CN102115534A - Dicyclopentadiene type unsaturated polyester modified by tung oil, and preparation method and application thereof - Google Patents
Dicyclopentadiene type unsaturated polyester modified by tung oil, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a dicyclopentadiene type unsaturated polyester modified by tung oil, and a preparation method and application thereof. The method comprises the following steps: reacting raw materials maleic anhydride and dicyclopentadiene under the action of a catalyst to obtain dicyclopentadiene semi-maleate; adding dihydric alcohol, dibasic acid and polymerization inhibitor, and heating to 190-210 DEG C for dehydration and esterification; when the acid value reaches 50-120 mg KOH/g, cooling to 120-180 DEG C, adding a certain amount of tung oil, and heating to 200-210 DEG C to continue the reaction; and after the acid value reaches 20-35 mg KOH/g under the action of esterification, cooling to 100-120 DEG C, diluting with styrene dissolved with a small amount of polymerization inhibitor, and uniformly dispersing to obtain the product. The dicyclopentadiene type unsaturated polyester modified by tung oil according to the method has the advantages of favorable air-drying property, aging resistance, biodegradability and the like. The product is suitable to be used as an unsaturated polyester paint for corrosion protection, insulation and binding.
Description
Technical field
The invention belongs to the preparation method of high molecular polymer type material, specifically relate to a kind of preparation method of tung oil-modified dicyclopentadiene type unsaturated polyester resin.The resin of this method preparation can be used as industries such as unsaturated polyester coating.
Background technology
Polymer materials is huge to human being's production and life influence.At present, its synthesis material mainly depends on oil.Yet, tellurian oil reserve at most only enough decades.In order to seek the resource that can substitute oil and protection environment, the wise move of can yet be regarded as of development renewable resources.Vegetables oil is exactly a kind of in the middle of these resources.Because its deposit is sufficient, possess biodegradability, but with and structure in the middle of contain the functional group of abundant chemical modification, therefore, increasing bibliographical information about utilizing the work of the polymer-modified material of vegetables oil.Wherein, utilize plant oil modified unsaturated polyester (UPR) material, also attracted numerous investigators' sight.
As the distinctive natural reproducible resource of China (China's tung oil output accounts for 80% of world wide production, produces per year more than 100,000 tons), tung oil is often only used by outlet and existing elementary processing, and its comprehensive development and utilization aspect also is nowhere near.Over the past two years, raw material tung oil market requirement depression, the tung oil price drops.Therefore, develop the tung oil deep process technology, can widen the marketing channel of tung oil, improve the tung oil value-added content of product greatly.
Tung oil is a kind of siccative oil, and can oxygen uptake crosslinked.The tung oil main component is an olein, and structural formula is:
Contain 3 conjugated double bonds in this grease molecule.80% eleostearic acid (18 carbon triolefins-[9,11,13]-acid) is arranged in the mixed fatty acid that tung oil contains.On reaction process, can utilize the unsaturated link(age) that contains in the tung oil structure, carboxyl etc., with the reaction of number of chemical such as Diels-Alder reaction, Friedel-Crafts reaction, oxypolymerization, radical polymerization, amidation and esterification, be incorporated in the preparation of universal unsaturated polyester.Zhou Juxing (CN 86108060A), Li Juncheng (" binding agent " 1990, (2): 60) and Zhao Guiying (" printing during chemical industry " 2007,31) etc. 21 (12): reported the unsaturated polyester resin after tung oil-modified respectively, have many advantages: toughness reinforcing, gas dried, corrosion-resistant, ageing-resistant, biodegradable, or the like.
On the other hand, as far back as the beginning of the eighties in last century, dicyclopentadiene (DCPD) just is introduced into the synthetic of unsaturated polyester.The dicyclopentadiene type unsaturated polyester resin has good performance, as high rigidity, air-drying property, resistance to chemical attack, ultraviolet resistance irradiation, good electric property with to advantages such as adhesivityes such as glass fibre, steel are better.But this resinoid is because molecular weight is little, fragility is big, has significant disadvantages when causing it to be used for unsaturated polyester coating: more crisp, more serious and thick being coated with of greening of filming after the curing is easy to turn white, or the like.Therefore, if want the good unsaturated polyester resin material of production performance, just need to overcome above-mentioned shortcoming.
