage deviates from the loaded down with trivial details of organic solvent technique.In addition, polyurethane backbone introduces hydrazide group, propenoic acid main chain is introduced ketone carbonyl, when film forming, during volatilization or heat treated along with moisture, start crosslinking reaction occurs between hydrazide group and ketone carbonyl, form crosslinked film.Enhancement is had to the density on glued membrane top layer, and final mechanical property and the patience improving glued membrane.
Technical solution of the present invention is as follows:
One) scheme one:
A kind of self-crosslinkable polyurethane-acrylate composite emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
Further, described reactive thinner be methyl methacrylate (MMA), butyl methacrylate (BMA), vinylformic acid isooctyl (2-EHA), butyl acrylate (BA) etc. containing can with the acrylic ester monomer of polyurethane reaction group.Take acrylate monomer as the thinner of urethane, avoid pollution that organic solvent causes and the later stage deviates from the loaded down with trivial details of organic solvent technique.
Further, the polyester polyol of described polyester polyol to be molecular weight be 1000-2000.
Further, described dibasic alcohol is the one in ethylene glycol, propylene glycol, BDO, pentanediol, glycol ether, neopentyl glycol etc.
Further, described initiator adopts the one in Diisopropyl azodicarboxylate, benzoyl peroxide, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Further, the solvent of described initiator dilution adopts the one in acetone, butanone, N-Methyl pyrrolidone.
Further, described hydrophilic chain extender is 2,2-dimethylol propionic acid, and described neutralizing agent is triethylamine.
Two) scheme two: a kind of preparation method of self-crosslinkable polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Anti-1) preparation of polyurethane prepolymer:
Add polyester polyol 24.00-26.00 part and isoflurane chalcone diisocyanate 25.36-30.18 part in the reactor, 80-85 DEG C is heated under 300-500rpm mixing speed and nitrogen protection, then ,-NCO content is measured, until measured-NCO content reaches theoretical value;
Then above-mentioned rotating speed and temperature is kept, the diacetone-acryloamide(DAA) of 0.88-2.20 part is dissolved in the reactive thinner of 42.00-46.00 part, afterwards above-mentioned thinner is joined regulation system viscosity in reaction system, then the dibutyl tin laurate of the hydrophilic chain extender of 4.00-5.00 part, the TriMethylolPropane(TMP) of 0.5-1 part, the dibasic alcohol of 2.66-3.27 part and 0.04-0.08 part is added, then-NCO content is measured, until when-NCO content reaches theoretical value, namely obtain polyurethane prepolymer;
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
Then keep above-mentioned rotating speed, by step 1) obtained polyurethane prepolymer cools to 30-40 DEG C, adds the neutralizing agent of 2.73-3.78 part, in and after 3-5min; Then add 131.00-192.00 part water, improve rotating speed to 1000-1500rpm, after dilution emulsification 15-25min, reduce mixing speed to 300-500rpm; Then the quadrol of 1.07-2.32 part is dissolved in the water of 24.00-26.00 part, with 10-20 minute, above-mentioned ethylenediamine solution is added drop-wise in reactor, reaction 5-10 minute, and then hexanodioic acid two hydrazine of 0.91-2.26 part is dissolved in 24.00-26.00 part water, then with 9-11 minute, hexanodioic acid two hydrazine solution is added drop-wise in reactor, at aqueous phase chain extending reaction 1-2 hour;
3) preparation of self-crosslinkable polyurethane acrylate composite emulsion:
Then, keep above-mentioned rotating speed, by step 2) obtained reaction system is warmed up to 80-85 DEG C, the initiator of 0.24-0.28 part is added the solvent cut of 4.00-5.00 part, then with 20-30 minute, initiator solution is added drop-wise in reaction system, keep 80-85 DEG C of thermotonus 3-4 hour, termination reaction.
Further, the measuring method of described-NCO content is Di-n-Butyl Amine back titration method.
Described self-crosslinking process refers to introduces hydrazide group in polyurethane backbone, and propenoic acid main chain is introduced ketone carbonyl, when film forming, during volatilization or heat treated along with moisture, starts crosslinking reaction occurs, form crosslinked film between hydrazide group and ketone carbonyl.
Inventive principle of the present invention is as follows:
This research using butyl methacrylate, methyl methacrylate as the thinner of polyurethane prepolymer, adopt method prepared by carboxylic acid type negatively charged ion, carboxyl is introduced in polyurethane structural, in and carboxyl, add water self-emulsifying, and polyurethane molecular is as high molecular emulsifying agent, heat up after emulsification and carry out the radical polymerization of Acrylic Acid Monomer, the present invention also introduces hydrazide group in polyurethane backbone, and propenoic acid main chain is introduced ketone carbonyl, has prepared the copolymerization latex of urethane acrylate of self-crosslinking.
