CN101250256B - Method for synthesizing unsaturated polyester resin - Google Patents
Method for synthesizing unsaturated polyester resin Download PDFInfo
- Publication number
- CN101250256B CN101250256B CN2008100471663A CN200810047166A CN101250256B CN 101250256 B CN101250256 B CN 101250256B CN 2008100471663 A CN2008100471663 A CN 2008100471663A CN 200810047166 A CN200810047166 A CN 200810047166A CN 101250256 B CN101250256 B CN 101250256B
- Authority
- CN
- China
- Prior art keywords
- acid
- unsaturated polyester
- organic
- oil
- polyester resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a process for synthesizing unsaturated polyester resin with renewable vegetable fat, which comprises generating acid ester through conducting alcoholysis reaction for vegetable oil and organic polyatomic alcohol, using as modified dihydric alcohol and being leading to the typical synthesis formulation of unsaturated polyester resin, completely replacing conventional dihydric alcohol, using for synthesizing unsaturated polyester, and then mixing with cross-linking monomer. The resin which is synthesized has excellent hue, appropriate viscosity, excellent heat stability, favorable alkali resistivity, wonderful flexible property and low shrinking rate, which is suitable for various composite material shaping technology such as hand lay-up, winding and spraying and the like. Renewable raw material of vegetable oil with cheap price is applied in the synthesis process of the invention, and the stability of product is excellent.
Description
Technical field
The present invention relates to the high molecular polymer technical field, the method for the synthetic unsaturated polyester resin of particularly a kind of renewable vegetables oil.
Background technology
In recent years, it is the highest that synthetic resins has become output, the synthetic materials that has the call; Wherein unsaturated polyester resin is that consumption is maximum in the thermosetting resin, and unsaturated polyester resin mainly is to improve resin formula at present, produces the resin with specific function; Widen its Application Areas; But these all are the raw materials of using chemical industry, and resin synthetic cost is higher relatively, also wastes resource.Therefore, practice thrift cost, utilize renewable resources to become current development trend.
Chinese patent CN1283645A discloses and has been entitled as " method of manufacture of unsaturated polyester and unsaturated polyester resin constituent "; This method with polyethylene terephthalate (PET) depolymerization, is added maleic anhydride to depolymerization product with polyvalent alcohol, makes their interreactions; Dicyclopentadiene is added in the reaction mixture; Addition reaction takes place, in the reaction product that obtains, add polyvalent alcohol and polyprotonic acid then, polycondensation takes place.This method also discloses the unsaturated polyester resin compositions that contains unsaturated polyester and polymerizable unsaturated monomer, and the moulding compound that contains unsaturated polyester resin compositions.This method has been used depleted PET and has been prepared unsaturated polyester resin, and synthetic cost is reduced.
Chinese patent CN1283684C discloses and has been entitled as " epoxy ester resin of improvement and preparation method "; This method is with cis-butenedioic anhydride vegetables oil, dehydration apple cis-butenedioic anhydride resin modified epoxy resin; Conjugated double bond and cis-butenedioic anhydride in the main appliable plant fatty acid oil chain carry out the Deils-Alder addition reaction, and the cis-butenedioic anhydride vegetables oil of gained carries out esterification with epoxy resin again.This method has mainly been used the characteristic of the two keys on the vegetable fatty chain, modified epoxy.
In " coating process " book, mention and come modified alkyd resin with Vegetable oil lipoprotein; The alcoholysis method manufacturing Synolac that relates to carries out glycerolysis reaction with oil and obtains the primary product monoglyceride; It is regarded as fatty acid modified divalent alcohol, with phthalic acid prepared in reaction Synolac.The present invention then is with reference to this kind method; Vegetables oil and polyvalent alcohol are carried out transesterification reaction; Obtain principal product one acid esters; In typical unsaturated polyester resin composition of raw materials, introduce this kind acid esters, replace conventional divalent alcohol fully, with the synthetic a kind of novel unsaturated polyester resin of unsaturated acid anhydride reactant.
Summary of the invention
Technical problem to be solved by this invention is: the method for the synthetic unsaturated polyester resin of a kind of renewable vegetables oil is provided, but the excellent resin of this method processability, and production cost can reduce.
