WO2023240924A1 - 一种玻璃纤维浸润剂及其制备方法和应用 - Google Patents
一种玻璃纤维浸润剂及其制备方法和应用 Download PDFInfo
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- WO2023240924A1 WO2023240924A1 PCT/CN2022/132205 CN2022132205W WO2023240924A1 WO 2023240924 A1 WO2023240924 A1 WO 2023240924A1 CN 2022132205 W CN2022132205 W CN 2022132205W WO 2023240924 A1 WO2023240924 A1 WO 2023240924A1
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- glass fiber
- sizing agent
- fiber sizing
- lubricant
- coupling agent
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 109
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 92
- 238000004513 sizing Methods 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
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- 229920002647 polyamide Polymers 0.000 claims abstract description 16
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 15
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000007822 coupling agent Substances 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical group 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
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- 239000000463 material Substances 0.000 abstract description 18
- 238000012545 processing Methods 0.000 abstract description 13
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/465—Coatings containing composite materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
Definitions
- the invention belongs to the technical field of glass fiber surface treatment, and specifically relates to a glass fiber sizing agent and its preparation method and application.
- High-performance glass fiber refers to that compared with ordinary glass fiber, it has higher mechanical properties, stronger corrosion resistance, higher heat-resistant temperature, excellent dielectric and electrical insulation properties, etc., as a high-performance composite material Reinforced substrates are mainly used in defense fields such as aviation, aerospace, weapons, and nuclear industry.
- Glass fiber is a highly polar inorganic substance, its main component is SiO 2 , and resin is a high molecular polymer. The two materials are completely incompatible. When glass fiber is used as a reinforcing material for resin, The interface bonding performance with resin is poor. Therefore, one of the key technologies for high-performance glass fiber reinforced composite materials is the sizing technology that determines the material processing technology and composite interface properties.
- the sizing agent is a glass fiber surface treatment agent. After the glass fiber flows out from the drain plate, it usually needs to be treated with a water-based sizing agent to give the glass fiber good textile processing properties and its composite materials excellent mechanical properties. Different sizing agents give different properties to glass fibers. Various twistless rovings used for textile and weaving must have good textile performance and good compatibility with the base material resin to meet various requirements. product demand. Therefore, it is crucial to develop sizing agents suitable for high-performance glass fibers and their composites.
- the processing method of high-temperature-resistant thermoplastic nylon resin composite materials is generally twin-screw extrusion and granulation followed by injection molding.
- the melting point of industrial PA6T is as high as 310-320°C, and the heat resistance of conventional film-forming agents cannot meet the standards.
- the color of PA6T is white, most composite products also have color requirements. If there are a large number of components with poor temperature resistance in the glass fiber sizing agent, it will not be able to promote and protect the combination of the base resin and the fiber. Instead, it will produce carbon residue, which will affect the performance and appearance of the combination of resin and glass fiber.
- the interface bonding ability of the composite material determines the stress transmission between the glass fiber and the base resin. This difference has an important impact on the mechanical properties of the composite material. have important influence.
- the technical problem to be solved by the present invention is to overcome the fact that the heat resistance of the glass fiber sizing agent in the prior art cannot meet the temperature requirements for the processing of high-temperature resistant thermoplastic nylon resin composite materials, and the interface bonding ability between the glass fiber and the base resin needs to be further improved. Improve defects such as this, thereby providing a glass fiber sizing agent and its preparation method and application.
- the present invention can provide the following technical solutions:
- the invention provides a glass fiber sizing agent, which includes the following components in terms of effective content:
- the film-forming agent includes 2-4% of low molecular weight water-based polyurethane with a number average molecular weight of 400-1500, and 0.5-2% of high molecular weight water-based polyurethane with a number average molecular weight of 2000-4000. %; water-based polyamide emulsion 0.5-2%;
- the coupling agent is a mixture of a silane coupling agent containing a benzene ring and a silane coupling agent containing an amino group and/or an epoxy functional group.
- the aqueous polyamide emulsion is an aqueous emulsion prepared by emulsification using polyamide resin as raw material.
- the lubricant includes 0.5-1.2% of non-ionic lubricant and 0.1-0.3% of ionic lubricant.
- the nonionic lubricant is at least one of a mineral oil lubricant, an ester lubricant, a long-chain flexible benzene ring-containing lubricant, a silicone lubricant or an amide lubricant.
- the ionic lubricant is at least one of lubricant 6760L and lubricant 8760.
- the coupling agent is a silane coupling agent with a thermal decomposition temperature above 300°C;
- the coupling agent includes 0.4-0.8% of a silane coupling agent containing a benzene ring and 0.1-0.4% of a silane coupling agent containing an amino and/or epoxy functional group.
- the total solid content of the glass fiber sizing agent is 5-6wt%.
- the pH of the glass fiber sizing agent is 5-7.
- a pH adjuster to adjust the pH of the glass fiber sizing agent.
- the pH adjuster is an organic acid.
- the organic acid is at least one of acetic acid, formic acid, succinic acid or citric acid.
- the balance of the glass fiber sizing agent is water.
- the invention also provides a method for preparing the above-mentioned glass fiber sizing agent, which includes the following steps:
- the amount of water used in step S1 is 4-6 times the mass of the coupling agent.
