Antibacterial polyvinyl acetate resin for basalt fiber pultrusion and preparation method and application thereof

Abstract

The invention provides antibacterial polyvinyl acetate resin for basalt fiber pultrusion as well as a preparation method and application of the antibacterial polyvinyl acetate resin, and relates to the technical field of composite materials. The antibacterial polyvinyl acetate resin is mainly prepared from the following raw materials: vinyl acetate, methanol, an emulsifier, an initiator, a pH value regulator, basalt fibers, an antibacterial agent, a low-surface-energy compound and the like. The antibacterial polyvinyl acetate resin is thermoplastic resin, can be repeatedly processed and is high in recoverability; moreover, the basalt fiber is added, so that the strength of the polyvinyl acetate resin is greatly improved; and by adding the antibacterial agent and the low-surface-energy compound, the polyvinyl acetate resin has excellent water and oil adhesion resistance and good bacterial adhesion resistance. Through cooperation of the raw materials, the prepared antibacterial polyvinyl acetate resin with different polymerization degrees has good strength and antibacterial property, also has recoverability, and meets various performance requirements.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials and relates to an antibacterial polyvinyl acetate resin for basalt fiber pultrusion molding and a preparation method and application thereof. Background Art

[0002] Most fiber pultrusion profiles use thermosetting resins, such as epoxy resins, vinyl resin phenolic resins, unsaturated polyester resins, etc. Using thermosetting resins as the matrix material, the product cannot change its shape once it is finalized, and it is also difficult to recycle, and has poor environmental friendliness. Compared with thermosetting resins, the advantages of thermoplastic resins are their reproducibility, excellent processing performance, cost-effectiveness, recyclability, etc. These advantages have made thermoplastic resins widely used in many fields such as packaging, automobiles, electronics, construction and medical treatment, but there are few reports on their application in fiber pultrusion.

[0003] In view of this, the present invention is proposed. Summary of the invention

[0004] The object of the present invention is to provide an antibacterial polyvinyl acetate resin and a preparation method and application thereof, so as to improve the above-mentioned problems existing in the prior art.

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] The first object of the present invention is to provide an antibacterial polyvinyl acetate resin for basalt fiber pultrusion molding, comprising the following raw materials in parts by weight:

[0007] 450-1700 parts of vinyl acetate, 100 parts of methanol, 25-80 parts of emulsifier, 0.009-0.350 parts of initiator, 0.01-0.05 parts of pH adjuster, 50-300 parts of basalt fiber, 0.1-3 parts of antibacterial agent and 0.1-1 parts of low surface energy compound.

[0008] Further, based on the above technical solution of the present invention, the emulsifier includes nonylphenol polyoxyethylene ether and / or polyvinyl alcohol;

[0009] And / or, the initiator comprises ammonium persulfate and / or azobisisobutyronitrile;

[0010] And / or, the pH adjuster includes acetic acid and / or citric acid.

[0011] Further, based on the above technical solution of the present invention, the antibacterial agent includes at least one of castor oil, hibiscus alcohol or chitosan;

[0012] and / or, the low surface energy compound comprises at least one of monohydroxy silicone oil, fluorosilicone oil, amino-modified silicone oil, dimethyl silicone oil or methylphenyl silicone oil;

[0013] And / or, the basalt fiber has a diameter of 5-15 μm and a length of 1-10 mm.

[0014] Furthermore, based on the above technical solution of the present invention, the degree of polymerization of the antibacterial polyvinyl acetate resin is 800-5000.

[0015] The second object of the present invention is to provide a method for preparing an antibacterial polyvinyl acetate resin for basalt fiber pultrusion, comprising the following steps:

[0016] S1. Vinyl acetate and methanol are stirred and mixed under a protective atmosphere, heated to a certain temperature, and then an emulsifier, an initiator solution and a pH adjuster are added to carry out a first polymerization reaction to obtain a polymerization reaction mixture;

[0017] S2. Add basalt fiber, antibacterial agent and low surface energy compound to the primary polymerization reaction mixture to carry out a second polymerization reaction to obtain antibacterial polyvinyl acetate resin.

[0018] Further, on the basis of the above technical solution of the present invention, in step S1, heating to 55-65° C.;

[0019] And / or, in step S1, the first polymerization reaction time is 2-3 hours and the temperature is 60-65°C.

[0020] Further, on the basis of the above technical solution of the present invention, in step S1, the initiator solution is a methanol solution containing an initiator;

[0021] And / or, in step S1, the pH adjuster is added in an amount such that the pH value of the polymerization reaction solution is 3-6.

[0022] Furthermore, based on the above technical solution of the present invention, in step S2, the time of the second polymerization reaction is 1-2h and the temperature is 60-65°C.

