Anti-migration electronic-grade glass fiber impregnating compound and preparation method thereof
By chemically linking the synthesized amine-acrylate Michael addition polymer with a silane coupling agent, the migration and yarn loss of glass fibers in polar solvents are reduced, the stability problem of the sizing agent under the action of polar solvents is solved, and high yield and performance improvement are achieved.
Patent Information
- Application Number
- CN202610359840.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-03-23
- Publication Date
- 2026-05-19
AI Technical Summary
Existing glass fiber impregnating agents are easily dissolved, migrated, and detached under the action of polar solvents, resulting in fuzz, broken fibers, and resin contamination of the glass fibers, which affects the overall performance.
The design synthesizes an amine-acrylate Michael addition polymer, grafts long-chain alkyl and silane coupling agents onto glass fibers, and forms a starch-based film-forming agent coating by cross-linking unreacted secondary amines with epoxidized soybean oil, thereby reducing migration.
This technology achieves low yarn shedding, low migration, and high yield of glass fiber, thus improving the stability and performance of glass fiber.
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Figure CN122060160A_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of glass fiber sizing agent technology, and specifically relates to a polymer, a glass fiber sizing agent, electronic-grade glass fiber, and their preparation methods and applications. Background Technology
[0002] Glass fiber is a high-performance inorganic non-metallic material with many varieties. Its advantages include excellent insulation, strong heat resistance, good corrosion resistance, and high mechanical strength. However, its disadvantages include brittleness and poor wear resistance. Glass fiber is commonly used as a reinforcing material in composite materials, as well as in electrical insulation, thermal insulation, and circuit boards, among other applications. The sizing agent, applied to the surface of the glass fiber during production, can be an aqueous emulsion or solution. By coating the glass fiber surface, it effectively combines organic and inorganic materials. The sizing agent functions as an adhesive, bundler, lubricant, antistatic agent, and mildew inhibitor. During glass fiber forming, it ensures smooth fiber drawing and improves subsequent processing of the glass fiber and matrix resin, thereby greatly enhancing interfacial compatibility and maximizing the material's physical and mechanical properties.
[0003] In the application of glass fiber in the preparation of copper clad laminates, it needs to be impregnated with epoxy resin and matching organic solvents. If the impregnating agent has poor stability, it will dissolve, migrate and fall off under the action of solvent, resulting in problems such as fuzz, broken fibers, resin contamination and overall performance degradation of glass fiber. Therefore, it is necessary to have an impregnating agent with anti-migration ability to solvents of different polarities to ensure that the glass fiber does not dissolve under the action of solvents of different polarities after impregnation. Summary of the Invention
[0004] To address the shortcomings of existing technologies, this application designs and synthesizes an amine-acrylate Michael addition polymer, and grafts long-chain alkyl and silane coupling agents onto it. The coupling agents chemically link the organic film-forming components with glass fibers. Then, the unreacted secondary amines in the polymer crosslink with epoxidized soybean oil at high temperature to form a film. This process encapsulates the starch-based film-forming agent, reducing its migration in different polar solvents, thereby achieving low yarn shedding, low migration, and high yield.
[0005] To achieve the above technical objectives, the technical solution adopted in this application is as follows: In a first aspect, a polymer is obtained by reacting a di(meth)acrylate containing at least one oxyethylene ether segment with a fatty amine to obtain a polymer containing a secondary amino group, and then adding a monoepoxide compound and an epoxy-containing silane coupling agent to the polymer to perform a ring-opening reaction. The general structural formula of the di(meth)acrylate of the at least one oxyethylene ether segment includes: or ; Where n and m are positive integers greater than or equal to 1, R1 is selected from hydrogen atoms or methyl groups, and R2 is selected from hydrocarbon groups with 4 to 20 carbon atoms.
[0006] The fatty amine is selected from trifunctional fatty amines, that is, each fatty amine molecule contains 3 active NH hydrogen atoms; Preferably, the fatty amine is selected from one or more combinations of 1-(2-aminoethyl)piperazine (AEPZ), 4-(aminomethyl)piperidine (AMPD), N-methylethylenediamine (MEDA), N-ethylethylenediamine (EEDA), N-hexylethylenediamine (HEDA), and N,N-dimethyldipropylenetriamine (DMDPTA).
