CN111704776A - PVC board shocks resistance - Google Patents
PVC board shocks resistance Download PDFInfo
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- CN111704776A CN111704776A CN202010726749.XA CN202010726749A CN111704776A CN 111704776 A CN111704776 A CN 111704776A CN 202010726749 A CN202010726749 A CN 202010726749A CN 111704776 A CN111704776 A CN 111704776A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to the technical field of high polymer materials, in particular to an impact-resistant PVC plate. The pure hard PVC product is crisp and has the notch impact strength of only 2.2kJ/m2And the material is easy to crack easily when being impacted, so that the use of the material as a structural material is limited. Based on the above problems, the present invention provides aThe impact resistant PVC board has material system added with self-made modified ACR impact modifier and modified ACR shell material with introduced small amount of SiO2The particles increase the surface roughness of the shell material to a certain extent, can play a role in stopping excessive development of silver lines in time, prevent destructive cracks from forming, achieve the aim of greatly improving the impact strength of the material, and have good commercial prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an impact-resistant PVC plate.
Background
Polyvinyl chloride (abbreviated as PVC) resin, together with polyethylene, polypropylene, polystyrene and ABS resin, is collectively called 5-size general-purpose resin, and PVC resin has excellent physical and chemical properties, mainly embodied in the following aspects: (1) the corrosion resistance is strong, and the chemical property is stable; (2) excellent flame retardancy and insulation resistance; (3) good plasticity, the PVC resin is thermoplastic resin, products meeting various requirements can be prepared by adopting various molding processing modes, and meanwhile, the PVC resin which is not crosslinked can be recycled, and (4) the PVC resin has excellent wear resistance, and the PVC products can be widely used as wear-resistant floors, wear-resistant pads, anticorrosive wear-resistant coatings and the like.
Although the PVC resin has good comprehensive performance, the impact resistance is poor in production and application, pure hard PVC products are brittle, and the notch impact strength is only 2.2kJ/m2The PVC is easy to brittle fracture when being impacted, so that the use of the PVC as a structural material is limited, and an impact modifier is generally required to be added in the processing and forming process to improve the impact resistance of the PVC.
The main function of the impact modifier is to improve the impact resistance of the plastic product and improve the plasticity and the easy processing property of the plastic product. The impact modifier commonly used at present comprises a plurality of categories such as acrylic ester copolymers (ACR) with a core-shell structure, Chlorinated Polyethylene (CPE), methyl methacrylate-butadiene-styrene copolymers (MBS), ethylene-vinyl acetate copolymers (EVA), acrylonitrile-butadiene-styrene copolymers (ABS) and the like. The ACR resin is a thermoplastic graft polymer obtained by polymerizing Methyl Methacrylate (MMA) and butyl acrylate through seed emulsion, has double functions of impact resistance modification and processing modification, is mainly used in hard and semi-hard polyvinyl chloride products, and is especially used in chemical building materials, such as profiles, pipe fittings, plates, foaming materials and the like. It can not only improve the shock resistance of PVC products, but also obviously improve the melt fluidity, thermal deformation, weather resistance, luster of the product surface and the like of the resin, and shows excellent comprehensive performance. At present, there are many production enterprises for producing ACR impact modifier in China, but the quality level of produced ACR is not high, the high quality requirement of chemical building materials cannot be met, the improvement of the impact resistance of PVC products is not very large, and ACR impact modifier with better performance also depends on import to a certain extent (Zhengninglai. PVC impact modifier and research thereof [ J ]. fine petrochemical engineering progress, 2007,8(001): 40-46.). Therefore, the impact resistance of ACR impact modifiers must be continuously improved in order to further improve the impact resistance of PVC articles.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: pureThe hard PVC product is brittle and has the notch impact strength of only 2.2kJ/m2And the material is easy to crack easily when being impacted, so that the use of the material as a structural material is limited.
