CN107501466B - A kind of emulsion type carbon fiber sizing agent and preparation method thereof - Google Patents
A kind of emulsion type carbon fiber sizing agent and preparation method thereof Download PDFInfo
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Abstract
The invention provides an emulsion type carbon fiber sizing agent, which is prepared by carrying out polymerization reaction on a functional hard monomer, acrylamide and long-carbon side chain acrylate under the action of an initiator; the functional hard monomer is methyl methacrylate, styrene, ethyl methacrylate, methyl acrylate, ethyl acrylate or acrylonitrile. The addition of the functional hard monomer can improve the strength of the emulsion adhesive film, and the acrylamide can improve the adhesion property of the emulsion adhesive film to the surface of the carbon fiber. The long carbon chain acrylate can provide long carbon side chains and improve the compatibility of the fiber and the thermoplastic resin matrix. The finally prepared carbon fiber sizing agent has lower solid content and higher hardness.
Description
Technical Field
The invention relates to the technical field of carbon fiber composite materials, in particular to an emulsion type carbon fiber sizing agent and a preparation method thereof.
Background
The carbon fiber is an excellent material with high specific modulus, high specific strength, low density, high temperature resistance and small thermal expansion coefficient, and is widely applied to the high-end fields of aerospace, automobile and the like. However, carbon fibers are subjected to certain abrasion, fluffing and damage in the production and processing processes, so that the mechanical properties of the carbon fibers are reduced, and the application of the carbon fibers is greatly influenced.
The sizing treatment of the coating can not only improve the bundling property of the carbon fiber and protect the carbon fiber, but also well improve the interface performance of the carbon fiber composite material, for example, the Chinese patent CN201610264018.1 proposes a sizing agent adopting an amphiphilic modified nano-sheet layer molybdenum diselenide auxiliary agent, and improves the wear resistance and lubricity of the carbon fiber in the processing process. However, the method adds a large amount of micromolecular silicone oil and a dispersing agent, which is not beneficial to the adhesion between the carbon fiber and the plastic matrix. At present, the development of a polymer sizing agent for improving compatibility and carbon fiber processability is a problem to be solved urgently.
The acrylic ester copolymer has wide raw material sources and good adhesive property and film-forming property, and Chinese patent CN201410509042.8 mentions that an acrylic ester emulsion with a core-shell structure is prepared by adopting an emulsion polymerization method to be used as a waterproof coating. However, the emulsion prepared by the method has low solid content and low film hardness, and cannot protect carbon fibers.
Based on the above, the development of the high-solid-content acrylate emulsion type carbon fiber sizing agent can form a protective film with certain strength on the surface of carbon fiber, improve the interface performance of the thermoplastic matrix composite material, and meet the requirement of the mechanical properties of the material, and becomes an important development direction.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an emulsion type carbon fiber sizing agent and a preparation method thereof, and in particular, to an acrylate-based emulsion type carbon fiber sizing agent and a preparation method thereof, wherein the prepared sizing agent has a low solid content and a high hardness.
In order to solve the technical problems, the invention provides an emulsion type carbon fiber sizing agent which is prepared by carrying out polymerization reaction on a functional hard monomer, acrylamide and long-carbon side chain acrylate under the action of an initiator;
the functional hard monomer is methyl methacrylate, styrene, ethyl methacrylate, methyl acrylate, ethyl acrylate or acrylonitrile.
The mass ratio of the functional hard monomer to the acrylamide to the long-carbon side chain acrylate is preferably (10-70): (1-5): (15-40).
The acrylamide is preferably N-hydroxyethyl acrylamide, N-hydroxymethyl acrylamide or N, N' -methylenebisacrylamide.
The long carbon side chain acrylate is preferably hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, n-dodecyl methacrylate, n-octadecyl methacrylate, isobornyl acrylate or isobornyl methacrylate.
The initiator is preferably ammonium persulfate, potassium persulfate or p-menthane hydroperoxide.
The emulsifier in the emulsion type carbon fiber sizing agent is preferably one or a mixture of more than two of Tween T-20, Tween T-40, Tween T-60, Tween T-80, Tween T-85, span S-20, span S-40, span S-60 and span S-80.
The invention provides a preparation method of the emulsion type carbon fiber sizing agent, which comprises the following steps:
A) dispersing and stirring part of emulsifier, functional hard monomer, acrylamide and long carbon side chain acrylate in water to obtain pre-emulsion;
B) and uniformly mixing the rest of the emulsifier and part of the initiator in water, heating to 70-100 ℃, respectively dropwise adding the pre-emulsion and the rest of the initiator, and carrying out polymerization reaction to obtain the emulsion type carbon fiber sizing agent.
