阅读说明：本技术 一种热塑玻璃纤维纱用成膜剂及制备方法和应用 (Film forming agent for thermoplastic glass fiber yarn, preparation method and application ) 是由 杨国明 李翠红 嵇安然 于 2021-07-22 设计创作，主要内容包括：本申请公开了一种热塑玻璃纤维纱用成膜剂,由以下原料制备而成,各原料的重量百分比表示如下：聚烯烃马来酸酐共聚物20-30％,一元醇8-16％,乳化剂4-6％,抗氧剂0.1-0.5％,pH值调节剂1-4％,水43.5-63.9％。采用该成膜剂制备的浸润剂涂覆生产的热塑玻璃纤维纱,具有良好的集束性、耐磨性,能大幅提升产品机械性能,改善颜色发黄,能提高制品的机械性能,由其进行增强生产的热塑性复合材料具有优异的物理和机械性能,满足市场和应用的需求。(The application discloses a film-forming agent for thermoplastic glass fiber yarns, which is prepared from the following raw materials in percentage by weight: 20-30% of polyolefin maleic anhydride copolymer, 8-16% of monohydric alcohol, 4-6% of emulsifier, 0.1-0.5% of antioxidant, 1-4% of pH value regulator and 43.5-63.9% of water. The thermoplastic glass fiber yarn produced by coating the impregnating compound prepared by the film forming agent has good bundling property and wear resistance, can greatly improve the mechanical property of products, improves the yellowing of colors, can improve the mechanical property of products, and can be used for enhancing the thermoplastic composite material produced by the impregnating compound, so that the thermoplastic composite material has excellent physical and mechanical properties and meets the requirements of the market and the application.)

1. The film forming agent for the thermoplastic glass fiber yarn is characterized by being prepared from the following raw materials in percentage by weight:

2. the film-forming agent for thermoplastic glass fiber yarns according to claim 1, wherein the weight percentages of the raw materials are as follows:

3. the film former for thermoplastic glass fiber yarn according to claim 1 or 2, wherein the polyolefin maleic anhydride copolymer is a polypropylene maleic anhydride copolymer and/or a polyethylene maleic anhydride copolymer.

4. The film forming agent for thermoplastic glass fiber yarn according to claim 1 or 2, wherein the emulsifier is a nonionic emulsifier; the antioxidant is a polyolefin antioxidant.

5. The film forming agent for thermoplastic glass fiber yarn according to claim 4, wherein the emulsifier is any one or a combination of several of nonylphenol polyoxyethylene ether NP-10, nonylphenol polyoxyethylene ether NP-20, and fatty alcohol polyoxyethylene ether.

6. The film forming agent for thermoplastic glass fiber yarn as claimed in claim 4, wherein the polyolefin antioxidant is any one or a combination of polyolefin antioxidant 168, polyolefin antioxidant 1010 and polyolefin antioxidant 5035.

7. The film forming agent for thermoplastic glass fiber yarn according to claim 1 or 2, wherein the pH value regulator is any one or a combination of several of hexamethylene diamine, ammonia water, methylamine and potassium hydroxide.

8. The method of producing a film former for thermoplastic glass fiber yarns according to any one of claims 1 to 7, comprising the steps of:

s1, alcoholysis of polyolefin maleic anhydride copolymer: adding polyolefin maleic anhydride copolymer and monohydric alcohol into a reaction bottle provided with a stirrer, a feeder, a reflux condenser and a thermometer, stirring and heating until the copolymer is completely dissolved, and preserving heat for 3-4 hours to ensure that the copolymer is completely reacted;

s2, emulsification: adding an emulsifier and an antioxidant into the reaction bottle in the step S1, stirring, adding water into the reaction bottle after uniformly stirring, and stirring until a stable emulsion is synthesized;

s3, adjusting the pH value: and adding a pH value regulator into the reaction bottle of S2, supplementing water, and regulating the pH value to 3-4 to obtain the film forming agent for the thermoplastic glass fiber yarns.

