CN102504122B - Preparation method of dicyclopentadiene unsaturated polyester resin for high-leveling coatings - Google Patents
Preparation method of dicyclopentadiene unsaturated polyester resin for high-leveling coatings Download PDFInfo
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Abstract
The invention discloses a preparation method of dicyclopentadiene unsaturated polyester resin for high-leveling coatings. The method comprises the following steps: A) synthesizing a resin intermediate with the hydroxyl equivalent of 130-300 from fatty acid and polyol which are utilized as raw materials; B) taking dibasic acid (anhydride) and deionized water to perform hydrolysis reaction, then dropwise adding dicyclopentadiene to perform hydrogen ion displacement reaction and diene addition reaction, and then adding dibasic alcohol, the polyol, the resin intermediate prepared in the step A), the dibasic acid or dibasic acid anhydride, an antioxidant and a polymerization inhibitor to perform polycondensation reaction; and C) adding the polymerization inhibitor and styrene crosslinking monomers to dilute, and uniformly mixing so as to get the dicyclopentadiene unsaturated polyester resin for the high-leveling coatings. The dicyclopentadiene unsaturated polyester resin prepared by the method disclosed by the invention is suitable for PE (polyethylene) colored primers, PE transparent primers and other coatings, can bright excellent paint film smooth performance, and is further good in transparency and resistance to cold and hot whitening.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the preparation method of a kind of high levelling coating with the dicyclopentadiene type unsaturated polyester resin.
Background technology
Unsaturated polyester resin (UPR) is a kind of thermosetting resin, is to carry out polycondensation by monounsaturated dicarboxylic acid (acid anhydride) or unsaturated dibasic acid (acid anhydride) and saturated dibasic alcohol (or polyvalent alcohol) etc. to form.Because it has good mechanical property, electric property and resistance to chemical corrosion, and raw material is easy to get, complete processing is easy, practical value is high, and it is produced and processing industry develops very rapid.The unsaturated polyester resin that is widely used in now coating industry is O-phthalic acid type (being called for short adjacent benzene type), allyl ethers type, dicyclopentadiene type unsaturated polyester resin etc. basically.
At present, the method for preparing the dicyclopentadiene type unsaturated polyester both at home and abroad mainly contains acid anhydrides method, hydrolysis method, half esterification process and blocking method etc., but all do not have the special exploitation dicyclopentadiene type resin of being correlated with to be applied to coating industry, and solve the method for coating industry painting effect.Chinese patent CN101153072 discloses a kind of " method that is prepared modified unsaturated polyester resin by technical grade dicyclopentadiene ", that to take unsaturated or monounsaturated dicarboxylic acid or acid anhydrides be raw material with separating the technical grade dicyclopentadiene obtained in mixed C 5 cuts, drip distilled water to it, after the hydrolysis addition reaction, add appropriate dibasic alcohol or polyvalent alcohol to carry out the polycondensation dehydration under an acidic catalyst effect, prepared product can be applicable to the fields such as glass reinforced plastic, molding, gel coat, sealing and tackiness agent again.Chinese patent CN101633729A also discloses a kind of " method of preparing unsaturated polyster resin by industrial dicyclopentadiene ", the method is first to add dicyclopentadiene and water in reaction system, then drip unsaturated dicarboxylic acid anhydride and carry out addition reaction under keeping warm mode, then add dibasic alcohol, diprotic acid (or acid anhydrides) to carry out polycondensation, finally add stopper and pour the vinyl cross-linking monomer into, making the product that can be applicable to light goods after mixing.Yet, after the dicyclopentadiene type unsaturated polyester resin that adopts existing method to make is applied to the coating industry construction, construction effect is still not ideal enough.
Summary of the invention
The purpose of this invention is to provide the preparation method of a kind of high levelling coating with the dicyclopentadiene type unsaturated polyester resin.Adopting dicyclopentadiene type unsaturated polyester resin that present method makes to be applicable to PE has the coating such as color bottom paint, PE transparent priming, can bring the smooth performance of splendid paint film, and transparency and the cold-and-heat resistent performance of turning white is good.