The technical scheme adopted by the invention for solving the technical problems is as follows: the invention provides an impact-resistant PVC plate which comprises the following components in parts by weight:
specifically, the modified ACR is prepared according to the following method:
(1) preparation of KH570 modified nano-silica
Adding dried 1g of nano-silica into 100mL of aqueous solution containing 0.03gKH570, ultrasonically dispersing for 1h, stirring the dispersion liquid at 110 ℃ for 8h after dispersion is finished, filtering, washing the obtained product with toluene, performing soxhlet extraction after vacuum filtration, and drying the product obtained by soxhlet extraction at 50 ℃ for 12h to obtain KH570 modified nano-silica;
(2) preparation of SiO2-g-GMA
Adding 1gKH570 modified nano-silica into 150mL deionized water, and sequentially adding 1g sodium dodecyl benzene sulfonate, 5mLGMA (glycidyl methacrylate) and 0.02g polymerization inhibitor CuSO4·5H2O, obtaining mixed emulsion, ultrasonically dispersing the mixed emulsion for 1h, then placing the mixed emulsion into a closed oxygen-free nitrogen bottle, irradiating the mixed emulsion for 1h in a drill source irradiation chamber with the irradiation dose of 3kGy, and adding 0.5mL of CaCl with the mass fraction of 1% into the irradiated mixed emulsion2Demulsifying the solution, vacuum filtering with nanofiltration membrane to obtain product, grinding, wrapping with filter paper, extracting with toluene for 72 hr, and vacuum drying at 50 deg.C to constant weight to obtain SiO2-g-GMA；
(3) Preparation of modified ACR
200mL of deionized water, 0.2g of NaOH and 1g of SDS (sodium dodecyl sulfate) are placed in a reactor, stirred for 30min and heated to 75 ℃, and then 30g of BA and 5mL of aqueous solution containing 1.5g of KPS (potassium persulfate) are simultaneously addedDropwise adding the mixture into the reactor, dropwise adding the mixture for 1 hour, and reacting for 2 hours to obtain a polymer core; 1g of SiO was added2-g-GMA, after stirring and dispersing uniformly, simultaneously dripping 100g of MMA and 1g of KPS into a reactor, dripping for 1h, reacting for 1h, and after the reaction is finished, adding 14g of CaCl with the mass concentration of 2%2And (3) stirring the solution at a high speed, adding water and heating after the emulsion becomes viscous to obtain obvious fine sand-shaped particles, stopping heating, and drying a product obtained by filtering at 50 ℃ to obtain the modified ACR.
Specifically, the mass ratio of the modified ACR to the CPE is 2: 1.
Specifically, the particle size of the light calcium carbonate is 500-600 meshes.
Specifically, the phthalate plasticizer is DOP, BBP, DCP, DBP or DMP.
Specifically, the calcium zinc stabilizer is German bear brand MC90224 KA.
Specifically, the fatty alcohol-based lubricant is pentaerythritol or xylitol.
Specifically, the impact-resistant PVC plate is prepared according to the following steps:
(1) weighing the raw materials according to the formula of the base material;
(2) putting PVC and CPE into a mixer, stirring for 8-13min at the temperature of 128-135 ℃, then sequentially adding stearic acid, calcium stearate, calcium-zinc heat stabilizer, fatty alcohol lubricant, modified ACR impact modifier, phthalate plasticizer and light calcium carbonate, and stirring for 10min at the temperature of 78-83 ℃; and then cooling to room temperature, heating and plasticizing by an extruder, extruding a film base material in a plasticized state by a die, feeding the film base material into a film laminating calender to be coated with a texture layer and a wear-resistant layer, then trimming the formed plate by a trimming and cutting device, drawing the plate to a shearing machine by a tractor to cut the plate with required specification, and finally preparing the PVC plate.
The invention has the beneficial effects that:
(1) the invention adopts the self-made modified ACR to improve the shock resistance of the PVC plate, obtains obvious effect,
(2) in the invention, SiO with double bonds is added in the modified ACR shell2-g-GMA，SiO2Emulsion polymerization of-g-GMA with MMA, which is a shell material of modified ACR, and SiO2The particles are introduced into the shell of the modified ACR, according to the action mechanism of the impact modifier, when the material is stressed, a large amount of silver streaks are induced on the equatorial plane of the impact modifier particles, a shear band is induced, a large amount of impact energy is absorbed, the impact modifier can control the development of the silver streaks, the silver streaks are stopped in time and are not developed into destructive cracks, and the impact strength of the material is obviously improved2The particles increase the surface roughness of the shell material to a certain extent, can play a role in stopping excessive development of silver lines in time, prevent destructive cracks from forming and achieve the purpose of greatly improving the impact strength of the material.
(3) When a small amount of SiO is introduced into the modified ACR shell material2When the particles are used, the impact resistance of the material can be obviously improved, but SiO2The content of the particles cannot be excessive, otherwise, the impact modifier is influenced to form a considerable amount of silver lines and shear bands under the action of external force, and the aim of improving the impact resistance of the PVC material cannot be achieved.
