CN104945778A - Water-vapor-resisting inflaming retarding PVC protecting sleeve material - Google Patents

Water-vapor-resisting inflaming retarding PVC protecting sleeve material Download PDF

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Publication number
CN104945778A
CN104945778A CN201510391573.6A CN201510391573A CN104945778A CN 104945778 A CN104945778 A CN 104945778A CN 201510391573 A CN201510391573 A CN 201510391573A CN 104945778 A CN104945778 A CN 104945778A
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water
parts
silane
silane coupling
nano
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CN201510391573.6A
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Inventor
程晓松
于德宝
孙玉萍
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Suzhou Hengli Communications Material Co Ltd
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Suzhou Hengli Communications Material Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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

Abstract

The invention discloses a water-vapor-resisting inflaming retarding PVC protecting sleeve material. The inflaming retarding PVC protecting sleeve material comprises the components, by weight, of polyvinyl chloride with the polymerization degree of 590-720, polyvinyl chloride with the polymerization degree of 1110-1340, trioctyl trimellitate, phthalandione isodecyl ester, environment-protecting calcium zinc compound stabilizers, composite rare earth stabilizers, antimonous oxide, lubricating agents, antioxygen agents, nano barium sulfate, calcined kaolin, nano-silica and silane coupling agents. The silane coupling agents are vinyl-(beta-methoxy-ethoxy) silane or vinyl trimethoxy silane or gamma-glycidoxy propyl trimethoxy silane. The silane coupling agents are used first for carrying out modification on the nano barium sulfate, the calcined kaolin and the nano-silica, water-tolerant improvers are prepared, and then the water-tolerant improvers are added into a blend to prepare the water-tolerant inflaming retarding PVC cable material. The water absorption of a cable protecting sleeve layer is greatly lowered, a product is used under a humid or water-soaking environment, electric performance reliability is further improved, product compactness is improved, material micropores are removed, water vapor cannot invade, and performance lowering is avoided.