The technical solution adopted for the present invention to solve the technical problems is: carry out alcoholysis reaction by renewable vegetables oil and organic polyhydric alcohol and generate an acid esters; It is regarded as the divalent alcohol of modification and introduces in the synthesis technique of unsaturated polyester resin; Substitute conventional divalent alcohol fully; Synthetic unsaturated polyester mixes with linking agent then, obtains unsaturated polyester resin.In mass, this resin is processed by renewable vegetables oil 30～70%, organic polyhydric alcohol 15～40%, organic unsaturated acid or acid anhydrides 8～30%, organic saturated acid or acid anhydrides 5～30%, catalyzer 0.005～0.5%, stopper 0.001～0.1% and linking agent 25～50%.
The present invention can make stable unsaturated polyester resin, and conversion unit is synthetic identical with conventional unsaturated polyester.Compared with prior art, prepared unsaturated polyester resin has following main advantage:
One of which. excellent performance: the hardness of this resin, tensile strength and flexural strength are better, and color and luster is good, viscosity is moderate, and Heat stability is good, alkali resistance is better, flexility is good (seeing table 1 and table 2).
They are two years old. and adopting the renewable resources Vegetable oil lipoprotein is raw material, has reduced production cost greatly.
They are three years old. and synthesis technique is simple, and cure shrinkage is lower.
They are four years old. and application prospect is good: can be used for the manufacturing of the toughness reinforcing and atom ash goods of other brittle resin, be fit to various composite material process plannings such as hand paste, winding and injection.
Embodiment
The compound method of unsaturated polyester resin provided by the invention; Specifically be to carry out alcoholysis reaction by renewable vegetables oil and organic polyhydric alcohol to generate an acid esters; It is regarded as the divalent alcohol of modification and introduces in the synthesis technique of unsaturated polyester resin alternative fully conventional divalent alcohol, synthetic unsaturated polyester; Mix with linking agent then, obtain unsaturated polyester resin.In mass, described unsaturated polyester resin is processed by renewable vegetables oil 30～70%, organic polyhydric alcohol 15～40%, organic unsaturated acid or acid anhydrides 8～30%, organic saturated acid or acid anhydrides 5～30%, catalyzer 0.005～0.5%, stopper 0.001～0.1% and linking agent 25～50%.
The compound method of unsaturated polyester resin provided by the invention, can adopt the method that may further comprise the steps:
(1) batching: take by weighing renewable vegetables oil, organic polyhydric alcohol, organic unsaturated acid or acid anhydrides, organic saturated acid or acid anhydrides, catalyzer, stopper and linking agent by prescription;
(2) alcoholysis, polycondensation: drop into renewable vegetables oil, the pure and mild catalyzer of organic multicomponent to reaction kettle, charging into N
2Stir under the situation of protection; And under 200～240 ℃ of temperature alcoholysis reaction 0.5～1.5h; Then the alcoholysis reaction temperature is reduced to 160～200 ℃ gradually, add organic unsaturated acid or acid anhydrides, organic saturated acid or acid anhydrides again, keep this temperature 3.5～5h to carry out polycondensation; When acid number reaches 40～60mgNaOH/g, be the polycondensation terminal point, add stopper at last;
(3) dilution: after the polycondensation, make temperature drop to 120～130 ℃, again with the linking agent blend, stirring is cooled to room temperature, promptly obtains unsaturated polyester resin.
Described organic polyhydric alcohol can adopt a kind of in TriMethylolPropane(TMP), USP Kosher, the tetramethylolmethane, or multiple.
Described organic unsaturated acid or acid anhydrides can adopt a kind of in vinylformic acid, maleic acid or acid anhydrides, FUMARIC ACID TECH GRADE, methylacrylic acid, fumaric acid, citraconic acid, methylene-succinic acid, propene dicarboxylic acid and the methyl-maleic acid, or multiple.
Described organic saturated acid can adopt a kind of in hexanodioic acid, m-phthalic acid, Tetra hydro Phthalic anhydride, terephthalic acid, oxalic acid, Succinic Acid, hydrogenation phthalic anhydride and the tetrachlorophthalic anhydride, or multiple.
Described catalyzer can adopt a kind of in Lithium Hydroxide MonoHydrate, calcium hydroxide, sodium hydroxide, yellow soda ash, Pottasium Hydroxide, sodium hydrogencarbonate and the plumbous oxide, or multiple.
Described stopper can adopt a kind of in quinhydrones, benzoquinones, naphthoquinones, Resorcinol, quaternary ammonium salt, tert-butyl catechol and the t-butyl catechol, or multiple.