9. A sizing agent for glass fibers, which is produced from the film-forming agent for thermoplastic glass fiber yarns according to any one of claims 1 to 7 as one of the raw materials.

10. A glass fiber product produced by coating the glass fiber with the sizing agent according to claim 9 and its use in the field of thermoplastic composites.

Technical Field

The application relates to the technical field of high polymer materials, in particular to a film forming agent for thermoplastic glass fiber yarns and a preparation method and application thereof.

Background

Thermoplastic composite materials have been gradually developed in recent years as novel composite materials with high performance, low cost and environmental protection, because of their characteristics of high strength, good impact resistance and fatigue resistance, recoverability, fast processing and forming, low cost, etc. In order to meet the market and production requirements for thermoplastic composites, thermoplastic glass fiber yarns used for reinforcing the strength of thermoplastic composites need to have good molding processability and dispersibility, and good compatibility with matrix resins, so that the composites can be endowed with excellent physical and mechanical properties.

In order to meet the requirements of thermoplastic composite materials on boiling resistance, high fatigue resistance, mechanical strength and the like, a film forming agent suitable for thermoplastic 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 thermoplastic glass fiber yarns, wherein the film forming agent is polyolefin maleic anhydride copolymer emulsion, is particularly suitable for the field of thermoplastic glass fiber chopped yarns, can enable products to have good bundling property and wear resistance, can greatly improve the mechanical property of products, simultaneously improves the problem of yellowing of colors, and meets the use requirement of reinforced thermoplastic composite materials.

According to one aspect of the application, the film forming agent for the thermoplastic glass fiber yarn is prepared from the following raw materials in percentage by weight:

wherein the weight percentages of the raw materials are as follows:

wherein the polyolefin maleic anhydride copolymer is a polypropylene maleic anhydride copolymer and/or a polyethylene maleic anhydride copolymer.

Wherein the emulsifier is a nonionic emulsifier; the antioxidant is a polyolefin antioxidant.

Wherein the emulsifier is any one or a combination of more of nonylphenol polyoxyethylene ether NP-10, nonylphenol polyoxyethylene ether NP-20 and fatty alcohol polyoxyethylene ether.

Wherein the polyolefin antioxidant is any one or a combination of more of a polyolefin antioxidant 168, a polyolefin antioxidant 1010 and a polyolefin antioxidant 5035.

Wherein the pH value regulator is any one or combination of more of hexamethylene diamine, ammonia water, methylamine and potassium hydroxide.

The raw materials for preparing the film forming agent for the thermoplastic glass fiber yarn comprise polyolefin maleic anhydride copolymer, and can be polypropylene maleic anhydride copolymer and/or polyethylene maleic anhydride copolymer. By grafting a functional group (carboxyl) with polarity and reactivity on a nonpolar polyolefin wax side chain, the bonding strength and the adhesive force of the glass fiber and the thermoplastic material can be enhanced, and the mechanical strength of the composite material is improved. The emulsion is easier to emulsify due to the existence of a large number of carboxyl groups in the molecular structure, so that the emulsion has higher stability. A large number of experiments show that the polyolefin maleic anhydride copolymer accounts for 20-30 wt%, the viscosity of the product can be well controlled, and if the dosage is too high, the viscosity is increased, so that the use process is influenced; on the other hand, the pH value of the product can be controlled, and the stability of the film forming agent in the using process is further ensured. Preferably, the polyolefin maleic anhydride copolymer is used in an amount of 22 to 28%.

The raw material of the film forming agent for the thermoplastic glass fiber yarn also comprises monohydric alcohol, and the monohydric alcohol is selected from one or a mixture of methanol and ethanol. Tests show that the proper using amount of the monohydric alcohol can open the ring of the anhydride and block part of carboxyl to stabilize the carboxyl and other components of the glass fiber sizing agent; if the consumption of the monohydric alcohol is too low, the ring-opening ratio of the anhydride is low, an ideal ring-opening effect cannot be obtained, and the product performance is influenced; the product cost is higher when the dosage is too high. Therefore, the application controls the using amount of the monohydric alcohol to be 8-16%; preferably, the monohydric alcohol is used in an amount of 9-15%.

