CN101941956A - Glycidyl ether ester with carbon-carbon double bond, synthetic method and use thereof - Google Patents
Glycidyl ether ester with carbon-carbon double bond, synthetic method and use thereof Download PDFInfo
- Publication number
- CN101941956A CN101941956A CN2010102348529A CN201010234852A CN101941956A CN 101941956 A CN101941956 A CN 101941956A CN 2010102348529 A CN2010102348529 A CN 2010102348529A CN 201010234852 A CN201010234852 A CN 201010234852A CN 101941956 A CN101941956 A CN 101941956A
- Authority
- CN
- China
- Prior art keywords
- carbon
- double bond
- carbon double
- racemic glycidol
- glycidol ether
- 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.)
- Pending
Links
- 0 *C(C(C(OC(*)(C1OC1)N)=O)=C)C(OC(*)(*)C1OC1)=O Chemical compound *C(C(C(OC(*)(C1OC1)N)=O)=C)C(OC(*)(*)C1OC1)=O 0.000 description 2
Images
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a glycidyl ether ester compound with a carbon-carbon double bond in a molecular structure, a synthetic method and an application in the preparation of novel water-based epoxy vinyl ester-modified epoxy resin emulsion. The synthetic method comprises the steps of adopting a hydroxy epoxy compound and carbon-carbon unsaturated diacid as raw materials, and carrying out two-step continuous reaction to prepare unsaturated glycidyl ether ester, has the advantages of simple synthetic operation, high efficiency, good safety and the like, and can avoid the high operation risk which is easily caused by on-site oxidation of an organic peroxide and epoxide enol ester in the prior art. The obtained glycidyl ether ester compound with the carbon-carbon double bond has good compatibility with epoxy resin, unsaturated polyester, bismaleimide and other matrix resins, and the carbon-carbon double bond and a reactive epoxy group can improve the chemical cross-linking density, be used as components of the formula of the epoxy vinyl ester-modified water-based epoxy resin emulsion and be used in surface sizing of carbon fiber and manufacturing engineering of the carbon fiber.
Description
Technical field
The invention belongs to functional compounds and organic functional material field, be particularly related to the Racemic glycidol ether ester compound that has carbon carbon unsaturated double-bond structure in a kind of molecular structure, can be synthetic through the multistep chemical reaction by initially set out raw material unsaturated dibasic acid and glycidyl ether, the Racemic glycidol ether-ether with carbon-carbon double bond of gained can be used as the function ingredients of novel aqueous epoxy resin latex prescription, and the aqueous epoxy resin emulsion that contains unsaturated glycidyl ether component that further prepares gained can be used as the novel carbon fiber sizing agent and uses.
Background technology
At present, with high-performance fiber (carbon fiber, high-strength glass fibre, aramid fiber, superhigh molecular weight polyethylene fibers etc.) serve as the fiber-reinforced polymeric resin based composites that strengthens body have low density, high specific strength, high-modulus, corrosion-resistant, be easy to the mechanical structure spare that integrated machine-shaping is complicated shape, become the key project material of industry developments such as Aeronautics and Astronautics, new forms of energy, advanced manufacturing, nuclear industry.Practical application request according to fiber-reinforced resin matrix compound material, the volume fraction of fortifying fibre reaches (" matrix material handbook benefit Xiao Su, Du Shanyi, Zhang Litong work more than 50%, Chemical Industry Press), therefore at enhancing body fiber/resin matrix interface that the internal structure of matrix material will produce huge specific surface area, the integrated situation of its interface structure and fiber/resin matrix is the apparent over-all properties of left and right sides fiber-reinforced resin matrix compound material greatly, also will restrict the final application of matrix material.In the machining process of carbon fiber preparation and carbon fiber-reinforced resin composite materials, because the fragility and the surface inertness of carbon fiber self, the nascent carbon fibre tow that obtains after the high temperature cabonization technology need carry out surface oxidation modification and surperficial starching, make up polymer-modified coating at carbon fiber surface, improve the snappiness of carbon filament, convergency, open fibre, expanding, fibre properties such as static resistance, simultaneously can be by the design of carbon fiber starching coating structure, the resin matrix consistency of regulation and control carbon fibre fabric member, wetting and wetting property makes up new interface and realizes the effective transmission of matrix material load to fortifying fibre.Therefore, the surperficial starching coating of high-performance carbon fibre and the interface structure of generated in-situ fiber-reinforced resin matrix compound material will become the key that restricts carbon fibre reinforced composite design, machine-shaping and practical application.
In carbon fiber enhancement resin base composite material is used, at present domestic and international Resins, epoxy (EP), unsaturated polyester (UP), bismaleimides (BMI), polyimide (PI) is comparatively general as the application of polymeric matrix, wherein because the low manufacturing cost of Resins, epoxy, chemical structure diversity and the material property that solidifies the back excellence, the epoxy resin base carbon fiber reinforced composite is in aviation, space flight and hi-tech industry are used widely, therefore research both at home and abroad at present, the carbon fiber sizing agent agent structure of using also is feature with Resins, epoxy, and the green cleaner production demand of adaptation carbon fiber manufacturing industry, what external carbon fiber sizing agent had been developed to VOC free by organic solvent type is the emulsion-type sizing agent of dispersion medium with water, and domestic research and application report are still fewer.Recently, Chinese patent CN101736593A reported with Resins, epoxy, polyglycol surfactants, water-soluble organic curing agent etc. and has been the aqueous epoxy resins carbon fiber sizing agent preparation method of main recipe ingredient, but reactive low between the outwardness preparation process complexity, prescription main ingredient, adopt the polyethet surfactant component to cause degradation problem under the composite structure humidity resistance easily in a large number.
