Synthesis method of special bio-based unsaturated polyester resin for zero-crystal silicon quartz stone

Abstract

The invention discloses a synthesis method of special bio-based unsaturated polyester resin for zero-crystalline silicon quartz stone, which comprises the following steps: firstly, putting bio-based dihydric alcohol, 2, 5-furandicarboxylic acid, itaconic acid, an antioxidant and a polymerization inhibitor into a reaction kettle, heating to 205-210 DEG C, carrying out polymerization reaction for 2-4 hours, then vacuumizing for 2-3 hours, and cooling to room temperature to obtain the special bio-based unsaturated polyester resin for zero-crystalline silicon quartz stone. When the reaction acid value is tested to be smaller than 25 mgKOH / g and the cone plate viscosity at 125 DEG C is 500-900 mpa.s, the reaction endpoint is reached, finally, a bio-based crosslinking monomer is added for dilution, and the bio-based unsaturated polyester resin special for the zero-crystallization silicon quartz stone is obtained. The bio-based unsaturated polyester resin special for the zero-crystalline silicon quartz stone synthesized by the method can meet the requirements of a zero-crystalline silicon quartz stone production process, and solves the problems that a zero-crystalline silicon quartz stone plate is easy to generate surface pulverization corrosion, glass explosion and the like.

Description

Technical Field

[0001] The invention relates to the field of macromolecular organic synthesis, and in particular to a method for synthesizing a bio-based unsaturated polyester resin specifically for zero-crystalline silicon quartz stone. Background Art

[0002] In the context of dual carbon emissions, China has a vast supply of renewable biomass resources annually, including grains, legumes, straw, and bamboo and wood flour. These raw materials are converted into biopolymers or monomers through biotransformation processes such as biosynthesis, bioprocessing, and biorefining. With increasing support for bio-based materials in the West, particularly the European Community, these materials will become indispensable for future product exports. With the maturity of biosynthesis technology, particularly the optimization of synthesis processes, bio-based materials will largely replace petrochemical materials in the future. These materials offer cost advantages and sustainability, aligning with the trends of green manufacturing and environmental sustainability. The use of bio-based materials to synthesize unsaturated polyester resins will become a key development direction for unsaturated resins.

[0003] Traditional quartz countertops are composed of approximately 80% silica. During the cutting, polishing, or sawing process, quartz countertops release large amounts of silica dust particles. Inhaling these particles can damage the lungs and increase the risk of silicosis. Australia has completely banned artificial stone countertops containing crystalline silica, and similar policies are being implemented in Europe and the United States. Stone manufacturers are actively developing artificial stone products with zero crystalline silica. The main alternative material currently is glass powder, which contains approximately 70% amorphous, zero-crystalline silica. The glass powder is mixed with an unsaturated polyester resin matrix, then subjected to a series of processes including spreading, shaking, and vacuum pressing. The artificial stone product is then cured by heating at 80°C using a heat-conducting plywood. However, the alkaline oxides present in glass powder, such as approximately 15% sodium oxide and 8% calcium oxide, are corrosive to the resin, especially in the presence of moisture. Therefore, the resin must exhibit higher alkali resistance, as well as better wetting, dispersion, and adhesion with the glass powder. Quartz stone slabs made of conventional unsaturated polyester resin are prone to surface powdering corrosion, glass explosion and other problems when exposed to water and sunlight. The main reason is the poor alkali resistance of the resin and the insufficient bonding strength between the resin and the glass powder. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for synthesizing a bio-based unsaturated polyester resin specifically for zero-crystalline silicon quartz stone. By using bio-based diols or dibasic acid materials to synthesize unsaturated polyester resins, the requirements of the production process of zero-crystalline silicon quartz stone are met, and the difficult problems of zero-crystalline silicon quartz stone plates being prone to surface powdering corrosion and glass explosion are solved.