Preferably, the dispersion stirring is specifically:
a) firstly, carrying out preliminary dispersion stirring, wherein the stirring speed is 50-500 rpm, and the stirring time is 10-30 min;
b) and then stirring by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 8000-20000 rpm to obtain the stable pre-emulsion.
The high-speed pre-emulsification is adopted to refine the particle size of the emulsion and concentrate the particle size distribution, so that the emulsion can be stably stored at a high solid content, the sizing agent can be better spread on the surface of the carbon fiber to form a film, and the processing performance of the carbon fiber is greatly improved.
The temperature of the step A) may be room temperature or heated. The heating temperature is preferably 25-50 ℃.
The mass ratio of the functional hard monomer, the acrylamide, the long-carbon side chain acrylate, the initiator and the nonionic emulsifier is preferably (10-70): (1-5): (15: 40): (0.1-5): (0.1-5).
In the step B), the dripping time of the pre-emulsion is preferably 3-6 h, and the dripping time of the rest initiator is preferably 4-8 h.
The reaction time in the step B) is preferably 0.5-3 h. The reaction is preferably carried out under the protection of an inert gas. The inert gas is preferably nitrogen.
Compared with the prior art, the invention provides an emulsion type carbon fiber sizing agent which is prepared by carrying out polymerization reaction on a functional hard monomer, acrylamide and long-carbon side chain acrylate under the action of an initiator; the functional hard monomer is methyl methacrylate, styrene, ethyl methacrylate, methyl acrylate, ethyl acrylate or acrylonitrile. The addition of the functional hard monomer can improve the strength of the emulsion adhesive film, and the acrylamide can improve the adhesion property of the emulsion adhesive film to the surface of the carbon fiber. The long carbon chain acrylate can provide long carbon side chains and improve the compatibility of the fiber and the thermoplastic resin matrix. The finally prepared carbon fiber sizing agent has lower solid content and higher hardness.
Drawings
FIG. 1 is a particle size distribution diagram of an emulsion type carbon fiber sizing agent prepared in example 2 of the present invention.
Detailed Description
In order to further illustrate the present invention, the following will describe the emulsion type carbon fiber sizing agent and the preparation method thereof in detail with reference to the examples.
Example 1
The emulsion comprises the following components in percentage by weight: tween-200.1%, ammonium persulfate 0.1%, methyl methacrylate 70%, N-hydroxyethyl acrylamide 1.8%, dodecyl methacrylate 28%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 50rpm for 10 min. Further stirring by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 8000rpm to obtain the stable reaction pre-emulsion.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 70 ℃, after the reaction temperature is reached, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle, dropwise adding the pre-emulsion for 3 hours, and dropwise adding the initiator for 4 hours. After the dropwise addition, the reaction is continued for 0.5 at constant temperature, and the reaction is terminated after the heat preservation is finished.
Example 2
The emulsion comprises the following components in percentage by weight: tween T-801.5%, ammonium persulfate 1.5%, methyl methacrylate 69%, N-hydroxyethyl acrylamide 1%, isobornyl methacrylate 27%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 100rpm for 15 min. Further stirring by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 10000rpm to obtain the stable reaction pre-emulsion.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 86 ℃, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle after the reaction temperature is reached, dropwise adding the pre-emulsion for 3.5h, and dropwise adding the initiator for 4 h. And (3) continuing the constant-temperature reaction 1 after the dropwise addition is finished, and stopping the reaction after the heat preservation is finished.
The particle size distribution of the prepared sizing agent is detected, and the result is shown in figure 1.
Example 3
The emulsion comprises the following components in percentage by weight: span 1.5%, p-menthane hydroperoxide 1.5%, ethyl methacrylate 52%, N-hydroxymethyl acrylamide 5%, heptyl methacrylate 40%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 200rpm for 17 min. Further stirring by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 12000rpm to obtain the stable reaction pre-emulsion.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 76 ℃, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle after the reaction temperature is reached, dropwise adding the pre-emulsion for 4 hours, and dropwise adding the initiator for 5 hours. After the dropwise addition, the reaction is continued for 1.5h at constant temperature, and the reaction is terminated after the heat preservation is finished.
Example 4
The emulsion comprises the following components in percentage by weight: span S-603%, ammonium persulfate 4%, styrene 62%, N-hydroxyethyl acrylamide 1%, N-dodecyl methacrylate 30%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 150rpm for 20 min. Further stirring with a high-speed shear dispersion emulsifier at 15000rpm to obtain a stable reaction pre-emulsion.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 90 ℃, after the reaction temperature is reached, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle, dropwise adding the pre-emulsion for 3 hours, and dropwise adding the initiator for 4 hours. After the dropwise addition, the reaction is continued for 2 hours at constant temperature, and the reaction is terminated after the heat preservation is finished.