Summary of the invention
Purpose of the present invention is intended to overcome existing universal unsaturated polyester and depends on petrochemical materials for a long time, and shortcoming such as poor toughness, difficult degradation and air-drying property be bad, can not satisfy the service requirements of unsaturated polyester coating.A kind of tung oil-modified dicyclopentadiene type unsaturated polyester and its production and application that utilizes is provided, has processing ease, constant product quality, lower-cost advantage.
Technical scheme of the present invention is: a kind of preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester comprises the following steps:
The first step, press the following formula reaction:
In second step, than the stopper that adds dibasic alcohol, diprotic acid and convention amount again, on four-hole boiling flask, install fractional column and water trap additional by metering, be warming up to 150 ℃, insulation 0.5～1h is warming up to 190～210 ℃ of dehydration esterifications after the end, control fractional column temperature≤105 ℃;
The 3rd step, when acid number reaches 50～120mgKOH/g, be cooled to 120～180 ℃ by metering ratio adding tung oil, be warming up to 200～210 ℃ again and continue reaction, esterifications to acid number 25～40mgKOH/g postcooling to 100～120 ℃, add the vinylbenzene that is dissolved with stopper and dilute, being uniformly dispersed obtains product.
Add catalyzer 80～140 ℃ of reactions in oxygen-free environment in the described the first step, described catalyzer is any or several mixture that forms with any proportioning in phosphoric acid, Witco 1298 Soft Acid, the tosic acid.
Described diprotic acid is FUMARIC ACID TECH GRADE or Tetra hydro Phthalic anhydride or both mixtures.
Described dibasic alcohol is any or several mixture that forms with any proportioning in ethylene glycol, propylene glycol, the glycol ether.
Described stopper is Resorcinol, para benzoquinone, 2, any in the 6-di-tert-butyl methyl phenol or several mixture that forms with any proportioning.
The general structure of the tung oil-modified dicyclopentadiene type unsaturated polyester of preparation is:
Wherein, R
1For: HO-CH
2-CH
2-,
HO-CH
2-CH
2-O-CH
2-CH
2-, H-; R
2For :-CH
2-CH
2-,
-CH
2-CH
2-O-CH
2-CH
2-; R
3For :-CH=CH-,
R
4Tung oil glyceryl ester affixture for remainder; M, n be 〉=1 integer.
Described tung oil-modified dicyclopentadiene type unsaturated polyester is as unsaturated polyester coating with as the application of anticorrosion, insulation and binding agent.
Beneficial effect:
(1) the present invention adopts the multistep processes synthetic technology, processing ease, and constant product quality, technology is simpler, is easy to industry and enlarges production, and is practical;
(2) molecular resin amount of the present invention is higher, and number-average molecular weight is 1100～1300; Acid number is stable, and acid number is at 22.6～33.9mgKOH/g, product viscosity 868～1430mPas.The gained resin has air-drying property, corrosion-resistant and aging, biodegradability etc., and the mechanics of material and thermal property satisfy the requirement of versatility unsaturated polyester resin coating.
(3) the material modified of preparation method's employing of the present invention is tung oil and DCPD, and price is lower, helps reducing cost.Unsaturated polyester resins for general purpose cost low 3～10% than similar not modification.
Embodiment
The following examples of the present invention are only as the further specifying of content of the present invention, can not be as scope perhaps in the qualification of the present invention.The invention will be further described below in conjunction with embodiment.
The tung oil-modified dicyclopentadiene type unsaturated polyester resin compound that the present invention relates to, number-average molecular weight reaches 1000～1300.Because the acid, the pure kind that wherein comprise are more, molecular structural formula can be expressed with following general formula:
In the formula
R
1For: HO-CH
2-CH
2-,
HO-CH
2-CH
2-O-CH
2-CH
2-, H-;
R
2For :-CH
2-CH
2-,
-CH
2-CH
2-O-CH
2-CH
2-;
R
3For :-CH=CH-,
R
4Be the tung oil glyceryl ester affixture of remainder, herein because tung oil is triglyceride structure, so R
4Also comprised the reaction on two other side chain;
M, n are the integer more than or equal to 1.