- Typical and non-limiting, the specific operations of the preparation method of the glass fiber sizing agent can be:
- the preparation method of the glass fiber sizing agent can be:
- the invention also provides an application of the above-mentioned glass fiber sizing agent in preparing thermoplastic high-temperature resistant composite materials.
- thermoplastic high-temperature resistant composite material is a composite material of glass fiber and base material resin.
- the base material resin is PA6 resin.
- the PA6 resin is PA6T resin.
- the glass fiber sizing agent provided by the present invention can impart good compatibility between the surface of the glass fiber and the matrix resin through the coordination between the components and the adjustment of the dosage, especially the selection of different types of film-forming agents and the use of specific coupling agents. properties, significantly improving the compatibility and interface bonding ability between glass fiber and base material resin.
- water-based polyurethane with different molecular weights is selected as the main film-forming agent, and water-based polyamide emulsion is used as the auxiliary film-forming agent to improve the high-temperature resistance of the sizing agent so that it can meet the processing temperature of high-temperature-resistant thermoplastic nylon resin composite materials.
- water-based polyurethane has good high temperature resistance
- water-based polyamide emulsion can improve the film-forming performance of the overall sizing agent while improving the matching performance of glass fiber and base material resin.
- high molecular weight polyurethane can provide a higher yarn coverage rate and effectively improve the wear resistance of glass fiber.
- Low molecular weight polyurethane can improve the softness of glass fiber and the elasticity of the sizing agent film on the surface of glass fiber, which partially improves lubrication. performance, and is conducive to improving the fatigue resistance of glass fiber; at the same time, polyurethane has more strong polar groups, and the viscosity of the film after film formation is higher, which can easily form a dense protective film on the surface of glass fiber.
- the present invention uses different types of film-forming agents to not only provide good compatibility and interface bonding properties between the glass fiber and the matrix resin, but also improves the resistance of the glass fiber yarn on the basis of ensuring the softness of the glass fiber yarn. Fatigue performance.
- water-based polyamide emulsion is added to the formula.
- the polyamide emulsion has good film-forming properties, excellent adhesion and abrasion resistance, and excellent temperature resistance. It not only gives the fiberglass yarn a certain degree of rigidity, but also combines with the nylon base.
- the material resin has good compatibility, which improves the bonding degree between the fiberglass yarn and the base material resin.
- the described silane coupling agent requires at least one high-temperature resistant silane coupling agent containing a benzene ring.
- it also includes a silane coupling agent containing amino or epoxy functional groups. Due to the presence of amino/epoxy functional groups and benzene rings in the structure, Similar to the resin substrate, it is very suitable as a bridge between resin and glass fiber.
- its structure is similar to that of the auxiliary film-forming agent polyamide emulsion, which can better combine with each other to form a network structure, improving the The bonding properties of the base resin.
- the present invention can also enhance the adhesion between the film-forming agent and the glass fiber by selecting a specific coupling agent, and can reduce the hairiness and breakage of the glass fiber during processing.
- the sizing agent formula of the present invention has simpler components and simplifies the configuration and preparation process.
- the formula gives the glass fiber good processing performance, has good compatibility with the thermoplastic high-temperature resistant base material resin, and improves the efficiency of the glass fiber. It improves the mechanical properties of fiber composite materials and reduces the color difference of composite materials.
- the new product glass fiber reinforced composite materials also has better strength and modulus.
- the glass fiber sizing agent provided by the present invention by further limiting the lubricant, has the functions of dry lubrication and wet lubrication at the same time. It lubricates the surface of glass fiber and reduces wear. At the same time, it promotes the bonding between glass fiber and base material resin, overcoming the shortcomings of conventional lubricants that are not conducive to the bonding between glass fiber and base material resin.
- Non-ionic lubricants can reduce the production of lint and improve the wear resistance of fibers.
- the nonionic lubricant of the present invention is preferably mineral oil, ester, benzene ring, silicone or amide lubricant.
- the contact angle can also play a wetting role, and it has excellent high temperature resistance.
- a small amount of efficient ionic lubricant is added as dry lubrication to reduce friction and static electricity generated during textile processing.
- the amount of acid used is determined by the type and dosage of the coupling agent used.
- the prepared sizing agent should be convenient for storage and application under certain pH conditions. Generally, an acidic environment with a pH value of 5 to 7 is better. .
- Figure 1 is a picture of the yarn in the experimental example of the present invention. From left to right are non-thermoplastic yarn (self-made), thermoplastic yarn suitable for ordinary thermoplastic resin (purchased from Taibo) and infiltration using Example 1. Yarn prepared from the agent.
- Embodiment 1 of the present invention has less color change after high-temperature injection molding and has better high-temperature resistance.
- Figure 2 is a device used for hairiness testing in experimental examples of the present invention.
- the sources of each raw material are as follows: the low molecular weight water-based polyurethane emulsion uses U series water-based polyurethane from Michelman Company, with an effective content of 30wt% and a number average molecular weight of 400-1500; the high molecular weight water-based polyurethane emulsion is Sinoma Technology's self-made emulsion, product model is 240-3, effective content is 25wt%, number average molecular weight is 2000-4000; water-based polyamide emulsion is provided by Michelman, product model is pa845H, effective content is 30wt%; lubricant TR-2382 is self-produced by Sinoma Technology, with an effective content of 99wt%; ionic lubricant 6760L is provided by Kekai, with an effective content of 99wt%; coupling agents Y-9669, A-1100, and A-187 are all provided by Momentive. Provided, effective content 99wt%.
