CN113087838B - Acrylate emulsion for glass fiber and preparation method and application thereof - Google Patents
Acrylate emulsion for glass fiber and preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses an acrylate emulsion for glass fibers, a preparation method and an application thereof, wherein the acrylate emulsion comprises the following components in percentage by mass: 20-50% of an acrylate monomer; 0.4-3% of an emulsifier; 0.05-0.5% of an initiator; the balance of water; wherein the acrylate monomer is an acrylate monomer containing an epoxy group. The acrylate emulsion is formed by polymerizing the acrylate monomer with the epoxy group, has high epoxy group content, can fully react with the terminal carboxyl on the PBT resin, and improves the hydrolysis resistance of the glass fiber reinforced PBT resin composite material.
Description
Technical Field
The invention relates to the technical field of glass fiber production and manufacturing, in particular to an acrylate emulsion for glass fibers and a preparation method and application thereof.
Background
Polybutylene terephthalate (PBT) is an engineering plastic with excellent performance and wide application. The glass fiber reinforced PBT resin can endow the composite material with more excellent mechanical properties, can reduce the production cost of the composite material, and is widely applied to various aspects of national production and life, such as the fields of automobiles, electronic appliances, mechanical equipment and the like. However, with the deep development of the material industry, in the process of continuously expanding the application field of the glass fiber reinforced PBT composite material, the limitation of the material characteristics is more and more obvious, and the most typical problem is that the hydrolysis resistance of the glass fiber reinforced PBT composite material is poor. Under the conditions of high heat and high humidity, polyester groups in the PBT resin are easy to generate hydrolysis chain scission reaction under the promotion of terminal carboxyl groups, so that the material degradation is caused, and the mechanical property is reduced, thereby greatly limiting the application of the PBT resin and the composite material thereof under the conditions of high heat and high humidity, such as the periphery of an automobile engine, air conditioner blades and the like.
Disclosure of Invention
The inventor researches and discovers that the consumption of the terminal carboxyl of the PBT resin is the core for solving the technical problem; based on the research, the invention provides an acrylate emulsion for glass fibers, and a preparation method and application thereof.
In order to achieve the above object, a first technical solution provided by the present invention is as follows:
the acrylic ester emulsion for the glass fiber comprises the following components in percentage by mass:
wherein the acrylate monomer is an acrylate monomer containing an epoxy group.
Further, the acrylate emulsion comprises the following components in percentage by mass:
still further, the acrylate emulsion comprises the following components in percentage by mass:
in the first aspect, the epoxy group number of the acrylate emulsion is maximized by using the acrylate monomer containing the epoxy group as the only monomer, and the hydrolysis resistance of the composite material is improved by the chemical reaction between the epoxy group contained in the acrylate emulsion and the terminal carboxyl group of the PBT resin. In some possible embodiments of the present disclosure, the epoxy group-containing acrylic monomer may be glycidyl acrylate, and the epoxy group-containing acrylic monomer may also be glycidyl methacrylate; the acrylic monomer containing an epoxy group may also be a combination of both glycidyl acrylate and glycidyl methacrylate. However, the inventor researches and discovers that when the acrylate monomer containing the epoxy group is glycidyl acrylate, the performance of the prepared acrylate emulsion is better.
In a second aspect, the invention employs a reactive emulsifier as a specific emulsifier species for the reaction during the preparation of the acrylate emulsion. The reactive emulsifier has reactive groups capable of participating in polymerization in addition to the hydrophilic groups and the lipophilic groups of conventional emulsifiers. The reactive emulsifier can participate in the polymer chain and firmly coat the polymer chain through emulsion polymerization, so that the migration problem of the traditional emulsifier can be avoided. When the acrylate emulsion and the aminosilane coupling agent are mixed to prepare the glass fiber sizing agent, the emulsifier of the acrylate emulsion prepared by the reactive emulsifier can not migrate, so that the instability of the sizing agent caused by the reaction of an epoxy group in the emulsion and an amino group in the aminosilane coupling agent in water can be avoided. Thus, the present invention employs a reactive emulsifier as the sole emulsifier. In some embodiments of the present invention, the reactive emulsifier may be an allyl reactive emulsifier, an acrylamide reactive emulsifier, or a maleate reactive emulsifier; of course, the emulsifier may be any two-by-two combination of an allyl type reactive emulsifier, an acrylamide type reactive emulsifier, and a maleate type reactive emulsifier; of course, the emulsifier may also be three combinations of an allyl type reactive emulsifier, an acrylamide type reactive emulsifier, and a maleate type reactive emulsifier. The inventor researches and discovers that when the reactive emulsifier is an allyl reactive emulsifier, the performance of the prepared acrylate emulsion is better; such as ammonium allyloxy fatty alcohol polyoxyethylene ether sulfate (SR-10) from Aidicke (China) investment Co.