Technical solution of the present invention is: the preparation method of dicyclopentadiene type unsaturated polyester resin for a kind of high levelling coating comprises the following steps:
A, get lipid acid and polyvalent alcohol that mol ratio is 1: 0.5～2,230 ± 3 ℃ of lower esterifications 1～2.5 hour, the acid number of question response system≤5 o'clock, be cooled to below 120 ℃, synthesizes the resin intermediate that hydroxyl equivalent is 130～300;
B, take appropriate diprotic acid or dibasic acid anhydride, take its molar weight as datum quantity, the deionized water that adds 1～1.2 times of datum quantity was 100 ℃～140 ℃ lower hydrolysis reaction 0.5～1 hour, the dicyclopentadiene that drips subsequently 0.4～1 times of datum quantity under 100 ℃～180 ℃ is carried out hydrogen ion sigmatropic reaction and Diene-addition reaction, after dropwising, at this temperature, react 1～3 hour, then the dibasic alcohol that adds 0.8～2 times of datum quantity, 0.1 the polyvalent alcohol of～0.6 times of datum quantity, 0.05 the resin intermediate made by steps A of～0.2 times of datum quantity, 0.1 the diprotic acid of～0.6 times of datum quantity or dibasic acid anhydride and account for steps A and step B feed intake gross weight 0.1 ‰～0.5 ‰ oxidation inhibitor and account for the feed intake stopper of gross weight 0.02 ‰～0.1 ‰ of steps A and step B, progressively be warming up to 200 ℃～210 ℃ and carry out polycondensation 2～4 hours, having reacted final vacuum dewaters to acid number≤40 and is cooled to below 130 ℃, obtain a solid resin,
Add in C, the solid resin that obtains at step B to account for the feed intake stopper of gross weight 0.05 ‰～0.20 ‰ and 20%～25% the vinylbenzene cross-linking monomer that accounts for this solid resin weight of steps A and step B and diluted, obtain described high levelling coating dicyclopentadiene type unsaturated polyester resin after mixing.
In the reaction system of the described esterification of above-mentioned steps A, also be added with and account for the feed intake agent of losing lustre of gross weight 0.8%～1.2% of steps A.The described agent of losing lustre is water-soluble inorganic acid, is preferably Hypophosporous Acid, 50.
In above-mentioned steps B, the time for adding of dicyclopentadiene is 1～2 hour.Because the dropping of dicyclopentadiene is an exothermic process, if time for adding is less than 1 hour, easily because of the too fast and uncontrollable temperature of reaction of heat release; If but time for adding is greater than 2 hours, is unfavorable for enhancing productivity.
In above-mentioned steps B, after the dicyclopentadiene insulation reaction, the time that is warming up to 200 ℃～210 ℃ is 4～6 hours.If the heating-up time is less than 4 hours, temperature rise rate is too fast, and lower boiling alcohol compound can not fully react, and the loss of alcohol compound is larger, and the final acid number of product can be higher; And the heating-up time more than 6 hours the time, product performance do not have marked difference, but extend the heating-up time, can cause production efficiency to reduce.
In above-mentioned steps B, the time of having reacted the final vacuum dehydration is 3～4 hours.
In preparation method of the present invention, the reaction in described steps A and step B is all carried out under nitrogen protection.
In preparation method of the present invention, described lipid acid is selected from lauric acid, behenic acid, ricinolic acid, dehydrated castor oleic acid, linolenic acid etc.; Described polyvalent alcohol is selected from glycerine, tetramethylolmethane, sorbyl alcohol etc.; Described dibasic acid anhydride is MALEIC ANHYDRIDE, and described diprotic acid is FUMARIC ACID TECH GRADE; Described dibasic alcohol is selected from one or more the mixing in ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, neopentyl glycol etc.; Described stopper is selected from one or more the mixing in Resorcinol, Tert. Butyl Hydroquinone, BHT, toluhydroquinone, copper naphthenate etc.; Described oxidation inhibitor is selected from triphenyl phosphite, antioxidant 1010 (i.e. four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester) etc.
