CN109722894B - Polyolefin resin-based carbon fiber suspension sizing agent and preparation method thereof - Google Patents
Polyolefin resin-based carbon fiber suspension sizing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyolefin resin-based carbon fiber suspension sizing agent and a preparation method thereof. The polyolefin resin-based carbon fiber suspension sizing agent consists of polyolefin resin powder, sodium polyacrylate, fatty alcohol-polyoxyethylene ether and deionized water; based on the total mass of the solid components as 100 percent, wherein: 65-75 wt% of polyolefin resin powder, 10-15 wt% of sodium polyacrylate and 15-20 wt% of fatty alcohol-polyoxyethylene ether. The sizing agent is used for preparing carbon fibers, and the prepared sized carbon fibers are suitable for intermediates such as carbon fiber fabrics and prepreg for polyolefin resin matrix composite materials and have good processing performance and interface bonding capability.
Description
Technical Field
The invention belongs to the technical field of carbon fiber sizing agents, and particularly relates to a polyolefin resin-based carbon fiber suspension type sizing agent and a preparation method thereof.
Background
The carbon fiber reinforced thermoplastic composite material is a reinforced material which is rapidly developed in recent years, and in the preparation process of the carbon fiber reinforced thermoplastic composite material, the carbon fiber is firstly cut into short fibers with the length of 5-20mm, then the short fibers are mixed with thermoplastic resin, and the mixture is further prepared into a composite material section of a continuous homogeneous system through processes such as extrusion injection molding and the like. The polyolefin resin has the advantages of rich raw materials, low price, easy processing and forming and excellent comprehensive performance, and is the most widely applied thermoplastic resin at present. The carbon fiber reinforced polyolefin resin-based composite material has good economical efficiency, processability and recyclability, and is gradually paid more attention by the industry at present.
The carbon fiber is subjected to a series of high-temperature treatment, the surface of the carbon fiber is relatively inert, and the whole fiber is loose. Therefore, a layer of sizing agent is required to be coated on the surface of the carbon fiber to protect the carbon fiber and improve the bundling property and the interface property of the carbon fiber tow. Most of the prior industrial sizing agents are epoxy resin type sizing agents which are easy to age and harden under the condition of high temperature or long-time storage, so that the sizing carbon fiber tows are stiff and the processing and interface properties are reduced. Therefore, in the production of polyolefin resin-based composite materials, it is desirable to surface-treat carbon fibers with a polyolefin resin-based sizing agent. Because the carbon fiber composite material has the same structural composition and process performance, matrix resin can be uniformly and deeply impregnated into the carbon fiber, and the processing difficulty is greatly reduced; meanwhile, the hole defects are reduced, and the performance of the composite material is effectively improved.
Chinese patent 201380046280.3 provides a modified polyolefin sizing agent, which comprises a copolymer of acid-modified polyolefin grafted with hydrophilic polymers, epoxy resin and other additives. The method disclosed by the patent improves the interface bonding capability of the carbon fiber and the polyolefin resin to a certain extent, but needs to add a large amount of acid groups, graft hydrophilic polymers and alkali neutralizing agents, adopts complex conditions for chemical modification and post-treatment, and is poor in economy and environmental protection. Meanwhile, the main agent also contains a large amount of epoxy resin components, so that the problem of easy aging and curing is not solved.
The pure polyolefin resin-based carbon fiber sizing agent prepared by the traditional method usually needs chemical grafting modification treatment on polyolefin resin or adopts a large amount of organic solvent for dissolution, has complex preparation process, relates to various solvents, hazardous wastes and other pollutants, has great influence on the environment and is poor in economical efficiency.
Disclosure of Invention
In order to solve various problems of the existing epoxy resin sizing agent in the polyolefin resin matrix composite material, the invention provides a stable suspension type carbon fiber sizing agent taking polyolefin resin powder as a main body and a preparation method thereof. The preparation process of the polyolefin resin powder adopted by the invention is mature and can be applied in an industrial scale. The sizing agent component only introduces polyolefin resin powder with a structure similar to that of matrix resin as a main agent, does not contain epoxy resin or other resin components, has high compatibility and matching property with the matrix resin, and avoids various application problems of aging hardening of the epoxy-based sizing agent and the like. The preparation method of the sizing agent provided by the invention avoids the problems of difficult preparation, large pollution, poor stability, low economic benefit and the like of the traditional chemical grafting modification. The carbon fiber sizing agent prepared by the method can be uniformly coated on the surface of carbon fiber, and the prepared sized carbon fiber can be used for polyolefin resin matrix composite materials and has good processability and interface bonding capability.
