CN101880967B - Method for preparing self-emulsifying carbon fiber sizing agent component - Google Patents
Method for preparing self-emulsifying carbon fiber sizing agent component Download PDFInfo
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- CN101880967B CN101880967B CN2010102172409A CN201010217240A CN101880967B CN 101880967 B CN101880967 B CN 101880967B CN 2010102172409 A CN2010102172409 A CN 2010102172409A CN 201010217240 A CN201010217240 A CN 201010217240A CN 101880967 B CN101880967 B CN 101880967B
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Abstract
The invention discloses a method for preparing a self-emulsifying carbon fiber sizing agent component, which comprises the following steps of: performing graft polymerization reaction on epoxy resin by adopting an emulsion polymerization method to prepare modified epoxy emulsion; and standing the modified epoxy emulsion at 80 DEG C for two hours, adding dropwise ammonia water into the solution after demulsification to make the solution alkaline, standing the solution at 95 DEG C in a sealing way, stirring and hydrolyzing the solution for 3 hours, taking the solution out, acidifying and neutralizing the redundant ammonia water, drying and rinsing the solution to produce modified bisphenol A epoxy resin, placing the synthesis product in the step and the bisphenol A epoxy resin into a container according to a certain weight ratio, and performing phase-inversion emulsification on the mixture at 70 DEG C to prepare a modified epoxy emulsion sizing agent component with certain solid content. The prepared carbon fiber sizing agent component has the characteristics of storage time longer than 12 months, high high-temperature stability, and high dilution stability, so that the method has huge breakthrough compared with the prior art. Carbon fibers sized by the sizing agent have high machining performance and improved inter-layer shear strength.
Description
Technical field
The invention belongs to the fine chemical technology field, relate to a kind of product that contains high molecular polymer and preparation method thereof, specifically, be meant a kind of preparation method of self-emulsifying carbon fiber sizing agent component.
Background technology
The carbon fiber sizing agent component of prior art for preparing normally based on epoxy resin, a certain amount ofly adds emulsifying agent, auxiliary agent and makes through being equipped with.When using as component of sizing agent, it generally can be on deflector roll residual resin down, comparing it with the solution-type sizing agent can be because of using the solvent contaminated environment.Prior art adopts bisphenol A type epoxy resin, with polyethylene glycol oxide nonyl phenolic ether (OP-10) and Tween 80 (T-80) compound emulsifying agent, uses modifier acrylic acid and vinylacetate, makes water-based emulsion type carbon fiber sizing agent.This method is because the compatibility of emulsifying agent and resin is bad, and the resting period is when long, because emulsifying agent and epoxy resin compatibility are poor, and usually demulsifying phenomenon can take place.The emulsion that makes with existing commercial emulsifying agent is placed under 50 ℃ of environment, is no more than and a week all demulsifying phenomenon can takes place.
Summary of the invention
In order to overcome the shortcoming of prior art, the invention provides a kind of preparation method of self-emulsifying carbon fiber sizing agent component.Preparation method provided by the invention carries out in two steps, and the first step is carried out graft modification with the conventional emulsion polymerization method to epoxy resin, introduces the ester group group on the epoxy resin side chain, makes modified epoxy resin emulsion; Add alkali behind the second modified epoxy resin emulsion breakdown of emulsion of step, make the ester group group hydrolysis on the epoxy resin side chain become hydroxyl, obtain hydroxylated modified epoxy formation.This step synthetic product and bisphenol A type epoxy resin are placed container with certain weight ratio, under 70 ℃, carry out the modified epoxy resin emulsion sizing agent component that phase reversal emulsification prepares certain solid content.