In preparation method of the present invention, described agent and the oxidation inhibitor of losing lustre is for preventing that resin is oxidized by oxygen, make the form and aspect of resin more shallow, if its consumption is crossed DeGrain at least, and consumption is crossed and can be reduced at most the stability of sold resin and the consistency of resin; And described stopper is for preventing that resin from the process of depositing, the self-polymerization gel occurring, too short if it's the time that can deposit is at least past its consumption, and consumption is crossed the dry reaction Speed Reduction that can make at most resin.
Key of the present invention is to prepare the resin intermediate that a kind of hydroxyl equivalent is 130～300 in steps A, it can replace polyvalent alcohol in step B, can promote the flow leveling of vibrin, can meet powder containing quantity in coating industry and surpass 35% system requirement.And, in prior art, the dicyclopentadiene type unsaturated polyester resin that adopts conventional dibasic alcohol and polyvalent alcohol to make, be difficult to reach the requirement of the high powder of coating industry PE priming paint system to flow leveling.
In the present invention, the resin intermediate that is 130～300 due to hydroxyl equivalent has good moisture dispersibility to color stuffing, can reduce its surface tension, therefore, after adopting dicyclopentadiene type unsaturated polyester resin that this intermediate makes to be applied to coating application, can bring splendid levelling effect, also there are the good characteristics such as anti-turning white property, cold-and-heat resistent and low-shrinkage simultaneously.In addition, owing to adopting the intermediate modification, saved cost, and production unit can with Device-General of the prior art, cost performance is high.
Embodiment
Below by specific embodiment, the present invention is further detailed explanation.
Embodiment 1
Resin intermediate A's is synthetic: to the Hypophosporous Acid, 50 that adds vegetable oil acid, the 1.30mol glycerine that the 1.30mol acid number is 201 in the 500ml four-hole reactor that nitrogen protection, agitator, thermometer, minute water condensing unit are housed and account for the gross weight 1% that the feeds intake agent of losing lustre; rise to fast 230 ℃; after esterification 1～2 hour; sampling detects acid number; when acid number≤5, be cooled to below 120 ℃.
Add 1.13mol MALEIC ANHYDRIDE and 1.65mol deionized water in the 500ml four-hole reactor that nitrogen protection, agitator, thermometer, fractional column device are housed; stop heating after being warming up to 80 ℃; naturally be warming up to 120 ℃; after stable; with within 2 hours, dripping the technical grade dicyclopentadiene that 0.64mol purity is 83%, then in 120 ℃ of insulation reaction 2 hours.Be cooled to subsequently 100 ℃, add 0.77mol Diethylene Glycol, 0.10mol tetramethylolmethane, 0.23mol FUMARIC ACID TECH GRADE, 0.10mol resin intermediate A, and the toluhydroquinone that accounts for the triphenyl phosphite of the gross weight 0.16 ‰ that feeds intake and account for the gross weight 0.04 ‰ that feeds intake, be warming up to 140 ℃, insulation reaction 1 hour, then be warming up to 200 ℃～210 ℃ with 4 hours, insulation reaction is to acid number≤80, vacuumize, when acid number≤40, viscosity are 15～18S/25 ℃/Ge Shi pipe, be cooled to 120 ℃.Then add the toluhydroquinone that accounts for the gross weight 0.16 ‰ that feeds intake, after stirring, add in the mixed solution made by the vinylbenzene that accounts for total resin weight 24% and the copper naphthenate that accounts for total resin weight 0.05 ‰ and diluted, dilution temperature≤60 ℃, make high levelling coating dicyclopentadiene type unsaturated polyester resin of the present invention after stirring.
Embodiment 2
Resin intermediate B's is synthetic: to the Hypophosporous Acid, 50 that adds vegetable oil acid, the 0.71mol tetramethylolmethane that the 1.42mol acid number is 195 in the 500m l four-hole reactor that nitrogen protection, agitator, thermometer, minute water condensing unit are housed and account for the total amount 1% that the feeds intake agent of losing lustre; rise to fast 230 ℃; after esterification 1～2 hour; sampling detects acid number; when acid number≤5, be cooled to below 120 ℃.