[0007] More preferably, the fatty amine is selected from one or more combinations of 1-(2-aminoethyl)piperazine (AEPZ) and 4-(aminomethyl)piperidine (AMPD); The monoepoxide compounds are selected from epoxy hydrocarbon groups or hydrocarbon glycidyl ethers with 10 to 30 carbon atoms.
[0008] Preferably, the monoepoxide compound is selected from cashew phenol glycidyl ether.
[0009] The epoxy-containing silane coupling agent is selected from one or more combinations of glycidyl ether type silane coupling agents and epoxycyclohexyl type silane coupling agents; The glycidyl ether type silane coupling agent is selected from one or more combinations of 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropylmethyldimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane and 3-glycidyl etheroxypropylmethyldiethoxysilane.
[0010] The epoxycyclohexyl silane coupling agent is selected from one or more combinations of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane.
[0011] Furthermore, the method for preparing the polymer includes the following steps: S1. A polymer containing a secondary amine is obtained by adding a di(meth)acrylate containing at least one oxyethylene ether segment to a fatty amine at room temperature to 60°C. S2. At 60-100℃, a monoepoxide compound and an epoxy-containing silane coupling agent are added sequentially to carry out a ring-opening reaction with the polymer containing secondary amino groups prepared in step S1.
[0012] Preferably, in step S1, the molar ratio of di(meth)acrylate containing at least one oxyethylene ether segment to aliphatic amine is (0.8-1):1; More preferably, in step S1, the molar ratio of di(meth)acrylate containing at least one oxyethylene ether segment to fatty amine is 1:1; Preferably, the sum of the molar amounts of the monoepoxide compound and the epoxy-containing silane coupling agent does not exceed 60% of the molar amount of the aliphatic amine; Even more preferably, the sum of the molar amounts of the monoepoxide compound and the epoxy-containing silane coupling agent does not exceed 50% of the molar amount of the aliphatic amine.
[0013] Secondly, the use of the polymers described above in the preparation of glass fiber impregnating agents.
[0014] Thirdly, a glass fiber impregnating agent, the raw materials of which include: starch film-forming agent, the polymers mentioned above, epoxidized vegetable oil, antistatic agent, defoamer, mildew inhibitor and water; The starch film-forming agent includes one or more of the following: high amylose content of not less than 55 wt%, etherified starch, esterified starch, and etherified / esterified starch; Preferably, the high amylose content of not less than 55 wt% is selected from high amylose corn starch with an amylose content of 55-70 wt%. Preferably, the etherified starch is selected from one or more combinations of carboxymethyl starch, hydroxyethyl starch, and hydroxypropyl starch; Preferably, the esterified starch is selected from one or more combinations of acetylated starch and phosphate starch; Preferably, the etherified / esterified starch is selected from one or more combinations of hydroxyethyl distarch phosphate and hydroxypropyl distarch phosphate; The epoxidized vegetable oil is selected from one or more of the following: epoxidized soybean oil, epoxidized linseed oil, epoxidized palm oil, and epoxidized rapeseed oil; The antistatic agent is selected from one or more combinations of imidazoline type antistatic agents, amino acid type antistatic agents, sulfobetaine type antistatic agents and amamidopropyl betaine type antistatic agents; The defoamer is selected from one or more combinations of silicone defoamers, polyether defoamers, and fatty alcohol defoamers; The antifungal agent is selected from isothiazolinone antifungal agents.
[0015] Further, by weight, the glass fiber impregnating agent described above comprises: 30-60 parts by weight of starch film-forming agent, 5-15 parts by weight of the polymer described above, 1-5 parts by weight of epoxidized vegetable oil, 0.5-2 parts by weight of antistatic agent, 0.05-0.2 parts by weight of defoamer, 0.1-1 parts by weight of mildew inhibitor, and 180-220 parts by weight of water.
[0016] Fourthly, the preparation method of the glass fiber impregnating agent mentioned above includes: mixing the components in the formula and then mechanically dispersing them; Preferably, a high-speed disperser is used for mechanical dispersion at a speed of 1000-2000 rpm.
