A high temperature resistant release PVA release film for artificial stone

Abstract

The present invention belongs to the field of polymer film materials. The present invention relates to a high temperature resistant release PVA demoulding film for artificial stone and a preparation method thereof, wherein the PVA demoulding film comprises the following raw materials in parts by weight: 100 parts of PVA resin; 20-30 parts of plasticizer; 1.0-3.0 parts of cross-linking agent; 0.3-0.5 parts of antioxidant; 0.1-0.5 parts of heat stabilizer; 0.1-0.5 parts of surfactant; 0.2-0.5 parts of lubricant, mixed in proportion, put into a granulator and a film blowing machine for preparation, and extruded. The novel high temperature resistant release PVA demoulding film for artificial stone effectively solves the problems of high temperature difference resistance and poor strength and toughness in the prior art, and can effectively reduce wrinkles and improve production efficiency.

Description

Technical Field

[0001] The invention relates to a high temperature resistant release PVA demoulding film for artificial stone and a preparation method thereof. The invention belongs to the field of polymer film materials. Background Art

[0002] In addition to being water-soluble, polyvinyl alcohol (PVA) also has the characteristics of good density, high crystallinity, and strong adhesion. The film made of it is not only flexible, smooth, and non-charged, but also oil-resistant, solvent-resistant, abrasion-resistant, and has good gas barrier properties. It has a wide range of application scenarios in industry. There are two main application areas, packaging film and carrier film. As a carrier film, PVA marble release film has good releasability and high temperature resistance with thermoplastics such as epoxy resins and unsaturated plastics. When using unsaturated polyester, epoxy resin or other thermal resin agents to make parts, the high softness of PVA can make the PVA film fit the mold better and improve the demolding quality. It has good releasability, no impurities are generated after demolding, and it is not easy to produce burrs, saving grinding time. It is safe and non-toxic, environmentally friendly, and can be decomposed and biodegraded in water. Although there have been reports on this issue and it is a mature application abroad, the technology has always been firmly in the hands of American and Japanese manufacturers. Domestic high-temperature films are produced by solution casting with low crystallinity. At the same time, in order to ensure the plasticizing effect, a large amount of plasticizers and a small amount of cross-linking agents are added, which seriously affects the heat resistance of the PVA release film. At present, domestic heat-resistant PVA release films can be used normally at 190°C. Due to the wide range of artificial stone raw materials, there is an obvious demand for higher heat resistance.

[0003] In addition, as a highly crystalline material, PVA is brittle, difficult to process, and has little practical value. It requires a large amount of plasticizer for processing. The large amount of plasticizer added will lead to a decrease in mechanical and thermal properties and the problem of plasticizer migration and precipitation, affecting the service life of the PVA material. Summary of the invention

[0004] The purpose of the present invention is to solve the problem that the release PVA release film used for artificial stone in the prior art is resistant to high temperature difference and has poor strength and toughness, and to provide a new type of high temperature resistant release PVA release film for artificial stone and a preparation method thereof. The product is environmentally friendly through formula design, using homemade plasticizers and cross-linking agents, and prepared by film blowing process. The technical solution adopted by the present invention to solve the technical problem is:

[0005] The present invention provides a method for preparing a plasticizer, comprising the following steps:

[0006] S11, coupling reaction of silicon dioxide A and epoxy silane coupling agent to obtain intermediate product 1I;

[0007] S12, subjecting the intermediate product 1I to a ring-opening reaction with a dibasic acid in the presence of a catalyst to obtain an intermediate product 1II; and

[0008] S13, esterifying the intermediate product 1II with a polyol to obtain the target product 1, i.e., a plasticizer.

[0009] Furthermore, the usage ratio of the silicon dioxide A to the epoxy silane coupling agent is 1g:4.0-6.0g; and

[0010] The silicon dioxide A is nano-scale silicon dioxide.

[0011] Furthermore, the intermediate product II and the dibasic acid are added in a molar ratio of epoxy group to dibasic acid of 1:1.

[0012] The dibasic acid contains an aromatic ring structure.

[0013] Further, the intermediate product III and the polyol are added at a molar ratio of carboxyl group to polyol of 1:1; and

[0014] The functionality of the polyol is ≥2.

[0015] The present invention also provides a plasticizer prepared by the above preparation method.

[0016] Another object of the present invention is to provide a method for preparing a cross-linking agent, comprising the following steps:

[0017] S21, coupling reaction of silica B with an aminosilane coupling agent to obtain an intermediate product 2I;

[0018] S22, subjecting the intermediate product 2I to a Michael addition reaction with a high temperature resistant acrylate monomer to obtain an intermediate product 2II; and

[0019] S23, the intermediate product 2II is subjected to Michael addition reaction with amino acid to obtain the target product 2, i.e., the cross-linking agent.

[0020] Further, the usage ratio of the silicon dioxide B to the aminosilane coupling agent is 1g:3.0-5.0g; and

[0021] The silicon dioxide B is nano-scale silicon dioxide.

[0022] Further,

[0023] The intermediate product 2I and the high temperature resistant acrylate monomer are added in a molar ratio of amino group to acryloxy group of 1:2-3; and

[0024] The functionality of the high temperature resistant acrylate monomer is 2-3.

[0025] Furthermore, the intermediate product 2II and the amino acid are added at a molar ratio of acryloyloxy to amino group of 1:1.

[0026] Another object of the present invention is to provide a cross-linking agent prepared by the above-mentioned preparation method.

[0027] Another object of the present invention is to provide a high temperature resistant release PVA release film for artificial stone, comprising the following raw materials in parts by weight:

[0028] 100 parts of PVA resin;

[0029] 20-30 parts of plasticizer;

[0030] 1.0-3.0 parts of cross-linking agent;

[0031] Antioxidant 0.3-0.5 parts;

[0032] Heat stabilizer 0.1-0.5 parts;

[0033] Surfactant 0.1-0.5 parts;

[0034] Lubricant 0.2-0.5 parts.

[0035] Furthermore, the surfactant is a non-ionic surfactant.

[0036] Another object of the present invention is to provide a method for preparing a high temperature resistant release PVA release film for artificial stone, comprising the following steps:

[0037] S31, mixing, extrusion, granulation, i.e.

[0038] Mix all the raw materials evenly according to the formula, add them into the extruder, plasticize, granulate and set aside;

[0039] S32, aging, blow molding, i.e.

[0040] After the pellets are sealed and aged, they are placed in the barrel of an extruder for feeding, extrusion, and film blowing; and

[0041] S33, post-processing and finalization, i.e.

[0042] The whole platform is pulled in, the product thickness and size are determined, the product is cooled, cut, shaped, packaged and put into storage, and the high temperature resistant release PVA demoulding film for artificial stone is obtained.

[0043] Beneficial effects of the present invention:

[0044] (1) The present invention provides a high temperature resistant release PVA demoulding film for artificial stone, wherein the formula system contains a self-made plasticizer, which is a hyperbranched small molecule polyol structure with nano-silicon dioxide as the core, containing a large number of ester groups, aromatic rings and a certain molecular chain length. First, the hydroxyl groups in the polyol structure can form new hydrogen bonds with the hydroxyl groups on the PVA molecular chain, inhibiting the crystallization of PVA, reducing the melting point, and having a good plasticizing effect; second, the hyperbranched structure has excellent dispersibility and better plasticizing properties; at the same time, since the multifunctional structure forms more sites, the precipitation in the product can be greatly reduced; third, the presence of the ester structure can also form hydrogen bonds with the hydroxyl groups in PVA, which can further disassemble the interaction between PVA molecules and further enhance the plasticizing effect; fourth, nano-silicon dioxide is an inorganic filler with excellent high temperature resistance, and the aromatic ring structure has excellent high temperature resistance. After effective dispersion, it can improve the high temperature resistance of the PVA film.

