CN103145951B - The viscosity reduction of low VOC cathode electrophoresis dope resin increases tough and in-situ synthetic method - Google Patents
The viscosity reduction of low VOC cathode electrophoresis dope resin increases tough and in-situ synthetic method Download PDFInfo
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- CN103145951B CN103145951B CN201310090649.2A CN201310090649A CN103145951B CN 103145951 B CN103145951 B CN 103145951B CN 201310090649 A CN201310090649 A CN 201310090649A CN 103145951 B CN103145951 B CN 103145951B
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Abstract
The present invention relates to the viscosity reduction of a kind of low VOC cathode electrophoresis dope resin and increase tough and in-situ synthetic method, it is specifically related in or reaction process initial in resin reaction process and adds part reactive thinner and catalyzer, substitute partial solvent, playing the effect reducing VOC emission in building-up process, reducing resin viscosity, gained final synthetic product resin toughness is good.
Description
Technical field
The invention belongs to new chemical materials field, the viscosity reduction being specifically related to a kind of low VOC cathode electrophoresis dope resin increases tough and in-situ synthetic method.
Background technology
At present, cathode electrodip painting is widely used in passenger car, commercial car and the Workpiece coating such as electromechanics, five metals. It has utilization ratio height, mechanize and level of automation height, is applicable to complex-shaped workpieces application, and the paint film of formation has the feature such as excellent preservative property, good sticking power.
Resin is the key factor being related to cathode electrodip painting quality quality. Current 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 relatively big, and viscosity is relatively big, therefore it is generally required to inside initial material or the reaction process later stage add a certain amount of solvent and reduce viscosity. Methyl iso-butyl ketone (MIBK), dimethylbenzene etc. is comprised through conventional solvent. When, after amination, these solvents need to be ripened extraction, to prevent emulsion intercalation method is had impact. This dramatically increases the discharge of organic volatile (VOC) in production of resins process.
In addition, epoxy resin because of its rigidity relatively big, the paint film formed after solidification is more crisp, it is necessary to introduce flexible resin or flexible group, it is carried out modification.
For the above-mentioned shortcoming of ability cathode electrophoresis coating resins, some people has done some work. CN1377925A reports a kind of cation paint composition, its feature is to become with epoxy resin amine additives physical mixed by polycaprolactone polyol, wherein polycaprolactone polyol is that polyvalent alcohol becomes with caprolactone polymerization, and polycaprolactone polyol serves plasticising and increases tough effect when film curing; For the VOC emission problem in cathode electrodip painting production of resins process, there is not yet the relevant Improving ways of domestic report.
Caprolactone generally uses as monomer, it is possible to form polyester polyol, and uses less as solvent. The proposition of the invention substitutes traditional organic solvent using caprolactone as " reactive thinner ", effectively reduce ring oxygen chain extension later stage viscosity, caprolactone self can be aggregated on epoxy resin simultaneously, increasing tough segment can simultaneously " original position " synthesis in epoxy resin production process, eliminate and first prepare polyester polyol step, can add less before amination or not add other solvents, reduce the discharge of VOC, after resin film forming, can effectively improve toughness. This synthetic method craft is simple, energy consumption is low, VOC emission is few, has stronger practical value.
Summary of the invention
The viscosity reduction that the present invention is intended to propose a kind of low VOC cathode electrophoresis dope resin increases tough and in-situ synthetic method, it is characterized in that: cathode electrophoresis dope resin initially or in reaction process adds part reactive thinner and catalyzer in reaction process, substitute partial solvent, playing the effect reducing VOC emission in building-up process, reducing resin viscosity, gained final synthetic product resin toughness is good.