Described linking agent can adopt vinylbenzene, Benzene Chloride ethene, 2, a kind of in 5-Dowspray 9, Vinyl toluene, Phthalic acid, diallyl ester, methylacrylic acid and the methacrylic ester, or multiple.
Described renewable vegetables oil can adopt a kind of in Oleum Cocois, Semen Maydis oil, tung oil, Viscotrol C, oleum lini, soya-bean oil, synourin oil, peanut oil, sunflower seed oil, rapeseed oil and the plam oil, or multiple.
The vegetables oil that the present invention uses can adopt the refined plant oil that produces all over China; It is the mixture that mixes sweet three esters; The lipid acid kind, carbon chain lengths, degree of unsaturation (two keys what) and the geometric configuration that constitute sweet three esters are all inequality; Composition is very complicated, and the general structure of vegetables oil staple can be expressed as usually:
Wherein: R is the carbochain of about 14～20 carbon atoms, and it has a plurality of pairs of keys or conjugated double bond, does not perhaps contain two keys or conjugated double bond.Because the fatty acid group in the fatty acid triglycercide molecule is different, uses R, R ' and R respectively " distinguish.
The compound method of unsaturated polyester resin provided by the invention, its composition principle is: at first Vegetable oil lipoprotein is carried out alcoholysis reaction and obtain an acid esters, for example carry out alcoholysis reaction with USP Kosher, reaction expression is following:
Vegetables oil and USP Kosher 200～240 ℃ with catalyzer in the presence of the generation lipid acid the effect of redistributing.The alcoholysis operation is a critical step in the unsaturated polyester building-up process; It affects the distribution of the molecular structure and the molecular weight of unsaturated polyester; The purpose of alcoholysis reaction is to process the fatty ester of glycerine, mainly is monoglyceride, and we regard it as fatty acid modified divalent alcohol; With monoglyceride and commonly used acid anhydrides such as MALEIC ANHYDRIDE, the synthetic unsaturated polyester resin of phthalic anhydride, the condensation polymerization reaction expression of vibrin is following then:
Wherein: m, n represent the polymerization degree, m=10～30, n=10～30; R representes fatty acid carbon chain, can be CH
3(CH
2)
7CH=CH (CH
2)
7-.The cardinal principle of reaction is two hydroxyls and the anhydride reaction of using in fatty acid glycerine one ester, and does not relate to two keys and the reaction of other group on the fatty acid carbon chain.Because the activity of MALEIC ANHYDRIDE is strong than Tetra hydro Phthalic anhydride; In building-up process, at first generate the polyester of MALEIC ANHYDRIDE; Carry out to a certain degree when polycondensation, just begin to generate the polyester of Tetra hydro Phthalic anhydride, when reaction continues deeply; Be mainly the block polymerization chain of the polyester of MALEIC ANHYDRIDE formation in the middle part of having formed, end capped long-chain macromolecule is carried out by the polyester that Tetra hydro Phthalic anhydride forms in two ends.
Below in conjunction with embodiment the present invention is described further, but does not limit the present invention.
Embodiment 1: according to the mass fraction, with oleum lini 60%, USP Kosher 17% drops in the reaction kettle with calcium hydroxide 0.05%, is charging into N
2Situation under violent stirring, under 220 ℃ of temperature, react 0.5～1.5h, temperature of reaction is reduced to 160 ℃～200 ℃ gradually; Add MALEIC ANHYDRIDE 10% again; Tetra hydro Phthalic anhydride 12.95% keeps this temperature 3.5～5h, and the acid number of system reaches and is reaction end about 50mgNaOH/g; When cooling to 120 ℃～130 ℃ and an amount of vinylbenzene blend, stirring is cooled to room temperature, promptly obtains unsaturated polyester resin.
Embodiment 2: according to the mass fraction, with Viscotrol C 50%, USP Kosher 15% drops in the reaction kettle with Lithium Hydroxide MonoHydrate 0.1%, is charging into N
2Situation under violent stirring, under 210 ℃ of temperature, react 1～1.5h, add MALEIC ANHYDRIDE 15% again, Tetra hydro Phthalic anhydride 19.9%, all the other are basically with embodiment 1.