[0045] (2) The present invention provides a high temperature resistant release PVA demoulding film for artificial stone, the formula system contains a self-made cross-linking agent, which is a small molecular polyacid structure with nano-silicon dioxide as the core, a large number of ester groups, a high temperature resistant structure and a certain molecular chain length. First, the carboxyl group in the polyacid structure can react with the hydroxyl group on the PVA molecular chain to increase the cross-linking density, improve the mechanical properties and thermal properties; second, the hyperbranched structure has multiple functionalities, which can improve the cross-linking of the spatial network, and the performance improvement effect is obvious; and the structure has a certain molecular chain length, which can improve the toughness of the material; third, the ester group and other structures are conducive to the dispersibility of the cross-linking agent in the system; fourth, the nano-silicon dioxide and the high temperature resistant structure can further effectively improve the mechanical properties and thermal properties of the PVA film.

[0046] (3) The present invention provides a high temperature resistant release PVA mold release film for artificial stone. Through formula design, a plasticizer and a crosslinking agent are compounded for use. Since both are nano-silicon dioxide structures, they have a heterogeneous nucleation effect and have a positive effect on improving mechanical and thermal properties. In addition, the heat stabilizer is an alkaline substance and can be used as a catalyst for the reaction between the crosslinking agent and PVA to carry out esterification crosslinking.

[0047] (4) The present invention provides a high temperature resistant release PVA mold release film for artificial stone. By formula design and adding surfactant, the rapid bonding and peeling of the PVA film and artificial stone can be promoted, thereby improving production efficiency. In addition, the non-ionic type can avoid the alkaline effect of the heat stabilizer. DETAILED DESCRIPTION

[0048] The present invention is described in detail below with reference to the examples. However, it should be understood that the following examples are only illustrative of the embodiments of the present invention, and are not intended to limit the scope of the present invention.

[0049] The purpose of the present invention is to develop an environmentally friendly, safe and pollution-free high-temperature-resistant release PVA demoulding film for artificial stone. The idea of ​​realization is: since the plasticizer is one of the necessary raw materials for the processing of PVA materials, the mechanical properties of PVA are improved by making a low-migration, high-temperature-resistant plasticizer; at the same time, a high-temperature-resistant cross-linking agent is made. The theoretical basis of realization is: for the plasticizer, firstly, with nano-silicon dioxide as the center, epoxy silane coupling reaction is carried out, then the high-temperature-resistant dibasic acid and epoxy are open-ringed, and finally the carboxyl group is capped with polyol to form a hyperbranched structure with nano-silicon as the center; for the cross-linking agent, firstly, with nano-silicon dioxide as the center, aminosilane coupling reaction is carried out, then the high-temperature-resistant acrylate monomer and amino group are subjected to Michael addition reaction, and finally the acrylate structure is capped with amino acid to form a hyperbranched structure with multiple carboxyl groups. So far, the plasticizer and cross-linking agent are prepared. First, due to the isotropy of the hyperbranched structure and the similarity of the molecular structure, it has excellent compatibility and low migration with PVA; and both the plasticizer and the crosslinking agent are high temperature resistant structures; second, through formula design, it is blended with a thermal stabilizer and a surfactant to further improve the mechanical properties and heat resistance, and at the same time can improve the demoulding and appearance. The embodiments of the present invention are as follows:

[0050] The embodiment of the present invention provides a method for preparing a plasticizer, comprising the following steps:

[0051] S11, place silica A in ethyl acetate A, ultrasonically disperse for 1 hour, add epoxy silane coupling agent and deionized water A, slowly heat to 60-80°C, heat and stir for 6-14 hours. After the reaction is completed, cool to room temperature, filter, wash with ethyl acetate B, and vacuum dry at 40°C to constant weight to obtain the target product, i.e., intermediate product 1I.

[0052] The usage ratio of the silicon dioxide A, ethyl acetate A, epoxy silane coupling agent, deionized water A, and ethyl acetate B is: 1.00 g: 50 mL: 4.0-6.0 g: 0.6 g: 200 mL.

[0053] The silicon dioxide A is nano-scale silicon dioxide with an average particle size of 50 nm, item number JL-SiO2-N50, purchased from Ningbo Jinlei Nanomaterial Technology Co., Ltd.

[0054] The epoxy silane coupling agent may be silane coupling agent KH560, silane coupling agent A1871, etc., and preferably silane coupling agent KH560.

[0055] S12, add the intermediate product 1I to N,N-dimethylformyl A, ultrasonicate, and add it dropwise to a reaction kettle containing a dibasic acid, a catalyst, and N,N-dimethylformyl B through a peristaltic pump, stir at 100-105°C for 12-15h, cool to room temperature, distill under reduced pressure, and vacuum dry at 60°C for 6h to obtain the intermediate product 1II.

[0056] The intermediate product 1I and the dibasic acid are added at a molar ratio of epoxy group to dibasic acid of 1:1;

[0057] The dosage ratio of the N,N-dimethylformamide A, the dibasic acid, and the N,N-dimethylformamide B is 100mL:0.1mol:300mL;

[0058] The dibasic acid contains an aromatic ring structure and may be terephthalic acid, isophthalic acid, 5-methylisophthalic acid, 2,6-naphthalene dicarboxylic acid, anthracene-2,6-dicarboxylic acid, or the like.

[0059] The amount of the catalyst used is 0.4% of the total mass of the reactants;

[0060] The catalyst may be triphenylphosphine or the like.

[0061] S13, adding the intermediate product 1II to toluene A, ultrasonicating, and dripping into a reactor containing polyol, composite catalyst, and toluene B through a peristaltic pump, reacting and stirring at 160-170°C until the water quality is constant; cooling to room temperature, distilling under reduced pressure, and vacuum drying at 60°C for 6h to obtain the target product 1, i.e., plasticizer.

[0062] The intermediate product III and the polyol are added at a molar ratio of carboxyl group to polyol of 1:1;

[0063] The functionality of the polyol is ≥2, and may be propylene glycol, glycerol, triethanolamine, trimethylolpropane, pentaerythritol, or the like.

[0064] The composite catalyst is a mixture of stannous octoate and p-toluenesulfonic acid in a mass ratio of 2:1; the amount used is 0.4% of the total mass of the reactants.

[0065] The present invention also provides a method for preparing a cross-linking agent, comprising the following steps:

[0066] S21, add silica B and aminosilane coupling agent to alcohol solvent, ultrasonically oscillate for 0.5 h, stand at room temperature for 2 h, react at 50-80° C. for 2-10 h, filter, take insoluble matter, and dry at 60° C. for 12 h to obtain intermediate product 2I.

[0067] The usage ratio of the silicon dioxide B, the aminosilane coupling agent and the alcohol solvent is 1g:3.0-5.0g:80mL.

[0068] The silicon dioxide B is nano-scale silicon dioxide with an average particle size of 300 nm, item number JL-SiO2-Y300, purchased from Ningbo Jinlei Nanomaterial Technology Co., Ltd.

[0069] The aminosilane coupling agent may be KH901, KH902, KH540, KH550, KH602, or KH792, and preferably KH550.

[0070] The alcohol solvent may be anhydrous methanol, anhydrous ethanol, anhydrous isopropanol, etc., and anhydrous ethanol is preferred.

[0071] S22, add the intermediate product 2I to N,N-dimethylformyl C, ultrasonicate, and add it dropwise to a reaction kettle containing a high-temperature resistant acrylate monomer, triethylamine A, and N,N-dimethylformyl D through a peristaltic pump. Slowly add dropwise at room temperature and stir. After the addition is completed, continue stirring for 2-4 hours, filter, distill under reduced pressure, and dry in a vacuum at 40°C for 8 hours to obtain the intermediate product 2II.