Description

Water vapor flame-proof PVC sheath material
Technical field
The present invention relates to a kind of PVC cable material and preparation technology thereof, particularly relate to a kind of water vapor flame-proof PVC sheath material.
Background technology
PVC CABLE MATERIALS is common for the cable insulation material in cable industry at present, and its good mechanical performance, good electrical property, scale resistance, photostabilization and erosion resistance are good.Along with widespread use in the field of PVC CABLE MATERIALS Highrise buildings, electronic component, automobile and space industry again, also more and more higher to the requirement of the flame retardant properties of CABLE MATERIALS.Polyvinyl chloride cable material is owing to having good mechanical and physical performance, electric property, and complete processing is simple, and processing characteristics is excellent, and price is lower, occupy prostatitis always, be widely used in CABLE MATERIALS industry total amount.PVC cable material is generally applied to the product such as mesolow, data corresponding class cable, and general purpose electric wire product, PVC cable material can meet insulation, sheath demand substantially.But along with the expansion of electric wire application scenario, improving constantly the requirement of PVC cable material, on the water-fast electrical insulation capability of PVC, is a difficult point always, be difficult to for a long time solve.Polyvinyl chloride resin itself has excellent water resistance, but due to CABLE MATERIALS produce must add all kinds of softening agent, stablizer, all kinds of weighting agent (potter's clay, calcium carbonate etc.), inevitably reduce the immersion electrical property of product.Prior art is difficult to find from document, but general employing high-quality softening agent, minimizing or the mode without weighting agent, product index performance is still difficult to meet the demands, and easily causes the indexs such as thermal distortion defective, the problems such as cost increase simultaneously.
Summary of the invention
The object of this invention is to provide a kind of water vapor flame-proof PVC sheath material, it greatly reduces the water-absorbent of the coat layer of power cable, product uses under moist or water-immerged environment, further increase electric property to stablize, substantially do not change, improve the tightness of product, get rid of material micropore, steam cannot invade and cause degradation.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of water vapor flame-proof PVC sheath material, and described flame-proof PVC sheath material is made up of the component of following weight part:
The polymerization degree is 590 ~ 720 polyvinyl chloride 55 ~ 65 parts,
The polymerization degree is 1110 ~ 1340 polyvinyl chloride 35 ~ 45 parts,
Trioctyl trimellitate (TOTM) 20 ~ 30 parts,
Phthalic acid isodecyl ester 15 ~ 25 parts,
Environmental protection calcium-zinc composite stabilizing agent 5 ~ 10 parts,
Compound rare-earth stablizer 5 ~ 10 parts,
Antimonous oxide 4 ~ 8 parts,
Lubricant 0.3 ~ 1 part,
0.1 ~ 0.5 part, oxidation inhibitor,
Nano barium sulfate 3.5 ~ 7 parts,
Calcined kaolin 2.6 ~ 5.2 parts,
Nano silicon 3.5 ~ 7 parts,
Silane coupling agent 0.18 ~ 0.36 part;
Silane coupling agent is first adopted to carry out joining after modification obtains resistance to water improver in blend thus obtained waterproof flame retardant PVC CABLE MATERIALS nano barium sulfate, calcined kaolin, nano silicon again;
Described silane coupling agent is that vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane and γ-glycidyl ether oxygen propyl trimethoxy silicane mix by 10:5:3 weight ratio.
The technical scheme improved further in above-mentioned waterproof flame retardant PVC cable material technical scheme is as follows:
1, in such scheme, described silane coupling agent is vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane.
2, in such scheme, described oxidation inhibitor be four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or dihydroxyphenyl propane.
3, in such scheme, described calcined kaolin is through adding the improver of gross weight 1.5 ~ 2%, calcination temperature 970 ~ 990 DEG C in calcination, the time is 30 ~ 40 minutes; Described improver is made up of cleaned coal, sodium sulfate and sodium-chlor, and this cleaned coal, sodium sulfate and sodium-chlor press the mixing of 10:0. 5:0. 3 weight.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
Water vapor flame-proof PVC sheath material of the present invention, overcome the water-absorbent that the softening agent of currently available products formula and weighting agent all have, thus easily there is the technological deficiency of product performance decline phenomenon in wet condition, contemplated by the invention all formula materials all with the problem of the consistency of water, select specific hydrophobic material and content.Carry out Surface coating process to after pulvis predrainage, improve the hydrophobic performance of product; Product uses under moist or water-immerged environment, and electric property is stablized, and does not substantially change; Water-proofing agent material selection nano level raw material, improves the tightness of product, and get rid of material micropore, steam cannot invade and cause degradation.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1 ~ 3: a kind of water vapor flame-proof PVC sheath material, described flame-proof PVC sheath material forms as shown in table 1 by the component of following weight part:
Table 1
More than be weight part.
Above-mentioned silane coupling agent is vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane.
Above-mentioned silane coupling agent is that vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane and γ-glycidyl ether oxygen propyl trimethoxy silicane mix by 10:5:3 weight ratio.
Above-mentioned lubricant embodiment 1 is polyethylene wax, and lubricant embodiment 2 is stearic acid, and lubricant embodiment 3 is polyethylene wax and stearic mixture.
Above-mentioned oxidation inhibitor embodiment 1 [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester that is four, embodiment 2 is dihydroxyphenyl propane, embodiment 3 [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester that is four.
Above-mentioned calcined kaolin is through adding the improver of gross weight 1.5 ~ 2%, calcination temperature 970 ~ 990 DEG C in calcination, the time is 30 ~ 40 minutes; Described improver is made up of cleaned coal, sodium sulfate and sodium-chlor, and this cleaned coal, sodium sulfate and sodium-chlor press the mixing of 10:0. 5:0. 3 weight.
The preparation technology of above-mentioned water vapor flame-proof PVC sheath material, comprises the following steps:
Step one, be 590 ~ 720 polyvinyl chloride 55 ~ 65 parts by the polymerization degree, to be 1110 ~ 1340 polyvinyl chloride be 35 ~ 45 parts to the polymerization degree under high-speed stirring state, is mixed to form mixture through high-speed mixer; Start stirring at low speed, rotating speed 500rpm, add trioctyl trimellitate 20 ~ 30 parts and phthalic acid isodecyl ester 15 ~ 25 parts, start high-speed stirring, rotating speed 1000rpm, treat that material temperature rises to that 80 DEG C add environmental protection calcium-zinc composite stabilizing agent 5 ~ 10 parts, compound rare-earth stablizer 5 ~ 10 parts, antimonous oxide 4 ~ 8 parts, lubricant 0.3 ~ 1 part, 0.1 ~ 0.5 part, oxidation inhibitor and water-proofing agent 10 ~ 20 parts, to continue to be stirred to temperature 110 DEG C of materials in dry powdered form, opens baiting valve blowing;
Step 2, the compound of step one put to carry out extrusion molding to twin screw mixing, then the granulation of singe screw extruding machine is entered, adopt die face fervent granulation process, the particle made enters first step whirlwind cooling separator by blower fan transport pipe, second stage whirlwind cooling separator, air-cooled vibratory screening apparatus, third stage whirlwind cooling separator obtain described waterproof flame retardant PVC cable material;
Described resistance to water improver obtains through following technique:
Step one, described nano barium sulfate 3.5 ~ 7 parts, calcined kaolin 2.6 ~ 5.2 parts, nano silicon 3.5 ~ 7 parts are carried out Surface coating process;
Step 2, dropped in high-speed mixer by the powder of said components, high-speed mixing carries out dehydration 3 ~ 5min to temperature 90 ~ 100 DEG C;
Step 3, silane coupling agent 0.18 ~ 0.36 part is carried out coated process to powder in vaporific spraying in high-speed mixer, continue high-speed mixing and carry out the coated processing reaction 3 ~ 5min of material surface;
Described resistance to water improver is obtained after step 4, cooling.
Above-mentioned calcined kaolin is through adding the improver of gross weight 1.5 ~ 2%, calcination temperature 970 ~ 990 DEG C in calcination, the time is 30 ~ 40 minutes; Described improver is made up of cleaned coal, sodium sulfate and sodium-chlor, and this cleaned coal, sodium sulfate and sodium-chlor press the mixing of 10:0. 5:0. 3 weight.
Preparation technology is with embodiment 1.
Water resistance test adopts " ASTM D2219-02 electric wire and cable pvc material specification " 5.5 test conditionss (electric current 60Hz frequency, immersion temperature: 50 ± 1 DEG C).
Test result analysis: product is through accelerating water absorption test, and change in dielectric constant rate is much smaller than standard (1 ~ 14d, 10%; 7 ~ 14d, 5%) requirement, product has good water resistance.
To sum up, water vapor flame-proof PVC sheath material of the present invention, overcomes the water-absorbent that the softening agent of currently available products formula and weighting agent all have, thus easily occurs the technological deficiency of product performance decline phenomenon in wet condition; Contemplated by the invention all formula materials all with the consistency of water, select hydrophobic material.Carry out Surface coating process to after pulvis predrainage, improve the hydrophobic performance of product; Product uses under moist or water-immerged environment, and electric property is stablized, and does not substantially change; Water-proofing agent material selection nano level raw material, improves the tightness of product, and get rid of material micropore, steam cannot invade and cause degradation.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (4)