[0023] The third object of the present invention is to provide a basalt fiber pultruded profile, which is made of the antibacterial polyvinyl acetate resin provided by the first object of the present invention or the antibacterial polyvinyl acetate resin prepared by the preparation method provided by the second object of the present invention.

[0024] The fourth object of the present invention is to provide the use of the above-mentioned antibacterial polyvinyl acetate resin, the antibacterial polyvinyl acetate resin prepared by the above-mentioned preparation method or the above-mentioned basalt fiber pultruded profile in the field of self-cleaning.

[0025] Compared with the prior art, the technical solution of the present invention has at least the following technical effects:

[0026] (1) The present invention provides an antibacterial polyvinyl acetate resin for basalt fiber pultrusion molding, which is mainly made of raw materials such as vinyl acetate, methanol, emulsifier, initiator, pH regulator, basalt fiber, antibacterial agent and low surface energy compound. The antibacterial polyvinyl acetate resin is a thermoplastic resin, which can be repeatedly processed and has strong recyclability; moreover, the addition of basalt fiber greatly increases the strength of the polyvinyl acetate resin; the addition of antibacterial agent and low surface energy compound makes the polyvinyl acetate resin have excellent waterproof oil adhesion performance and good anti-bacterial adhesion performance, and at the same time, it can also improve the tensile strength and other mechanical properties of the polyvinyl acetate resin to a certain extent. Through the combination of the above raw materials, the obtained antibacterial polyvinyl acetate resin with different polymerization degrees has good strength, antibacterial and self-cleaning properties, and is also recyclable, meeting various performance requirements.

[0027] (2) The present invention also provides a method for preparing an antibacterial polyvinyl acetate resin for basalt fiber pultrusion molding. The preparation method has simple process control and strong operability, and can realize the preparation of thermoplastic polyvinyl acetate resins with different polymerization degrees and different strengths and good antibacterial and self-cleaning properties.

[0028] (3) The present invention also provides a basalt fiber pultruded profile, which is made of the antibacterial polyvinyl acetate resin provided by the present invention. In view of the advantages of the antibacterial polyvinyl acetate resin of the present invention, the basalt fiber pultruded profile also has the same advantages, so that it has a wide application prospect in the field of antifouling and self-cleaning. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. The process parameters of the following embodiments that do not specify specific conditions are usually based on conventional conditions.

[0030] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0031] According to a first aspect of the present invention, there is provided an antibacterial polyvinyl acetate resin for basalt fiber pultrusion molding, comprising the following raw materials in parts by weight:

[0032] 450-1700 parts of vinyl acetate, 100 parts of methanol, 25-80 parts of emulsifier, 0.009-0.350 parts of initiator, 0.01-0.05 parts of pH adjuster, 50-300 parts of basalt fiber, 0.1-3 parts of antibacterial agent and 0.1-1 parts of low surface energy compound.

[0033] In the present invention, vinyl acetate is used as a reactive monomer of polyvinyl acetate resin, methanol is mainly used as a solvent for polymerization reaction, and emulsifier, initiator, and pH regulator are used as reaction aids in polymerization reaction. There are certain restrictions on the amount of the above raw materials. Typical but non-limiting weight portions of vinyl acetate are 450 parts, 500 parts, 600 parts, 80 parts, 900 parts, 1000 parts, 1100 parts, 1200 parts, 1400 parts, 1500 parts, 1600 parts or 1700 parts, etc., and the numerical range between any two points. Typical but non-limiting weight portions of emulsifier are 25 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts or 80 parts, etc., and the numerical range between any two points. Typical but non-limiting weight portions of the initiator are 0.009 parts, 0.01 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts and 0.35 parts, etc., and the numerical range between any two points. Typical but non-limiting weight portions of the pH adjuster are 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts or 0.05 parts, etc., and the numerical range between any two points.

[0034] As a new type of inorganic environmentally friendly green high-performance fiber material, basalt fiber not only has high strength, but also has excellent wear resistance. At the same time, it also has multiple excellent properties such as electrical insulation, corrosion resistance, and high temperature resistance. In the present invention, basalt fiber is mainly used to improve the strength of polyvinyl acetate resin. The amount of basalt fiber should not be too high (higher than 300 parts), otherwise it is easy to cause uneven dispersion of basalt fiber and serious agglomeration, affecting product performance. The amount of basalt fiber should not be too low (lower than 50 parts), otherwise it is easy to cause the basalt fiber reinforcement effect to weaken, affecting product strength performance. Therefore, the typical but non-restrictive weight portions of basalt fiber are 50 parts, 100 parts, 150 parts, 200 parts, 250 parts or 300 parts, etc. and the numerical range between any two points.

