CN104987566A - High-tenacity wear-resisting organosilane crosslinked polyethylene insulating composite material and preparing method thereof - Google Patents

High-tenacity wear-resisting organosilane crosslinked polyethylene insulating composite material and preparing method thereof Download PDF

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Publication number
CN104987566A
CN104987566A CN201510338016.8A CN201510338016A CN104987566A CN 104987566 A CN104987566 A CN 104987566A CN 201510338016 A CN201510338016 A CN 201510338016A CN 104987566 A CN104987566 A CN 104987566A
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China
Prior art keywords
parts
crosslinked polyethylene
organosilane crosslinked
composite material
matrix material
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CN201510338016.8A
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Chinese (zh)
Inventor
夏云
夏建生
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BENGBU ZHENGYUAN ELECTRONIC TECHNOLOGY Co Ltd
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BENGBU ZHENGYUAN ELECTRONIC TECHNOLOGY Co Ltd
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Priority to CN201510338016.8A priority Critical patent/CN104987566A/en
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08L2205/03—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a high-tenacity wear-resisting organosilane crosslinked polyethylene insulating composite material. The composite material is characterized by being prepared by, by weight, 120-150 parts of low-intensity polyethylene resin, 10-15 parts of attapulgite, 5-10 parts of white carbon black, 2-4 parts of phenolic novolac resin, 3-5 parts of cellulose acetate butyrate, 2-4 parts of polyvinyl butyral, 2-3 parts of polypropylene glycol, 0.3-0.5 part of methylene diphenyl diisocyanate, 2-4 part of polypropylene glycol adipate, 1-2 parts of stearic acid and 3-6 parts of silane complexing agents. The organosilane crosslinked polyethylene insulating composite material has good intensity, toughness, weather resistance, water resistance and corrosion resistance and is high in tenacity, excellent in wear resistance, good in use performance and wide in application range.