- the chemical composition of the glass fiber sizing agent is as shown in the following table in terms of effective content:
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Example 6
- Low molecular weight water-based polyurethane emulsion U5 2.5% 2% 3% 2.5% 2.5% 2.5%
- Polymer polyurethane emulsion 240-3 1.2%
- Water-based polyamide emulsion 0.8% 0.8% 0.8% 0.8% 0.8% 0.8% 0.8%
- Lubricant TR-2382 0.7% 0.7% 0.7% 0.5% 0.8% 0.7%
- Lubricant 6760L 0.2% 0.2% 0.2% 0.1% 0.3% 0.2%
- the glass fiber sizing agent provided in the Examples and Comparative Examples is applied to the preparation of 1000tex PA6T composite material, in which the glass fiber content is 40wt%.
- the specific source of glass fiber is HS4 high-strength glass fiber made by Sinoma Technology. Glass fiber raw filaments must be dried in an oven before subsequent processing to increase the bundling of the raw filaments and improve the wear resistance of the yarn. The drying temperature of raw silk is divided into three stages, namely 90°C, 90min; 105°C, 180min; 125°C, 180min. Test various performance indicators of the product. The specific test methods are as follows:
- Combustible content According to GB/T 9914.2 Test methods for reinforced products Part 2: Determination of combustible content of glass fiber.
- Hairiness including the weight of all hairs produced during the friction between the twistless roving and the wear-resistant device, in milligrams, using multiple points, multiple friction materials, and multiple friction angles, and using a constant winding rate. The sample is destroyed, and the amount of hairiness collected is measured after the process; the specific test device is shown in Figure 2.
- Stiffness test method Use the national standard GB/T7690.4-2001 to test the stiffness of twistless roving.
- Example 1 Example 2
- Example 3 Example 4
- Example 6 Combustible content, % 0.68 0.61 0.69 0.66 0.67 0.68 Product dry yarn tensile strength N/TEX 0.71 0.72 0.72 0.72 0.70 0.70 Product stiffness/mm 63 69 63 61 66 65 Number of hairiness mg/500m 7.4 16.7 13.3 18.9 6.9 8.9 Drape/mm 9 10 10 13 19.6 13 sample
- Example 7 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
- Dry yarn strength represents the mechanical properties of glass fiber
- Stiffness represents the softness and hardness of the yarn, the higher it is, the harder it is
- Hairiness represents the roughness of the yarn surface, the higher it is, the hairier it is
- Drape represents the looseness of the yarn, the higher it is, the hairier it is. scattered.
- the performance of glass fiber dry yarn is mainly affected by film-forming agents and lubricants.
- the main function of film-forming agents is to form a dense film on the surface of glass fiber, repair micro-cracks on the surface of glass fiber, and improve the strength of glass fiber and the degree of bonding with resin. .
- Example 2 because there is too much high molecular weight film-forming agent, the yarn is hard and has a lot of hairiness.
- Example 4 too little lubricant resulted in yarn hairiness and high hairiness.
- Example 5 too much lubricant resulted in loose yarn and high drape. However, both of them can meet the needs of regular use.
- Comparative Examples 1-4 Since the film-forming agent formula type and ratio are not within the scope of the claims of the present invention, a continuous smooth film cannot be formed on the surface of the glass fiber, resulting in low yarn tensile strength. At the same time, Comparative Examples 1. Due to the lack of water-based polyamide emulsion, the yarn is too hard and the hairiness is high; Comparative Example 2 is due to the lack of polymer film-forming agent, which results in the yarn being too soft and the drape is increased. Comparative Example 3 is due to the lack of low-molecular film-forming agent.
- Comparative Example 5 has little effect on the performance of dry glass fiber yarn, it has a greater impact on the performance of composite materials.
- the self-made non-thermoplastic yarn is Sinoma Technology product SC-1200BG7(6) aviation yarn, and the commercially available yarn is a certain brand of thermoplastic yarn from Taibo with the same specifications.
- the film-forming agent of the main body of the sizing agent is made of high-temperature-resistant components, which effectively prevents carbon residues produced during composite processing due to the sizing agent not being resistant to high temperatures.
- the addition of water-based polyamide emulsion greatly improves the contact between the resin and the fiber.
- Mechanical properties, especially the bending properties that characterize the interface bonding ability, the bending modulus is above 18GPa, and the bending strength is above 320MPa, which is much higher than that of the comparative example.
- the lubricant ensures the fiber processing performance while minimizing its impact on the fiber.
- the impact of interface integration The coupling agent is selected in a specific combination ratio to maximize the bonding between the resin and the fiber during the high-temperature bonding process.
- the products of the Examples and Comparative Examples of the present invention are granulated at high temperature (330°C, 3min) using a twin-screw extruder and then made into composite pellets, and then melted at high temperature (330°C) by an injection molding machine and then injection molded into strips. .