In the invention, in order to ensure that the polyolefin resin powder can be well dispersed in an aqueous medium, sodium polyacrylate is introduced as a main dispersing agent, is negatively charged after ionization and can be adsorbed on the surface of the polyolefin resin powder, so that electrostatic repulsion force is generated among powder particles, an electric double layer stability is formed, and a good dispersing effect is achieved. Meanwhile, the fatty alcohol-polyoxyethylene ether is introduced as a stabilizing auxiliary agent, and the long-chain aliphatic oleophylic group of the stabilizing auxiliary agent can be effectively combined with the long chain of the polyolefin, so that the amphiphilic property is good, and the stability of the polyolefin resin powder micelle particles in water is further improved.
The technical scheme of the invention is specifically introduced as follows.
The invention provides a polyolefin resin-based carbon fiber suspension sizing agent, which consists of polyolefin resin powder, sodium polyacrylate, fatty alcohol-polyoxyethylene ether and deionized water; based on the total mass of the solid components as 100 percent, wherein:
65-75 wt% of polyolefin resin powder
10-15 wt% of sodium polyacrylate
15-20 wt% of fatty alcohol-polyoxyethylene ether.
The polyolefin resin powder may include, but is not limited to, general-purpose polyolefin resins such as polyethylene, polypropylene, polybutylene, polyisobutylene, and the like, and may be adjusted accordingly according to the type of the matrix resin for the carbon fiber composite material, and a polyolefin type corresponding to the matrix resin is preferable, and polypropylene is particularly preferable.
The number average molecular weight of the polyolefin resin powder is 1.0 to 4.0 ten thousand, preferably 1.5 to 3.0 ten thousand.
The polyolefin resin powder has an average diameter of 10 to 60 μm, preferably 20 to 40 μm.
The number average molecular weight of the sodium polyacrylate is 1000-5000, preferably 2000-4000.
The fatty alcohol-polyoxyethylene ether has the following structure:
wherein: r is selected from C10～C20Any one of alkyl groups, wherein n is a polymerization degree and is an integer selected from 25 to 40.
The mass content of the solid components in the sizing agent of the polyolefin resin-based carbon fiber suspension is 5-30%.
The invention also provides a preparation method of the polyolefin resin-based carbon fiber suspension sizing agent, which comprises the following specific steps:
(1) putting polyolefin resin powder and sodium polyacrylate into a mixing container according to a proportion, adding deionized water, starting a machine to stir when the added water amount reaches 25-35 wt% of the total feeding amount of the polyolefin resin powder and the sodium polyacrylate, and continuously adding the rest water; controlling the stirring speed to be 50-250 rpm, and stirring for 30-60 min for homogenizing and dispersing to obtain uniform white emulsion;
(2) transferring the materials into a closed device provided with a high-speed emulsifier, and adding quantitative fatty alcohol-polyoxyethylene ether to ensure that the mass percentage of all solid components in the suspension sizing agent is 5-30%;
(3) starting a high-speed emulsifying machine, and continuously stirring for 10-30 min at the rotating speed of 3000-10000 rpm to obtain the uniform and stable milky white suspension sizing agent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polyolefin resin powder is used as a main body, does not contain epoxy resin, other modifier components and organic solvent; simple preparation process, low equipment requirement, safety, environmental protection and low comprehensive cost.
(2) In the suspension preparation process, sodium polyacrylate is introduced as a main dispersing agent to form a double electric layer effect so as to enable polyolefin resin powder to achieve good dispersion, and meanwhile, fatty alcohol-polyoxyethylene ether with long-chain aliphatic lipophilic groups is introduced as a stabilizing auxiliary agent so as to improve the stability of micelle particles in water. The suspension type carbon fiber sizing agent is prepared by adopting a pure physical mixing method, the sizing agent is stable in storage and application, and the engineering process requirements are met.
(3) The carbon fiber sized by the sizing agent can be used for preparing polyolefin resin matrix composite materials, has good processing performance and interface bonding capability, has no risk of storage, aging and curing, and is stable and reliable.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Comparative example 1
The traditional epoxy resin emulsion type carbon fiber sizing agent is adopted to carry out an online sizing test on a carbon fiber engineering line. The sizing agent is SP-1 (produced by Shanghai organic of Chinese academy of sciences), and the main components are bisphenol A type epoxy resin and nonionic surfactant. And (3) adopting dipping type sizing, wherein the concentration of a sizing agent is 3.3%, the dipping time is 35s, and drying and collecting filaments to obtain the epoxy resin-based sizing carbon fiber.