Description

Tear-resistant organosilane crosslinked polyethylene insulation matrix material of a kind of high tenacity and preparation method thereof
Technical field
The present invention relates to field of compound material, be specifically related to tear-resistant organosilane crosslinked polyethylene insulation matrix material of a kind of high tenacity and preparation method thereof.
Background technology
Polyethylene production is large, abundance, cheap, be a kind of broad-spectrum resin.But poly consistency is low, weathering resistance and mechanical property Shortcomings, over-all properties is poor, needs improving SNR.Wherein, carrying out cross-linking modified to polyethylene is one of important means improving polyethylene performance, can improve the mechanical property of polyethylene products, chemical resistance and resistance to cracking energy etc., widen poly range of application.
Polyethylene crosslinking technology comprises radiation crosslinking, peroxide crosslinking, crosslinked with silicane etc., and wherein organosilane crosslinked polyethylene has that processing unit is simple, the feature of flexible and convenient operation, good economy performance, is paid close attention to widely and payes attention to.Organosilane crosslinked polyethylene has good insulating property, in being mainly used in, the production of low tension wire, cable, has good market outlook and high economic benefit.Along with further developing of the market requirement, silane crosslinked polyethylene also needs the defect improving the aspect such as mechanical property, weathering resistance further, and develop skill index, thus meets the particular requirement of every field.
Summary of the invention
The object of this invention is to provide the tear-resistant organosilane crosslinked polyethylene insulation matrix material of a kind of high tenacity, mechanical property, weathering resistance are good, applied range.
The present invention is achieved by the following technical solutions:
The tear-resistant organosilane crosslinked polyethylene insulation matrix material of a kind of high tenacity, it is obtained by the raw material of following weight parts:
Ldpe resin 120-150, attapulgite 10-15, white carbon black 5-10, linear phenolic resin 2-4, cellulose acetate butyrate 3-5, polyvinyl butyral acetal 2-4, polypropylene glycol 2-3, diphenylmethanediisocyanate 0.3-0.5, polypropylene adipate (PPA) 2-4, stearic acid 1-2, silane recombiner 3-6;
Wherein silane recombiner is obtained by the raw material of following weight parts: silane coupling A-151 1-3, fluorocarbon surfactant FC-4430 0.2-0.4, dicumyl peroxide 0.05-0.1, dibutyl tin laurate 0.1-0.2, antioxidant 1010 0.2-0.5; Preparation method is by the mixing of silane coupling A-151, dicumyl peroxide, dibutyl tin laurate and antioxidant 1010 and 200-400r/min adds fluorocarbon surfactant FC-443 600-800r/min stirring 3-5min again after stirring 10-15min, to obtain final product.
A preparation method for the tear-resistant organosilane crosslinked polyethylene insulation matrix material of high tenacity, comprises the following steps:
(1) by 600-800 DEG C of calcining 1-2h after attapulgite and white carbon black mixing, after cooling, grinding evenly, crosses 600-800 mesh sieve, obtain mixed fillers;
(2) polypropylene glycol is added vacuum-drying 0.5-1h in reactor, then temperature is adjusted to 70-80 DEG C, and add diphenylmethanediisocyanate 200-400r/min stirring reaction 2-4h under vacuum condition, obtain base polyurethane prepolymer for use as;
(3) linear phenolic resin is added after being mixed with the base polyurethane prepolymer for use as in (2) by the mixed fillers in (1), 1-2h is stirred prior to 800-1000r/min, add the common ball milling 2-4h of cellulose acetate butyrate, polypropylene adipate (PPA) and stearic acid again, obtain modified filler;
(4) first the modified filler in (3) is mixed with ldpe resin, add all the other raw materials again and mix 5-10min under 80-90 DEG C of condition in high-speed mixer, melt extrude finally by twin screw extruder 165-195 DEG C, granulation, packaging, obtain the tear-resistant organosilane crosslinked polyethylene insulation matrix material of high tenacity.
Advantage of the present invention is:
The present invention is cross-linked polyvinyl resin by fluorocarbon surfactant and the composite silane recombiner of silane coupling agent, improve the weathering resistance of matrix material, water tolerance, by base polyurethane prepolymer for use as and resol, composite modified process is carried out to filler simultaneously, both the toughness of filler had been improved, be conducive to the tensile property improving matrix material, turn improve the consistency between filler and matrix, filler is uniformly dispersed in resin, play the effect of reinforcement increase-volume, improve the physical strength of matrix material; Pass through the composite of all the other raw materials simultaneously, make the organosilane crosslinked polyethylene insulation matrix material obtained have good intensity, toughness, weathering resistance and water-fast, corrosion resistance nature good, there is high tenacity and excellent tear-resistant performance simultaneously, use properties is good, has wide range of applications.
Embodiment
Non-limiting examples of the present invention is as follows:
The tear-resistant organosilane crosslinked polyethylene insulation matrix material of a kind of high tenacity, is prepared from by the component raw material of following weight (kg):
Ldpe resin 140, attapulgite 12, white carbon black 8, linear phenolic resin 3, cellulose acetate butyrate 4, polyvinyl butyral acetal 3, polypropylene glycol 2.5, diphenylmethanediisocyanate 0.4, polypropylene adipate (PPA) 3, stearic acid 1.5, silane recombiner 5;
Wherein silane recombiner is obtained by the component raw material of following weight (kg): silane coupling A-151 2, fluorocarbon surfactant FC-4430 0.3, dicumyl peroxide 0.08, dibutyl tin laurate 0.15, antioxidant 1010 0.4; Preparation method is by the mixing of silane coupling A-151, dicumyl peroxide, dibutyl tin laurate and antioxidant 1010 and 200r/min adds fluorocarbon surfactant FC-443 800r/min stirring 3min again after stirring 15min, to obtain final product.
The preparation method of the tear-resistant organosilane crosslinked polyethylene insulation matrix material of high tenacity comprises the following steps:
(1) by attapulgite and the rear 800 DEG C of calcining 1h of white carbon black mixing, after cooling, grinding evenly, crosses 800 mesh sieves, obtain mixed fillers;
(2) polypropylene glycol is added vacuum-drying 0.5h in reactor, then temperature is adjusted to 80 DEG C, and add diphenylmethanediisocyanate 400r/min stirring reaction 2h under vacuum condition, obtain base polyurethane prepolymer for use as;
(3) add linear phenolic resin after being mixed with the base polyurethane prepolymer for use as in (2) by the mixed fillers in (1), stir 1h prior to 1000r/min, then add the common ball milling 2h of cellulose acetate butyrate, polypropylene adipate (PPA) and stearic acid, obtain modified filler;
(4) first the modified filler in (3) is mixed with ldpe resin, add all the other raw materials again and mix 5min under 90 DEG C of conditions in high-speed mixer, melt extrude finally by twin screw extruder 165-195 DEG C, granulation, packaging, obtain the tear-resistant organosilane crosslinked polyethylene insulation matrix material of high tenacity.
Carry out performance test to above-mentioned obtained matrix material, result is as shown in table 1:
Table 1 organosilane crosslinked polyethylene insulation composite property test result
Numbering Project
1 Tensile strength (MPa) 27.7MPa
2 Elongation at break (%) 721
3 Heat aging performance DEG C × h 135×168
3.1 Tensile strength velocity of variation (%) +9
3.2 Elongation at break velocity of variation (%) -8

Claims (2)