On the one hand, the present invention is a kind of preparation method of self-emulsifying carbon fiber sizing agent component, realizes as follows:
The first step adopts emulsion polymerisation process to carry out graft polymerization reaction on epoxy resin; Be specially:
(a) elder generation adds half of distilled water in adding emulsifying agent, makes emulsifier solution;
(b) in initator, add residue distilled water and make initiator solution;
(c) epoxy resin is distributed in the emulsifier solution, is mixed with pre-emulsion;
(d) pre-emulsion is added drop-wise in the initiator solution, temperature is controlled in 62～65 ℃ of scopes, is stirred with 800 rev/mins speed simultaneously, and slowly adds modifier, makes the modified epoxy resin emulsion of band ester group;
Second step, modified epoxy resin emulsion was placed two hours under 80 ℃ of environment, behind the breakdown of emulsion in solution dropping ammonia, make solution be alkalescence, place 95 ℃ of environment lower seals to place and constantly stir solution and make its hydrolysis, reacted three hours, making hydrolysis of ester group is hydroxyl, take out solution and add the unnecessary ammoniacal liquor of acid neutralization, the hydroxyl modified epoxy and the bisphenol A type epoxy resin that obtain are placed container with certain weight ratio, hydroxyl modified epoxy serves as the effect of emulsifying agent, carries out phase reversal emulsification under 70 ℃ of temperature, promptly prepares the modified epoxy emulsion sizing agent component of certain solid content.About first step emulsion polymerisation, the emulsion polymerisation proportion of raw materials is as follows: main raw material has epoxy resin, emulsifying agent, initator, modifier and water, epoxy resin adopts bisphenol A type epoxy resin, emulsifying agent is a polyethylene glycol oxide nonyl phenolic ether (OP-10), the compound of Tween 80 (T-80) and neopelex (DBS), initator adopts ammonium persulfate, modifier adopts vinylacetate, water is distilled water, after epoxy resin and modifier consumption were determined, the percentage by weight (Wt%) of other ingredients constitute epoxy resin and modifier consumption sum was:
Polyethylene glycol oxide nonyl phenolic ether (OP-10) 4～8%
Tween 80 (T-80) 1～4%
Neopelex (DBS) 0.1～1%
Ammonium persulfate 0.5～3%
Distilled water 50～60%
Wherein the mass ratio of epoxy resin and modifier is (1: 1.5)～(1.5: 1).
About the ester group group hydrolysis on the second step epoxy resin side chain, detailed process is earlier the emulsion that forms to be placed breakdown of emulsion under 80 ℃ of temperature, adding ammoniacal liquor makes solution system be alkalescence, stirred 3 hours at 95 ℃ of environment temperature lower seals, be that the side chain hydrolysis of ester group is a hydroxyl, after finishing, reaction adds the acid neutralization, make solution be neutral, solution evaporate to dryness washing back places container with bisphenol A type epoxy resin with certain weight ratio, carries out the modified epoxy emulsion sizing agent component that phase reversal emulsification prepares certain solid content under 70 ℃.
Advantage of the present invention is as follows:
Aspect stable owing to do not use and do not add emulsifying agent, the hydroxyl modification epoxy emulsifying agent and the bisphenol A type epoxy resin compatibility that obtain after second step are good, so this emulsion leaves standstill good stability, the high-temperature stability excellence, dilution stability is good;
2. the emulsion particle diameter that obtains is evenly distributed, modest viscosity, and starch finishing effect is good;
3. prepare sizing agent with this sizing agent component, the carbon fiber that sizing agent is coated more not starching carbon fiber lousiness amount significantly reduces, and cluster performance is good.
4. this sizing agent component has raising to the ILSS (interlaminar shear strength at interface) of composite in theory.
5. aspect manufacturability, the present invention has adopted method of emulsion polymerization that epoxy resin is carried out graft modification, and this method makes that the graft reaction system viscosity is lower, and it is very fast to conduct heat, and is convenient to pipeline and carries, and course of reaction is easy to control.
The specific embodiment
Specify the preparation method of self-emulsifying carbon fiber sizing agent component provided by the invention below in conjunction with embodiment.
Embodiment 1:The preparation self-emulsifying carbon fiber sizing agent component.
The first step is carried out graft modification with emulsion polymerisation process to epoxy resin E-51, introduces the ester group group on the epoxy resin side chain;
Second step obtained hydroxyl with the hydrolysis of ester group on the side chain, made modified epoxy resin emulsion with modified epoxy emulsifying agent and the bisphenol A type epoxy resin of going up hydroxyl by phase reversal technology.
