CN104861371A - High-strength high-toughness polycarbonate modified polyvinyl chloride composite material - Google Patents
High-strength high-toughness polycarbonate modified polyvinyl chloride composite material Download PDFInfo
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- CN104861371A CN104861371A CN201410847583.1A CN201410847583A CN104861371A CN 104861371 A CN104861371 A CN 104861371A CN 201410847583 A CN201410847583 A CN 201410847583A CN 104861371 A CN104861371 A CN 104861371A
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- polyvinyl chloride
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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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses a high-strength high-toughness polycarbonate modified polyvinyl chloride composite material. The composite material comprises, by mass, 30-40% of polyvinyl chloride, 15-25% of polycarbonate, 2-4% of a styrene grafted maleic anhydride copolymer, 8-12% of a glass fiber, 5-10% of a calcium carbonate composite particle, 4-7% of di(2-ethylhexyl) phthalate, 5-8% of a methacrylate-acrylate copolymer, 1-3% of an antistatic agent, 0.5-2% of a light stabilizer UV-326, 0.5-1% of a calcium and zinc composite stabilizer, 0.5-1% of a glass fiber rich surface inhibition agent, 0.5-1% of calcium stearate, 0.1-0.5% of an antioxidant 1010 and 6-9% of a fire retardant. The high-strength high-toughness polycarbonate modified polyvinyl chloride composite material integrates respective original advantages of polyvinyl chloride and polycarbonate, and also has greatly improved impact strength, tensile strength, fire retardation, heat stability, weather resistance and processability.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of high-strength and high ductility matrix material of polycarbonate modified polyvinyl chloride.
Background technology
Polyvinyl chloride (PVC) is the thermoplastic resin be polymerized under initiator effect by vinylchlorid, because it has the advantages such as chemical proofing is high, electrical insulation capability good, physical and chemical performance is stable, cheap, each fields such as industry, agricultural, traffic, building, communication and health care are widely used at present.But simple polyvinyl chloride exists poor heat stability, resistance to impact shock is low, creep resistant is bad, the ageing-resistant defect such as bad, its result of use in each field will be significantly limit.In order to improve polyvinyl chloride use properties, usually needing to add other component and carrying out modification.Polycarbonate (PC) is a kind of thermoplastic engineering plastic of excellent combination property, there is outstanding shock resistance, resistance to creep and good stability of the dimension, higher mechanical strength can be kept in higher temperature range, nontoxic, dielectric properties are excellent, are the engineering plastics that rapid development is the fastest and the size of capacity is maximum in recent years.Therefore, matrix material prepared by PVC modified polycarbonate had good practical value and application prospect.
Summary of the invention
The object of the present invention is to provide a kind of high-strength and high ductility matrix material of polycarbonate modified polyvinyl chloride.
The technical solution adopted for the present invention to solve the technical problems is: a kind of high-strength and high ductility matrix material of polycarbonate modified polyvinyl chloride, its component by mass percent proportioning is: polyvinyl chloride 30% ~ 40%, polycarbonate 15% ~ 25%, styrene-grafted copolymer-maleic anhydride 2% ~ 4%, glass fibre 8% ~ 12%, calcium carbonate composite fine particle 5% ~ 10%, phthalic acid two (2-ethylhexyl) ester 4% ~ 7%, Methylacrylate-Acrylate Copolymer 5% ~ 8%, static inhibitor 1% ~ 3%, photostabilizer UV-326 0.5% ~ 2%, calcium-zinc composite stabilizing agent 0.5% ~ 1%, anti-glass emergence on the surface agent 0.5% ~ 1%, calcium stearate 0.5% ~ 1%, antioxidant 1010 0.1% ~ 0.5%, fire retardant 6% ~ 9%.
The mean polymerisation degree of described polyvinyl chloride 800 ~ 1200, weight-average molecular weight is in 50000 ~ 120000 scopes.
Described polycarbonate is the bisphenol A-type aromatic copolycarbonate of weight-average molecular weight in 20000 ~ 40000 scopes.
Described glass fibre be surface through γ-aminopropyltrimethoxysilane process and mean diameter at the alkali-free short glass fiber of 4 ~ 17 μm.
Described calcium carbonate composite fine particle is the nano level water-ground limestone particulate that surface grafting has vinyl cyanide and methyl methacrylate dual MCU system.
Described static inhibitor is the one in polyethylene oxide, polyether ester amides, polyether ester imide, polyethylene glycol alkyl ether, glycerol monostearate, alkyl sodium sulfonate.
Described photostabilizer UV-326 is 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole.