- high temperature 330°C, 3min
- a twin-screw extruder a twin-screw extruder
- melted at high temperature 330°C
- Figure 1 is a picture of composite material splines after high-temperature injection molding. From left to right are non-thermoplastic yarn (homemade) splines, thermoplastic yarn (commercially purchased) splines suitable for ordinary thermoplastic resins and application examples.
- the yarn splines prepared with the sizing agent 1 have a glass fiber content of 30%. It can be seen from the figure that the product provided by Embodiment 1 of the present invention has the lightest color after high-temperature injection molding and has better high-temperature resistance.
- the pictures of other embodiments are similar to those of Embodiment 1 and will not be shown one by one.
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Abstract
本发明属于玻璃纤维表面处理技术领域，具体涉及一种玻璃纤维浸润剂及其制备方法和应用。本发明提供的玻璃纤维浸润剂，通过各组分之间的配合以及用量的调整，特别是选用不同类型的成膜剂搭配使用以及选用分子量不同的水性聚氨酯为主成膜剂，采用聚酰胺乳液作为辅助成膜剂，提升了浸润剂的耐高温性能，使其能够满足耐高温热塑性尼龙树脂复合材料的加工的温度要求，显著提高了玻璃纤维与基材树脂之间的相容性和结合能力。
Description
本发明属于玻璃纤维表面处理技术领域，具体涉及一种玻璃纤维浸润剂及其制备方法和应用。
高性能玻璃纤维是指相对普通玻璃纤维而言，具有更高的力学性能、更强的耐腐蚀性能、更高的耐热温度、优良的介电和电绝缘性能等，其作为高性能复合材料的增强基材，主要用于航空、航天、兵器、核工业等国防领域。
玻璃纤维是一种极性很强的无机物，其主要成分为SiO
2，而树脂是一种高分子聚合物，这两种材料是完全不相容的，玻璃纤维作为树脂的增强材料时，与树脂的界面结合性能较差，因此，高性能玻璃纤维增强复合材料的关键技术之一是决定材料加工工艺和复合材料界面等性能的浸润剂技术。
浸润剂是一种玻璃纤维表面处理剂，玻璃纤维从漏板流出后通常需要用水性的浸润剂进行处理，赋予玻璃纤维良好的纺织加工性能及其复合材料优异的力学性能。不同的浸润剂所赋予玻璃纤维的性能不同，各种用于纺织、编织用的无捻粗纱必须具有良好的纺织使用性能以及与基材树脂之间具有良好的相容性才能满足各种不同的产品需求。因此开发适用于高性能玻璃纤维及其复合材料的浸润剂至关重要。
耐高温热塑性尼龙树脂复合材料加工方式一般为双螺杆挤出造粒后进行注塑，以最典型的PA6T为例，工业用PA6T熔点高达310-320℃，常规成膜剂耐热性能无法达标，同时，因为PA6T颜色为白色，大部分复合材料产品对颜色也有所要求，若玻璃纤维浸润剂中存在大量耐温性不佳的组分，不但无法对基材树脂与纤维的结合起到促进与保护的作用，反而会由于产生残碳，影响树脂与玻璃纤维结合的性能与外观表现。另外，当玻璃纤维与基材树脂的性能都达到最佳状态时，复合材料的界面结合能力则决定着玻璃纤维与基材树脂之间的应力传递好坏，这种差异对复合材料的力学性能具有重要影响。
发明内容
因此，本发明要解决的技术问题在于克服现有技术中的玻璃纤维浸润剂的耐热性不能满足耐高温热塑性尼龙树脂复合材料加工的温度要求、玻璃纤维与基材树脂的界面结合能力有待进一步提高等缺陷，从而提供一种玻璃纤维浸润剂及其制备方法和应用。
为此，本发明能够提供如下技术方案：
本发明提供一种玻璃纤维浸润剂，以有效含量计，包括如下质量百分含量的组分：
成膜剂3-8％，润滑剂0.5-1.5％，偶联剂0.5-1.2％；
其中，以玻璃纤维浸润剂总质量计，所述成膜剂中包括数均分子量为400-1500的低分子量水性聚氨酯2-4％，数均分子量为2000-4000的高分子量水性聚氨酯0.5-2％；水性聚酰胺乳液0.5-2％；
