Organic silicon modified polyacrylic acid fiber reinforcing agent for glass fiber yarn weaving and preparation method of organic silicon modified polyacrylic acid fiber reinforcing agent

Abstract

The invention provides an organic silicon modified polyacrylic acid fiber reinforcing agent for glass fiber yarn weaving as well as a preparation method and application thereof. The organic silicon modified polyacrylic acid fiber reinforcing agent comprises organic silicon modified acrylic resin, a functional auxiliary agent and the like. The glass fiber yarn sizing agent provided by the invention forms a protective film for glass fiber yarns, the phenomena of broken yarns, hairiness and the like in the weaving process of the glass fiber yarns are reduced, after the sizing agent is used for improving, a yarn path can be kept clear and smooth after warp yarns run for a long time, and the strength of the glass fiber yarns is effectively improved. When the woven glass fiber cloth is used as the epoxy glass fiber composite material, desizing is not needed, the problems of energy consumption, three wastes and the like needed in the desizing procedure are effectively solved, and meanwhile the problem that the strength of glass fibers is reduced in the desizing procedure is solved.

Description

Technical Field

[0001] The invention relates to the field of electronic-grade glass fiber yarn weaving, and in particular to an organosilicon-modified polyacrylic acid fiber reinforcing agent for glass fiber yarn weaving and a preparation method thereof. Background Art

[0002] When glass fiber yarn is weaving, the warp yarn swings left and right during the unwinding process of the loom shaft. Due to static electricity generated by friction and a slight stickiness of the warp yarn after sizing, it is easy to cross with the adjacent yarns and become inseparable. After the yarn crosses, it is very easy to be entangled and inseparable before entering the dropper during weaving, resulting in frequent twisting and breaking of the warp yarn, which seriously affects the operation efficiency of the loom. In order to solve the problems of hairiness and broken yarns of glass fiber yarn, sizing agents or fiber reinforcement agents, impregnation agents, etc. can be used to slow down the occurrence of such problems. There are many research works to solve the weaving problems of glass fiber composite materials. For example, patent CN109371682A provides a sizing agent prepared by mixing polyvinyl alcohol PVA-205 and polyvinyl alcohol P-401 to solve the weaving efficiency and warp breaking problems of electronic grade glass fiber yarn. However, PVA has the problem of being difficult to degrade. The patent uses starch and PVA as glass fiber sizing agents. TWI796354B uses acrylic resin components, rubber components, and liquid rosin ester resin to prepare glass fiber sizing agents. Patent CN115625944A uses glass fiber to prepare FRP materials for wind turbine blades. The sizing agents used are epoxy resin, carbon nanotubes, graphene oxide, curing agent, and accelerators, etc., and are burned in air at 350-380°C for 0.6-0.8h to remove the surface adhesive coating. Because the sizing agent will affect the performance of glass fiber composite materials. Patent CN111518294A uses a treatment agent containing a silane coupling agent and a maleic anhydride grafted polymer to treat the glass fiber surface, which can improve the adhesion of the glass fiber for resin reinforcement to the thermoplastic resin. By using the glass fiber for resin reinforcement that has been surface treated with the treatment agent, a reinforced thermoplastic resin composition with excellent mechanical properties and reduced mold pollution can be obtained.

[0003] In short, the sizing agents for glass fiber mainly include starch, PVA and acrylic esters. With the increasing application of glass fiber in reinforced composite materials, glass fiber cloth must be desized before preparing composite materials. The main method to remove glass fiber sizing agents is high-temperature calcination. High-temperature calcination not only wastes energy, but also pollutes the environment. High-end calcination will also damage the strength of glass fiber. Therefore, it is urgent to solve the problem of glass fiber sizing agents that do not require desizing.

[0004] The present invention mainly provides a functional fiber reinforcing agent for glass fiber, overcomes the shortcomings of the prior art, and provides a slurry for weaving glass fiber yarn which is environmentally friendly, has less warp breakage, improves weaving efficiency, reduces friction, is anti-static, and does not require desizing, and a preparation method thereof. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a silicone-modified polyacrylic fiber reinforcement for glass fiber yarn weaving and a preparation method thereof, which can provide a slurry that is environmentally friendly and improves the weaving efficiency of glass fiber yarn.