Embodiment 3: according to the mass fraction, with peanut oil 55%, tetramethylolmethane 18% drops in the reaction kettle with sodium hydrogencarbonate 0.08%, is charging into N
2Situation under violent stirring, under 200 ℃～220 ℃ temperature, react 0.5～2h, continue to add MALEIC ANHYDRIDE 20%, Tetra hydro Phthalic anhydride 6.92%, all the other are basically with embodiment 1.
Subordinate list
The typical quality index of institute's synthetic resins is following in each instance of table 1:
The typical mechanical performance index of table 2 synthetic resins casting matrix is following:
| Index | Numerical value | Testing standard |
| Tensile strength (MPa) | 55 | GB/T2568-1995 |
| Modulus in tension (MPa) | 3000 | GB/T2568-1995 |
| Flexural strength (MPa) | 107 | GB/T2570-1995 |
| Bending elastic modulus (MPa) | 3400 | GB/T2570-1995 |
Claims (7)
1. the compound method of a unsaturated polyester resin; It is characterized in that carrying out alcoholysis reaction by renewable vegetables oil and organic polyhydric alcohol generates an acid esters; It is regarded as the divalent alcohol of modification and introduces in the synthesis technique of unsaturated polyester resin alternative fully conventional divalent alcohol, synthetic unsaturated polyester; Mix with linking agent then; Obtain unsaturated polyester resin, in mass, this resin is processed by renewable vegetables oil 30～70%, organic polyhydric alcohol 15～40%, organic unsaturated acid or acid anhydrides 8～30%, organic saturated acid or acid anhydrides 5～30%, catalyzer 0.005～0.5%, stopper 0.001～0.1% and linking agent 25～50%; A kind of in wherein said employing Oleum Cocois, Semen Maydis oil, tung oil, Viscotrol C, oleum lini, soya-bean oil, synourin oil, peanut oil, sunflower seed oil, rapeseed oil and the plam oil, or multiple;
Said unsaturated polyester resin adopts the method that may further comprise the steps:
(1) batching: take by weighing renewable vegetables oil, organic polyhydric alcohol, organic unsaturated acid or acid anhydrides, organic saturated acid or acid anhydrides, catalyzer, stopper and linking agent by prescription;
(2) alcoholysis, polycondensation: drop into renewable vegetables oil, the pure and mild catalyzer of organic multicomponent to reaction kettle, charging into N
2Stir under the situation of protection; And under 200～240 ℃ of temperature alcoholysis reaction 0.5～1.5h; Then the alcoholysis reaction temperature is reduced to 160～200 ℃ gradually, add organic unsaturated acid or acid anhydrides, organic saturated acid or acid anhydrides again, keep this temperature 3.5～5h to carry out polycondensation; When acid number reaches 40～60mgNaOH/g, be the polycondensation terminal point, add stopper at last;
(3) dilution: after the polycondensation, make temperature drop to 120～130 ℃, again with the linking agent blend, stirring is cooled to room temperature, promptly obtains unsaturated polyester resin.
2. compound method according to claim 1 is characterized in that organic polyhydric alcohol adopts a kind of in TriMethylolPropane(TMP), USP Kosher, the tetramethylolmethane, or multiple.
3. compound method according to claim 1; It is characterized in that described organic unsaturated acid or acid anhydrides; It adopts a kind of in vinylformic acid, maleic acid or acid anhydrides, FUMARIC ACID TECH GRADE, methylacrylic acid, fumaric acid, citraconic acid, methylene-succinic acid, propene dicarboxylic acid and the methyl-maleic acid, or multiple.
4. compound method according to claim 1 is characterized in that organic saturated acid adopts a kind of in hexanodioic acid, m-phthalic acid, Tetra hydro Phthalic anhydride, terephthalic acid, oxalic acid, Succinic Acid, hydrogenation phthalic anhydride and the tetrachlorophthalic anhydride, or multiple.
5. compound method according to claim 1 is characterized in that catalyzer adopts a kind of in Lithium Hydroxide MonoHydrate, calcium hydroxide, sodium hydroxide, yellow soda ash, Pottasium Hydroxide, sodium hydrogencarbonate and the plumbous oxide, or multiple.
6. compound method according to claim 1 is characterized in that stopper adopts a kind of in quinhydrones, benzoquinones, naphthoquinones, Resorcinol, quaternary ammonium salt, tert-butyl catechol and the t-butyl catechol, or multiple.