The synthetic method of the tung oil-modified DCPD type unsaturated polyester resin that the present invention relates to is as follows:
(1) with reaction raw materials MALEIC ANHYDRIDE, dicyclopentadiene according to 0.8-1.2: 1 mole proportioning input has in the four-hole boiling flask device of reflux condensing tube, and adds the catalyzer of material gross weight 0.4-0.8%; Be warming up to 80-100 ℃ behind the logical shielding gas and drip a certain amount of water, hierarchy of control temperature is lower than 140 ℃; After water added, insulation 1.5-2h obtained dicyclopentadiene maleic acid half ester, sees structural formula (I).
(2) add metering again than just making that the molar ratio of alcohol to acid of whole material system is 2.05-2.15: the stopper of 1 dibasic alcohol, diprotic acid and material gross weight 0.05-0.1%, on four-hole boiling flask, install fractional column and water trap additional, be warming up to 150 ℃, insulation 0.5-1h, be warming up to 190-210 ℃ of dehydration esterification after the end, control fractional column temperature≤105 ℃ is to reduce the loss of lower boiling dibasic alcohol.
(3) when acid number reaches 50-120mgKOH/g, be cooled to 120-180 ℃ of tung oil that adds the metering ratio, be warming up to 200-210 ℃ again and continue reaction.Esterification, adds the vinylbenzene that is dissolved with a small amount of stopper and dilutes to 100-120 ℃ to acid number 25-40mgKOH/g postcooling, and being uniformly dispersed obtains product.
Described diprotic acid is FUMARIC ACID TECH GRADE or Tetra hydro Phthalic anhydride; It also can be the mixture that FUMARIC ACID TECH GRADE and Tetra hydro Phthalic anhydride form with any proportioning.
Described dibasic alcohol is any or any two mixture that forms with any proportioning in ethylene glycol, propylene glycol, the glycol ether.
Described catalyzer is any one or two kinds of mixtures that form with any proportioning in phosphoric acid, Witco 1298 Soft Acid, the tosic acid.
Described stopper is Resorcinol, para benzoquinone, 2, any one or two kinds of mixtures that form with any proportioning in the 6-di-tert-butyl methyl phenol.
Described cinnamic add-on is preferably the 30-35% of synthetic polymer weight.
The tung oil-modified dicyclopentadiene type unsaturated polyester resin of described synthetic is suitable for makes coating, sizing agent etc.
The tung oil-modified dicyclopentadiene type unsaturated polyester product viscosity 868-1430mPas of the present invention's preparation, acid number 22.6-33.9mgKOH/g, number-average molecular weight 1100-1300.
Embodiment 1:
30g (0.3mol) MALEIC ANHYDRIDE, 40g (0.3mol) dicyclopentadiene and 0.7g phosphoric acid input are had in the four-hole boiling flask device of reflux condensing tube, logical shielding gas is warming up to the water of 80-100 ℃ of Dropwise 5 .4g (0.3mol), and hierarchy of control temperature is lower than 140 ℃; After water added, insulation 1.5-2h obtained dicyclopentadiene maleic acid half ester.Add 22.8g (0.3mol) propylene glycol again, 21.2g (0.2mol) glycol ether, 7.4g (0.05mol) Tetra hydro Phthalic anhydride, 29g (0.25mol) FUMARIC ACID TECH GRADE and 0.09g Resorcinol, on four-hole boiling flask, install fractional column and water trap additional, be warming up to 150 ℃, be warming up to 190-210 ℃ of dehydration esterification after insulation 0.5-1h finishes, control fractional column temperature≤105 ℃ is to reduce the loss of lower boiling dibasic alcohol.When acid number reaches about 70mgKOH/g, be cooled to 140 ℃ and add 5g tung oil, be warming up to again and continue reaction about 200-210 ℃; Esterification is diluted to the 75g styrene monomer that ℃ adding of acid number 28.6mgKOH/g postcooling to 120 is dissolved with the 0.05g Resorcinol, obtains the tung oil-modified DCPD type of xanchromatic unsaturated polyester product.Viscosity is 1430mPas, and number-average molecular weight is 1100.