Add 1.17mol MALEIC ANHYDRIDE and 1.21mol deionized water in the 500ml four-hole reactor that nitrogen protection, agitator, thermometer, fractional column device are housed; stop heating after being warming up to 80 ℃; naturally be warming up to 120 ℃; after stable; with within 2 hours, dripping the technical grade dicyclopentadiene that 0.58mol purity is 83%, then in 105 ℃ of insulation reaction 2 hours.Be cooled to subsequently 100 ℃, add 1.01mol ethylene glycol, 0.32mol glycerine, 0.24mol FUMARIC ACID TECH GRADE, 0.04mol resin intermediate B, and the toluhydroquinone that accounts for the triphenyl phosphite of the gross weight 0.16 ‰ that feeds intake and account for the gross weight 0.04 ‰ that feeds intake, be warming up to 140 ℃, insulation reaction 1 hour, then be warming up to 200 ℃～210 ℃ with 5 hours, insulation reaction is to acid number≤80, vacuumize, when acid number≤40, viscosity are 15～18S/25 ℃/Ge Shi pipe, be cooled to 120 ℃.Then add the toluhydroquinone that accounts for the total amount 0.14 ‰ that feeds intake, after stirring, add in the mixed solution made by the vinylbenzene that accounts for total resin weight 25% and the copper naphthenate that accounts for total resin weight 0.06 ‰ and diluted, dilution temperature≤60 ℃, make high levelling coating dicyclopentadiene type unsaturated polyester resin of the present invention after stirring.
Embodiment 3
Resin intermediate C's is synthetic: to the Hypophosporous Acid, 50 that adds vegetable oil acid, the 1.30mol glycerine that the 1.30mol acid number is 208 in the 500ml four-hole reactor that nitrogen protection, agitator, thermometer, minute water condensing unit are housed and account for the total amount 1% that the feeds intake agent of losing lustre; rise to fast 230 ℃; after esterification 1～2 hour; sampling detects acid number; when acid number≤5, be cooled to below 120 ℃.
Add 1.14mol MALEIC ANHYDRIDE and 1.18mol deionized water in the 500m l four-hole reactor that nitrogen protection, agitator, thermometer, fractional column device are housed; stop heating after being warming up to 80 ℃; naturally be warming up to 120 ℃; after stable; with within 2 hours, dripping the technical grade dicyclopentadiene that 0.65mol purity is 83%, then in 140 ℃ of insulation reaction 2 hours.Be cooled to subsequently 100 ℃, add 0.78mol neopentyl glycol, 0.09mol tetramethylolmethane, 0.23mol FUMARIC ACID TECH GRADE, 0.08mol resin intermediate C and account for the triphenyl phosphite of the gross weight 0.16 ‰ that feeds intake and account for the Resorcinol of the gross weight 0.06 ‰ that feeds intake, be warming up to 140 ℃, insulation reaction 1 hour, then be warming up to 200 ℃～210 ℃ with 6 hours, insulation reaction, to acid number≤80, vacuumizes, when acid number≤40, viscosity are 15～18S/25 ℃/Ge Shi pipe, be cooled to 120 ℃.Then add the Tert. Butyl Hydroquinone that accounts for the gross weight 0.16 ‰ that feeds intake, after stirring, add in the mixed solution made by the vinylbenzene that accounts for total resin weight 24% and the copper naphthenate that accounts for total resin weight 0.05 ‰ and diluted, dilution temperature≤60 ℃, make high levelling coating dicyclopentadiene type unsaturated polyester resin of the present invention after stirring.
Controlled trial 1
Get four sections of resins that often are applied to PE priming paint on the products and marketing that the present invention makes and carry out the performance control experiment, experimental result is as follows:
Remarks:
1,5 being divided into basis point in the performance test hurdle, surpassing 5 and be divided into more outstandingly, is poor lower than 5 minutes persons; In gloss one hurdle, gloss the higher person is excellent; In greening one hurdle, without the greening person, be excellent.