This research using butyl methacrylate, methyl methacrylate as the thinner of polyurethane prepolymer, adopt method prepared by carboxylic acid type negatively charged ion, dimethylol propionic acid (DMPA) is selected to be hydrophilic chain extender, carboxyl is introduced in polyurethane structural, in addition, polyurethane backbone introduces hydrazide group, propenoic acid main chain is introduced ketone carbonyl, when normal temperature or moisture do not volatilize, crosslinking reaction can not be carried out, when film forming, during volatilization or heat treated along with moisture, start crosslinking reaction occurs between hydrazide group and ketone carbonyl, form crosslinked film.Chemically crosslinked point increases, and the corresponding increase of cross-linking density, has enhancement to the density on glued membrane top layer, and final hardness and the patience improving glued membrane.Prepare the nucleocapsid structure copolymerization latex of urethane acrylate of self-crosslinking.
The present invention compared with prior art, has the following advantages:
1) this preparation method is using polyurethane prepolymer as self-emulsifier, avoids the water tolerance decline problem that additional emulsifying agent causes;
2) take acrylate monomer as the thinner of polyurethane prepolymer, the copolyreaction of later stage urethane acrylate can be participated in, avoid pollution that organic solvent causes and the later stage extracts the loaded down with trivial details of organic solvent technique out.
3) copolymerization latex of urethane acrylate prepared of the present invention, propenoic acid main chain is introduced ketone carbonyl, when normal temperature or moisture do not volatilize, crosslinking reaction can not be carried out, when film forming, during volatilization or heat treated along with moisture, start crosslinking reaction occurs between hydrazide group and ketone carbonyl, form crosslinked film.Chemically crosslinked point increases, and the corresponding increase of cross-linking density, has enhancement to the density on glued membrane top layer, and final hardness and the patience improving glued membrane.
Embodiment
Below in conjunction with embodiment, embodiment, content of the present invention is described in detail:
(1) embodiment
A preparation for self-crosslinkable polyurethane-acrylate composite emulsion, is characterized in that: it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Add polyester polyol 24.00-26.00 part and isoflurane chalcone diisocyanate 25.36-30.18 part in the reactor, 80-85 DEG C is heated under 300-500rpm mixing speed and nitrogen protection, then ,-NCO content is measured, until measured-NCO content reaches theoretical value;
Then above-mentioned rotating speed and temperature is kept, the diacetone-acryloamide(DAA) of 0.88-2.20 part is dissolved in the reactive thinner of 42.00-46.00 part, afterwards above-mentioned thinner is joined regulation system viscosity in reaction system, then the dibutyl tin laurate of the hydrophilic chain extender of 4.00-5.00 part, the TriMethylolPropane(TMP) of 0.5-1 part, the dibasic alcohol of 2.66-3.27 part and 0.04-0.08 part is added, then-NCO content is measured, until when-NCO content reaches theoretical value, namely obtain polyurethane prepolymer;
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
Then keep above-mentioned rotating speed, by step 1) obtained polyurethane prepolymer cools to 30-40 DEG C, adds the neutralizing agent of 2.73-3.78 part, in and after 3-5min; Then add 131.00-192.00 part water, improve rotating speed to 1000-1500rpm, after dilution emulsification 15-25min, reduce mixing speed to 300-500rpm; Then the quadrol of 1.07-2.32 part is dissolved in the water of 24.00-26.00 part, with 10-20 minute, above-mentioned ethylenediamine solution is added drop-wise in reactor, reaction 5-10 minute, and then hexanodioic acid two hydrazine of 0.91-2.26 part is dissolved in 24.00-26.00 part water, then with 9-11 minute, hexanodioic acid two hydrazine solution is added drop-wise in reactor, at aqueous phase chain extending reaction 1-2 hour;
3) preparation of self-crosslinkable polyurethane acrylate composite emulsion:
Then, keep above-mentioned rotating speed, by step 2) obtained reaction system is warmed up to 80-85 DEG C, the initiator of 0.24-0.28 part is added the solvent cut of 4.00-5.00 part, then with 20-30 minute, initiator solution is added drop-wise in reaction system, keep 80-85 DEG C of thermotonus 3-4 hour, termination reaction.