[0005] In order to achieve the above object, the solution of the present invention is: A method for synthesizing a bio-based unsaturated polyester resin specifically for zero-crystallinity silica quartz stone comprises the following steps: firstly, placing a bio-based diol, 2,5-furandicarboxylic acid, itaconic acid, an antioxidant, and a polymerization inhibitor in a reactor, heating the reactor to 205-210° C. for polymerization reaction for 2-4 hours, then vacuuming the reactor for 2-3 hours, reaching the reaction endpoint when the reaction acid value is less than 25 mgKOH / g and the cone-plate viscosity at 125° C. is 500-900 mPa·s, and finally, adding a bio-based cross-linking monomer for dilution to obtain the bio-based unsaturated polyester resin specifically for zero-crystallinity silica quartz stone, wherein the bio-based diol is selected from one or more of 1,2-pentanediol, 1,5-pentanediol, and 1,4-butanediol, and the bio-based cross-linking monomer is selected from one or more of ethyl acrylate, 2-octyl acrylate, and isobornyl acrylate.

[0006] The antioxidant is antioxidant PL-90.

[0007] The polymerization inhibitor is polymerization inhibitor THQ.

[0008] The heating rate is 8-12°C / h.

[0009] The vacuum degree of the vacuum pumping is -0.08 ~ -0.09 MPa.

[0010] The raw materials of the bio-based unsaturated polyester resin for zero-crystallized silica quartz stone are used in the following amounts, by weight: 100-150 parts of bio-based diol, 90-100 parts of 2,5-furandicarboxylic acid, 80-90 parts of itaconic acid, 135-150 parts of bio-based cross-linking monomer, 0.1-0.2 parts of antioxidant and 0.03-0.05 parts of polymerization inhibitor.

[0011] After adopting the above technical scheme, the present invention provides a method for synthesizing a bio-based unsaturated polyester resin specifically for zero-crystalline silicon quartz stone. The method adopts a bio-based diol synthesized from renewable biomass resources to replace the diol of traditional petrochemical materials, adopts a bio-based 2,5-furandicarboxylic acid raw material to replace traditional phthalic anhydride and terephthalic acid, introduces a five-membered furan aromatic heterocycle containing oxygen atoms to replace the benzene ring structure, and the presence of the oxygen group improves the bonding effect between the resin and the powder and improves the binding force. At the same time, itaconic acid is used to replace conventional maleic anhydride, the reactivity of the double bond is higher, the reaction curing is faster and more complete, and the risk of alkaline corrosion of glass powder is reduced. Finally, a biosynthesized green cross-linking monomer is used to replace the potentially carcinogenic styrene monomer. Combined with formula design and control of polymerization parameters such as the viscosity of the polyester vertebral plate, a bio-based unsaturated polyester resin specifically for zero-crystalline silicon quartz stone is synthesized, which can meet the requirements of the zero-crystalline silicon quartz stone production process and solve the problems of surface powdering corrosion and glass explosion in zero-crystalline silicon quartz stone plates. DETAILED DESCRIPTION

[0012] In order to further explain the technical solution of the present invention, the present invention is described in detail below through specific embodiments.

[0013] A method for synthesizing a bio-based unsaturated polyester resin specifically for zero-crystalline silica quartz stone comprises the following steps: firstly, placing a bio-based diol, 2,5-furandicarboxylic acid, itaconic acid, an antioxidant, and a polymerization inhibitor in a reactor; heating the reactor to 205-210°C at a rate of 8-12°C / h for polymerization reaction; the reaction time is 2-4 hours; then, vacuuming the reactor for 2-3 hours, maintaining a vacuum degree of -0.08-0.09 MPa; reaching the reaction endpoint when the tested reaction acid value is less than 25 mgKOH / g and the cone-plate viscosity at 125°C is 500-900 MPa·s; and finally, adding a bio-based cross-linking monomer for dilution to obtain the bio-based unsaturated polyester resin specifically for zero-crystalline silica quartz stone.

[0014] Among them, the bio-based diol is selected from one or more of 1,2-pentanediol, 1,5-pentanediol and 1,4-butanediol. 1,2-pentanediol and 1,5-pentanediol are purchased from Shandong Yinuo Biomass Materials Co., Ltd., and 1,4-butanediol is purchased from Shandong Landian Biotechnology Co., Ltd. The bio-based cross-linking monomer is selected from one or more of ethyl acrylate, 2-octyl acrylate and isobornyl acrylate. Ethyl acrylate and 2-octyl acrylate are purchased from BASF, Germany, and isobornyl acrylate is purchased from Jining Sanshi Biotechnology Co., Ltd.