[0017] Fifthly, an electronic-grade glass fiber treated with the glass fiber sizing agent described above.
[0018] Sixthly, the use of the electronic-grade glass fiber described above in the manufacture of copper-clad laminates.
[0019] The beneficial effects of the above-proposed technical solution are as follows: The amine-acrylate Michael addition polymer is designed and synthesized, wherein the acrylate contains an EO segment, and subsequently grafted with long-chain alkyl / cainol epoxy and an epoxy-containing silane coupling agent, along with a starch-based film-forming agent as a wetting agent. The epoxy silane coupling agent acts as a bridge between the organic film-forming component and the glass fiber, chemically linking the two. Then, the unreacted secondary amine reacts with epoxidized soybean oil at high temperature to form a film. When used for glass fiber impregnation treatment, electronic-grade glass fiber with low yarn loss, low migration, and high yield can be obtained. Attached Figure Description
[0020] To more clearly illustrate the technical solutions in the embodiments of this application and to more completely understand this application and its beneficial effects, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0021] Figure 1 The image shows the attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectrum of the polymer prepared in Example 4. Detailed Implementation
[0022] 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. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present invention. It should be noted that the terminology used herein is only for describing specific implementations and is not intended to limit the exemplary implementations of the present invention.
[0023] Unless otherwise specified, the experimental conditions used in the examples are generally in accordance with conventional conditions in the art or the conditions recommended by the reagent company. Unless otherwise specified, the materials and reagents used in the examples can be purchased commercially.
[0024] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings: The terms "and / or," "or / and," and "and / or" as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical AND," and also undoubtedly includes technical solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: A, B, and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, a technical solution that is connected by "logical OR"), as well as any and all combinations of A, B, C, and D, that is, combinations of any two or three of A, B, C, and D, and also combinations of all four of A, B, C, and D (that is, a technical solution that is connected by "logical AND").
[0025] In this application, the terms "multiple", "various", "multiple times", "multi-dimensional", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.
[0026] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.
[0027] In this application, the technical features described in an open-ended manner include both closed technical solutions composed of the listed features and open technical solutions composed of the listed features.
[0028] Example 1
[0029] The polymer was prepared by Michael addition reaction using N-aminoethylpiperazine as the amine component and tetraethylene glycol diacrylate as the acrylate component. 51.8 g (0.4 mol) of N-aminoethylpiperazine and 128.2 g (0.4 mol) of tetraethylene glycol diacrylate were weighed and added to a reaction vessel. 0.3 g of p-hydroxyanisole was added as a polymerization inhibitor. The mixture was stirred at room temperature for 1 hour, then heated to 50 °C and reacted for another hour. Infrared spectra were measured at 1630 cm⁻¹. -1 The disappearance of the nearby absorption peak indicates that the double bond of tetraethylene glycol diacrylate was fully involved in the reaction.
[0030] Subsequently, 26.8 g (0.1 mol) of 1,2-epoxyoctadecane and 0.3 g of hexadecyltrimethylammonium bromide were added to the reaction vessel, the temperature was raised to 80 °C and the reaction was carried out for 2 hours. Infrared spectra were measured at 920 cm⁻¹. -1 The disappearance of the nearby absorption peak indicates that the epoxy group of 1,2-epoxyoctadecane reacted completely with the secondary amino group. Subsequently, 22.0 g (0.1 mol) of 3-glycidyl etheroxypropylmethyldiethoxysilane (KH-563) was added, and the reaction was continued at 80°C for 2 hours. The infrared spectrum was measured at 920 cm⁻¹. -1 The disappearance of the nearby absorption peak indicates that the epoxy groups of KH-563 have reacted completely.
[0031] Example 2
[0032] The polymer was prepared using N-aminoethylpiperazine as the amine component and tetraethylene glycol diacrylate as the acrylate component. The amounts of both and the steps for the Michael addition reaction were the same as in Example 1.
