CN114044990A - High-strength polyvinyl chloride foam board and preparation method thereof - Google Patents
High-strength polyvinyl chloride foam board and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
Abstract
The application relates to the field of preparation of polyvinyl chloride foam boards, in particular to a high-strength polyvinyl chloride foam board and a preparation method thereof, and specifically discloses a high-strength polyvinyl chloride foam board which comprises the following raw materials in parts by weight: 70-80 parts of polyvinyl chloride, 60-80 parts of filler, 3-5 parts of stabilizer, 1.5-3 parts of foaming agent, 10-15 parts of foaming regulator, 1-1.5 parts of lubricant, 0.3-0.8 part of plasticizer and 0.1-0.2 part of brightener; the foaming agent comprises a white foaming agent and a yellow foaming agent; the white foaming agent is sodium bicarbonate; the yellow foaming agent is composed of 4,4' -oxybis-benzenesulfonyl hydrazide and azodicarbonamide according to the mass ratio of (3-4) to (1-2). The preparation method has the advantage of improving the impact strength of the prepared polyvinyl chloride foamed plate.
Description
Technical Field
The application relates to the field of preparation of polyvinyl chloride foam boards, in particular to a high-strength polyvinyl chloride foam board and a preparation method thereof.
Background
Polyvinyl chloride is a polymer formed by polymerizing a polyethylene monomer with initiators such as peroxide and azo compounds under the action of light and heat according to a free radical polymerization reaction mechanism; polyvinyl chloride is usually prepared into a polyvinyl chloride foam board for use, and the polyvinyl chloride foam board is usually used in the fields of interior decoration, engineering packaging, automobiles, transportation and the like because of the advantages of light weight, flame retardancy, corrosion resistance, moisture resistance, heat preservation, shock absorption, long service life, good strength, good environmental stress resistance and the like; the use of the polyvinyl chloride foam board conforms to the national advocated of replacing wood with plastic and replacing gold with plastic, and has profound significance in the aspect of saving energy.
With respect to the above-described related art, the inventors consider that: because the polyvinyl chloride foam board is subjected to foaming treatment, the interior of the polyvinyl chloride foam board is fully distributed with foam holes; the uniformity of the cell distribution has a great influence on the impact strength of the polyvinyl chloride foamed sheet.
Disclosure of Invention
In order to improve the impact strength of the prepared polyvinyl chloride foamed plate, the application provides a high-strength polyvinyl chloride foamed plate and a preparation method thereof
In a first aspect, the application provides a high strength polyvinyl chloride foam board, adopts following technical scheme:
a high-strength polyvinyl chloride foam board: the composite material comprises the following raw materials in parts by weight: 70-80 parts of polyvinyl chloride, 60-80 parts of filler, 3-5 parts of stabilizer, 1.5-3 parts of foaming agent, 10-15 parts of foaming regulator, 1-1.5 parts of lubricant, 0.3-0.8 part of plasticizer and 0.1-0.2 part of brightener; the foaming agent comprises a white foaming agent and a yellow foaming agent; the white foaming agent is sodium bicarbonate; the yellow foaming agent is composed of 4,4' -oxybis-benzenesulfonyl hydrazide and azodicarbonamide according to the mass ratio of (3-4) to (1-2).
By adopting the technical scheme, the white foaming agent and the yellow foaming agent are compounded to prepare the foaming agent; the 4,4' -oxo-diphenyl sulfonyl hydrazide in the yellow foaming agent has stable performance, the prepared foam cell structure is fine and uniform, and meanwhile, the decomposed product is non-toxic, odorless and does not pollute products; compared with 4,4' -oxo-bis-benzenesulfonylhydrazide, azodicarbonamide has the advantages of higher foaming rate, good elasticity of foamed cells, difficult breakage and difficult bubble crossing after foaming; however, the decomposition product of azodicarbonamide can affect the color of the product; compared with a yellow foaming agent, the sodium bicarbonate has lower required foaming temperature and is easy to decompose by heating, and simultaneously, the sodium bicarbonate can activate the 4,4' -oxybis-benzenesulfonyl hydrazide, reduce the decomposition temperature of the 4,4' -oxybis-benzenesulfonyl hydrazide and improve the foaming rate of the 4,4' -oxybis-benzenesulfonyl hydrazide; therefore, the foaming rate of the foaming agent and the fine density and uniformity of generated foam holes are improved through the combined action of the sodium bicarbonate, the 4,4' -oxybis-benzenesulfonylhydrazide and the azodicarbonamide, the generation of a foam string phenomenon is reduced, the pollution to the plate after foaming is reduced, and the impact strength of the polyvinyl chloride foamed plate is improved; 0.6 part of anti-aging agent and 0.6 part of flame retardant are also added in the scheme.
