CN107459680A - A kind of preparation method of ultra-high molecular weight polyethylene rubber composite - Google Patents

A kind of preparation method of ultra-high molecular weight polyethylene rubber composite Download PDF

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Publication number
CN107459680A
CN107459680A CN201710873670.8A CN201710873670A CN107459680A CN 107459680 A CN107459680 A CN 107459680A CN 201710873670 A CN201710873670 A CN 201710873670A CN 107459680 A CN107459680 A CN 107459680A
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China
Prior art keywords
molecular weight
high molecular
fiber
weight polyethylene
parts
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CN201710873670.8A
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Chinese (zh)
Inventor
章云
张贝尼
张娃妮
柯模松
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Anhui Yi Caini Fibrous Material Science And Technology Ltd
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Anhui Yi Caini Fibrous Material Science And Technology Ltd
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Priority to CN201710873670.8A priority Critical patent/CN107459680A/en
Publication of CN107459680A publication Critical patent/CN107459680A/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
    • C08L7/00—Compositions of natural rubber
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • 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
    • C08J2307/00—Characterised by the use of natural rubber
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • 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
    • C08L2207/068—Ultra high molecular weight polyethylene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

A kind of preparation method of ultra-high molecular weight polyethylene rubber composite, belongs to rubber composite preparing technical field, comprises the following steps：Ultrasonic wave combination chromic acid solution carries out surface modification treatment, Natural rubber to superhigh molecular weight polyethylene fibers and plasticates, fiber and other mixing ingredients, elastomeric compound film, elastomeric compound film vulcanizing treatment is made.Duplex surface modification processing is carried out to superhigh molecular weight polyethylene fibers using ultrasonic wave combination chromic acid solution, effectively increase the roughness and oxygen-containing functional group content of fiber surface, increase the surface-active of fiber, so as to strengthen the affinity with its rubber mass, composite modified technique adds the interface adhesion between fiber and NR matrixes.

