CN103145951A - Viscosity-reduction toughness-increasing and in-situ synthesizing method of low VOC (Volatile Organic Compound) cathode electrophoretic paint resin - Google Patents
Viscosity-reduction toughness-increasing and in-situ synthesizing method of low VOC (Volatile Organic Compound) cathode electrophoretic paint resin Download PDFInfo
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- CN103145951A CN103145951A CN2013100906492A CN201310090649A CN103145951A CN 103145951 A CN103145951 A CN 103145951A CN 2013100906492 A CN2013100906492 A CN 2013100906492A CN 201310090649 A CN201310090649 A CN 201310090649A CN 103145951 A CN103145951 A CN 103145951A
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Abstract
The invention relates to a viscosity-reduction toughness-increasing and in-situ synthesizing method of low VOC (Volatile Organic Compound) cathode electrophoretic paint resin. A part of active diluents or catalyst is added at the initial stage of the resin reaction process or in the reaction process to replace a part of solvent, so that the VOC emission and the resin viscosity are reduced during the synthesis process; and the finally synthesized product resin has good toughness.
Description
Technical field
The invention belongs to the new chemical materials field, be specifically related to the toughness reinforcing and in-situ synthetic method of a kind of viscosity reduction of low VOC cathode electrophoresis dope resin.
Background technology
At present, cathode electrodip painting is widely used in the Workpiece coatings such as passenger car, commercial car and electromechanics, five metals.It has that utilization ratio is high, mechanize and level of automation is high, be fit to the complex-shaped workpieces application, and the paint film of formation has good preservative property, the good characteristics such as sticking power.
Resin is the key factor that is related to the cathode electrodip painting quality.At present cathode electrodip painting mainly with the epoxy-amide adduct of higher molecular weight as main filmogen.In the epoxy resin chain extension process later stage, molecular weight is larger, and viscosity is larger, thus generally need to be in initial material the inside or the reaction process later stage add a certain amount of solvent to reduce viscosity.Comprise methyl iso-butyl ketone (MIBK), dimethylbenzene etc. through solvent commonly used.After amination, these solvents need to be ripened extraction, to prevent stable influential to emulsion.This has significantly increased the discharging of organic volatile (VOC) in the production of resins process.
In addition, epoxy resin is larger because of its rigidity, and the paint film that forms after solidifying is more crisp, is necessary to introduce flexible resin or flexible group, and it is carried out modification.
For the above-mentioned shortcoming of ability cathode electrophoresis coating resins, some people has done a few thing.CN1377925A has reported a kind of cation paint composition, its characteristics are to be formed by polycaprolactone polyol and epoxy resin amine additives physical mixed, wherein polycaprolactone polyol is that polyvalent alcohol and caprolactone polymerization form, and polycaprolactone polyol has played the toughness reinforcing effect of plasticising when film curing; For the VOC emission problem in cathode electrodip painting production of resins process, there is not yet the relevant improvement way of domestic report.
Caprolactone generally uses as monomer, can form polyester polyol, and uses less as solvent.The proposition of the invention substitutes traditional organic solvent with caprolactone as " reactive thinner ", effectively reduce epoxy chain extension later stage viscosity, caprolactone self can be aggregated on epoxy resin simultaneously, toughness reinforcing segment can be in the epoxy resin production process simultaneously " original position " synthetic, save and first prepared the polyester polyol step, can add less before amination or not add other solvents, having reduced the discharging of VOC, can effectively improve toughness after the resin film forming.This synthetic method craft is simple, energy consumption is low, the VOC discharging is few, and stronger practical value is arranged.
Summary of the invention
The present invention is intended to propose the toughness reinforcing and in-situ synthetic method of a kind of viscosity reduction of low VOC cathode electrophoresis dope resin, it is characterized in that: the cathode electrophoresis dope resin initially or in reaction process adds part reactive thinner and catalyzer in reaction process, the Substitute For Partial solvent, play the effect that reduces the VOC discharging in building-up process, reduce resin viscosity, the final synthetic product resin of gained toughness is good.