Preferably, the mass ratio of the white foaming agent to the yellow foaming agent in the foaming agent is (1-2) to (0.5-1).
By adopting the technical scheme, the mass ratio of the white foaming agent to the yellow foaming agent is adjusted, the yellow foaming agent composed of the 4,4' -oxybis-benzenesulfonyl hydrazide and the azodicarbonamide has better dispersibility in a polymer, but the decomposition temperature is higher than that of sodium bicarbonate of the white foaming agent, and a large amount of heat can be released in the decomposition process, so that the gas forming speed is higher, the gas forming amount is larger and is difficult to control when materials are melted in equipment, and a plurality of bubbles are easy to break and converge to form large bubbles due to limited internal space of the equipment; the compactness and uniformity of the inner foam pores of the prepared foaming plate are influenced, and the prepared product is easy to yellow; the white foaming agent can absorb heat in the decomposition process, the foaming rate of the white foaming agent is slow, and the gas forming amount in the material melting process is small; by adjusting the mass ratio of the white foaming agent to the yellow foaming agent, the white foaming agent can absorb the heat released by the decomposition of the yellow foaming agent in the decomposition process, so that the foaming rate and the foaming amount of the foaming agent in the material melting process are adjusted, the bubble convergence phenomenon is reduced, the uniformity of the inner bubbles of the prepared polyvinyl chloride foaming plate is improved, and the impact strength of the prepared polyvinyl chloride foaming plate is further improved.
Preferably, the filler consists of light calcium carbonate and heavy calcium carbonate according to the mass ratio of (2-3) to (1.4-1.6).
By adopting the technical scheme, the heavy calcium carbonate and the light calcium carbonate are mixed together to prepare the filler, the addition of the light calcium carbonate can improve the toughness of the prepared polyvinyl chloride foamed board, and the heavy calcium carbonate can improve the impact strength of the prepared polyvinyl chloride foamed board; meanwhile, due to the addition of the yellow foaming agent, the prepared polyvinyl chloride foaming board contains yellow light inside, and the light calcium carbonate contains blue light, so that the yellow light can be eliminated, the whiteness of the prepared polyvinyl chloride foaming board is improved, and the prepared polyvinyl chloride foaming board not only has better impact strength, but also improves the whiteness of a finished product by mixing the light calcium carbonate and the heavy calcium carbonate together.
Preferably, the filler is calcium carbonate with a particle size of 3-5 μm.
By adopting the technical scheme, the particle size of the filler is adjusted, because the filler can be used as a nucleating agent to adsorb foaming gas to form cell nuclei, when the particle size of the filler is too large, cells formed by the foaming gas are easy to be larger, and the fine density of the cells in the foaming plate is reduced; when the filler is too small, the filler is easy to agglomerate, so that the dispersibility of the filler in the foam board is poor, and the uniformity of the foam holes of the polyvinyl chloride foam board is influenced, therefore, the uniformity of the foam holes distributed in the polyvinyl chloride foam board is improved by adjusting the particle size of the filler, and the impact strength of the polyvinyl chloride foam board is further improved.
Preferably, the filler is subjected to modification treatment before use, and the modification treatment comprises the following steps:
1) mixing the filler with water, and then carrying out ultrasonic treatment to prepare a mixture;
2) adding an aluminum titanate coupling agent into the mixture prepared in the step 1), stirring for 1-2h, and drying to obtain the aluminum titanate coupling agent mixture, wherein the temperature of the mixture is 75-85 ℃; the mass ratio of the aluminum titanate coupling agent to the filler is (1.8-2.2): 100.
By adopting the technical scheme, the filler has stronger hydrophilic hydroxyl groups on the surface and is hydrophilic and oleophobic, so that the filler has poorer affinity with polyvinyl chloride, and meanwhile, due to the electrostatic action and the surface energy of the filler surface, aggregates are easily generated to influence the dispersion degree of the filler in the polyvinyl chloride foam board; the surface of calcium carbonate is modified by the aluminum titanate coupling agent, so that the dispersibility and compatibility of the filler in the polyvinyl chloride foam board are improved, the filling effect of the filler on the polyvinyl chloride foam board is better, and the impact strength of the prepared polyvinyl chloride foam board is improved; the mass ratio of the filler to water used depends on the actual situation, and the mass ratio of the filler to water used in step 1) of the present application is 1: 5.