(2) embodiment:
Embodiment 1
A kind of self-crosslinkable polyurethane-acrylate composite emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation for self-crosslinkable polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 24.00 parts and isoflurane chalcone diisocyanate 25.36 parts, 80 DEG C are heated under 300rpm mixing speed and nitrogen protection, reaction to measured-NCO content reaches theoretical value (16.94%), then the diacetone-acryloamide(DAA) (DAAM) of 0.88 part is dissolved into the methyl methacrylate of 12.2 parts, in the butyl methacrylate of 29.8 parts, after abundant dissolving, join regulation system viscosity in reaction system, add the hydrophilic chain extender 2 of 4 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 0.5 part, 2.66 parts 1, the dibutyl tin laurate (T-12) of 4-butyleneglycol and 0.04 part, react under the condition of 85 DEG C,-NCO content (2.36%) is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value, namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
Keep above-mentioned rotating speed, polyurethane prepolymer cooled to 40 DEG C, add the neutralizing agent triethylamine of 2.73 parts, in and after 5min, add 121 parts of water dilution emulsifications, improve rotating speed to 1000rpm, emulsification 20min.Then mixing speed is reduced to 300rpm, the quadrol of 1.07 parts is dissolved in the water of 24.00 parts, be added drop-wise in reactor, drip 10 minutes, react after 30 minutes, hexanodioic acid two hydrazine (ADH) of 0.91 part is dissolved in 24.00 parts of water, drips 10 minutes in reactor, aqueous phase chain extending reaction 30 minutes.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Be warmed up to 80 DEG C, the initiator of 0.24 part added the solvent cut of 4.00 parts, drip 20 minutes in reaction flask, 80 DEG C of reactions 4 hours, discharging.
Embodiment 2
A kind of self-crosslinkable polyurethane-acrylate composite emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 26 parts and isoflurane chalcone diisocyanate 30.18 parts, mixing speed is at 500rpm, be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (18.76%), then the diacetone-acryloamide(DAA) (DAAM) of 2.20 parts is dissolved into the methyl methacrylate of 14.2 parts, in the butyl methacrylate of 31.8 parts, after abundant dissolving, join regulation system viscosity in reaction system, add the hydrophilic chain extender 2 of 5 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 1.00 parts, 3.27 parts 1, the dibutyl tin laurate (T-12) of 4-butyleneglycol and 0.08 part, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (3.95%), namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
Polyurethane prepolymer is cooled to 40 DEG C, adds the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 192 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Reduce mixing speed to 500rpm, the quadrol of 2.32 parts is dissolved in the water of 26 parts, be added drop-wise in reactor, drip 10 minutes, react after 30 minutes, hexanodioic acid two hydrazine (ADH) of 2.26 parts is dissolved in 26 parts of water, drips 10 minutes in reactor, at aqueous phase chain extending reaction 30min.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Be warmed up to 80 DEG C, the initiator of 0.28 part added the solvent cut of 5 parts, drip 20 minutes in reaction flask, 80 DEG C of reactions 4 hours, discharging.
Embodiment 3
A kind of self-crosslinkable polyurethane-acrylate composite emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 25 parts and isoflurane chalcone diisocyanate 30.18 parts, mixing speed is at 500rpm, be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (18.76%), then the diacetone-acryloamide(DAA) (DAAM) of 2.2 parts is dissolved into the methyl methacrylate of 17.5 parts, in the butyl methacrylate of 26.5 parts, after abundant dissolving, join regulation system viscosity in reaction system, add the hydrophilic chain extender 2 of 5 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 0.5 part, 2.66 parts 1, 4-butyleneglycol, the dibutyl tin laurate (T-12) of 0.06 part, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (3.98%), namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
Keep above-mentioned rotating speed, polyurethane prepolymer cooled to 40 DEG C, add the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 192 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Then mixing speed is reduced to 500rpm, the quadrol of 2.13 parts is dissolved in the water of 25 parts, be added drop-wise in reactor, drip 10 minutes, react after 30 minutes, hexanodioic acid two hydrazine (ADH) of 2.26 parts is dissolved in 25 parts of water, drips 10 minutes in reactor, aqueous phase chain extending reaction 30 minutes.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Keep above-mentioned rotating speed, be warmed up to 80 DEG C, the initiator of 0.26 part is added the solvent cut of 5 parts, drip 20 minutes in reaction flask, 80 DEG C of reactions 4 hours, discharging.