Described anti-glass emergence on the surface agent is modification ethylene bis-fatty acid amides TAF.
Described antioxidant 1010 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Described fire retardant is the one in TDE, melamine cyanurate, polyphenylene phosphonic acids sulfobenzide ester.
The preparation method of the high-strength and high ductility matrix material of above-mentioned a kind of polycarbonate modified polyvinyl chloride, comprises the following steps:
(1), prepare calcium carbonate composite fine particle: 75%:2%:3%:10%:10% takes nano level water-ground limestone successively by weight ratio, dispersing agent C H-1A, ammonium persulphate, acrylonitrile monemer and methyl methacrylate monomer, again nano level light calcium carbonate deionized water is mixed with the suspension that mass percent concentration is 10% ~ 20%, add dispersing agent C H-1A again, under ultra-sonic oscillation and mechanical stirring, process 30 ~ 45min, dripping 37% salt acid for adjusting pH value is 6.5 ~ 7.0, then add in the reactor with nitrogen protection, when being heated with stirring to 60 DEG C ~ 80 DEG C with 500 ~ 800r/min, add ammonium persulphate, keep stirring 10 ~ 15min, then acrylonitrile monemer is dripped, drip methyl methacrylate monomer again, react 2 ~ 4h at 60 DEG C ~ 80 DEG C temperature after, stop heating, to be cooled to room temperature, carry out vacuum filtration, again filtrate is put into vacuum drying oven, dry 12 ~ 24h at 95 DEG C ~ 120 DEG C temperature, i.e. obtained described calcium carbonate composite fine particle,
(2) take each component, by weight ratio, comprise the calcium carbonate composite fine particle that step (1) is obtained;
(3), polyvinyl chloride, phthalic acid two (2-ethylhexyl) ester and calcium-zinc composite stabilizing agent are added barrel temperature 80 DEG C ~ 90 DEG C, rotating speed is in the mixing machine of 50 ~ 80r//min, stir 20 ~ 30min, then polycarbonate and styrene-grafted copolymer-maleic anhydride, stir 10 ~ 20min, add other component except glass fibre again, comprise and add the obtained calcium carbonate composite fine particle of step (1), make to stir 20 ~ 40min together, after mixing completely, discharging;
(4) master, the material that step (3) obtains being added twin screw extruder feeds mouth, add glass fibre from time hello the mouth of twin screw extruder simultaneously, extruding pelletization after twin screw extruder is mixing, obtains the high-strength and high ductility matrix material of described a kind of polycarbonate modified polyvinyl chloride.
The invention has the beneficial effects as follows, the present invention combines polyvinyl chloride and polycarbonate original advantage separately, but also significantly improving resistance to impact shock, tensile strength, flame retardant resistance, thermostability, weathering resistance and processing characteristics etc., its mechanical property is good, and intensity is high, good toughness, weather-proof anti ageing property is excellent, and cost is low, and flame retardant properties is good, wide accommodation, is easy to apply.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with concrete preferred embodiment.
Embodiment 1:
A high-strength and high ductility matrix material for polycarbonate modified polyvinyl chloride, its component by mass percent proportioning is: polyvinyl chloride 30%, polycarbonate 15%, styrene-grafted copolymer-maleic anhydride 4%, glass fibre 12%, calcium carbonate composite fine particle 10%, phthalic acid two (2-ethylhexyl) ester 7%, Methylacrylate-Acrylate Copolymer 8%, polyethylene oxide 3%, photostabilizer UV-326 2%, calcium-zinc composite stabilizing agent 1%, TAF 1%, calcium stearate 0.5%, antioxidant 1010 0.5%, melamine cyanurate 6%, the mean polymerisation degree of described polyvinyl chloride is 800 ~ 1200, weight-average molecular weight is in 50000 ~ 120000 scopes, and described polycarbonate is the bisphenol A-type aromatic copolycarbonate of weight-average molecular weight in 20000 ~ 40000 scopes, and described glass fibre is that surface is through γ-aminopropyltrimethoxysilane process, and mean diameter is at the alkali-free short glass fiber of 4 ~ 17 μm, described calcium carbonate composite fine particle is the nano level water-ground limestone particulate that surface grafting has vinyl cyanide and methyl methacrylate dual MCU system.