On the other hand, the important low cost of a big class, the polymeric matrix of high performance-price ratio fibre reinforced composites have been developed at present to contain the unsaturated polyester that carbon-carbon double bond is a constitutional features (UP), its resin is characterized as and contains a large amount of carbon carbon unsaturated link(age)s, be convenient to further solidify after the premolding, obtaining increasingly extensive application.In order to realize strengthening consistency good between body carbon fiber surface starching layer and the unsaturated polyester matrix resin and later stage curing cross-linked intensity, necessary research and development, application can be formed carbon fiber sizing agent towards the new texture that unsaturated polyester matrix resin is used.World patent WO2009/140087A2 and U.S. Pat 6329475B1 have reported the epoxy vinyl resin of DERAKANE trade mark, and are used to make large size fibre reinforced composites blade of wind-driven generator as unsaturated polyester.In addition, Chinese patent CN200810036708.7 discloses a kind of preparation method of air-dry type oxirene ester resin, adopting (methyl) vinylformic acid, bisphenol A epoxide resin, dicyclopentadiene, fumaric acid etc. is main synthesis material, in the presence of catalyzer and stopper, prepared in reaction epoxy unsaturated polyester.In the above-mentioned epoxy vinyl resin preparation process, all need to dilute the full-bodied epoxy unsaturated polyester of gained as the low viscosity reactive diluent, to obtain the rosin products that viscosity is fit to final application requiring with liquid phenenyl vinyl monomer under the normal temperature of 30～50% content.Yet, the existence of a large amount of high volatile volatiles, low polar vinylbenzene thinner, objectively make the high hydrophobicity epoxy unsaturated polyester of above method gained be difficult to be applied to prepare the unsaturated polyester modified carbon fiber in epoxy emulsion pasting agent of stabilized aqueous as the composition of effectively filling a prescription.
In order to realize preparing the unsaturated polyester modified epoxy resin latex of stable epoxy, improve the content of carbon carbon unsaturated double-bond in the sizing agent prescription and the chemically crosslinked of later stage composite material interface, the research and development that solve the novel carbon fiber sizing agent prepare a difficult problem, and the present invention will provide a kind of Racemic glycidol ether-ether, synthetic method with carbon-carbon double bond to reach as the preparation method of the modified epoxy type water-based carbon fiber sizing agent of recipe ingredient.In order to prepare unsaturated Racemic glycidol ether-ether, the clear 55-43082 of Japanese Patent discloses and a kind ofly has been the raw material that sets out with fumaric acid and vinylcarbinol, after over-churning obtains fumaric acid propylene alcohol ester intermediate, further in the presence of the oxygenant organo-peroxide, vinylcarbinol building block carbon-carbon double bond selective oxidation, epoxidation prepare fumaric acid 2-glycidyl ether-ether (FBG).In addition, U.S. Pat 4562274 provides above-mentioned oxidation, the purification of epoxidation reaction crude product, separation method.Yet the employing of organic peroxide catalyst and high toxicity vinylcarbinol raw material makes the danger of execute-in-place increase, and is difficult to adapt to a large amount of industrialized preparation demands, and the problems referred to above will be the targets of the present invention's solution of endeavouring.
Content of the present invention
One of purpose of the present invention aims to provide the glycidyl ether ester function compound that has carbon-carbon double bond in a kind of molecular structure.
Two of purpose of the present invention aims to provide chemosynthesis, the preparation method of the glycidyl ether ester function compound that has carbon-carbon double bond in a kind of molecular structure.
Three of purpose of the present invention aims to provide the effective recipe ingredient of glycidyl ether ester function compound conduct with carbon-carbon double bond according to preparation method's gained of the present invention, prepares the method for novel epoxy vinyl acetate modified epoxy water-based emulsion sizing agent.
Four of purpose of the present invention is to provide the purposes of method gained novel epoxy vinyl acetate modified epoxy water-based emulsion sizing agent produced according to the present invention in the carbon fiber preparation.
Can represent by structural formula (1) or (2) according to the Racemic glycidol ether ester compound that has carbon-carbon double bond in a kind of molecular structure provided by the present invention:
R in its structural formula (1) and (2)
1, R
2Can be 1～4 saturated straight chain or branched-chain alkyl substituted radical for hydrogen atom (H) or carbonatoms, and R
1Can equal R
2R
3, R
3' can be hydrogen atom (H) or methyl substituted group, and R
3Can equal R
3'; R
4Can be 1～3 saturated straight chain or branched-chain alkyl substituted radical for hydrogen atom (H) or carbonatoms.
The Racemic glycidol ether ester compound that has carbon-carbon double bond in a kind of molecular structure shown in said structure formula (1) or (2) can prepare via the synthetic two step successive reactions synthetic, (two) unsaturated Racemic glycidol ether-ether of (one) unsaturated diacid chloride.
Synthesizing of the unsaturated diacid chloride of above-mentioned synthesis step (), the synthesis material of its reaction system is unsaturated diacid, sulfur oxychloride and stopper, and its reaction batching mass ratio is as follows:
Unsaturated diacid 14.9～4.0%
Sulfur oxychloride 85.0～95.0%
Stopper 0.1～1.0%,
According to a kind of synthetic method provided by the present invention, prepare the unsaturated diacid structural of raw material shown in molecular formula (3) or (4), wherein R with unsaturated diacid chloride of Racemic glycidol ether ester compound synthesis step () of carbon-carbon double bond
1, R
2Can be 1～4 saturated straight chain or branched-chain alkyl substituted radical for hydrogen atom (H) or carbonatoms, and R
1Can equal R
2R
4Can be 1～3 saturated straight chain or branched-chain alkyl substituted radical for hydrogen atom (H) or carbonatoms.Above-mentioned unsaturated diacid compounds can be fumaric acid, toxilic acid, furoate clothing or lemon acid etc.
According to a kind of synthetic method provided by the present invention with unsaturated diacid chloride of Racemic glycidol ether ester compound synthesis step () of carbon-carbon double bond, used stopper is Resorcinol, cuprous chloride, para benzoquinone or 2, the 6-ditertbutylparacresol, above-mentioned stopper can use separately, also can two kinds or use two or more the mixing with any proportioning.
Preparation method according to the unsaturated diacid chloride of above-mentioned synthesis step (), at first by proportioning raw materials unsaturated diacid, sulfur oxychloride and stopper being put in reactor for example has in the reaction unit of stirring, can adopt normal pressure at the uniform velocity to stir down the boiling point that progressively is heated to sulfur oxychloride, continue to keep the constant temperature back flow reaction 10～30 hours preferred reflux time 18～30 hours.The volatile acidic gaseous by-product that produces in the above-mentioned reaction can neutralize with alkaline solution absorption.After reaction finishes, can first underpressure distillation remove the sulfur oxychloride of excess reactant, and then underpressure distillation obtains having the unsaturated diacid chloride intermediate of carbon-carbon double bond, structure is suc as formula shown in (5) or (6).