Preferably, the lubricant consists of an internal lubricant and an external lubricant according to the mass ratio of (1-2) to (1.4-1.6).
By adopting the technical scheme, the external lubricant can increase the lubricity of the surface of the polyvinyl chloride in the processing process and reduce the damage to the polyvinyl chloride during processing and melting; the internal lubricant can reduce the friction force in the polyvinyl chloride, reduce the viscosity of the melt and improve the foaming uniformity of the foaming agent in the melt; by adjusting the mass ratio of the internal lubricant to the external lubricant, the processing performance of the polyvinyl chloride foam board is improved together, and the uniform compactness of inner foam holes of the polyvinyl chloride foam board is improved, so that the impact strength of the polyvinyl chloride foam board is improved.
Preferably, the internal lubricant is at least one of polyethylene wax and n-butyl stearate; the external lubricant consists of solid paraffin and calcium stearate according to the mass ratio of (3.4-3.6) to 1.
By adopting the technical scheme, the polyethylene wax and the n-butyl stearate both have good internal lubricating effect on the polyvinyl chloride foam board; the solid paraffin can be used as an external lubricant of polyvinyl chloride to improve the gloss of the surface of the polyvinyl chloride foaming plate, but the surface of the solid paraffin is provided with nonpolar straight-chain hydrocarbon, so that the wetting effect on the metal surface in the equipment is poor, and the polyvinyl chloride is easily adhered to the metal wall in the equipment; the calcium stearate contains two long-chain alkyl groups, the solubility of the calcium stearate with polyvinyl chloride is low, the long-chain alkyl groups can be randomly deformed and moved into the polyvinyl chloride chain section, and a lubricating film is formed on the surface of the polyvinyl chloride chain section, so that the polyvinyl chloride is not easily adhered to a metal wall in equipment; the processing performance of the polyvinyl chloride foam board is improved while the surface of the polyvinyl chloride foam board has good gloss through the combined action of the solid paraffin and the calcium stearate.
Preferably, the internal lubricant is composed of polyethylene wax and n-butyl stearate according to a mass ratio of (2-3): 1.
By adopting the technical scheme, the polyethylene wax contains very long nonpolar carbon chains, so that the affinity between the polyethylene wax and the polyvinyl chloride is poor, the bonding strength between a lubricating film formed by the polyethylene wax and the polyvinyl chloride is low, and the lubricating film is easy to damage under the action of high temperature and shearing force; the n-butyl stearate can be mutually complexed with the polyvinyl chloride to form a complexing system, so that a lubricating film formed by the polyethylene wax is more firmly fixed in the polyvinyl chloride; thereby further improving the lubricating effect of the internal lubricant on the interior of the polyvinyl chloride.
In a second aspect, the present application provides a method for preparing a high-strength polyvinyl chloride foam board, which adopts the following technical scheme:
the preparation method of the high-strength polyvinyl chloride foam board comprises the following steps:
s1, mixing materials: mixing polyvinyl chloride, a filling agent, a stabilizing agent, a foaming regulator, a lubricating agent, a plasticizer and a whitening agent to prepare a prepared material;
s2, high-speed kneading: kneading the prepared material prepared in the step S1 at a high speed, cooling and standing to prepare a re-processed material;
s3, forming: and (4) performing melt extrusion on the composite processing material prepared in the step S2 through a double-screw extruder to prepare an extruded material, and performing die pressing, cooling and forming to obtain the composite material.
By adopting the technical scheme, after polyvinyl chloride, a filling agent, a stabilizing agent, a foaming regulator, a lubricant, a plasticizer and a whitening agent are mixed together, the raw materials are subjected to high-speed kneading, and in the high-speed kneading process, the raw materials are mutually collided and rubbed, so that the raw materials are adsorbed on polyvinyl chloride molecules, and the mixing effect of the polyvinyl chloride and other raw materials is enhanced; and then, the polyvinyl chloride foamed plate is prepared by melt extrusion and compression molding, and the prepared polyvinyl chloride foamed plate has more uniform and fine foam hole distribution in the inner part by the foaming effect of the foaming agent in the melting process of the reprocessing material and the lubricating effect of the lubricating agent, so that the foam hole crossing phenomenon is reduced, and the impact strength of the prepared polyvinyl chloride foamed plate is improved.
