CN102504122A - 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 divalent 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, it is produced and processing industry develops very rapid.The unsaturated polyester resin that is widely used in coating industry now 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 will 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 "; Be to be raw material to separate the technical grade dicyclopentadiene that obtains in unsaturated or monounsaturated dicarboxylic acid or acid anhydrides and mixed C 5 cuts; Drip zero(ppm) water to it; Under an acidic catalyst effect, carry out the polycondensation dehydration through adding an amount of divalent alcohol or polyvalent alcohol after the hydrolysis addition reaction again, prepared product can be applicable to fields such as glass reinforced plastic, moulding, gel coat, sealing and tackiness agent.Chinese patent CN101633729A also discloses a kind of " method of preparing unsaturated polyster resin by industrial dicyclopentadiene "; This method is in reaction system, to add NSC 7352 and water earlier; Under keeping warm mode, drip unsaturated dicarboxylic acid anhydride then and carry out addition reaction; Then add divalent alcohol, diprotic acid (or acid anhydrides) carries out polycondensation, adds stopper at last and pours the vinyl cross-linking monomer into, makes 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 was applied to the coating industry construction, construction effect was 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.The dicyclopentadiene type unsaturated polyester resin that adopts present method to make is applicable to that PE has 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: a kind of high levelling coating may further comprise the steps with the preparation method of dicyclopentadiene type unsaturated polyester resin:
A, to get mol ratio be 1: 0.5～2 lipid acid and polyvalent alcohol, and 230 ± 3 ℃ of following esterifications 1～2.5 hour, the acid number of question response system≤5 o'clock were cooled to below 120 ℃, synthesizes hydroxyl equivalent and be 130～300 resin intermediate;
B, take by weighing an amount of diprotic acid or dibasic acid anhydride; With its molar weight is datum quantity; The deionized water that adds 1～1.2 times of datum quantity was 100 ℃～140 ℃ following hydrolysis reaction 0.5～1 hour; Carry out hydrogen ion sigmatropic reaction and diene addition reaction at 100 ℃～180 ℃ NSC 7352s that drip 0.4～1 times of datum quantity down subsequently; Dropwising the back reacted under this temperature 1～3 hour; Add the diprotic acid or the dibasic acid anhydride of the resin intermediate that makes by steps A of the polyvalent alcohol of the divalent alcohol of 0.8～2 times of datum quantity, 0.1～0.6 times of datum quantity, 0.05～0.2 times of datum quantity, 0.1～0.6 times of datum quantity then and account for steps A and step B feed intake gross weight 0.1 ‰～0.5 ‰ oxidation inhibitor and account for steps A and the feed intake stopper of gross weight 0.02 ‰～0.1 ‰ of step B; Progressively be warming up to 200 ℃～210 ℃ and carried out polycondensation 2～4 hours, reaction completion final vacuum dewaters to acid number≤40 and is cooled to below 130 ℃, obtains a solid resin;
C, in the solid resin that step B obtains, add and 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 dilute, promptly obtain described high levelling coating after mixing and use the dicyclopentadiene type unsaturated polyester resin.
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 said agent of losing lustre is water-soluble inorganic acid, is preferably Hypophosporous Acid, 50.
In above-mentioned steps B, the dropping time of NSC 7352 is 1～2 hour.Because the dropping of NSC 7352 is an exothermic process, if the dropping time is less than 1 hour, easily because of the too fast and uncontrollable temperature of reaction of heat release; But if the dropping time greater than 2 hours, then is unfavorable for enhancing productivity.
In above-mentioned steps B, after the NSC 7352 insulation reaction finished, the time that is warming up to 200 ℃～210 ℃ was 4～6 hours.TRT, if temperature rise rate was too fast less than 4 hours, and lower boiling alcohol compound can not fully react, and the loss of alcohol compound is bigger, and the final acid number of product can be higher; And the TRT more than 6 hours the time, product performance do not have marked difference, can cause production efficiency to reduce but prolong the TRT.
In above-mentioned steps B, the time that the final vacuum dehydration is accomplished in reaction is 3～4 hours.
In preparation method of the present invention, the reaction among said steps A and the step B is all carried out under nitrogen protection.
