CN106221053A - There is the PVC fire proofing of hydrophobic performance - Google Patents

There is the PVC fire proofing of hydrophobic performance Download PDF

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Publication number
CN106221053A
CN106221053A CN201610426627.2A CN201610426627A CN106221053A CN 106221053 A CN106221053 A CN 106221053A CN 201610426627 A CN201610426627 A CN 201610426627A CN 106221053 A CN106221053 A CN 106221053A
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Prior art keywords
parts
hydrophobic performance
silane coupler
pvc
barium sulfate
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Pending
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CN201610426627.2A
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Chinese (zh)
Inventor
程晓松
于德宝
郑晓龙
廖永江
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Suzhou Hengli Communications Material Co Ltd
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Suzhou Hengli Communications Material Co Ltd
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Priority to CN201610426627.2A priority Critical patent/CN106221053A/en
Publication of CN106221053A publication Critical patent/CN106221053A/en
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C08K9/00—Use of pretreated ingredients
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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
    • 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
    • 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

A kind of PVC fire proofing with hydrophobic performance of the present invention, is made up of the component of following weight portion: polrvinyl chloride, trioctyl trimellitate (TOTM), diisooctyl phthalate, environmental protection calcium-zinc composite stabilizing agent, compound rare-earth stabilizer, antimony oxide, lubricant, antioxidant, nano barium sulfate, calcined kaolin, nano silicon, silane coupler；Nano barium sulfate, calcined kaolin, nano silicon are carried out Surface coating process；Being put in high-speed mixer by the powder of said components, mixed at high speed is dehydrated；It is that vaporific spraying into carries out cladding process to powder in high-speed mixer by silane coupler, continues mixed at high speed and carry out material surface cladding process；Described water-proofing agent is obtained after cooling.Product of the present invention uses under moist or water-immerged environment, and electric property is stable, does not the most produce change.