所述偶联剂为含苯环的硅烷偶联剂与含氨基和/或环氧官能团的硅烷偶联剂的混合物。
可选的，所述水性聚酰胺乳液是以聚酰胺树脂为原料，通过乳化制备而成的水性乳液。
可选的，以玻璃纤维浸润剂总质量计，所述润滑剂包括非离子型润滑剂0.5-1.2％；离子型润滑剂0.1-0.3％。
可选的，所述非离子型润滑剂为矿物油类润滑剂，酯类润滑剂，长链柔性含苯环类润滑剂，有机硅类润滑剂或酰胺类润滑剂中的至少一种。
可选的，所述离子型润滑剂为润滑剂6760L，润滑剂8760中的至少一种。
可选的，所述偶联剂为热分解温度在300℃以上的硅烷偶联剂；
可选的，以玻璃纤维浸润剂总质量计，所述偶联剂包括含苯环的硅烷偶联剂0.4-0.8％，含氨基和/或环氧官能团的硅烷偶联剂0.1-0.4％。
可选的，所述玻璃纤维浸润剂的总固含量为5-6wt％。
可选的，所述玻璃纤维浸润剂的pH为5-7。
可选的，采用pH调节剂调节玻璃纤维浸润剂的pH。
可选的，pH调节剂为有机酸。
可选的，有机酸为醋酸，甲酸，琥珀酸或柠檬酸中的至少一种。
可选的，所述玻璃纤维浸润剂中，余量为水。
本发明还提供一种上述的玻璃纤维浸润剂的制备方法，包括如下步骤：
S1，将偶联剂分散至水中，调节pH，得偶联剂溶液；
S2，将成膜剂、润滑剂混合，再与所述偶联剂溶液混合，调节pH，得到所述玻璃纤维浸润剂。
可选的，步骤S1中水的用量为偶联剂质量的4-6倍。
可选的，步骤S1和S2中均调节pH至5-7。
典型非限定性的，所述玻璃纤维浸润剂的制备方法的具体操作可以为：
(1)在所述偶联剂中加入偶联剂用量5倍的水，再加入pH调节剂将pH调整至5-7，充分混合至所述偶联剂分散均匀，得偶联剂溶液；
(2)将成膜剂、润滑剂充分分散于水中，再与所述偶联剂溶液混合均匀，最后通过pH调节剂将混合液pH调节至5-7，即得所述玻璃纤维浸润剂。
进一步优选的，所述玻璃纤维浸润剂的制备方法可以为：
(1)向第一混合容器中加入所述偶联剂，加入偶联剂质量5倍的去离子水，搅拌并加入pH调节剂至水溶液pH为5-7，持续搅拌至液体表面澄清，得到偶联剂溶液；
(2)向第二混合容器中加入低分子量水性聚氨酯和高分子量水性聚氨酯，再加入聚氨酯乳液总用量5倍质量的去离子水，搅拌均匀；
(3)将水性聚酰胺乳液用其8倍质量的去离子水充分稀释后加入到第二混合容器中，搅拌均匀；
(4)将润滑剂用其10倍质量的去离子水充分稀释后加入到第二混合容器中，搅拌均匀；
(5)将第一混合容器中的硅烷偶联剂溶液加入到第二混合容器中，搅拌均匀，添加剩余的去离子水，调节pH至5-7，即得浸润剂成品。
本发明还提供一种上述的玻璃纤维浸润剂在制备热塑性耐高温复合材料中的应用。
可选的，热塑性耐高温复合材料为玻璃纤维与基材树脂的复合材料。
可选的，所述基材树脂为PA6树脂。
可选的，所述PA6树脂为PA6T树脂。
本发明技术方案，具有如下优点：
本发明提供的玻璃纤维浸润剂，通过各组分之间的配合以及用量的调整，特别是选用不同类型的成膜剂搭配使用特定的偶联剂，赋予玻璃纤维表面与基体树脂良好的相容性，显著提高了玻璃纤维与基材树脂之间的相容性和界面结合能力。具体地，选用分子量不同的水性聚氨酯为主成膜剂，采用水性聚酰胺乳液作为辅助成膜剂，提升了浸润剂的耐高温性能，使其能够满足耐高温热塑性尼龙树脂复合材料的加工的温度要求，水性聚氨酯具有良好的耐高温性能，水性聚酰胺乳液能够在提升整体浸润剂成膜性能的同时提升玻璃纤维与基材树脂的匹配性能。其中，高分子量聚氨酯可提供较高的纱线包覆率，有效提高玻璃纤维耐磨性，低分子量聚氨酯则可提升玻璃纤维的柔软度以及玻璃纤维表面浸润剂膜的弹性，起到一部分提升润滑性能的作用，并有利于提升玻璃纤维的抗疲劳性能；同时，聚氨酯具有较多的强极性基团，在成膜后膜的粘度较高，易使玻璃纤维表面形成一层致密保护膜，进而将玻璃纤维与外界隔离，有效阻止水分进入玻璃纤维微裂纹，进一步提高玻璃纤维的加工性能。本发明采用不同类型的成膜剂搭配使用，不仅赋予玻璃纤维与基体树脂间良好的相容性和界面结合性能，而且，在保证玻纤纱柔软的基础上，还提高了玻纤纱的耐疲劳性能。同时，在配方中加入水性聚酰胺乳液，聚酰胺乳液具有良好的成膜性、优异的粘结性和抗磨损性，并且耐温性能优异，在赋予玻纤纱一定程度刚性的同时与尼龙基材树脂有较好的相容性，提升玻纤纱与基材树脂的结合程度。所述的硅烷偶联剂至少需要一种含苯环的耐高温硅烷偶联剂，此外还包括含氨基或环氧官能团的硅烷偶联剂，结构上由于存在氨基/环氧官能团与苯环，与树脂基材有相似之处，作为树脂与玻璃纤维结合的桥梁十分适合，同时，其结构与辅助成膜剂聚酰胺乳液具有相似的结构，可以更好的相互结合形成网状结构，提升与基材树脂的结合性能。另外，本发明通过选用特定的偶联剂还能够增强成膜剂与玻璃纤维的粘接性，可降低玻璃纤维在加工过程中的毛羽量和断头。与现有的技术相比，本发明所述的浸润剂配方组分更加简单，简化配置制备工艺，该配方赋予玻璃纤维良好的加工性能，与热塑性耐高温基材树脂相容性好，提高玻璃纤维复合材料的力学性能，同时减少复材色差，新产品玻璃纤维增强复合材料还具有较 好的强度和模量。
