CN114685063A - Glass fiber yarn impregnating compound and preparation method and application thereof - Google Patents

Glass fiber yarn impregnating compound and preparation method and application thereof Download PDF

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Publication number
CN114685063A
CN114685063A CN202011604582.6A CN202011604582A CN114685063A CN 114685063 A CN114685063 A CN 114685063A CN 202011604582 A CN202011604582 A CN 202011604582A CN 114685063 A CN114685063 A CN 114685063A
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glass fiber
fiber yarn
water
modified
impregnating compound
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张伟权
张驰
张骁
彭群
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Yixing Weiye Glass Fiber Material Co ltd
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Yixing Weiye Glass Fiber Material Co ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Composite Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Abstract

The invention relates to a glass fiber yarn impregnating compound and a preparation method and application thereof, wherein the impregnating compound comprises the following materials: acetic acid, a silane coupling agent, modified waterborne epoxy resin, epoxy modified polyester, modified waterborne polyurethane and water. The preparation method comprises the following steps: adding part of water and acetic acid into a container, stirring to enable the pH value to be 2.5-5, dropwise adding a silane coupling agent, and obtaining a hydrolysate after complete hydrolysis; uniformly stirring the modified waterborne epoxy resin, the epoxy modified polyester, the modified waterborne polyurethane and water to obtain a resin mixed solution; and adding the resin mixed solution into the hydrolysate, adding water, and continuously stirring to obtain the glass fiber yarn impregnating compound. The invention provides an environment-friendly glass fiber yarn impregnating compound which can meet the operation requirements of glass fiber forming, twisting, weaving and the like; the silane coupling agent is not required to be removed before the glass fiber yarn is used for preparing the composite material, and the requirements on dielectric constant and strength of the insulating composite material can be met.

Description

Glass fiber yarn impregnating compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a glass fiber yarn impregnating compound and a preparation method and application thereof.
Background
Glass fiber (hereinafter referred to as glass fiber) is an inorganic non-metallic material with excellent performance, and has the advantages of good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but has the defects of brittle property and poor wear resistance. Are commonly used as reinforcement in composites, electrical insulation and thermal insulation. Glass fiber products are widely applied to various fields of national economy, wherein electronics, transportation and buildings are the three most important application fields, and represent the development trend of the glass fiber industry in the future years. The baby bottle yarn is a textile glass fiber or reinforced textile type, is named after a baby bottle after being molded, has a true diameter of less than or equal to 11 mu m, and is generally used for printed circuit boards, cable coating layers, insulating sleeves, insulating materials of various electrical appliances and the like.
The impregnating compound needs to be coated on the surface of the glass fiber in the production process of the glass fiber, and the impregnating compound determines the purpose and the performance of the glass fiber. The sizing agent has the functions of protecting fragile glass fibers and bonding and bundling (namely, a plurality of monofilaments are bonded into a bundle), can meet the performance of subsequent processing of the glass fibers, such as twisting, stranding, chopping, dispersing and the like, and plays a role in connecting inorganic materials and organic material bridges when the glass fibers and matrix resin are made into composite materials. The more excellent the performance of the impregnating compound is, the better the performance of the prepared composite material is.
The raw materials and the formula technology of the impregnating compound are the most critical technology for reflecting the internal quality of various glass fiber products (including yarns, cloth and felts) and are essential industrial consumables in glass fiber production. The industry often equates ITs importance to the "chip manufacturing technology" of the IT industry. The technical core is divided into two parts: firstly, the synthesis manufacturing technology of the most important component film-forming agent in the components of the raw materials of the impregnating compound, namely the chip manufacturing technology; secondly, the formula application technology of each component in the impregnating compound, namely the chip combination technology, belongs to the fine chemical industry and the glass fiber industry respectively. The two technologies are not high in degree of specialization and serialization in China, and the two technologies are mutually crossed, so that the domestic impregnating compound raw material and formula technology are only in the situation of low-grade level in the world. With the rapid development of tank furnace technology in China and the mass export of products, more and more manufacturers realize that the competition of glass fiber products depends on the raw materials and formula technology of the impregnating compound to a great extent, and the technology is directly related to the internal quality of various glass fiber products (including yarns, cloth and felts), and has become one of the core competitiveness of various glass fiber production enterprises for maintaining sustainable development.