Description

There is the PVC fire proofing of hydrophobic performance
Technical field
The present invention relates to a kind of PVC fire proofing, particularly relate to a kind of PVC fire proofing with hydrophobic performance.
Background technology
PVC cable insulating material is one of general synthetic plastic, is the second largest plastics being only second to polyethylene at present in the world Kind.Polyvinyl chloride cable material is simple owing to having good mechanical and physical performance, electric property, and processing technique, processability Can be excellent, price is relatively low, occupy prostatitis in CABLE MATERIALS industry total amount always, is widely used.PVC cable material is low in being generally used for The products such as pressure, data communication class cable, general purpose electric wire product, PVC cable material disclosure satisfy that insulation, sheath substantially Demand.But being as the extension of electric wire application scenario, the requirement to PVC cable material improves constantly, at the water-fast electric insulation of PVC In performance, always one difficult point, it is difficult to for a long time solve.
Polyvinyl chloride resin itself has excellent water resistance, but must add all kinds of plasticizer owing to CABLE MATERIALS produces, stablize Agent, all kinds of filler (potter's clay, calcium carbonate etc.), inevitably reduce the immersion electrical property of product.Prior art is from document On be difficult to find, but typically use high-quality plasticizer, reduce or without the mode of filler, product index performance is still difficult to meet The problems such as requirement, easily causes the indexs such as thermal deformation defective simultaneously, cost increase.
Summary of the invention
It is an object of the invention to provide a kind of PVC fire proofing with hydrophobic performance, this PVC fire proofing is substantially reduced The water absorption of the coat layer of power cable, product uses under moist or water-immerged environment, further increases electric property stable, substantially Do not produce change, improve the compactness of product, get rid of material micropore.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of fire-retardant material of PVC with hydrophobic performance Material, described in there is the PVC material of hydrophobic performance for being coated on cable core outer surface, described PVC material is by the group of following weight portion It is grouped into:
Polrvinyl chloride 100 parts, trioctyl trimellitate (TOTM) 25 parts, diisooctyl phthalate 20 parts, environmental protection Ca Zn composite are stable Agent 8 parts, compound rare-earth stabilizer 5 parts, antimony oxide 8 parts, lubricant 0.9 part, 0.3 part of antioxidant, nano barium sulfate 6.5 Part, calcined kaolin 4 parts, nano silicon 6.8 parts, silane coupler 0.35 part；
Wherein, described nano barium sulfate, calcined kaolin, nano silicon and silane coupler are formed by following technique Water-proofing agent:
Step one, described nano barium sulfate, calcined kaolin, nano silicon are carried out Surface coating process；
Step 2, the powder of said components is put in high-speed mixer, mixed at high speed to temperature 90 ~ 100 DEG C carries out being dehydrated 3 ~ 5min；
Step 3, it is that vaporific spraying into carries out cladding process to powder in high-speed mixer by silane coupler, continues mixed at high speed Carry out material surface cladding and process reaction 3 ~ 5min；
Described water-proofing agent is obtained after step 4, cooling.
The technical scheme improved further in above-mentioned waterproof flame retardant restrictive coating technical scheme is as follows:
1, in such scheme, described silane coupler is vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl trimethoxy Silane or γ-glycidyl ether oxygen propyl trimethoxy silicane.
2, in such scheme, described antioxidant [3-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] tetramethylolmethane that is four Ester or bisphenol-A.
Due to the utilization of technique scheme, the present invention compared with prior art has the advantage that
The present invention has the PVC fire proofing of hydrophobic performance, and the plasticizer and the filler which overcome existing product formula all have Water absorption, thus the most easily occur properties of product decline phenomenon technological deficiency, the present invention considers all Formula materials all with the problem of the compatibility of water, select specific hydrophobic material and content.To carrying out surface after powder predrainage Cladding processes, and improves the hydrophobic performance of product；Product uses under moist or water-immerged environment, and electric property is stable, does not produces Changing；Water-proofing agent material selection nanoscale raw material, improves the compactness of product, gets rid of material micropore, and steam cannot invade and make Become hydraulic performance decline.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment: a kind of PVC fire proofing with hydrophobic performance, described cable includes cable core and is coated on cable core outer surface Flame retardant jacket materials, described flame retardant jacket materials is made up of the component of following weight portion:
Polrvinyl chloride 100 parts,
Trioctyl trimellitate (TOTM) (TOTM) 25 parts,
Diisooctyl phthalate 20 parts,
Environmental protection calcium-zinc composite stabilizing agent 8 parts,
Compound rare-earth stabilizer 5 parts,
Antimony oxide 8 parts,
Lubricant 0.9 part,
0.3 part of antioxidant,
Nano barium sulfate 6.5 parts,
Calcined kaolin 4 parts,
Nano silicon 6.8 parts,
Silane coupler 0.35 part；
More than it is weight portion.
Above-mentioned silane coupler be vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltrimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane.
Above-mentioned calcined kaolin is the improver of addition gross weight 1.5 ~ 2% when in calcination, calcination temperature 970 ~ 990 DEG C, Time is 30 ~ 40 minutes；Described improver is made up of cleaned coal, sodium sulfate and sodium chloride, and this cleaned coal, sodium sulfate and sodium chloride are pressed 10:0. 5:0. 3 weight mixes.
The preparation technology of the above-mentioned PVC fire proofing with hydrophobic performance, comprises the following steps:
Step one, by the degree of polymerization be 590～720 polrvinyl chloride, the degree of polymerization be that 1110～1340 polrvinyl chloride are through high-speed mixer It is mixed to form mixture under high-speed stirred state；Start stirring at low speed, rotating speed 500rpm, add trioctyl trimellitate (TOTM) and neighbour Phthalic acid isodecyl ester, start high-speed stirred, rotating speed 1000rpm, treat material temperature rise to 80 DEG C add environmental protection calcium-zinc composite stabilizing agents, Compound rare-earth stabilizer, antimony oxide, lubricant, antioxidant and water-proofing agent, continuation stirring are dry powder to 110 DEG C of materials of temperature Shape, opens baiting valve blowing；
Step 2, the compound of step one is put that to carry out extrusion molding to twin screw mixing, subsequently into single multiple screw extruder pelletize, adopt By the fervent prilling of die face, the particle made enters first order whirlwind cooling separator, the second level by blower fan conveyance conduit Whirlwind cooling separator, air-cooled vibrosieve, third level 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, calcined kaolin, nano silicon are carried out Surface coating process；
Step 2, the powder of said components is put in high-speed mixer, mixed at high speed to temperature 90 ~ 100 DEG C carries out being dehydrated 3 ~ 5min；
Step 3, silane coupler 0.18 ~ 0.36 part is carried out cladding process in vaporific spraying in high-speed mixer to powder, continue Continuous mixed at high speed carries out material surface cladding and processes reaction 3 ~ 5min；
Described resistance to water improver is obtained after step 4, cooling.
Manufacturing process is with embodiment 1.
Water resistance test uses " ASTM D2219-02 electric wire and cable pvc material specification " 5.5 tests Condition (electric current 60Hz frequency, temperature of soaking: 50 ± 1 DEG C).
Test result analysis: the accelerated water absorption test of product, change in dielectric constant rate much smaller than standard (1 ~ 14d, 10%；7~ 14d, 5%) requirement, product has good water resistance.
To sum up, when using the above-mentioned PVC fire proofing with hydrophobic performance, the plasticizer of existing product formula is which overcomed And the water absorption that filler all has, thus the most easily occur that properties of product decline the technological deficiency of phenomenon；This Bright consider all of formula materials all with the compatibility of water, select hydrophobic material.To carrying out Surface coating after powder predrainage Process, improve the hydrophobic performance of product；Product uses under moist or water-immerged environment, and electric property is stable, does not the most produce change Change；Water-proofing agent material selection nanoscale raw material, improves the compactness of product, gets rid of material micropore, and steam cannot invade causing property Can decline.
Above-described embodiment, only for technology design and the feature of the explanation present invention, its object is to allow person skilled in the art Scholar will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this.All according to the present invention The equivalence that spirit is made changes or modifies, and all should contain within protection scope of the present invention.