7. compound method according to claim 1 is characterized in that linking agent adopts vinylbenzene, Benzene Chloride ethene, 2, a kind of in 5-Dowspray 9, Vinyl toluene, Phthalic acid, diallyl ester, methylacrylic acid and the methacrylic ester, or multiple.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100471663A CN101250256B (en) | 2008-03-28 | 2008-03-28 | Method for synthesizing unsaturated polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100471663A CN101250256B (en) | 2008-03-28 | 2008-03-28 | Method for synthesizing unsaturated polyester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101250256A CN101250256A (en) | 2008-08-27 |
| CN101250256B true CN101250256B (en) | 2012-07-04 |
Family
ID=39953872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100471663A Active CN101250256B (en) | 2008-03-28 | 2008-03-28 | Method for synthesizing unsaturated polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101250256B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836563A (en) * | 2017-11-29 | 2019-06-04 | 北京旭阳科技有限公司 | A kind of preparation method of the unsaturated polyester resin containing glycerol monomethyl ether unit |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120121839A1 (en) * | 2009-03-25 | 2012-05-17 | Marian Henryk Szkudlarek | Process for preparing unsaturated polyester |
| CN101747608A (en) * | 2009-12-11 | 2010-06-23 | 上海新天和树脂有限公司 | Dicyclopentadiene-type unsaturated polyester mould pressing resin as well as preparation method and application thereof |
| CN102417749B (en) * | 2011-11-18 | 2014-06-04 | 天长市通天化工有限责任公司 | Environmentally friendly putty |
| CN102504635B (en) * | 2011-11-18 | 2014-06-04 | 天长市通天化工有限责任公司 | Preparation method of environment-friendly putty |
| CN104086756A (en) * | 2014-07-28 | 2014-10-08 | 营口康辉石化有限公司 | Production method of optical transparent film-level polyester |
| CN104946102B (en) * | 2015-07-23 | 2017-09-08 | 安吉祺隆新型建材有限公司 | A kind of preparation method of coating |
| CN104962183A (en) * | 2015-07-30 | 2015-10-07 | 浙江乔兴建设集团有限公司 | Brushing method of functional environment-friendly paint |
| CN106748767B (en) * | 2015-11-19 | 2020-03-17 | 中国石油化工股份有限公司 | Low-hydroxyl-value vegetable oil-based polyol and preparation method thereof |
| CN105418902B (en) * | 2015-12-29 | 2017-07-18 | 中国林业科学研究院林产化学工业研究所 | A kind of tung oil base unsaturation ester resin and its synthetic method and the application altogether of moulding compound |
| CN106589338A (en) * | 2016-12-12 | 2017-04-26 | 衡阳山泰化工有限公司 | Unsaturated polyester resin used for coating and preparing method thereof |
| CN106866951A (en) * | 2017-02-03 | 2017-06-20 | 江苏赛鑫树脂有限公司 | A kind of special unsaturated polyester resin of atomized ash and preparation method thereof |
| CN107141460B (en) * | 2017-06-12 | 2019-03-19 | 浙江大学 | The synthetic method of one vegetable oil based thermoplastic polyester |
| CN107254021A (en) * | 2017-06-20 | 2017-10-17 | 江苏锐康新材料科技有限公司 | A kind of regenerating and modifying method of thermosetting unsaturated polyester resin waste |
| CN108300199B (en) * | 2017-08-29 | 2020-03-20 | 金晨粉末涂料（江苏）有限公司 | Powder coating for engineering machinery and preparation method thereof |
| CN108587100A (en) * | 2018-05-18 | 2018-09-28 | 深圳永昌和科技有限公司 | Environment and human body friendly vegetable oil base ultraviolet light cure 3D printing resin |
| CN110105552B (en) * | 2019-04-19 | 2021-09-14 | 广东大盈新材料科技有限公司 | Biomass environment-friendly polyester polyol and preparation method thereof |
| CN110511364A (en) * | 2019-07-30 | 2019-11-29 | 曹建康 | A kind of preparation method of high density type gutter oil unsaturated polyester material |
| CN111040141B (en) * | 2019-11-22 | 2022-04-19 | 山东齐鲁漆业有限公司 | Water-based alkyd resin and application thereof |
| CN112831038A (en) * | 2020-12-14 | 2021-05-25 | 山东奔腾漆业股份有限公司 | Modified alkyd resin and preparation method and application thereof |
| CN114031470A (en) * | 2021-12-14 | 2022-02-11 | 新洋丰农业科技股份有限公司 | Preparation method of alkyd resin controlled-release fertilizer |
-
2008
- 2008-03-28 CN CN2008100471663A patent/CN101250256B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| JP平9-255738A 1997.09.30 |
| N. Dutta etc..Synthesis and characterization of polyester resins based onNahar seed oil.Progress in Organic Coatings49 2.2004,49(2),146-152. |