2, " day dragon 2801 " is the universal PE resin of 2801# that sky, Changzhou Wujin dragon chemical industry company limited produces.
3, " long-range 9902 " are the universal PE resin of 9902# that Shunde District, Foshan City long-range chemical industry company limited produces.
4, " Changxing 2309 " is the ETERSET 2309 type PE resins that Changxing synthetic resins (Changshu) company limited produces.
5, " side prosperous 998 " is the FX-988 type PE air-drying property bottom paint resin that Changzhou side prosperous chemical industry goods and materials company limited produces.
The testing method of above-mentioned property indices is as follows:
Grinability: press GB/T 1770-2008 standard test.
Levelling property: evenly spray 15 ± 0.3g paint film on the sticky paperboard of 30cm * 20cm, after the film forming drying, its planeness is intuitively contrasted and estimated with 5 minutes systems.
The transparency: blade coating on the wet film preparing device that is SZQ-200um by the model transparent glass sheet thick at 5mm, after the film forming drying, by contrast directly perceived and with 5 minutes systems, estimated.
Gloss: press GB/T 9754-2007 standard test.
Gel time: press the GB7193.6-87 standard test.
The cold-and-heat resistent performance of turning white: even spraying 15 ± 0.3g paint film on the sticky paperboard of 30cm * 20cm, put into 60 ℃ and-25 ℃ of each 12h of isoperibol after the film forming drying, circulate 3 times, contrast its paint film situation of turning white, and estimated with 5 minutes systems.
Controlled trial 2
The resin that will be made by dissimilar polyvalent alcohol is applied to respectively powder containing quantity and surpasses in 40% PE paint base system, and its levelling property is tested, and test-results is as follows:
Remarks: adopt the levelling property testing method in controlled trial 1 to be estimated the levelling property of above-mentioned sample.
In the prior art, the levelling property of neopentyl glycol system and 1,2-PD system is better than the levelling property of other polyvalent alcohol system, and the levelling effect of the resin intermediate system that the present invention makes more obviously is better than other polyvalent alcohol system.
Above-listed detailed description is for the illustrating of one of the present invention possible embodiments, and this embodiment is not in order to limit the scope of the claims of the present invention, and the equivalence that all the present invention of disengaging do is implemented or change, all should be contained in the scope of the claims of this case.
Claims (4)
1. the preparation method of dicyclopentadiene type unsaturated polyester resin for one kind high levelling coating comprises the following steps:
A, get lipid acid and polyvalent alcohol that mol ratio is 1:0.5～2,230 ± 3 ℃ of lower esterifications 1～2.5 hour, the acid number of question response system≤5 o'clock, be cooled to below 120 ℃, synthesizes the resin intermediate that hydroxyl equivalent is 130～300;
B, take appropriate diprotic acid or dibasic acid anhydride, take its molar weight as datum quantity, the deionized water that adds 1～1.2 times of datum quantity was 100 ℃～140 ℃ lower hydrolysis reaction 0.5～1 hour, the dicyclopentadiene that drips subsequently 0.4～1 times of datum quantity under 100 ℃～180 ℃ is carried out hydrogen ion sigmatropic reaction and Diene-addition reaction, after dropwising, at this temperature, react 1～3 hour, then the dibasic alcohol that adds 0.8～2 times of datum quantity, 0.1 the polyvalent alcohol of～0.6 times of datum quantity, 0.05 the resin intermediate made by steps A of～0.2 times of datum quantity, 0.1 the diprotic acid of～0.6 times of datum quantity or dibasic acid anhydride and account for steps A and step B feed intake gross weight 0.1 ‰～0.5 ‰ oxidation inhibitor and account for the feed intake stopper of gross weight 0.02 ‰～0.1 ‰ of steps A and step B, progressively be warming up to 200 ℃～210 ℃ and carry out polycondensation 2～4 hours, having reacted final vacuum dewaters to acid number≤40 and is cooled to below 130 ℃, obtain a solid resin,
Add in C, the solid resin that obtains at step B to account for the feed intake stopper of gross weight 0.05 ‰～0.20 ‰ and 20%～25% the vinylbenzene cross-linking monomer that accounts for this solid resin weight of steps A and step B and diluted, obtain described high levelling coating dicyclopentadiene type unsaturated polyester resin after mixing;
Described lipid acid is selected from lauric acid, behenic acid, ricinolic acid, dehydrated castor oleic acid or linolenic acid;
Described polyvalent alcohol is selected from glycerine, tetramethylolmethane or sorbyl alcohol;
Described dibasic acid anhydride is MALEIC ANHYDRIDE; Described diprotic acid is FUMARIC ACID TECH GRADE;
Described dibasic alcohol is selected from one or more the mixing in ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, neopentyl glycol;
Described stopper is selected from one or more the mixing in Resorcinol, Tert. Butyl Hydroquinone, BHT, toluhydroquinone, copper naphthenate;
Described oxidation inhibitor is selected from triphenyl phosphite or antioxidant 1010.