[0035] The addition of antimicrobial agents is mainly to improve the antimicrobial properties of the resin, and at the same time, to a certain extent, it can also improve the processing fluidity of polyvinyl acetate resin, that is, the antimicrobial agent improves the fluidity and processing properties of polyvinyl acetate, thereby indirectly affecting its tensile strength. The dosage of the antimicrobial agent should not be too high (higher than 3 parts), otherwise it is easy to interfere with the normal polymerization reaction of polyvinyl acetate resin, resulting in a decrease in the physical and chemical properties of the resin; the dosage of the antimicrobial agent should not be too low (lower than 0.1 parts), and too low dosage makes the effective concentration of the antimicrobial agent insufficient to fully exert the antimicrobial effect, resulting in polyvinyl acetate resin products being easily contaminated and eroded by microorganisms during use. Therefore, the typical but non-restrictive weight portions of the antimicrobial agent are 0.1 parts, 0.5 parts, 1 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.5 parts, 2.8 parts and 3.0 parts, etc., and the numerical range between any two points.

[0036] The addition of low surface energy compounds is mainly to make the surface of the molded resin material have low surface energy, so that the bacterial surface is difficult to interact with the strongly cross-linked polyvinyl acetate surface, thereby reducing bacterial adhesion. The amount of low surface energy compounds should not be too high (higher than 1 part), otherwise it is easy to reduce the mechanical properties of the molded resin material, and it is easy to be damaged or broken during use, and it will also change the processing properties of the resin. The amount of low surface energy compounds should not be too low (lower than 0.1 parts). If the amount of low surface energy compounds is too low, it is not enough to give full play to its self-cleaning and antibacterial effects, resulting in the resin products being easily contaminated and eroded by microorganisms during use. Therefore, the typical but non-restrictive weight portions of low surface energy compounds are 0.1 parts, 0.2 parts, 0.5 parts, 0.6 parts, 0.8 parts or 1 parts, etc., and the numerical range between any two points.

[0037] The present invention adopts vinyl acetate as a reaction monomer, methanol mainly as a solvent, an emulsifier, an initiator, and a pH value regulator as reaction aids in a polymerization reaction, and the polymerization reaction generates a polyvinyl acetate resin. The polyvinyl acetate resin is a thermoplastic resin, which can be repeatedly processed and has strong recyclability. In addition, adding basalt fiber to the polyvinyl acetate resin can greatly increase the strength of the polyvinyl acetate resin. The addition of antibacterial agents and low surface energy compounds makes the polyvinyl acetate resin have excellent waterproof oil adhesion performance and good anti-bacterial adhesion performance. Through the coordination of the above-mentioned raw materials, the obtained antibacterial polyvinyl acetate resin with different polymerization degrees has good strength and antibacterial properties, and is also recyclable, meeting various performance requirements.

[0038] As an optional embodiment of the present invention, the emulsifier includes nonylphenol polyoxyethylene ether and / or polyvinyl alcohol.

[0039] As an optional embodiment of the present invention, the initiator includes ammonium persulfate and / or azobisisobutyronitrile.

[0040] As an optional embodiment of the present invention, the pH adjuster includes acetic acid and / or citric acid.

[0041] It should be noted that in the present invention, "nonylphenol polyoxyethylene ether and / or polyvinyl alcohol", "ammonium sulfate and / or azobisisobutyronitrile" and "acetic acid and / or citric acid" can all be written in the form of "A and / or B", which means that it can include only A, only B, or both A and B.

[0042] As an optional embodiment of the present invention, the antibacterial agent includes at least one of castor oil, hibiscus alcohol or chitosan. Castor oil, hibiscus alcohol and chitosan are natural antibacterial agents, and adding them to polyvinyl acetate resin can improve the antibacterial properties of the resin. At the same time, the above antibacterial agents have good compatibility with polyvinyl acetate resin, and can improve the processing fluidity of polyvinyl acetate resin to a certain extent, thereby indirectly improving the tensile strength of polyvinyl acetate resin.

[0043] As an optional embodiment of the present invention, the low surface energy compound includes at least one of monohydroxy silicone oil, fluorosilicone oil, amino-modified silicone oil, dimethyl silicone oil or methylphenyl silicone oil. When the low surface energy compound is a mixture of the above-mentioned multiple silicone oils, the mixing ratio of each silicone oil is not limited and can be mixed in any ratio.

[0044] By limiting the specific types of low surface energy compounds, the surface properties of resin materials can be more accurately controlled to meet the needs of different fields.

[0045] As an optional embodiment of the present invention, the diameter of the basalt fiber is 5-15 μm and the length is 1-10 mm. Typical but non-limiting basalt fiber diameters are 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 13 μm, 14 μm or 15 μm, etc.

[0046] By further limiting the diameter and length of basalt fibers, its physical and chemical properties can be precisely controlled, thereby preparing antibacterial polyvinyl acetate resin with excellent properties.