本发明提供的玻璃纤维浸润剂，通过对润滑剂的进一步限定，使其同时具有干润滑和湿润滑的作用，在湿态(拉丝过程中)和干态(原丝退并、纺织加工时)起润滑玻璃纤维表面、减少磨损作用，同时，对玻璃纤维与基材树脂的结合起到促进作用，克服了常规润滑剂的使用不利于玻璃纤维与基材树脂结合的弊端。非离子型润滑剂可以降低毛丝的产生，同时改善纤维的耐磨性。本发明所述的非离子型润滑剂优选为矿物油类，酯类，苯环类，有机硅类或酰胺类润滑剂，在起到润滑作用的同时，还可以降低浸润体系与玻璃纤维表面的接触角，可以同时起到润湿作用，并且其耐高温性能优异，在与基材树脂的高温混合状态时，仍可在复合材料挤出过程中对玻璃纤维进行保护，防止毛刺产生。同时，添加少量的高效的离子型润滑剂作为干润滑，用以减少纤维在纺织加工时产生的摩擦和静电。
本发明提供的玻璃纤维浸润剂，酸的用量根据所用偶联剂种类及用量决定，配好的浸润剂要在一定pH条件下利于储存和适用，一般pH值为5～7的酸性环境较好。
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实验例中纱线的图片，从左到右分别为非热塑性纱线(自制)，适用于普通热塑树脂的热塑性纱线(购自泰玻)及采用实施例1的浸润剂制备得到的纱线。
从图中可以看出，本发明实施例1提供的产品在高温注塑后颜色变化较小，耐高温性能较好。
图2是本发明实验例中毛羽量测试采用的装置。
附图标记：
(1)纱架；(2)纱团；(3)电机；(4)收卷装置；(5)纱线；(6)摩擦点。
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品，均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。
实施例和对比例
以下实施例和对比例中，各原料的来源如下：低分子量水性聚氨酯乳液采用麦可门公司的U系列水性聚氨酯，有效含量为30wt％，数均分子量为400-1500；高分子水性聚氨酯乳液为中材科技自制乳液，商品型号为240-3，有效含量为25wt％，数均分子量为2000-4000；水性聚酰胺乳液由麦可门提供，商品型号为pa845H，有效含量为30wt％；润滑剂TR-2382为中材科技自产，有效含量为99wt％；离子型润滑剂6760L由科凯提供有效含量为99wt％；偶联剂Y-9669，A-1100，A-187均由迈图公司提供，有效含量99wt％。
各实施例和对比例中，以有效含量计，玻璃纤维浸润剂的化学组成如下表所示：
表1
| 组分 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 |
| 低分子水性聚氨酯乳液U5 | 2.5％ | 2％ | 3％ | 2.5％ | 2.5％ | 2.5％ |
| 高分子聚氨酯乳液240-3 | 1.2％ | 2％ | 1.5％ | 1.2％ | 1.2％ | 1.2％ |
| 水性聚酰胺乳液 | 0.8％ | 0.8％ | 0.8％ | 0.8％ | 0.8％ | 0.8％ |
| 润滑剂TR-2382 | 0.7％ | 0.7％ | 0.7％ | 0.5％ | 0.8％ | 0.7％ |
| 润滑剂6760L | 0.2％ | 0.2％ | 0.2％ | 0.1％ | 0.3％ | 0.2％ |
| 偶联剂Y-9669 | 0.6％ | 0.6％ | 0.6％ | 0.6％ | 0.6％ | 0.4％ |
| 偶联剂A-187 | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.1％ |
| pH | 6.3 | 6.3 | 6.3 | 6.3 | 6.3 | 6.3 |
| 组分 | 实施例7 | 对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 |
| 低分子水性聚氨酯乳液U5 | 2.5％ | 3.0％ | 3.7％ | / | 3.3％ | 2.5％ |
| 高分子聚氨酯乳液240-3 | 1.2％ | 1.5％ | / | 3.7％ | / | 1.2％ |
| 水性聚酰胺乳液 | 0.8％ | / | 0.8％ | 0.8％ | 1.2％ | 0.8％ |
| 润滑剂TR-2382 | 0.7％ | 0.8％ | 0.7％ | 0.7％ | 0.7％ | 0.7％ |
| 润滑剂6760L | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.2％ |
| 偶联剂Y-9669 | 0.8％ | 0.6％ | 0.6％ | 0.6％ | 0.6％ | / |
| 偶联剂A-187 | 0.4％ | 0.2％ | 0.2％ | 0.2％ | 0.2％ | 0.8％ |