During the manufacturing process of the glass fiber feeding bottle yarn, the impregnating compound needs to be coated, the impregnating compound coating on the surface of the glass fiber plays a role in protecting the glass fiber forming and the subsequent weaving process, and the requirements on bundling and forming performance in the subsequent weaving process can be met. The traditional nursing bottle yarn impregnating compound has a paraffin type impregnating compound and a starch type impregnating compound, and the coating of the impregnating compound contains a large amount of hydrophilic groups or components which can not be combined with matrix resin, so that before the resin base material is combined, the coating of the impregnating compound needs to be removed by burning or washing, the mechanical strength, the thermal deformation strength and the dielectric constant of the base material are ensured, the process of removing the coating of the impregnating compound by burning or washing is not environment-friendly, a large amount of toxic and harmful pollutants can be generated, such as waste gas or waste water, and the post-treatment cost is higher. In addition, in the production process of the glass fiber, in order to ensure the strength of the glass fiber, a part of silane coupling agent is added into the impregnating compound, the silane coupling agent is removed before the glass fiber is used, and then in order to ensure the bonding strength of the composite material, the silane coupling agent is impregnated again, so that the length of the process line is increased, and waste is caused.
Disclosure of Invention
In order to solve the technical problem of pollution caused by the fact that the traditional nursing bottle yarn impregnating compound needs to be removed before being combined with matrix resin, a glass fiber yarn impregnating compound, a preparation method and application thereof are provided. The method provided by the invention is an environment-friendly glass fiber yarn impregnating compound, which can meet the operation requirements of glass fiber forming, twisting, weaving and the like; and the requirements of dielectric constant and strength of the insulating composite material can be met without removing a silane coupling agent before the insulating composite material is prepared after the insulating composite material is used for glass fiber yarns.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a glass fiber yarn impregnating compound comprises the following materials in percentage by weight:
0.03 to 0.1 percent of acetic acid,
0.3 to 0.7 percent of silane coupling agent,
3.5 to 5 percent of modified waterborne epoxy resin,
0.6 to 1 percent of epoxy modified polyester,
6 to 8 percent of modified waterborne polyurethane,
The balance being water.
Further, the acetic acid is glacial acetic acid; the coupling agent is KH 560. Glacial acetic acid, during the preparation process of the impregnating compound, KH560 can be rapidly hydrolyzed under a lower pH condition, so that the prepared impregnating compound is acidic and the stability of the aqueous resin is ensured; the dosage of the water quality adjusting agent is adjusted within the range according to the pH value of the water quality and the process requirement. KH560 is capable of improving the adhesion of the inorganic filler to the organic substrate to improve the physical properties of the resulting composite material, particularly the mechanical strength, water resistance, electrical properties, heat resistance, etc. of the composite material, and has a high retention rate in a wet state.
Further, the preparation method of the modified waterborne epoxy resin comprises the following steps: dissolving diethanolamine in ethanol to obtain a mixed solution; putting the epoxy resin into a reaction kettle, heating to 75-80 ℃, introducing cooling water, dropwise adding the mixed solution for 30-150 min, carefully controlling the speed and reaction temperature of the dropwise added mixed solution to prevent flushing during the dropwise adding process, keeping the temperature for continuous reaction for 120-240 min after the dropwise adding is finished, cooling to 50-60 ℃ after the reaction is finished, adding glacial acetic acid, uniformly stirring, adding water, cooling to below 40 ℃, and discharging to prepare the modified waterborne epoxy resin.