In some embodiments of the present invention, the initiator of the present invention may be ammonium persulfate, potassium persulfate, or sodium persulfate; the initiator can also be any two of ammonium persulfate, potassium persulfate and sodium persulfate; the initiator may also be a combination of ammonium persulfate, potassium persulfate, and sodium persulfate. The initiator is used in the reaction of the present invention primarily to initiate polymerization of the acrylate monomer. The relative molecular weight of the acrylate emulsion is determined by the using amount of the initiator, and under the condition of ensuring normal production, the smaller the using amount of the initiator is, the more the acrylate monomer is, the higher the relative molecular weight of the emulsion is, and the more excellent the hydrolysis resistance of the final composite material is.
The second technical scheme provided by the invention is as follows: the preparation method of the acrylic ester emulsion for the glass fiber comprises the following steps:
s1: dissolving an initiator by using water with the mass being 20-100 times of that of the initiator to prepare an initiator solution;
s2: adding an emulsifier and the rest water into a reaction kettle, heating while stirring, dripping the initiator solution and the acrylate monomer in a constant temperature state when the temperature in the reaction kettle is raised to 80-90 ℃, and finishing dripping within 3-4 hours;
s3: and (3) after the dropwise addition is finished, carrying out heat preservation reaction for 2-3 hours, and after the reaction is finished, reducing the temperature in the reaction kettle to 20-50 ℃ for filtering to obtain the acrylate emulsion.
The third technical scheme provided by the invention is as follows: the acrylic ester emulsion for the glass fiber is used for preparing a glass fiber impregnating compound;
the following describes a method for preparing a glass fiber sizing agent by taking an aminosilane coupling agent A1100 as an example:
adding 0.6 mass part of aminosilane coupling agent A1100 into a clean container, stirring and hydrolyzing with 20 mass parts of water, adding 6 mass parts of acrylate emulsion (diluted by 1 mass part of water), adding 0.1 mass part of lubricant PEG600 (diluted by 10 mass parts of water), adding 0.01 mass part of defoaming agent BYK-051 (diluted by 10 mass parts of water), supplementing the weight of the impregnating compound to a set value by water, and fully stirring for 20 minutes to obtain the impregnating compound with the solid mass of 6.71%.
In the preparation process of the glass fiber sizing agent, the amount of each component is not only used, but the amount is only used for illustration.
Further, the impregnating compound is used for coating glass fibers, and the glass fibers are used for preparing the reinforced PBT resin composite material, so that the obtained PBT resin composite material has excellent hydrolysis resistance. Specifically, the reinforced PBT resin composite material is prepared by the following steps:
coating the prepared impregnating compound on glass fiber with the diameter of a single fiber of 10 mu m by an impregnating compound oiling machine, and preparing the glass fiber into glass fiber chopped yarn with the chopped length of 3 mm. The chopped strand and a reinforced polybutylene terephthalate resin (L2100 of Chingsu Chinghua chemical fiber Co., Ltd.) were subjected to an extrusion and injection molding process to prepare a chopped strand reinforced PBT resin composite material having a glass fiber content of 30%.
Similarly, the single fiber diameter of the glass fiber and the chopped glass fiber length are also given as examples.
Compared with the prior art, the acrylate emulsion is formed by polymerizing the acrylate monomer with the epoxy group, has high epoxy group content, can fully react with the terminal carboxyl on the PBT resin, and improves the hydrolysis resistance of the glass fiber reinforced PBT resin composite material. Meanwhile, the acrylate emulsion prepared by the reactive emulsifier and the aminosilane coupling agent have good blending stability and are suitable for glass fiber sizing agents.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The acrylate emulsion for glass fibers is prepared from solid components and deionized water; wherein the solid component comprises an acrylate monomer containing an epoxy group, a reactive emulsifier and an initiator.