[0033] Subsequently, 36 g (0.1 mol) of cashew phenol glycidyl ether and 0.3 g of cetyltrimethylammonium bromide were added to the reaction vessel, and the mixture was heated to 80 °C and reacted for 2 hours. Infrared spectra were then measured at 920 cm⁻¹. -1 The disappearance of the nearby absorption peak indicates that the epoxy group of cashew phenol glycidyl ether reacted completely with the secondary amino group. Subsequently, 23.6 g (0.1 mol) of 3-glycidyl oxypropyltrimethoxysilane (KH-560) was added, and the reaction was continued at 80℃ for 2 hours. The infrared spectrum was measured at 920 cm⁻¹. -1 The disappearance of the nearby absorption peak indicates that the epoxy groups of KH-560 have reacted completely.
[0034] Example 3
[0035] The polymer was prepared by Michael addition reaction using N-aminoethylpiperazine as the amine component and bisphenol A diacrylate (10EO-BPADMA) as the acrylate component. 51.8 g (0.4 mol) of N-aminoethylpiperazine and 310.8 g (0.4 mol) of bisphenol A diacrylate were weighed and added to a reaction vessel, along with 0.4 g of p-hydroxyanisole as a polymerization inhibitor. The mixture was stirred at room temperature for 1 hour, followed by heating to 60 °C and reacting for another hour. Infrared spectra were measured at 1630 cm⁻¹. -1 The disappearance of the nearby absorption peaks indicates that the double bonds of 10EO-BPADMA were fully involved in the reaction.
[0036] Subsequently, 18.4 g (0.1 mol) of 1,2-epoxydodecane and 0.2 g of hexadecyltrimethylammonium bromide were added to the reaction vessel, the temperature was raised to 80 °C and the reaction was carried out for 2 hours. Infrared spectra were measured at 920 cm⁻¹. -1 The disappearance of the nearby absorption peak indicates that the epoxy group of 1,2-epoxydodecane reacted completely with the secondary amino group. Subsequently, 25.8 g (0.1 mol) of 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane was added, and the reaction was continued at 80 °C for 2 hours. The infrared spectrum was measured at 920 cm⁻¹. -1 The disappearance of the nearby absorption peak indicates that the epoxy group of 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane has reacted completely.
[0037] Example 4
[0038] The polymer was prepared using N-aminoethylpiperazine as the amine component and bisphenol A diacrylate ethoxylate (10EO-BPADMA) as the acrylate component. The amounts of both and the steps for the Michael addition reaction were the same as in Example 3.
[0039] Subsequently, 36 g (0.1 mol) of cashew phenol glycidyl ether and 0.3 g of cetyltrimethylammonium bromide were added to the reaction vessel, and the mixture was heated to 80 °C and reacted for 2 hours. Infrared spectra were then measured at 920 cm⁻¹. -1 The disappearance of the nearby absorption peak indicates that the epoxy group of cashew phenol glycidyl ether reacted completely with the secondary amino group. Subsequently, 28.8 g (0.1 mol) of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane was added, and the reaction was continued at 80°C for 2 hours. The infrared spectrum was measured at 920 cm⁻¹. -1 The disappearance of the nearby absorption peak indicates that the epoxy group of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane has reacted completely.
[0040] The ATR-FTIR spectra of the polymer are listed in Figure 1In the diagram, a represents the stretching vibration peaks of OH and NH of hydroxyl and secondary amino groups in the polymer, b represents the stretching vibration of CH in the benzene ring, c represents the stretching vibration of CH in the aliphatic side chain, d represents the stretching vibration of carbonyl C=O, and e represents the characteristic absorption peak of COC in the oxyethylene ether segment. This confirms that aliphatic chains, oxyethylene ether chains, benzene rings, and acryloyl groups have been introduced into the polymer.
[0041] Example 5
[0042] The wetting agent composition, by weight, comprises: 20 parts by weight of HI-70 high amylose corn starch, 15 parts by weight of hydroxypropyl distarch phosphate, 10 parts by weight of hydroxyethyl starch, 9 parts by weight of the polymer prepared in Example 1, 3 parts by weight of epoxidized soybean oil, 0.8 parts by weight of cocamidopropyl betaine, 0.1 parts by weight of defoamer AFE-3168, 0.5 parts by weight of antifungal agent octylisothiazolinone, and 200 parts by weight of water.