| N. Dutta etc..Synthesis and characterization of polyester resins based onNahar seed oil.Progress in Organic Coatings49 2.2004,49(2),146-152. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836563A (en) * | 2017-11-29 | 2019-06-04 | 北京旭阳科技有限公司 | A kind of preparation method of the unsaturated polyester resin containing glycerol monomethyl ether unit |
| CN109836563B (en) * | 2017-11-29 | 2021-02-19 | 北京旭阳科技有限公司 | Preparation method of unsaturated polyester resin containing glycerol monomethyl ether unit |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101250256A (en) | 2008-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101250256B (en) | Method for synthesizing unsaturated polyester resin | |
| Lyu et al. | Natural-sourced benzoxazine resins, homopolymers, blends and composites: A review of their synthesis, manufacturing and applications | |
| CN102702480B (en) | Modified epoxy acrylate and preparation method thereof | |
| España et al. | Properties of biobased epoxy resins from epoxidized soybean oil (ESBO) cured with maleic anhydride (MA) | |
| CN101153072B (en) | Method for producing modified unsaturated polyester resins by low purity technical grade dicyclopentadiene | |
| CN101735405B (en) | Imitation marble unsaturated polyester resin and preparation method thereof | |
| CN110128611B (en) | Low-temperature curing bio-based benzoxazine resin and preparation method thereof | |
| CN101280056B (en) | Method for preparing C21dicarboxylic acid polyamide epoxy hardener from methyl eleostearate | |
| CN104892858A (en) | High biomass content epoxy resin composition, and curing method and applications thereof | |
| Warth et al. | Polyester networks based upon epoxidized and maleinated natural oils | |
| CN111978444B (en) | Organic polyacid-based photocuring resin and preparation method and application thereof | |
| CN111100454A (en) | Low-dielectric high-strength glass fiber reinforced bio-based PA material and preparation method thereof | |
| CN103159946A (en) | Silicon resin modified unsaturated polyester resin and preparation method thereof | |
| CN104031205B (en) | A kind of bio-based Cured up resin and preparation method thereof | |
| CN102115534B (en) | Dicyclopentadiene type unsaturated polyester modified by tung oil, and preparation method and application thereof | |
| CN110950823B (en) | Vegetable oil-based fatty acid epoxy monomer and preparation method thereof | |
| CN102533071A (en) | Insulating paint for motor elements and electronic products | |
| CN105418902A (en) | Tung oil base unsaturated co-ester resin for moulding compound, synthesis method and applications thereof | |
| CN105418903B (en) | One kind is without colophony type high solid alkyd resin and preparation method thereof | |
| CN107189370A (en) | Off-course brake is every pad and preparation method thereof | |
| CN110527266A (en) | A method of improving unsaturated polyester resin glass-reinforced plastic material pultrusion | |
| CN102994033B (en) | Polyester adhesive | |
| CN104761892A (en) | Nylon composite material with strong acid and alkali corrosion resistance and preparation method thereof | |
| CN101230131B (en) | Method for preparing thickenable dicyclopentadiene unsaturated polyester resin | |
| Sankar lal et al. | Recent advances in bio-based sustainable aliphatic and aromatic epoxy resins for composite applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150925 Address after: 430400 Hubei province Dongxihu District of Wuhan City Road No. 2 Zhang Patentee after: WUHAN KEDA MARBLE PROTECTIVE MATERIALS Co.,Ltd. Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122 scientific research department of Wuhan University of Technology Patentee before: Wuhan University of Technology |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230829 Address after: No. 6 Danjin Road, Industrial Concentration Zone, Baita Town, Jintan District, Changzhou City, Jiangsu Province, 213299 Patentee after: Jiangsu Hercules Marble Care Materials Co.,Ltd. Address before: No. 2 Zhangbai Road, Dongxihu District, Wuhan City, Hubei Province, 430400 Patentee before: WUHAN KEDA MARBLE PROTECTIVE MATERIALS Co.,Ltd. |