[0072] The intermediate product 2I and the high temperature resistant acrylate monomer are added in a molar ratio of amino group to acryloxy group of 1:2-3;

[0073] The dosage ratio of the N,N-dimethylformamide C, the high temperature resistant acrylate monomer, and the N,N-dimethylformamide D is 100mL: 0.1mol: 300mL;

[0074] The amount of triethylamine A used is 1wt% of the total mass of the reactants.

[0075] The functionality of the high temperature resistant acrylate monomer is 2-3. The high temperature resistant acrylate monomer is an acrylate monomer with a relatively high Tg (>200°C), and the structure usually contains a heterocyclic or polycyclic structure, and may be tricyclodecane dimethanol diacrylate or tris(2-hydroxyethyl)isocyanuric acid triacrylate, etc.

[0076] S23, add the intermediate product 2II, amino acid, and triethylamine B to N,N-dimethylformamide E, stir at 30-50°C for 2-6 hours, filter, distill under reduced pressure, add deionized water B for washing, filter, take the insoluble matter, and dry it in vacuo at 40°C for 8 hours to obtain the target product 2, i.e., the cross-linking agent.

[0077] The intermediate product 2II and the amino acid are added at a molar ratio of acryloyloxy to amino group of 1:1;

[0078] The amino acid and triethylamine B are added in a molar ratio of carboxyl to triethylamine of 1:1;

[0079] The usage ratio of the amino acid, N,N-dimethylformyl E and deionized water B is 0.1 mol: 300 mL: 200 mL.

[0080] The amino acid is a neutral amino acid or an acidic amino acid;

[0081] The neutral amino acid can be glycine, alanine, cysteine, threonine or serine;

[0082] The acidic amino acid may be aspartic acid or glutamic acid.

[0083] The embodiment of the present invention further provides a high temperature resistant release PVA release film for artificial stone, comprising the following raw materials in parts by weight:

[0084] 100 parts of PVA resin;

[0085] 20-30 parts of plasticizer;

[0086] 1.0-3.0 parts of cross-linking agent;

[0087] Antioxidant 0.3-0.5 parts;

[0088] Heat stabilizer 0.1-0.5 parts;

[0089] Surfactant 0.1-0.5 parts;

[0090] Lubricant 0.2-0.5 parts.

[0091] The degree of polymerization of the PVA resin is 1700-2400. When the degree of polymerization is greater than 2400, the processing difficulty increases; when the degree of polymerization is less than 1700, the mechanical properties of the material are poor; the degree of alcoholysis is 88-99%, and when the alcoholysis degree is too low, the mechanical properties of the material are low. The PVA resin can be PVA1750, PVA1778, PVA1788 or PVA1798, etc.; and the PVA resin described in the following embodiments of the present invention is PVA1798.

[0092] The antioxidant is a hindered phenol antioxidant; and the antioxidant described in the following embodiments of the present invention is antioxidant 1076.

[0093] The heat stabilizer is sodium hydroxide and sodium oxalate in a mass ratio of 1:0.3-3.0.

[0094] The surfactant is a nonionic surfactant, which can be an alkyl phenyl ether type such as polyoxyethylene octyl phenyl ether; an alkyl ester type such as polyoxyethylene laurate; an alkyl amine type such as polyoxyethylene lauryl amino ether; an alkyl amide type such as polyoxyethylene lauric acid amide; a polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; an alkanolamide type such as lauric acid diethanolamide and oleic acid diethanolamide; an allyl phenyl ether type such as polyoxyalkylene allyl phenyl ether, etc.; and the surfactant described in the following embodiments of the present invention is lauric acid diethanolamide.

[0095] The lubricant is one of polyethylene wax, stearic acid, zinc stearate, oxidized polyethylene wax, paraffin, polyamide wax or stearic acid amide; and, the lubricant in the following embodiments of the present invention is oxidized polyethylene wax.

[0096] The embodiment of the present invention also provides a method for preparing a high temperature resistant release PVA release film for artificial stone, comprising the following steps:

[0097] S31, mixing, extrusion, granulation, i.e.

[0098] Add all raw materials into the mixer according to the formula, stir at 60℃ for 20min to mix evenly, add into the granulator, plasticize, granulate and set aside;

[0099] The temperature of each zone of the granulator is 100-190°C, and the screw speed is 40-100rpm.

[0100] S32, aging, blow molding, i.e.

[0101] After the pellets are sealed and aged for 30-50 hours, they are placed in the barrel of the film blowing machine for feeding, extrusion, and film blowing;

[0102] The temperature of each zone of the film blowing machine is 150-210° C., the die head temperature is 190-200° C., the aspect ratio L / D is 40, the screw speed is 20-50 rpm, and the film blowing frequency is 1.5.

[0103] S33, post-processing and finalization, i.e.

[0104] Enter the whole platform for traction, determine the product thickness and size, cool, cut, shape, package and store, and obtain the high temperature resistant release PVA release film for artificial stone;

[0105] The thickness of the release film is 30-40μm, and the width is 1800-3000mm; the thickness can be 30μm, 32μm, 35μm, 38μm, 40μm, or a range value consisting of any two values; the width can be 1800mm, 2000mm, 2100mm, 2200mm, 2400mm, 2500mm, 2600mm, 2800mm, 3000mm, or a range value consisting of any two values.

[0106] In order to further understand the present invention, a high temperature resistant release PVA release film for artificial stone provided by the present invention is described in detail below in conjunction with specific embodiments, and the protection scope of the present invention is not limited by the following embodiments.

[0107] A method for preparing a plasticizer comprises the following steps:

[0108] S11, silica A is placed in ethyl acetate A, and after ultrasonic dispersion for 1 hour, silane coupling agent KH560 and deionized water A are added, and the temperature is slowly raised to 70°C, and heated and stirred for 9 hours. After the reaction is completed, it is cooled to room temperature, filtered, washed with ethyl acetate B, and vacuum dried at 40°C to constant weight to obtain the target product, i.e., intermediate product 1I.

[0109] The usage ratio of the silicon dioxide A, ethyl acetate A, silane coupling agent KH560, deionized water A, and ethyl acetate B is: 1.00 g: 50 mL: 5.0 g: 0.6 g: 200 mL.

[0110] Its infrared data is as follows: 3378cm -1 :-OH exists and weakens; 1265cm -1 、938cm -1 、801cm -1 : Epoxy groups are present; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0111] S12, add the intermediate product 1I to N,N-dimethylformyl A, ultrasonicate, and add it dropwise to a reaction kettle containing terephthalic acid, triphenylphosphine, and N,N-dimethylformyl B through a peristaltic pump, stir at 105°C for 12 hours, cool to room temperature, distill under reduced pressure, and vacuum dry at 60°C for 6 hours to obtain the intermediate product 1II.

[0112] The intermediate product 1I and terephthalic acid are added in a molar ratio of epoxy group to terephthalic acid of 1:1;

[0113] The dosage ratio of the N,N-dimethylformamide A, terephthalic acid and N,N-dimethylformamide B is 100 mL: 0.1 mol: 300 mL.

[0114] The amount of triphenylphosphine used is 0.4% of the total mass of the reactants.