Still further, the weight fractions of the raw materials used in the preparation process of the modified waterborne epoxy resin are as follows: epoxy resin E5190-130 parts, diethanolamine 30-40 parts, ethanol 30-40 parts, glacial acetic acid 45-65 parts and deionized water 30-40 parts; the solid content of the modified waterborne epoxy resin is (75 +/-2) wt%. Carrying out ring-opening modification on epoxy resin by adopting organic ammonia, and finally adding acid for neutralization and salification to obtain a cationic aqueous epoxy resin solution containing amino; the modified waterborne epoxy resin prepared by the invention has good stability and film-forming property under an acidic condition, and provides good stiffness and bundling property for glass fibers.
Further, the preparation method of the epoxy modified polyester comprises the following steps: adding polyester 400, epoxy resin and benzyldimethylamine into a reaction kettle, heating to 115-125 ℃ for reaction for 3-5 h, then cooling to 80-90 ℃, dripping diethanolamine within 30-60 min, keeping the temperature at 80-90 ℃ for continuous reaction for 3-5 h after dripping is finished, cooling to 50-60 ℃ after reaction is finished, adding glacial acetic acid, adding water after stirring uniformly, cooling to below 40 ℃, and discharging to prepare the epoxy modified polyester.
Still further, the weight fractions of the raw materials used in the epoxy modified polyester are: 100 parts of polyester 40080-; the solid content of the epoxy modified polyester is (30 +/-2) wt%. Reacting polyester 400 containing long-chain ester groups with one epoxy group of epoxy resin by using a benzyl dimethylamine catalyst, then reacting diethanol amine with the other epoxy group, and finally adding acid for neutralization and salifying to obtain cationic epoxy modified polyester solution containing amino; the epoxy modified polyester has good stability under an acidic condition, and provides good flexibility and lubricity for glass fibers.
Further, the preparation method of the modified waterborne polyurethane comprises the following steps: adding polyester 400 into a reaction kettle, heating to 80 ℃, performing reduced pressure dehydration for 30min, then adding triethylene diamine, cooling to 40-50 ℃, dripping Hexamethylene Diisocyanate (HDI) within 2.5h, keeping the temperature for 3-4 h after dripping, heating to 55-65 ℃, adding a chain extender, keeping the temperature for reaction for 2-3 h, adding glacial acetic acid, stirring uniformly, adding water, cooling to below 40 ℃, discharging, and thus obtaining the modified waterborne polyurethane.
Still further, the weight fractions of the raw materials used in the modified waterborne polyurethane are as follows: 120 parts of polyester 40090-; the solid content of the modified waterborne polyurethane is (30 +/-2) wt%. In the invention, triethylene diamine is used as a catalyst to catalyze polyester 400 to react with diisocyanate, after the reaction is finished, dihydroxy compounds containing amino are added as chain extenders to react, and finally acid is added to neutralize and form salt, so that cationic waterborne polyurethane with amino is prepared; the modified waterborne polyurethane prepared by the invention has good stability and film-forming property under an acidic condition, and provides good stiffness and bundling property for glass fibers.
The invention also provides a preparation method of the glass fiber yarn impregnating compound, which comprises the following steps:
(1) weighing the materials according to the formula; adding part of water and acetic acid into a container, stirring to enable the pH value to be 2.5-5, dropwise adding a silane coupling agent, continuously stirring for at least 30min after the dropwise adding is finished, and obtaining a hydrolysate after the silane coupling agent is completely hydrolyzed;
(2) uniformly stirring the modified waterborne epoxy resin, the epoxy modified polyester, the modified waterborne polyurethane and part of water to obtain a resin mixed solution;
(3) and adding the resin mixed solution into the hydrolysate, and supplementing the rest water and continuing stirring for 10-15 min to obtain the glass fiber yarn impregnating compound.
The last aspect of the invention provides application of the glass fiber yarn impregnating compound, wherein the impregnating compound is used for producing glass fiber yarns, and the prepared glass fiber yarns containing the impregnating compound are compounded with an insulating base material to obtain an insulating composite material.