In summary, the present application has the following beneficial effects:
the foaming agent is prepared by mixing a yellow foaming agent consisting of 4,4' -oxo-diphenyl sulfonyl hydrazide and azodicarbonamide and a white foaming agent consisting of sodium bicarbonate under the combined action of polyvinyl chloride, a filling agent, a stabilizer, a foaming agent, a foaming regulator, a lubricant, a plasticizer and a whitening agent, and the foaming rate is regulated under the combined action of the white foaming agent and the yellow foaming agent; the bubble breakage and the bubble string phenomenon in the foaming process are reduced, so that the bubble distribution generated inside the polyvinyl chloride foam board is more fine and uniform, and the impact strength of the prepared polyvinyl chloride foam board is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The polyvinyl chloride used in the application is injection molding type polyvinyl chloride granules; the melting temperature is 190 ℃;
the filler is formed by mixing light calcium carbonate and heavy calcium carbonate; the bulk density of the ground calcium carbonate used was 1g/cm3(ii) a The bulk density of the light calcium carbonate used was 0.6g/cm3；
The stabilizer is a stabilizer for a commercial polyvinyl chloride foam board, and the stabilizer used in the application is a calcium-zinc stabilizer with the purity of 99 percent; the foaming regulator is a commercial foaming regulator for polyvinyl chloride foam boards, and the foaming regulator is HF-90 foaming regulator produced by Shandong Hongfu chemical Co., Ltd, and has an apparent density of 0.45g/cm3；
The lubricant is formed by mixing an internal lubricant and an external lubricant; the internal lubricant is at least one of polyethylene wax and n-butyl stearate; the purity of the polyethylene wax is 99 percent; the CAS number of the used n-butyl stearate is 123-95-5;
the external lubricant is formed by mixing solid paraffin and calcium stearate; the solid paraffin is industrial-grade solid paraffin; the purity of the calcium stearate is 99 percent;
the plasticizer used in the method is oxidized polyethylene wax with the purity of 99 percent;
the whitening agent can be a whitening agent for a commercial polyvinyl chloride foam board; the brightener used in this application is a fluorescent brightener with a purity of 99.99%;
the anti-aging agent used in the application is n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; CAS number 2082-79-3;
the flame retardant used in the present application is decabromodiphenyl ether; CAS numbers 1163-19-5;
the aluminum titanate coupling agent used in the modification treatment of the filler is a commercially available aluminum titanate coupling agent, and the aluminum titanate coupling agent used in the modification treatment of the filler is an aluminum titanate coupling agent produced by Nanjing Quanxi chemical company Limited, and the purity of the aluminum titanate coupling agent is 99%.
Examples
Example 1
The application provides a preparation method of a high-strength polyvinyl chloride foam board, which comprises the following steps:
s1, mixing materials: taking 70kg of polyvinyl chloride, 60kg of filling agent, 3kg of stabilizer, 1.5kg of foaming agent, 10kg of foaming regulator, 1kg of lubricant, 0.3kg of plasticizer, 0.1kg of brightener, 0.6kg of age resister and 0.6kg of flame retardant, adding the materials into a stirring barrel with a stirring paddle, setting the stirring speed of the stirring paddle to be 40r/min, and mixing for 10min to obtain a prepared material; the foaming agent consists of a white foaming agent and a yellow foaming agent according to the mass ratio of 1: 1; the white foaming agent is sodium bicarbonate; the yellow foaming agent is composed of 4,4' -oxo-diphenyl sulfonyl hydrazide and azodicarbonamide according to the mass ratio of 3: 2; the filler consists of light calcium carbonate and heavy calcium carbonate according to the mass ratio of 2:1.5, and the particle size is 3 mu m; the stabilizer is calcium zinc stabilizer; the foaming regulator is HF-90 foaming regulator; the used lubricant consists of an internal lubricant and an external lubricant according to the mass ratio of 1: 1.5; the internal lubricant is polyethylene wax, and the external lubricant is composed of solid paraffin and calcium stearate according to the mass ratio of 3.5: 1; the plasticizer is oxidized polyethylene wax; the whitening agent is fluorescent whitening agent; the anti-aging agent is n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the flame retardant is decabromodiphenyl ether;
s2, high-speed kneading: kneading the prepared material prepared in the step S1 at a high speed, meshing for 30min, taking out, standing and cooling to prepare a re-processed material;
s3, forming: and (4) performing melt extrusion on the composite processing material prepared in the step S2 through a double-screw extruder to prepare an extruded material, feeding the extruded material into a mould for compression molding, and cooling and cutting to obtain the composite material.