[0115] Its infrared data are as follows: 3382cm -1 :-OH exists and is significantly enhanced; 1760cm -1 :-C=O (carboxyl) exists; 1735cm -1 :-C=O (ester group) exists; 3011cm -1 、1595cm -1 、1498cm -1 : benzene ring exists; 1265cm -1 、938cm -1 、801cm -1 :Epoxy group does not exist; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0116] S13, adding the intermediate product 1II to toluene A, ultrasonicating, and dripping into a reactor containing trimethylolpropane, a composite catalyst, and toluene B through a peristaltic pump, reacting and stirring at 165°C until the water quality is constant; cooling to room temperature, distilling under reduced pressure, and vacuum drying at 60°C for 6h to obtain the target product 1, i.e., a plasticizer.

[0117] The intermediate product III and trimethylolpropane are added at a molar ratio of carboxyl to trimethylolpropane of 1:1;

[0118] The composite catalyst is a mixture of stannous octoate and p-toluenesulfonic acid in a mass ratio of 2:1; the amount used is 0.4% of the total mass of the reactants.

[0119] Its infrared data are as follows: 3382cm -1 :-OH exists and is significantly enhanced; 1760cm -1 :-C=O (carboxyl) does not exist; 1735cm -1 :-C=O (ester group) exists and is enhanced; 3011cm -1 、1595cm -1 、1498cm -1 : benzene ring exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0120] A method for preparing a cross-linking agent comprises the following steps:

[0121] S21, add silica B and silane coupling agent KH550 to anhydrous ethanol, ultrasonically oscillate for 0.5 h, stand at room temperature for 2 h, react at 60°C for 5 h, filter, take the insoluble matter, and dry at 60°C for 12 h to obtain the intermediate product 2I.

[0122] The usage ratio of the silicon dioxide B, the silane coupling agent KH550 and the anhydrous ethanol is 1 g:4.0 g:80 mL.

[0123] Its infrared data is as follows: 3378cm -1 :-OH exists and weakens; 1560 cm -1 : -NH sharp peak exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0124] S22, add the intermediate product 2I to N,N-dimethylformyl C, ultrasonicate, and add it dropwise to the reaction kettle containing tricyclodecane dimethanol diacrylate, triethylamine A, and N,N-dimethylformyl D through a peristaltic pump, slowly dropwise add at room temperature, and stir. After the addition is completed, continue stirring for 3 hours, filter, distill under reduced pressure, and dry in vacuo at 40°C for 8 hours to obtain the intermediate product 2II.

[0125] The intermediate product 2I and tricyclodecane dimethanol diacrylate are added in a molar ratio of amino group to acryloyloxy group of 1:2;

[0126] The dosage ratio of the N,N-dimethylformamide C, tricyclodecane dimethanol diacrylate, and N,N-dimethylformamide D is 100mL: 0.1mol: 300mL;

[0127] The amount of triethylamine A used is 1wt% of the total mass of the reactants.

[0128] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists and weakens; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0129] S23, add the intermediate product 2II, glutamic acid and triethylamine B to N,N-dimethylformamide E, stir at 40°C for 4.5 hours, filter, distill under reduced pressure, add deionized water B for washing, filter, take the insoluble matter, and dry it in vacuo at 40°C for 8 hours to obtain the target product 2, i.e., the cross-linking agent.

[0130] The intermediate product 2II and glutamic acid are added in a molar ratio of acryloyloxy to amino of 1:1;

[0131] The glutamic acid and triethylamine B are added in a molar ratio of carboxyl to triethylamine of 1:1;

[0132] The usage ratio of the glutamic acid, N,N-dimethylformyl E and deionized water B is 0.1 mol: 300 mL: 200 mL.

[0133] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists; 1760cm -1 :-C=O (carboxyl) exists; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- does not exist; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0134] A high temperature resistant release PVA demoulding film for artificial stone, comprising the following raw materials in parts by weight:

[0135] 100 parts of PVA resin;

[0136] 25 parts of plasticizer;

[0137] 2.0 parts of cross-linking agent;

[0138] 0.4 parts of antioxidant;

[0139] 0.4 parts of heat stabilizer;

[0140] 0.4 parts of surfactant;

[0141] 0.35 parts of lubricant.

[0142] The heat stabilizer is sodium hydroxide and sodium oxalate in a mass ratio of 1:1.

[0143] A method for preparing a high temperature resistant release PVA release film for artificial stone, comprising the following steps:

[0144] S31, mixing, extrusion, granulation, i.e.

[0145] Add all raw materials into the mixer according to the formula, stir at 60℃ for 20min to mix evenly, add into the granulator, plasticize, granulate and set aside;

[0146] The temperature of each zone of the granulator is 110°C (zone 1), 140°C (zone 2), 165°C (zone 3), 180°C (zone 4), 190°C (zone 5), 182°C (zone 6), and the screw speed is 80rpm.

[0147] S32, aging, blow molding, i.e.

[0148] After the pellets are sealed and aged for 35 hours, they are placed in the barrel of a film blowing machine for feeding, extrusion, and film blowing;

[0149] The temperatures of each zone of the film blowing machine are 160°C (zone 1), 180°C (zone 2), 195°C (zone 3), 210°C (zone 4), and 200°C (zone 5), the die head temperature is 195°C, the aspect ratio L / D is 40, the screw speed is 30rpm, and the film blowing frequency is 1.5.

[0150] S33, post-processing and finalization, i.e.

[0151] Enter the whole platform for traction, determine the product thickness and size, cool, cut, shape, package and store, and obtain the high temperature resistant release PVA release film for artificial stone;

[0152] The release film has a thickness of 30 μm and a width of 1800 mm.

[0153] The rest is the same as in Example 1, except that:

[0154] A method for preparing a plasticizer comprises the following steps:

[0155] S11, silica A is placed in ethyl acetate A, and after ultrasonic dispersion for 1 hour, silane coupling agent KH560 and deionized water A are added, and the temperature is slowly raised to 60°C, and heated and stirred for 14 hours. After the reaction is completed, it is cooled to room temperature, filtered, washed with ethyl acetate B, and vacuum dried at 40°C to constant weight to obtain the target product, i.e., intermediate product 1I.

[0156] The usage ratio of the silicon dioxide A, ethyl acetate A, silane coupling agent KH560, deionized water A, and ethyl acetate B is: 1.00 g: 50 mL: 6.0 g: 0.6 g: 200 mL.

[0157] Its infrared data is as follows: 3378cm -1 :-OH exists and weakens; 1265cm -1 、938cm -1 、801cm -1 : Epoxy groups are present; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0158] S12, add the intermediate product 1I to N,N-dimethylformyl A, ultrasonicate, and add it dropwise to a reactor containing terephthalic acid, triphenylphosphine, and N,N-dimethylformyl B through a peristaltic pump, stir at 100°C for 15 hours, cool to room temperature, distill under reduced pressure, and vacuum dry at 60°C for 6 hours to obtain the intermediate product 1II.

[0159] The intermediate product 1I and terephthalic acid are added in a molar ratio of epoxy group to terephthalic acid of 1:1;

[0160] The dosage ratio of the N,N-dimethylformamide A, terephthalic acid and N,N-dimethylformamide B is 100 mL: 0.1 mol: 300 mL.

[0161] The amount of triphenylphosphine used is 0.4% of the total mass of the reactants.

[0162] Its infrared data are as follows: 3382cm -1 :-OH exists and is significantly enhanced; 1760cm -1 :-C=O (carboxyl) exists; 1735cm -1 :-C=O (ester group) exists; 3011cm -1 、1595cm -1 、1498cm -1 : benzene ring exists; 1265cm -1 、938cm -1 、801cm -1 :Epoxy group does not exist; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0163] S13, adding the intermediate product 1II to toluene A, ultrasonicating, and dripping into a reactor containing propylene glycol, a composite catalyst, and toluene B through a peristaltic pump, reacting and stirring at 170°C until the water quality is constant; cooling to room temperature, distilling under reduced pressure, and vacuum drying at 60°C for 6h to obtain the target product 1, i.e., a plasticizer.

