CN115849734A - Glass fiber film forming agent and preparation method and application thereof - Google Patents
Glass fiber film forming agent and preparation method and application thereof Download PDFInfo
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- CN115849734A CN115849734A CN202211562138.1A CN202211562138A CN115849734A CN 115849734 A CN115849734 A CN 115849734A CN 202211562138 A CN202211562138 A CN 202211562138A CN 115849734 A CN115849734 A CN 115849734A
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- glass fiber
- olefin
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- maleic anhydride
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract description 47
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- -1 ethylene, propylene, butylene, isobutylene Chemical group 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 6
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011208 reinforced composite material Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 206010020112 Hirsutism Diseases 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012681 fiber drawing Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Abstract
The application discloses a film-forming agent for glass fibers, which comprises the following components in percentage by weight: 12 to 40 percent of olefin and maleic anhydride copolymer; 1.0 to 11.0 percent of neutralizer; 1.0 to 9.0 percent of surfactant; 40 to 86 percent of water; wherein the olefin in the olefin and maleic anhydride copolymer is an unsaturated olefin with 2-5 carbon atoms, and the olefin and maleic anhydride are block copolymerized, and the molar ratio of the two is 1-2. The glass fiber yarn produced by coating the impregnating compound prepared by the film forming agent has high smoothness, less product filoplume and high bonding performance with a PA matrix resin interface, can effectively improve the mechanical property and hydrolysis resistance of the glass fiber reinforced PA composite material, and meets the requirements of the market and application.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a film forming agent for glass fiber yarns, and a preparation method and application thereof.
Background
The glass fiber is an inorganic non-metallic material with excellent performance, has the advantages of good insulativity, strong heat resistance, good corrosion resistance and the like, and is widely applied to various fields of national economy. In the production process of the glass fiber, in order to achieve relevant performance indexes, a layer of chemical agent is coated on the surface of the glass fiber, and the glass fiber is called as a sizing agent in the industry. The film forming agent is an important component in the raw materials of the sizing agent, wherein the film forming agent has three functions: firstly, the glass fiber monofilaments are bonded into a strand of precursor in the wire drawing process, so that the glass fibers are protected from being worn; secondly, the glass fiber is endowed with processing performance, for example, the glass fiber can have certain stiffness and short cutting performance; and thirdly, the compatibility of the glass fiber and the reinforced matrix resin is determined, and further the use performance of the glass fiber is determined.
The film forming agent of the impregnating compound for the glass fiber, which is conventionally used at present, mainly comprises polyvinyl acetate emulsion, epoxy emulsion, polyurethane emulsion and unsaturated polyester emulsion, and the hydrolysis resistance of the glass fiber reinforced PA (polyamide) composite material produced by coating the impregnating compound prepared by the conventional film forming agent can not meet the current use requirement temporarily.
In order to meet the use requirement of the current glass fiber reinforced PA composite material on hydrolysis resistance, a suitable film forming agent for glass fiber yarns needs to be developed and designed.
Disclosure of Invention
The technical problem to be solved by the application is to provide a film forming agent for glass fibers, the glass fibers produced by coating the impregnating compound prepared from the film forming agent have the advantages of good short cutting property, good production smoothness and good compatibility with PA resin (reinforced resin), the production efficiency and the mechanical property, hydrolysis resistance and fatigue resistance of a composite material product can be greatly improved, and the use requirement of the hydrolysis resistance of the current PA composite material is met.
According to one aspect of the application, a glass fiber film forming agent is provided, which comprises the following components in percentage by weight:
wherein the olefin in the olefin and maleic anhydride copolymer is an unsaturated olefin with 2-5 carbon atoms, and the olefin and maleic anhydride are block copolymerized, and the molar ratio of the two is 1-2.
Wherein the weight percentages of the components are as follows:
wherein the weight average molecular weight of the olefin and maleic anhydride copolymer is 5000-120000.
Wherein, the unsaturated olefin is one or a mixture of any more of ethylene, propylene, butylene, isobutene, butadiene and pentadiene.
Wherein the neutralizer is one or a mixture of any more of ammonia water, sodium hydroxide, ethylenediamine and butanediamine.