Example 2
The application provides a preparation method of a high-strength polyvinyl chloride foam board, which comprises the following steps:
s1, mixing materials: adding 80kg of polyvinyl chloride, 80kg of filler, 5kg of stabilizer, 3kg of foaming agent, 15kg of foaming regulator, 1.5kg of lubricant, 0.8kg of plasticizer, 0.2kg of brightener, 0.6kg of anti-aging agent and 0.6kg of flame retardant into a stirring barrel with a stirring paddle, setting the stirring speed of the stirring paddle to be 40r/min, and mixing for 10min to obtain a prepared material; the foaming agent consists of a white foaming agent and a yellow foaming agent according to the mass ratio of 1: 1; the white foaming agent is sodium bicarbonate; the yellow foaming agent is composed of 4,4' -oxo-diphenyl sulfonyl hydrazide and azodicarbonamide according to the mass ratio of 3: 2; the filler consists of light calcium carbonate and heavy calcium carbonate according to the mass ratio of 2:1.5, and the particle size is 3 mu m; the stabilizer is calcium zinc stabilizer; the foaming regulator is HF-90 foaming regulator; the used lubricant consists of an internal lubricant and an external lubricant according to the mass ratio of 1: 1.5; the internal lubricant is polyethylene wax, and the external lubricant is composed of solid paraffin and calcium stearate according to the mass ratio of 3.5: 1; the plasticizer is oxidized polyethylene wax; the whitening agent is fluorescent whitening agent; the anti-aging agent is n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the flame retardant is decabromodiphenyl ether;
s2, high-speed kneading: kneading the prepared material prepared in the step S1 at a high speed, meshing for 30min, taking out, standing and cooling to prepare a re-processed material;
s3, forming: and (4) performing melt extrusion on the composite processing material prepared in the step S2 through a double-screw extruder to prepare an extruded material, feeding the extruded material into a mould for compression molding, and cooling and cutting to obtain the composite material.
Example 3
The application provides a preparation method of a high-strength polyvinyl chloride foam board, which comprises the following steps:
s1, mixing materials: adding 75kg of polyvinyl chloride, 75kg of filler, 3.5kg of stabilizer, 2.2kg of foaming agent, 12.5kg of foaming regulator, 1.2kg of lubricant, 0.5kg of plasticizer, 0.15kg of brightener, 0.6kg of anti-aging agent and 0.6kg of flame retardant into a stirring barrel with a stirring paddle, setting the stirring speed of the stirring paddle to be 40r/min, and mixing for 10min to obtain a prepared material; the foaming agent consists of a white foaming agent and a yellow foaming agent according to the mass ratio of 1: 1; the white foaming agent is sodium bicarbonate; the yellow foaming agent is composed of 4,4' -oxo-diphenyl sulfonyl hydrazide and azodicarbonamide according to the mass ratio of 3: 2; the filler consists of light calcium carbonate and heavy calcium carbonate according to the mass ratio of 2:1.5, and the particle size is 3 mu m; the stabilizer is calcium zinc stabilizer; the foaming regulator is HF-90 foaming regulator; the used lubricant consists of an internal lubricant and an external lubricant according to the mass ratio of 1: 1.5; the internal lubricant is polyethylene wax, and the external lubricant is composed of solid paraffin and calcium stearate according to the mass ratio of 3.5: 1; the plasticizer is oxidized polyethylene wax; the whitening agent is fluorescent whitening agent; the anti-aging agent is n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the flame retardant is decabromodiphenyl ether;
s2, high-speed kneading: kneading the prepared material prepared in the step S1 at a high speed, meshing for 30min, taking out, cooling and standing to prepare a reprocessing material;
s3, forming: and (4) performing melt extrusion on the composite processing material prepared in the step S2 through a double-screw extruder to prepare an extruded material, feeding the extruded material into a mould for compression molding, and cooling and cutting to obtain the composite material.
Example 4
The method for preparing a high-strength polyvinyl chloride foamed sheet of this example was different from that of example 3 in that the yellow foaming agent used was composed of 4,4' -oxybis-benzenesulfonylhydrazide and azodicarbonamide at a mass ratio of 4:1, and the rest was the same as in example 3.