[0164] The intermediate product III and propylene glycol are added at a molar ratio of carboxyl to propylene glycol of 1:1;

[0165] The composite catalyst is a mixture of stannous octoate and p-toluenesulfonic acid in a mass ratio of 2:1; the amount used is 0.4% of the total mass of the reactants.

[0166] Its infrared data are as follows: 3382cm -1 :-OH exists and is significantly enhanced; 1760cm -1 :-C=O (carboxyl) does not exist; 1735cm -1:-C=O (ester group) exists and is enhanced; 3011cm -1 、1595cm -1 、1498cm -1 : benzene ring exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0167] A method for preparing a cross-linking agent comprises the following steps:

[0168] S21, add silica B and silane coupling agent KH550 to anhydrous ethanol, ultrasonically oscillate for 0.5 h, stand at room temperature for 2 h, react at 80°C for 2 h, filter, take the insoluble matter, and dry at 60°C for 12 h to obtain the intermediate product 2I.

[0169] The usage ratio of the silicon dioxide B, the silane coupling agent KH550 and the anhydrous ethanol is 1 g:4.0 g:80 mL.

[0170] Its infrared data is as follows: 3378cm -1 :-OH exists and weakens; 1560 cm -1 : -NH sharp peak exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0171] S22, add the intermediate product 2I to N,N-dimethylformyl C, ultrasonicate, and add it dropwise to the reaction kettle containing tricyclodecane dimethanol diacrylate, triethylamine A, and N,N-dimethylformyl D through a peristaltic pump, slowly dropwise add at room temperature, and stir. After the addition is completed, continue stirring for 3 hours, filter, distill under reduced pressure, and dry in vacuo at 40°C for 8 hours to obtain the intermediate product 2II.

[0172] The intermediate product 2I and tricyclodecane dimethanol diacrylate are added in a molar ratio of amino group to acryloyloxy group of 1:2;

[0173] The dosage ratio of the N,N-dimethylformamide C, tricyclodecane dimethanol diacrylate, and N,N-dimethylformamide D is 100mL: 0.1mol: 300mL;

[0174] The amount of triethylamine A used is 1wt% of the total mass of the reactants.

[0175] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists and weakens; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm-1 :-C=C- exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0176] S23, add the intermediate product 2II, aspartic acid and triethylamine B to N,N-dimethylformyl E, stir at 40°C for 4.5 hours, filter, distill under reduced pressure, add deionized water B for washing, filter, take the insoluble matter, and dry it in vacuo at 40°C for 8 hours to obtain the target product 2, i.e., the cross-linking agent.

[0177] The intermediate product 2II and aspartic acid are added in a molar ratio of acryloyloxy to amino of 1:1;

[0178] The aspartic acid and triethylamine B are added in a molar ratio of carboxyl to triethylamine of 1:1;

[0179] The dosage ratio of aspartic acid, N,N-dimethylformyl E and deionized water B is 0.1 mol: 300 mL: 200 mL.

[0180] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists; 1760cm -1 :-C=O (carboxyl) exists; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- does not exist; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0181] The rest is the same as in Example 1, except that:

[0182] A method for preparing a plasticizer comprises the following steps:

[0183] S11, silica A is placed in ethyl acetate A, and after ultrasonic dispersion for 1 hour, silane coupling agent KH560 and deionized water A are added, and the temperature is slowly raised to 80°C, and heated and stirred for 6 hours. After the reaction is completed, it is cooled to room temperature, filtered, washed with ethyl acetate B, and vacuum dried at 40°C to constant weight to obtain the target product, i.e., intermediate product 1I.

[0184] The usage ratio of the silicon dioxide A, ethyl acetate A, silane coupling agent KH560, deionized water A, and ethyl acetate B is: 1.00 g: 50 mL: 4.0 g: 0.6 g: 200 mL.

[0185] Its infrared data is as follows: 3378cm-1 :-OH exists and weakens; 1265cm -1 、938cm -1 、801cm -1 : Epoxy groups are present; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0186] S12, add the intermediate product 1I to N,N-dimethylformyl A, ultrasonicate, and add it dropwise to a reactor containing terephthalic acid, triphenylphosphine, and N,N-dimethylformyl B through a peristaltic pump, stir at 105°C for 14 hours, cool to room temperature, distill under reduced pressure, and vacuum dry at 60°C for 6 hours to obtain the intermediate product 1II.

[0187] The intermediate product 1I and terephthalic acid are added in a molar ratio of epoxy group to terephthalic acid of 1:1;

[0188] The dosage ratio of the N,N-dimethylformamide A, terephthalic acid, and N,N-dimethylformamide B is 100mL:0.1mol:300mL;

[0189] The amount of triphenylphosphine used is 0.4% of the total mass of the reactants.

[0190] Its infrared data are as follows: 3382cm -1 :-OH exists and is significantly enhanced; 1760cm -1 :-C=O (carboxyl) exists; 1735cm -1 :-C=O (ester group) exists; 3011cm -1 、1595cm -1 、1498cm -1 : benzene ring exists; 1265cm -1 、938cm -1 、801cm -1 :Epoxy group does not exist; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0191] S13, adding the intermediate product 1II to toluene A, ultrasonicating, and dripping into a reactor containing pentaerythritol, a composite catalyst, and toluene B through a peristaltic pump, reacting and stirring at 160°C until the water quality is constant; cooling to room temperature, distilling under reduced pressure, and vacuum drying at 60°C for 6h to obtain the target product 1, i.e., a plasticizer.

[0192] The intermediate product III and pentaerythritol are added at a molar ratio of carboxyl to pentaerythritol of 1:1;

[0193] The composite catalyst is a mixture of stannous octoate and p-toluenesulfonic acid in a mass ratio of 2:1; the amount used is 0.4% of the total mass of the reactants.

[0194] Its infrared data are as follows: 3382cm -1 :-OH exists and is significantly enhanced; 1760cm -1 :-C=O (carboxyl) does not exist; 1735cm -1 :-C=O (ester group) exists and is enhanced; 3011cm -1 、1595cm -1 、1498cm -1 : benzene ring exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0195] A method for preparing a cross-linking agent comprises the following steps:

[0196] S21, add silica B and silane coupling agent KH550 to anhydrous ethanol, ultrasonically oscillate for 0.5 h, stand at room temperature for 2 h, react at 50°C for 10 h, filter, take the insoluble matter, and dry at 60°C for 12 h to obtain the intermediate product 2I.

[0197] The usage ratio of the silicon dioxide B, the silane coupling agent KH550 and the anhydrous ethanol is 1 g:4.0 g:80 mL.

[0198] Its infrared data is as follows: 3378cm -1 :-OH exists and weakens; 1560 cm -1 : -NH sharp peak exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0199] S22, add the intermediate product 2I to N,N-dimethylformyl C, ultrasonicate, and add it dropwise to the reaction kettle containing tricyclodecane dimethanol diacrylate, triethylamine A, and N,N-dimethylformyl D through a peristaltic pump, slowly dropwise add at room temperature, and stir. After the addition is completed, continue stirring for 3 hours, filter, distill under reduced pressure, and dry in vacuo at 40°C for 8 hours to obtain the intermediate product 2II.

[0200] The intermediate product 2I and tricyclodecane dimethanol diacrylate are added in a molar ratio of amino group to acryloyloxy group of 1:2;

[0201] The dosage ratio of the N,N-dimethylformamide C, tricyclodecane dimethanol diacrylate, and N,N-dimethylformamide D is 100mL: 0.1mol: 300mL;

[0202] The amount of triethylamine A used is 1wt% of the total mass of the reactants.