Detailed Description
The present invention will now be described in further detail with reference to examples.
The light calcium carbonate used in the following examples and comparative examples of the present invention has a particle size of 500-600 mesh.
The phthalate plasticizer used in the following examples and comparative examples of the present invention was DOP, BBP, DCP, DBP or DMP.
The calcium zinc stabilizer used in the following examples and comparative examples of the present invention is german bear MC90224 KA.
The fatty alcohol-based lubricant used in the following examples and comparative examples of the present invention was pentaerythritol or xylitol.
The PVC used in the following examples and comparative examples of the present invention was PVC SG-5.
The modified ACR used in the following examples of the invention was prepared as follows:
(1) preparation of KH570 modified nano-silica
Adding dried 1g of nano-silica into 100mL of aqueous solution containing 0.03gKH570, ultrasonically dispersing for 1h, stirring the dispersion liquid at 110 ℃ for 8h after dispersion is finished, filtering, washing the obtained product with toluene, performing soxhlet extraction after vacuum filtration, and drying the product obtained by soxhlet extraction at 50 ℃ for 12h to obtain KH570 modified nano-silica;
(2) preparation of SiO2-g-GMA
Adding 1gKH570 modified nano-silicon dioxide into 150mL deionized water, and then sequentially adding 1g sodium dodecyl benzene sulfonate, 5mLGMA and 0.02g polymerization inhibitor CuSO4·5H2O, obtaining mixed emulsion, ultrasonically dispersing the mixed emulsion for 1h, then placing the mixed emulsion into a closed oxygen-free nitrogen bottle, irradiating the mixed emulsion for 1h in a drill source irradiation chamber with the irradiation dose of 3kGy, and adding 0.5mL of CaCl with the mass fraction of 1% into the irradiated mixed emulsion2Demulsifying the solution, vacuum filtering with nanofiltration membrane to obtain product, grinding, wrapping with filter paper, extracting with toluene for 72 hr, and vacuum drying at 50 deg.C to constant weight to obtain SiO2-g-GMA；
(3) Preparation of modified ACR
Putting 200mL of deionized water, 0.2g of NaOH and 1g of SDS into a reactor, stirring for 30min, heating to 75 ℃, simultaneously dripping 30g of BA and 5mL of aqueous solution containing 1.5g of KPS into the reactor, dripping for 1h, and reacting for 2h to obtain a polymer core; 1g of SiO was added2-g-GMA, after stirring and dispersing uniformly, simultaneously dripping 100g of MMA and 1g of KPS into a reactor, dripping for 1h, reacting for 1h, and after the reaction is finished, adding 14g of CaCl with the mass concentration of 2%2And (3) stirring the solution at a high speed, adding water and heating after the emulsion becomes viscous to obtain obvious fine sand-shaped particles, stopping heating, and drying a product obtained by filtering at 50 ℃ to obtain the modified ACR.
Example 1
The impact-resistant PVC plate comprises the following components in parts by weight:
example 2
The impact-resistant PVC plate comprises the following components in parts by weight:
example 3
The impact-resistant PVC plate comprises the following components in parts by weight:
comparative example 1 the same as example 3 except that the modified ACR was prepared according to the following procedure:
(1) preparation of KH570 modified nano-silica
Adding dried 1g of nano-silica into 100mL of aqueous solution containing 0.03gKH570, ultrasonically dispersing for 1h, stirring the dispersion liquid at 110 ℃ for 8h after dispersion is finished, filtering, washing the obtained product with toluene, performing soxhlet extraction after vacuum filtration, and drying the product obtained by soxhlet extraction at 50 ℃ for 12h to obtain KH570 modified nano-silica;
(2) preparation of SiO2-g-GMA
Adding 1gKH570 modified nano-silicon dioxide into 150mL deionized water, and then sequentially adding 1g sodium dodecyl benzene sulfonate, 5mLGMA and 0.02g polymerization inhibitor CuSO4·5H2O, obtaining mixed emulsion, ultrasonically dispersing the mixed emulsion for 1h, then placing the mixed emulsion into a closed oxygen-free nitrogen bottle, irradiating the mixed emulsion for 1h in a drill source irradiation chamber with the irradiation dose of 3kGy, and adding 0.5mL of CaCl with the mass fraction of 1% into the irradiated mixed emulsion2Demulsifying the solution, vacuum filtering with nanofiltration membrane to obtain product, grinding, wrapping with filter paper, extracting with toluene for 72 hr, and extracting at 50 deg.CDrying in vacuum to constant weight to obtain SiO2-g-GMA；
(3) Preparation of modified ACR
Putting 200mL of deionized water, 0.2g of NaOH and 1g of SDS into a reactor, stirring for 30min, heating to 75 ℃, simultaneously dripping 30g of BA and 5mL of aqueous solution containing 1.5g of KPS into the reactor, dripping for 1h, and reacting for 2h to obtain a polymer core; 5g of SiO were added2-g-GMA, after stirring and dispersing uniformly, simultaneously dripping 100g of MMA and 1g of KPS into a reactor, dripping for 1h, reacting for 1h, and after the reaction is finished, adding 14g of CaCl with the mass concentration of 2%2And (3) stirring the solution at a high speed, adding water and heating after the emulsion becomes viscous to obtain obvious fine sand-shaped particles, stopping heating, and drying a product obtained by filtering at 50 ℃ to obtain the modified ACR.