[0006] To achieve the above objectives, the technical solution of the present invention is implemented through the following technical solutions:

[0007] The present invention provides an organosilicon-modified acrylic slurry for weaving glass fiber spun yarn, comprising an organosilicon-modified acrylic resin and a functional additive, wherein the specific preparation method is as follows:

[0008] S1: Accurately weigh the propylene monomer, cosolvent, initiator and the like into the reactor, then gradually heat up to 70-95°C for polymerization, with a reaction time of 0.5-4h;

[0009] S2: adding the remaining initiator, cosolvent and organosilicon, the polymerization time is 0.5 to 2 hours;

[0010] S3: After the polymerization reaction is completed, a neutralizing agent is added to salt the polymer to increase its solubility in water, and then deionized water is added to fully disperse the polymer to form a water-based silicone-modified acrylic resin;

[0011] S4: Finally, the functional additive is added to obtain the organosilicon-modified polyacrylic fiber reinforcement.

[0012] Preferably, the mass ratio of the organosilicon-modified acrylic resin to the functional additive is (10-20): (0.01-0.5).

[0013] Preferably, the organosilicon-modified acrylic resin is prepared by free radical polymerization of the acrylic monomer and the organosilicon. Preferably, the molecular weight of the organosilicon-modified acrylic resin is 50,000 to 600,000; more preferably, the molecular weight is 100,000 to 400,000.

[0014] Preferably, the acrylic monomer comprises at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, lauryl acrylate, isononyl acrylate, octadecyl acrylate, octadecyl methacrylate, etc.

[0015] Preferably, the acrylic monomer comprises at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, lauryl acrylate, isononyl acrylate, octadecyl acrylate, octadecyl methacrylate and the like.

[0016] Preferably, the silicone is a reactive silicone containing silane segments and olefinic bonds, including at least one of single-ended (meth)acryloxy silicone, (meth)acrylate silicone oil ester, etc.; preferably, the molecular weight of the monomethacryloxy silicone is 1000 to 10000; the molecular weight of the (meth)acrylate silicone oil ester is at least one of 400 to 5000, etc.

[0017] Preferably, the co-solvent is isopropanol or ethanol;

[0018] Preferably, the initiator is azobisisobutyronitrile or benzoyl peroxide;

[0019] Preferably, the functional additive comprises at least one of a lubricant, a wetting agent, an antistatic agent, and the like.

[0020] Preferably, the neutralizing agent is at least one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, ammonia water, triethylamine, N,N-dimethylethanolamine, diethanolamine, AMP-5, etc.

[0021] The invention also provides an organosilicon-modified polyacrylic acid fiber reinforcing agent prepared by a method for preparing the organosilicon-modified polyacrylic acid fiber reinforcing agent for glass fiber spun yarn weaving.

[0022] The present invention also provides a method for preparing an organosilicon-modified polyacrylic acid fiber reinforcing agent for glass fiber spun yarn weaving or use of the organosilicon-modified polyacrylic acid fiber reinforcing agent in preparing a product of glass fiber spun yarn for weaving.

[0023] The beneficial effects of the present invention are:

[0024] (1) The prepared organosilicon-modified acrylic slurry contains polar groups such as -COOH and -COO- which have good adhesion to glass fiber filaments and have good bundling properties for glass fiber yarns, thereby improving the weaving efficiency of glass fiber yarns;

[0025] (2) The prepared silicone-modified acrylic slurry contains a large amount of silane segments and long carbon alkyl segments, which can effectively reduce the fluff and yarn breakage caused by the friction of glass fibers during the manufacturing process, and promote the strength improvement of glass fiber cloth.

[0026] (3) The prepared silicone-modified acrylic slurry has good compatibility with glass fiber cloth composite epoxy materials, eliminating the need for a desizing process, and reducing energy consumption and the decrease in glass fiber cloth strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the infrared spectrum of Example 1 of the present invention.