[0043] Example 6
[0044] The wetting agent composition, by weight, comprises: 15 parts by weight of hydroxypropyl distarch phosphate, 30 parts by weight of hydroxypropyl starch, 9 parts by weight of the polymer prepared in Example 1, 3 parts by weight of epoxidized soybean oil, 0.8 parts by weight of cocamidopropyl betaine, 0.1 parts by weight of defoamer AFE-3168, 0.5 parts by weight of antifungal agent octylisothiazolinone, and 200 parts by weight of water.
[0045] Example 7
[0046] The sizing agent composition, by weight, comprises: 20 parts by weight of HI-70 high amylose corn starch, 15 parts by weight of hydroxypropyl distarch phosphate, 10 parts by weight of hydroxyethyl starch, 9 parts by weight of the polymer prepared in Example 2, 3 parts by weight of epoxidized soybean oil, 0.8 parts by weight of cocamidopropyl betaine, 0.1 parts by weight of defoamer AFE-3168 (Dow Chemical), 0.5 parts by weight of antifungal agent octylisothiazolinone, and 200 parts by weight of water.
[0047] Example 8
[0048] The wetting agent composition, by weight, comprises: 15 parts by weight of hydroxypropyl distarch phosphate, 30 parts by weight of hydroxypropyl starch, 9 parts by weight of the polymer prepared in Example 2, 3 parts by weight of epoxidized soybean oil, 0.8 parts by weight of cocamidopropyl betaine, 0.1 parts by weight of defoamer AFE-3168 (Dow Chemical), 0.5 parts by weight of antifungal agent octylisothiazolinone, and 200 parts by weight of water.
[0049] Example 9
[0050] The sizing agent composition, by weight, comprises: 20 parts by weight of HI-70 high amylose corn starch, 15 parts by weight of hydroxypropyl distarch phosphate, 10 parts by weight of hydroxyethyl starch, 9 parts by weight of the polymer prepared in Example 3, 3 parts by weight of epoxidized soybean oil, 0.8 parts by weight of cocamidopropyl betaine, 0.1 parts by weight of defoamer AFE-3168 (Dow Chemical), 0.5 parts by weight of antifungal agent octylisothiazolinone, and 200 parts by weight of water.
[0051] Example 10
[0052] The wetting agent composition, by weight, comprises: 15 parts by weight of hydroxypropyl distarch phosphate, 30 parts by weight of hydroxypropyl starch, 9 parts by weight of the polymer prepared in Example 3, 3 parts by weight of epoxidized soybean oil, 0.8 parts by weight of cocamidopropyl betaine, 0.1 parts by weight of defoamer AFE-3168 (Dow Chemical), 0.5 parts by weight of antifungal agent octylisothiazolinone, and 200 parts by weight of water.
[0053] Example 11
[0054] The sizing agent composition, by weight, comprises: 20 parts by weight of HI-70 high amylose corn starch, 15 parts by weight of hydroxypropyl distarch phosphate, 10 parts by weight of hydroxyethyl starch, 9 parts by weight of the polymer prepared in Example 4, 3 parts by weight of epoxidized soybean oil, 0.8 parts by weight of cocamidopropyl betaine, 0.1 parts by weight of defoamer AFE-3168 (Dow Chemical), 0.5 parts by weight of antifungal agent octylisothiazolinone, and 200 parts by weight of water.
[0055] Example 12
[0056] The wetting agent composition, by weight, comprises: 15 parts by weight of hydroxypropyl distarch phosphate, 30 parts by weight of hydroxypropyl starch, 9 parts by weight of the polymer prepared in Example 4, 3 parts by weight of epoxidized soybean oil, 0.8 parts by weight of cocamidopropyl betaine, 0.1 parts by weight of defoamer AFE-3168 (Dow Chemical), 0.5 parts by weight of antifungal agent octylisothiazolinone, and 200 parts by weight of water.
[0057] Comparative Example 1 The wetting agent composition, by weight, comprises: 15 parts by weight of hydroxypropyl distarch phosphate, 30 parts by weight of hydroxypropyl starch, 2.4 parts by weight of N-aminoethylpiperazine, 4.5 parts by weight of tetraethylene glycol diacrylate, 1.2 parts by weight of cashew phenol glycidyl ether, 1.2 parts by weight of 3-glycidyl etheroxypropyltrimethoxysilane, 0.1 parts by weight of hexadecyltrimethylammonium bromide, 3 parts by weight of epoxidized soybean oil, 0.8 parts by weight of cocamidopropyl betaine, 0.1 parts by weight of defoamer AFE-3168 (Dow Chemical), 0.5 parts by weight of antifungal agent octylisothiazolinone, and 200 parts by weight of water.