According to a kind of preparation method with unsaturated Racemic glycidol ether-ether of Racemic glycidol ether ester compound synthesis step (two) of carbon-carbon double bond provided by the present invention, the synthesis material of reaction system is that the unsaturated diacid chloride of above-mentioned synthesis step () gained and hydroxyl epoxy compounds and acid are captured agent in-20～0 ℃ of organic solvent neutralization reaction 2～6 hours down.Described unsaturated diacid chloride, the hydroxyl epoxy compounds, the batching mol ratio that agent is captured in acid is recommended as 1.0: 1.8～and 3.0: 2.0～5.0, batching mol ratio at hydroxyl epoxy compounds and unsaturated diacid chloride is lower than at 2.0 o'clock, unsaturated diacid chloride compound reaction is insufficient, and when the batching mol ratio of hydroxyl epoxy compounds and unsaturated diacid chloride is higher than 3.0, the utilization ratio of hydroxyl epoxy compounds material is low, and cause the separation of crude product, purifying complex, therefore unsaturated diacid chloride, the hydroxyl epoxy compounds, the batching mol ratio that agent is captured in acid is preferably 1.0: 2.0～and 2.3: 2.0～2.5.
The above-mentioned middle solvent that uses of Racemic glycidol ether ester compound synthesis step (two) with carbon-carbon double bond is recommended as chloroparaffin, as methylene dichloride, ethylene dichloride, chloroform, trichloroethane etc., also can be tetrahydrofuran (THF), dioxane etc., preferred methylene dichloride, ethylene dichloride.The volumetric usage of above-mentioned solvent is recommended as 40～80% of reaction system cumulative volume, preferred 55～70% in the synthetic preparation.
According to a kind of preparation method provided by the present invention with unsaturated Racemic glycidol ether-ether of Racemic glycidol ether ester compound synthesis step (two) of carbon-carbon double bond, the hydroxyl epoxy compounds shown in structural formula (7), R in its structural formula
3, R
3' can be hydrogen atom (H) or methyl substituted group, and R
3Can equal R
3'.The hydroxyl epoxy compounds can for glycidyl ether, 3-methyl glycidyl ether or 3,3 '-dimethyl glycidyl ether etc.
The by-product hydrochloric acid that the agent purpose is capture reaction is captured in the above-mentioned middle acid of using of Racemic glycidol ether ester compound synthesis step (two) with carbon-carbon double bond, reduces the concentration of by product, fast reaction speed.It can be triethylamine, pyridine or picoline etc. that agent is captured in acid, preferred triethylamine.
According to a kind of preparation method provided by the present invention with unsaturated Racemic glycidol ether-ether of Racemic glycidol ether ester compound synthesis step (two) of carbon-carbon double bond, recommending at first hydroxyl epoxy compounds, acid to be captured agent and solvent joins in the reaction unit that has prolong and stirring, in cryosel is bathed, but the limit is stirred the unsaturated diacid chloride intermediate of synthesis step () preparation gained is added drop-wise in the above-mentioned reaction unit slowly, after dropwising, continue to keep reaction more than 2 hours.Stopped reaction then, the filtering reaction mixed solution is removed insolubles, and gained solution can be through repeatedly washing, and recrystallization, separation, drying obtain suc as formula the Racemic glycidol ether ester compound that has carbon-carbon double bond shown in (1) or (2) in the solvent.
Method according to novel epoxy vinyl acetate modified epoxy water-based emulsion sizing agent provided by the present invention, with the Racemic glycidol ether ester compound with carbon-carbon double bond of above-mentioned synthetic gained as the epoxy resin modification component, by following material proportion mass fraction, according to the aqueous epoxy resin emulsion preparation technology method of generally openly knowing (preparation and the application of special emulsion chemical " milk sap and emulsifying technology newly use-", burnt wink, the He Mingbo chief editor, Chemical Industry Press, 2005), by phase inversion point method, the high speed shear dispersion and emulsion prepares novel epoxy vinyl acetate modified epoxy resin emulsion sizing agent, its resin solid content is 40～60%, the emulsion median size is 180～350 nanometers, surface tension 35～48mN/m, emulsion room temperature rotary viscosity is 10～500 centipoises.
55～80 parts of bisphenol A epoxide resins
15～5 parts of Racemic glycidol ether ester compounds with carbon-carbon double bond
25～10 parts of negatively charged ion polyethet surfactants
Auxiliary agent is further recommended 5 parts for 1～10 part
66～150 parts of deionized waters.
The molecular weight of above-mentioned bisphenol A epoxide resin is recommended as 350～2500 gram/moles, Resins, epoxy E826, E828, E1001, E1002 or E1004 etc. as Shell Co. Ltd, perhaps home-made Resins, epoxy E51, E44, E20 or E21 etc., above bisphenol A epoxide resin can be used alone, but also also mix together.Simultaneously, above-mentioned negatively charged ion polyethet surfactant is recommended as SIOC-S7 and has structure as the formula (8):
Described negatively charged ion polyethet surfactant SIOC-S7 system is an initiator by cumyl phenol, further adopt known epoxyethane ring-expansion polymerization method and continuously the reaction of sulphur ammonium obtain.
In the preparation prescription according to novel epoxy vinyl acetate modified epoxy water-based emulsion sizing agent provided by the present invention, auxiliary agent is the mixture of compounds such as softening agent, antioxidant, membrane-forming agent, defoamer, static inhibitor, be recommended as SIOC-A7, described auxiliary agent SIOC-A7 is formed by softening agent, organosilicon membrane-forming agent, antioxidant, the configuration of silicone antifoam agent mechanically mixing.
Can prepare the starching carbon fiber by general known carbon fiber sizing technique method according to novel epoxy vinyl acetate modified epoxy water-based emulsion sizing agent provided by the present invention.Be applied as example with the starching of T300 grade carbon fiber, the starching amount is 1.2 ± 0.2%, 120～170 ℃ of drying temperatures, and preferred 130～160 ℃, 1～5 minute time of drying, preferred 1～3 minute time of drying, preparation gained carbon fiber starching surface is evenly glossy.
