CN104592589B - A kind of nitrile rubber/polyvinyl chloride composite materials and preparation method thereof - Google Patents
A kind of nitrile rubber/polyvinyl chloride composite materials and preparation method thereof Download PDFInfo
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- CN104592589B CN104592589B CN201510014351.2A CN201510014351A CN104592589B CN 104592589 B CN104592589 B CN 104592589B CN 201510014351 A CN201510014351 A CN 201510014351A CN 104592589 B CN104592589 B CN 104592589B
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- polyvinyl chloride
- nitrile rubber
- nitrile
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- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 102
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 100
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 150000002825 nitriles Chemical class 0.000 claims abstract description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
- 229910052582 BN Inorganic materials 0.000 claims abstract description 23
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 22
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 21
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000919 ceramic Substances 0.000 claims abstract description 20
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 18
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007921 spray Substances 0.000 claims abstract description 18
- 239000008117 stearic acid Substances 0.000 claims abstract description 18
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011787 zinc oxide Substances 0.000 claims abstract description 17
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 17
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 16
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004073 vulcanization Methods 0.000 claims abstract description 16
- 239000004014 plasticizer Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims description 14
- 230000005855 radiation Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 229920001971 elastomer Polymers 0.000 abstract description 13
- 238000005987 sulfurization reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 230000001050 lubricating effect Effects 0.000 abstract description 4
- 239000000314 lubricant Substances 0.000 abstract description 3
- 239000012744 reinforcing agent Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 6
- 239000003595 mist Substances 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 241001354491 Lasthenia californica Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- -1 propylene Nitrile Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
-
- 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
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—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
- 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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a kind of nitrile rubber/polyvinyl chloride composite materials and preparation method thereof, prepared by following raw material: superelevation nitrile nitrile rubber, middle high nitrile nitrile rubber part, polyvinyl chloride, porous ceramics, nm-class boron nitride, nano-silicon nitride part, spray carbon black, zinc oxide, stearic acid, zinc stearate, plasticizer DOP, trithiocyanuric acid, ultra-fine form of finely divided powder, mehtod polyvinyl chloride, Vulcanization accelerator TMTD, altax, anti-aging agent RD, antioxidant MB.The present invention, using porous ceramics replacement part carbon black as reinforcing agent, uses nano-silicon nitride and nm-class boron nitride simultaneously, again through sulfurization after mixing, thus forms lubricating film in rubber article and is produced from lubricant effect, improves the wearability of material；Ultra-fine form of finely divided powder, mehtod polyvinyl chloride, as vulcanizing agent, improves stability, heat resistance and the hardness of material.Therefore, nitrile rubber/polyvinyl chloride composite materials that prepared by the present invention has good hardness, elasticity, heat resistance and wearability.
Description
Technical field
The present invention relates to the technical field of modification of nitrile rubber, particularly relate to a kind of nitrile rubber/
Polyvinyl chloride composite materials and preparation method thereof.
Background technology
Nitrile rubber (NBR) have good tear resistance, relatively low compression,
Excellent anti-wear performance and oil resistance, the purposes of its maximum is to produce oil-resisting rubber hose, fire-retardant defeated
Send band and oil resistant rubber gasket material, be widely used to automobile, Aero-Space, oil field
The fields such as chemical industry.At present, nitrile rubber is carried out blending and modifying with find new reinforcement system with
And vulcanizing system has become as the important channel optimizing nitrile rubber performance.
At present, utilize the technology such as dynamic vulcanization technology, prepared NBR/polyvinyl chloride,
NBR/polypropylene, NBR/second the third glue, NBR/polystyrene, NBR/chlorosulfonation are gathered
The blend product such as ethene, NBR/polyamide, NBR/butyl rubber, wherein NBR/polychlorostyrene
Ethene Blend rubber purposes is the most extensive.Compared with single nitrile rubber, the stretching of blended rubber is strong
Degree and tear resistance are improved, and wearability, oil resistivity and resistance to ozone cracking are significantly improved,
Improve fire resistance simultaneously, thus be widely used in wires and cables industry.