Specifically, the epoxy group number of the acrylate emulsion is maximized by using the acrylate monomer containing the epoxy group as the only monomer, and the hydrolysis resistance of the composite material is improved by the chemical reaction between the epoxy group contained in the acrylate emulsion and the terminal carboxyl group of the PBT resin. In some possible embodiments of the present disclosure, the epoxy group-containing acrylic monomer may be glycidyl acrylate, and the epoxy group-containing acrylic monomer may also be glycidyl methacrylate; the acrylic monomer containing an epoxy group may also be a combination of both glycidyl acrylate and glycidyl methacrylate. However, the inventor researches and discovers that when the acrylate monomer containing the epoxy group is glycidyl acrylate, the performance of the prepared acrylate emulsion is better. In a specific embodiment of the present invention, the epoxy group-containing acrylate monomer accounts for 20 to 50% by mass of the acrylate emulsion, preferably 25 to 45% by mass of the acrylate emulsion, and more preferably 30 to 40% by mass of the acrylate emulsion.
The invention adopts the reactive emulsifier as the specific emulsifier type to react in the process of preparing the acrylic ester emulsion. The reactive emulsifier has reactive groups capable of participating in polymerization in addition to the hydrophilic groups and the lipophilic groups of conventional emulsifiers. The reactive emulsifier can participate in the polymer chain and firmly coat the polymer chain through emulsion polymerization, so that the migration problem of the traditional emulsifier can be avoided. When the acrylate emulsion and the aminosilane coupling agent are mixed to prepare the glass fiber sizing agent, the emulsifier of the acrylate emulsion prepared by the reactive emulsifier can not migrate, so that the instability of the sizing agent caused by the reaction of an epoxy group in the emulsion and an amino group in the aminosilane coupling agent in water can be avoided. Thus, the present invention employs a reactive emulsifier as the sole emulsifier. In some embodiments of the present invention, the reactive emulsifier may be an allyl reactive emulsifier, an acrylamide reactive emulsifier, or a maleate reactive emulsifier; of course, the emulsifier may be any two-by-two combination of an allyl type reactive emulsifier, an acrylamide type reactive emulsifier, and a maleate type reactive emulsifier; of course, the emulsifier may also be three combinations of an allyl type reactive emulsifier, an acrylamide type reactive emulsifier, and a maleate type reactive emulsifier. The inventor researches and discovers that when the reactive emulsifier is an allyl reactive emulsifier, the performance of the prepared acrylate emulsion is better; such as ammonium allyloxy fatty alcohol polyoxyethylene ether sulfate (SR-10) from Aidicke (China) investment Co. The reactive emulsifier accounts for 0.4-3% of the acrylate emulsion by mass, preferably 0.7-2.5% of the acrylate emulsion by mass, and more preferably 1-2% of the acrylate emulsion by mass.
The initiator used in the process of preparing the acrylate emulsion can be ammonium persulfate, potassium persulfate or sodium persulfate; the initiator can also be any two of ammonium persulfate, potassium persulfate and sodium persulfate; the initiator may also be a combination of ammonium persulfate, potassium persulfate, and sodium persulfate. The initiator is used in the reaction of the present invention primarily to initiate polymerization of the acrylate monomer. The relative molecular weight of the acrylate emulsion is determined by the using amount of the initiator, and under the condition of ensuring normal production, the smaller the using amount of the initiator is, the more the acrylate monomer is, the higher the relative molecular weight of the emulsion is, and the more excellent the hydrolysis resistance of the final composite material is. Therefore, the initiator accounts for 0.05-0.5% of the acrylate emulsion by mass, preferably 0.05-0.3% of the acrylate emulsion by mass, and more preferably 0.05-0.2% of the acrylate emulsion by mass.
Based on 100 percent of the total mass of the acrylate emulsion, the rest is deionized water except the acrylate monomer containing the epoxy group, the reactive emulsifier and the initiator.
The invention utilizes the components and prepares the acrylic ester emulsion for the glass fiber by the following method:
s1: dissolving an initiator by using water with the mass being 20-100 times of that of the initiator to prepare an initiator solution;
s2: adding an emulsifier and the rest water into a reaction kettle, heating while stirring, dripping the initiator solution and the acrylate monomer in a constant temperature state when the temperature in the reaction kettle is raised to 80-90 ℃, and finishing dripping within 3-4 hours;
s3: and (3) after the dropwise addition is finished, carrying out heat preservation reaction for 2-3 hours, and after the reaction is finished, reducing the temperature in the reaction kettle to 20-50 ℃, and filtering to obtain the acrylate emulsion.