Wherein the surfactant is a nonionic surfactant.
The nonionic surfactant is one or a mixture of any more of polyoxyethylene sorbitan fatty acid ester, fatty alcohol polyoxyethylene ether and fatty acid polyoxyethylene ether.
The film forming agent for the glass fiber yarn selects the olefin and maleic anhydride copolymer with proper type and dosage, changes the physical structure and chemical structure of the surface of the glass fiber, thereby improving the surface performance of the glass fiber and improving the production smoothness of the glass fiber. In addition, the film forming agent can react with PA matrix resin, and can improve the interface bonding of the glass fiber reinforced matrix resin, so that the mechanical property and hydrolysis resistance of the composite material are improved.
Wherein, in the olefin and maleic anhydride copolymer, the olefin is unsaturated olefin with 2-5 carbon atoms, preferably one or mixture of any several of ethylene, propylene, butylene, isobutene, butadiene and pentadiene. The olefin and the maleic anhydride are block copolymerized, the molar ratio of the olefin to the maleic anhydride is 1-2, and the production of the alternating copolymer of the unsaturated olefin and the maleic anhydride with the copolymerization ratio of 1. An alternating copolymer having a copolymerization ratio of unsaturated olefin and maleic anhydride of 1 has the general formula (C) 4 H 2 O 3 ) X (C n H 2n ) y Wherein n is more than or equal to 2 and less than or equal to 6; or (C) 4 H 2 O 3 ) X (C n H 2n-2 ) Wherein n is more than or equal to 4 and less than or equal to 6, y is more than or equal to y and less than or equal to 2y. In the copolymer of olefin and maleic anhydride, the mass ratio of maleic anhydride in the copolymer is relatively large (the mass ratio of maleic anhydride is relatively large)>60 percent and up to 80 percent) can provide reaction activity and can also achieve the aim of hydrolysis resistance. Further, the weight average molecular weight of the olefin and maleic anhydride copolymer is in the range of 5000 to 120000. Tests show that if the weight average molecular weight of the olefin and maleic anhydride copolymer is less than 5000, the mechanical property and the water resistance of the glass fiber reinforced composite material produced by coating the impregnating compound prepared from the olefin and maleic anhydride copolymer are poor; the weight average molecular weight of the olefin-maleic anhydride copolymer is more than 120000, so that the viscosity of the sizing agent prepared by the olefin-maleic anhydride copolymer is too high, and the production efficiency of the glass fiber is adversely affected. A large number of experiments show that when the weight percentage of the olefin and maleic anhydride copolymer is 12-40%, the mechanical property of the glass fiber reinforced composite material can be improved, and the hydrolysis resistance can be improved at the same time. Too high a dosage can result in poor water solubility and poor reactivity; too small amount of the compound can increase water solubility, which can result in the reduction of hydrolysis resistance. Preferably, the weight percentage of the olefin and maleic anhydride copolymer is 15 to 35%.
The film forming agent for the glass fiber yarns further comprises a neutralizer, wherein the neutralizer is one or a mixture of any of ammonia water, sodium hydroxide, ethylenediamine and butanediamine. The addition of the neutralizing agent is beneficial to the water solubility of the auxiliary raw material components, and the compatibility of the film forming agent and other components of the impregnating compound is improved. Wherein, the dosage of the neutralizer needs to be kept in a proper range, and the water resistance of the raw materials is deteriorated due to excessive dosage of the neutralizer; if the amount is too small, the compatibility with other components of the impregnating compound is poor, and the impregnating compound system is unstable. Therefore, the amount of the neutralizer used is controlled to be 1.0-11.0%, preferably 2.0-10.0%.
In the components of the film forming agent for the glass fiber yarns, the nonionic surfactant is selected as the surfactant, so that the film forming agent is free from conflict with other components of the impregnating compound, and the compatibility is good. The selection of the surfactant is based on the requirement, so that the stability of the raw materials can be ensured, and the mechanical property and hydrolysis resistance of the glass fiber reinforced composite material cannot be influenced. Preferably, the surfactant of the present application is one or a mixture of any several of polyoxyethylene sorbitan fatty acid ester, fatty alcohol polyoxyethylene ether and fatty acid polyoxyethylene ether. In addition, the dosage of the surfactant needs to be controlled, and tests show that the stability of the film forming agent is poor due to too small dosage of the surfactant; and too much dosage can affect the mechanical property of the composite material. Therefore, the weight percentage of the surfactant of the present application is controlled to be 1.0 to 9.0%, preferably 2.0 to 8.0%.