In preparation method of the present invention, described lipid acid is selected from LAURIC ACID 99 MIN, 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 a MALEIC ANHYDRIDE, and described diprotic acid is a FUMARIC ACID TECH GRADE; Described divalent alcohol is selected from one or more the mixing in terepthaloyl moietie, Ucar 35, glycol ether, DPG, the NSC 6366 etc.; Described stopper is selected from Resorcinol, Tert. Butyl Hydroquinone, 2, the mixing of one or more in 6-di-tert-butyl methyl phenol, toluhydroquinone, the copper naphthenate etc.; Described oxidation inhibitor is selected from triphenyl phosphite, antioxidant 1010 (i.e. four [β-(3, the 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 to be used to prevent that resin is by dioxygen oxidation; Make the form and aspect of resin more shallow, if its consumption crosses DeGrain at least, and consumption is crossed and can be reduced the stability of sold resin and the consistency of resin at most; And described stopper is to be used for preventing that resin from the process of depositing the self-polymerization gel taking place, and is 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 resin at most.
Key of the present invention is that in steps A, to prepare a kind of hydroxyl equivalent be 130～300 resin intermediate; It can replace polyvalent alcohol in step B; Can promote the flow leveling of vibrin, make it can satisfy powder containing quantity in the coating industry and surpass 35% system requirement.And in the prior art, the dicyclopentadiene type unsaturated polyester resin that adopts conventional divalent alcohol and polyvalent alcohol to make is difficult to reach the requirement of the high powder of coating industry PE priming paint system to flow leveling.
Among the present invention; Because hydroxyl equivalent is 130～300 resin intermediate color stuffing had good moisture dispersibility; Can reduce its surface tension, therefore, after the dicyclopentadiene type unsaturated polyester resin that adopts this midbody to make is applied to coating application; Can bring splendid levelling effect, also have good characteristics such as anti-turning white property, cold-and-heat resistent property and low-shrinkage simultaneously.In addition,, practiced thrift cost owing to adopt the midbody modification, and production unit can with Device-General of the prior art, cost performance is high.
Embodiment
Through specific embodiment the present invention is done further detailed explanation below.
Embodiment 1
Resin intermediate A's is synthetic: in the 500ml four-hole reactor drum that nitrogen protection, whisking appliance, TM, branch water condensing unit are housed, add the 1.30mol acid number and be the agent of losing lustre of 201 vegetable oil acid, 1.30mol glycerine and the Hypophosporous Acid, 50 that accounts for the gross weight 1% that feeds intake; Rise to 230 ℃ fast; After the esterification 1～2 hour; Sampling detects acid number, when acid number≤5, is cooled to below 120 ℃.
In the 500ml four-hole reactor drum that nitrogen protection, whisking appliance, TM, separation column device are housed, add 1.13mol MALEIC ANHYDRIDE and 1.65mol deionized water; Stop heating after being warming up to 80 ℃; Naturally be warming up to 120 ℃; After stable, using 2 hours dropping 0.64mol purity is 83% technical grade dicyclopentadiene, then in 120 ℃ of insulation reaction 2 hours.Be cooled to 100 ℃ subsequently, 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 was warming up to 200 ℃～210 ℃ with 4 hours then; Insulation reaction to acid number≤80; Vacuumize, when acid number≤40, viscosity are 15～18S/25 ℃/Ge Shi pipe, be cooled to 120 ℃.Add the toluhydroquinone that accounts for the gross weight 0.16 ‰ that feeds intake then; After stirring; Dilute in the mixed solution that adding is made by vinylbenzene that accounts for total resin weight 24% and the copper naphthenate that accounts for total resin weight 0.05 ‰; Dilution temperature≤60 ℃ promptly make high levelling coating of the present invention and use the dicyclopentadiene type unsaturated polyester resin after stirring.
Embodiment 2
Resin intermediate B's is synthetic: in the 500m l four-hole reactor drum that nitrogen protection, whisking appliance, TM, branch water condensing unit are housed, add the 1.42mol acid number and be the agent of losing lustre of 195 vegetable oil acid, 0.71mol tetramethylolmethane and the Hypophosporous Acid, 50 that accounts for the total amount 1% that feeds intake; Rise to 230 ℃ fast; After the esterification 1～2 hour; Sampling detects acid number, when acid number≤5, is cooled to below 120 ℃.
