CN104963200A - Preparation method and application of water-soluble carbon fiber sizing agent - Google Patents
Preparation method and application of water-soluble carbon fiber sizing agent Download PDFInfo
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- CN104963200A CN104963200A CN201510458334.8A CN201510458334A CN104963200A CN 104963200 A CN104963200 A CN 104963200A CN 201510458334 A CN201510458334 A CN 201510458334A CN 104963200 A CN104963200 A CN 104963200A
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Abstract
The invention discloses a preparation method and application of a water-soluble carbon fiber sizing agent. The water-soluble carbon fiber sizing agent is prepared from the following components in parts by weight: 5-45 parts of a water-soluble polymer, 0.01-1.2 parts of a dispersing agent, 0.08-2 parts of an emulsifying agent, and 62-95 parts of a solvent, wherein the water-soluble polymer is characterized in that a large number of active functional groups exist in molecules. The preparation method comprises the following steps: under temperature of 60-100 DEG C, adding the water-soluble polymer into the solvent, stirring so that the water-soluble polymer can be completely dissolved, adjusting to the proper temperature, adding the dispersing agent and the emulsifying agent into the solution, stirring for dissolving to obtain an integrated solution which is the water-soluble carbon fiber sizing agent. According to the invention, all the raw materials are non-toxic and easily available, are convenient for pulp mixing and sizing, and have good protection effect on carbon fibers; after the carbon fibers are treated by adopting the water-soluble carbon fiber sizing agent, the surfaces of the carbon fibers contain a large number of hydrophilic functional groups, so that the hydrophily and the dispersibility of the surfaces of the carbon fibers can be effectively improved, the carbon fibers can be well adapted to water treatment and other aspects having requirements for good dispersibility of the carbon fibers.
Description
Technical field
The invention belongs to carbon fiber sizing agent technical field, be specifically related to a kind of preparation method and purposes of water-soluble carbon fiber sizing agent.
Background technology
The strength and modulus of carbon fiber is high, and filament diameter is little, and specific area is large, and non-corrosive, not mouldy, without putrefaction in water, having compatibility with microorganism, is the good material of repairing contaminant water ecological environment.And the research of current carbon fiber each side at home is mainly concentrated on the composite, carbon fiber sizing agent is also to improve the compatibility with matrix resin on the basis of protection carbon fiber surface, but the hydrophily of carbon fiber and dispersiveness are very undesirable.Surface energy without the unsized carbon fiber of surface treatment is low, and hydrophily is bad, and uses inconvenient; Although the carbon fiber surface energy after surface treatment increases, improve hydrophily, not starching also affects transport because there being a large amount of lousiness and using; The dispersiveness of universal sizing agent to carbon fiber is unfavorable, be not suitable for water treatment direction and to carbon fiber have good dispersion require other side.
The existing carbon fiber for water treatment aspect of China maintains by import, and cost is very high, and this also greatly limit the market of carbon fiber in China's water treatment direction.For this reason, develop a kind of water-soluble carbon fiber sizing agent, make carbon fiber better must be applicable to water treatment direction and to carbon fiber have good dispersion require other side.
Summary of the invention
The invention provides one and can improve carbon fiber hydrophily and dispersive property, and to environment, the biological harmless water-soluble carbon fiber sizing agent being suitable for industrial applications, and the preparation method of this sizing agent.
Another object of the present invention is to the purposes that above-mentioned water-soluble carbon fiber sizing agent is provided.
The object of the invention is to be realized by following measures:
A kind of water-soluble carbon fiber sizing agent, its raw materials comprises the composition of following mass percent: water-soluble polymer 5 ~ 45 parts, dispersant 0.01 ~ 1.2 part, emulsifying agent 0.08 ~ 2 part, solvent 62 ~ 95 parts.
Described water-soluble polymer refers to one or more containing one or more in great amount of hydroxy group, amino, amide groups, ether and carboxylic acid group in molecule, in preferably polyethylene imines, polyvinyl acetate, Sodium Polyacrylate, carboxymethyl cellulose, polyvinylpyridine.
Containing one or more in polycarboxylate sodium, high molecular weight polyethylene glycol ester compound, the polyacrylate of acidic-group modification, polyacrylic acid sodium salt in described dispersant.
Described emulsifying agent is one or more in emulsifying agent SOPE series.
Containing one or both in ethanol and deionized water in described solvent.
The preparation method of sizing agent of the present invention is specifically: at 60 ~ 100 DEG C, added by water-soluble polymer in the solvent of 20 ~ 50% of solvent total amount, make it to be dissolved in solvent, more remaining solvent under adding normal temperature, regulates temperature; Add in above-mentioned solution by dispersant and emulsifying agent again, stirring and dissolving makes it into the solution be integrated, and can obtain.