Embodiment 2:
The add-on of tung oil is increased to 10g, and other is with embodiment 1 (summary).Final acid number is 22.4mgKOH/g, and viscosity is 1328mPas, and number-average molecular weight is 1100.
Embodiment 3:
The add-on of tung oil is increased to 15g, and other is with embodiment 1 (summary).Final acid number is 29.7mgKOH/g, and viscosity is 1315mPas, and number-average molecular weight is 1100.
Embodiment 4:
The add-on of tung oil is increased to 20g, and the vinylbenzene amount increases to 80g, and other is with embodiment 1 (summary).Final acid number is 30.6mgKOH/g, and viscosity is 1284mPas, and number-average molecular weight is 1400.
Embodiment 5:
The add-on of tung oil is increased to 25g, and the vinylbenzene amount increases to 80g, and other is with embodiment 1 (summary).Final acid number is 22.6mgKOH/g, and viscosity is 1226mPas, and number-average molecular weight is 1100.
Embodiment 6:
The add-on of tung oil is increased to 30g, and the vinylbenzene amount increases to 80g, and other is with embodiment 1 (summary).Final acid number is 33.9mgKOH/g, and viscosity is 868mPas, and number-average molecular weight is 1100.
Embodiment 7:
The add-on of tung oil is 20g, and the phthalic anhydride amount increases to 14.8g (0.1mol), the FUMARIC ACID TECH GRADE amount is reduced to 23.2g (0.2mol), and other is with embodiment 1 (summary).Final acid number is 31.2mgKOH/g, and viscosity is 1354mPas, and number-average molecular weight is respectively 1300.
Embodiment 8:
The add-on of tung oil is 20g, and the phthalic anhydride amount increases to 22.2g (0.15mol), the FUMARIC ACID TECH GRADE amount is reduced to 17.4g (0.15mol), and other is with embodiment 1 (summary).Final acid number is 29.2mgKOH/g, and viscosity is 1328mPas, and number-average molecular weight is 1000.
Embodiment 9:
The add-on of tung oil is 20g, adds 9.3g (0.15mol) ethylene glycol, and the amount of propylene glycol is reduced to 11.4g (0.15mol), and other is with embodiment 1 (summary).Final acid number is 27.1mgKOH/g, and viscosity is 1430mPas, and number-average molecular weight is respectively 1100.
Embodiment 10:
Change catalyzer phosphoric acid into the 0.9g Witco 1298 Soft Acid, other is with embodiment 1 (summary).Final acid number is 30.5mgKOH/g, and viscosity is 1333mPas, and number-average molecular weight is 1000.
Embodiment 11:
Change catalyzer phosphoric acid into the 0.8g tosic acid, other is with embodiment 1 (summary).Final acid number is 23.7mgKOH/g, and viscosity is 1265mPas, and number-average molecular weight is 1000.
Embodiment 12:
Change hydroquinone of polymerization retarder into para benzoquinone, other is with embodiment 1 (summary).Final acid number is 25.8mgKOH/g, and viscosity is 1418mPas, and number-average molecular weight is 1000.
Embodiment 13:
Change hydroquinone of polymerization retarder into 2, the 6-di-tert-butyl methyl phenol, other is with embodiment 1 (summary).Final acid number is 26.7mgKOH/g, and viscosity is 1302mPas, and number-average molecular weight is 1000.
Embodiment 14-19:
Get each 10g of this embodiment 1-6 sample, add 0.2g methylethyl ketone peroxide and 0.1g cobalt naphthenate, mixing is coated on the tinplate sheet, and the sample post-processing temperature is 80 degree 30min.Acquisition has gloss, the good coating of cohesiveness, and this coating is water-fast, acid-proof alkaline is good.Carry out the film performance test then, the main curing performance index of embodiment 1-6 sample relatively sees Table 1.