In the 500ml four-hole reactor drum that nitrogen protection, whisking appliance, TM, separation column device are housed, add 1.17mol MALEIC ANHYDRIDE and 1.21mol deionized water; Stop heating after being warming up to 80 ℃; Naturally be warming up to 120 ℃; After stable, using 2 hours dropping 0.58mol purity is 83% technical grade dicyclopentadiene, then in 105 ℃ of insulation reaction 2 hours.Be cooled to 100 ℃ subsequently, add 1.01mol terepthaloyl moietie, 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 was warming up to 200 ℃～210 ℃ with 5 hours then; Insulation reaction to acid number≤80; Vacuumize, when acid number≤40, viscosity are 15～18S/25 ℃/Ge Shi pipe, be cooled to 120 ℃.Add the toluhydroquinone that accounts for the total amount 0.14 ‰ that feeds intake then; After stirring; Dilute in the mixed solution that adding is made by vinylbenzene that accounts for total resin weight 25% and the copper naphthenate that accounts for total resin weight 0.06 ‰; Dilution temperature≤60 ℃ promptly make high levelling coating of the present invention and use the dicyclopentadiene type unsaturated polyester resin after stirring.
Embodiment 3
Resin intermediate C's is synthetic: in the 500ml four-hole reactor drum that nitrogen protection, whisking appliance, TM, branch water condensing unit are housed, add the 1.30mol acid number and be the agent of losing lustre of 208 vegetable oil acid, 1.30mol glycerine and the Hypophosporous Acid, 50 that accounts for the total amount 1% that feeds intake; Rise to 230 ℃ fast; After the esterification 1～2 hour; Sampling detects acid number, when acid number≤5, is cooled to below 120 ℃.
In the 500m l four-hole reactor drum that nitrogen protection, whisking appliance, TM, separation column device are housed, add 1.14mol MALEIC ANHYDRIDE and 1.18mol deionized water; Stop heating after being warming up to 80 ℃; Naturally be warming up to 120 ℃; After stable, using 2 hours dropping 0.65mol purity is 83% technical grade dicyclopentadiene, then in 140 ℃ of insulation reaction 2 hours.Be cooled to 100 ℃ subsequently, add 0.78mol NSC 6366,0.09mol 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; Be warming up to 200 ℃～210 ℃ with 6 hours then, insulation reaction to acid number≤80 vacuumize; When acid number≤40, viscosity are 15～18S/25 ℃/Ge Shi pipe, be cooled to 120 ℃.Add the Tert. Butyl Hydroquinone that accounts for the gross weight 0.16 ‰ that feeds intake then; After stirring; Dilute in the mixed solution that adding is made by vinylbenzene that accounts for total resin weight 24% and the copper naphthenate that accounts for total resin weight 0.05 ‰; Dilution temperature≤60 ℃ promptly make high levelling coating of the present invention and use the dicyclopentadiene type unsaturated polyester resin after stirring.
Controlled trial 1
Get that four sections of resins that often are applied to PE priming paint carry out the performance control experiment on the products and marketing that the present invention makes, experimental result is following:
Remarks:
1,5 is divided into the benchmark branch in the performance test hurdle, surpasses 5 and be divided into more outstandingly, be lower than 5 fens persons for relatively poor; In gloss one hurdle, gloss the higher person is excellent; In greening property one hurdle, no greening person is excellent.
2, " day dragon 2801 " is the universal PE resin of 2801# that sky, Changzhou Wujin dragon chemical industry ltd produces.
3, " long-range 9902 " are the universal PE resin of 9902# that Shunde District, Foshan City long-range chemical industry ltd produces.
4, " Changxing 2309 " is the ETERSET 2309 type PE resins that Changxing synthetic resins (Changshu) ltd 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 ltd produces.
The testing method of above-mentioned each item performance index is following:
Grinability: press GB/T 1770-2008 standard test.
Leveling characteristics: on the paster plate of 30cm * 20cm, evenly spray 15 ± 0.3g paint film, after the film forming drying its planeness is intuitively contrasted and estimate with 5 fens systems.
The transparency: be wet film preparing device blade coating on the thick transparent glass sheet of 5mm of SZQ-200um through model, estimate through contrast directly perceived and with 5 fens systems after the film forming drying.
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 paster plate of 30cm * 20cm, put into after the film forming drying 60 ℃ with-25 ℃ of each 12h of isoperibol, circulate 3 times, contrast its paint film situation of turning white, and made with 5 minutes and to estimate.
Controlled trial 2
The resin that will be made by dissimilar polyvalent alcohols is applied to powder containing quantity respectively and surpasses in 40% the PE paint base system, and its leveling characteristics is tested, and test-results is following:
Remarks: adopt the leveling characteristics testing method in the controlled trial 1 that the leveling characteristics of above-mentioned sample is estimated.
In the prior art, NSC 6366 system and 1, the leveling characteristics of 2-propylene glycol system is better than the leveling characteristics of other polyvalent alcohol system, and the levelling effect of the resin intermediate system that the present invention makes then more obviously is superior to other polyvalent alcohol system.