Description

A kind of preparation method of ultra-high molecular weight polyethylene rubber composite
Technical field
The invention belongs to rubber composite preparing technical field, and in particular to a kind of ultra-high molecular weight polyethylene rubber is answered The preparation method of condensation material.
Background technology
Composite is that have different physics and chemical property, in the form of microcosmic or be macroscopical by two or more Compound and composition heterogeneous material.Because of simple natural rubber or synthetic rubber, whether unvulcanized rubber or vulcanizate, its Physical and mechanical properties is very poor to be difficult to meet the requirement used.Therefore, fibre property is improved, is elastomeric material hair by fiber composite One of inexorable trend of exhibition.
China is that the fiber such as rubber industry big producer, tire, conveyer belt, sebific duct/rubber composite is important army The dual-purpose product of the people, and high-performance fiber is the preferable framework material of rubber, but current high-performance fiber is in rubber Application do not popularize yet.And influence orientation that principal element that fiber applies in rubber is fiber in rubber mass, Scattered and between fiber and rubber mass interfacial adhesion is horizontal.
The content of the invention
According to problems of the prior art, the invention provides a kind of ultra-high molecular weight polyethylene rubber composite Preparation method so that fiber disperses more uniformly, and to further increase the boundary of fiber and rubber mass in rubber mass Face level of adhesion.
In order to solve problems of the prior art, the present invention uses following technical scheme：
A kind of preparation method of ultra-high molecular weight polyethylene rubber composite, comprises the following steps：
Step 1：By potassium bichromate, water and the concentrated sulfuric acid according to mass ratio 7:12:150 are configured to chromic acid solution, open ultrasound Ripple cleaning device, super high molecular weight polythene chopping fiber is immersed into chromic acid solution, and is put into 35 DEG C of ultrasonic washing instrument Middle oxidation 5min, wherein ultrasonic frequency are 100kHz, processing time 10min, by the ultra-high molecular weight polyethylene after processing Chopped strand with deionized water clean at 3 times, 50 DEG C dry after it is standby；
Step 2：Natural rubber is plasticated 15-20min on a mill, more than 8h is stood, to eliminate Natural rubber Internal axial stress；
Step 3：Dispensing is carried out by following parts by weight：100 parts of Natural rubber, ultra-high molecular weight polyethylene are chopped fine 5 parts of dimension, 3 parts of zinc oxide, 2 parts of stearic acid, 1.2 parts of accelerator NS, 1.5 parts of anti-aging agent RD, 1.5 parts of antioxidant 4010NA, hard charcoal Black 30 parts, 1.2 parts of sulphur；Natural rubber is added in mill and is kneaded, other are added after Natural rubber bag roller Dispensing, charging sequence are followed successively by zinc oxide, stearic acid, accelerator, age resistor, white carbon, sulphur, are eventually adding super high molecular weight Polythene chopping fiber；
Step 4：Triangle bag is beaten, after fiber is uniformly dispersed, adjusts roller square, to fiber be orientated then bottom sheet, is made Elastomeric compound film；
Step 5：Elastomeric compound film is placed into a night, eliminates axial stress, and vulcanized on vulcanizing press, sulphur Change temperature is 143 DEG C, cure time is 20 minutes.
Preferably, the melting temperature described in step 3 is 30-50 DEG C.
Preferably, roll spacing is adjusted to 0.5mm in step 4, and uses the method for alignment of a bottom sheet, then doubling twice, The elastomeric compound film that thickness is 2.0mm is made.
Preferably, the time control of the packing triangle described in step 4 is within 10min.
Preferably, the length of described super high molecular weight polythene chopping fiber is 1-25mm.
The beneficial effects of the present invention are：
1) superhigh molecular weight polyethylene fibers/rubber composite is by fiber and rubber mix, and is allowed in rubber matrix In be suitably oriented, to play the strengthening action of chopped fiber, so as to effectively combine the flexibility of rubber and the rigidity of fiber.Ensureing Rubber have it is unique it is elastomeric improve the modulus of rubber simultaneously, it possessed high-modulus, high rigidity, tear-resistant, resistance to cut Cut, a series of excellent properties such as low-heat-generation, creep resistant, so as to greatly widen the use range of rubber.
2) duplex surface modification processing is carried out to superhigh molecular weight polyethylene fibers using ultrasonic wave combination chromic acid solution, had The roughness and oxygen-containing functional group content of fiber surface are added to effect, increases the surface-active of fiber, so as to strengthen and its rubber The affinity of gel matrix, composite modified technique add the interface adhesion between fiber and NR matrixes.
Embodiment
Below by the description to embodiment, the present invention is further detailed explanation, to help people in the art Member has more complete, accurate and deep understanding to inventive concept of the invention, technical scheme.
Embodiment 1
A kind of preparation method of ultra-high molecular weight polyethylene rubber composite, comprises the following steps：
Step 1：By potassium bichromate, water and the concentrated sulfuric acid according to mass ratio 7:12:150 are configured to chromic acid solution, open ultrasound Ripple cleaning device, super high molecular weight polythene chopping fiber is immersed into chromic acid solution, and is put into 35 DEG C of ultrasonic washing instrument Middle oxidation 5min, wherein ultrasonic frequency are 100kHz, processing time 10min, by the ultra-high molecular weight polyethylene after processing Chopped strand with deionized water clean at 3 times, 50 DEG C dry after it is standby；
Step 2：Natural rubber is plasticated 15-20min on a mill, more than 8h is stood, to eliminate Natural rubber Internal axial stress；
Step 3：Dispensing is carried out by following parts by weight：100 parts of Natural rubber, ultra-high molecular weight polyethylene are chopped fine 5 parts of dimension, 3 parts of zinc oxide, 2 parts of stearic acid, 1.2 parts of accelerator NS, 1.5 parts of anti-aging agent RD, 1.5 parts of antioxidant 4010NA, hard charcoal Black 30 parts, 1.2 parts of sulphur；Natural rubber is added in mill and is kneaded, other are added after Natural rubber bag roller Dispensing, charging sequence are followed successively by zinc oxide, stearic acid, accelerator, age resistor, white carbon, sulphur, are eventually adding super high molecular weight Polythene chopping fiber；
Step 4：Triangle bag is beaten, after fiber is uniformly dispersed, adjusts roller square, to fiber be orientated then bottom sheet, is made Elastomeric compound film；
Step 5：Elastomeric compound film is placed into a night, eliminates axial stress, and vulcanized on vulcanizing press, sulphur Change temperature is 143 DEG C, cure time is 20 minutes.
Melting temperature described in step 3 is 30-50 DEG C.
Roll spacing is adjusted to 0.5mm in step 4, and using the method for alignment of a bottom sheet, then doubling twice, is made thickness Spend the elastomeric compound film for 2.0mm.
The time control of packing triangle described in step 4 is within 10min.
The length of described super high molecular weight polythene chopping fiber is 1-25mm.