A kind of Racemic glycidol ether-ether, synthetic method and application in the carbon fiber sizing agent preparation thereof provided by the present invention with carbon-carbon double bond, not only have advantages such as synthetic operation is easy, efficient is high, security is good, avoided the known high operational danger that is caused easily by the on-the-spot oxidation of organo-peroxide, epoxidation enol ester.Matrix resins such as the Racemic glycidol ether ester compound with carbon-carbon double bond of gained of the present invention and Resins, epoxy, unsaturated polyester, bismaleimides have good consistency, its carbon carbon unsaturated double-bond and reactive epoxy groups can improve chemical crosslinking density, can be used as oxyethylene ester modified further describe as follows:
(1) the Racemic glycidol ether-ether of preparation gained contains active epoxy group and carbon carbon unsaturated double-bond simultaneously, can and multiple matrix resin such as Resins, epoxy, unsaturated polyester resin, bimaleimide resin between have good consistency, can pass through the processed and applied temperature controlling, realize the chemical crosslinking density of epoxide group and carbon carbon unsaturated double-bond and matrix resin and carbon fiber surface, improve the interface shear strength of matrix material.
(2) according to the synthesis preparation method with Racemic glycidol ether-ether of carbon-carbon double bond of the present invention, avoided the dangerous organic oxygen compound oxidation of disclosed employing, epoxidation prepares approach, synthetic operation is safer, easily industrialization amplification and scale production.
(3) synthetic method with Racemic glycidol ether-ether of carbon-carbon double bond provided by the present invention has versatility, goes for being prepared by multiple unsaturated dibasic acid the unsaturated glycidyl ether of different series.
(4) the Racemic glycidol ether-ether with carbon-carbon double bond of preparation gained can be used as effective recipe ingredient, prepare the water-based emulsion sizing agent of novel epoxy vinyl acetate modified epoxy, its resin solid content is 40～60%, median size is 180～350 nanometers, surface tension 35～48mN/m, emulsion and diluent good stability, the carbon fiber wetting property is good, can be applied to the production of carbon fiber.
(5) according to a kind of Racemic glycidol ether-ether and synthetic method with carbon-carbon double bond provided by the present invention, the synthesis material cost is low, and technology is easy, is easy to suitability for industrialized production, has broad application prospects.
The test characterizing method is as follows:
The utilization Varian VXR-300 of the 1H nmr spectrum system fourier transform nuclear magnetic resonance analyser test of synthetic preparation gained intermediate and final product obtains among the present invention, and solvent is a deuterochloroform, and TMS is the chemical shift reference.The viscosity of preparation gained water-based emulsion adopts the test of Brookfield DV-II Pro rotational viscosimeter to obtain.The surface tension of emulsion adopts the DCAT21 type dynamic contact angle of German DataPhysics company and surface tension instrument test to obtain, and probe temperature is 25 ℃.The Zetasizer NanoZS90 type dynamic laser scatterometer DLS test that the median size of water-based emulsion adopts Britain Ma Erwen instrument company to produce obtains, and probe temperature is 25 ℃.The Q500 TGA instrument test of thermogravimetic analysis (TGA) utilization U.S. TA company, Range of measuring temp are room temperature to 500 degree, and temperature scanning speed is per minute 10 degree.
Description of drawings
Fig. 1 is a FUMARIC ACID TECH GRADE Racemic glycidol ether-ether (fumaric acid Racemic glycidol ether-ether)
1H NMR collection of illustrative plates, the structure ownership of its NMR signal is described in detail in an embodiment, and reference numbers is the integrated value of corresponding NMR signal intensity among the figure.
Fig. 2 is the TGA thermogravimetic analysis (TGA) collection of illustrative plates of FUMARIC ACID TECH GRADE Racemic glycidol ether-ether (fumaric acid Racemic glycidol ether-ether), and the mobile atmosphere of test is high pure nitrogen, and longitudinal axis signal is the real-time quality maintenance percentage of sample under the corresponding temperature among the figure.
Embodiment
Below by embodiment is specifically described the present invention, will help the understanding of the present invention, but not limit content of the present invention.
In following specific embodiment, novel epoxy vinyl acetate modified water-soluble epoxy emulsion preparation prescription is as follows:
55～80 parts of bisphenol A epoxide resins
15～5 parts of Racemic glycidol ether ester compounds with carbon-carbon double bond
25～10 parts in tensio-active agent
Auxiliary agent is further recommended 5 parts for 1～10 part
66～150 parts of deionized waters
Illustrate, above-mentioned recipe ingredient bisphenol A epoxide resin can be by commercialization trade mark E44, E21 Resins, epoxy by mass ratio 0～100: 100～0 mix and obtain, further the Racemic glycidol ether ester compound that its synthetic preparation gained with decide mass ratio is had carbon-carbon double bond is positioned in the high speed machine mixing kettle, be heated to after 80～95 degree mix homogeneous, add tensio-active agent SIOC-S7 and auxiliary agent SIOC-A7 and continue to mix to evenly.Then, according to general known polymer emulsion preparation technology method, progressively add deionized water in high speed shear emulsification still, final emulsification homogeneous prepares aqueous epoxy resin emulsion.
20 gram FUMARIC ACID TECH GRADE, 250 gram sulfur oxychlorides and 1.4 gram cuprous chlorides are placed the 500ml pyriform bottle that has magnetic stirring apparatus, be heated to backflow, continue more than 18 hours, after steaming desolventized, decompression steamed acyl chlorides.7.77 gram (0.105mol) glycidyl ethers, 21.25 gram (0.21mol) triethylamines and 100ml methylene dichloride are placed the 250ml there-necked flask that has prolong and mechanical stirring device, under cryosel is bathed, 7.95 gram (0.0523mol) fumaryl chlorides are added drop-wise in the flask very slowly, react again more than 2 hours after dropwising.Mother liquor filters, and use the dilute hydrochloric acid solution pickling earlier, and the sodium carbonate solution alkali cleaning is washed to neutrality with saturated common salt again, get organic phase with anhydrous magnesium sulfate drying after, solvent is removed in distillation, behind the recrystallization 9.22 restrain FUMARIC ACID TECH GRADE Racemic glycidol ether-ethers, productive rate 77.28%.