[0047] As an optional embodiment of the present invention, the degree of polymerization of the antibacterial polyvinyl acetate resin is 800-5000. Typical but non-limiting degrees of polymerization of the antibacterial polyvinyl acetate resin are 800, 1000, 1200, 1500, 1600, 1800, 2000, 2500, 2800, 3000, 3500, 4000, 4200, 4500, 4800 or 5000.

[0048] According to a second aspect of the present invention, there is also provided a method for preparing an antibacterial polyvinyl acetate resin for basalt fiber pultrusion, comprising the following steps:

[0049] S1: stirring and mixing vinyl acetate and methanol solution under a protective atmosphere, heating to a certain temperature, adding an emulsifier, an initiator solution and a pH adjuster, and performing a first polymerization reaction to obtain a primary polymerization reaction mixture;

[0050] S2: adding basalt fiber, antibacterial agent and low surface energy compound to the primary polymerization reaction mixture to carry out a second polymerization reaction to obtain antibacterial polyvinyl acetate resin.

[0051] Step S1 of the present invention is mainly to preliminarily form polyvinyl acetate and to achieve regulation of the molecular weight, molecular distribution, crystallinity and other properties of polyvinyl acetate.

[0052] Step S2 is mainly for adding functional materials (such as basalt fiber, antibacterial agent and low surface energy compound) so that the functional materials and polyvinyl acetate can be well combined in the later stage of the polymerization reaction, which can give full play to the advantages of both and improve the comprehensive performance of the antibacterial polyvinyl acetate resin.

[0053] The invention provides a method for preparing an antibacterial polyvinyl acetate resin. The method has simple process control and strong operability, and can realize the preparation of thermoplastic polyvinyl acetate resins with different polymerization degrees and different strengths.

[0054] As an optional embodiment of the present invention, in step S1, heating is performed to 55-65°C; typical but non-limiting heating temperatures are 55°C, 56°C, 58°C, 60°C, 62°C, 64°C or 65°C, and the like, and the numerical range between any two points.

[0055] Firstly heating vinyl acetate and methanol to this temperature and then adding emulsifier, initiator solution and pH adjuster is beneficial to the polymerization reaction of vinyl acetate and methanol and the formation of products, and reduces the occurrence of side reactions.

[0056] As an optional embodiment of the present invention, in step S1, the time of the first polymerization reaction is 2-3 hours and the temperature is 60-65°C.

[0057] A typical but non-limiting reaction time for the first polymerization reaction is 2 h, 2.5 h or 3 h, etc., and a typical but non-limiting reaction temperature is 60°C, 61°C, 62°C, 63°C, 64°C or 65°C, etc., and a numerical range between any two points.

[0058] By limiting the time and temperature of the first polymerization reaction in step S1, precise control of the molecular weight, molecular distribution, crystallinity and other properties of polyvinyl acetate can be achieved.

[0059] As an optional embodiment of the present invention, in step S1, the initiator solution is a methanol solution containing an initiator.

[0060] As a preferred embodiment of the present invention, in step S1, the mass concentration of the initiator in the methanol solution containing the initiator is 0.008-0.012% (for example, 0.008%, 0.009%, 0.010%, 0.011% or 0.012%, etc.), preferably 0.01%.

[0061] As an optional embodiment of the present invention, in step S1, the amount of pH adjuster added is such that the pH value of the polymerization reaction solution reaches 3-6.

[0062] As an optional embodiment of the present invention, in step S2, the second polymerization reaction time is 1-2 hours and the temperature is 60-65°C.

[0063] A typical but non-limiting reaction time for the second polymerization reaction is 1 h, 1.5 h or 2 h, etc., and a typical but non-limiting reaction temperature is 60°C, 61°C, 62°C, 63°C, 64°C or 65°C, etc., and a numerical range between any two points.

[0064] By limiting the time and temperature of the second polymerization reaction in step S2, a polymer with ideal molecular weight, molecular structure and properties can be obtained.

[0065] According to a third aspect of the present invention, there is also provided a basalt fiber pultruded profile, which is made of the above-mentioned antibacterial polyvinyl acetate resin.

[0066] In view of the advantages of the antibacterial polyvinyl acetate resin of the present invention, the basalt fiber pultruded profile also has the same advantages, so that the basalt fiber pultruded profile has a wide application prospect in the field of antifouling and self-cleaning.

[0067] The preparation method of basalt fiber pultruded profile is not specifically limited. For example, the basalt fiber pultruded profile can be made by using basalt fiber as reinforcement and antibacterial polyvinyl acetate resin as matrix resin, impregnating basalt fiber in antibacterial polyvinyl acetate resin, and then molding and curing. It should be noted that the preparation method of basalt fiber pultruded profile is not limited to this, and can be set according to the actual product application field and performance requirements.