The low VOC cathode electrophoresis dope resin of one of the present invention, it is characterised in that the raw material of cathode electrophoresis dope resin is that epoxy resin, dihydroxyphenyl propane, reactive thinner, catalyzer, amine, non-reacted additive etc. are formed, wherein:
Epoxy resin of the present invention, can be the one in the difunctionality epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, polyether-type epoxy resin or two kinds and above mixture, the molecular weight of epoxy resin is between 200-10000, and wherein preferred molecular weight is between 200-5000; Epoxy resin massfraction is between 15-75%;
Amine of the present invention can be the one in diethylamine, diethanolamine, Mono Methyl Ethanol Amine or both above mixtures; The massfraction of amine is between 0.1-10%;
Reactive thinner of the present invention, it is possible to be the one in γ-hexalactone, δ-caprolactone, 6-caprolactone or two kinds and above mixture; Wherein preferred 6-caprolactone; Reactive thinner massfraction is between 1-30%;
Catalyzer of the present invention, is made up of catalyst A and catalyst B two portions, and catalyst A can be the one in dimethyl benzylamine, triethylamine, triphenyl phosphorus or two kinds and above mixture, and massfraction is between 0.01%-5%; Catalyst B can be the one in stannous octoate, dibutyl tin laurate, four titanium butoxide etc. or two kinds and above mixture, and massfraction is between 0.01-5%;
The viscosity reduction of a kind of low VOC cathode electrophoresis dope resin of the present invention increases tough in-situ synthetic method, it is characterised in that becoming by two-step reaction, the first step is carried out by ring oxygen chain extension and caprolactone open loop addition simultaneously, and the 2nd step is aminating reaction;
In-situ synthetic method of the present invention, it is characterised in that the first step temperature of reaction is between 120-200 ° of C, it is preferable that temperature of reaction is between 140-160 ° of C; 2nd step temperature of reaction is between 80-150 ° of C, it is preferable that temperature range is between 90-120 ° of C;
In-situ synthetic method of the present invention, it is characterised in that the terminal of the first step reaction is controlled by epoxy equivalent (weight), and epoxy equivalent (weight) scope is between 700-1500; 2nd step reaction end controls with 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, it is characterised in that the use of reactive thinner, serves the effect reducing VOC;
The synthetic method of a kind of cathode electrophoresis dope resin of the present invention, it is characterised in that the use of reactive thinner, serves the effect reducing resin viscosity in reaction process;
The synthetic method of a kind of cathode electrophoresis dope resin of the present invention, it is characterised in that the use of reactive thinner, the polymerization of reactive thinner is synchronous with Epoxy resin chain extension, increases tough segment fabricated in situ, serves the effect reducing energy consumption;
The low VOC cathode electrophoresis dope resin of one of the present invention, it is characterised in that after using it for electrophoretic paint, there is good toughness.
Embodiment
Further describe the present invention below by example, but it is not limited to these embodiments.
Embodiment 1
1000ml there-necked flask adds 270g epoxy resin (epoxy equivalent (weight) 188) successively, 80g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, 6-caprolactone 60g, stannous octoate 0.1g, be warmed up to 160 ° of C, to epoxy equivalent (weight) 1250, it is cooled to 100 ° of C, adds 26.3g Mono Methyl Ethanol Amine, be incubated 2h at 110 ° of C, with gas chromatographic detection 6-caprolactone content 0.5%, not containing dimethylbenzene, cooling, obtains target product A1.
Control experiment 1:
Neopentyl glycol 10g, 6-caprolactone 120g, stannous octoate 0.2g, be warming up to 160 ° of C, insulation to gas chromatographic detection 6-caprolactone content 0.5%, cooling, obtain target product a1;
1000ml there-necked flask adds 270g epoxy resin (epoxy equivalent (weight) 188) successively, 80g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, dimethylbenzene 30g, is warmed up to 160 ° of C, keep backflow, to epoxy equivalent (weight) 1130(terminal ring oxygen molecule amount with upper be similar to); Being cooled to 100 ° of C, add 60g product a1,26.3g Mono Methyl Ethanol Amine, be incubated 2h at 110 ° of C, with gas chromatographic detection 6-caprolactone content 0.1%, xylene content is 5.0%, and cooling, obtains target product B1.
Embodiment 2
1000ml there-necked flask adds 135g epoxy resin (epoxy equivalent (weight) 188) successively, 35g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, 6-caprolactone 40g, stannous octoate 0.1g, be warmed up to 180 ° of C, to epoxy equivalent (weight) 1200, it is cooled to 100 ° of C, adds 14.3g Mono Methyl Ethanol Amine, be incubated 2h at 100 ° of C, with gas chromatographic detection 6-caprolactone content 0.2%, not containing dimethylbenzene, cooling, obtains target product A2.
Control experiment 2:
Neopentyl glycol 10g, 6-caprolactone 100g, stannous octoate 0.1g, be warming up to 140 ° of C, insulation to gas chromatographic detection 6-caprolactone content 0.5%, cooling, obtain target product b1;
1000ml there-necked flask adds 135g epoxy resin (epoxy equivalent (weight) 188) successively, 35g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, dimethylbenzene 20g, is warmed up to 180 ° of C, keep backflow, to epoxy equivalent (weight) 1090(terminal ring oxygen molecule amount with upper be similar to); Being cooled to 100 ° of C, add 40g product b1,14.3g Mono Methyl Ethanol Amine, be incubated 2h at 100 ° of C, with gas chromatographic detection 6-caprolactone content 0.1%, xylene content is 7.0%, and cooling, obtains target product B2.
Controlled trial 3:
1000ml there-necked flask adds 135g epoxy resin (epoxy equivalent (weight) 188) successively, 35g dihydroxyphenyl propane, dimethyl benzylamine 0.2g, dimethylbenzene 20g, is warmed up to 180 ° of C, keep backflow, to epoxy equivalent (weight) 1090(terminal ring oxygen molecule amount with upper be similar to); Being cooled to 100 ° of C, add 14.3g Mono Methyl Ethanol Amine, be incubated 2h at 100 ° of C, with gas chromatographic detection xylene content 9.1%, cooling, obtains target product B3.