As communications industry is fast-developing, the demand to electric wire for the market increases day by day, NBR
The consumption of/polyvinyl chloride is rising year by year, and the requirement day of the combination property to electric wire
Benefit is harsh, it is desirable to broader operating temperature range and higher service life.Therefore, butyronitrile rubber
Glue must have higher comprehensive mechanical property as electric wire and cable material and heat-resistant is aging, resistance to
Low temperature, oil resistivity and low compression set.The China of Application No. 201110006865.5 is specially
Profit document reports a kind of electric wire flame-retardant thermoset butyronitrile polyvinyl chloride rubber, this rubber
Intensity, stretch rate and fire resistance is all good than General Purpose Rubber, but the performances such as its consistency and elasticity
Await improving further.
Content of the invention
Present invention solves the technical problem that and be to provide a kind of nitrile rubber/polyvinyl chloride composite wood
Material and preparation method thereof, it has good hardness, elasticity, heat resistance and wearability.
In view of this, the invention provides a kind of nitrile rubber/polyvinyl chloride composite materials, by with
Prepared by lower raw material: superelevation nitrile nitrile rubber 70-80 weight portion, middle high nitrile nitrile rubber 20-30
Weight portion, polyvinyl chloride 35-50 weight portion, porous ceramics 5-10 weight portion, nm-class boron nitride
10-15 weight portion, nano-silicon nitride 10-15 weight portion, spray carbon black 20-30 weight portion, oxygen
Change zinc 4-8 weight portion, stearic acid 2-4 weight portion, zinc stearate 1-2 weight portion, plasticizer
DOP 5-10 weight portion, trithiocyanuric acid 0.7-1.2 weight portion, ultra-fine form of finely divided powder, mehtod polychlorostyrene
Ethene 10-15 weight portion, Vulcanization accelerator TMTD 0.5-2 weight portion, altax 1-2.5 weight
Amount part, anti-aging agent RD 2-5 weight portion, antioxidant MB 2-5 weight portion.
Preferably, described ultra-fine form of finely divided powder, mehtod polyvinyl chloride is prepared as follows:
In polyvinyl chloride emulsion, by 3～8% addition cross-linking radiation auxiliary agents of dry glue weight
TMPTA, then carries out cross-linking radiation, obtains ultra-fine sulfide powder polyvinyl chloride after spray drying.
Accordingly, the present invention also provides the preparation side of a kind of nitrile rubber/polyvinyl chloride composite materials
Method, comprises the following steps: step a) is by 70-80 weight portion superelevation nitrile nitrile rubber, 20-30
In weight portion, high nitrile nitrile rubber and 35-50 weight portion polyvinyl chloride put in banbury, heating
To 80～90 DEG C, plasticate 10～30 minutes；Step b) is warming up to 110～130 DEG C, adds 5-10
Weight portion porous ceramics, 10-15 weight portion nm-class boron nitride, 10-15 weight portion nano-silicon nitride,
20-30 weight portion spray carbon black, 4-8 part by weight of zinc oxide, 2-4 weight portion stearic acid, 1-2 weight
Amount part zinc stearate, 5-10 parts by weight of plasticizer DOP, 2-5 weight portion anti-aging agent RD and 2-5
Weight portion antioxidant MB, kneads 10～30 minutes, cools down, obtain elastomeric compound after discharge；Step
Suddenly c) described elastomeric compound is put in mill, addition 0.7-1.2 weight portion trithiocyanuric acid,
10-15 weight portion ultra-fine form of finely divided powder, mehtod polyvinyl chloride, 0.5-2 weight portion Vulcanization accelerator TMTD and
1-2.5 weight portion altax, thin logical after obtain nitrile rubber/polyvinyl chloride composite materials.
Preferably, described ultra-fine form of finely divided powder, mehtod polyvinyl chloride is prepared as follows:
In polyvinyl chloride emulsion, by 3～8% addition cross-linking radiation auxiliary agents of dry glue weight
TMPTA, then carries out cross-linking radiation, obtains ultra-fine sulfide powder polyvinyl chloride after spray drying.
Preferably, described zinc oxide is 8 weight portions.
Preferably, described stearic acid is 4 weight portions.
Preferably, the time of plasticating is 15～20 minutes.