Comparative example 2 is the same as example 3 except that the mass fraction of modified ACR is 6 parts and the mass fraction of CPE is 6 parts.
Examples 1-3 and comparative examples 1-2 PVC sheets were prepared as follows:
(1) weighing the raw materials according to the formula of the base material;
(2) putting PVC and CPE into a mixer, stirring for 10min at the temperature of 130 ℃, then sequentially adding stearic acid, calcium stearate, calcium-zinc heat stabilizer, fatty alcohol lubricant, modified ACR impact modifier, phthalate plasticizer and light calcium carbonate, and stirring for 10min at the temperature of 80 ℃; and then cooling to room temperature, heating and plasticizing by an extruder, extruding a film base material in a plasticized state by a die, feeding the film base material into a film laminating calender to be coated with a texture layer and a wear-resistant layer, then trimming the formed plate by a trimming and cutting device, drawing the plate to a shearing machine by a tractor to cut the plate with required specification, and finally preparing the PVC plate.
And (3) performance testing:
the impact strength of the simply supported beam and the impact strength retention rate of the notch of the simply supported beam of the PVC sheets prepared in examples 1-3 and comparative examples 1-2 under the condition of 6000h of artificial weathering resistance are tested according to ISO179-2000 for testing the impact strength of the plastic simply supported beam, the flexural modulus of elasticity is tested according to GB/T9341-2008 for testing the flexural performance of the plastic, and the tensile impact strength is tested according to GB/T13525-1992 for testing the tensile impact performance of the plastic.
The results of the performance tests of the PVC sheets prepared in examples 1-3 and comparative examples 1-2 are shown in Table 1:
TABLE 1
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. An impact-resistant PVC plate is characterized by comprising the following components in parts by weight:
2. an impact-resistant PVC sheet according to claim 1, wherein: the modified ACR is prepared according to the following method:
(1) preparation of KH570 modified nano-silica
Adding dried 1g of nano-silica into 100mL of aqueous solution containing 0.03gKH570, ultrasonically dispersing for 1h, stirring the dispersion liquid at 110 ℃ for 8h after dispersion is finished, filtering, washing the obtained product with toluene, performing soxhlet extraction after vacuum filtration, and drying the product obtained by soxhlet extraction at 50 ℃ for 12h to obtain KH570 modified nano-silica;
(2) preparation of SiO2-g-GMA
Adding 1gKH570 modified nano-silicon dioxide into 150mL deionized water, and then sequentially adding 1g sodium dodecyl benzene sulfonate, 5mLGMA and 0.02g polymerization inhibitor CuSO4·5H2O, obtaining mixed emulsion, ultrasonically dispersing the mixed emulsion for 1h, then placing the mixed emulsion into a closed oxygen-free nitrogen bottle, irradiating the mixed emulsion for 1h in a drill source irradiation chamber with the irradiation dose of 3kGy, and adding 0.5mL of CaCl with the mass fraction of 1% into the irradiated mixed emulsion2Demulsifying the solution, vacuum filtering with nanofiltration membrane to obtain product, grinding, wrapping with filter paper, extracting with toluene for 72 hr, and vacuum drying at 50 deg.C to constant weight to obtain SiO2-g-GMA；
(3) Preparation of modified ACR
Putting 200mL of deionized water, 0.2g of NaOH and 1g of SDS into a reactor, stirring for 30min, heating to 75 ℃, simultaneously dripping 30g of BA and 5mL of aqueous solution containing 1.5g of KPS into the reactor, dripping for 1h, and reacting for 2h to obtain a polymer core; 1g of SiO was added2-g-GMA, after stirring and dispersing uniformly, simultaneously dripping 100g of MMA and 1g of KPS into a reactor, dripping for 1h, reacting for 1h, and after the reaction is finished, adding 14g of CaCl with the mass concentration of 2%2And (3) stirring the solution at a high speed, adding water and heating after the emulsion becomes viscous to obtain obvious fine sand-shaped particles, stopping heating, and drying a product obtained by filtering at 50 ℃ to obtain the modified ACR.