[0058] The components in the formulation amounts of the above examples and comparative examples were added to the mixing tank and dispersed at 1200 rpm and room temperature for 1 hour using a high-speed disperser to obtain the wetting agent.
[0059] The sizing agent was applied to alkali-free glass fibers with a monofilament diameter of (9±0.3)μm, a single fiber number of 400, a twist of 28 twists / meter, and a linear density of 68.7 tex. The oiling speed was 20m / min, and the baking process was to bake at 120℃ for 40 seconds.
[0060] Test section Yarn shedding test: The amount of yarn shedding of glass fiber was tested using the frictional weight loss method. Glass fibers treated with sizing agent were passed at a speed of 50 m / min through a smooth friction bar (φ6 mm, R). a ≤0.8μm), collect all detached debris and weigh it, and calculate the amount of fiber loss per kilogram of glass fiber (mg / kg).
[0061] Yield: Visually select glass fibers without obvious defects and impurities as finished products, record their quantity, and calculate the yield of the glass fiber samples.
[0062] Migration amount: The migration amount of glass fiber samples was tested according to the method of GB / T 31604.8-2021, in which the extraction solvents were 75% ethanol solution and dichloromethane, and the migration amount per kilogram of glass fiber (mg / kg) was tested respectively.
[0063] The performance test results of the glass fibers treated with the sizing agent in Examples 5-12 and Comparative Example 1 are recorded in Table 1.
[0064]
[0065] The amine-acrylate Michael addition polymers prepared in Examples 1-4 above are further grafted with long-chain alkyl / cainol epoxy and epoxy silane coupling agents, and used as film-forming components of starch-based film-forming agents as sizing agents. The epoxy silane coupling agent acts as a bridge between the organic film-forming components and the glass fibers, chemically linking them. Then, the unreacted secondary amines in the polymer crosslink with epoxidized soybean oil at high temperature to form a film, thereby encapsulating the starch-based film-forming agent and reducing migration. Analysis of the data in Table 1 shows that the sizing agents of Examples 5-12 provide stable overall performance after impregnation of glass fibers, achieving a balance of low yarn shedding, high yield, and excellent migration resistance. Michael addition polymers use fatty amines and tetraethylene glycol diacrylate or 10EO-BPADMA containing oxyethylene ether (EO) segments as reactants. Subsequently, long-chain epoxy groups are used to perform a ring-opening reaction with amines that have not participated in the addition reaction. The formulation uses epoxidized soybean oil containing long alkyl side chains as a component participating in the reaction, thereby introducing long-chain alkyl groups and EO segments into the sizing agent and playing a lubricating role, reducing frictional damage during the continuous production of glass fibers and reducing the amount of fiber shedding.
[0066] Analysis of the data in Table 1 shows that the introduction of cashew phenol glycidyl ether can significantly reduce yarn loss and migration, and improve the wear resistance and anti-migration properties of glass fiber. The use of epoxy cyclohexyl silane coupling agents is more effective than conventional linear epoxy silane coupling agents for grafting polymers in reducing the migration of sizing agents under the action of different polar solvents (ethanol, dichloromethane). Using hydroxypropyl distarch phosphate and hydroxypropyl starch as starch film-forming agents can reduce yarn loss and improve the yield.
[0067] Comparative Example 1 did not prepare the amine-acrylate Michael addition polymer beforehand, but directly mixed the raw materials together as a sizing agent. As a result, the specific (amine-acrylate) block structure and epoxy-amine crosslinking structure could not be formed during the baking process. The amount of fiber shedding and migration after sizing was significantly higher, and the yield also decreased significantly.
[0068] Finally, it should be noted that the above-described embodiments are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be pointed out that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. Furthermore, it should be understood that after reading the above teachings of this application, those skilled in the art can make various alterations or modifications to this application, and the equivalent forms obtained also fall within the scope of protection of this application. It should also be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.