A kind of low VOC cathode electrophoresis dope resin of the present invention, the raw material that it is characterized in that the cathode electrophoresis dope resin is the formations such as epoxy resin, dihydroxyphenyl propane, reactive thinner, catalyzer, amine, non-reacted additive, wherein:
Epoxy resin of the present invention, can be a kind of or two kinds and the above mixture in the difunctionality epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, polyether-type epoxy resin, the molecular weight of epoxy resin is between 200-10000, and wherein preferred molecular weight is between 200-5000; The epoxy resin massfraction is between 15-75%;
Amine of the present invention can be a kind of or both the above mixtures in diethylamine, diethanolamine, Mono Methyl Ethanol Amine; The massfraction of amine is between 0.1-10%;
Reactive thinner of the present invention can be a kind of or two kinds and the above mixture in γ-hexalactone, δ-caprolactone, 6-caprolactone; Preferred 6-caprolactone wherein; The reactive thinner massfraction is between 1-30%;
Catalyzer of the present invention is comprised of catalyst A and catalyst B two portions, and catalyst A can be a kind of or two kinds and the above mixture in dimethyl benzylamine, triethylamine, triphenyl phosphorus, and massfraction is between 0.01%-5%; Catalyst B can be a kind of or two kinds and the above mixture in stannous octoate, dibutyl tin laurate, four titanium butoxide etc., and massfraction is between 0.01-5%;
The toughness reinforcing in-situ synthetic method of viscosity reduction of a kind of low VOC cathode electrophoresis dope resin of the present invention is characterized in that being formed by two-step reaction, and the first step is carried out simultaneously by epoxy chain extension and caprolactone open loop addition, and second step is aminating reaction;
In-situ synthetic method of the present invention is characterized in that the first step temperature of reaction between 120-200 ° of C, and preferable reaction temperature is between 140-160 ° of C; The second step temperature of reaction is between 80-150 ° of C, and preferred range is between 90-120 ° of C;
In-situ synthetic method of the present invention is characterized in that the terminal point of the first step reaction is controlled by epoxy equivalent (weight), and the epoxy equivalent (weight) scope is between 700-1500; The second step reaction end is controlled with the reactive thinner residual quantity, and residual quantity is between 0-3%;
The synthetic method of a kind of cathode electrophoresis dope resin of the present invention is characterized in that the use of reactive thinner, has played the effect that reduces VOC;
The synthetic method of a kind of cathode electrophoresis dope resin of the present invention is characterized in that the use of reactive thinner, has played the effect that reduces resin viscosity in reaction process;
The synthetic method of a kind of cathode electrophoresis dope resin of the present invention is characterized in that the use of reactive thinner, and the polymerization of reactive thinner is synchronizeed with the epoxy resin chain extension, and toughness reinforcing segment original position is synthetic, has played the effect that reduces energy consumption;
A kind of low VOC cathode electrophoresis dope resin of the present invention after it is characterized in that using it for electrophoretic paint, has good toughness.
Embodiment
Further describe the present invention below by example, but be not limited to these embodiment.
Embodiment 1
Add successively 270g epoxy resin (epoxy equivalent (weight) 188) in the 1000ml there-necked flask, 80g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, 6-caprolactone 60g, stannous octoate 0.1g is warmed up to 160 ° of C, to epoxy equivalent (weight) 1250, be cooled to 100 ° of C, add the 26.3g Mono Methyl Ethanol Amine, at 110 ° of C insulation 2h, with gas chromatographic detection 6-caprolactone content 0.5%, do not contain dimethylbenzene, cooling gets target product A1.
Control experiment 1:
Neopentyl glycol 10g, 6-caprolactone 120g, stannous octoate 0.2g is warming up to 160 ° of C, and insulation is to using gas chromatographic detection 6-caprolactone content 0.5%, and cooling gets target product a1;
Add successively 270g epoxy resin (epoxy equivalent (weight) 188) in the 1000ml there-necked flask, the 80g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, dimethylbenzene 30g is warmed up to 160 ° of C, keeps refluxing, to epoxy equivalent (weight) 1130(terminal point epoxy molecular weight and upper approximate); Be cooled to 100 ° of C, add 60g product a1, the 26.3g Mono Methyl Ethanol Amine, at 110 ° of C insulation 2h, 0.1%, xylene content is 5.0% with gas chromatographic detection 6-caprolactone content, and cooling gets target product B1.