According to the application, the film forming agent in an aqueous emulsion state is prepared from olefin, maleic anhydride copolymer, a neutralizer, a surfactant and water, and then the impregnating compound is prepared to be uniformly coated on the surface of the glass fiber and can react with PA matrix resin, so that the interface binding force of the glass fiber reinforced matrix resin is improved, and the mechanical property and the hydrolysis resistance of the composite material are improved.
According to another aspect of the present application, there is provided a method for preparing the above film-forming agent for glass fiber, comprising the steps of:
s1, pre-dissolving a neutralizer: adding 1/5-1/3 of the total amount of water into a container, adding a neutralizing agent, stirring and dissolving to prepare a first aqueous solution; preferably, the water is deionized water, and the using amount is 1/4 of the total amount;
s2, pre-dissolving olefin and maleic anhydride copolymer: slowly adding the olefin and maleic anhydride copolymer into a container S1, stirring while adding, and controlling the stirring speed at 150-350r/min until the olefin and maleic anhydride copolymer are dissolved at room temperature to prepare a second aqueous solution;
s3, pre-dissolving a surfactant: adding a surfactant into the S2 container, stirring while dissolving, and controlling the stirring speed at 150-350r/min to prepare a third aqueous solution;
s4, dissolving and dispersing: heating the S3 container, heating the third aqueous solution to 80-95 ℃, controlling the stirring speed at 150-350r/min, and stirring for 2.5-3.5 hours;
s5, adjusting the concentration of the solution: and cooling the third aqueous solution to room temperature, and supplementing the balance of water to obtain the film forming agent for the glass fiber yarns.
According to a third aspect of the present application, there is provided a sizing agent for glass fiber, which is prepared from the film-forming agent for glass fiber yarns.
According to a fourth aspect of the present application, there is provided a glass fiber product produced by coating the aforementioned glass fibers with a sizing agent.
According to a fifth aspect of the present application, there is provided the use of the aforementioned glass fiber product in the field of reinforced PA composites.
Compared with the prior art, the application has the beneficial effects that: the glass fiber yarn is produced by coating the impregnating compound prepared by the film-forming agent, so that the physical structure and the chemical structure of the surface of the glass fiber can be changed, the surface performance of the glass fiber is improved, and the production smoothness of the glass fiber is improved; the composite material has good compatibility with PA resin (reinforced resin), can greatly improve the production efficiency and the mechanical property, hydrolysis resistance and fatigue resistance of composite material products, and meets the use requirement of the current PA composite material on hydrolysis resistance.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present application clearer, the embodiments of the present application will be described clearly and completely in conjunction with the specific embodiments of the present application, and it is obvious that the described embodiments are some, but not all embodiments of the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The film forming agent for glass fiber comprises the following components in percentage by weight:
preferably, the weight percentages of the components are as follows:
wherein, the olefin in the copolymer of olefin and maleic anhydride is unsaturated olefin with 2-5 carbon atoms, and the weight-average molecular weight is 5000-120000; the olefin and the maleic anhydride are block copolymerized, and the molar ratio of the olefin to the maleic anhydride is 1-2.
The unsaturated olefin is one or a mixture of any more of ethylene, propylene, butylene, isobutene, butadiene and pentadiene.
The neutralizer is one or a mixture of any more of ammonia water, sodium hydroxide, ethylenediamine and butanediamine.
The surfactant is a nonionic surfactant; preferably, the polyoxyethylene sorbitan fatty acid ester is one or a mixture of any more of polyoxyethylene sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether and fatty acid-polyoxyethylene ether.