[0068] According to a fourth aspect of the present invention, there is also provided application of the above-mentioned antibacterial polyvinyl acetate resin or basalt fiber pultruded profile in the field of self-cleaning.

[0069] The field of self-cleaning can involve a variety of specific application scenarios, such as:

[0070] 1. Medical facilities: In medical environments, antibacterial properties are crucial. Antibacterial polyvinyl acetate resin or basalt fiber pultrusion profiles (antibacterial pultrusion profiles) can be used to manufacture medical devices, operating room equipment, hospital beds, etc. to reduce the risk of cross infection.

[0071] 2. Public health places: In public places such as schools, kindergartens, libraries, gyms, etc., antibacterial polyvinyl acetate resin or basalt fiber pultruded profiles (antibacterial pultruded profiles) can be used to make door handles, tables and chairs, handrails, etc., effectively inhibiting the growth of bacteria and improving the level of environmental hygiene.

[0072] 3. Food processing and catering industry: In food processing and catering places, antibacterial polyvinyl acetate resin or basalt fiber pultruded profiles (antibacterial pultruded profiles) can be used to make kitchen equipment, tableware, dining tables, etc. to ensure the hygiene and safety of food contact surfaces and reduce the risk of food contamination.

[0073] 4. Transportation: In public transportation such as buses, subways, trains, etc., antibacterial polyvinyl acetate resin or basalt fiber pultruded profiles (antibacterial pultruded profiles) can be used to make handrails, seats, etc., to provide passengers with a safer and more hygienic riding environment.

[0074] 5. Home life: Antibacterial polyvinyl acetate resin or basalt fiber pultruded profiles (antibacterial pultruded profiles) can be used to make furniture, doors and windows, bathroom equipment, etc., to provide a healthy and comfortable living environment for the family.

[0075] The present invention is further described in detail below in conjunction with specific examples and comparative examples. Those skilled in the art should understand that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention. Unless otherwise specified, the raw materials used in the present invention can be obtained from commercially available products. Among them, polyvinyl alcohol 1788 has a molecular weight of 74,800, purchased from Inner Mongolia Shuangxin Environmental Protection Materials Co., Ltd.; the molecular weight of monohydroxy silicone oil PMX-0156 is 800, purchased from Dow Chemical Company; fluorosilicone oil FS1265FLUID is a vinyl-terminated polymer, belongs to modified silicone oil, purchased from Dow Chemical Company.

[0076] Example 1

[0077] This embodiment provides an antibacterial polyvinyl acetate resin for basalt fiber pultrusion, comprising the following raw materials in parts by weight:

[0078] 600 parts of vinyl acetate, 100 parts of methanol, 30 parts of emulsifier, 0.1 parts of initiator, 0.02 parts of pH adjuster, 100 parts of basalt fiber, 0.5 parts of antibacterial agent and 0.3 parts of low surface energy compound.

[0079] Among them, the emulsifier is polyvinyl alcohol, the initiator is azobisisobutyronitrile, the pH regulator is citric acid, the antibacterial agent is castor oil, the low surface energy compound is monohydroxy silicone oil, and the average diameter of the basalt fiber is 10 μm and the average length is 8 mm.

[0080] This embodiment also provides a method for preparing the above antibacterial polyvinyl acetate resin, comprising the following steps:

[0081] S1. The initiator in the formula amount is prepared into a methanol solution containing the initiator, and the mass concentration of the initiator in the methanol solution containing the initiator is 0.01%.

[0082] S2. Under nitrogen protection, the formula amount of vinyl acetate and methanol is put into the reactor, heated and stirred, and the formula amount of emulsifier, initiator solution and pH adjuster are added at a temperature of 55-65°C for the first polymerization reaction. The reaction time is 3h, the reaction temperature is about 65°C, and the pH value of the polymerization reaction liquid reaches about 4 to obtain a polymerization reaction mixture;

[0083] S3. Add the formulated amount of basalt fiber, antibacterial agent and low surface energy compound to the primary polymerization reaction mixture for a second polymerization reaction. The polymerization reaction time is 1 hour and the reaction temperature is about 65° C. to obtain a thermoplastic antibacterial polyvinyl acetate resin.

[0084] Example 2

[0085] This embodiment provides an antibacterial polyvinyl acetate resin, comprising the following raw materials in parts by weight:

[0086] 1000 parts of vinyl acetate, 100 parts of methanol, 40 parts of emulsifier, 0.140 parts of initiator, 0.02 parts of pH adjuster, 80 parts of basalt fiber, 1 part of antibacterial agent and 0.3 parts of low surface energy compound.

[0087] Among them, the emulsifier is polyvinyl alcohol, the initiator is ammonium sulfate, the pH adjuster is acetic acid, the antibacterial agent is cypermethrin, the low surface energy compound is fluorosilicone oil, and the average diameter of the basalt fiber is 10 μm and the average length is 8 mm.