Embodiment 4
A kind of self-crosslinkable polyurethane-acrylate composite emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 25 parts and isoflurane chalcone diisocyanate 27.17 parts, mixing speed is at 500rpm, be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (17.70%), then the diacetone-acryloamide(DAA) (DAAM) of 1.32 parts is dissolved into the methyl methacrylate of 20.1 parts, in the butyl methacrylate of 23.9 parts, after abundant dissolving, join regulation system viscosity in reaction system, add the hydrophilic chain extender 2 of 4 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 0.5 part, 3.27 parts 1, the dibutyl tin laurate (T-12) of 4-butyleneglycol and 0.06 part, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (3.04%), namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
Polyurethane prepolymer is cooled to 40 DEG C, adds the neutralizing agent triethylamine of 2.73 parts, in and after 5min, add 166 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Then mixing speed is reduced to 500rpm, the quadrol of 1.64 parts is dissolved in the water of 25 parts, be added drop-wise in reactor, drip 10 minutes, react after 30 minutes, hexanodioic acid two hydrazine (ADH) of 1.36 parts is dissolved in 25 parts of water, drips 10 minutes in reactor, aqueous phase chain extending reaction 30 minutes.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Keep above-mentioned rotating speed, be warmed up to 80 DEG C, the initiator of 0.26 part is added the solvent cut of 5 parts, drip 20 minutes in reaction flask, 80 DEG C of reactions 4 hours, discharging.
Embodiment 5
A kind of self-crosslinkable polyurethane-acrylate composite emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 25 parts and isoflurane chalcone diisocyanate 27.17 parts, mixing speed is at 500rpm, be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (17.70%), then the diacetone-acryloamide(DAA) (DAAM) of 1.32 parts is dissolved into the methyl methacrylate of 17.5 parts, in the butyl methacrylate of 26.5 parts, after abundant dissolving, join regulation system viscosity in reaction system, add the hydrophilic chain extender 2 of 5 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 1 part, 3.16 parts 1, the dibutyl tin laurate (T-12) of 4-butyleneglycol and 0.06 part, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (2.06%), namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
Then keep above-mentioned rotating speed, polyurethane prepolymer cooled to 40 DEG C, add the neutralizing agent triethylamine of 3.78 parts, in and 5min.Then add 131 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Then mixing speed is reduced to 500rpm, the quadrol of 1.07 parts is dissolved in the water of 25 parts, be added drop-wise in reactor, drip 10 minutes, react after 30 minutes, hexanodioic acid two hydrazine (ADH) of 1.36 parts is dissolved in 25 parts of water, drips 10 minutes in reactor, aqueous phase chain extending reaction 30 minutes.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Be warmed up to 80 DEG C, the initiator of 0.26 part added the solvent cut of 5 parts, drip 20 minutes in reaction flask, 80 DEG C of reactions 4 hours, discharging.
In above each embodiment:
The CMA-44 of the preferred Hua Da chemistry of described polyester polyol;
Described isoflurane chalcone diisocyanate is preferably the IPDI that Bayer is produced;
Described methyl methacrylate, butyl methacrylate, 2,2-dimethylol propionic acids, TriMethylolPropane(TMP), BDO, Diisopropyl azodicarboxylate, butanone, quadrol are preferably Aladdin reagent.
Described dibutyl tin laurate is preferably the product of the triumphant auspicious chemical Science and Technology Ltd. in Changzhou.
The product of the preferred Guangzhou Ming Qi trade Co., Ltd of described diacetone-acryloamide(DAA) (DAAM), hexanodioic acid two hydrazine (ADH).
Self-crosslinkable polyurethane-acrylate composite emulsion is carried out to the performance tests such as size, hardness, film-forming temperature, water tolerance, resistance to vinegar, alcohol resistance.
Sreen analysis: adopt Malvern company 3000SHA type nano-particle size analysis instrument test emulsion particle diameter.
Gloss (60 DEG C): according to the test of GB/T9754 regulation.
Hardness: test according to GB/T6739 regulation.
Sticking power: test according to GB/T9286-1998 regulation, drawing compartment distance is 2mm.
Water tolerance: test according to GB/T4893.1-2005 regulation.Water-fast 24 hours, whether paint film there is exception.
Alcohol resistance: testing method is identical with water tolerance, test solution is the ethanolic soln of 50% (volume fraction), and experimental period is 1h, tests after 1 hour, whether normally observes paint film.
Resistance to vinegar: select making vinegar, tested after 1 hour, whether normally observed paint film.