The preparation method of sizing agent of the present invention can also be specifically: at 60 ~ 100 DEG C, water-soluble polymer is added in all solvents, is stirred to a certain degree, then dispersant and emulsifying agent are added in above-mentioned solution, stirring and dissolving makes it into the solution be integrated, and can obtain.
Above-mentioned water-soluble carbon fiber sizing agent can be used in be exclusively used in water treatment direction carbon fiber on; also may be used for having on the carbon fiber of the other side that good dispersion requires to carbon fiber; to protect based on carbon fiber, improve hydrophily and the dispersiveness of carbon fiber surface.
A kind of carbon fiber, containing above-mentioned water-soluble carbon fiber sizing agent, the quality of water-soluble carbon fiber sizing agent is 0.1 ~ 5% of carbon fiber gross mass.
The water-soluble carbon fiber sizing agent of the present invention, raw materials used all nontoxic, environmental sound, is convenient to slurry and starching; There is good permeability and good adhesion strength, can carry out boning and give carbon fiber good processing characteristics in infiltrated fiber bundle inside; Obtained water-soluble carbon fiber sizing agent can play a very good protection to carbon fiber.After on carbon fiber, complete slurry is dried, solvent all vapors away, and can not remain in fiber surface.After water-soluble carbon fiber sizing agent Treatment of Carbon, carbon fiber surface contains a large amount of active function groups (in hydroxyl, amino, amide groups, ether and carboxylic acid group one or more), effectively can improve hydrophily and the dispersiveness of carbon fiber surface, and can ensure that carbon fiber has good smoothness, flexibility, pliability simultaneously.Preparation method of the present invention is simple, and effective, cost is low, can meet the requirement of batch production.
Accompanying drawing explanation
Fig. 1 is the deployment conditions of non-starching impregnated carbon fiber in water after 20s, Fig. 2 is the deployment conditions of impregnated carbon fiber in water after 20s after domestic epoxy resin starching, adopts the deployment conditions of impregnated carbon fiber in water after 20s after water-soluble carbon fiber sizing agent starching in Fig. 3 detailed description of the invention three.
Detailed description of the invention
Below further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
Detailed description of the invention one: a kind of carbon fiber sizing agent, it is made up of the emulsifying agent of polymine, high molecular weight polyethylene glycol ester compound, SOPE-10 specification and ethanol water, and weight proportion is 25:0.5:0.5:74.During making, first at 60 ~ 70 DEG C, 25 parts of polymines are joined in 74 parts of ethanol waters, stirring makes it to dissolve completely, treat moderate temperature, add in above-mentioned solution by the emulsifying agent of 0.5 part of high molecular weight polyethylene glycol ester compound and 0.5 part of SOPE-10 specification again, stirring and dissolving makes it into the solution be integrated, and namely obtains a kind of water-soluble carbon fiber sizing agent.
Containing slurry weight fraction with the carbon fiber after this sizing agent starching is 3.88%; After drawing starching by contact angle test, the contact angle of carbon fiber and water is compared with reducing 20% before starching, and hydrophily makes moderate progress; Disperse after about 10s after in impregnated carbon fiber water after starching.
Detailed description of the invention two: a kind of carbon fiber sizing agent, it is made up of the mixture of carboxymethyl cellulose and polyvinylpyridine, the polyacrylate of acidic-group modification, the emulsifying agent of SOPE-7 specification, ethanol water, and weight proportion is 15:0.5:0.5:84.During making, first at 70 ~ 80 DEG C, the mixture of 15 parts of carboxymethyl celluloses and polyvinylpyridine is joined in 40 parts of ethanol waters, stir and make it to dissolve completely, then add 44 parts of residue ethanol waters, adjust the temperature to 30 ~ 50 DEG C; Add in above-mentioned solution by the emulsifying agent of the polyacrylate of 0.5 part of acidic-group modification and 0.5 part of SOPE-7 specification again, stirring and dissolving makes it into the solution be integrated, and namely obtains a kind of water-soluble carbon fiber sizing agent.
Containing slurry weight fraction with the carbon fiber after this sizing agent starching is 1.96%; After drawing starching by contact angle test, the contact angle of carbon fiber and water is compared with reducing 27% before starching, and hydrophily makes moderate progress; Disperse after about 3s after in impregnated carbon fiber water after starching.
Detailed description of the invention three: a kind of carbon fiber sizing agent, it is made up of the mixture of polymine and vinylacetate, polyacrylic acid sodium salt, the emulsifying agent of SOPE-15 specification, deionized water, and weight proportion is 6:0.3:0.2:94.During making, first at 80 ~ 100 DEG C, the mixture of 6 parts of polymines and vinylacetate is joined in 94 parts of deionized waters, stirring makes it to dissolve completely, treat moderate temperature, add in above-mentioned solution by the emulsifying agent of 0.3 part of polyacrylic acid sodium salt and 0.2 part of SOPE-15 specification again, stirring and dissolving makes it into the solution be integrated, and namely obtains a kind of water-soluble carbon fiber sizing agent.