Preferably, mixing time is 15～20 minutes.
Preferably, cool time is 20～30 hours.
Preferably, thin logical number of times is 6～8 times.
The invention provides a kind of nitrile rubber/polyvinyl chloride composite materials and preparation method thereof, by
Prepared by following raw material: superelevation nitrile nitrile rubber, middle high nitrile nitrile rubber part, and polyvinyl chloride is many
Hole pottery, nm-class boron nitride, nano-silicon nitride part, spray carbon black, zinc oxide, stearic acid,
Zinc stearate, plasticizer DOP, trithiocyanuric acid, ultra-fine form of finely divided powder, mehtod polyvinyl chloride, promote
Enter agent TMTD, altax, anti-aging agent RD, antioxidant MB.Compared with prior art,
The present invention using porous ceramics replace part carbon black as reinforcing agent, simultaneously use nano-silicon nitride and
Nm-class boron nitride, again through sulfurization after mixing, thus forms lubricating film in rubber article
And it is produced from lubricant effect, improve the wearability of material；Ultra-fine form of finely divided powder, mehtod polyvinyl chloride
As vulcanizing agent, improve stability, heat resistance and the hardness of material.Therefore, system of the present invention
Standby nitrile rubber/polyvinyl chloride composite materials has good hardness, elasticity, heat resistance and resistance to
Mill property.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment to the preferred embodiment of the invention
It is described, but it is to be understood that these describe simply as further illustrating inventive feature
And advantage, rather than limiting to the claimed invention.
The embodiment of the invention discloses the preparation side of a kind of nitrile rubber/polyvinyl chloride composite materials
Method, comprises the following steps: step a) is by 70-80 weight portion superelevation nitrile nitrile rubber, 20-30
In weight portion, high nitrile nitrile rubber and 35-50 weight portion polyvinyl chloride put in banbury, heating
To 80～90 DEG C, plasticate 10～30 minutes；Step b) is warming up to 110～130 DEG C, adds 5-10
Weight portion porous ceramics, 10-15 weight portion nm-class boron nitride, 10-15 weight portion nano-silicon nitride,
20-30 weight portion spray carbon black, 4-8 part by weight of zinc oxide, 2-4 weight portion stearic acid, 1-2 weight
Amount part zinc stearate, 5-10 parts by weight of plasticizer DOP, 2-5 weight portion anti-aging agent RD and 2-5
Weight portion antioxidant MB, kneads 10～30 minutes, cools down, obtain elastomeric compound after discharge；Step
Suddenly c) described elastomeric compound is put in mill, addition 0.7-1.2 weight portion trithiocyanuric acid,
10-15 weight portion ultra-fine form of finely divided powder, mehtod polyvinyl chloride, 0.5-2 weight portion Vulcanization accelerator TMTD and
1-2.5 weight portion altax, thin logical after obtain nitrile rubber/polyvinyl chloride composite materials.
Wherein, nitrile rubber carries out grade classification by the classification of bound acrylonitrile amount, specific as follows:
Superelevation nitrile nitrile rubber: bound acrylonitrile amount is 42%；Middle high nitrile nitrile rubber: combine propylene
Nitrile amount is 31-35%.Polyvinyl chloride (PVC) has certain polarity, and nitrile rubber (NBR)
In contain substantial amounts of polar bond, therefore compatibility when NBR and PVC is blended is preferable.The present invention
Use superelevation nitrile nitrile rubber and middle high nitrile nitrile rubber (NBR) to be primary raw material, add poly-
Vinyl chloride (PVC) carries out blending and modifying to nitrile rubber, by the common friendship of NBR and PVC
Connection reaction improves the consistency and elasticity of material.
The vulcanizing agent trithiocyanuric acid (TCY) that the present invention adds and nitrile rubber and polyvinyl chloride
All can react, the heat aging performance of nitrile rubber and polyvinyl chloride blend and resistance to can be improved
Oiliness energy；Ultra-fine form of finely divided powder, mehtod polyvinyl chloride, as vulcanizing agent, can improve NBR's simultaneously
Stability, heat resistance and hardness.Nitrile rubber/polyvinyl chloride composite materials prepared by the present invention with
Trithiocyanuric acid and ultra-fine form of finely divided powder, mehtod polyvinyl chloride are as vulcanizing agent, the strength of materials obtaining
Height, elastic modelling quantity height, weatherability, cold resistance and the ozone aging resistance of the diaphragm, oil resistant, wear-resisting, resistance to tearing and
Flame resistant improves, and cost also decreases.