The preparation method of the film forming agent for the glass fiber yarn comprises the following steps:
s1, pre-dissolving a neutralizer: adding 1/5-1/3 of the total amount of water into a container, adding a neutralizing agent, stirring and dissolving to prepare a first aqueous solution;
s2, pre-dissolving olefin and maleic anhydride copolymer: slowly adding the olefin and maleic anhydride copolymer into a container S1, stirring while adding, and controlling the stirring speed at 150-350r/min until the olefin and maleic anhydride copolymer are dissolved at room temperature to prepare a second aqueous solution;
s3, pre-dissolving a surfactant: adding a surfactant into the S2 container, stirring while dissolving, and controlling the stirring speed at 150-350r/min to prepare a third aqueous solution;
s4, dissolving and dispersing: heating the S3 container, heating the third aqueous solution to 80-95 ℃, controlling the stirring speed at 150-350r/min, and stirring for 2.5-3.5 hours;
s5, adjusting the concentration of the solution: and cooling the third aqueous solution to room temperature, and supplementing the balance of water to obtain the film forming agent for the glass fiber yarns.
Some specific examples of film formers for glass fiber yarns of the present application are set forth below.
Examples
In order to further illustrate the beneficial effects of the selected types of the components and the content ranges of the components in the glass fiber film forming agent of the present application, some examples of the values of the components included in the glass fiber film forming agent of the present application are listed below.
The specific formula of some examples of the film forming agent for glass fiber is shown in table 1, and the numerical value in table 1 is the percentage of the solid mass of the effective component to the total mass of the film forming agent.
It should be noted that the specific types, amounts and combinations of the components selected in table 1 do not limit the scope of the present application.
TABLE 1 proportioning of the effective components of the film forming agent
In order to better illustrate the technical effects of the application, the film-forming agent and the comparative film-forming agent of the embodiments of the application are prepared into the impregnating compound according to a conventional impregnating compound preparation method, and are used for performing glass fiber drawing operation on a machine to test the mechanical properties of the glass fibers. Wherein, the comparative examples adopt the externally purchased film forming agent (Coxichu, baybond PU 403, weak anion polyurethane film forming agent with 39% solid content) which is conventionally used at present and the acrylic emulsion film forming agent which is grafted and modified by maleic anhydride, and respectively correspond to comparative examples 1, 2 and 3.
Wherein, the film forming agent of the comparative example or the embodiment, polyurethane emulsion, lubricant, silane coupling agent and deionized water are prepared into impregnating compound. Wherein the solid mass ratio of the film forming agent to the polyurethane to the lubricant to the silane coupling agent is 28:56:5:11. the stability test is an industry conventional test method, and specifically comprises the following steps: and testing the solid content of the upper layer after the impregnating compound is prepared, testing the solid content of the upper layer after the impregnating compound is placed for 24 hours, and representing the stability by using the ratio of the two. Higher ratios indicate better stability. The results of the mechanical properties and the appearance color properties of the glass fiber reinforced PA66 composite materials produced by using the film forming agents of the examples and the comparative examples are shown in Table 2.
TABLE 2 testing of glass fiber reinforced PA66 composites for twin screw extrusion Molding Process
The performance of each of the examples and comparative examples was tested separately, with tensile strength using the test standard ISO527; the test standard for flexural strength is ISO178; the test standard for unnotched impact strength is ISO179.
Hydrolysis resistance conditions: the composite material is subjected to water boiling for 48 hours at the water and ethylene glycol ratio of 1 and the temperature of 135 ℃ to test the tensile strength retention rate of a product.
Amount of hairiness: 150 g of chopped strands are placed in a vibrating screen with a 10-mesh screen and 3 rubber balls with a diameter of 1cm, the voltage is 380V and the frequency is 50Hz. Pouring 150 g of chopped strands into a 10-mesh screen of a vibrating screen machine, covering a cover plate, starting the vibrating screen machine, setting the vibrating screen amplitude to be 1mm and the vibrating screen time to be 2 minutes, and weighing the hairiness mass on the 10-mesh screen.
TABLE 3 testing of glass fiber reinforced PA6 composites for twin screw extrusion Molding Process
In table 2, the tensile strength, the post-poaching tensile strength and the tensile strength retention rate of the glass fiber reinforced PA66 composite materials for the twin-screw extrusion molding processes of examples 1 to 9 are all significantly greater than those of comparative examples 1 to 3, which shows that the film-forming agent prepared by the present application has advantages over the existing film-forming agents in terms of mechanical properties and hydrolysis resistance of the composite materials.