[0015] 2,5-Furandicarboxylic acid and itaconic acid were purchased from Guangzhou Yuanda New Materials Co., Ltd.

[0016] The antioxidant was pentaerythritol didecyl diphosphite PL-90, which was purchased from Jiangsu Evergreen New Materials Technology Co., Ltd.

[0017] The polymerization inhibitor was o-methylhydroquinone THQ, which was purchased from Weifang Tongrun Chemical Co., Ltd.

[0018] Example 1 A method for synthesizing a bio-based unsaturated polyester resin specifically for zero-crystalline silica quartz stone comprises the following steps: firstly, placing 800 g of 1,2-pentanediol, 600 g of 1,5-pentanediol, 1000 g of 2,5-furandicarboxylic acid, 800 g of itaconic acid, 1.5 g of an antioxidant PL-90, and 0.3 g of a polymerization inhibitor THQ in a reactor; heating the reactor to 205° C. at a rate of 10° C. / h to carry out a polymerization reaction for 3 hours; then, evacuating the reactor for 3 hours while maintaining a vacuum degree of -0.08 MPa; reaching a reaction endpoint when a tested reaction acid value is less than 22.5 mgKOH / g and a cone-plate viscosity at 125° C. is 850 MPa·s; finally, adding 1500 g of ethyl acrylate for dilution to obtain the bio-based unsaturated polyester resin specifically for zero-crystalline silica quartz stone; and testing the liquid indexes and mechanical properties of the unsaturated polyester resin.

[0019] Example 2 A method for synthesizing a bio-based unsaturated polyester resin specifically for zero-crystalline silica quartz stone comprises the following steps: firstly, placing 1000 g of 1,2-pentanediol, 200 g of 1,4-butanediol, 950 g of 2,5-furandicarboxylic acid, 850 g of itaconic acid, 1.5 g of an antioxidant PL-90, and 0.3 g of a polymerization inhibitor THQ in a reactor; heating the reactor to 208° C. at a rate of 8° C. / h for a polymerization reaction; and then evacuating the reactor for 2 hours while maintaining a vacuum degree of -0.08 MPa. The reaction endpoint is reached when a tested reaction acid value is less than 23.2 mgKOH / g and a cone-plate viscosity at 125° C. is 800 MPa·s. Finally, 1400 g of 2-octyl acrylate is added for dilution to obtain the bio-based unsaturated polyester resin specifically for zero-crystalline silica quartz stone, and the liquid indexes and mechanical properties of the unsaturated polyester resin are tested.

[0020] Example 3 A method for synthesizing a bio-based unsaturated polyester resin specifically for zero-crystallinity silica quartz stone comprises the following steps: firstly, placing 200g of 1,2-pentanediol, 600g of 1,5-pentanediol, 300g of 1,4-butanediol, 900g of 2,5-furandicarboxylic acid, 800g of itaconic acid, 1.5g of antioxidant PL-90, and 0.3g of polymerization inhibitor THQ in a reactor; heating the reactor to 206°C at a rate of 12°C / h for polymerization reaction for 4 hours; then, evacuating the reactor for 3 hours while maintaining the vacuum degree at -0.09 MPa; reaching the reaction endpoint when the tested reaction acid value is less than 21.8 mgKOH / g and the cone-plate viscosity at 125°C is 665 MPa·s; finally, adding 1050g of ethyl acrylate and 300g of isobornyl acrylate for dilution to obtain the bio-based unsaturated polyester resin specifically for zero-crystallinity silica quartz stone; and testing the liquid indexes and mechanical properties of the unsaturated polyester resin.

[0021] Table 1 shows a comparison of the performance of the bio-based unsaturated polyester resin for zero-crystalline silica quartz stone synthesized in each example and the conventional o-phthalic unsaturated resin 8996 (from Quanzhou Yongyue New Materials Co., Ltd.).

[0022] Table 1 Performance data of bio-based unsaturated polyester resin for zero-crystalline silica quartz stone and o-phthalic unsaturated polyester resin 8996

[0023] The bio-based unsaturated polyester resins specifically for zero-crystalline silica quartz synthesized in each example exhibit excellent performance, with a tensile strength of approximately 60 MPa, a flexural strength exceeding 110 MPa, a Barcol hardness exceeding 40, and excellent impact toughness, comparable to the performance of the conventional ortho-phthalic unsaturated resin 8996 for zero-crystalline silica quartz. However, under the same testing conditions, the bio-based unsaturated polyester resins specifically for zero-crystalline silica quartz synthesized in each example exhibited significantly faster gel times, reached their exothermic peak significantly faster than the 8996 resin, and had an exothermic peak temperature approximately 15°C higher. This demonstrates that the resins synthesized using the present invention have faster curing speeds, more concentrated exothermic release, and more complete curing.