[0028] Figure 2 It is the infrared spectrum of comparative example 1 of the present invention. DETAILED DESCRIPTION

[0029] S1: Accurately weigh 15g of ethyl acrylate, 15g of butyl acrylate, 9g of acrylic acid, 10g of methyl methacrylate, 6g of lauryl methacrylate and 0.6g of azobisisobutyronitrile, and 10g of isopropanol, stir evenly, gradually heat to 78°C, and react for 3h;

[0030] S2: Add 5 g of silicone methacrylate (molecular weight 450), 5 g of isopropanol and 0.2 g of azobisisobutyronitrile and continue the polymerization for 3 h;

[0031] S3: adding sodium bicarbonate and 180 g of deionized water to react the carboxyl groups in the system to form salts;

[0032] S4: gradually cool down to 40°C, add 0.5g of BASF WE 3650 wetting agent and 0.5g of antistatic agent P. Add deionized water to 20%; stir evenly to obtain the organosilicon-modified polyacrylic fiber reinforcing agent.

[0033] Embodiment 2:

[0034] In Example 1, 9 g of acrylic acid was replaced by 10 g of methacrylic acid; the rest was the same.

[0035] Embodiment 3:

[0036] In Example 1, 6 g of lauryl methacrylate was replaced with 6 g of octadecyl methacrylate; the rest was the same.

[0037] Embodiment 4:

[0038] In Example 1, 10 g of methyl methacrylate was replaced by 15 g of butyl methacrylate, and S2, the reaction temperature was adjusted to 90° C., the reaction time was 1 h, and the rest were the same.

[0039] Embodiment 5:

[0040] In Example 1, 15 g of ethyl acrylate was replaced by 13 g of methyl acrylate and 2 g of hydroxypropyl acrylate, and the rest was the same.

[0041] Embodiment 6:

[0042] In Example 1, 15 g of butyl acrylate was replaced by 15 g of isononyl acrylate, and the subsequent methacrylate silicone oil was replaced by methacrylate silicone oil with a molecular weight of 3000, and the rest was the same.

[0043] Embodiment 7:

[0044] The organic silicon 5g (meth)acrylate silicone oil (molecular weight 450) in Example 1 was replaced with 5g single-end (meth)acryloxy organic silicon (molecular weight 2000), and the rest was the same.

[0045] Embodiment 8:

[0046] In Example 1, reaction step S1: the reaction temperature is adjusted to 85° C., the reaction time is 2 h, and the rest are the same.

[0047] Comparative Example 1: The organosilicon-modified polyacrylic fiber reinforcement agent without adding methacrylate silicone oil ester is the same as in Example 1.

[0048] Blank sample: glass fiber without sizing treatment.

[0049] Detection:

[0050] (1) Sizing of glass fiber

[0051] The glass fiber yarn is sized by a single yarn sizing machine, the solid content of the organosilicon-modified polyacrylic acid glass fiber reinforcing agent is controlled to be 6%, the drying temperature is 100-130° C., and the vehicle speed is 30 m / min.

[0052] (2) Sizing abrasion resistance test

[0053] Test method: According to the operation steps of the Y731 cohesion tester, fix the sizing yarn on the sizing yarn wear tester, apply a certain tension, record the friction times when the sizing yarn is worn off, and calculate the average of the wear times of 20 sizing yarns as the wear resistance performance index of the sizing yarn. Place the prepared silk thread in a constant temperature and humidity environment of 50℃ and 80% relative humidity for 24 hours, then test the cohesion, and the obtained value is the high temperature and high humidity wear resistance.

[0054] (3) Sizing yarn breaking strength test

[0055] Test method: According to the operation method of the yarn strength and elongation tester, each sizing yarn sample and the original yarn are placed in a constant temperature and humidity chamber for 24 hours, and the samples are taken out for strength measurement. Each group of samples is measured 20 times, and the average breaking strength of each group of formula sizing yarn is calculated.

[0056] The test results of the organosilicon-modified polyacrylic acid glass fiber reinforcements prepared in Examples 1 to 8 are shown in Table 1 below.

[0057] Table 1. Test results of organosilicon-modified polyacrylic acid glass fiber reinforcement prepared in Examples 1 to 8

[0058]

[0059]

[0060] The specific combination of acrylic monomers and silicones in silicone-modified acrylic slurry is determined by synergistic selection, and the effect of other combinations is slightly reduced. The silicone-modified polyacrylic glass fiber reinforcement can significantly improve the cohesion and strength of glass fibers and reduce the breakage and hairiness of glass fiber yarns during the manufacturing process.