2. preparation method according to claim 1, it is characterized in that: the reaction in described steps A and step B is all carried out under nitrogen protection.
3. preparation method according to claim 1 is characterized in that: in the reaction system of the described esterification of steps A, also be added with and account for the feed intake agent of losing lustre of gross weight 0.8%～1.2% of steps A; The described agent of losing lustre is water-soluble inorganic acid.
4. preparation method according to claim 1, it is characterized in that: in step B, the time for adding of dicyclopentadiene is 1～2 hour; After the dicyclopentadiene insulation reaction, the time that is warming up to 200 ℃～210 ℃ is 4～6 hours; The time of having reacted the final vacuum dehydration is 3～4 hours.
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| CN103342803B (en) * | 2013-07-19 | 2015-09-09 | 山东日新复合材料有限公司 | Low-temperature catalyzed method produces dicyclo bio-based polyester resin process |
| CN103834254B (en) * | 2013-12-17 | 2016-01-06 | 常州华日新材有限公司 | Double-component coat unsaturated polyester resin and preparation using method thereof |
| CN103937386A (en) * | 2014-04-10 | 2014-07-23 | 上海长润发涂料有限公司 | Unsaturated polyester coated white primer |
| CN104311810A (en) * | 2014-09-17 | 2015-01-28 | 英德市雅家涂料有限公司 | Cheap dicyclopentadiene modified unsaturated polyester resin and preparation method thereof |
| CN105566577A (en) * | 2015-04-16 | 2016-05-11 | 湖南省金海科技有限公司 | Preparing method for styrene-free low-volatile-matter unsaturated polyester resin |
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| CN105838050B (en) * | 2016-03-31 | 2019-02-12 | 昌亚新材料科技有限公司 | A kind of preparation method of the modified low-shrinkage sheet molding compound of epoxidized soybean oil |
| CN106749902A (en) * | 2017-01-23 | 2017-05-31 | 江苏赛鑫树脂有限公司 | A kind of PE priming resin compositions and preparation method |
| CN109369897B (en) * | 2018-10-25 | 2020-05-08 | 江门市长河化工实业集团有限公司 | Soybean oil fatty acid modified dicyclopentadiene type unsaturated polyester resin |
| CN109535401A (en) * | 2018-11-22 | 2019-03-29 | 广东百川化工有限公司 | Ordor removing, unsaturated polyester resin and preparation method thereof |
| CN109535400A (en) * | 2018-11-29 | 2019-03-29 | 三棵树涂料股份有限公司 | A kind of preparation method of unsaturated polyester resin |
| CN109880071A (en) * | 2019-01-23 | 2019-06-14 | 新阳科技集团有限公司 | A kind of preparation method of dicyclopentadiene type unsaturated polyester resin |
| CN110964415A (en) * | 2019-10-22 | 2020-04-07 | 上海嘉宝莉涂料有限公司 | Polyester top-coat paint |
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| CN1215414A (en) * | 1996-04-03 | 1999-04-28 | 黑尔伯有限公司 | Modified polyester resin/organic peroxide systems for powder coatings which are applicable to temperature sentitive and metallic substrates |
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