Embodiment 3
It is equipped with cathode electrodip painting modelling verification formula by following component and mass ratio thereof:
*Obtained by ethanol, butyl glycol ether, hexanolactam and diphenylmethanediisocyanate (MDI) reaction;
Above-mentioned group is proportionally mixed, adds lactic acid aqueous solution emulsification (degree of neutralization 50%) altogether, obtain cathodic electrodeposition paint emulsion. Stir slaking 24 hours. When just preparing and slaking after 24 hours respectively with xylene content in gas-chromatography test trough liquid. Emulsion and mill base prepare grooving liquid according to 4:1 ratio, slaking, electrophoresis 2 minutes under 200V voltage, and 160 ° of C toast 20 minutes, obtain film performance as follows:
*Surveyed data and it is opposed slot liquid quality.
A) according to GB/T1732 standard test.
B) according to GB/T9286 standard test.
C) measure according to ASTMD1654.
D) according to GB/T9753 standard test.
From the above results, A1 group, B1 group are compared, and adopt novel method, and VOC emission amount reduces 0.9%(opposed slot liquid quality), A2 group, B2 group compare, and adopt novel method VOC emission amount to reduce 1.1%.
From mechanical performance compare, A1 group, A2 group are all than B3 group good impact resistance.
From anticorrosion character, A1 group is slightly more excellent than B1 group, and A2 group is slightly more excellent than B2 group, and A1, A2, B1, B2 all have greater advantage than B3 group.
Claims (9)
1. the viscosity reduction of one kind low VOC cathode electrophoresis dope resin increases tough and in-situ synthetic method, it is characterized in that: cathode electrophoresis dope resin initially or in reaction process adds part reactive thinner, amine raw material and catalyzer in reaction process, substituting partial solvent, direct in-situ generates the coating resin of modification;
Wherein said cathode electrophoresis dope resin is epoxy resin, and massfraction is between 15-75%;
Described reactive thinner is the one in γ-hexalactone, δ-caprolactone, 6-caprolactone or two kinds and above mixture, and massfraction is between 1-30%;
Described amine raw material is the one in diethylamine, diethanolamine, Mono Methyl Ethanol Amine or both above mixtures, and massfraction is between 0.1-10%;
Described catalyzer is made up of catalyst A and catalyst B two portions, and catalyst A is the one in dimethyl benzylamine, triethylamine, triphenylphosphine or two kinds and above mixture, and massfraction is between 0.01%-5%; Catalyst B is the one in stannous octoate, dibutyl tin laurate, four titanium butoxide or two kinds and above mixture, and massfraction is between 0.01-5%.
2. the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 1 increases tough and in-situ synthetic method, and wherein, in reaction process, ring oxygen chain extension and caprolactone open loop addition carry out simultaneously, do not add other organic solvents as thinner in this process.
3. the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 1 increases tough and in-situ synthetic method, wherein, described epoxy resin is the mixture of a kind of in bisphenol A type epoxy resin, bisphenol f type epoxy resin or two kinds, and the molecular weight of epoxy resin is between 200-10000.
4. the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 3 increases tough and in-situ synthetic method, and wherein, the molecular weight of epoxy resin is preferably between 200-5000.
5. the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 1 increases tough and in-situ synthetic method, and wherein, described reaction process is become by two-step reaction, and the first step is carried out by ring oxygen chain extension and caprolactone open loop addition simultaneously, and the 2nd step is aminating reaction.
6. the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 5 increases tough and in-situ synthetic method, and wherein, the first step temperature of reaction is between 120-200 DEG C, and the 2nd step temperature of reaction is between 80-150 DEG C.
7. the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 6 increases tough and in-situ synthetic method, and wherein, the first step temperature of reaction is between 140-160 DEG C, and the 2nd step temperature of reaction is between 90-120 DEG C.
8. the viscosity reduction of low VOC cathode electrophoresis dope resin according to claim 5 increases tough and in-situ synthetic method, and wherein, the terminal of the first step reaction is controlled by epoxy equivalent (weight), and epoxy equivalent (weight) scope is between 700-1500;2nd step reaction end controls with reactive thinner residual quantity, and residual quantity is between 0-3%.
9. a low VOC cathode electrophoresis dope, it comprises by the resin that viscosity reduction increasing is tough and in-situ synthetic method is obtained of a kind of low VOC cathode electrophoresis dope resin according to claim 1.
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Citations (3)
| 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 |
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| BR112014000689A2 (en) * | 2011-07-13 | 2017-02-14 | Nissan Motor | painting composition and method for forming coating film using the same |
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| 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 |
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