[0088] This embodiment also provides a method for preparing the above antibacterial polyvinyl acetate resin, comprising the following steps:

[0089] S1. The initiator in the formula amount is prepared into a methanol solution containing the initiator, and the mass concentration of the initiator in the methanol solution containing the initiator is 0.01%.

[0090] S2. Under nitrogen protection, the formula amount of vinyl acetate and methanol is put into the reactor, heated and stirred, and the formula amount of emulsifier, initiator solution and pH adjuster are added at a temperature of 55-65°C to carry out the first polymerization reaction. The reaction time is 2h, the reaction temperature is about 60°C, and the pH value of the polymerization reaction liquid reaches about 5 to obtain a polymerization reaction mixture;

[0091] S3. Add the formulated amount of basalt fiber, antibacterial agent and low surface energy compound to the primary polymerization reaction mixture for a second polymerization reaction. The polymerization reaction time is 2 hours and the reaction temperature is about 65° C. to obtain a thermoplastic antibacterial polyvinyl acetate resin.

[0092] Example 3

[0093] This embodiment provides an antibacterial polyvinyl acetate resin. Except for adjusting the weight of basalt fiber in the raw material from 100 parts to 60 parts, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0094] Example 4

[0095] This embodiment provides an antibacterial polyvinyl acetate resin. Except for adjusting the weight portion of the antibacterial agent in the raw materials from 0.5 parts to 1 part, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0096] Example 5

[0097] This embodiment provides an antibacterial polyvinyl acetate resin. Except that the weight portion of the low surface energy compound in the raw material is adjusted from 0.3 parts to 1 part, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0098] Comparative Example 1

[0099] This comparative example provides an antibacterial polyvinyl acetate resin. Except that the basalt fiber in the raw material is replaced by glass fiber with a diameter and length equivalent to that of the basalt fiber, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0100] Comparative Example 2

[0101] This comparative example provides an antibacterial polyvinyl acetate resin. Except that no antibacterial agent is added to the raw materials, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0102] Comparative Example 3

[0103] This comparative example provides an antibacterial polyvinyl acetate resin, except that the weight portion of the antibacterial agent in the raw materials is adjusted from 0.6 parts to 4 parts, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0104] Comparative Example 4

[0105] This comparative example provides an antibacterial polyvinyl acetate resin. Except that no low surface energy compound is added to the raw materials, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0106] Comparative Example 5

[0107] This comparative example provides an antibacterial polyvinyl acetate resin, in which the types, amounts and preparation methods of the other raw materials are the same as those in Example 1, except that the weight portion of the low surface energy compound in the raw materials is adjusted from 0.3 parts to 2 parts.

[0108] Comparative Example 6

[0109] This comparative example provides an antibacterial polyvinyl acetate resin, except that the weight portion of the low surface energy compound in the raw materials is adjusted from 0.3 parts to 0.05 parts, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0110] Comparative Example 7

[0111] This comparative example provides an antibacterial polyvinyl acetate resin, except that basalt fiber is not added to the raw materials, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0112] Comparative Example 8

[0113] This comparative example provides an antibacterial polyvinyl acetate resin. Except for adjusting the weight of basalt fiber in the raw material from 100 parts to 400 parts, the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0114] Comparative Example 9

[0115] This comparative example provides an antibacterial polyvinyl acetate resin, in which methanol is replaced by an equal amount of ethanol, and the other raw material types, amounts and preparation methods are the same as those in Example 1.

[0116] Comparative Example 10

[0117] This comparative example provides an antibacterial polyvinyl acetate resin, and the specific raw material types and amounts are the same as those in Example 1.

[0118] The preparation method of the antibacterial polyvinyl acetate resin of this comparative example comprises the following steps:

[0119] S1. The initiator in the formula amount is prepared into a methanol solution containing the initiator, and the mass concentration of the initiator in the methanol solution containing the initiator is 0.01%.

[0120] S2. Under nitrogen protection, put the formulated amount of vinyl acetate and methanol into a reactor, heat and stir, add the formulated amount of emulsifier, initiator solution, pH adjuster, basalt fiber, antibacterial agent and low surface energy compound at a temperature of 55-65°C to carry out polymerization reaction. The reaction time is 4 hours and the reaction temperature is 65°C to obtain thermoplastic antibacterial polyvinyl acetate resin.

[0121] Comparative Example 11

[0122] This comparative example provides an antibacterial polyvinyl acetate resin, and the specific raw material types and amounts are the same as those in Example 1.

[0123] The preparation method of the antibacterial polyvinyl acetate resin of this comparative example comprises the following steps:

[0124] S1. The initiator in the formula amount is prepared into a methanol solution containing the initiator, and the mass concentration of the initiator in the methanol solution containing the initiator is 0.01%.