Example 5
The emulsion comprises the following components in percentage by weight: tween T-852%, potassium persulfate 2%, acrylonitrile 58%, N, N' -methylene bisacrylamide 8%, and N-dodecyl methacrylate 30%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 230rpm for 25 min. Further stirring by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 17000rpm to obtain the stable reaction pre-emulsion.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 78 ℃, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle after the reaction temperature is reached, dropwise adding the pre-emulsion for 5 hours, and dropwise adding the initiator for 6 hours. After the dropwise addition, the reaction is continued for 3 hours at constant temperature, and the reaction is terminated after the heat preservation is finished.
Example 6
The emulsion comprises the following components in percentage by weight: span S-403%, potassium persulfate 3%, methyl acrylate 51%, N, N' -methylene bisacrylamide 8%, nonyl methacrylate 35%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 450rpm for 25 min. And further stirring by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 18000rpm to obtain the stable reaction pre-emulsion.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 83 ℃, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle after the reaction temperature is reached, dropwise adding the pre-emulsion for 5 hours, and dropwise adding the initiator for 7 hours. After the dropwise addition, the reaction is continued for 3 hours at constant temperature, and the reaction is terminated after the heat preservation is finished.
Example 7
The emulsion comprises the following components in percentage by weight: span S-201%, potassium persulfate 1%, methyl acrylate 50%, N, N' -methylene bisacrylamide 8%, and N-octadecyl methacrylate 40%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 500rpm for 25 min. Further stirring with a high-speed shearing dispersion emulsifying machine at 19000rpm to obtain a stable reaction pre-emulsion.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 93 ℃, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle after the reaction temperature is reached, dropwise adding the pre-emulsion for 6 hours, and dropwise adding the initiator for 6 hours. After the dropwise addition, the reaction is continued for 1.5h at constant temperature, and the reaction is terminated after the heat preservation is finished.
Example 8
The emulsion comprises the following components in percentage by weight: span S-401%, p-menthane hydroperoxide 1%, methyl methacrylate 65%, N, N' -methylene bisacrylamide 8%, heptyl methacrylate 25%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 350rpm for 30 min. Further stirring by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 17500rpm to obtain the stable reaction pre-emulsion.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 84 ℃, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle after the reaction temperature is reached, dropwise adding the pre-emulsion for 4 hours, and dropwise adding the initiator for 4.5 hours. After the dropwise addition, the reaction is continued for 1.5h at constant temperature, and the reaction is terminated after the heat preservation is finished.
Example 9
The emulsion comprises the following components in percentage by weight: span S-805%, potassium persulfate 5%, methyl methacrylate 60%, N-hydroxymethyl acrylamide 5%, stearyl methacrylate 25%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 500rpm for 30 min. Further stirring by using a high-speed shearing dispersion emulsifying machine, wherein the stirring speed is 20000rpm, and obtaining the stable reaction pre-emulsion.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 100 ℃, after the reaction temperature is reached, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle, dropwise adding the pre-emulsion for 6 hours, and dropwise adding the initiator for 8 hours. After the dropwise addition, the reaction is continued for 3 hours at constant temperature, and the reaction is terminated after the heat preservation is finished.
Comparative example 1
The emulsion comprises the following components in percentage by weight: tween T-801.5%, ammonium persulfate 1.5%, N-hydroxyethyl acrylamide 28%, dodecyl methacrylate 69%
The procedure was as in example 2.
Comparative example 2
The emulsion comprises the following components in percentage by weight: tween T-801.5%, ammonium persulfate 1.5%, methyl methacrylate 69%, N-hydroxyethyl acrylamide 1%, isobornyl methacrylate 27%
(1) Preparation of the Pre-emulsion
Under room temperature or heating condition, half of the emulsifier, deionized water and the reaction monomer are initially dispersed and stirred at the stirring speed of 100rpm for 15 min.
(2) Polymerisation reaction
Adding the rest of emulsifier and a part of initiator into reaction medium water, fully stirring in a reaction container protected by nitrogen atmosphere, heating to 86 ℃, dropwise adding the pre-emulsion and the rest of initiator into the reaction kettle after the reaction temperature is reached, dropwise adding the pre-emulsion for 3.5h, and dropwise adding the initiator for 4 h. And (3) continuing the constant-temperature reaction 1 after the dropwise addition is finished, and stopping the reaction after the heat preservation is finished.