1. a water vapor flame-proof PVC sheath material, is characterized in that: described flame-proof PVC sheath material is made up of the component of following weight part:
The polymerization degree is 590 ~ 720 polyvinyl chloride 55 ~ 65 parts,
The polymerization degree is 1110 ~ 1340 polyvinyl chloride 35 ~ 45 parts,
Trioctyl trimellitate (TOTM) 20 ~ 30 parts,
Phthalic acid isodecyl ester 15 ~ 25 parts,
Environmental protection calcium-zinc composite stabilizing agent 5 ~ 10 parts,
Compound rare-earth stablizer 5 ~ 10 parts,
Antimonous oxide 4 ~ 8 parts,
Lubricant 0.3 ~ 1 part,
0.1 ~ 0.5 part, oxidation inhibitor,
Nano barium sulfate 3.5 ~ 7 parts,
Calcined kaolin 2.6 ~ 5.2 parts,
Nano silicon 3.5 ~ 7 parts,
Silane coupling agent 0.18 ~ 0.36 part;
Silane coupling agent is first adopted to carry out joining after modification obtains resistance to water improver in blend thus obtained waterproof flame retardant PVC CABLE MATERIALS nano barium sulfate, calcined kaolin, nano silicon again;
Described silane coupling agent is that vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane and γ-glycidyl ether oxygen propyl trimethoxy silicane mix by 10:5:3 weight ratio.
2. water vapor flame-proof PVC sheath material according to claim 1, is characterized in that: described silane coupling agent is vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltrimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane.
3. water vapor flame-proof PVC sheath material according to claim 1, is characterized in that: described oxidation inhibitor be four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or dihydroxyphenyl propane.
4. water vapor flame-proof PVC sheath material according to claim 1, is characterized in that: described calcined kaolin is through adding the improver of gross weight 1.5 ~ 2%, calcination temperature 970 ~ 990 DEG C in calcination, the time is 30 ~ 40 minutes; Described improver is made up of cleaned coal, sodium sulfate and sodium-chlor, and this cleaned coal, sodium sulfate and sodium-chlor press the mixing of 10:0. 5:0. 3 weight.
CN201510391573.6A 2012-12-04 2012-12-04 Water-vapor-resisting inflaming retarding PVC protecting sleeve material Pending CN104945778A (en)