In table 3, the tensile strength after boiling, and the retention rate of the tensile strength of the glass fiber reinforced PA6 composite material tested by the twin-screw extrusion molding process of examples 1 to 9 are all significantly greater than the ratio of 1 to 3, which indicates that the film forming agent prepared by the present application has an advantage over the existing film forming agent in hydrolysis resistance of the composite material.
In conclusion, the glass fiber impregnating compound for thermoplastic PA reinforcement produced by the film forming agent can improve the smoothness of glass fibers in the short cutting process, reduce the hairiness of the glass fibers, improve the interface bonding performance of the glass fibers and PA matrix resin, and effectively improve the mechanical property and hydrolysis resistance of a glass fiber reinforced composite material. In addition, the film-forming agent has good compatibility with the matrix PA, and can react with the matrix PA, so that the mechanical strength and the stability of the composite material are improved.
The above-described variants can be implemented individually or in various combinations, and these variants are within the scope of protection of the present application.
Finally, it should be noted that: the above examples are only for illustrating the technical solutions of the present application, and are not limited thereto. Although the present application has been described in detail with reference to the foregoing embodiments, it should 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 in the embodiments of the present application.
Claims (11)
1. The film forming agent for the glass fiber is characterized by comprising the following components in percentage by weight:
wherein the olefin in the olefin and maleic anhydride copolymer is an unsaturated olefin with 2-5 carbon atoms, and the olefin and maleic anhydride are block copolymerized, and the molar ratio of the two is 1-2.
2. The film-forming agent for glass fiber yarn according to claim 1, wherein the weight percentages of the components are as follows:
3. the film forming agent for glass fiber yarn according to claim 1 or 2, wherein the weight average molecular weight of the olefin and maleic anhydride copolymer is 5000 to 120000.
4. The film forming agent for glass fiber yarn according to claim 1 or 2, wherein the unsaturated olefin is one or a mixture of any of ethylene, propylene, butylene, isobutylene, butadiene and pentadiene.
5. The film forming agent for glass fiber yarns as claimed in claim 1 or 2, wherein the neutralizing agent is one or a mixture of any more of ammonia, sodium hydroxide, ethylenediamine and butanediamine.
6. The film-forming agent for glass fiber yarn according to claim 1 or 2, wherein the surfactant is a nonionic surfactant.
7. The film forming agent for glass fiber yarns according to claim 6, wherein the nonionic surfactant is one or a mixture of any more of polyoxyethylene sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether and fatty acid-polyoxyethylene ether.
8. The method for preparing the film forming agent for glass fiber yarn according to any one of claims 1 to 7, comprising the steps of:
s1, pre-dissolving a neutralizer: adding 1/5-1/3 of the total amount of water into a container, adding a neutralizing agent, stirring and dissolving to prepare a first aqueous solution;
s2, pre-dissolving olefin and maleic anhydride copolymer: slowly adding the olefin and maleic anhydride copolymer into a container S1, stirring while adding, and controlling the stirring speed at 150-350r/min until the olefin and maleic anhydride copolymer are dissolved at room temperature to prepare a second aqueous solution;
s3, pre-dissolving a surfactant: adding a surfactant into the S2 container, stirring while dissolving, and controlling the stirring speed at 150-350r/min to prepare a third aqueous solution;
s4, dissolving and dispersing: heating the S3 container, heating the third aqueous solution to 80-95 ℃, controlling the stirring speed at 150-350r/min, and stirring for 2.5-3.5 hours;
s5, adjusting the concentration of the solution: and cooling the third aqueous solution to room temperature, and supplementing the balance of water to obtain the film forming agent for the glass fiber yarns.
9. A sizing agent for glass fiber, which is produced from the film-forming agent for glass fiber yarn according to any one of claims 1 to 7.
10. A glass fiber product produced by coating the glass fiber of claim 9 with an impregnating compound.
11. Use of the glass fiber product of claim 10 in the field of reinforced PA composites.
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