Described emulsion polymerisation process adopts raw material as follows: epoxy resin adopts epoxy resin E-51, the emulsifying agent that first step emulsion polymerisation is used adopts the compound of polyethylene glycol oxide nonyl phenolic ether (OP-10), Tween 80 (T-80) and neopelex (DBS), initator adopts ammonium persulfate, and modifier adopts vinylacetate.
After epoxy resin E-51 and modifier vinylacetate consumption were determined, the percentage by weight (Wt%) of other ingredients constitute epoxy resin E-51 and vinylacetate consumption sum was:
Polyethylene glycol oxide nonyl phenolic ether (OP-10) 6%
Tween 80 (T-80) 1%
Neopelex (DBS) 0.5%
Ammonium persulfate 3%
Distilled water 50%
Wherein, the mass ratio of vinylacetate and epoxy resin E-51 is 1.5: 1.
Concrete scheme is:
(1) in the compound of polyethylene glycol oxide nonyl phenolic ether (OP-10), Tween 80 (T-80) and neopelex (DBS), adds half of distilled water, make emulsifier solution;
(2) in ammonium persulfate, add residue distilled water and make initiator solution;
(3) epoxy resin E-51 is distributed in the emulsifier solution, is mixed with pre-emulsion;
(4) pre-emulsion is added drop-wise in the initiator solution, temperature is controlled in 62～65 ℃ of scopes, and slowly adds the modifier vinylacetate.Vinylacetate successfully is grafted on the epoxy resin as side chain, has just introduced the ester group group on the epoxy resin side chain.
Second step, the modified epoxy resin emulsion that forms is placed two hours breakdowns of emulsion under 80 ℃ of temperature, add alkali behind the breakdown of emulsion, ester group group on the epoxy resin E-51 side chain is stirred at 95 ℃ of environment temperature lower seals made the ester group reaction that is hydrolyzed in 3 hours, the ester group group hydrolysis on the epoxy resin E-51 side chain becomes hydroxyl; React after three hours, in hydrating solution, add the acid neutralization, make solution be neutral, obtain epoxy resin after the washing of solution evaporate to dryness through hydroxyl modification, this step synthetic product and bisphenol A type epoxy resin are placed container with certain weight ratio, and carrying out phase reversal emulsification under 70 ℃, to prepare solid content be 20% modified epoxy emulsion sizing agent component.
The lousiness amount: carbon fiber bundle is wiped (size 40mm * 5mm * 5mm at two polyurethane sponges, heavily about 0.35g) under the clamping, whole polyurethane sponge is wiped load 200g, and carbon fiber bundle passes through with 3m/min speed, survey the weight that is attached to the lousiness on the sponge after 10 minutes, be the friction lousiness amount of fibre bundle.Computational methods: carbon fiber is W by sponge quality before
1(g), carbon fiber is W by quality afterwards
2(g), the lousiness amount is (W
2-W
1) g.
The above-mentioned sizing agent component for preparing is carried out performance test, and the result is as follows:
1. increase the pH value scope that the second step post-modification epoxy-stabilized exists: 1-14, and the pH value scope of the modified epoxy emulsion-stabilizing after the first step is 4-12;
2. increase by the second step post-modification epoxy emulsion room temperature and leave standstill the storage life: more than 12 months, and the modified epoxy emulsion room temperature after the first step to leave standstill the storage life be 3 months;
3. dilution stability: increase by the second step post-modification epoxy emulsion and be diluted to not breakdown of emulsion of back 7 days of solids content to 10%, and the modified epoxy emulsion after the first step to be diluted to solids content to 10% be breakdown of emulsion in back 1 day;
4. solids content: the second step back sizing agent component solid content can be controlled allotment, and the uncontrollable allotment of solid content after the first step;
5. viscosity: the sizing agent component viscosity that second step obtained can be controlled, and the sizing agent component viscosity that the first step obtains can only rely on the reduction solid content merely, sacrifices stability of emulsion and reaches the purpose that reduces viscosity;
6. the lousiness amount of carbon fiber sees Table 1 after solid content is 6% hydroxylating epoxy emulsion starching:
Table 1 lousiness measures test result
| Lousiness amount (g) | |
| No pulp fibres | 0.0017 |
| Fiber after the starching | 0.0006 |
Embodiment 2
Choose vinylacetate and epoxy resin E-51 according to 1: 1.5 mass ratio, after vinylacetate and epoxy resin E-51 consumption were determined, the percentage by weight (Wt%) of other ingredients constitute vinylacetate and epoxy resin E-51 consumption sum was:
Polyethylene glycol oxide nonyl phenolic ether (OP-10) 6%
Tween 80 (T-80) 1%
Neopelex (DBS) 0.5%
Ammonium persulfate 2%
Distilled water 60%
The preparation method is with embodiment 1, and this embodiment solid content is 30%, and the sizing agent component for preparing is carried out performance test, and the result is as follows:
1. increase the pH value scope that the second step post-modification epoxy-stabilized exists: 1-14, and the pH value scope of the modified epoxy emulsion-stabilizing after the first step is 4-12;
2. increase by the second step post-modification epoxy emulsion room temperature and leave standstill the storage life: more than 12 months, and the modified epoxy emulsion room temperature after the first step to leave standstill the storage life be 1 month;
3. dilution stability: increase by the second step post-modification epoxy emulsion and be diluted to not breakdown of emulsion of back 7 days of solids content to 10%, and the modified epoxy emulsion after the first step to be diluted to solids content to 10% be breakdown of emulsion in back 1 day;
4. solids content: the second step back sizing agent component solid content can be controlled allotment, and the uncontrollable allotment of solid content after the first step;
5. viscosity: the sizing agent component viscosity that second step obtained can be controlled, and the sizing agent component viscosity that the first step obtains can only rely on the reduction solid content merely, sacrifices stability of emulsion and reaches the purpose that reduces viscosity;
6. the lousiness amount such as the table 2 of carbon fiber after solid content is 6% hydroxylating epoxy emulsion starching:
Table 2 lousiness measures test result
| Lousiness amount (g) | |
| No pulp fibres | 0.0028 |
| Fiber after the starching | 0.0012 |
Embodiment 3
Choose vinylacetate and bisphenol A type epoxy resin according to 1: 1 mass ratio, after vinylacetate and bisphenol A type epoxy resin consumption were determined, the percentage by weight (Wt%) of other ingredients constitute vinylacetate and bisphenol A type epoxy resin consumption sum was:
Polyethylene glycol oxide nonyl phenolic ether (OP-10) 4%
Tween 80 (T-80) 3%
Neopelex (DBS) 1%
Ammonium persulfate 0.5%
Distilled water 50%
The preparation method is with embodiment 1, and this embodiment solid content is 50%, and the sizing agent component for preparing is carried out performance test, and the result is as follows:
1. increase the pH value scope that the second step post-modification epoxy-stabilized exists: 1-14, and the pH value scope of the modified epoxy emulsion-stabilizing after the first step is 6-12;
2. increase by the second step post-modification epoxy emulsion room temperature and leave standstill the storage life: more than 12 months, and the modified epoxy emulsion room temperature after the first step to leave standstill the storage life be 3 months;
3. dilution stability: increase by the second step post-modification epoxy emulsion and be diluted to not breakdown of emulsion of back 7 days of solids content to 10%, and the modified epoxy emulsion after the first step to be diluted to solids content to 10% be breakdown of emulsion in back 1 day;
4. solids content: the second step back sizing agent component solid content can be controlled allotment, and the uncontrollable allotment of solid content after the first step;
5. viscosity: the sizing agent component viscosity that second step obtained can be controlled, and the sizing agent component viscosity that the first step obtains can only rely on the reduction solid content merely, sacrifices stability of emulsion and reaches the purpose that reduces viscosity;
6. the lousiness amount such as the table 3 of carbon fiber after solid content is 6% hydroxylating epoxy emulsion starching:
Table 3 lousiness measures test result
| Lousiness amount (g) | |
| No pulp fibres | 0.0028 |
| Fiber after the starching | 0.0012 |
Obtain by the foregoing description, second step is most important to the sizing agent component performance.Can allocate through the sizing agent component solid content that preparation method provided by the invention obtains, use the fiber after this sizing agent component carries out starching, the lousiness amount is few, leave standstill good stability, the dilution stability excellence, viscosity can be controlled, and is can stable existence between the 1-14 at pH value.Can predict, hydroxylated epoxy emulsion sizing agent has better cluster performance and interface interlaminar shear strength.