The main curing performance index of table 1 embodiment 1-6 sample
| Test subject | Test method | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Gel time (min) | GB/T?7193-08 | 18.3 | 19.9 | 18.8 | 18.7 | 22.6 | 25.8 |
| Surface drying time (min) | GB?6753-86 | 55 | 50 | 50 | 45 | 50 | 40 |
| Do solid work the time (min) | GB/T?1728-79 | 120 | 130 | 120 | 110 | 130 | 110 |
| 80 ℃ of thermostabilitys (h) | GB/T?7193-08 | 4.5 | 3.5 | 3.5 | 3 | 3.5 | 3 |
| Sticking power (level) | GB/T?1720-79 | 2 | 1 | 1 | 2 | 2 | 2 |
| Snappiness (mm) | GB/T?6742-86 | 0.5 | 1 | 1 | 1 | 2 | 2 |
Embodiment 20-25:
Get each 100g of this embodiment 1-6 sample, add the new N that steams of 2g benzoyl peroxide and 2.5g, accelerine is cured film forming, and the sample post-processing temperature is 80 degree 2 hours, 150 degree 2 hours.The Main physical performance index of sample relatively see Table 2.As seen its physical index all satisfies the requirement of general universal resin film forming.
The Main physical performance index of table 2 embodiment 1-6 sample
| Test subject | Test method | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Tensile strength (MPa) | GB/T2568-95 | 60.2 | 56.8 | 54.2 | 53.3 | 46.7 | 46.9 |
| Modulus in tension (GPa) | GB/T2568-95 | 2.85 | 2.67 | 2.63 | 2.47 | 2.23 | 1.98 |
| Breaking ductility (%) | GB/T2568-95 | 3.9 | 4.2 | 4.8 | 4.9 | 5.7 | 6.8 |
| Flexural strength (MPa) | GB/T2570-95 | 110.1 | 116.1 | 117.7 | 125.4 | 126.1 | 125.1 |
| Bending elastic modulus (GPa) | GB/T2570-95 | 3.1 | 3.2 | 3.6 | 3.9 | 3.9 | 3.8 |
| Shock strength (KJ/m 2) | GB/T2571-95 | 10.1 | 10.0 | 10.7 | 9.1 | 8.7 | 9.5 |
| Heat-drawn wire (℃) | GB?1634-04 | 73.3 | 70.2 | 66.8 | 67.5 | 61.2 | 62.3 |
| Barcol hardness | GB?3854-83 | 38 | 36 | 32 | 37 | 29 | 26 |
The invention is not restricted to the foregoing description, content of the present invention is described all can implement and have described good result.
Claims (7)
1. a preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester is characterized in that, comprises the following steps:
The first step, press the following formula reaction:
In second step, than the stopper that adds dibasic alcohol, diprotic acid and convention amount again, on four-hole boiling flask, install fractional column and water trap additional by metering, be warming up to 150 ℃, insulation 0.5～1h is warming up to 190～210 ℃ of dehydration esterifications after the end, control fractional column temperature≤105 ℃;
The 3rd step, when acid number reaches 50～120mgKOH/g, be cooled to 120～180 ℃ by metering ratio adding tung oil, be warming up to 200～210 ℃ again and continue reaction, esterifications to acid number 25～40mgKOH/g postcooling to 100～120 ℃, add the vinylbenzene that is dissolved with stopper and dilute, being uniformly dispersed obtains product.
2. by the described preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1, it is characterized in that, add catalyzer 80～140 ℃ of reactions in oxygen-free environment in the described the first step, described catalyzer is any or several mixture that forms with any proportioning in phosphoric acid, Witco 1298 Soft Acid, the tosic acid.
3. by the described preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1, it is characterized in that described diprotic acid is FUMARIC ACID TECH GRADE or Tetra hydro Phthalic anhydride or both mixtures.
4. by the described preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1, it is characterized in that described dibasic alcohol is any or several mixture that forms with any proportioning in ethylene glycol, propylene glycol, the glycol ether.
5. by the described preparation method who utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1, it is characterized in that: described stopper is Resorcinol, para benzoquinone, 2, any in the 6-di-tert-butyl methyl phenol or several mixture that forms with any proportioning.
6. the tung oil-modified dicyclopentadiene type unsaturated polyester of the described preparation method's preparation that utilizes tung oil-modified dicyclopentadiene type unsaturated polyester of claim 1 is characterized in that general structure is:
Wherein, R
1For: HO-CH
2-CH
2-,
HO-CH
2-CH
2-O-CH
2-CH
2-, H-:R
2For :-CH
2-CH
2-,
-CH
2-CH
2-O-CH
2-CH
2-; R
3For :-CH=CH-,
R
4Tung oil glyceryl ester affixture for remainder; M, n be 〉=1 integer.