1. the tear-resistant organosilane crosslinked polyethylene insulation matrix material of high tenacity, is characterized in that, it is obtained by the raw material of following weight parts:
Ldpe resin 120-150, attapulgite 10-15, white carbon black 5-10, linear phenolic resin 2-4, cellulose acetate butyrate 3-5, polyvinyl butyral acetal 2-4, polypropylene glycol 2-3, diphenylmethanediisocyanate 0.3-0.5, polypropylene adipate (PPA) 2-4, stearic acid 1-2, silane recombiner 3-6;
Described silane recombiner is obtained by the raw material of following weight parts: silane coupling A-151 1-3, fluorocarbon surfactant FC-4430 0.2-0.4, dicumyl peroxide 0.05-0.1, dibutyl tin laurate 0.1-0.2, antioxidant 1010 0.2-0.5; Preparation method is by the mixing of silane coupling A-151, dicumyl peroxide, dibutyl tin laurate and antioxidant 1010 and 200-400r/min adds fluorocarbon surfactant FC-443 600-800r/min stirring 3-5min again after stirring 10-15min, to obtain final product.
2. the preparation method of the tear-resistant organosilane crosslinked polyethylene insulation matrix material of a kind of high tenacity according to claim 1, is characterized in that, comprise the following steps:
(1) by 600-800 DEG C of calcining 1-2h after attapulgite and white carbon black mixing, after cooling, grinding evenly, crosses 600-800 mesh sieve, obtain mixed fillers;
(2) polypropylene glycol is added vacuum-drying 0.5-1h in reactor, then temperature is adjusted to 70-80 DEG C, and add diphenylmethanediisocyanate 200-400r/min stirring reaction 2-4h under vacuum condition, obtain base polyurethane prepolymer for use as;
(3) linear phenolic resin is added after being mixed with the base polyurethane prepolymer for use as in (2) by the mixed fillers in (1), 1-2h is stirred prior to 800-1000r/min, add the common ball milling 2-4h of cellulose acetate butyrate, polypropylene adipate (PPA) and stearic acid again, obtain modified filler;
(4) first the modified filler in (3) is mixed with ldpe resin, add all the other raw materials again and mix 5-10min under 80-90 DEG C of condition in high-speed mixer, melt extrude finally by twin screw extruder 165-195 DEG C, granulation, packaging, obtain the tear-resistant organosilane crosslinked polyethylene insulation matrix material of high tenacity.
CN201510338016.8A 2015-06-17 2015-06-17 High-tenacity wear-resisting organosilane crosslinked polyethylene insulating composite material and preparing method thereof Pending CN104987566A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002181A (en) * 2010-12-23 2011-04-06 南京聚隆科技股份有限公司 High-toughness and high-strength polyethylene composite material and preparation method thereof
CN102532649A (en) * 2010-12-24 2012-07-04 江苏亨通电力电缆有限公司 Novel low-smoke halogen-free flame-retardant cable sheath material
CN102827454A (en) * 2012-08-28 2012-12-19 安徽双荣电器电缆有限公司 Polyethylene insulated power cable for coal mines and preparation method thereof
CN102942761A (en) * 2012-10-24 2013-02-27 常州大学 Low smoke halogen-free environment-protection fire-retardation type sheet molding compound and preparation method thereof
CN102993537A (en) * 2011-09-09 2013-03-27 滁州格美特科技有限公司 Weather-proof flame retardation antistatic crosslinking polyethylene tubing, preparation method and application
CN103201333A (en) * 2010-10-06 2013-07-10 英威达技术有限公司 Polymer compositions including cellulose ester
CN104072848A (en) * 2014-06-23 2014-10-01 李雪红 Polyethylene wear-resistant plastic
CN104086794A (en) * 2014-07-01 2014-10-08 中国林业科学研究院林产化学工业研究所 Preparation method of polyurethane prepolymer-toughened modified phenolic foam plastic
CN104371188A (en) * 2014-02-21 2015-02-25 解波 High strength and high gloss recycled plastic and preparation method thereof

Patent Citations (9)

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CN103201333A (en) * 2010-10-06 2013-07-10 英威达技术有限公司 Polymer compositions including cellulose ester
CN102002181A (en) * 2010-12-23 2011-04-06 南京聚隆科技股份有限公司 High-toughness and high-strength polyethylene composite material and preparation method thereof
CN102532649A (en) * 2010-12-24 2012-07-04 江苏亨通电力电缆有限公司 Novel low-smoke halogen-free flame-retardant cable sheath material
CN102993537A (en) * 2011-09-09 2013-03-27 滁州格美特科技有限公司 Weather-proof flame retardation antistatic crosslinking polyethylene tubing, preparation method and application
CN102827454A (en) * 2012-08-28 2012-12-19 安徽双荣电器电缆有限公司 Polyethylene insulated power cable for coal mines and preparation method thereof
CN102942761A (en) * 2012-10-24 2013-02-27 常州大学 Low smoke halogen-free environment-protection fire-retardation type sheet molding compound and preparation method thereof
CN104371188A (en) * 2014-02-21 2015-02-25 解波 High strength and high gloss recycled plastic and preparation method thereof
CN104072848A (en) * 2014-06-23 2014-10-01 李雪红 Polyethylene wear-resistant plastic
CN104086794A (en) * 2014-07-01 2014-10-08 中国林业科学研究院林产化学工业研究所 Preparation method of polyurethane prepolymer-toughened modified phenolic foam plastic

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Application publication date: 20151021