| pH | 6.3 | 6.3 | 6.3 | 6.3 | 6.3 | 6.3 |
上述实施例和对比例中提供的玻璃纤维浸润剂的制备方法为：
(1)向第一混合容器中加入所述偶联剂，加入偶联剂质量5倍的去离子水，搅拌并加入pH调节剂至水溶液pH为5-7，持续搅拌至液体表面澄清，得到偶联剂溶液；
(2)向第二混合容器中加入低分子量水性聚氨酯乳液和高分子量水性聚氨酯乳液，再加入聚氨酯乳液5倍质量的去离子水，搅拌均匀；
(3)将水性聚酰胺乳液用其8倍质量的去离子水充分稀释后加入到第二混合容器中，搅拌均匀；
(4)将润滑剂分别用其10倍质量的去离子水充分稀释后加入到第二混合容器中，搅拌均匀；
(5)将第一混合容器中的硅烷偶联剂溶液加入到第二混合容器中，搅拌均匀，添加剩余的去离子水，调节pH至5-7，即得浸润剂成品。
实验例
1、常规指标测试
对实施例和对比例提供的玻璃纤维浸润剂应用于1000tex的PA6T复合材料的制备，其中玻璃纤维含量为40wt％。玻璃纤维的具体来源为中材科技自制的HS4高强玻纤。玻璃纤维原丝在经过后道加工前要经过烘箱烘干，增加原丝的集束性，可提高纱线耐磨性。原丝的烘干温度分三个阶段，分别为 90℃，90min；105℃，180min；125℃，180min。测试产品的各项性能指标，具体的测试方法如下：
(1)可燃物含量：按照GB/T 9914.2增强制品试验方法第2部分：玻璃纤维可燃物含量的测定。
(2)干纱拉伸强度：按照GB/T7690.3增强材料纱线试验方法第3部分：玻璃纤维断裂强力和断裂伸长的测定。
(3)毛羽量：包括无捻粗纱与耐磨装置在摩擦期间产生的所有毛丝重量，单位为毫克，采用多点、多种摩擦材料、多种摩擦角度摩擦，以恒定的绕曲速率使试样破坏，过程结束后测量收集的毛羽量；具体测试装置见图2。
(4)硬挺度测试方法：采用国标GB/T7690.4-2001进行无捻粗纱硬挺度测试。
(5)参考GB18369附录B把无捻粗纱水平放置于间距10m的支架上，并施加一定程度的张力(0.098N/Tex)，把玻璃纤维原丝最大和最小悬垂度之差作为无捻粗纱的悬垂度，当张力为0时称为自然悬垂高度。
(6)按照国标GB/T1449-2005纤维增强塑料弯曲性能测试方法进行复合材料弯曲性能测试。
(7)按照国标GB/T1447-2005纤维增强塑料拉伸性能测试方法进行复合材料拉伸性能测试。
(8)按照国标GB/T1451-2005纤维增强塑料简支梁式冲击韧性试验方法进行复合材料冲击性能测试。
表2 玻璃纤维干纱性能
| 样品 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 |
| 可燃物含量，％ | 0.68 | 0.61 | 0.69 | 0.66 | 0.67 | 0.68 |
| 产品干纱拉伸强度N/TEX | 0.71 | 0.72 | 0.72 | 0.72 | 0.70 | 0.70 |
| 产品硬挺度/mm | 63 | 69 | 63 | 61 | 66 | 65 |
| 毛羽数量mg/500m | 7.4 | 16.7 | 13.3 | 18.9 | 6.9 | 8.9 |
| 悬垂度/mm | 9 | 10 | 10 | 13 | 19.6 | 13 |
| 样品 | 实施例7 | 对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 |
| 可燃物含量，％ | 0.73 | 0.73 | 0.68 | 0.67 | 0.68 | 0.71 |
| 产品干纱拉伸强度N/TEX | 0.70 | 0.67 | 0.66 | 0.68 | 0.67 | 0.71 |
| 产品硬挺度/mm | 67 | 82 | 53 | 87 | 58 | 63 |
| 毛羽数量mg/500m | 15.9 | 21.3 | 6.9 | 26.8 | 8.9 | 7.5 |
| 悬垂度/mm | 23 | 17 | 37 | 6 | 29 | 9 |
干纱强度：表征玻纤力学性能；硬挺度：表征纱线软硬，越高越硬；毛羽：表征纱线表面毛糙程度，越高越毛；悬垂度：表征纱线松散程度，越高越散。
玻璃纤维干纱性能主要受成膜剂及润滑剂影响，其中成膜剂的主要作用是在玻纤表面形成一层致密膜，修复玻纤表面微裂纹，提升玻纤强度以及与树脂的结合程度。实施例2因为高分子量成膜剂过多，所以纱线发硬，毛羽多。实施例4由于润滑剂过少导致纱线发毛，毛羽高，实施例5由于润滑剂过多导致纱线松散，悬垂度高，但均能满足常规使用需求。
对比例1-4由于成膜剂配方种类及配比不在本发明的权利要求范围内，未能在玻纤表面性能连续的平整的膜，因此导致纱线拉伸强度较低，同时，对比例1由于缺少水性聚酰胺乳液导致纱线过硬，毛羽量高；对比例2则是由于缺少高分子成膜剂导致纱线过软，悬垂度增大，对比例3则是缺少低分子成膜剂导致纱线过硬，毛羽多；对比例4缺少高分子成膜剂会导致纱线过软，力学性能降低，悬垂度增大；对比例1-4的部分性能已经不能满足常规使用要求。