[0125] S2. Under nitrogen protection, the formula amount of vinyl acetate and methanol was put into the reactor, heated and stirred, and the formula amount of emulsifier, initiator solution, pH adjuster was added at a temperature of 55-65 ° C to carry out polymerization reaction, the reaction time was 3h, the reaction temperature was 65 ° C, the pH value of the polymerization reaction solution reached about 4, to obtain polyvinyl acetate resin;

[0126] S3. Mixing the methanol solution of polyvinyl acetate resin with the antibacterial agent and basalt fiber, and drying the mixture to prepare antibacterial polyvinyl acetate resin.

[0127] In order to compare the technical effects of the above embodiments and comparative examples, the following experimental examples are specially designed.

[0128] Experimental Example 1

[0129] The relevant properties of the polyvinyl acetate resins prepared in the embodiments and comparative examples were tested, and the specific results are shown in Table 1. Among them, the tensile strength test method is based on GB / T 1040.2-2022 Determination of tensile properties of plastics Part 2: Test conditions for molded and extruded plastics, the antibacterial test method is based on GB / T 31402-2023 Determination of antibacterial activity on the surface of plastics and other non-porous materials, and the self-cleaning test method is based on GB / T 31815-2015 Self-cleaning coatings for exterior surfaces of buildings.

[0130] Table 1

[0131]

[0132]

[0133] It can be seen from the data in Table 1 that the degree of polymerization of the polyvinyl acetate resin prepared in each embodiment of the present invention is 2000-3000, all between 800-5000, its tensile strength is 34.4-38.5MPa, the antibacterial rate is 96.6-99.5%, and the contact angle is 10-17°, and its performance in all aspects is significantly better than that in the comparative example.

[0134] Specifically, Comparative Example 1 is a comparative experiment of Example 1, and the only difference between it and Example 1 is the different fiber types. From the data in the table, it can be seen that the tensile strength, antibacterial rate and self-cleaning performance of Comparative Example 1 are significantly reduced, which is mainly due to the lower strength and corrosion resistance of glass fiber than basalt fiber, which not only directly affects the tensile strength and other mechanical properties of polyvinyl acetate resin, but also indirectly affects the full play of other properties (antibacterial performance and self-cleaning performance) due to the poor interface bonding between glass fiber and polyvinyl acetate resin.

[0135] Comparative Examples 2 and 3 are also comparative experiments of Example 1, which mainly investigate the effect of the amount of antimicrobial agent on product performance. It can be seen from the relevant data in Table 1 that when the amount of antimicrobial agent is too much or no antimicrobial agent is added, the tensile properties, antimicrobial properties and self-cleaning properties of polyvinyl acetate resin are significantly reduced. This is mainly due to the good compatibility of the antimicrobial agent of the specific type of the present invention with polyvinyl acetate resin, and the addition of the antimicrobial agent can improve the processing fluidity of polyvinyl acetate resin to a certain extent, that is, the antimicrobial agent improves the fluidity and processing properties of polyvinyl acetate, thereby indirectly affecting its tensile strength. The dispersibility of the antimicrobial agent in the matrix material is a key factor. When the antimicrobial agent is added too much, it causes it to agglomerate in the matrix material to form larger particles or agglomerates. The agglomerated antimicrobial agent particles are poorly bonded to the interface of the matrix material, thereby weakening the antimicrobial properties and self-cleaning properties of polyvinyl acetate resin.

[0136] The difference between Comparative Examples 4 to 6 and Example 1 is mainly the difference in the amount of low surface energy compound used. From the data in Table 1, it can be seen that the addition of low surface energy compounds and the amount used mainly affect the antibacterial and self-cleaning properties of polyvinyl acetate resin. When the amount of low surface energy compound used is too small (such as Comparative Example 6), although the self-cleaning and antibacterial effects are not fully exerted, the tensile strength has a certain improvement effect. However, when the amount of low surface energy compound used is too much (such as Comparative Example 5), it has an adverse effect on the tensile strength and other mechanical properties of polyvinyl acetate resin.

[0137] Compared with Example 1, the main difference between Comparative Examples 7 and 8 is the different amount of basalt fiber used. It can be seen from the above data in Table 1 that when no basalt fiber is added or an excessive amount of basalt fiber is added, the tensile strength of polyvinyl acetate resin will be reduced. At the same time, excessive basalt fiber will also affect the antibacterial and self-cleaning properties of polyvinyl acetate resin. This is mainly because the inappropriate basalt fiber content cannot fully exert the strength, antibacterial and self-cleaning properties of basalt fiber-enhanced polyvinyl acetate resin. When the fiber content is too high, the pultruded profile will become more brittle and hard. When the fiber content is too low, the basalt fiber cannot well enhance the performance of the pultruded profile, so that various properties cannot be fully exerted, resulting in a decrease in overall performance.