Film-forming temperature: adopt Britain RHOPOINT company MFFTBar-60 minimum film forming temperature tester, the minimum film-forming temperature of test emulsion.Through the test to each embodiment, the detection data results of self-crosslinkable polyurethane-acrylate composite emulsion of the present invention is as shown in following table:
Can obviously find out from table one, various embodiments of the present invention all have good water tolerance, alcohol resistance and stain resistance under difficult environmental conditions, and size distribution, all at about 100nm, has very high sticking power and hardness, has good using value.
In sum, the self-crosslinkable polyurethane-acrylate composite emulsion of various embodiments of the present invention has very high hardness and sticking power, has good water tolerance, alcohol resistance and stain resistance.
Above-mentioned embodiment is just explained in detail technical scheme of the present invention; the present invention has more than and is only confined to above-described embodiment; those skilled in the art should be understood that; every improvement on basis of the present invention according to above-mentioned principle and spirit, substitute, all should within protection scope of the present invention.
The experimental data of each embodiment test of table one polyurethane-acrylate composite emulsion
Claims (9)
1. self-crosslinkable polyurethane-acrylate composite emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
2. self-crosslinkable polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described reactive thinner be not containing can with the acrylic ester monomer of polyurethane reaction group.
3. self-crosslinkable polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: the polyester polyol of described polyester polyol to be molecular weight be 1000-2000.
4. self-crosslinkable polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described dibasic alcohol is the one in ethylene glycol, propylene glycol, BDO, pentanediol, glycol ether or neopentyl glycol.
5. self-crosslinkable polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described initiator is the one in Diisopropyl azodicarboxylate, benzoyl peroxide or 2,2'-Azobis(2,4-dimethylvaleronitrile).
6. self-crosslinkable polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described initiator diluting solvent is the one in acetone, butanone or N-Methyl pyrrolidone.
7. self-crosslinkable polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described hydrophilic chain extender is 2,2-dimethylol propionic acid, and described neutralizing agent is triethylamine.
8. a preparation method for self-crosslinkable polyurethane-acrylate composite emulsion, is characterized in that: it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Add polyester polyol 24.00-26.00 part and isoflurane chalcone diisocyanate 25.36-30.18 part in the reactor, 80-85 DEG C is heated under 300-500rpm mixing speed and nitrogen protection, then ,-NCO content is measured, until measured-NCO content reaches theoretical value;
Then above-mentioned rotating speed and temperature is kept, the diacetone-acryloamide(DAA) of 0.88-2.20 part is dissolved in the reactive thinner of 42.00-46.00 part, afterwards above-mentioned thinner is joined regulation system viscosity in reaction system, then the dibutyl tin laurate of the hydrophilic chain extender of 4.00-5.00 part, the TriMethylolPropane(TMP) of 0.5-1 part, the dibasic alcohol of 2.66-3.27 part and 0.04-0.08 part is added, then-NCO content is measured, until when-NCO content reaches theoretical value, namely obtain polyurethane prepolymer;
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension:
Then keep above-mentioned rotating speed, by step 1) obtained polyurethane prepolymer cools to 30-40 DEG C, adds the neutralizing agent of 2.73-3.78 part, in and after 3-5min; Then add 131.00-192.00 part water, improve rotating speed to 1000-1500rpm, after dilution emulsification 15-25min, reduce mixing speed to 300-500rpm; Then the quadrol of 1.07-2.32 part is dissolved in the water of 24.00-26.00 part, with 10-20 minute, above-mentioned ethylenediamine solution is added drop-wise in reactor, reaction 5-10 minute, and then hexanodioic acid two hydrazine of 0.91-2.26 part is dissolved in 24.00-26.00 part water, then with 9-11 minute, above-mentioned hexanodioic acid two hydrazine solution is added drop-wise in reactor, at aqueous phase chain extending reaction 1-2 hour;
3) preparation of self-crosslinkable polyurethane acrylate composite emulsion:
Then, keep above-mentioned rotating speed, by step 2) obtained reaction system is warmed up to 80-85 DEG C, the initiator of 0.24-0.28 part is added the solvent cut of 4.00-5.00 part, then with 20-30 minute, above-mentioned initiator solution is added drop-wise in reaction system, keep 80-85 DEG C of thermotonus 3-4 hour, termination reaction.
9. the preparation method of self-crosslinkable polyurethane-acrylate composite emulsion according to claim 8, is characterized in that: the measuring method of described-NCO content is Di-n-Butyl Amine back titration method.
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Application publication date: 20151223 |