Preparation method: (1), prepare calcium carbonate composite fine particle: 75%:2%:3%:10%:10% takes nano level water-ground limestone successively by weight ratio, dispersing agent C H-1A, ammonium persulphate, acrylonitrile monemer and methyl methacrylate monomer, again nano level light calcium carbonate deionized water is mixed with the suspension that mass percent concentration is 10% ~ 20%, add dispersing agent C H-1A again, under ultra-sonic oscillation and mechanical stirring, process 30 ~ 45min, dripping 37% salt acid for adjusting pH value is 6.5 ~ 7.0, then add in the reactor with nitrogen protection, when being heated with stirring to 60 DEG C ~ 80 DEG C with 500 ~ 800r/min, add ammonium persulphate, keep stirring 10 ~ 15min, then acrylonitrile monemer is dripped, drip methyl methacrylate monomer again, react 2 ~ 4h at 60 DEG C ~ 80 DEG C temperature after, stop heating, to be cooled to room temperature, carry out vacuum filtration, again filtrate is put into vacuum drying oven, dry 12 ~ 24h at 95 DEG C ~ 120 DEG C temperature, i.e. obtained described calcium carbonate composite fine particle, (2) take each component, by weight ratio, comprise the calcium carbonate composite fine particle that step (1) is obtained, (3), polyvinyl chloride, phthalic acid two (2-ethylhexyl) ester and calcium-zinc composite stabilizing agent are added barrel temperature 80 DEG C ~ 90 DEG C, rotating speed is in the mixing machine of 50 ~ 80r//min, stir 20 ~ 30min, then polycarbonate and styrene-grafted copolymer-maleic anhydride, stir 10 ~ 20min, add other component except glass fibre again, comprise and add the obtained calcium carbonate composite fine particle of step (1), make to stir 20 ~ 40min together, after mixing completely, discharging, (4) master, the material that step (3) obtains being added twin screw extruder feeds mouth, add glass fibre from time hello the mouth of twin screw extruder simultaneously, extruding pelletization after twin screw extruder is mixing, obtains the high-strength and high ductility matrix material of described a kind of polycarbonate modified polyvinyl chloride.
Embodiment 2:
A high-strength and high ductility matrix material for polycarbonate modified polyvinyl chloride, its component by mass percent proportioning is: polyvinyl chloride 40%, polycarbonate 23%, styrene-grafted copolymer-maleic anhydride 2%, glass fibre 8%, calcium carbonate composite fine particle 5%, phthalic acid two (2-ethylhexyl) ester 4%, Methylacrylate-Acrylate Copolymer 5%, glycerol monostearate 1.5%, photostabilizer UV-326 0.5%, calcium-zinc composite stabilizing agent 0.8%, TAF 0.5%, calcium stearate 0.6%, antioxidant 1010 0.1%, TDE 9%, the mean polymerisation degree of described polyvinyl chloride is 800 ~ 1200, weight-average molecular weight is in 50000 ~ 120000 scopes, and described polycarbonate is the bisphenol A-type aromatic copolycarbonate of weight-average molecular weight in 20000 ~ 40000 scopes, and described glass fibre is that surface is through γ-aminopropyltrimethoxysilane process, and mean diameter is at the alkali-free short glass fiber of 4 ~ 17 μm, described calcium carbonate composite fine particle is the nano level water-ground limestone particulate that surface grafting has vinyl cyanide and methyl methacrylate dual MCU system.
Preparation method: (1), prepare calcium carbonate composite fine particle: 75%:2%:3%:10%:10% takes nano level water-ground limestone successively by weight ratio, dispersing agent C H-1A, ammonium persulphate, acrylonitrile monemer and methyl methacrylate monomer, again nano level light calcium carbonate deionized water is mixed with the suspension that mass percent concentration is 10% ~ 20%, add dispersing agent C H-1A again, under ultra-sonic oscillation and mechanical stirring, process 30 ~ 45min, dripping 37% salt acid for adjusting pH value is 6.5 ~ 7.0, then add in the reactor with nitrogen protection, when being heated with stirring to 60 DEG C ~ 80 DEG C with 500 ~ 800r/min, add ammonium persulphate, keep stirring 10 ~ 15min, then acrylonitrile monemer is dripped, drip methyl methacrylate monomer again, react 2 ~ 4h at 60 DEG C ~ 80 DEG C temperature after, stop heating, to be cooled to room temperature, carry out vacuum filtration, again filtrate is put into vacuum drying oven, dry 12 ~ 24h at 95 DEG C ~ 120 DEG C temperature, i.e. obtained described calcium carbonate composite fine particle, (2) take each component, by weight ratio, comprise the calcium carbonate composite fine particle that step (1) is obtained, (3), polyvinyl chloride, phthalic acid two (2-ethylhexyl) ester and calcium-zinc composite stabilizing agent are added barrel temperature 80 DEG C ~ 90 DEG C, rotating speed is in the mixing machine of 50 ~ 80r//min, stir 20 ~ 30min, then polycarbonate and styrene-grafted copolymer-maleic anhydride, stir 10 ~ 20min, add other component except glass fibre again, comprise and add the obtained calcium carbonate composite fine particle of step (1), make to stir 20 ~ 40min together, after mixing completely, discharging, (4) master, the material that step (3) obtains being added twin screw extruder feeds mouth, add glass fibre from time hello the mouth of twin screw extruder simultaneously, extruding pelletization after twin screw extruder is mixing, obtains the high-strength and high ductility matrix material of described a kind of polycarbonate modified polyvinyl chloride.