The beneficial technical effects are as follows:
the glass fiber yarn impregnating compound prepared by the invention is applied to the production process of glass fibers, the impregnating compound does not need to be dried in the production process of the glass fibers, and the glass fiber yarn impregnating compound can be naturally air-dried to form a film, so that the energy consumption can be effectively reduced; the glass fiber yarns produced by the treating compound prepared by the method can effectively improve the utilization efficiency of the treating compound without burning to remove the silane coupling agent when the composite material is prepared by processing and molding, and reduce the generation of waste gas/smoke and waste water. The cost of the impregnating compound is slightly higher than that of the traditional paraffin impregnating compound but lower than that of a starch impregnating compound. The invention can reduce the adverse effect caused by removing the coupling agent in the construction process and avoid the problem of cost increase caused by repeatedly adding the coupling agent, the cost of the prepared composite material is lower than that of a paraffin type impregnating compound, and the composite material has relatively better mechanical property. The impregnating compound is used for manufacturing and molding the glass fiber, regardless of paraffin wax type or starch type, and a coating formed by the used traditional impregnating compound is compounded with the matrix resin at the later stage, and the structure or group existing in the traditional impregnating compound cannot be combined or dissolved with the matrix resin, namely, an unconnected isolating layer exists between the glass fiber and the matrix resin. The sizing agent can meet the manufacturing and forming requirements of glass fibers, and a large amount of active amino cations are reserved in the modified waterborne epoxy resin, the epoxy modified polyester and the modified waterborne polyurethane which are used as main film forming agents, can completely participate in reaction when being compounded with matrix resin at the later stage, and is an effective bridge between fibers and a base material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement set by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
The polyester 400 used in the examples below is HALLSTAR DIOPLEX400, a product of U.S. import;
the chemical structural formula of the cationic chain extender 8566 is as follows: h2NCH2CH2NHCH2CH2NHCH2CHOHCH2Cl。
Example 1
A glass fiber yarn impregnating compound comprises the following materials in percentage by weight: glacial acetic acid 0.03%, silane coupling agent KH 5600.35%, modified waterborne epoxy resin 3.5%, epoxy modified polyester 0.82%, modified waterborne polyurethane 6.55% and the balance of water.
The preparation method of the modified waterborne epoxy resin comprises the following steps: dissolving 40 parts by weight of diethanolamine in 30 parts by weight of ethanol to obtain a mixed solution; putting 90 parts by weight of epoxy resin E51 into a reaction kettle, heating to 80 ℃, introducing cooling water, dropwise adding the mixed solution within 60min, carefully controlling the speed and the reaction temperature of the dropwise added mixed solution to prevent flushing, keeping the temperature of 80 ℃ for continuous reaction for 120min after the dropwise adding is finished, cooling to 60 ℃ after the reaction is finished, adding 50 parts by weight of glacial acetic acid, uniformly stirring, adding water, cooling to below 40 ℃, discharging, and preparing the modified waterborne epoxy resin with the solid content of (75 +/-2) wt%.
The preparation method of the epoxy modified polyester comprises the following steps: adding 100 parts by weight of polyester 400, 75 parts by weight of epoxy resin E51 and 2.2 parts by weight of benzyldimethylamine into a reaction kettle, heating to 125 ℃ for reaction for 5 hours, then cooling to 80 ℃, dripping 40 parts by weight of diethanolamine within 60 minutes, keeping the temperature at 80 ℃ for continuing reaction for 5 hours after dripping is finished, cooling to 60 ℃ after the reaction is finished, adding 35 parts by weight of glacial acetic acid, stirring uniformly, adding water, cooling to below 40 ℃, discharging, and preparing the epoxy modified polyester with the solid content of (30 +/-2) wt%.
The preparation method of the modified waterborne polyurethane comprises the following steps: putting 90 parts by weight of polyester 400 into a reaction kettle, heating to 80 ℃, performing reduced pressure dehydration for 30min, cooling to 40-50 ℃, dripping 25 parts by weight of Hexamethylene Diisocyanate (HDI) within 2h, keeping the temperature for 3h after dripping, heating to 65 ℃, adding 50 parts by weight of cationic chain extender 8566, keeping the temperature for reaction for 3h, adding 30 parts by weight of glacial acetic acid, stirring uniformly, adding water, cooling to below 40 ℃, discharging, and preparing the modified waterborne polyurethane with the solid content of (30 +/-2) wt%.