Comparative example 2
The modified epoxy resin emulsion type carbon fiber sizing agent is adopted to carry out an online sizing test on a carbon fiber engineering line. The sizing agent is SP-1S (produced by Shanghai organic of Chinese academy of sciences), and the main components are modified bisphenol A epoxy resin and anionic surfactant. And (3) adopting dipping type sizing, wherein the concentration of a sizing agent is 4.6%, the dipping time is 40s, and drying and collecting filaments to obtain the epoxy resin-based sizing carbon fiber.
Examples 1 to 8
Sequentially adding a certain amount of polypropylene resin powder and sodium polyacrylate into a stirring kettle A, gradually dropwise adding deionized water, starting mechanical stirring when the water adding amount reaches 30 wt% of the total feeding amount, continuously stirring at a certain rotating speed, continuously adding the rest amount of water, stirring for a certain time to obtain uniform white emulsion, discharging, transferring to a stirring kettle B provided with a high-speed emulsifier, adding a certain amount of fatty alcohol-polyoxyethylene ether, starting a high-speed emulsifier, continuously stirring at a fixed rotating speed, and discharging to obtain the milky suspension sizing agent.
The polypropylene resin powder is from China petrochemical company, and the sodium polyacrylate and the fatty alcohol polyoxyethylene ether are from BASF corporation. The solid components of the suspension sizing agents prepared in the examples 1 to 8 are shown in table 1, the composition and the dosage of the sizing agents are shown in table 2, and the preparation process parameters of the sizing agents are shown in table 3.
By adopting the polypropylene resin-based suspension sizing agent prepared by the embodiment, dipping sizing is carried out on a carbon fiber engineering line for 50s, and sizing carbon fiber is obtained after drying and filament winding.
TABLE 1 solid components of sizing agent
TABLE 2 sizing agent composition amounts
TABLE 3 sizing agent preparation Process parameters
Test analysis
The pH value of the sizing agent is tested by adopting a Mettler pH meter; the rotational viscosity of the sizing agent was measured using a BROOKFIELD DV Pro VISCOMETER VISCOMETER; observing whether the prepared sizing agent has obvious layering by adopting a visual inspection method; the concentration of the prepared suspension is tested by adopting a drying and weighing method, the stability of the prepared sizing agent is characterized by the change rate of the concentration of the lower layer relative to the concentration of the upper layer, and the stability is calculated according to the following formula:
lower layer concentration change rate (%) - (lower layer concentration-upper layer concentration)/upper layer concentration 100%
The results of evaluating the properties of the obtained suspension sizing agent are shown in Table 4. As can be seen from the results in the table, no delamination phenomenon is found in the prepared suspension, and the concentrations of the upper layer and the lower layer are basically consistent and are basically neutral, which indicates that the prepared suspension is stable and reliable. The viscosity is low, the fluidity is good in the using process, the roller is not easy to stick, and the sizing effect is more uniform.
TABLE 4 evaluation results of performance of suspension sizing agent
Testing by using an OCA20 contact angle measuring instrument to obtain a contact angle between the polypropylene resin and the sizing carbon fiber; the interfacial shear strength of the polypropylene resin and the sized carbon fiber is obtained by testing with a MODEL HM410 interfacial performance evaluation device of the Japan Donglong industry company.
And (3) mixing the sized carbon fibers with polypropylene resin according to the ratio of 4: 6, extruding and granulating by using a double-screw extruder, and preparing the carbon fiber reinforced polypropylene composite material standard sample strip according to related test standards. And (3) performing sample preparation test on the tensile strength and the elongation at break of the sample strip according to the national standard GB/T1040-2006, and testing the bending strength of the sample strip according to the national standard GB/T9341-2008.
The performance test results of the sized carbon fibers and the prepared composite material are shown in table 5. As can be seen from the data in Table 5, compared with comparative examples 1-2, the contact angle between the sized carbon fiber prepared in the examples and the polyolefin resin is smaller, the polyolefin resin is more easily spread and soaked on the surface and inside of the carbon fiber, the shear strength of the two-phase interface is higher, and meanwhile, the carbon fiber reinforced composite material has more excellent comprehensive properties such as tensile strength, elongation at break, bending strength and the like.