Claims (6)
1. the high-strength and high ductility matrix material of a polycarbonate modified polyvinyl chloride, it is characterized in that, its component by mass percent proportioning is: polyvinyl chloride 30% ~ 40%, polycarbonate 15% ~ 25%, styrene-grafted copolymer-maleic anhydride 2% ~ 4%, glass fibre 8% ~ 12%, calcium carbonate composite fine particle 5% ~ 10%, phthalic acid two (2-ethylhexyl) ester 4% ~ 7%, Methylacrylate-Acrylate Copolymer 5% ~ 8%, static inhibitor 1% ~ 3%, photostabilizer UV-326 0.5% ~ 2%, calcium-zinc composite stabilizing agent 0.5% ~ 1%, anti-glass emergence on the surface agent 0.5% ~ 1%, calcium stearate 0.5% ~ 1%, antioxidant 1010 0.1% ~ 0.5%, fire retardant 6% ~ 9%.
2. the high-strength and high ductility matrix material of a kind of polycarbonate modified polyvinyl chloride according to claim 1, it is characterized in that, described glass fibre be surface through γ-aminopropyltrimethoxysilane process and mean diameter at the alkali-free short glass fiber of 4 ~ 17 μm.
3. the high-strength and high ductility matrix material of a kind of polycarbonate modified polyvinyl chloride according to claim 1, is characterized in that, described calcium carbonate composite fine particle is the nano level water-ground limestone particulate that surface grafting has vinyl cyanide and methyl methacrylate dual MCU system.
4. the high-strength and high ductility matrix material of a kind of polycarbonate modified polyvinyl chloride according to claim 1, it is characterized in that, described static inhibitor is the one in polyethylene oxide, polyether ester amides, polyether ester imide, polyethylene glycol alkyl ether, glycerol monostearate, alkyl sodium sulfonate.
5. the high-strength and high ductility matrix material of a kind of polycarbonate modified polyvinyl chloride according to claim 1, is characterized in that, described fire retardant is the one in TDE, melamine cyanurate, polyphenylene phosphonic acids sulfobenzide ester.
6. the preparation method of the high-strength and high ductility matrix material of a kind of polycarbonate modified polyvinyl chloride according to claim 1, is characterized in that, comprise the following steps:
(1), prepare calcium carbonate composite fine particle: 75%:2%:3%:10%:10% takes nano level water-ground limestone successively by weight ratio, dispersing agent C H-1A, ammonium persulphate, acrylonitrile monemer and methyl methacrylate monomer, again nano level light calcium carbonate deionized water is mixed with the suspension that mass percent concentration is 10% ~ 20%, add dispersing agent C H-1A again, under ultra-sonic oscillation and mechanical stirring, process 30 ~ 45min, dripping 37% salt acid for adjusting pH value is 6.5 ~ 7.0, then add in the reactor with nitrogen protection, when being heated with stirring to 60 DEG C ~ 80 DEG C with 500 ~ 800r/min, add ammonium persulphate, keep stirring 10 ~ 15min, then acrylonitrile monemer is dripped, drip methyl methacrylate monomer again, react 2 ~ 4h at 60 DEG C ~ 80 DEG C temperature after, stop heating, to be cooled to room temperature, carry out vacuum filtration, again filtrate is put into vacuum drying oven, dry 12 ~ 24h at 95 DEG C ~ 120 DEG C temperature, i.e. obtained described calcium carbonate composite fine particle,
(2) take each component, by weight ratio, comprise the calcium carbonate composite fine particle that step (1) is obtained;
(3), polyvinyl chloride, phthalic acid two (2-ethylhexyl) ester and calcium-zinc composite stabilizing agent are added barrel temperature 80 DEG C ~ 90 DEG C, rotating speed is in the mixing machine of 50 ~ 80r//min, stir 20 ~ 30min, then polycarbonate and styrene-grafted copolymer-maleic anhydride, stir 10 ~ 20min, add other component except glass fibre again, comprise and add the obtained calcium carbonate composite fine particle of step (1), make to stir 20 ~ 40min together, after mixing completely, discharging;