The preparation method of the glass fiber yarn impregnating compound comprises the following steps:
(1) weighing the materials according to a formula; adding one third of deionized water and glacial acetic acid in the formula amount into a container, stirring until the pH value is 2.5-5, dropwise adding silane coupling agent KH560 in the formula amount, and continuously stirring for at least 30min after dropwise adding, so as to obtain hydrolysate after the silane coupling agent KH560 is completely hydrolyzed;
(2) uniformly stirring the modified waterborne epoxy resin, the epoxy modified polyester and the modified waterborne polyurethane with the formula ratio and water, wherein the amount of the water is 5 times of the weight of the mixed resin, and adding water for diluting to obtain a resin mixed solution;
(3) and adding the resin mixed solution into the hydrolysate, complementing the residual water amount, and continuously stirring for 15min to obtain the glass fiber yarn impregnating compound.
The pH value of the glass fiber yarn impregnating compound product obtained in the embodiment is within the range of 3.5-5.5; the product of the embodiment is kept stand for 48 hours, has no phenomena of layering, oil splash, precipitation, flocculation and the like, and has better uniformity and stability; the product of this example had a solids content of 5.0 wt.% to 6.5 wt.% and an appearance of a pale yellow translucent liquid.
Example 2
A glass fiber yarn impregnating compound comprises the following materials in percentage by weight: glacial acetic acid 0.065%, silane coupling agent KH 5600.55%, modified waterborne epoxy resin 4.3%, epoxy modified polyester 0.88%, modified waterborne polyurethane 7.2% and the balance of water.
The preparation method of the modified waterborne epoxy resin comprises the following steps: dissolving 35 parts by weight of diethanolamine in 35 parts by weight of ethanol to obtain a mixed solution; adding 100 parts by weight of epoxy resin E51 into a reaction kettle, heating to 75 ℃, introducing cooling water, dropwise adding the mixed solution within 80min, carefully controlling the speed and the reaction temperature of the dropwise added mixed solution to prevent flushing, keeping the temperature at 75 ℃ for continuously reacting for 180min after dropwise adding, cooling to 50 ℃ after the reaction is finished, adding 60 parts by weight of glacial acetic acid, uniformly stirring, adding water, cooling to below 40 ℃, discharging, and preparing the modified waterborne epoxy resin with the solid content of (75 +/-2) wt%.
The preparation method of the epoxy modified polyester comprises the following steps: putting 90 parts by weight of polyester 400, 65 parts by weight of epoxy resin E51 and 2 parts by weight of benzyldimethylamine into a reaction kettle, heating to 120 ℃ for reaction for 4 hours, then cooling to 85 ℃, dripping 32 parts by weight of diethanolamine within 40min, keeping the temperature at 85 ℃ after dripping is finished, continuing the reaction for 4 hours, cooling to 50 ℃ after the reaction is finished, adding 40 parts by weight of glacial acetic acid, adding water after stirring uniformly, cooling to below 40 ℃, discharging, and preparing the epoxy modified polyester with the solid content of (30 +/-2) wt%.
The preparation method of the modified waterborne polyurethane comprises the following steps: putting 115 parts by weight of polyester 400 into a reaction kettle, heating to 80 ℃, performing reduced pressure dehydration for 30min, cooling to 40-50 ℃, dripping 30 parts by weight of Hexamethylene Diisocyanate (HDI) within 2h, keeping the temperature for 3h after dripping, heating to 60 ℃, adding 55 parts by weight of cationic chain extender 8566, keeping the temperature for reaction for 2h, adding 32 parts by weight of glacial acetic acid, stirring uniformly, adding water, cooling to below 40 ℃, discharging, and preparing the modified waterborne polyurethane with the solid content of (30 +/-2) wt%.