Claims
1. A polymer, characterized in that, A polymer containing a secondary amino group is obtained by adding a di(meth)acrylate containing at least one oxyethylene ether segment to a fatty amine, and then a monoepoxide compound and an epoxy-containing silane coupling agent are added to the polymer to carry out a ring-opening reaction. The general structural formula of the di(meth)acrylate of the at least one oxyethylene ether segment includes: or ; Where n and m are positive integers greater than or equal to 1, R1 is selected from hydrogen atoms or methyl groups, and R2 is selected from hydrocarbon groups with 4 to 20 carbon atoms; The fatty amine is selected from trifunctional fatty amines; The monoepoxide compounds are selected from epoxy hydrocarbon groups or hydrocarbon glycidyl ethers with 10 to 30 carbon atoms; The epoxy-containing silane coupling agent is selected from one or more combinations of glycidyl ether type silane coupling agents and epoxy cyclohexyl type silane coupling agents.
2. The polymer according to claim 1, characterized in that, The preparation method of the polymer includes the following steps: S1. A polymer containing a secondary amine is obtained by adding a di(meth)acrylate containing at least one oxyethylene ether segment to a fatty amine at room temperature to 60°C. S2. At 60-100℃, a monoepoxide compound and an epoxy-containing silane coupling agent are added sequentially to carry out a ring-opening reaction with the polymer containing secondary amino groups prepared in step S1.
3. The polymer according to claim 2, characterized in that, In step S1, the molar ratio of di(meth)acrylate containing at least one oxyethylene ether segment to a fatty amine is (0.8-1):
1. And / or, the sum of the molar amounts of the monoepoxide compound and the epoxy-containing silane coupling agent shall not exceed 60% of the molar amount of the aliphatic amine.
4. Use of the polymer according to any one of claims 1-3 in the preparation of glass fiber impregnating agents.
5. A glass fiber impregnating agent, characterized in that, The raw materials for the glass fiber impregnating agent include: starch film-forming agent, polymer as described in any one of claims 1-3, epoxidized vegetable oil, antistatic agent, defoamer, mildew inhibitor, and water; The starch film-forming agent includes one or more of the following: high amylose content of not less than 55 wt%, etherified starch, esterified starch, and etherified / esterified starch; The epoxidized vegetable oil is selected from one or more of the following: epoxidized soybean oil, epoxidized linseed oil, epoxidized palm oil, and epoxidized rapeseed oil; The antistatic agent is selected from one or more combinations of imidazoline type antistatic agents, amino acid type antistatic agents, sulfobetaine type antistatic agents and amamidopropyl betaine type antistatic agents; The defoamer is selected from one or more combinations of silicone defoamers, polyether defoamers, and fatty alcohol defoamers; The antifungal agent is selected from isothiazolinone antifungal agents.
6. The glass fiber impregnating agent according to claim 5, characterized in that, The high amylose content of not less than 55 wt% is selected from high amylose corn starch with an amylose content of 55-70 wt%. And / or, the etherified starch is selected from one or more combinations of carboxymethyl starch, hydroxyethyl starch and hydroxypropyl starch; And / or, the esterified starch is selected from one or more combinations of acetylated starch and phosphate starch; And / or, the etherified / esterified starch is selected from one or more combinations of hydroxyethyl distarch phosphate and hydroxypropyl distarch phosphate.
7. The glass fiber impregnating agent according to claim 5, characterized in that, The glass fiber impregnating agent comprises: 30-60 parts by weight of starch film-forming agent, 5-15 parts by weight of polymer, 1-5 parts by weight of epoxidized vegetable oil, 0.5-2 parts by weight of antistatic agent, 0.05-0.2 parts by weight of defoamer, 0.1-1 parts by weight of mildew inhibitor, and 180-220 parts by weight of water.
8. A method for preparing the glass fiber impregnating agent as described in any one of claims 5-7, comprising: The mixture of the components in the formula is then mechanically dispersed.
9. An electronic-grade glass fiber treated with the glass fiber sizing agent as described in any one of claims 5-7.
10. Use of the electronic-grade glass fiber as described in claim 9 in the manufacture of copper-clad laminates.