Example 5
The preparation method of the high-strength polyvinyl chloride foamed sheet of the embodiment is different from that of the embodiment 3 in that; the yellow foaming agent used was composed of 4,4' -oxybis-benzenesulfonylhydrazide and azodicarbonamide at a mass ratio of 3.5:1.5, and the rest was the same as in example 3.
Example 6
The method for manufacturing the high-strength polyvinyl chloride foamed sheet of this example is different from that of example 5 in that the foaming agent used in step S1 is composed of a white foaming agent and a yellow foaming agent at a mass ratio of 2:0.5, and the rest is the same as that of example 5.
Example 7
The method for manufacturing the high-strength polyvinyl chloride foamed sheet of this example is different from that of example 5 in that the foaming agent used in step S1 is composed of a white foaming agent and a yellow foaming agent in a mass ratio of 1.5:0.7, and the rest is the same as that of example 5.
Example 8
The method for manufacturing the high strength polyvinyl chloride foamed sheet of this example was different from example 7 in that the filler used in step S1 had a particle size of 5 μm, and the rest was the same as in example 7.
Example 9
The method for manufacturing the high strength polyvinyl chloride foamed sheet of this example was different from example 7 in that the filler used in step S1 had a particle size of 4 μm, and the rest was the same as in example 7.
Example 10
The method for manufacturing the high-strength polyvinyl chloride foamed sheet of this example is different from that of example 9 in that the filler used in step S1 is composed of light calcium carbonate and heavy calcium carbonate in a mass ratio of 3:1.5, and the rest is the same as that of example 9.
Example 11
The method for manufacturing the high-strength polyvinyl chloride foamed sheet of this example was different from example 9 in that the filler used in step S1 was composed of light calcium carbonate and heavy calcium carbonate at a mass ratio of 2.5:1.5, and the rest was the same as in example 9.
Example 12
The application provides a preparation method of a high-strength polyvinyl chloride foam board, which comprises the following steps:
s1, taking a filling agent, wherein the filling agent consists of light calcium carbonate and heavy calcium carbonate according to a mass ratio of 2.5: 1.5; putting the filler and water into a stirring barrel with a stirring paddle together according to the mass ratio of 1:5, mixing by the stirring paddle, and then carrying out ultrasonic treatment for 1h to prepare a mixture; then adding the aluminum titanate coupling agent into the mixture, heating to 80 ℃, setting the stirring speed of a stirring paddle to be 40r/min, stirring for 2 hours at constant temperature, filtering and drying to obtain a modified filler; the mass ratio of the aluminum titanate coupling agent to the filler is 2: 100;
mixing materials: adding 75kg of polyvinyl chloride, 75kg of modified filler, 3.5kg of stabilizer, 2.2kg of foaming agent, 12.5kg of foaming regulator, 1.2kg of lubricant, 0.5kg of plasticizer, 0.15kg of brightener, 0.6kg of anti-aging agent and 0.6kg of flame retardant into a stirring barrel with a stirring paddle, setting the stirring speed of the stirring paddle to be 40r/min, and mixing for 10min to obtain a prepared material; the foaming agent consists of a white foaming agent and a yellow foaming agent according to the mass ratio of 1.5: 0.7; the white foaming agent is sodium bicarbonate; the yellow foaming agent is composed of 4,4' -oxo-bis-benzenesulfonyl hydrazide and azodicarbonamide according to the mass ratio of 3.5: 1.5; the stabilizer is calcium zinc stabilizer; the foaming regulator is HF-90 foaming regulator; the used lubricant consists of an internal lubricant and an external lubricant according to the mass ratio of 1: 1.5; the internal lubricant is polyethylene wax, and the external lubricant is solid paraffin and calcium stearate according to the mass ratio of 3.5: 1; the plasticizer is oxidized polyethylene wax; the whitening agent is fluorescent whitening agent; the anti-aging agent is n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the flame retardant is decabromodiphenyl ether;
s2, high-speed kneading: kneading the prepared material prepared in the step S1 at a high speed, meshing for 30min, taking out, cooling and standing to prepare a reprocessing material;
s3, forming: and (4) performing melt extrusion on the composite processing material prepared in the step S2 through a double-screw extruder to prepare an extruded material, feeding the extruded material into a mould for compression molding, and cooling and cutting to obtain the composite material.