Claims (3)

1. there is a PVC fire proofing for hydrophobic performance, described in there is the PVC material of hydrophobic performance for being coated on cable core Outer surface, it is characterised in that: described PVC material is made up of the component of following weight portion: polrvinyl chloride 100 parts, tri trimellitate Monooctyl ester 25 parts, diisooctyl phthalate 20 parts, environmental protection calcium-zinc composite stabilizing agent 8 parts, compound rare-earth stabilizer 5 parts, three oxygen Change 8 parts of two antimony, lubricant 0.9 part, 0.3 part of antioxidant, nano barium sulfate 6.5 parts, calcined kaolin 4 parts, nano silicon 6.8 parts, silane coupler 0.35 part；
Wherein, described nano barium sulfate, calcined kaolin, nano silicon and silane coupler are formed by following technique Water-proofing agent:
Step one, described nano barium sulfate, calcined kaolin, nano silicon are carried out Surface coating process；
Step 2, the powder of said components is put in high-speed mixer, mixed at high speed to temperature 90 ~ 100 DEG C carries out being dehydrated 3 ~ 5min；
Step 3, it is that vaporific spraying into carries out cladding process to powder in high-speed mixer by silane coupler, continues mixed at high speed Carry out material surface cladding and process reaction 3 ~ 5min；
Described water-proofing agent is obtained after step 4, cooling.
The PVC fire proofing with hydrophobic performance the most according to claim 1, it is characterised in that: described silane coupler For vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltrimethoxy silane or γ-glycidyl ether oxygen propyl front three TMOS.
The PVC fire proofing with hydrophobic performance the most according to claim 1, it is characterised in that: described antioxidant is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester or bisphenol-A.
CN201610426627.2A 2012-12-04 2012-12-04 There is the PVC fire proofing of hydrophobic performance Pending CN106221053A (en)

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CN201210512702.9A CN103849084B (en) 2012-12-04 2012-12-04 Waterproof flame retardant restrictive coating and manufacturing process thereof for cable
CN201610426627.2A CN106221053A (en) 2012-12-04 2012-12-04 There is the PVC fire proofing of hydrophobic performance

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CN201610425093.1A Pending CN105949662A (en) 2012-12-04 2012-12-04 Flame-retardant jacket material for low-medium voltage cable
CN201610426627.2A Pending CN106221053A (en) 2012-12-04 2012-12-04 There is the PVC fire proofing of hydrophobic performance
CN201210512702.9A Active CN103849084B (en) 2012-12-04 2012-12-04 Waterproof flame retardant restrictive coating and manufacturing process thereof for cable

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CN104072914B (en) * 2014-07-09 2016-04-06 苏州亨利通信材料有限公司 Cold-resistant flame retarding PVC composition for cable
CN104371216A (en) * 2014-10-30 2015-02-25 安徽电信器材贸易工业有限责任公司 Water-resistant polyvinyl chloride cable sheath material and preparation method thereof
CN104356542A (en) * 2014-10-30 2015-02-18 安徽电信器材贸易工业有限责任公司 Flame-retardant PVC (polyvinyl chloride) sheath material for ultrahigh-voltage cables and preparation method of material
CN109096653A (en) * 2018-08-21 2018-12-28 山东寰宇线缆有限公司 A kind of applicable high-speed production automobile polyvinyl chloride cable material and preparation method thereof
CN109265861A (en) * 2018-08-31 2019-01-25 安庆市泽烨新材料技术推广服务有限公司 Network system cable sheath 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
CN113981741B (en) * 2021-09-30 2023-08-01 浙江天益塑业有限公司 Heat-resistant flame-retardant paper-plastic composite bag and preparation method thereof

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CN103849084A (en) 2014-06-11
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