The above glass yarn sizing agent was prepared in the same manner as in example 1.
The pH value of the glass fiber yarn impregnating compound product obtained in the embodiment is within the range of 3.5-5.5; the product of the embodiment is kept stand for 48 hours, has no phenomena of layering, oil stain, precipitation, flocculation and the like, and has better uniformity and stability; the product of this example had a solids content of 5.0 wt.% to 6.5 wt.% and an appearance of a pale yellow translucent liquid.
Example 3
A glass fiber yarn impregnating compound comprises the following materials in percentage by weight: glacial acetic acid 0.1%, silane coupling agent KH 5600.7%, modified waterborne epoxy resin 4.8%, epoxy modified polyester 0.96%, modified waterborne polyurethane 7.65% and the balance of water.
The preparation method of the modified waterborne epoxy resin comprises the following steps: dissolving 30 parts by weight of diethanolamine in 40 parts by weight of ethanol to obtain a mixed solution; adding 120 parts by weight of epoxy resin E51 into a reaction kettle, heating to 75 ℃, introducing cooling water, dropwise adding the mixed solution within 100min, carefully controlling the speed and the reaction temperature of the dropwise adding mixed solution to prevent flushing, keeping the temperature at 75 ℃ for continuous reaction for 120min after the dropwise adding is finished, cooling to 50 ℃ after the reaction is finished, adding 65 parts by weight of glacial acetic acid, uniformly stirring, adding water, cooling to below 40 ℃, discharging, and preparing the modified waterborne epoxy resin with the solid content of (75 +/-2) wt%.
The preparation method of the epoxy modified polyester comprises the following steps: adding 80 parts by weight of polyester 400, 55 parts by weight of epoxy resin E51 and 0.8 part by weight of benzyldimethylamine into a reaction kettle, heating to 115 ℃ for reaction for 3 hours, then cooling to 90 ℃, dripping 25 parts by weight of diethanolamine within 30min, keeping the temperature at 90 ℃ for continuous reaction for 3 hours after dripping is finished, cooling to 50 ℃ after the reaction is finished, adding 45 parts by weight of glacial acetic acid, stirring uniformly, adding water, cooling to below 40 ℃, discharging, and preparing the epoxy modified polyester with the solid content of (30 +/-2) wt%.
The preparation method of the modified waterborne polyurethane comprises the following steps: adding 120 parts by weight of polyester 400 into a reaction kettle, heating to 80 ℃, performing reduced pressure dehydration for 30min, cooling to 40-50 ℃, dripping 35 parts by weight of Hexamethylene Diisocyanate (HDI) within 2h, keeping the temperature for 4h after dripping, heating to 65 ℃, adding 60 parts by weight of cationic chain extender 8566, keeping the temperature for reaction for 3h, adding 32 parts by weight of glacial acetic acid, stirring uniformly, adding water, cooling to below 40 ℃, discharging, and preparing the modified waterborne polyurethane with the solid content of (30 +/-2) wt%.
The above glass yarn sizing agent was prepared in the same manner as in example 1.
The pH value of the glass fiber yarn impregnating compound product obtained in the embodiment is within the range of 3.5-5.5; the product of the embodiment is kept stand for 48 hours, has no phenomena of layering, oil stain, precipitation, flocculation and the like, and has better uniformity and stability; the product of this example had a solids content of 5.0 wt.% to 6.5 wt.% and an appearance of a pale yellow translucent liquid.
Application example 1
The performance of the application of the sizing agents of the embodiments 1 to 3 of the invention in the production of glass fiber yarns is compared with the performance of the application of the conventional paraffin type sizing agent in the glass fiber yarns. The glass fiber yarns prepared from the two impregnating compounds are woven into mesh cloth (specification is 14 meshes 85 g, warp yarns EC 9-44X 1S35 and weft yarns EC9-66), and the performance data are shown in Table 1.