Claims (3)
1. the preparation method of self-emulsifying carbon fiber sizing agent component is characterized in that:
The first step adopts emulsion polymerisation process to carry out graft polymerization reaction on epoxy resin; Be specially:
(a) elder generation adds half of distilled water in emulsifying agent, makes and adds emulsifier solution;
(b) in initator, add residue distilled water and make initiator solution;
(c) epoxy resin is distributed to adds in the emulsifier solution, be mixed with pre-emulsion;
(d) pre-emulsion is added drop-wise in the initiator solution, temperature is controlled in 62～65 ℃ of scopes, is stirred with 800 rev/mins speed simultaneously, and slowly adds modifier, makes the modified epoxy resin emulsion of band ester group;
Second step, modified epoxy resin emulsion was placed two hours under 80 ℃ of environment, behind the breakdown of emulsion in solution dropping ammonia, make solution be alkalescence, place 95 ℃ of environment lower seals to place and constantly stir solution and make its hydrolysis, reacted three hours, making hydrolysis of ester group is hydroxyl, take out solution and add the unnecessary ammoniacal liquor of acid neutralization, the hydroxyl modified epoxy and the bisphenol A type epoxy resin that obtain are placed container with certain weight ratio, hydroxyl modified epoxy serves as the effect of emulsifying agent, carries out phase reversal emulsification under 70 ℃ of temperature, promptly prepares the modified epoxy emulsion sizing agent component of certain solid content;
Described emulsifying agent is the compound of polyethylene glycol oxide nonyl phenolic ether, Tween 80 and neopelex, modifier is vinylacetate, initator is an ammonium persulfate, epoxy resin is the bisphenol A type epoxy resin monomer, after modifier and monomer consumption were determined, the percentage by weight of other ingredients constitute monomer and modifier consumption summation was:
The mass ratio of described modifier and epoxy resin 1: 1.5～1.5: 1.
2. the preparation method of self-emulsifying carbon fiber sizing agent component according to claim 1 is characterized in that: the oil loving epoxide group of end group band of modified epoxy, and band hydrophily oh group on the side chain, modified epoxy can use as emulsifying agent.
3. the preparation method of self-emulsifying carbon fiber sizing agent component according to claim 1, it is characterized in that: the sizing agent component solid content is allocated as required, and the variation of solid content can not influence stability of emulsion.
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| CN102828416B (en) * | 2012-09-20 | 2014-06-11 | 金发科技股份有限公司 | Emulsion carbon fiber sizing agent as well as preparation method and application of sizing agent |
| CN103046346B (en) * | 2012-12-24 | 2014-07-02 | 金发科技股份有限公司 | Sizing agent for emulsion type carbon fiber, preparation method and application thereof |
| CN103174026B (en) * | 2013-04-09 | 2014-08-20 | 中国科学院山西煤炭化学研究所 | Polyamide acid aqueous sizing agent as well as preparation method and application thereof |
| CN106082709A (en) * | 2016-06-08 | 2016-11-09 | 常州天马集团有限公司（原建材二五三厂） | Automotive natural gas bottle glass fibre dedicated film-forming agent and preparation method thereof |
| CN111574719B (en) * | 2020-04-09 | 2023-06-06 | 深圳航天科技创新研究院 | Thermoplastic epoxy resin and application thereof, and surface modifier for carbon fiber |
| CN114481618B (en) * | 2022-03-21 | 2023-10-24 | 江苏恒神股份有限公司 | Carbon fiber sizing agent for water-based treatment, and preparation method and application thereof |
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| JP4456245B2 (en) * | 2000-09-12 | 2010-04-28 | 竹本油脂株式会社 | Carbon fiber sizing agent and carbon fiber sizing method |
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| CN1325369A (en) * | 1998-10-30 | 2001-12-05 | 欧文斯科尔宁格公司 | Sizing for glass fibres having low nonionic and cationic lubricant content |
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