Example 13
The method for manufacturing the high-strength polyvinyl chloride foamed sheet of this example is different from example 12 in that the lubricant used in step S1 consists of an internal lubricant and an external lubricant in a mass ratio of 1.5:1.5, and the rest is the same as in example 12.
Example 14
The method for manufacturing the high strength pvc foam board of this example is different from example 13 in that the internal lubricant used in step S1 is n-butyl stearate, and the rest is the same as in example 13.
Example 15
The method for manufacturing a high-strength polyvinyl chloride foamed sheet of this example is different from example 13 in that the internal lubricant used in step S1 consists of polyethylene wax and n-butyl stearate in a mass ratio of 2:1, and the rest is the same as in example 13.
Example 16
The preparation method of the high-strength polyvinyl chloride foamed sheet of the present example is different from that of example 13 in that the used lubricant consists of polyethylene wax and n-butyl stearate as internal lubricants in a mass ratio of 3:1, and the rest is the same as that of example 13.
Example 17
The method for manufacturing the high-strength polyvinyl chloride foamed sheet of this example is different from example 13 in that the lubricant used in step S1 is composed of polyethylene wax and n-butyl stearate as internal lubricants in a mass ratio of 2.5:1, and the rest is the same as that of example 13.
Comparative example
Comparative example 1
The method for preparing the high-strength polyvinyl chloride foamed sheet of this comparative example is different from that of example 1 in that the foaming agent used in step S1 is sodium bicarbonate, and the rest is the same as that of example 1.
Comparative example 2
The manufacturing method of the high strength polyvinyl chloride foamed sheet of this comparative example is different from that of example 1 in that the foaming agent used in step S1 is 4,4' -oxybis-benzenesulfonylhydrazide, and the rest is the same as that of example 1.
Comparative example 3
The method for preparing a high-strength polyvinyl chloride foamed sheet of this comparative example is different from that of example 1 in that the foaming agent used in step S1 is azodicarbonamide, and the rest is the same as that of example 1.
Detection method
High-strength polyvinyl chloride foamed sheets were prepared as samples according to the methods for preparing high-strength polyvinyl chloride foamed sheets of examples 1 to 17 and comparative examples 1 to 3, and the prepared samples were measured for their impact strength according to national standard GB11548-1989 "method for testing impact resistance of rigid plastic panels", and the measurement results are shown in Table 1:
TABLE 1 impact Strength test results of high-Strength polyvinyl chloride foamed sheets prepared in examples 1 to 17 and comparative examples 1 to 3
| Serial number | Impact strength (KJ/m)2) |
| Example 1 | 15.3 |
| Example 2 | 15.8 |
| Example 3 | 16.1 |
| Example 4 | 16.4 |
| Example 5 | 16.8 |
| Example 6 | 16.5 |
| Example 7 | 17.3 |
| Example 8 | 17.4 |
| Examples9 | 17.8 |
| Example 10 | 17.5 |
| Example 11 | 18.0 |
| Example 12 | 18.4 |
| Example 13 | 18.6 |
| Example 14 | 18.3 |
| Example 15 | 18.9 |
| Example 16 | 19.1 |
| Example 17 | 19.5 |
| Comparative example 1 | 13.4 |
| Comparative example 2 | 13.8 |
| Comparative example 3 | 12.9 |
As can be seen by combining examples 3 to 7 and comparative examples 1 to 3, and by combining Table 1, by composing the white foam and the yellow foam in a mass ratio of 1.5:0.7, meanwhile, the white foaming agent is sodium bicarbonate, and the yellow foaming agent is composed of 4,4' -oxo-diphenyl sulfonyl hydrazide and azodicarbonamide according to the mass ratio of 3.5:1.5, the yellow foaming agent is decomposed to release heat so as to accelerate the foaming rate of the polyvinyl chloride, meanwhile, the white foaming agent absorbs heat and activates the 4,4' -oxo-diphenyl sulfonyl hydrazide, so that the foam holes generated in the polyvinyl chloride foam board are finer and more uniform, through the combined action of the yellow foaming agent and the white foaming agent, the foaming speed of the polyvinyl chloride is improved, the fine density and the uniformity of generated foam holes are improved, the generation of foam crossing phenomenon is reduced, and the impact strength of the prepared polyvinyl chloride foamed plate is improved;
in combination with examples 9 to 11 and table 1, it can be seen that when the filler in the polyvinyl chloride foamed sheet is composed of light calcium carbonate and heavy calcium carbonate in a mass ratio of 2.5:1.5, the toughness of the prepared polyvinyl chloride foamed sheet can be improved due to the addition of the light calcium carbonate, and the strength of the prepared polyvinyl chloride foamed sheet can be improved due to the synergistic effect of the light calcium carbonate and the heavy calcium carbonate, so that the prepared polyvinyl chloride foamed sheet has good impact strength;