Embodiment 2
Add successively 135g epoxy resin (epoxy equivalent (weight) 188) in the 1000ml there-necked flask, 35g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, 6-caprolactone 40g, stannous octoate 0.1g is warmed up to 180 ° of C, to epoxy equivalent (weight) 1200, be cooled to 100 ° of C, add the 14.3g Mono Methyl Ethanol Amine, at 100 ° of C insulation 2h, with gas chromatographic detection 6-caprolactone content 0.2%, do not contain dimethylbenzene, cooling gets target product A2.
Control experiment 2:
Neopentyl glycol 10g, 6-caprolactone 100g, stannous octoate 0.1g is warming up to 140 ° of C, and insulation is to using gas chromatographic detection 6-caprolactone content 0.5%, and cooling gets target product b1;
Add successively 135g epoxy resin (epoxy equivalent (weight) 188) in the 1000ml there-necked flask, the 35g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, dimethylbenzene 20g is warmed up to 180 ° of C, keeps refluxing, to epoxy equivalent (weight) 1090(terminal point epoxy molecular weight and upper approximate); Be cooled to 100 ° of C, add 40g product b1, the 14.3g Mono Methyl Ethanol Amine, at 100 ° of C insulation 2h, 0.1%, xylene content is 7.0% with gas chromatographic detection 6-caprolactone content, and cooling gets target product B2.
Controlled trial 3:
Add successively 135g epoxy resin (epoxy equivalent (weight) 188) in the 1000ml there-necked flask, the 35g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, dimethylbenzene 20g is warmed up to 180 ° of C, keeps refluxing, to epoxy equivalent (weight) 1090(terminal point epoxy molecular weight and upper approximate); Be cooled to 100 ° of C, add the 14.3g Mono Methyl Ethanol Amine, at 100 ° of C insulation 2h, 9.1%, cooling gets target product B3 with the gas chromatographic detection xylene content.
Embodiment 3
Be equipped with cathode electrodip painting modelling verification formula by following component and mass ratio thereof:
*Made by ethanol, butyl glycol ether, hexanolactam and diphenylmethanediisocyanate (MDI) reaction;
Above-mentioned group is proportionally mixed, add lactic acid aqueous solution emulsification (degree of neutralization 50%) altogether, get cathodic electrodeposition paint emulsion.Stir slaking 24 hours.When just preparing and slaking after 24 hours respectively with xylene content in gas-chromatography test tank liquor.Emulsion and mill base are mixed with tank liquor according to the 4:1 ratio, slaking, and electrophoresis is 2 minutes under 200V voltage, and 160 ° of C toasted 20 minutes, got film performance as follows:
*The data of surveying are relative tank liquor quality.
A) according to the GB/T1732 standard test.
B) according to the GB/T9286 standard test.
C) measure according to ASTM D1654.
D) according to the GB/T9753 standard test.
By the above results as can be known, A1 group, B1 group are compared, and adopt novel method, and the VOC quantity discharged has reduced the relative tank liquor quality of 0.9%(), A2 group, B2 organize relatively, adopt novel method VOC quantity discharged to reduce by 1.1%.
From mechanical performance compare, A1 group, A2 group are all than B3 group good impact resistance.
From anticorrosion character, the A1 group is slightly more excellent than the B1 group, and the A2 group is slightly more excellent than the B2 group, and A1, A2, B1, B2 all have greater advantage than the B3 group.
Claims (9)
1. the toughness reinforcing and in-situ synthetic method of the viscosity reduction of one kind low VOC cathode electrophoresis dope resin, it is characterized in that: the cathode electrophoresis dope resin initially or in reaction process adds part reactive thinner, amine raw material and catalyzer in reaction process, the Substitute For Partial solvent, direct in-situ generates the coating resin of modification;
Wherein said material resin is epoxy resin, and massfraction is between 15-75%;
Described reactive thinner is a kind of or two kinds and the above mixture in γ-hexalactone, δ-caprolactone, 6-caprolactone, and massfraction is between 1-30%;
Described amine raw material is a kind of or both the above mixtures in diethylamine, diethanolamine, Mono Methyl Ethanol Amine, and massfraction is between 0.1-10%;
Described catalyzer is comprised of catalyst A and catalyst B two portions, and catalyst A is a kind of or two kinds and the above mixture in dimethyl benzylamine, triethylamine, triphenylphosphine, and massfraction is between 0.01%-5%; Catalyst B is a kind of or two kinds and the above mixture in stannous octoate, dibutyl tin laurate, four titanium butoxide etc., and massfraction is between 0.01-5%.