Above-listed detailed description is to the specifying of one of the present invention possible embodiments, and this embodiment is not in order to limiting claim 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 claim of this case.
Claims (10)
1. one kind high levelling coating may further comprise the steps with the preparation method of dicyclopentadiene type unsaturated polyester resin:
A, to get mol ratio be 1: 0.5～2 lipid acid and polyvalent alcohol, and 230 ± 3 ℃ of following esterifications 1～2.5 hour, the acid number of question response system≤5 o'clock were cooled to below 120 ℃, synthesizes hydroxyl equivalent and be 130～300 resin intermediate;
B, take by weighing an amount of diprotic acid or dibasic acid anhydride; With its molar weight is datum quantity; The deionized water that adds 1～1.2 times of datum quantity was 100 ℃～140 ℃ following hydrolysis reaction 0.5～1 hour; Carry out hydrogen ion sigmatropic reaction and diene addition reaction at 100 ℃～180 ℃ NSC 7352s that drip 0.4～1 times of datum quantity down subsequently; Dropwising the back reacted under this temperature 1～3 hour; Add the diprotic acid or the dibasic acid anhydride of the resin intermediate that makes by steps A of the polyvalent alcohol of the divalent alcohol of 0.8～2 times of datum quantity, 0.1～0.6 times of datum quantity, 0.05～0.2 times of datum quantity, 0.1～0.6 times of datum quantity then and account for steps A and step B feed intake gross weight 0.1 ‰～0.5 ‰ oxidation inhibitor and account for steps A and the feed intake stopper of gross weight 0.02 ‰～0.1 ‰ of step B; Progressively be warming up to 200 ℃～210 ℃ and carried out polycondensation 2～4 hours, reaction completion final vacuum dewaters to acid number≤40 and is cooled to below 130 ℃, obtains a solid resin;
C, in the solid resin that step B obtains, add and 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 dilute, promptly obtain described high levelling coating after mixing and use the dicyclopentadiene type unsaturated polyester resin.
2. preparation method according to claim 1 is characterized in that: the reaction among said steps A and the 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 is characterized in that: in step B, the dropping time of NSC 7352 is 1～2 hour; After the NSC 7352 insulation reaction finished, the time that is warming up to 200 ℃～210 ℃ was 4～6 hours; The time that the final vacuum dehydration is accomplished in reaction is 3～4 hours.
5. preparation method according to claim 1 is characterized in that: described lipid acid is selected from LAURIC ACID 99 MIN, behenic acid, ricinolic acid, dehydrated castor oleic acid or linolenic acid.
6. preparation method according to claim 1 is characterized in that: described polyvalent alcohol is selected from glycerine, tetramethylolmethane or sorbyl alcohol.
7. preparation method according to claim 1 is characterized in that: described dibasic acid anhydride is a MALEIC ANHYDRIDE; Described diprotic acid is a FUMARIC ACID TECH GRADE.
8. preparation method according to claim 1 is characterized in that: described divalent alcohol is selected from one or more the mixing in terepthaloyl moietie, Ucar 35, glycol ether, DPG, the NSC 6366.
9. preparation method according to claim 1 is characterized in that: described stopper is selected from Resorcinol, Tert. Butyl Hydroquinone, 2, the mixing of one or more in 6-di-tert-butyl methyl phenol, toluhydroquinone, the copper naphthenate.
10. preparation method according to claim 1 is characterized in that: described oxidation inhibitor is selected from triphenyl phosphite or antioxidant 1010.
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| CN103342803A (en) * | 2013-07-19 | 2013-10-09 | 山东日新复合材料有限公司 | Process for producing double-ring biopolyester resin via low-temperature catalysis method |
| CN103834254A (en) * | 2013-12-17 | 2014-06-04 | 常州华日新材有限公司 | Bi-component coating unsaturated polyester resin and preparation 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 |
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| CN102719167A (en) * | 2012-07-04 | 2012-10-10 | 佛山市顺德区伊诗德新材料科技有限公司 | UV (Ultra Violet) photo-curing powder coating and preparation method thereof |
| CN103342803A (en) * | 2013-07-19 | 2013-10-09 | 山东日新复合材料有限公司 | Process for producing double-ring biopolyester resin via low-temperature catalysis method |
| 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 |
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| 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 |
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| CN105199053A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Recoat-able polishing-free unsaturated polyester resin for piano lacquer and preparation method of unsaturated polyester resin |
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| 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 |
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