as can be seen by combining examples 12 to 17 with Table 1, when the lubricant used consists of an internal lubricant and an external lubricant at a mass ratio of 1.5:1.5, the internal lubricant used consists of polyethylene wax and n-butyl stearate at a mass ratio of 2.5: 1; the n-butyl stearate and the polyvinyl chloride are mutually complexed to form a complexing system, so that a lubricating film formed by the polyethylene wax is firmly fixed in the polyvinyl chloride, and the internal lubricating effect on the polyvinyl chloride is improved; when the external lubricant is composed of solid paraffin and calcium stearate according to the mass ratio of 3.5:1, a lubricating film can be formed on the surface of polyvinyl chloride through the matching of the solid paraffin and the calcium stearate, so that the polyvinyl chloride is not easily adhered to a metal wall inside equipment, the processing performance of the polyvinyl chloride foam board is improved, meanwhile, the uniformity of foam holes inside the foam board is improved through the internal lubricant, and the impact strength of the prepared polyvinyl chloride foam board is further improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. A high strength polyvinyl chloride foam board which characterized in that: the composite material comprises the following raw materials in parts by weight: 70-80 parts of polyvinyl chloride, 60-80 parts of filler, 3-5 parts of stabilizer, 1.5-3 parts of foaming agent, 10-15 parts of foaming regulator, 1-1.5 parts of lubricant, 0.3-0.8 part of plasticizer and 0.1-0.2 part of brightener; the foaming agent comprises a white foaming agent and a yellow foaming agent; the white foaming agent is sodium bicarbonate; the yellow foaming agent is composed of 4,4' -oxybis-benzenesulfonyl hydrazide and azodicarbonamide according to the mass ratio of (3-4) to (1-2).
2. The high strength polyvinyl chloride foamed sheet according to claim 1, wherein: the mass ratio of the white foaming agent to the yellow foaming agent is (1-2) to (0.5-1).
3. The high strength polyvinyl chloride foamed sheet according to claim 1, wherein: the filler consists of light calcium carbonate and heavy calcium carbonate according to the mass ratio of (2-3) to (1.4-1.6).
4. The high strength polyvinyl chloride foamed sheet according to claim 3, wherein: the particle size of the filler is 3-5 μm.
5. The high strength polyvinyl chloride foamed sheet according to claim 4, wherein: the filler is subjected to modification treatment before use, and the modification treatment comprises the following steps:
1) mixing the filler with water, and then carrying out ultrasonic treatment to prepare a mixture;
2) adding an aluminum titanate coupling agent into the mixture prepared in the step 1), stirring for 1-2h, and drying to obtain the aluminum titanate coupling agent mixture, wherein the temperature of the mixture is 75-85 ℃; the mass ratio of the aluminum titanate coupling agent to the filler is (1.8-2.2): 100.
6. The high strength polyvinyl chloride foamed sheet according to claim 5, wherein: the lubricant consists of an internal lubricant and an external lubricant according to the mass ratio of (1-2) to (1.4-1.6).
7. The high strength polyvinyl chloride foamed sheet according to claim 6, wherein: the internal lubricant is at least one of polyethylene wax and n-butyl stearate; the external lubricant consists of solid paraffin and calcium stearate according to the mass ratio of (3.4-3.6) to 1.
8. The high strength polyvinyl chloride foamed sheet according to claim 7, wherein: the internal lubricant consists of polyethylene wax and n-butyl stearate according to the mass ratio of (2-3) to 1.
9. The method for preparing a high-strength polyvinyl chloride foamed sheet according to any one of claims 1 to 8, wherein: the method comprises the following steps:
s1, mixing materials: mixing polyvinyl chloride, a filling agent, a stabilizing agent, a foaming regulator, a lubricating agent, a plasticizer and a whitening agent to prepare a prepared material;
s2, high-speed kneading: kneading the prepared material prepared in the step S1 at a high speed, cooling and standing to prepare a re-processed material;
s3, forming: and (4) performing melt extrusion on the composite processing material prepared in the step S2 through a double-screw extruder to prepare an extruded material, and performing die pressing, cooling and forming to obtain the composite material.
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