2. the toughness reinforcing and in-situ synthetic method of the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 1, wherein, epoxy chain extension and caprolactone open loop addition are carried out simultaneously in reaction process, do not add other organic solvents as thinner in this process.
3. the toughness reinforcing and in-situ synthetic method of the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 1, wherein, described epoxy resin is a kind of or two kinds and the above mixture in bisphenol A type epoxy resin, bisphenol f type epoxy resin, polyether-type epoxy resin difunctionality epoxy resin, and the molecular weight of epoxy resin is between 200-10000.
4. the toughness reinforcing and in-situ synthetic method of the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 3, wherein, the molecular weight of epoxy resin is preferably between 200-5000.
5. the toughness reinforcing in-situ synthetic method of viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 1, wherein, described reaction process is formed by two-step reaction, and the first step is carried out simultaneously by epoxy chain extension and caprolactone open loop addition, and second step is aminating reaction.
6. the toughness reinforcing in-situ synthetic method of viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 5, wherein, the first step temperature of reaction is between 120-200 ° of C, and the second step temperature of reaction is between 80-150 ° of C.
7. the toughness reinforcing in-situ synthetic method of viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 6, wherein, the first step temperature of reaction is between 140-160 ° of C, and the second step temperature of reaction is between 90-120 ° of C.
8. the toughness reinforcing in-situ synthetic method of viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 5, wherein, the terminal point of the first step reaction is controlled by epoxy equivalent (weight), and the epoxy equivalent (weight) scope is between 700-1500; The second step reaction end is controlled with the reactive thinner residual quantity, and residual quantity is between 0-3%.
9. one kind low VOC cathode electrophoresis dope, it comprises the resin that the toughness reinforcing in-situ synthetic method of viscosity reduction by a kind of low VOC cathode electrophoresis dope resin claimed in claim 1 makes.
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| CN201310090649.2A CN103145951B (en) | 2013-03-20 | 2013-03-20 | The viscosity reduction of low VOC cathode electrophoresis dope resin increases tough and in-situ synthetic method |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483772A (en) * | 2003-08-04 | 2004-03-24 | 江苏鸿业涂料科技产业有限公司 | Low temp. solidifeed resin emulion used for cathode electrolytic coating |
| CN101760126A (en) * | 2009-12-30 | 2010-06-30 | 上海金力泰化工股份有限公司 | Cathode electrophoretic coating composition and preparation method thereof |
| CN102533044A (en) * | 2010-12-10 | 2012-07-04 | 比亚迪股份有限公司 | Cathode electrophoretic coating and preparation method thereof and cathode electrophoretic coating method |
| WO2013008640A1 (en) * | 2011-07-13 | 2013-01-17 | 日産自動車株式会社 | Coating composition and method for forming coating film using same |
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- 2013-03-20 CN CN201310090649.2A patent/CN103145951B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483772A (en) * | 2003-08-04 | 2004-03-24 | 江苏鸿业涂料科技产业有限公司 | Low temp. solidifeed resin emulion used for cathode electrolytic coating |
| CN101760126A (en) * | 2009-12-30 | 2010-06-30 | 上海金力泰化工股份有限公司 | Cathode electrophoretic coating composition and preparation method thereof |
| CN102533044A (en) * | 2010-12-10 | 2012-07-04 | 比亚迪股份有限公司 | Cathode electrophoretic coating and preparation method thereof and cathode electrophoretic coating method |
| WO2013008640A1 (en) * | 2011-07-13 | 2013-01-17 | 日産自動車株式会社 | Coating composition and method for forming coating film using same |
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