[0203] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists and weakens; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0204] S23, add the intermediate product 2II, aspartic acid and triethylamine B to N,N-dimethylformyl E, stir at 40°C for 4.5 hours, filter, distill under reduced pressure, add deionized water B for washing, filter, take the insoluble matter, and dry it in vacuo at 40°C for 8 hours to obtain the target product 2, i.e., the cross-linking agent.

[0205] The intermediate product 2II and aspartic acid are added in a molar ratio of acryloyloxy to amino of 1:1;

[0206] The aspartic acid and triethylamine B are added in a molar ratio of carboxyl to triethylamine of 1:1;

[0207] The dosage ratio of aspartic acid, N,N-dimethylformyl E and deionized water B is 0.1 mol: 300 mL: 200 mL.

[0208] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists; 1760cm -1 :-C=O (carboxyl) exists; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- does not exist; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0209] The rest is the same as in Example 1, except that:

[0210] The terephthalic acid is replaced by 2,6-naphthalene dicarboxylic acid.

[0211] The rest is the same as in Example 1, except that:

[0212] A method for preparing a cross-linking agent comprises the following steps:

[0213] S21, add silica B and silane coupling agent KH550 to anhydrous ethanol, ultrasonically oscillate for 0.5 h, stand at room temperature for 2 h, react at 60°C for 5 h, filter, take the insoluble matter, and dry at 60°C for 12 h to obtain the intermediate product 2I.

[0214] The usage ratio of the silicon dioxide B, the silane coupling agent KH550 and the anhydrous ethanol is 1 g:3.0 g:80 mL.

[0215] Its infrared data is as follows: 3378cm -1 :-OH exists and weakens; 1560 cm -1 : -NH sharp peak exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0216] S22, add the intermediate product 2I to N,N-dimethylformyl C, ultrasonicate, and add it dropwise into a reaction kettle containing tri(2-hydroxyethyl)isocyanurate triacrylate, triethylamine A, and N,N-dimethylformyl D through a peristaltic pump. Slowly add dropwise at room temperature and stir. After the addition is completed, continue stirring for 4 hours, filter, distill under reduced pressure, and dry in a vacuum at 40°C for 8 hours to obtain the intermediate product 2II.

[0217] The intermediate product 2I and tris(2-hydroxyethyl)isocyanuric acid triacrylate are added in a molar ratio of amino group to acryloxy group of 1:3;

[0218] The dosage ratio of the N,N-dimethylformamide C, tris(2-hydroxyethyl)isocyanuric acid triacrylate, and N,N-dimethylformamide D is 100mL:0.1mol:300mL;

[0219] The amount of triethylamine A used is 1wt% of the total mass of the reactants.

[0220] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists and weakens; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- exists; 1593 cm -1 、1462 cm -1 、1398 cm -1 : triazine ring exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0221] S23, add the intermediate product 2II, glutamic acid and triethylamine B to N,N-dimethylformamide E, stir at 50°C for 2h, filter, distill under reduced pressure, add deionized water B for washing, filter, take the insoluble matter, and dry it in vacuo at 40°C for 8h to obtain the target product 2, i.e., the cross-linking agent.

[0222] The intermediate product 2II and glutamic acid are added in a molar ratio of acryloyloxy to amino of 1:1;

[0223] The glutamic acid and triethylamine B are added in a molar ratio of carboxyl to triethylamine of 1:1;

[0224] The usage ratio of the glutamic acid, N,N-dimethylformyl E and deionized water B is 0.1 mol: 300 mL: 200 mL.

[0225] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists; 1760cm -1 :-C=O (carboxyl) exists; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- does not exist; 1593 cm -1 、1462 cm -1 、1398 cm -1 : triazine ring exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0226] The rest is the same as in Example 1, except that:

[0227] A method for preparing a cross-linking agent comprises the following steps:

[0228] S21, add silica B and silane coupling agent KH550 to anhydrous ethanol, ultrasonically oscillate for 0.5 h, stand at room temperature for 2 h, react at 60°C for 5 h, filter, take the insoluble matter, and dry at 60°C for 12 h to obtain the intermediate product 2I.

[0229] The usage ratio of the silicon dioxide B, the silane coupling agent KH550 and the anhydrous ethanol is 1 g:5.0 g:80 mL.

[0230] Its infrared data is as follows: 3378cm -1 :-OH exists and weakens; 1560 cm -1 : -NH sharp peak exists; 1109 cm -1 、801cm -1:-Si-O- exists.

[0231] S22, add the intermediate product 2I to N,N-dimethylformyl C, ultrasonicate, and add it dropwise to the reaction kettle containing tricyclodecane dimethanol diacrylate, triethylamine A, and N,N-dimethylformyl D through a peristaltic pump, slowly dropwise add at room temperature, and stir. After the addition is completed, continue stirring for 2 hours, filter, distill under reduced pressure, and dry in vacuo at 40°C for 8 hours to obtain the intermediate product 2II.

[0232] The intermediate product 2I and tricyclodecane dimethanol diacrylate are added in a molar ratio of amino group to acryloyloxy group of 1:2;

[0233] The dosage ratio of the N,N-dimethylformamide C, tricyclodecane dimethanol diacrylate, and N,N-dimethylformamide D is 100mL: 0.1mol: 300mL;

[0234] The amount of triethylamine A used is 1wt% of the total mass of the reactants.

[0235] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists and weakens; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- exists; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0236] S23, add the intermediate product 2II, glycine and triethylamine B to N,N-dimethylformamide E, stir at 30°C for 6 hours, filter, distill under reduced pressure, add deionized water B for washing, filter, take the insoluble matter, and dry it in vacuo at 40°C for 8 hours to obtain the target product 2, i.e., the cross-linking agent.

[0237] The intermediate product 2II and glycine are added in a molar ratio of acryloyloxy to amino of 1:1;

[0238] The glycine and triethylamine B are added in a molar ratio of carboxyl to triethylamine of 1:1;

[0239] The usage ratio of glycine, N,N-dimethylformyl E and deionized water B is 0.1 mol: 300 mL: 200 mL.

[0240] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists; 1760cm-1 :-C=O (carboxyl) exists; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- does not exist; 1109 cm -1 、801cm -1 :-Si-O- exists.

[0241] The rest is the same as in Example 1, except that:

[0242] The glutamic acid was replaced with glycine.

[0243] The rest is the same as in Example 1, except that:

[0244] A high temperature resistant release PVA demoulding film for artificial stone, comprising the following raw materials in parts by weight:

[0245] 100 parts of PVA resin;

[0246] 30 parts of plasticizer;

[0247] 1.0 part of cross-linking agent;

[0248] 0.5 parts of antioxidant;

[0249] 0.5 parts of heat stabilizer;

[0250] 0.1 part of surfactant;

[0251] 0.5 parts of lubricant.

[0252] The heat stabilizer is sodium hydroxide and sodium oxalate in a mass ratio of 1:3.0.

[0253] A method for preparing a high temperature resistant release PVA release film for artificial stone, comprising the following steps:

[0254] S31, mixing, extrusion, granulation, i.e.

[0255] Add all raw materials into the mixer according to the formula, stir at 60℃ for 20min to mix evenly, add into the granulator, plasticize, granulate and set aside;

[0256] The temperature of each zone of the granulator is 100°C (zone 1), 130°C (zone 2), 155°C (zone 3), 175°C (zone 4), 190°C (zone 5), 180°C (zone 6), and the screw speed is 100rpm.

[0257] S32, aging, blow molding, i.e.