1HNMR(300MHZ，CDCl
3，δ)：2.68(2H)，2.89(2H)，3.26(2H)，4.05(2H)，4.54(2H)，6.93(2H)。
The above-mentioned FUMARIC ACID TECH GRADE Racemic glycidol ether-ether that further in aqueous epoxy emulsion preparation prescription, adds 6.5% (mass ratio), preparing the water-based emulsion median size is 222.3 ± 2.3nm, particle size dispersion coefficient PDI is 0.024, surface tension 43.0mN/m, can dilute the starching of T300 grade carbon fiber, the starching amount 1.2 ± 0.2% of being used for.
20 gram maleic acids, 250 gram sulfur oxychlorides and 1.4 gram cuprous chlorides are placed the 500ml pyriform bottle that has magnetic stirring apparatus, be heated to backflow, continue more than 18 hours, after steaming desolventized, decompression steamed acyl chlorides.7.77 gram (0.105mol) glycidyl ethers, 21.25 gram (0.21mol) triethylamines and 100ml methylene dichloride are placed the 250ml there-necked flask that has prolong and mechanical stirring device, under cryosel is bathed, 7.95 gram (0.0523mol) maleoyl-chlorine are added drop-wise in the flask very slowly, react again more than 2 hours after dropwising.Mother liquor filters, and use the dilute hydrochloric acid solution pickling earlier, and the sodium carbonate solution alkali cleaning is washed to neutrality with saturated common salt again, get organic phase with anhydrous magnesium sulfate drying after, boil off solvent, behind the recrystallization 7.14 gram maleic acid Racemic glycidol ether-ethers, productive rate 59.3%.
1HNMR(300MHZ，CDCl
3，δ)：2.42(2H)，2.71(2H)，3.15(2H)，4.18(2H)，4.44(2H)，6.31(2H)。
The above-mentioned maleic acid Racemic glycidol ether-ether that further in aqueous epoxy emulsion preparation prescription, adds 7.5% (mass ratio), obtaining water-based sizing agent emulsion median size is 257.5 ± 1.0nm, particle size dispersion coefficient PDI is 0.050, surface tension 43.25mN/m, can dilute the starching of T300 grade carbon fiber, the starching amount 1.2 ± 0.2% of being used for.
15 gram maleic acids, 200 gram sulfur oxychlorides and 1.0 gram Resorcinol are placed the 500ml pyriform bottle that has magnetic stirring apparatus, be heated to backflow, continue more than 18 hours, after steaming desolventized, decompression steamed acyl chlorides.9.24 gram (0.105mol) 3-methyl glycidyl ethers, 21.25 gram (0.21mol) triethylamines and 100ml methylene dichloride are placed the 250ml there-necked flask that has prolong and mechanical stirring device, under cryosel is bathed, 7.95 gram (0.0523mol) maleoyl-chlorine are added drop-wise in the flask very slowly, react again more than 2 hours after dropwising.Mother liquor filters, and use the dilute hydrochloric acid solution pickling earlier, and the sodium carbonate solution alkali cleaning is washed to neutrality with saturated common salt again, get organic phase with anhydrous magnesium sulfate drying after, steaming desolventizes, behind the recrystallization 9.41 gram maleic acid 3-methyl glycidyl ether esters, productive rate 70.3%.
1HNMR(300MHZ，CDCl
3，δ)：1.37(6H)，2.38(2H)，2.63(2H)，3.12(2H)，4.35(2H)，6.31(2H)。
The above-mentioned maleic acid 3-methyl glycidyl ether ester that further in aqueous epoxy emulsion preparation prescription, adds 7.3% (mass ratio), preparing water-based sizing agent emulsion median size is 255.3 ± 3.1nm, particle size dispersion coefficient PDI is 0.044, surface tension 41.88mN/m, can dilute T 300 grade carbon fiber starchings, the starching amount 1.2 ± 0.2% of being used for.
15 gram FUMARIC ACID TECH GRADE, 200 gram sulfur oxychlorides and 1.0 gram 2,6 ditertiary butyl p cresol are placed the 500ml pyriform bottle that has magnetic stirring apparatus, be heated to backflow, continue more than 18 hours, after steaming desolventized, decompression steamed acyl chlorides.11.78 gram (0.137mol) 3-methyl glycidyl ethers, 27.63 gram (0.27mol) triethylamines and 150ml methylene dichloride are placed the 500ml there-necked flask that has prolong and mechanical stirring device, under cryosel is bathed, 10.37 gram (0.0680mol) fumaryl chlorides are added drop-wise in the flask very slowly, react again more than 2 hours after dropwising.Mother liquor filters, and uses earlier dilute hydrochloric acid solution pickling, sodium carbonate solution alkali cleaning, be washed to neutrality with saturated common salt again, get organic phase with anhydrous magnesium sulfate drying after, steaming desolventizes, get 11.87 gram FUMARIC ACID TECH GRADE 3-methyl glycidyl ether esters behind the recrystallization, productive rate 76.5%.
1HNMR(300MHZ，CDCl
3，δ)：1.36(6H)，2.39(2H)，2.65(2H)，3.13(2H)，4.45(2H)，6.92(2H)。
The above-mentioned FUMARIC ACID TECH GRADE 3-methyl glycidyl ether ester that further in aqueous epoxy emulsion preparation prescription, adds 8.0% (mass ratio), preparing water-based sizing agent emulsion median size is 219.2 ± 2.8nm, particle size dispersion coefficient PDI is 0.032, surface tension 42.09mN/m, can dilute and be used for the starching of T300 grade carbon fiber, carbon fiber starching amount is 1.2 ± 0.2%.
15 gram FUMARIC ACID TECH GRADE, 200 gram sulfur oxychlorides and 1.0 gram para benzoquinone are placed the 500ml pyriform bottle that has magnetic stirring apparatus, be heated to backflow, continue more than 18 hours, after steaming desolventized, decompression steamed acyl chlorides.9.24 gram (0.105mol) 3-methyl glycidyl ethers, 21.25 gram (0.21mol) triethylamines and 100ml methylene dichloride are placed the 250ml there-necked flask that has prolong and mechanical stirring device, under cryosel is bathed, 8 gram (0.0523mol) fumaryl chlorides are added drop-wise in the flask very slowly, react again more than 2 hours after dropwising.Mother liquor filters, and uses earlier dilute hydrochloric acid solution pickling, sodium carbonate solution alkali cleaning, be washed to neutrality with saturated common salt again, get organic phase with anhydrous magnesium sulfate drying after, steaming desolventizes, obtain 9.69 gram FUMARIC ACID TECH GRADE 3-methyl glycidyl ether esters behind the recrystallization, productive rate 72.4%.