对比例5虽然对玻璃纤维干纱性能影响不大，但是对复合材料的性能影响较大。
表3 复合材料性能
注：自制非热塑为中材科技产品SC-1200BG7(6)航空纱，市购纱线为同规格泰玻某牌号热塑型纱线。
从上表中的数据可知，由本发明提供的浸润剂配方制得的纱线整体复材性能较现有产品有较大提升。浸润剂主体的成膜剂选用耐高温成分，有效防止了在复材加工过程中由于浸润剂不耐高温而产生的残碳；同时，水性聚酰胺乳液的加入，大大提升了树脂与纤维接触的力学性能，特别是表征界面结合能力的弯曲性能，弯曲模量均在18GPa以上，弯曲强度均在320MPa以上，远高于对比例，润滑剂在保证纤维加工性能的同时最大程度的减小其对界面结合的影响。偶联剂选用特定组合配比，在高温结合过程中最大的加强了树脂与纤维的结合。
2、耐高温性能测试
将本发明实施例和对比例的产品在经过双螺杆挤出机高温预融(330℃，3min)造粒后制成复材料粒，并通过注塑机高温熔融(330℃)后注塑成样条。玻纤在加工过程中，需经过高温预混合，如浸润剂中部分组分耐温性较差，会在此过程中分解并产生残碳，导致纱线表面及复合材料颜色变深，影响复材外观形貌。
图1是高温注塑后的复合材料样条的图片，从左到右分别为非热塑性纱线(自制)样条，适用于普通热塑树脂的热塑性纱线(市购)样条及采用实施例1的浸润剂制备得到的纱线样条，三者玻纤含量均为30％。从图中可以看出，本发明实施例1提供的产品在高温注塑后颜色最浅，耐高温性能较好。其它实施例的图片与实施例1类似，不再一一展示。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (18)
- 一种玻璃纤维浸润剂，其特征在于，以有效含量计，包括如下质量百分含量的组分：成膜剂3-8％，润滑剂0.5-1.5％，偶联剂0.5-1.2％；其中，以玻璃纤维浸润剂总质量计，所述成膜剂中包括数均分子量为400-1500的低分子量水性聚氨酯2-4％，数均分子量为2000-4000的高分子量水性聚氨酯0.5-2％；水性聚酰胺乳液0.5-2％；所述偶联剂为含苯环的硅烷偶联剂与含氨基和/或环氧官能团的硅烷偶联剂的混合物。
- 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，以玻璃纤维浸润剂总质量计，所述润滑剂包括非离子型润滑剂0.5-1.2％；离子型润滑剂0.1-0.3％。
- 根据权利要求2所述的玻璃纤维浸润剂，其特征在于，所述非离子型润滑剂为矿物油类润滑剂，酯类润滑剂，长链柔性含苯环类润滑剂，有机硅类润滑剂或酰胺类润滑剂中的至少一种。
- 根据权利要求2所述的玻璃纤维浸润剂，其特征在于，所述离子型润滑剂为润滑剂6760L，润滑剂8760中的至少一种。
- 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，所述偶联剂为热分解温度在300℃以上的硅烷偶联剂。
- 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，以玻璃纤维浸润剂总质量计，所述偶联剂包括含苯环的硅烷偶联剂0.4-0.8％，含氨基和/或环氧官能团的硅烷偶联剂0.1-0.4％。
- 根据权利要求1-6任一项所述的玻璃纤维浸润剂，其特征在于，所述玻璃纤维浸润剂的总固含量为5-6wt％。
- 根据权利要求1-6任一项所述的玻璃纤维浸润剂，其特征在于，所述玻璃纤维浸润剂的pH为5-7。
- 根据权利要求8所述的玻璃纤维浸润剂，其特征在于，采用pH调节剂调节玻璃纤维浸润剂的pH。
- 根据权利要求9所述的玻璃纤维浸润剂，其特征在于，pH调节剂为 有机酸。
- 根据权利要求10所述的玻璃纤维浸润剂，其特征在于，有机酸为醋酸，甲酸，琥珀酸或柠檬酸中的至少一种。
- 根据权利要求7所述的玻璃纤维浸润剂，其特征在于，余量为水。
- 一种权利要求1-12任一项所述的玻璃纤维浸润剂的制备方法，其特征在于，包括如下步骤：S1，将偶联剂分散至水中，调节pH，得偶联剂溶液；S2，将成膜剂、润滑剂混合，再与所述偶联剂溶液混合，调节pH，得到所述玻璃纤维浸润剂。
- 根据权利要求13所述的制备方法，其特征在于，步骤S1中水的用量为偶联剂质量的4-6倍。
- 根据权利要求13所述的制备方法，其特征在于，步骤S1和S2中均调节pH至5-7。
- 一种权利要求1-12任一项所述的玻璃纤维浸润剂在制备热塑性耐高温复合材料中的应用。
- 根据权利要求16所述的应用，其特征在于，热塑性耐高温复合材料为玻璃纤维与基材树脂的复合材料，所述基材树脂为PA6树脂。
- 根据权利要求17所述的应用，其特征在于，所述PA6树脂为PA6T树脂。
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