The acrylate emulsion prepared by the invention can be used for preparing a glass fiber sizing agent, and the preparation method of the glass fiber sizing agent is explained by taking an aminosilane coupling agent A1100 as an example:
adding 0.6 mass part of aminosilane coupling agent A1100 into a clean container, stirring and hydrolyzing with 20 mass parts of water, adding 6 mass parts of acrylate emulsion (diluted by 1 mass part of water), adding 0.1 mass part of lubricant PEG600 (diluted by 10 mass parts of water), adding 0.01 mass part of defoaming agent BYK-051 (diluted by 10 mass parts of water), supplementing the weight of the impregnating compound to a set value by water, and fully stirring for 20 minutes to obtain the impregnating compound with the solid mass of 6.71%. It should be noted that, in the preparation process of the glass fiber sizing agent, the amount of each component is not exclusive, and the amount is only exemplified.
Further, the impregnating compound is used for coating glass fibers, and the glass fibers are used for preparing the reinforced PBT resin composite material, so that the obtained PBT resin composite material has excellent hydrolysis resistance. Specifically, the reinforced PBT resin composite material is prepared by the following steps:
coating the prepared impregnating compound on glass fiber with the diameter of a single fiber of 10 mu m by an impregnating compound oiling machine, and preparing the glass fiber into glass fiber chopped yarn with the chopped length of 3 mm. The chopped strand and a reinforced polybutylene terephthalate resin (L2100 of Jiangsu instrumented chemical fiber company, Inc.) were subjected to extrusion and injection molding processes to prepare a chopped strand reinforced PBT resin composite material having a glass fiber content of 30%. Similarly, the single fiber diameter of the glass fiber and the chopped glass fiber length are also given as examples.
Some specific examples of the acrylate emulsions according to the invention are listed below:
example 1
S1: dissolving 0.05 part by mass of ammonium persulfate by 5 parts by mass of water to prepare an initiator solution;
s2: adding 0.4 part by mass of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate and 74.55 parts by mass of water into a reaction kettle, stirring and heating, when the temperature in the reaction kettle rises to 80 ℃, simultaneously dropwise adding the initiator solution prepared in the step S1 and 20 parts by mass of glycidyl acrylate, controlling the reaction temperature to be 80-82 ℃, and after dropwise adding is completed, carrying out heat preservation reaction for 3 hours;
s3: and after the reaction is finished, stopping heating, and filtering to obtain the acrylate emulsion after the temperature in the reaction kettle is reduced to 30 ℃.
EXAMPLES 2
S1: dissolving 0.1 part by mass of ammonium persulfate by 5 parts by mass of water to prepare an initiator solution;
s2: adding 1 part by mass of allyloxy fatty alcohol-polyoxyethylene ether ammonium sulfate and 63.9 parts by mass of water into a reaction kettle, heating while stirring, when the temperature in the reaction kettle rises to 90 ℃, simultaneously dropwise adding the initiator solution prepared in the step S1 and 30 parts by mass of glycidyl acrylate for 3 hours, controlling the reaction temperature to be 88-90 ℃, and preserving heat for reacting for 2 hours after dropwise adding is completed;
s3: and (3) cooling the temperature in the reaction kettle to 50 ℃, and filtering to obtain the acrylate emulsion.
EXAMPLE 3
S1: dissolving 0.05 part by mass of ammonium persulfate by 2.5 parts by mass of water to prepare an initiator solution;
s2: adding 1 part by mass of allyloxy fatty alcohol-polyoxyethylene ether ammonium sulfate and 56.45 parts by mass of water into a reaction kettle, stirring and heating, when the temperature in the reaction kettle rises to 85 ℃, simultaneously dropwise adding the initiator solution prepared in the step S1 and 40 parts by mass of glycidyl acrylate, wherein the dropwise adding time is 3 hours, the reaction temperature is controlled to be 84-86 ℃, and after the dropwise adding is finished, carrying out heat preservation reaction for 3 hours;
s3: and (3) after the temperature in the reaction kettle is reduced to 20 ℃, filtering to obtain the acrylate emulsion.