(4) master, the material that step (3) obtains being added twin screw extruder feeds mouth, add glass fibre from time hello the mouth of twin screw extruder simultaneously, extruding pelletization after twin screw extruder is mixing, obtains the high-strength and high ductility matrix material of described a kind of polycarbonate modified polyvinyl chloride.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131470A (en) * | 2015-09-23 | 2015-12-09 | 江苏蓝湾生物科技有限公司 | Preparation method of medical deodorization packaging material |
| CN105131473A (en) * | 2015-09-23 | 2015-12-09 | 江苏蓝湾生物科技有限公司 | Preparation method of high temperature resistant medical deodorization material |
| CN105385068A (en) * | 2015-12-22 | 2016-03-09 | 合肥仲农生物科技有限公司 | Polyvinyl chloride (PVC) composite material |
| CN105949655A (en) * | 2016-05-31 | 2016-09-21 | 苏州市奎克力电子科技有限公司 | Anti-aging insulating plastic shell material and preparation method thereof |
| CN106280122A (en) * | 2016-08-28 | 2017-01-04 | 安徽优丽普科技股份有限公司 | The special surface of a kind of hook type metal Os Draconis is without screw PVC frid |
| CN106366494A (en) * | 2016-08-28 | 2017-02-01 | 安徽优丽普科技股份有限公司 | Novel multifunctional PVC hanging plate for product storage |
| CN106366493A (en) * | 2016-08-28 | 2017-02-01 | 安徽优丽普科技股份有限公司 | High-strength single-body type hanging PVC trough plate |
| CN106751663A (en) * | 2016-12-13 | 2017-05-31 | 德阳力久云智知识产权运营有限公司 | A kind of flame-retardant modified plastics of high tenacity and preparation method thereof |
| CN107383702A (en) * | 2017-09-07 | 2017-11-24 | 苏州浩焱精密模具有限公司 | A kind of wear-resistant plastic and preparation method thereof |
| CN108988246A (en) * | 2018-08-16 | 2018-12-11 | 镇江朝阳机电科技有限公司 | A kind of assembly type PVC cabling channel |
| WO2020211188A1 (en) * | 2019-04-15 | 2020-10-22 | 王叶训 | Method for making nano shell powder plastic ingot |
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2014
- 2014-12-29 CN CN201410847583.1A patent/CN104861371A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131470A (en) * | 2015-09-23 | 2015-12-09 | 江苏蓝湾生物科技有限公司 | Preparation method of medical deodorization packaging material |
| CN105131473A (en) * | 2015-09-23 | 2015-12-09 | 江苏蓝湾生物科技有限公司 | Preparation method of high temperature resistant medical deodorization material |
| CN105385068A (en) * | 2015-12-22 | 2016-03-09 | 合肥仲农生物科技有限公司 | Polyvinyl chloride (PVC) composite material |
| CN105949655A (en) * | 2016-05-31 | 2016-09-21 | 苏州市奎克力电子科技有限公司 | Anti-aging insulating plastic shell material and preparation method thereof |
| CN106280122A (en) * | 2016-08-28 | 2017-01-04 | 安徽优丽普科技股份有限公司 | The special surface of a kind of hook type metal Os Draconis is without screw PVC frid |
| CN106366494A (en) * | 2016-08-28 | 2017-02-01 | 安徽优丽普科技股份有限公司 | Novel multifunctional PVC hanging plate for product storage |
| CN106366493A (en) * | 2016-08-28 | 2017-02-01 | 安徽优丽普科技股份有限公司 | High-strength single-body type hanging PVC trough plate |
| CN106751663A (en) * | 2016-12-13 | 2017-05-31 | 德阳力久云智知识产权运营有限公司 | A kind of flame-retardant modified plastics of high tenacity and preparation method thereof |
| CN107383702A (en) * | 2017-09-07 | 2017-11-24 | 苏州浩焱精密模具有限公司 | A kind of wear-resistant plastic and preparation method thereof |
| CN108988246A (en) * | 2018-08-16 | 2018-12-11 | 镇江朝阳机电科技有限公司 | A kind of assembly type PVC cabling channel |
| WO2020211188A1 (en) * | 2019-04-15 | 2020-10-22 | 王叶训 | Method for making nano shell powder plastic ingot |
| CN111825885A (en) * | 2019-04-15 | 2020-10-27 | 王叶训 | Method for manufacturing nano shell powder plastic ingot |
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Application publication date: 20150826 |