The emulsifier in the raw materials adopts a non-ionic emulsifier, so that the emulsifier and other components of the glass fiber impregnating compound can be stabilized; preferably, the emulsifier can adopt any one or a combination of more of nonylphenol polyoxyethylene ether NP-10, nonylphenol polyoxyethylene ether NP-20 and fatty alcohol polyoxyethylene ether. Meanwhile, the dosage of the emulsifier needs to be controlled, the dosage of the emulsifier is too small to achieve the emulsion stabilizing effect, and too much dosage can cause the film-forming agent to migrate in the application process, so that the surface of the produced glass fiber is sticky, and the glass fiber yarn is yellow in the baking process, thereby affecting the product quality. Thus, the emulsifiers are used in amounts of 4 to 6% by weight.

The antioxidant is a polyolefin antioxidant, and is specifically selected from any one or a combination of a plurality of polyolefin antioxidants 168, 1010 and 5035. The antioxidant is used to effectively prevent the film forming agent from high-temperature decomposition. The antioxidant with the weight percentage of 0.1-0.5% is added, so that the required effect can be achieved; an excessively high amount of the compound causes a problem of cost increase and poor compatibility with the resin, while an excessively low amount of the compound does not provide an effect of preventing oxidation.

The raw materials of the film forming agent for the thermoplastic glass fiber yarn also comprise 1-4% of a pH value regulator, and specifically comprise any one or a combination of more of hexamethylene diamine, ammonia water, methylamine and potassium hydroxide. The pH value range selected by a large number of experiments is 3-4, so that the stability of the film forming agent and other components in the impregnating compound can be ensured.

The sizing agent is prepared by preparing a film forming agent in an aqueous emulsion state from a polyolefin maleic anhydride copolymer, monohydric alcohol, an emulsifier, an antioxidant, a pH value regulator and water, and then uniformly coating the sizing agent on the surface of glass fibers, so that the sizing agent can play a role in bonding and bundling; and can provide the desired characteristics for further processing and application of the glass fiber.

According to another aspect of the present application, there is provided a method for preparing the film forming agent for thermoplastic glass fiber yarn, comprising the steps of:

s1, alcoholysis of polyolefin maleic anhydride copolymer: adding polyolefin maleic anhydride copolymer and monohydric alcohol into a four-neck flask provided with a stirrer, a feeder, a reflux condenser and a thermometer, stirring and heating to a first preset temperature to completely dissolve the copolymer, and preserving heat for 3-4 hours to completely react;

s2, emulsification: adding an emulsifier and an antioxidant into the reaction bottle of S1, stirring at a first preset rotating speed for a first preset time, after uniformly stirring, slowly adding water into the reaction bottle, stirring at a second preset rotating speed, and synthesizing to obtain a stable emulsion with continuous and uniform appearance;

s3, adjusting the pH value: and adding a pH value regulator into the reaction bottle of S2, supplementing water, and regulating the pH value to 3-4 to obtain the film forming agent for the thermoplastic glass fiber yarns.

Preferably, the first predetermined temperature in the step S1 is 60-80 ℃.

Preferably, the first predetermined rotation speed in the step S2 is 500-; the first predetermined time is 1-2 hours; the second predetermined rotation speed is 2500-.

In the above steps, the setting of parameters such as reaction temperature, stirring speed, pH value and the like can ensure the synthesis of stable film-forming agent emulsion.

According to a third aspect of the present application, there is provided a sizing for glass fiber produced using the film-forming agent for glass yarn as one of the raw materials.

According to a fourth aspect of the present application, there is provided a glass fiber product produced by coating the above-mentioned sizing agent and its use in the field of thermoplastic composites.

Compared with the prior art, the application has the beneficial effects that: the thermoplastic glass fiber yarn produced by coating the impregnating compound prepared by the film forming agent has good bundling property and wear resistance, can greatly improve the mechanical property of products, improve the yellowing of colors and improve the mechanical property of products, and the thermoplastic composite material produced by reinforcing the thermoplastic glass fiber yarn has excellent physical and mechanical properties and meets the requirements of market and application.