TABLE 1 glass fibre yarn made of different impregnating compounds and its weaving method
Figure BDA0002872677100000081
(Note: Paraffin type means a glass fiber produced by a paraffin type impregnating compound, and the glass fiber is a product produced by glass fiber Co., Ltd. in Shandong.)
It can be seen from table 1 that the strength in the warp and weft directions after dipping (referred to as the sizing agent of the present invention) is significantly better than that of the paraffin type sizing agent in the case of equivalent glue content by using the sizing agent of the present invention in the production of glass fiber yarns to produce glass fiber yarns and weaving into mesh cloth.
After the glass fiber yarn containing the sizing agent, the paraffin type sizing agent and the starch type sizing agent of the invention and an insulating base material (such as organic silicon resin) are compounded to prepare the insulating sleeve, the performance structure is shown in table 2.
TABLE 2 Properties of insulating sleeves made of glass fiber yarns containing different sizing agents
Figure BDA0002872677100000082
Figure BDA0002872677100000091
As can be seen from Table 2, the performance index of the insulating sleeve made of the glass fiber yarn containing the sizing agent is slightly lower than that of starch type data, but is equivalent to that of stone model 30863, and the insulating sleeve made of the glass fiber yarn containing the sizing agent can completely meet the standard value requirement. From the application detection data, the performance of the glass fiber produced by adopting the impregnating compound can completely meet the performance requirement required by the subsequent processing, and the aims of emission reduction and environmental protection are effectively fulfilled.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. The glass fiber yarn impregnating compound is characterized by comprising the following materials in percentage by weight:
0.03 to 0.1 percent of acetic acid,
0.3 to 0.7 percent of silane coupling agent,
3.5 to 5 percent of modified waterborne epoxy resin,
0.6 to 1 percent of epoxy modified polyester,
6 to 8 percent of modified waterborne polyurethane,
The balance being water.
2. The glass fiber yarn size as claimed in claim 1, wherein said acetic acid is glacial acetic acid; the coupling agent is KH 560.
3. The glass fiber yarn impregnating compound according to claim 1, wherein the preparation method of the modified water-based epoxy resin comprises the following steps: dissolving diethanolamine in ethanol to obtain a mixed solution; putting the epoxy resin into a reaction kettle, heating to 75-80 ℃, introducing cooling water, dropwise adding the mixed solution for 30-150 min, carefully controlling the speed and reaction temperature of the dropwise added mixed solution to prevent flushing during the dropwise adding process, keeping the temperature for continuous reaction for 120-240 min after the dropwise adding is finished, cooling to 50-60 ℃ after the reaction is finished, adding glacial acetic acid, uniformly stirring, adding water, cooling to below 40 ℃, and discharging to prepare the modified waterborne epoxy resin.
4. The glass fiber yarn size as claimed in claim 3, wherein the weight fraction of the raw materials used in the preparation of the modified water-based epoxy resin is as follows: epoxy resin E5190-130 parts, diethanolamine 30-40 parts, ethanol 30-40 parts, glacial acetic acid 45-65 parts and deionized water 30-40 parts; the solid content of the modified waterborne epoxy resin is (75 +/-2) wt%.
5. The glass fiber yarn sizing agent according to claim 1, wherein the preparation method of the epoxy modified polyester comprises the following steps: adding polyester 400, epoxy resin and benzyldimethylamine into a reaction kettle, heating to 115-125 ℃ for reaction for 3-5 h, then cooling to 80-90 ℃, dripping diethanolamine within 30-60 min, keeping the temperature at 80-90 ℃ for continuous reaction for 3-5 h after dripping is finished, cooling to 50-60 ℃ after reaction is finished, adding glacial acetic acid, adding water after stirring uniformly, cooling to below 40 ℃, and discharging to prepare the epoxy modified polyester.
6. The glass fiber yarn size as claimed in claim 5, wherein the weight fractions of the raw materials used in the epoxy-modified polyester are as follows: 100 portions of polyester 40080-; the solid content of the epoxy modified polyester is (30 +/-2) wt%.