Applications Claiming Priority (1)

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CN201210510995.7A CN103044802B (en) 2012-12-04 2012-12-04 Waterproof flame retardant PVC cable material and preparation technology thereof

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CN201510611657.6A Pending CN105131469A (en) 2012-12-04 2012-12-04 Preparation process for hydrophobic PVC cable material
CN201510612073.0A Pending CN105153590A (en) 2012-12-04 2012-12-04 High-water-resistance compact compound PVC cable material
CN201510391788.8A Pending CN104945779A (en) 2012-12-04 2012-12-04 High-insulating cable sheath material
CN201210510995.7A Active CN103044802B (en) 2012-12-04 2012-12-04 Waterproof flame retardant PVC cable material and preparation technology thereof
CN201510611656.1A Pending CN105131468A (en) 2012-12-04 2012-12-04 Moisture-resistant waterproof polyvinyl chloride cable sheath material
CN201510391582.5A Active CN105017684B (en) 2012-12-04 2012-12-04 The preparation method of flame retardant type high reliability CABLE MATERIALS
CN201510391573.6A Pending CN104945778A (en) 2012-12-04 2012-12-04 Water-vapor-resisting inflaming retarding PVC protecting sleeve material

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CN201510611657.6A Pending CN105131469A (en) 2012-12-04 2012-12-04 Preparation process for hydrophobic PVC cable material
CN201510612073.0A Pending CN105153590A (en) 2012-12-04 2012-12-04 High-water-resistance compact compound PVC cable material
CN201510391788.8A Pending CN104945779A (en) 2012-12-04 2012-12-04 High-insulating cable sheath material
CN201210510995.7A Active CN103044802B (en) 2012-12-04 2012-12-04 Waterproof flame retardant PVC cable material and preparation technology thereof
CN201510611656.1A Pending CN105131468A (en) 2012-12-04 2012-12-04 Moisture-resistant waterproof polyvinyl chloride cable sheath material
CN201510391582.5A Active CN105017684B (en) 2012-12-04 2012-12-04 The preparation method of flame retardant type high reliability CABLE MATERIALS

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CN103509294B (en) * 2013-10-12 2016-03-02 绿宝电缆（集团）有限公司 A kind of cold-resistant fire-retardant PVC CABLE MATERIALS
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CN108831598A (en) * 2018-06-20 2018-11-16 江苏汉兴电缆有限公司 A kind of novel cable insulation sleeve
CN109486053A (en) * 2018-09-18 2019-03-19 百通赫思曼工业（苏州）有限公司 A kind of PVC cable material of low-k
CN109593290B (en) * 2018-10-19 2021-04-30 中广核三角洲（中山）高聚物有限公司 Silane crosslinked flame-retardant polyvinyl chloride cable material and preparation method thereof
CN109776999A (en) * 2018-12-29 2019-05-21 安徽天康(集团)股份有限公司 A kind of high temperature resistance control cable
CN112795111A (en) * 2020-12-28 2021-05-14 宜宾天亿新材料科技有限公司 High-fluidity low-cost PVC (polyvinyl chloride) cable material and preparation method thereof
CN114530293B (en) * 2022-03-01 2024-04-05 广东新亚光电缆股份有限公司 Preparation method of 1 kilovolt overhead insulated cable
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CN100999610A (en) * 2006-01-12 2007-07-18 中国林业科学研究院木材工业研究所 Wood plastic composite material composection and formed board thereof and their preparation process
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CN102585396A (en) * 2011-12-28 2012-07-18 上海特缆电工科技有限公司 Water-resistant polyvinyl chloride (PVC) cable insulating material

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CN113754965A (en) * 2021-08-20 2021-12-07 湖南联塑科技实业有限公司 High-compression-resistance PVC (polyvinyl chloride) water leading and draining pipe material and preparation method and application thereof
CN113754965B (en) * 2021-08-20 2022-09-16 湖南联塑科技实业有限公司 High-compression-resistance PVC (polyvinyl chloride) water leading and draining pipe material and preparation method and application thereof

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CN104945779A (en) 2015-09-30
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CN103044802A (en) 2013-04-17
CN105153590A (en) 2015-12-16
CN103044802B (en) 2016-01-20
CN105131468A (en) 2015-12-09
CN105017684B (en) 2018-03-09

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