[0138] Comparative Example 9 is compared with Example 1, and mainly investigates the influence of solvent types during polymerization reaction. As can be seen from the data in the table, the difference of solvents has a significant impact on the polymerization degree, tensile strength, antibacterial property and self-cleaning performance of polyvinyl acetate resin, which is mainly due to the fact that methanol is a good solvent in the synthesis of polyvinyl acetate, and methanol contributes to the synthesis of polyvinyl acetate by improving dissolving power, reaction rate, lowering temperature and convenient separation and recovery. At the same time, it is also possible to well control the polymerization degree of polyvinyl acetate resin, thereby improving tensile strength, antibacterial property and self-cleaning performance. Although ethanol can also be used as a solvent, there are many side reactions, such as the transesterification reaction of ethanol and vinyl acetate, which will affect the efficiency of the free radical transfer agent at the same time.

[0139] Comparative Examples 10 and 11 are both comparative experiments of Example 1. The preparation methods of the polyvinyl acetate resin in Comparative Examples 10 and 11 are different from the preparation methods of the present invention. By comparison, it can be seen that only by adopting the specific preparation method of the present invention (including a specific feeding sequence and two polymerization reaction steps before and after) can a polyvinyl acetate resin product with a suitable degree of polymerization and excellent tensile properties, antibacterial properties and self-cleaning properties be obtained.

[0140] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention are within the scope of protection of the pending claims of the present invention.

Claims

1. An antibacterial polyvinyl acetate resin for basalt fiber pultrusion molding, characterized in that: The following raw materials are included in parts by weight: 450-1700 parts of vinyl acetate, 100 parts of methanol, 25-80 parts of emulsifier, 0.009-0.350 parts of initiator, 0.01-0.05 parts of pH adjuster, 50-300 parts of basalt fiber, 0.1-3 parts of antibacterial agent and 0.1-1 parts of low surface energy compound.

2. The antibacterial polyvinyl acetate resin for basalt fiber pultrusion molding according to claim 1, characterized in that: The emulsifier includes nonylphenol polyoxyethylene ether and / or polyvinyl alcohol; And / or, the initiator comprises ammonium persulfate and / or azobisisobutyronitrile; And / or, the pH adjuster includes acetic acid and / or citric acid.

3. The antibacterial polyvinyl acetate resin for basalt fiber pultrusion molding according to claim 1, characterized in that: The basalt fiber has a diameter of 5-15 μm and a length of 1-10 mm; and / or, the antibacterial agent comprises at least one of castor oil, hibiscus alcohol or chitosan; And / or, the low surface energy compound includes at least one of monohydroxy silicone oil, fluorosilicone oil, amino-modified silicone oil, dimethyl silicone oil or methylphenyl silicone oil.

4. The antibacterial polyvinyl acetate resin for basalt fiber pultrusion according to any one of claims 1 to 3, characterized in that: The degree of polymerization of the antibacterial polyvinyl acetate resin is 800-5000.

5. The method for preparing the antibacterial polyvinyl acetate resin for basalt fiber pultrusion molding according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1. Vinyl acetate and methanol are stirred and mixed under a protective atmosphere, heated to a certain temperature, and then an emulsifier, an initiator solution and a pH adjuster are added to carry out a first polymerization reaction to obtain a polymerization reaction mixture; S2. Add basalt fiber, antibacterial agent and low surface energy compound to the primary polymerization reaction mixture to carry out a second polymerization reaction to obtain antibacterial polyvinyl acetate resin.

6. The method for preparing the antibacterial polyvinyl acetate resin according to claim 5, characterized in that: In step S1, heating to 55-65°C; And / or, in step S1, the first polymerization reaction time is 2-3 hours and the temperature is 60-65°C.

7. The method for preparing the antibacterial polyvinyl acetate resin according to claim 5, characterized in that: In step S1, the initiator solution is a methanol solution containing an initiator; And / or, in step S1, the pH adjuster is added in an amount such that the pH value of the polymerization reaction solution is 3-6.

8. The method for preparing the antibacterial polyvinyl acetate resin according to any one of claims 5 to 7, characterized in that: In step S2, the second polymerization reaction time is 1-2 hours and the temperature is 60-65°C.

9. A basalt fiber pultruded profile, characterized in that: The antibacterial polyvinyl acetate resin is made from the antibacterial polyvinyl acetate resin described in any one of claims 1 to 4 or the antibacterial polyvinyl acetate resin prepared by the preparation method described in any one of claims 5 to 8.

10. Use of the antibacterial polyvinyl acetate resin according to any one of claims 1 to 4, the antibacterial polyvinyl acetate resin obtained by the preparation method according to any one of claims 5 to 8, or the basalt fiber pultruded profile according to claim 9 in the field of self-cleaning.

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