1HNMR(300MHZ，CDCl
3，δ)：1.36(6H)，2.38(2H)，2.65(2H)，3.12(2H)，4.43(2H)，6.92(2H)。
Further at the above-mentioned FUMARIC ACID TECH GRADE 3-methyl glycidyl ether ester that in aqueous epoxy emulsion preparation prescription, adds 7.2% (mass ratio), preparing water-based sizing agent emulsion median size is 228.9 ± 1.5nm, particle size dispersion coefficient PDI is 0.036, surface tension 41.72mN/m, can dilute and be used for the starching of T300 grade carbon fiber, carbon fiber starching amount is 1.2 ± 0.2%.
15 gram methylfumaric acids, 200 gram sulfur oxychlorides and 1.0 gram 2,6 ditertiary butyl p cresol are placed the 500ml pyriform bottle that has magnetic stirring apparatus, be heated to backflow, continue more than 18 hours, after steaming desolventized, decompression steamed acyl chlorides.With 9.32 gram 0.126mol) glycidyl ether, 25.50 restrains (0.21mol) triethylamines and the 150ml methylene dichloride places the 500ml there-necked flask that has prolong and mechanical stirring device, under cryosel is bathed, 10.42 gram (0.0628mol) methyl fumaryl chlorides are added drop-wise in the flask very slowly, react again more than 2 hours after dropwising.Mother liquor filters, and uses the dilute hydrochloric acid solution pickling earlier, and the sodium carbonate solution alkali cleaning is washed to neutrality with saturated common salt again, get organic phase with anhydrous magnesium sulfate drying after, steaming desolventizes, and obtains 10.28g methylfumaric acid Racemic glycidol ether-ether behind the recrystallization, productive rate 67.61g.
1HNMR(300MHZ，CDCl
3，δ)：2.41(3H)，2.39(2H)，2.63(2H)，3.13(2H)，4.16(2H)，4.45(2H)，7.21(2H)。
Further at the above-mentioned methylfumaric acid Racemic glycidol ether-ether that in aqueous epoxy emulsion preparation prescription, adds 6.8% (mass ratio), preparing water-based sizing agent emulsion median size is 244.5 ± 1.022nm, particle size dispersion coefficient PDI is 0.047, surface tension 44.16mN/m, can dilute and be used for the starching of T300 grade carbon fiber, carbon fiber starching amount is 1.1 ± 0.2%.
15 gram FUMARIC ACID TECH GRADE, 200 gram sulfur oxychlorides and 1.0 gram 2,6 ditertiary butyl p cresol are placed the 500ml pyriform bottle that has magnetic stirring apparatus, be heated to backflow, continue more than 18 hours, after steaming desolventized, decompression steamed acyl chlorides.7.77 gram (0.105mol) glycidyl ethers, 21.25 gram (0.21mol) triethylamines and 100ml methylene dichloride are placed the 250ml there-necked flask that has prolong and mechanical stirring device, under cryosel is bathed, 7.95 gram (0.0523mol) fumaryl chlorides are added drop-wise in the flask very slowly, react again more than 2 hours after dropwising.Mother liquor filters, and use the dilute hydrochloric acid solution pickling earlier, and the sodium carbonate solution alkali cleaning is washed to neutrality with saturated common salt again, get organic phase with anhydrous magnesium sulfate drying after, steaming desolventizes, recrystallization obtains 9.2 and restrains FUMARIC ACID TECH GRADE Racemic glycidol ether-ethers, productive rate 77.1g.
1HNMR(300MHZ，CDCl
3，δ)：2.68(2H)，2.89(2H)，3.26(2H)，4.05(2H)，4.54(2H)，6.93(2H)。
25 gram maleic acids, 300 gram sulfur oxychlorides and 1.7 gram para benzoquinone are placed the 500ml pyriform bottle that has magnetic stirring apparatus, be heated to backflow, continue more than 18 hours, after steaming desolventized, decompression steamed acyl chlorides.11.66 gram (0.158mol) glycidyl ethers, 31.87 gram (0.315mol) triethylamines and 150ml methylene dichloride are placed the 500ml there-necked flask that has prolong and mechanical stirring device, under cryosel is bathed, 11.92 gram (0.0785mol) maleoyl-chlorine are added drop-wise in the flask very slowly, react again more than 2 hours after dropwising.Mother liquor filters, and uses the dilute hydrochloric acid solution pickling earlier, and the sodium carbonate solution alkali cleaning is washed to neutrality with saturated common salt again, get organic phase with anhydrous magnesium sulfate drying after, steaming desolventizes, and obtains 9.78g maleic acid Racemic glycidol ether-ether behind the recrystallization, productive rate is 54.5%.
1HNMR(300MHZ，CDCl
3，δ)：2.41(2H)，2.69(2H)，3.15(2H)，4.18(2H)，4.45(2H)，6.32(2H)。
Embodiment 9
15 gram maleic acids, 200 gram sulfur oxychlorides and 1.0 gram 2,6 ditertiary butyl p cresol are placed the 500ml pyriform bottle that has magnetic stirring apparatus, be heated to backflow, continue more than 18 hours, after steaming desolventized, decompression steamed acyl chlorides.7.77 gram (0.105mol) glycidyl ethers, 21.25 gram (0.21mol) triethylamines and 100ml methylene dichloride are placed the 250ml there-necked flask that has prolong and mechanical stirring device, under cryosel is bathed, 7.95 gram (0.0523mol) maleoyl-chlorine are added drop-wise in the flask very slowly, react again more than 2 hours after dropwising.Mother liquor filters, and use the dilute hydrochloric acid solution pickling earlier, and the sodium carbonate solution alkali cleaning is washed to neutrality with saturated common salt again, get organic phase with anhydrous magnesium sulfate drying after, steaming desolventizes, the recrystallization after drying obtains 7.01 and restrains maleic acid Racemic glycidol ether-ethers, productive rate 55.2%.