3. An impact-resistant PVC sheet according to claim 1, wherein: the mass ratio of the modified ACR to the CPE is 2: 1.
4. An impact-resistant PVC sheet according to claim 1, wherein: the particle size of the light calcium carbonate is 500-600 meshes.
5. An impact-resistant PVC sheet according to claim 1, wherein: the phthalate plasticizer is DOP, BBP, DCP, DBP or DMP.
6. An impact-resistant PVC sheet according to claim 1, wherein: the calcium zinc stabilizer is German bear brand MC90224 KA.
7. An impact-resistant PVC sheet according to claim 1, wherein: the fatty alcohol lubricant is pentaerythritol or xylitol.
8. An impact-resistant PVC sheet according to any one of claims 1 to 7, characterized in that it is prepared according to the following steps:
(1) weighing the raw materials according to the formula of the base material;
(2) putting PVC and CPE into a mixer, stirring for 8-13min at the temperature of 128-135 ℃, then sequentially adding stearic acid, calcium stearate, calcium-zinc heat stabilizer, fatty alcohol lubricant, modified ACR impact modifier, phthalate plasticizer and light calcium carbonate, and stirring for 10min at the temperature of 78-83 ℃; and then cooling to room temperature, heating and plasticizing by an extruder, extruding a film base material in a plasticized state by a die, feeding the film base material into a film laminating calender to be coated with a texture layer and a wear-resistant layer, then trimming the formed plate by a trimming and cutting device, drawing the plate to a shearing machine by a tractor to cut the plate with required specification, and finally preparing the PVC plate.
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| CN202010726749.XA CN111704776A (en) | 2020-07-25 | 2020-07-25 | PVC board shocks resistance |
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| CN202010726749.XA CN111704776A (en) | 2020-07-25 | 2020-07-25 | PVC board shocks resistance |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210175A (en) * | 2020-10-29 | 2021-01-12 | 南京联塑科技实业有限公司 | Low-temperature impact resistant PVC product and preparation method and application thereof |
| CN114736468A (en) * | 2022-03-30 | 2022-07-12 | 兰州金睿合新材料科技有限责任公司 | High-toughness PVC (polyvinyl chloride) blending material and preparation method thereof |
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| CN101445637A (en) * | 2008-12-23 | 2009-06-03 | 广东工业大学 | Preparation method of nano SiO2/ACR composite particles and application thereof |
| CN102352077A (en) * | 2011-07-07 | 2012-02-15 | 鹤山联塑实业发展有限公司 | Environment-friendly aging-resistant polyvinyl chloride (PVC) section |
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2020
- 2020-07-25 CN CN202010726749.XA patent/CN111704776A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101445637A (en) * | 2008-12-23 | 2009-06-03 | 广东工业大学 | Preparation method of nano SiO2/ACR composite particles and application thereof |
| CN102352077A (en) * | 2011-07-07 | 2012-02-15 | 鹤山联塑实业发展有限公司 | Environment-friendly aging-resistant polyvinyl chloride (PVC) section |
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| 孙贵生 等: "纳米二氧化硅表面改性及辐射引发接枝GMA的研究", 《辐射研究与辐射工艺学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210175A (en) * | 2020-10-29 | 2021-01-12 | 南京联塑科技实业有限公司 | Low-temperature impact resistant PVC product and preparation method and application thereof |
| CN112210175B (en) * | 2020-10-29 | 2022-01-28 | 南京联塑科技实业有限公司 | Low-temperature impact resistant PVC product and preparation method and application thereof |
| CN114736468A (en) * | 2022-03-30 | 2022-07-12 | 兰州金睿合新材料科技有限责任公司 | High-toughness PVC (polyvinyl chloride) blending material and preparation method thereof |
| CN114736468B (en) * | 2022-03-30 | 2023-10-20 | 兰州金睿合新材料科技有限责任公司 | High-toughness PVC (polyvinyl chloride) blending material and preparation method thereof |
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