Example 4
S1: dissolving 0.1 part by mass of potassium persulfate by 5 parts by mass of water to prepare an initiator solution;
s2: adding 1.5 parts by mass of sodium acrylamido isopropyl sulfonate and 53.4 parts by mass of water into a reaction kettle, stirring and heating, when the temperature in the reaction kettle rises to 85 ℃, simultaneously dropwise adding the initiator solution prepared in the step S1 and 40 parts by mass of glycidyl acrylate, wherein the dropwise adding time is 3 hours, the reaction temperature is controlled to be 84-86 ℃, and after the dropwise adding is finished, carrying out heat preservation reaction for 3 hours;
s3: and (3) after the temperature in the reaction kettle is reduced to 20 ℃, filtering to obtain the acrylate emulsion.
Example 5
S1: dissolving 0.3 mass part of potassium persulfate by 15 mass parts of water to prepare an initiator solution;
s2: adding 3 parts by mass of sodium acrylamido isopropyl sulfonate and 41.7 parts by mass of water into a reaction kettle, stirring and heating, when the temperature in the reaction kettle rises to 85 ℃, simultaneously dropwise adding the initiator solution prepared in the step S1 and 40 parts by mass of glycidyl acrylate for 3 hours, controlling the reaction temperature to be 84-86 ℃, and after dropwise adding is finished, carrying out heat preservation reaction for 3 hours;
s3: and (3) cooling the temperature in the reaction kettle to 20 ℃, and filtering to obtain the acrylate emulsion.
Example 6
S1: dissolving 0.05 parts by mass of potassium persulfate by 2.5 parts by mass of water to prepare an initiator solution;
s2: adding 1 part by mass of acrylamide isopropyl sodium sulfonate and 56.45 parts by mass of water into a reaction kettle, stirring and heating, when the temperature in the reaction kettle rises to 85 ℃, simultaneously dropwise adding the initiator solution prepared in the step S1 and 40 parts by mass of glycidyl methacrylate for 3 hours, controlling the reaction temperature to be 84-86 ℃, and after dropwise adding is finished, carrying out heat preservation reaction for 3 hours;
s3: and (3) cooling the temperature in the reaction kettle to 20 ℃, and filtering to obtain the acrylate emulsion.
Example 7
S1: dissolving 0.05 parts by mass of sodium persulfate by 2.5 parts by mass of water to prepare an initiator solution;
s2: adding 1 part by mass of sodium monododecyl maleate propyl sulfonate and 56.45 parts by mass of water into a reaction kettle, stirring and heating, when the temperature in the reaction kettle is raised to 85 ℃, simultaneously dropwise adding the initiator solution prepared in the step S1, 20 parts by mass of glycidyl methacrylate and 20 parts by mass of glycidyl acrylate, wherein the dropwise adding time is 3 hours, the reaction temperature is controlled to be 84-86 ℃, and after the dropwise adding is finished, carrying out heat preservation reaction for 3 hours;
s3: and (3) cooling the temperature in the reaction kettle to 20 ℃, and filtering to obtain the acrylate emulsion.
Example 8
S1: dissolving 0.5 mass part of sodium persulfate by 10 mass parts of water to prepare an initiator solution;
s2: adding 2 parts by mass of sodium monododecyl maleate propyl sulfonate and 37.5 parts by mass of water into a reaction kettle, heating while stirring, when the temperature in the reaction kettle rises to 80 ℃, simultaneously dropwise adding the initiator solution prepared in the step S1 and 50 parts by mass of glycidyl acrylate, wherein the dropwise adding time is 4 hours, the reaction temperature is controlled to be 80-82 ℃, and after the dropwise adding is finished, carrying out heat preservation reaction for 3 hours;
s3: and (3) after the temperature in the reaction kettle is reduced to 40 ℃, filtering to obtain the acrylate emulsion.
Comparative example 1
Acrylate emulsion, grade: BLJ-5619, manufacturer: shanghai Baolijia chemical Co., Ltd.
Comparative example 2
Epoxy emulsion, grade: epikote5003-W-55A, manufacturer: vast chemical industry management (Shanghai) Limited.
Experimental example 1
The acrylic emulsion obtained in examples 1 to 8, the commercially available acrylic emulsion described in comparative example 1, and the epoxy emulsion described in comparative example 2 were used to prepare sizing agents by the following steps:
adding 0.6 mass part of aminosilane coupling agent A1100 into a clean container, stirring and hydrolyzing with 20 times of water by mass part, adding 6 mass parts of film forming agents (namely, the acrylate emulsion and the epoxy emulsion of the examples and the comparative examples, diluting with 1 time of water by mass part), then adding 0.1 mass part of lubricant PEG600 (diluting with 10 times of water by mass part), then adding 0.01 mass part of defoaming agent BYK-051 (diluting with 10 times of water by mass part), finally supplementing the weight of the impregnating compound to a set value by water, fully stirring for 20 minutes to obtain the impregnating compound with the solid mass of 6.71% for later use.