1HNMR(300MHZ，CDCl
3，δ)：2.39(2H)，2.70(2H)，3.14(2H)，4.18(2H)，4.46(2H)，6.32(2H)。
Further at the above-mentioned maleic acid Racemic glycidol ether-ether that in aqueous epoxy emulsion preparation prescription, adds 8% (mass ratio), the median size that emulsification prepares water-based sizing agent emulsion is 259.2 ± 4.2nm, particle size dispersion coefficient PDI is 0.051, surface tension 42.12mN/m.Further it is diluted to the sizing agent thin liquid of 1.8～2.3% mass concentrations, viscosity 1.2～1.8 centipoises under the room temperature, surface tension is 44.5～46.5mN/m, is applied to the starching of homemade T300 grade carbon fiber.The dipping time of the carbon fiber of starching engineering in sizing liquor is 2～30 seconds, the warm air drying temperature of starching carbon fiber is 130～165 degree, be 1～5 minute time of drying, and final starching layer accounts for 1.2 ± 0.2% of starching carbon fiber total mass, and the starching carbon fiber strength is 3.GPa.
Above-mentioned dried starching carbon fiber is placed the down fixed temperature and humidity degree proofing box 6～24 hours of 60～70%RH of 25 degree, and the saturated moisture absorption of carbon fiber is got damp rate less than 0.1%.Further adopting Resins, epoxy E828 is matrix resin, and according to GB/T 3357-1982 specified test, the interlaminar shear strength that obtains carbon fibre reinforced composite is 85～110MPa, satisfies application requiring.
Though the present invention discloses preferred embodiment as above; so it is not in order to limit content of the present invention; anyly be familiar with this skill person; in not breaking away from main spirit of the present invention and context; when doing various changes and retouching, therefore the protection domain of invention should be as the criterion with the basic right claimed range of applying for a patent.
Claims (9)
1. Racemic glycidol ether ester compound with carbon-carbon double bond is characterized in that having following structural formula:
Or
R in the said structure formula
1, R
2For hydrogen atom or carbonatoms are 1～4 saturated straight chain or branched-chain alkyl substituted radical, and R
1, R
2Be identical or different group; R
3, R
3' be hydrogen atom or methyl substituted group, and R
3, R
3' be identical or different group; R
4For hydrogen atom or carbonatoms 1～3 saturated straight chain or branched-chain alkyl substituted radical.
2. a kind of synthetic method with Racemic glycidol ether ester compound of carbon-carbon double bond as claimed in claim 1 is characterized in that obtaining via step () and (two):
(1) under the reflux temperature of sulfur oxychloride, unsaturated diacid, sulfur oxychloride and stopper reacted 10～30 hours, obtain unsaturated diacid chloride, the mass percent of described unsaturated diacid, sulfur oxychloride and stopper is as follows: unsaturated diacid 14.9～4.0%, sulfur oxychloride 85.0～95.0%, stopper 0.1～1.0%; Described stopper is selected from least a in Resorcinol, cuprous chloride, para benzoquinone or the 2,6 ditertiary butyl p cresol; Shown in the following structural formula of described unsaturated diacid,
R wherein
1, R
2And R
4According to claim 1;
(2) in organic solvent, unsaturated diacid chloride that step () is obtained and hydroxyl epoxy compounds and acid are captured agent-20～0 ℃ of reaction 2～6 hours, obtain the described a kind of Racemic glycidol ether-ether with carbon-carbon double bond of claim 1; The mol ratio that agent is captured in described unsaturated diacid chloride, hydroxyl epoxy compounds, acid is 1.0: 1.8～3.0: 2.0～5.0; It is triethylamine, pyridine or picoline that agent is captured in described acid; Shown in the following structural formula of described hydroxyl epoxy compounds,
R wherein
3, R
3' according to claim 1.
3. synthetic method as claimed in claim 2 is characterized in that the organic solvent in the described step (two) is chloroparaffin, tetrahydrofuran (THF) or dioxane, and the volumetric usage of solvent is 40～80% of a reaction system cumulative volume.
4. a kind of purposes with Racemic glycidol ether ester compound of carbon-carbon double bond as claimed in claim 1 is characterized in that being used to prepare carbon fiber sizing agent.
5. a kind of purposes with Racemic glycidol ether ester compound of carbon-carbon double bond as claimed in claim 4 is characterized in that described carbon fiber sizing agent is the ester modified epoxy emulsion sizing agent of oxyethylene.
6. the described a kind of purposes of claim 5 with Racemic glycidol ether ester compound of carbon-carbon double bond, it is characterized in that the ester modified epoxy emulsion sizing agent of described oxyethylene, prepare by Racemic glycidol ether ester compound that has carbon-carbon double bond in the described a kind of molecular structure of claim 1 and component as described below mass fraction combination emulsification homogeneous as described below:
55～80 parts of bisphenol A epoxide resins,
Claim 1 is described to have 15～5 parts of Racemic glycidol ether ester compounds of carbon-carbon double bond,
25～10 parts of negatively charged ion polyethet surfactants,
1～10 part of auxiliary agent,
66～150 parts of deionized waters.
7. a kind of purposes with Racemic glycidol ether ester compound of carbon-carbon double bond as claimed in claim 6, the molecular weight that it is characterized in that described bisphenol A epoxide resin is 350～2500 gram/moles.