Containing slurry weight fraction with the carbon fiber after this sizing agent starching is 1.86%; After drawing starching by contact angle test, the contact angle of carbon fiber and water is compared with reducing 30% before starching, and hydrophily makes moderate progress; Disperse after about 2s after in impregnated carbon fiber water after starching.
Detailed description of the invention four: a kind of carbon fiber sizing agent, it is made up of the mixture of vinylacetate, polyacrylic acid sodium salt and high molecular weight polyethylene glycol ester compound, SOPE-20 specification emulsifying agent and deionized water, and weight proportion is 10:0.4:0.2:90.During making, first at 80 ~ 100 DEG C, 10 parts of vinylacetates are joined in 50 parts of deionized waters, stir and make it to dissolve completely, then add 40 parts of residue deionized waters, adjust the temperature to 40 ~ 60 DEG C; Add in above-mentioned solution by 0.4 part of polyacrylic acid sodium salt and the mixture of high molecular weight polyethylene glycol ester compound and the emulsifying agent of 0.2 part of SOPE-20 specification again, stirring and dissolving makes it into the solution be integrated, and namely obtains a kind of water-soluble carbon fiber sizing agent.
Containing slurry weight fraction with the carbon fiber after this sizing agent starching is 2.01%; After drawing starching by contact angle test, the contact angle of carbon fiber and water is compared with reducing 32% before starching, and hydrophily makes moderate progress; Disperse immediately after in impregnated carbon fiber water after starching.
Detailed description of the invention five: a kind of carbon fiber sizing agent, it is made up of the emulsifying agent of the mixture of Sodium Polyacrylate and polymine, polycarboxylate sodium, SOPE-10 specification and deionized water, and weight proportion is 8:0.3:0.5:92.During making, first at 80 ~ 90 DEG C, the mixture of 8 parts of Sodium Polyacrylates and polymine is joined in 40 parts of deionized waters, stir and make it to dissolve completely, then add 52 parts of residue deionized waters, adjust the temperature to 40 ~ 60 DEG C; Add in above-mentioned solution by the emulsifying agent of 0.3 part of polycarboxylate sodium and 0.5 part of A-110 specification again, stirring and dissolving makes it into the solution be integrated, and namely obtains a kind of water-soluble carbon fiber sizing agent.
Containing slurry weight fraction with the carbon fiber after this sizing agent starching is 1.36%; After drawing starching by contact angle test, the contact angle of carbon fiber and water is compared with reducing 25% before starching, and hydrophily makes moderate progress; Disperse after about 4s after in impregnated carbon fiber water after starching.
Claims (9)
1. a water-soluble carbon fiber sizing agent, is characterised in that: its raw materials comprises the composition of following mass percent: water-soluble polymer 5 ~ 45 parts, dispersant 0.01 ~ 1.2 part, emulsifying agent 0.08 ~ 2 part, solvent 62 ~ 95 parts.
2. water-soluble carbon fiber sizing agent according to claim 1, be characterised in that: described water-soluble polymer refers to one or more containing one or more in great amount of hydroxy group, amino, amide groups, ether and carboxylic acid group in molecule, in preferably polyethylene imines, polyvinyl acetate, Sodium Polyacrylate, carboxymethyl cellulose, polyvinylpyridine.
3. water-soluble carbon fiber sizing agent according to claim 1, is characterised in that: containing one or more in polycarboxylate sodium, high molecular weight polyethylene glycol ester compound, the polyacrylate of acidic-group modification, polyacrylic acid sodium salt in described dispersant.
4. water-soluble carbon fiber sizing agent according to claim 1, is characterised in that: described emulsifying agent is one or more in emulsifying agent SOPE series.
5. water-soluble carbon fiber sizing agent according to claim 1, is characterised in that: containing one or both in ethanol and deionized water in described solvent.
6. the preparation method of the water-soluble carbon fiber sizing agent described in any one of Claims 1 to 5, it is characterized in that comprising the following steps: at 60 ~ 100 DEG C, water-soluble polymer is added in the solvent of 20 ~ 50% of solvent total amount, make it to be dissolved in solvent, remaining solvent under adding normal temperature again, regulates temperature; Add in above-mentioned solution by dispersant and emulsifying agent again, stirring and dissolving makes it into the solution be integrated, and can obtain water-soluble carbon fiber sizing agent.
7. the preparation method of the water-soluble carbon fiber sizing agent described in any one of Claims 1 to 5, it is characterized in that comprising the following steps: at 60 ~ 100 DEG C, water-soluble polymer is added in all solvents, be stirred to a certain degree, again dispersant and emulsifying agent are added in above-mentioned solution, stirring and dissolving makes it into the solution be integrated, and can obtain water-soluble carbon fiber sizing agent.