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, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within 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 the thermoplastic glass fiber yarn is prepared from the following raw materials in percentage by weight:

it is further preferred that the first and second liquid crystal compositions,

wherein the polyolefin maleic anhydride copolymer is polypropylene maleic anhydride copolymer and/or polyethylene maleic anhydride copolymer.

The monohydric alcohol is any one or combination of methanol and ethanol.

The emulsifier is nonionic emulsifier, and can be one or more of nonylphenol polyoxyethylene ether NP-10, nonylphenol polyoxyethylene ether NP-20 and fatty alcohol polyoxyethylene ether.

The antioxidant is a polyolefin antioxidant, and can be any one or a combination of polyolefin antioxidant 168, polyolefin antioxidant 1010 and polyolefin antioxidant 5035.

The pH value regulator is any one or combination of more of hexamethylene diamine, ammonia water, methylamine and potassium hydroxide.

The preparation method of the film forming agent for the thermoplastic glass fiber yarn comprises the following steps:

s1: alcoholysis of polyolefin maleic anhydride copolymer: adding polyolefin maleic anhydride copolymer and monohydric alcohol into a four-neck flask provided with a stirrer, a feeder, a reflux condenser and a thermometer, stirring and heating to 60-80 ℃ to completely dissolve the copolymer, and keeping the temperature for 3-4 hours to completely react.

S2: emulsification: adding an emulsifier and an antioxidant into an S1 reaction bottle, stirring for 1-2 hours at the rotation speed of 500-;

s3: adjusting the pH value: and adding a pH value regulator into the reaction bottle of S2, supplementing water, and regulating the pH value to 3-4 to obtain the film forming agent for the thermoplastic glass fiber yarns.

Some specific examples of film formers for use in the thermoplastic glass fiber yarns of the present application are set forth below.

Examples

The specific raw material formulation of this example is shown in Table 1

Table 1 example of the dosage ratios of the raw materials

In order to better illustrate the technical effects of the content of the application, the application adopts an externally-purchased film forming agent (ISOBAM-304) which is conventionally used at present as a comparative example, the self-prepared film forming agent and the comparative example film forming agent in the embodiment of the application are respectively prepared into an impregnating compound according to a conventional impregnating compound preparation method, and the impregnating compound is processed on a machine to perform glass fiber drawing operation and test the mechanical properties of the glass fiber.

The film forming agent of the comparative example or the embodiment is prepared with a silane coupling agent, a polyurethane film forming agent, an antistatic agent and deionized water to form an impregnating compound, and the impregnating compound is subjected to a 24-hour stability tracking test. Wherein the solid mass ratio of the film forming agent to the silane coupling agent to the polyurethane film forming agent to the antistatic agent is 5: 4: 0.9: 0.1. 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. The results of the relevant tests are shown in table 2.

TABLE 2 mechanical and color Properties of the examples and comparative examples

TABLE 3 mechanical and color Properties of the examples and comparative examples

As can be seen from the above examples, the production process of the film forming agent in the examples of the application is smooth, no abnormal phenomenon occurs, and the physical properties of the product meet the standards; the stirring hairiness (the lower the stirring hairiness data is, the better the bundling property is), and the mechanical property is superior to that of the conventional outsourcing film forming agent of the comparative example; the film forming agent endows the glass fiber product with good bundling property and wear resistance, can greatly improve the mechanical property of the product, improves the yellowing of color, and can improve the mechanical property of the product.

In conclusion, the thermoplastic glass fiber yarns produced by coating the impregnating compound prepared by the film-forming agent for the thermoplastic glass fiber yarns have good bundling property and wear resistance, the mechanical property of the products can be greatly improved, the yellowing of the colors can be improved, the mechanical property of the products can be improved, and the thermoplastic composite materials produced by reinforcing the thermoplastic glass fiber yarns have excellent physical and mechanical properties and meet the requirements of the market and application.

The above-described aspects may be implemented individually or in various combinations, and such variations are within the scope 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.