[0258] After the pellets are sealed and aged for 30 hours, they are placed in the barrel of a film blowing machine for feeding, extrusion, and film blowing;

[0259] The temperatures of each zone of the film blowing machine are 150°C (zone 1), 170°C (zone 2), 185°C (zone 3), 200°C (zone 4), and 195°C (zone 5), the die head temperature is 190°C, the aspect ratio L / D is 40, the screw speed is 50rpm, and the film blowing frequency is 1.5.

[0260] S33, post-processing and finalization, i.e.

[0261] Enter the whole platform for traction, determine the product thickness and size, cool, cut, shape, package and store, and obtain the high temperature resistant release PVA release film for artificial stone;

[0262] The release film has a thickness of 30 μm and a width of 1800 mm.

[0263] The rest is the same as in Example 1, except that:

[0264] A high temperature resistant release PVA demoulding film for artificial stone, comprising the following raw materials in parts by weight:

[0265] 100 parts of PVA resin;

[0266] 20 parts of plasticizer;

[0267] 3.0 parts of cross-linking agent;

[0268] 0.3 parts of antioxidant;

[0269] Heat stabilizer 0.1 part;

[0270] 0.5 parts of surfactant;

[0271] 0.2 parts of lubricant.

[0272] The heat stabilizer is sodium hydroxide and sodium oxalate in a mass ratio of 1:0.3.

[0273] A method for preparing a high temperature resistant release PVA release film for artificial stone, comprising the following steps:

[0274] S31, mixing, extrusion, granulation, i.e.

[0275] Add all raw materials into the mixer according to the formula, stir at 60℃ for 20min to mix evenly, add into the granulator, plasticize, granulate and set aside;

[0276] The temperature of each zone of the granulator is 115°C (zone 1), 145°C (zone 2), 160°C (zone 3), 170°C (zone 4), 190°C (zone 5), 185°C (zone 6), and the screw speed is 40rpm.

[0277] S32, aging, blow molding, i.e.

[0278] After the pellets are sealed and aged for 50 hours, they are placed in the barrel of a film blowing machine for feeding, extrusion, and film blowing;

[0279] The temperatures of each zone of the film blowing machine are 160°C (zone 1), 180°C (zone 2), 195°C (zone 3), 210°C (zone 4), and 210°C (zone 5), the die head temperature is 200°C, the aspect ratio L / D is 40, the screw speed is 20rpm, and the film blowing frequency is 1.5.

[0280] S33, post-processing and finalization, i.e.

[0281] Enter the whole platform for traction, determine the product thickness and size, cool, cut, shape, package and store, and obtain the high temperature resistant release PVA release film for artificial stone;

[0282] The release film has a thickness of 30 μm and a width of 1800 mm.

[0283] The following comparative examples are compared with specific embodiment 1:

[0284] Comparative Example 1

[0285] The rest is the same as in Example 1, except that:

[0286] No plasticizer is added to the formula of the high-temperature resistant release PVA demoulding film for artificial stone.

[0287] Comparative Example 2

[0288] The rest is the same as in Example 1, except that:

[0289] The plasticizer was replaced with trimethylolpropane.

[0290] Comparative Example 3

[0291] The rest is the same as in Example 1, except that:

[0292] In a method for preparing a plasticizer, the terephthalic acid is replaced by suberic acid.

[0293] Comparative Example 4

[0294] The rest is the same as in Example 1, except that:

[0295] A method for preparing a plasticizer comprises the following steps:

[0296] S11, adding terephthalic acid to toluene A, stirring, and dripping into a reactor containing trimethylolpropane, a composite catalyst, and toluene B through a peristaltic pump, reacting and stirring at 165°C until the water quality is constant; cooling to room temperature, distilling under reduced pressure, and vacuum drying at 60°C for 6 hours to obtain the target product 1, i.e., a plasticizer.

[0297] The terephthalic acid and trimethylolpropane are added in a molar ratio of 1:1;

[0298] The composite catalyst is a mixture of stannous octoate and p-toluenesulfonic acid in a mass ratio of 2:1; the amount used is 0.4% of the total mass of the reactants.

[0299] Its infrared data are as follows: 3382cm -1 :-OH exists and weakens; 1760cm -1 :-C=O (carboxyl) does not exist; 1735cm -1 :-C=O (ester group) exists; 3011cm -1 、1595cm -1 、1498cm -1 : Benzene ring exists.

[0300] Comparative Example 5

[0301] The rest is the same as in Example 1, except that:

[0302] No cross-linking agent is added to the formula of the high-temperature resistant release PVA demoulding film for artificial stone.

[0303] Comparative Example 6

[0304] The rest is the same as in Example 1, except that:

[0305] In a method for preparing a cross-linking agent, the tricyclodecane dimethanol diacrylate is replaced with tripropylene glycol diacrylate.

[0306] Comparative Example 7

[0307] The rest is the same as in Example 1, except that:

[0308] A method for preparing a cross-linking agent comprises the following steps:

[0309] S21, tricyclodecane dimethanol diacrylate, glutamic acid, and triethylamine B are added to N,N-dimethylformamide E, stirred at 40°C for 4.5 hours, filtered, distilled under reduced pressure, and dried in vacuo at 40°C for 8 hours to obtain the target product 2, i.e., the cross-linking agent.

[0310] The tricyclodecane dimethanol diacrylate and glutamic acid are added in a molar ratio of acryloyloxy to amino of 1:1;

[0311] The glutamic acid and triethylamine B are added in a molar ratio of carboxyl to triethylamine of 1:1;

[0312] The usage ratio of the glutamic acid, N,N-dimethylformyl E and deionized water B is 0.1 mol: 300 mL: 200 mL.

[0313] Its infrared data are as follows: 3380cm -1 :-OH exists; 1560 cm -1 : -NH peak exists; 1760cm -1 :-C=O (carboxyl) exists; 1735cm -1 :-C=O (ester group) exists; 1606cm -1 、811cm -1 :-C=C- does not exist.

[0314] Comparative Example 8

[0315] The rest is the same as in Example 1, except that:

[0316] The preparation method of the plasticizer is the same as that of Comparative Example 4; and

[0317] The preparation method of the cross-linking agent is the same as that of Comparative Example 7.

[0318] Comparative Example 9

[0319] The rest is the same as in Example 1, except that:

[0320] No heat stabilizer is added to the formula of the high-temperature resistant release PVA demoulding film for artificial stone.

[0321] Comparative Example 10

[0322] The rest is the same as in Example 1, except that:

[0323] No surfactant is added to the formula of the high-temperature resistant release PVA demoulding film for artificial stone.

[0324] Comparative Example 11

[0325] The rest is the same as in Example 1, except that:

[0326] The surfactant lauric acid diethanolamide was replaced with sodium dodecylbenzene sulfonate.

[0327] The physical properties of the high temperature resistant release PVA release films for artificial stone prepared in the embodiments of the present invention and the comparative examples were measured respectively, and the results are shown in Table 1.