Claims (5)

1. a kind of preparation method of ultra-high molecular weight polyethylene rubber composite, it is characterised in that comprise the following steps：
Step 1：By potassium bichromate, water and the concentrated sulfuric acid according to mass ratio 7:12:150 are configured to chromic acid solution, and it is clear to open ultrasonic wave Instrument is washed, super high molecular weight polythene chopping fiber is immersed into chromic acid solution, and is put into oxygen in 35 DEG C of ultrasonic washing instrument Change 5min, wherein ultrasonic frequency is 100kHz, processing time 10min, the ultra-high molecular weight polyethylene after processing is chopped Fiber with deionized water clean at 3 times, 50 DEG C dry after it is standby；
Step 2：Natural rubber is plasticated 15-20min on a mill, more than 8h is stood, to eliminate inside Natural rubber Axial stress；
Step 3：Dispensing is carried out by following parts by weight：100 parts of Natural rubber, super high molecular weight polythene chopping fiber 5 Part, 3 parts of zinc oxide, 2 parts of stearic acid, 1.2 parts of accelerator NS, 1.5 parts of anti-aging agent RD, 1.5 parts of antioxidant 4010NA, white carbon 30 Part, 1.2 parts of sulphur；Natural rubber is added in mill and is kneaded, other dispensings are added after Natural rubber bag roller, Charging sequence is followed successively by zinc oxide, stearic acid, accelerator, age resistor, white carbon, sulphur, is eventually adding superhigh molecular weight polyethylene Alkene chopped strand；
Step 4：Triangle bag is beaten, after fiber is uniformly dispersed, adjusts roller square, to fiber be orientated then bottom sheet, is made and is kneaded Glue film；
Step 5：Elastomeric compound film is placed into a night, eliminates axial stress, and is vulcanized on vulcanizing press, vulcanization temperature It is 20 minutes to spend for 143 DEG C, cure time.
2. a kind of preparation method of ultra-high molecular weight polyethylene rubber composite according to claim 1, its feature exist In：Melting temperature described in step 3 is 30-50 DEG C.
3. a kind of preparation method of ultra-high molecular weight polyethylene rubber composite according to claim 1, its feature exist In：Roll spacing is adjusted to 0.5mm in step 4, and using the method for alignment of a bottom sheet, then doubling twice, thickness, which is made, is 2.0mm elastomeric compound film.
4. a kind of preparation method of ultra-high molecular weight polyethylene rubber composite according to claim 1, its feature exist In：The time control of packing triangle described in step 4 is within 10min.
5. a kind of preparation method of ultra-high molecular weight polyethylene rubber composite according to claim 1, its feature exist In：The length of described super high molecular weight polythene chopping fiber is 1-25mm.
CN201710873670.8A 2017-09-25 2017-09-25 A kind of preparation method of ultra-high molecular weight polyethylene rubber composite Pending CN107459680A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108395675A (en) * 2018-03-09 2018-08-14 天津工业大学 A kind of tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof
CN112961417A (en) * 2021-01-16 2021-06-15 江西江缆科技有限公司 High-flexibility fireproof cable and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101457476A (en) * 2007-12-14 2009-06-17 上海化工研究院天地科技发展有限公司 Ultra-high molecular weight polyethylene fiber surface treatment method
CN104278511A (en) * 2013-07-10 2015-01-14 宁波大学 Composite surface modification method for ultra-high molecular weight polyethylene (UHMWPE) fibers
CN104292510A (en) * 2013-07-18 2015-01-21 宁波大学 Ultrahigh molecular weight polyethylene fiber/rubber composite material and preparation method thereof
CN104592614A (en) * 2015-01-26 2015-05-06 清华大学深圳研究生院 Ultra-high molecular weight polyethylene composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101457476A (en) * 2007-12-14 2009-06-17 上海化工研究院天地科技发展有限公司 Ultra-high molecular weight polyethylene fiber surface treatment method
CN104278511A (en) * 2013-07-10 2015-01-14 宁波大学 Composite surface modification method for ultra-high molecular weight polyethylene (UHMWPE) fibers
CN104292510A (en) * 2013-07-18 2015-01-21 宁波大学 Ultrahigh molecular weight polyethylene fiber/rubber composite material and preparation method thereof
CN104592614A (en) * 2015-01-26 2015-05-06 清华大学深圳研究生院 Ultra-high molecular weight polyethylene composite material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108395675A (en) * 2018-03-09 2018-08-14 天津工业大学 A kind of tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof
CN112961417A (en) * 2021-01-16 2021-06-15 江西江缆科技有限公司 High-flexibility fireproof cable and preparation method thereof

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Application publication date: 20171212