8. a kind of purposes with Racemic glycidol ether ester compound of carbon-carbon double bond as claimed in claim 6 is characterized in that described negatively charged ion polyethet surfactant has following structure:
9. a kind of purposes as claimed in claim 6 with Racemic glycidol ether ester compound of carbon-carbon double bond, the resin solid content that it is characterized in that the ester modified epoxy resin latex sizing agent of described oxyethylene is 40～60%, the emulsion median size is 180～350 nanometers, surface tension 35～48mN/m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102348529A CN101941956A (en) | 2010-07-23 | 2010-07-23 | Glycidyl ether ester with carbon-carbon double bond, synthetic method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102348529A CN101941956A (en) | 2010-07-23 | 2010-07-23 | Glycidyl ether ester with carbon-carbon double bond, synthetic method and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101941956A true CN101941956A (en) | 2011-01-12 |
Family
ID=43434191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102348529A Pending CN101941956A (en) | 2010-07-23 | 2010-07-23 | Glycidyl ether ester with carbon-carbon double bond, synthetic method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101941956A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073701A (en) * | 2013-01-23 | 2013-05-01 | 宏昌电子材料股份有限公司 | Fatty acid modified epoxy resin and preparation method thereof |
| CN106188478A (en) * | 2016-07-26 | 2016-12-07 | 巨石集团有限公司 | A kind of modified polyurethane emulsion film former and its preparation method and application |
| CN106592241A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Modified epoxy resin small filament bundle universal carbon fiber sizing agent, and preparation method and application thereof |
| CN106592242A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Modified epoxy resin large tow general-purpose type carbon fiber sizing agent, preparation method and applications thereof |
| CN106811966A (en) * | 2017-01-24 | 2017-06-09 | 哈尔滨工业大学 | A kind of method of acrylic amide aqueous solution grafting modified carbon fiber surface size agent |
| CN106835695A (en) * | 2017-01-24 | 2017-06-13 | 哈尔滨工业大学 | A kind of method of acrylic amide organic solution grafting modified carbon fiber surface size agent |
| CN109252373A (en) * | 2018-07-30 | 2019-01-22 | 江苏澳盛复合材料科技有限公司 | A kind of carbon fiber surface sizing agent and its application |
-
2010
- 2010-07-23 CN CN2010102348529A patent/CN101941956A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073701A (en) * | 2013-01-23 | 2013-05-01 | 宏昌电子材料股份有限公司 | Fatty acid modified epoxy resin and preparation method thereof |
| CN106592241B (en) * | 2015-10-14 | 2020-11-06 | 中国石油化工股份有限公司 | Modified epoxy resin small tow universal carbon fiber sizing agent, preparation method and application thereof |
| CN106592241A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Modified epoxy resin small filament bundle universal carbon fiber sizing agent, and preparation method and application thereof |
| CN106592242A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Modified epoxy resin large tow general-purpose type carbon fiber sizing agent, preparation method and applications thereof |
| CN106592242B (en) * | 2015-10-14 | 2020-11-06 | 中国石油化工股份有限公司 | Modified epoxy resin large tow universal carbon fiber sizing agent, preparation method and application thereof |
| CN106188478B (en) * | 2016-07-26 | 2019-09-20 | 巨石集团有限公司 | A kind of modified polyurethane emulsion film forming agent and its preparation method and application |
| CN106188478A (en) * | 2016-07-26 | 2016-12-07 | 巨石集团有限公司 | A kind of modified polyurethane emulsion film former and its preparation method and application |
| CN106835695B (en) * | 2017-01-24 | 2019-05-14 | 哈尔滨工业大学 | A kind of method of acrylic amide organic solution grafting modified carbon fiber surface size agent |
| CN106811966B (en) * | 2017-01-24 | 2019-05-14 | 哈尔滨工业大学 | A kind of method of acrylic amide aqueous solution grafting modified carbon fiber surface size agent |
| CN106835695A (en) * | 2017-01-24 | 2017-06-13 | 哈尔滨工业大学 | A kind of method of acrylic amide organic solution grafting modified carbon fiber surface size agent |
| CN106811966A (en) * | 2017-01-24 | 2017-06-09 | 哈尔滨工业大学 | A kind of method of acrylic amide aqueous solution grafting modified carbon fiber surface size agent |
| CN109252373A (en) * | 2018-07-30 | 2019-01-22 | 江苏澳盛复合材料科技有限公司 | A kind of carbon fiber surface sizing agent and its application |
| CN109252373B (en) * | 2018-07-30 | 2020-03-31 | 江苏澳盛复合材料科技有限公司 | Carbon fiber surface sizing agent and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101941956A (en) | Glycidyl ether ester with carbon-carbon double bond, synthetic method and use thereof | |
| CN106567274B (en) | A method of preparing aramid paper with p-aramid fiber nanofiber | |
| CN104356356B (en) | A kind of preparation method of hydrophobic cellulose material | |
| CN102031698B (en) | Preparation method of non-ironing finishing agent of modified self-crosslinking organosilicon anti-wrinkle microemulsion | |
| WO2021197637A1 (en) | Aqueous binder composition | |
| CN110272679A (en) | Hyperbranched super-amphiphobic anticorrosive paint of ultraviolet-cured paint phenolic group and preparation method thereof | |
| CN104726022A (en) | Environment-friendly water-based composite wax emulsion release material for electric aluminum and preparation method of material | |
| CN108624995A (en) | A kind of preparation method of polyamide spinning finisher | |
| CN107892527A (en) | A kind of ultra-high performance concrete prepared using wet granite stone powder and preparation method thereof | |
| CN106977683A (en) | No-solvent type polyurethane nano TiO2Composite membrane and preparation method thereof | |
| CN102161767A (en) | Oxidized-polyethylene-modified organosilicon polymer | |
| CN108947275A (en) | A kind of hydrophober and its preparation method and application that graphene oxide is modified | |
| US8263705B2 (en) | Method for preparing polyvinyl alcohol and polyvinyl acetate latex by use of the bottom residue from vinyl acetate production process | |
| CN117304804B (en) | Environment-friendly waterproof agent for plates and preparation method thereof | |
| CN114030250A (en) | High-elasticity-modulus high-strength glass fiber laminated board and preparation method thereof | |
| CN106977692A (en) | Attapulgite clay compounded film of no-solvent type polyurethane nano and preparation method thereof | |
| CN106592241A (en) | Modified epoxy resin small filament bundle universal carbon fiber sizing agent, and preparation method and application thereof | |
| Ma et al. | The structure and properties of eucalyptus fiber/phenolic foam composites under N-β (aminoethyl)--aminopropyl trimethoxy silane pretreatments | |
| Zhang et al. | Application of noise reduction and heat insulation based on controlled-size polystyrene hollow microspheres | |
| CN108239174A (en) | A kind of sulfonation composite modified starch | |
| CN108943273A (en) | A kind of bamboo plasticizing process | |
| CN105586775A (en) | An emulsion sizing agent used for carbon fibers with high wear resistance, and preparation and applications thereof | |
| CN104479054A (en) | Chlorinated rubber and method for preparing chlorinated rubber from recovered desulfurized tire rubber | |
| TWI833358B (en) | Low-dielectric and low-thermal-conductivity aerogel composite and preparation method thereof | |
| CN110041794A (en) | A kind of toughening type epoxy powder coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110112 |