TABLE 5 evaluation results of performance of sized carbon fiber and carbon fiber reinforced polypropylene composite
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A sizing agent for polyolefin resin-based carbon fiber suspension is characterized in that: it is composed of polyolefin resin powder, sodium polyacrylate, fatty alcohol-polyoxyethylene ether and deionized water; based on the total mass of the solid components as 100 percent, wherein:
65-75 wt% of polyolefin resin powder
10-15 wt% of sodium polyacrylate
15-20 wt% of fatty alcohol-polyoxyethylene ether;
the preparation method comprises the following specific steps:
(1) putting polyolefin resin powder and sodium polyacrylate into a mixing container according to a proportion, adding deionized water, starting a machine to stir when the added water amount reaches 25-35 wt% of the total feeding amount of the polyolefin resin powder and the sodium polyacrylate, and continuously adding the rest water; controlling the stirring speed to be 50-250 rpm, and stirring for 30-60 min for homogenizing and dispersing to obtain uniform white emulsion;
(2) transferring the materials into a closed device provided with a high-speed emulsifier, and adding fatty alcohol-polyoxyethylene ether to ensure that the mass percentage of all the solid components in the suspension sizing agent is 5-30%;
(3) starting a high-speed emulsifying machine, and continuously stirring for 10-30 min at the rotating speed of 3000-10000 rpm to obtain the uniform and stable milky white suspension sizing agent.
2. The polyolefin resin-based carbon fiber suspension sizing agent according to claim 1, characterized in that: the polyolefin resin powder includes general polyolefin resin of polyethylene, polypropylene, polybutylene or polyisobutylene.
3. The polyolefin resin-based carbon fiber suspension sizing agent according to claim 1, characterized in that: the number average molecular weight of the polyolefin resin powder is between 1.0 ten thousand and 4.0 ten thousand.
4. The polyolefin resin-based carbon fiber suspension sizing agent according to claim 1, characterized in that: the average diameter of the polyolefin resin powder is 10-60 micrometers.
5. The polyolefin resin-based carbon fiber suspension sizing agent as claimed in claim 1, wherein the number average molecular weight of the sodium polyacrylate is 1000-5000.
6. The polyolefin resin-based carbon fiber suspension sizing agent according to claim 1, characterized in that: the fatty alcohol polyoxyethylene ether has the following structure:
wherein: r is selected from any one of C10-C20 alkyl, n is polymerization degree and is an integer selected from 25-40.
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| CN104204342A (en) * | 2012-03-09 | 2014-12-10 | 帝人株式会社 | Carbon fiber bundle and process for producing same |
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| JP2005226193A (en) * | 2004-02-13 | 2005-08-25 | Mitsubishi Rayon Co Ltd | Sizing agent for reinforcing fiber, carbon fiber bundle, thermoplastic resin composition and molded product thereof |
| EP2924164B1 (en) * | 2012-11-26 | 2018-04-25 | Mitsubishi Chemical Corporation | Chopped carbon fiber bundles and method for producing chopped carbon fiber bundles |
| CN105531325B (en) * | 2013-10-29 | 2019-03-01 | 东丽株式会社 | Moulding material, its manufacturing method and the masterbatch for it |
| WO2015133569A1 (en) * | 2014-03-05 | 2015-09-11 | 三菱レイヨン株式会社 | Carbon fiber bundle for resin reinforcement and method for manufacturing carbon fiber bundle for resin reinforcement, carbon fiber-reinforced thermoplastic resin composition, and molded body |
| CN104963200A (en) * | 2015-07-30 | 2015-10-07 | 北京化工大学常州先进材料研究院 | Preparation method and application of water-soluble carbon fiber sizing agent |
| CN105862428B (en) * | 2016-05-05 | 2018-01-23 | 中国科学院宁波材料技术与工程研究所 | Preparation method of carbon fiber sizing agent that a kind of graphene is modified and products thereof |
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| CN104204342A (en) * | 2012-03-09 | 2014-12-10 | 帝人株式会社 | Carbon fiber bundle and process for producing same |
| CN103790019A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Epoxy-based carbon fiber sizing agent emulsion, its preparation method and its application |
| CN104562698A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of sizing agent of carbon fibers for reinforcement of thermoplastic resin |
| CN106400489A (en) * | 2016-08-31 | 2017-02-15 | 成路凯尔服装（苏州）有限公司 | Sizing technology of yarn of polyester-cotton-ramie blended fabric |
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