The performance of the carbon fiber sizing agents prepared in the above examples 1 to 9 and comparative examples 1 to 2 was tested, and the results are shown in table 1:
TABLE 1 Performance test results for examples 1-9 and comparative examples 1-2
| Solid content% | Particle size nm | Particle size distribution | Hardness of the film | |
| Example 1 | 48.37％ | 213 | 0.055 | HB |
| Example 2 | 58.48％ | 150 | 0.041 | 3H |
| Example 3 | 47.38％ | 161 | 0.061 | 2H |
| Example 4 | 57.32％ | 143 | 0.054 | 2H |
| Example 5 | 49.21％ | 167 | 0.071 | 2H |
| Example 6 | 60.29％ | 189 | 0.038 | HB |
| Example 7 | 46.38％ | 153 | 0.044 | HB |
| Example 8 | 47.29％ | 164 | 0.069 | HB |
| Example 9 | 55.75％ | 112 | 0.033 | 2H |
| Comparative example 1 | 56.48％ | 179 | 0.045 | B |
| Comparative example 2 | 23.57％ | 659 | 0.13 | 2B |
The chopped carbon fibers were treated with the sizing agents prepared in examples 1-9 and comparative examples 1-2, and the ratio of 3: 7 proportion and polyethylene are blended and compounded to obtain the carbon fiber composite material, the mechanical property test is carried out, and the result is shown in Table 2
TABLE 2 Performance test results for examples 1-9 and comparative examples 1-2
The carbon fiber sizing agent prepared by the invention has higher adhesive film hardness, and can effectively protect carbon fibers and enhance the interface performance to thermoplastic plastics.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (6)
1. An emulsion type carbon fiber sizing agent is characterized in that the sizing agent is prepared by carrying out polymerization reaction on a functional hard monomer, acrylamide and long carbon side chain acrylate under the action of an initiator;
the functional hard monomer is methyl methacrylate, styrene, ethyl methacrylate, methyl acrylate, ethyl acrylate or acrylonitrile;
the mass ratio of the functional hard monomer to the acrylamide to the long-carbon side chain acrylate is (10-70): (1-5): (15-40);
the emulsion type carbon fiber sizing agent is prepared by the following method:
A) dispersing and stirring part of emulsifier, functional hard monomer, acrylamide and long carbon side chain acrylate in water to obtain pre-emulsion;
B) uniformly mixing the rest of the emulsifier and part of the initiator in water, heating to 70-100 ℃, respectively dropwise adding the pre-emulsion and the rest of the initiator, and carrying out polymerization reaction to obtain an emulsion type carbon fiber sizing agent;
the acrylamide is N-hydroxyethyl acrylamide, N-hydroxymethyl acrylamide or N, N' -methylene bisacrylamide;
the long-carbon side chain acrylate is hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, n-dodecyl methacrylate, n-octadecyl methacrylate, isobornyl acrylate or isobornyl methacrylate;
the dispersion stirring specifically comprises the following steps:
a) firstly, carrying out preliminary dispersion stirring, wherein the stirring speed is 50-500 rpm, and the stirring time is 10-30 min;
b) and then stirring by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 8000-20000 rpm to obtain the stable pre-emulsion.
2. An emulsion-type carbon fiber sizing agent according to claim 1, wherein the initiator is ammonium persulfate, potassium persulfate or p-menthane hydroperoxide.
3. The emulsion-type carbon fiber sizing agent according to claim 1, wherein the emulsifier in the emulsion-type carbon fiber sizing agent is one or more of tween-20, tween-40, tween-60, tween-80, tween-85, span S-20, span S-40, span S-60 and span S-80.
4. The preparation method of the emulsion type carbon fiber sizing agent according to any one of claims 1 to 3, characterized by comprising the following steps:
A) dispersing and stirring part of emulsifier, functional hard monomer, acrylamide and long carbon side chain acrylate in water to obtain pre-emulsion;
B) uniformly mixing the rest of the emulsifier and part of the initiator in water, heating to 70-100 ℃, respectively dropwise adding the pre-emulsion and the rest of the initiator, and carrying out polymerization reaction to obtain an emulsion type carbon fiber sizing agent;
the dispersion stirring specifically comprises the following steps:
a) firstly, carrying out preliminary dispersion stirring, wherein the stirring speed is 50-500 rpm, and the stirring time is 10-30 min;
b) and then stirring by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 8000-20000 rpm to obtain the stable pre-emulsion.
5. The method according to claim 4, wherein the emulsifier is a nonionic emulsifier;
the mass ratio of the functional hard monomer to the acrylamide to the long-carbon side chain acrylate to the initiator to the nonionic emulsifier is (10-70): (1-5): (15-40): (0.1-5): (0.1-5).
6. The preparation method of claim 4, wherein in the step B), the dropping time of the pre-emulsion is 3-6 h, and the dropping time of the rest of the initiator is 4-8 h.
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| CN104204341A (en) * | 2012-03-29 | 2014-12-10 | 松本油脂制药株式会社 | Sizing agent for reinforcing fibers, and use thereof |
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