[0328] Table 1 Physical test performance of each embodiment

[0329] performance Example Appearance Mechanical properties Thermal properties Artificial stone surface wrinkles Water washability Tensile strength / MPa Elongation at break / % Tm / ℃ Td / ℃ Example 1 Uniform crystal-free 67.4 487 238.2 258.4 ○ yes Example 2 Uniform crystal-free 63.8 445 238.9 258.7 ○ yes Example 3 Uniform crystal-free 68.5 461 237.1 257.6 ○ yes Example 4 Uniform crystal-free 68.1 484 239.8 260.3 ○ yes Example 5 Uniform crystal-free 68.3 437 238.4 259.0 ○ yes Example 6 Uniform crystal-free 67.0 442 237.5 257.9 ○ yes Example 7 Uniform crystal-free 62.1 403 235.3 254.1 ○ yes Example 8 Uniform crystal-free 59.6 554 234.1 255.4 ◎ yes Example 9 Uniform crystal-free 74.8 396 231.4 260.2 ○ yes Comparative Example 1 Polycrystalline 161.2 45 242.1 259.5 ○ yes Comparative Example 2 Polycrystalline point, oily precipitation 42.4 355 192.2 215.6 ◎ yes Comparative Example 3 Uniform crystal-free 62.2 481 217.6 238.8 ◎ yes Comparative Example 4 Crystal point 48.7 330 198.7 221.4 ◎ yes Comparative Example 5 No crystal point, fog 50.5 354 191.0 215.2 ◎ yes Comparative Example 6 No crystal point 65.8 493 200.4 225.8 ◎ yes Comparative Example 7 No crystal point 62.1 432 196.6 224.0 ◎ yes Comparative Example 8 No crystal point 53.7 365 178.4 201.2 ● yes Comparative Example 9 No crystal point, yellow 63.0 449 191.5 213.1 ◎ yes Comparative Example 10 Uniform crystal-free 68.2 478 238.8 258.7 ● yes Comparative Example 11 Uniform crystal-free 67.1 485 232.2 253.4 ◎ yes

[0330] First, it can be concluded from Examples 1-9 in Table 1 that the high temperature resistant release PVA release film for artificial stone of the present invention has excellent mechanical properties, thermal properties, etc.

[0331] It can be observed from Example 1 and Comparative Examples 1-4 that the high temperature resistant release PVA release film for artificial stone in the present invention uses a homemade plasticizer, which has better mechanical properties, heat resistance and film appearance. It can be observed from the examples and Comparative Examples 1-2 that the homemade plasticizer in the present invention has excellent plasticization, and the hyperbranched structure and system have more hydrogen bonding points and lower mobility; it can be observed from Examples 3-4 that the homemade plasticizer in the present invention contains nano-silicon dioxide and a benzene ring structure, and also has excellent heat resistance.

[0332] It can be observed from Example 1 and Comparative Examples 5-7 that the high temperature resistant release PVA release film for artificial stone in the present invention uses a homemade cross-linking agent, which can effectively improve the mechanical properties and heat resistance through molecular structure design.

[0333] It can be observed from Example 1 and Comparative Example 8 that nano-silicon dioxide has excellent heat resistance; at the same time, it can effectively improve the mechanical properties of the film by serving as the center point of the hyperbranched structure.

[0334] It can be observed from Example 1 and Comparative Example 9 that, through formula design, the heat stabilizer promotes the dehydration cross-linking reaction of the PVA hydroxyl group and increases the cross-linking density, thereby having a positive effect on improving heat resistance and mechanical properties.

[0335] It can be observed from Example 1 and Comparative Examples 10-11 that, through formula design, the surfactant has excellent wettability to artificial stone, and has a positive effect on the rapid spreading of artificial stone material on the PVA film and reducing wrinkles; and the non-ionic type can avoid the influence of the alkalinity of the heat stabilizer compared to the anionic type, and has a more excellent effect.

[0336] In addition, there are many surface wrinkles in Comparative Examples 2-9, which may be caused by the poor heat resistance of the PVA film.

[0337] In summary, the high temperature resistant release PVA demoulding film for artificial stone of the present invention is formulated, uses homemade plasticizers and cross-linking agents, and is formed by granulation and film blowing. It has excellent mechanical strength, toughness and heat resistance, can maintain the integrity of the film at 230°C, and also has the advantages of low wrinkles and improved production efficiency.

[0338] The test method is as follows:

[0339] (1) Appearance: After being placed at 23°C and 45% RH for two days, the membrane block was held high and the uniformity of the membrane block was observed with the naked eye under natural light.

[0340] (2) Mechanical properties: Tested according to the method described in GB / T 1040.3-2006.

[0341] (3) Thermal properties / T m : Differential scanning calorimetry, heating rate 10℃ / min, N2 atmosphere.

[0342] (4) Thermal properties / T d :Thermogravimetric analysis, tested in N2 atmosphere; heating rate 10℃ / min; temperature range room temperature ~ 600℃.

[0343] (5) Artificial stone surface wrinkles: Visually check whether there are wrinkles on the surface. The presence of wrinkles is marked as follows: no wrinkles, marked as "○"; a small amount of wrinkles, marked as "◎"; a large amount of wrinkles, marked as "●".

[0344] (6) Water solubility: Take a 6cm*6cm PVA film and place it in 80℃ water and stir it to test whether it is water-soluble.

[0345] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A method for preparing a plasticizer, characterized in that: The following steps are involved: S11, coupling reaction of silicon dioxide A and epoxy silane coupling agent to obtain intermediate product 1I; S12, subjecting the intermediate product 1I to a ring-opening reaction with a dibasic acid in the presence of a catalyst to obtain an intermediate product 1II; and S13, the intermediate product 1II is esterified with a polyol to obtain the target product 1, ie, a plasticizer; The usage ratio of the silicon dioxide A to the epoxy silane coupling agent is 1g:4.0-6.0g; and The silicon dioxide A is nano-scale silicon dioxide; The intermediate product II and the dibasic acid are added in a molar ratio of epoxy group to dibasic acid of 1:1; and The dibasic acid is an aromatic ring structure; The intermediate product III and the polyol are added at a molar ratio of carboxyl group to polyol of 1:1; and The functionality of the polyol is ≥2.

2. A plasticizer, characterized in that Prepared by the preparation method of the plasticizer as claimed in claim 1.

3. A high temperature resistant release PVA release film for artificial stone, characterized in that: The invention comprises the following raw materials in parts by weight: 100 parts of PVA resin; 20-30 parts of plasticizer; 1.0-3.0 parts of cross-linking agent; Antioxidant 0.3-0.5 parts; Heat stabilizer 0.1-0.5 parts; Surfactant 0.1-0.5 parts; Lubricant 0.2-0.5 parts; The plasticizer is selected from the plasticizer as claimed in claim 2; The cross-linking agent is prepared as follows: S21, coupling reaction of silica B with an aminosilane coupling agent to obtain an intermediate product 2I; S22, subjecting the intermediate product 2I to a Michael addition reaction with a high temperature resistant acrylate monomer to obtain an intermediate product 2II; as well as S23, subjecting the intermediate product 2II to a Michael addition reaction with an amino acid to obtain a target product 2, i.e., a cross-linking agent; The usage ratio of the silicon dioxide B to the aminosilane coupling agent is 1g:3.0-5.0g; and The silicon dioxide B is nano-scale silicon dioxide; The intermediate product 2I and the high temperature resistant acrylate monomer are added in a molar ratio of amino group to acryloxy group of 1:2-3; and The functionality of the high temperature resistant acrylate monomer is 2-3; The intermediate product 2II and the amino acid are added in a molar ratio of acryloyloxy to amino group of 1:

1.

4. The high temperature resistant release PVA release film for artificial stone according to claim 3, characterized in that: The surfactant is a nonionic surfactant.

5. A method for preparing a high temperature resistant release PVA release film for artificial stone according to claim 3 or 4, characterized in that: The following steps are involved: S31, mixing, extrusion, granulation, i.e. Mix all the raw materials evenly according to the formula, add them into the extruder, plasticize, granulate and set aside; S32, aging, blow molding, i.e. After the pellets are sealed and aged, they are placed in the barrel of the extruder for feeding, extrusion, and film blowing; as well as S33, post-processing and finalization, i.e. The whole platform is pulled in, the product thickness and size are determined, the product is cooled, cut, shaped, packaged and put into storage, and the high temperature resistant release PVA demoulding film for artificial stone is obtained.