Coating the prepared impregnating compound on glass fiber with the diameter of a single fiber of 10 mu m by an impregnating compound oiling machine, and preparing the glass fiber into glass fiber chopped yarn with the chopped length of 3 mm. The chopped strand and a reinforced polybutylene terephthalate resin (L2100 of Jiangsu instrumented chemical fiber company, Inc.) were subjected to extrusion and injection molding processes to prepare a chopped strand reinforced PBT resin composite material having a glass fiber content of 30%.
The above chopped strand reinforced PBT resin composite material with 30% glass fiber content was tested for tensile strength, notched impact strength, tensile strength after boiling and tensile strength retention. Wherein, the tensile strength is tested by adopting ISO527 test standard, and the larger the value, the higher the tensile strength is; the notch impact strength is tested by adopting an ISO179 test standard, and the larger the numerical value is, the higher the notch impact strength is; the hydrolysis resistance condition is that the composite material is boiled in water at 120 ℃ in an autoclave for 200 h.
The test results are shown in table 1:
TABLE 1 Performance test results for reinforced PBT resin composites
As can be seen from the above table:
the tensile strength, the tensile strength after poaching and the tensile strength retention rate of the reinforced PBT resin composite material correspondingly obtained in the embodiments 1-8 are obviously higher than those of the comparative example 1, which shows that the acrylic ester emulsion prepared by the invention has more advantages on the mechanical property and hydrolysis resistance of the composite material than the commercially available acrylic ester emulsion.
The tensile strength of the examples 1-8 is equivalent to that of the comparative example 2, but the tensile strength and the tensile strength retention rate after poaching of the examples 1-8 are greater than that of the comparative example 2, which shows that the acrylate emulsion prepared by the invention has more advantages on hydrolysis resistance of the composite material than the commercially available epoxy emulsion.
In conclusion, when the acrylate emulsion prepared by the component formula and the method is used for preparing the reinforced PBT resin composite material, the mechanical property and hydrolysis resistance of the PBT resin composite material can be obviously enhanced.
The above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. The acrylic ester emulsion for the glass fiber is characterized by comprising the following components in percentage by mass:
wherein the acrylate monomer is an acrylate monomer containing an epoxy group;
the emulsifier is a reactive emulsifier; the reactive emulsifier includes at least one of an allyloxy type, an acrylamide type, and a maleate type reactive emulsifier.
2. The acrylic ester emulsion for glass fiber according to claim 1, wherein the acrylic ester emulsion comprises the following components by mass percent:
3. the acrylic ester emulsion for glass fiber according to claim 1, wherein the acrylic ester emulsion comprises the following components by mass percent:
4. the acrylic ester emulsion for glass fiber according to claim 1, wherein the acrylic ester monomer containing an epoxy group comprises at least one of glycidyl acrylate and glycidyl methacrylate.
5. The acrylic ester emulsion for glass fiber according to claim 1, wherein the initiator comprises at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
6. A method for preparing the acrylic ester emulsion for glass fiber according to any one of claims 1 to 5, comprising the steps of:
s1: dissolving an initiator by using water with the mass being 20-100 times of that of the initiator to prepare an initiator solution;
s2: adding an emulsifier and the rest water into a reaction kettle, heating while stirring, dripping the initiator solution and the acrylate monomer in a constant temperature state when the temperature in the reaction kettle is raised to 80-90 ℃, and finishing dripping within 3-4 hours;
s3: and (3) after the dropwise addition is finished, carrying out heat preservation reaction for 2-3 hours, and after the reaction is finished, reducing the temperature in the reaction kettle to 20-50 ℃ for filtering to obtain the acrylate emulsion.
7. A glass fiber sizing composition, characterized in that the sizing composition is prepared from the acrylic ester emulsion for glass fibers as defined in any one of claims 1 to 5.
8. A method of using the sizing of claim 7 to coat glass fibers and using the glass fibers to make reinforced polybutylene terephthalate resin composites.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110463238.8A CN113087838B (en) | 2021-04-27 | 2021-04-27 | Acrylate emulsion for glass fiber and preparation method and application thereof |
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