8. the water-soluble carbon fiber sizing agent described in any one of Claims 1 to 5 is used for water treatment direction and has good dispersion to require other side to carbon fiber.
9. a carbon fiber, is characterized in that: containing described in any one of Claims 1 to 5 water-soluble carbon fiber sizing agent, the quality of water-soluble carbon fiber sizing agent is 0.1 ~ 5% of carbon fiber gross mass.
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Cited By (10)
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| CN109722745A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyetherimide resin based composites carbon fiber and preparation method thereof |
| CN109722894A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyolefin resin base carbon fibre suspension sizing agent and preparation method thereof |
| CN109722899A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyetherimide resin base carbon fibre suspension sizing agent and preparation method thereof |
| CN109722901A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polysulfone resin base carbon fibre suspension sizing agent and preparation method thereof |
| CN109722903A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polysulfone resin based composites carbon fiber and preparation method thereof |
| CN110168161A (en) * | 2017-02-24 | 2019-08-23 | 东丽株式会社 | Be coated with the carbon fiber bundle of sizing agent, thermoplastic resin composition, formed body, be coated with sizing agent carbon fiber bundle manufacturing method and formed body manufacturing method |
| CN110372212A (en) * | 2019-07-24 | 2019-10-25 | 东莞市唯美陶瓷工业园有限公司 | Adobe film forming moisturizer, ink-jet printing ink and decoration glue and preparation method |
| CN111851068A (en) * | 2020-08-12 | 2020-10-30 | 四川大学 | Method for repairing surface interface of modified carbon fiber and application thereof |
| CN114134715A (en) * | 2021-11-30 | 2022-03-04 | 江苏亨博复合材料有限公司 | Special sizing agent for water-based carbon fiber material and application thereof |
| CN115748253A (en) * | 2022-12-20 | 2023-03-07 | 武汉纺织大学 | Preparation method and application method of photocuring carbon fiber sizing agent |
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| CN110168161A (en) * | 2017-02-24 | 2019-08-23 | 东丽株式会社 | Be coated with the carbon fiber bundle of sizing agent, thermoplastic resin composition, formed body, be coated with sizing agent carbon fiber bundle manufacturing method and formed body manufacturing method |
| US10738171B2 (en) * | 2017-02-24 | 2020-08-11 | Toray Industries, Inc. | Sizing-coated carbon fiber bundle, thermoplastic resin composition, molded body, method for manufacturing sizing-coated carbon fiber bundle, and method for manufacturing molded body |
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| CN109722903A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polysulfone resin based composites carbon fiber and preparation method thereof |
| CN109722745B (en) * | 2017-10-27 | 2021-12-07 | 中国石油化工股份有限公司 | Carbon fiber for polyetherimide resin matrix composite material and preparation method thereof |
| CN109722899B (en) * | 2017-10-27 | 2022-02-11 | 中国石油化工股份有限公司 | Polyetherimide resin-based carbon fiber suspension sizing agent and preparation method thereof |
| CN109722901A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polysulfone resin base carbon fibre suspension sizing agent and preparation method thereof |
| CN109722899A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyetherimide resin base carbon fibre suspension sizing agent and preparation method thereof |
| CN109722894A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyolefin resin base carbon fibre suspension sizing agent and preparation method thereof |
| CN109722901B (en) * | 2017-10-27 | 2021-12-07 | 中国石油化工股份有限公司 | Polysulfone resin-based carbon fiber suspension sizing agent and preparation method thereof |
| CN109722745A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyetherimide resin based composites carbon fiber and preparation method thereof |
| CN109722903B (en) * | 2017-10-27 | 2021-12-07 | 中国石油化工股份有限公司 | Carbon fiber for polysulfone resin-based composite material and preparation method thereof |
| CN110372212A (en) * | 2019-07-24 | 2019-10-25 | 东莞市唯美陶瓷工业园有限公司 | Adobe film forming moisturizer, ink-jet printing ink and decoration glue and preparation method |
| CN111851068A (en) * | 2020-08-12 | 2020-10-30 | 四川大学 | Method for repairing surface interface of modified carbon fiber and application thereof |
| CN111851068B (en) * | 2020-08-12 | 2022-01-14 | 四川大学 | Method for repairing surface interface of modified carbon fiber and application thereof |
| CN114134715A (en) * | 2021-11-30 | 2022-03-04 | 江苏亨博复合材料有限公司 | Special sizing agent for water-based carbon fiber material and application thereof |
| CN115748253A (en) * | 2022-12-20 | 2023-03-07 | 武汉纺织大学 | Preparation method and application method of photocuring carbon fiber sizing agent |
| CN115748253B (en) * | 2022-12-20 | 2024-03-22 | 武汉纺织大学 | Preparation method and application method of photo-curing carbon fiber sizing agent |
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