7. The glass fiber yarn sizing agent according to claim 1, wherein the preparation method of the modified waterborne polyurethane comprises the following steps: adding polyester 400 into a reaction kettle, heating to 80 ℃, performing reduced pressure dehydration for 30min, cooling to 40-50 ℃, dripping Hexamethylene Diisocyanate (HDI) within 2.5h, keeping the temperature for 3-4 h after dripping, heating to 55-65 ℃, adding a chain extender, keeping the temperature for reaction for 2-3 h, adding glacial acetic acid, stirring uniformly, adding water, cooling to below 40 ℃, and discharging to obtain the modified waterborne polyurethane.
8. The glass fiber yarn size as claimed in claim 7, wherein the weight fraction of the raw materials used in the modified aqueous polyurethane is: 120 parts of polyester 40090-; the solid content of the modified waterborne polyurethane is (30 +/-2) wt%.
9. The method for preparing the glass fiber yarn impregnating compound according to any one of claims 1 to 8, characterized by comprising the following steps:
(1) weighing the materials according to the formula; adding part of water and acetic acid into a container, stirring to enable the pH value to be 2.5-5, dropwise adding a silane coupling agent, continuously stirring for at least 30min after dropwise adding is finished, and obtaining hydrolysate after the silane coupling agent is completely hydrolyzed;
(2) uniformly stirring the modified waterborne epoxy resin, the epoxy modified polyester, the modified waterborne polyurethane and part of water to obtain a resin mixed solution;
(3) and adding the resin mixed solution into the hydrolysate, and supplementing the rest water and continuing stirring for 10-15 min to obtain the glass fiber yarn impregnating compound.
10. The application of the glass fiber yarn impregnating compound according to any one of claims 1 to 8, wherein the impregnating compound is used for producing glass fiber yarns, and the prepared glass fiber yarns containing the impregnating compound are compounded with an insulating matrix material to obtain an insulating composite material.
CN202011604582.6A 2020-12-30 2020-12-30 Glass fiber yarn impregnating compound and preparation method and application thereof Pending CN114685063A (en)

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CN101831078A (en) * 2010-05-25 2010-09-15 中材科技股份有限公司 Preparation method of film forming agent and impregnating compound containing film forming agent
CN102432200A (en) * 2011-08-23 2012-05-02 重庆国际复合材料有限公司 Epoxy resin film-forming agent and preparation method thereof
CN105152550A (en) * 2015-08-10 2015-12-16 巨石集团有限公司 Impregnating agent for highly-universal alkali-free glass fiber direct roving
CN105585256A (en) * 2015-12-18 2016-05-18 中材科技股份有限公司 High-performance fiberglass winding yarn sizing agent and preparation method thereof
CN107500569A (en) * 2017-09-30 2017-12-22 山东玻纤集团股份有限公司 A kind of tape edge felt e-glass fiber roving size
CN108559055A (en) * 2018-04-04 2018-09-21 吉林乾仁新材料有限公司 The preparation method of cation aqueous polyurethane type sizing agent/size/film forming agent of self assembly self-emulsifying size tunable
CN110255928A (en) * 2019-06-28 2019-09-20 中材科技股份有限公司 A kind of film forming agent suitable for glass fibre, the preparation method and application comprising the size of the film forming agent and the size

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101831078A (en) * 2010-05-25 2010-09-15 中材科技股份有限公司 Preparation method of film forming agent and impregnating compound containing film forming agent
CN102432200A (en) * 2011-08-23 2012-05-02 重庆国际复合材料有限公司 Epoxy resin film-forming agent and preparation method thereof
CN105152550A (en) * 2015-08-10 2015-12-16 巨石集团有限公司 Impregnating agent for highly-universal alkali-free glass fiber direct roving
CN105585256A (en) * 2015-12-18 2016-05-18 中材科技股份有限公司 High-performance fiberglass winding yarn sizing agent and preparation method thereof
CN107500569A (en) * 2017-09-30 2017-12-22 山东玻纤集团股份有限公司 A kind of tape edge felt e-glass fiber roving size
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