[0024] Moreover, when the bending strength of pure resins is similar, the bending strength of quartz stone products made by mixing different resins and glass powder varies greatly. The bending strength of zero-crystalline silicon quartz stone products made by using the resin synthesized by the present invention is higher than that of conventional resin products, with the bending strength increased by more than 30%. In particular, the bending strength retention rate after accelerated aging in distilled water at 60°C for 2 weeks is significantly different. This shows that the resin synthesized by the present invention has better bonding between the resin matrix and the glass powder due to the hydrogen bonding effect of O—H···O formed by the oxygen atom in the furan ring of 2,5-furandicarboxylic acid and the silicon hydroxyl bond. In addition, the terminal olefin group of itaconic acid has higher reaction activity than the double bond of the maleic anhydride chain segment, and the reaction curing is faster and more complete, which can form a denser structure. Water molecules are not easy to penetrate and destroy the resin structure, so it has a higher bending strength retention rate and is not easy to be corroded or the glass bursting problem occurs.

[0025] Therefore, the unsaturated polyester resin synthesized from all-biobased materials in the present invention can meet the requirements of the production process of zero-crystalline silicon quartz stone, and solve the problems of surface powdering corrosion and glass explosion of zero-crystalline silicon quartz stone plates.

[0026] The above embodiments do not limit the product form and style of the present invention. Any appropriate changes or modifications made by ordinary technicians in the relevant technical field should be deemed to be within the patent scope of the present invention.

Claims

1. A method for synthesizing a bio-based unsaturated polyester resin specifically for zero-crystalline silicon quartz stone, characterized by: The following steps are involved: First, a bio-based diol, 2,5-furandicarboxylic acid, itaconic acid, an antioxidant and a polymerization inhibitor are placed in a reactor, and the temperature is raised to 205-210° C. for polymerization reaction. The reaction time is 2-4 hours, and then vacuum is applied for 2-3 hours. When the test reaction acid value is less than 25 mgKOH / g and the cone-plate viscosity at 125° C. is 500-900 mPa·s, the reaction reaches the end point. Finally, a bio-based cross-linking monomer is added for dilution to obtain the bio-based unsaturated polyester resin for zero-crystalline silica quartz stone, wherein the bio-based diol is selected from one or more of 1,2-pentanediol, 1,5-pentanediol and 1,4-butanediol, and the bio-based cross-linking monomer is selected from one or more of ethyl acrylate, 2-octyl acrylate and isobornyl acrylate.

2. The method for synthesizing a bio-based unsaturated polyester resin for zero-crystalline silicon quartz stone according to claim 1, characterized in that: The antioxidant is antioxidant PL-90.

3. The method for synthesizing a bio-based unsaturated polyester resin for zero-crystalline silicon quartz stone according to claim 1, characterized in that: The polymerization inhibitor is polymerization inhibitor THQ.

4. The method for synthesizing a bio-based unsaturated polyester resin for zero-crystalline silicon quartz stone according to claim 1, characterized in that: The heating rate is 8-12°C / h.

5. The method for synthesizing a bio-based unsaturated polyester resin for zero-crystalline silicon quartz stone according to claim 1, characterized in that: The vacuum degree of the vacuum pumping is -0.08 ~ -0.09 MPa.

6. The method for synthesizing a bio-based unsaturated polyester resin for zero-crystalline silicon quartz stone according to claim 1, characterized in that: The raw materials of the bio-based unsaturated polyester resin for zero-crystallized silica quartz stone are used in the following amounts, by weight: 100-150 parts of bio-based diol, 90-100 parts of 2,5-furandicarboxylic acid, 80-90 parts of itaconic acid, 135-150 parts of bio-based cross-linking monomer, 0.1-0.2 parts of antioxidant and 0.03-0.05 parts of polymerization inhibitor.

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