[0061] Can be obtained from Figure 1 and Figure 2 By comparison, 1723cm -1 It is the characteristic peak of the ester bond in the polyacrylate segment, 1025cm -1 With 1160cm -1 The characteristic peaks of COC and Si-O overlap at 847 cm -1 This indicates that the product has a methylsilane structure, thus indicating that the synthesis of the silicone-modified polyacrylic acid slurry is successful.

[0062] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a silicone-modified polyacrylic fiber reinforcing agent for glass fiber yarn weaving, characterized in that: It comprises silicone-modified acrylic resin and functional additives, wherein the specific preparation method is as follows: S1: Accurately weigh the propylene monomer, cosolvent, initiator and the like into the reactor, then gradually heat up to 70-95°C for polymerization, with a reaction time of 0.5-4h; S2: adding the remaining initiator, cosolvent and organosilicon, the polymerization time is 0.5 to 2 hours; S3: After the polymerization reaction is completed, a neutralizing agent is added to salt the polymer to increase its solubility in water, and then deionized water is added to fully disperse the polymer to form a water-based silicone-modified acrylic resin; S4: Finally, the functional additive is added to obtain the organosilicon-modified polyacrylic fiber reinforcement.

2. The method for preparing a silicone-modified polyacrylic fiber reinforcing agent for glass fiber spun yarn weaving according to claim 1, characterized in that: The mass ratio of the organosilicon-modified acrylic resin to the functional additive is (10-20): (0.01-0.5).

3. The method for preparing a silicone-modified polyacrylic fiber reinforcing agent for glass fiber spun yarn weaving according to claim 1, characterized in that: The organosilicon-modified acrylic resin is prepared by free radical polymerization of the acrylic monomer and the organosilicon. Preferably, the molecular weight of the organosilicon-modified acrylic resin is 50,000 to 600,000; more preferably, the molecular weight is 100,000 to 400,000.

4. The method for preparing a silicone-modified polyacrylic fiber reinforcing agent for glass fiber spun yarn weaving according to claim 1, characterized in that: The acrylic monomers include at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, lauryl acrylate, isononyl acrylate, octadecyl acrylate, octadecyl methacrylate, etc.

5. The method for preparing a silicone-modified polyacrylic fiber reinforcing agent for glass fiber spun yarn weaving according to claim 1, characterized in that: The acrylic monomers include at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, lauryl acrylate, isononyl acrylate, octadecyl acrylate, octadecyl methacrylate and the like.

6. The method for preparing a silicone-modified polyacrylic fiber reinforcing agent for glass fiber spun yarn weaving according to claim 1, characterized in that: The organosilicon is a reactive organosilicon containing silane segments and olefinic bonds, and includes at least one of single-ended (meth)acryloxy organosilicon, (meth)acrylate silicone oil ester, etc. Preferably, the molecular weight of the monomethacryloxy organosilicon is 1000 to 10000; the molecular weight of the (meth)acrylate silicone oil ester is at least one of 400 to 5000, etc.

7. The method for preparing a silicone-modified polyacrylic fiber reinforcing agent for glass fiber spun yarn weaving according to claim 1, characterized in that: The functional additives include at least one of lubricants, wetting agents, antistatic agents, etc.

8. The method for preparing a silicone-modified polyacrylic fiber reinforcing agent for glass fiber spun yarn weaving according to claim 1, characterized in that: The neutralizing agent is at least one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, ammonia water, triethylamine, N,N-dimethylethanolamine, diethanolamine, AMP-5 and the like.

9. The organosilicon-modified polyacrylic acid fiber reinforcement prepared according to the method for preparing the organosilicon-modified polyacrylic acid fiber reinforcement for glass fiber spun yarn weaving according to any one of claims 1 to 8.

10. A method for preparing an organosilicon-modified polyacrylic fiber reinforcement for glass fiber yarn weaving according to any one of claims 1 to 8, or use of the organosilicon-modified polyacrylic fiber reinforcement according to claim 9 in preparing a product of glass fiber yarn for weaving.

Images