7. the described tung oil-modified dicyclopentadiene type unsaturated polyester of claim 6 is as unsaturated polyester coating with as the application of anticorrosion, insulation and binding agent.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087300A (en) * | 2011-10-31 | 2013-05-08 | 常州市华润复合材料有限公司 | Unsaturated polyester comprising glycerol monocarboxylate, and resin and application thereof |
| CN103122190A (en) * | 2013-02-01 | 2013-05-29 | 陕西宏业电工电子新材料有限公司 | Class-H insulation dry-type air-core reactor wire epoxy polyester low-solvent bonding paint and production method thereof |
| CN103614059A (en) * | 2013-11-20 | 2014-03-05 | 合肥工业大学 | Preparation method of aqueous tung oil/acrylic resin insulating paint |
| 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 |
| CN105418902A (en) * | 2015-12-29 | 2016-03-23 | 中国林业科学研究院林产化学工业研究所 | Tung oil base unsaturated co-ester resin for moulding compound, synthesis method and applications thereof |
| CN106750215A (en) * | 2016-12-21 | 2017-05-31 | 中国林业科学研究院林产化学工业研究所 | A kind of unsaturated polyester (UP) biological nano hybrid resin and its synthetic method and application |
| CN109369897A (en) * | 2018-10-25 | 2019-02-22 | 江门市长河化工实业集团有限公司 | Soya fatty acid is modified dicyclopentadiene type unsaturated polyester resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108060A (en) * | 1986-12-06 | 1988-07-13 | 北京师范大学 | Tung oil modified unsaturated polyester paint and synthesis method |
-
2011
- 2011-01-07 CN CN2011100021714A patent/CN102115534B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108060A (en) * | 1986-12-06 | 1988-07-13 | 北京师范大学 | Tung oil modified unsaturated polyester paint and synthesis method |
Non-Patent Citations (1)
| Title |
|---|
| 《化工时刊》 20071231 赵桂英 桐油改性不饱和聚酯树脂的研究 31-33 1-7 第21卷, 第12期 * |
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| CN103087300A (en) * | 2011-10-31 | 2013-05-08 | 常州市华润复合材料有限公司 | Unsaturated polyester comprising glycerol monocarboxylate, and resin and application thereof |
| CN103087300B (en) * | 2011-10-31 | 2014-07-23 | 常州市华润复合材料有限公司 | Unsaturated polyester comprising glycerol monocarboxylate, and resin and application thereof |
| CN103122190A (en) * | 2013-02-01 | 2013-05-29 | 陕西宏业电工电子新材料有限公司 | Class-H insulation dry-type air-core reactor wire epoxy polyester low-solvent bonding paint and production method thereof |
| CN103614059A (en) * | 2013-11-20 | 2014-03-05 | 合肥工业大学 | Preparation method of aqueous tung oil/acrylic resin insulating paint |
| CN103614059B (en) * | 2013-11-20 | 2016-01-06 | 合肥工业大学 | A kind of preparation method of water-based tung oil/acrylic resin insulation paint |
| 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 |
| CN105418902A (en) * | 2015-12-29 | 2016-03-23 | 中国林业科学研究院林产化学工业研究所 | Tung oil base unsaturated co-ester resin for moulding compound, synthesis method and applications thereof |
| CN106750215A (en) * | 2016-12-21 | 2017-05-31 | 中国林业科学研究院林产化学工业研究所 | A kind of unsaturated polyester (UP) biological nano hybrid resin and its synthetic method and application |
| CN106750215B (en) * | 2016-12-21 | 2019-03-05 | 中国林业科学研究院林产化学工业研究所 | A kind of unsaturated polyester (UP) biological nano hybrid resin and its synthetic method and application |
| CN109369897A (en) * | 2018-10-25 | 2019-02-22 | 江门市长河化工实业集团有限公司 | Soya fatty acid is modified dicyclopentadiene type unsaturated polyester resin |
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