The porous ceramics that the present invention adds is with emergy, carborundum, cordierite etc. as main material,
The one prepared through overmolding and special high-sintering process has open pore size, high open pore
A kind of porous ceramic materials of rate, has light weight, specific surface area big, high temperature resistant, chemically
The features such as matter is stable, can replace part carbon black to improve the intensity of material, prevent cracking, and
And the elasticity of material can be improved；The nm-class boron nitride and the nano-silicon nitride that add can replace portion
Dividing carbon black to improve the intensity of material, nm-class boron nitride has the lamellar structure of similar graphite, changes
Learn character extremely stable, high temperature resistant, corrosion-resistant, thermal coefficient of expansion is low, greasy property is excellent,
Oil-resisting and heat-resisting and the processing characteristics of material can be effectively improved；Nano-silicon nitride mechanical strength is high,
Resistance to chemical corrosion is good, and has self-lubricating property, forms trickle disperse in the composite
Phase, thus improve the combination property of material, nm-class boron nitride and nano-silicon nitride are made jointly simultaneously
With, from vulcanizate spray when can rubber article formed lubricating film and be produced from lubrication effect
Really, the wearability of material is improved.
Preferably, described ultra-fine form of finely divided powder, mehtod polyvinyl chloride is preferably as follows
Preparation: in polyvinyl chloride emulsion, by 3～8% addition cross-linking radiation auxiliary agents of dry glue weight
TMPTA, then carries out cross-linking radiation, contains super in the polyvinyl chloride emulsion after irradiated crosslinking
Thin vulcanized polyvinyl chloride particle, obtains ultra-fine sulfide powder polyvinyl chloride after spray drying.
Preferably, the parts by weight to each raw material for the present invention are adjusted, described oxygen
Change zinc and be preferably 8 weight portions；Described stearic acid is preferably 4 weight portions.
Preferably, the time of plasticating is preferably 15～20 minutes；Mixing time is preferably
15～20 minutes；It is preferably 20～30 hours cool time；Thin logical number of times is preferably 6～10 times,
More preferably 6～8 times.
From above scheme it can be seen that the present invention replaces part carbon black as reinforcement using porous ceramics
Agent, uses nano-silicon nitride and nm-class boron nitride simultaneously, again through sulfurization after mixing, thus
Form lubricating film in rubber article and be produced from lubricant effect, improve the wearability of material；
Ultra-fine form of finely divided powder, mehtod polyvinyl chloride, as vulcanizing agent, improves stability, the heat resistance of material
And hardness.Therefore, nitrile rubber/polyvinyl chloride composite materials that prepared by the present invention has good
Hardness, elasticity, heat resistance and wearability.
In order to be further appreciated by the present invention, the technical side that the present invention provided below in conjunction with embodiment
Case is described in detail, and protection scope of the present invention is not limited by the following examples.
The raw material that the present invention uses is superelevation nitrile nitrile rubber and middle high nitrile nitrile rubber, and uses
Polyvinyl chloride is modified.
The filler that the present invention uses is porous ceramics, nm-class boron nitride, nano-silicon nitride and spray
Mist carbon black.
The vulcanizing agent that the present invention uses is trithiocyanuric acid, ultra-fine form of finely divided powder, mehtod polyvinyl chloride,
Vulcanizing activator is zinc oxide, zinc stearate, Vulcanization accelerator TMTD, altax, anti-old
Agent RD and antioxidant MB.
Superelevation nitrile nitrile rubber used in the following example of the present invention and middle high nitrile nitrile rubber
It is purchased from the prosperous and powerful Chemical Co., Ltd. in Shanghai.
It is limited that porous ceramics used in the following example of the present invention is purchased from Yixing City gold field porcelain industry
Company.
Nm-class boron nitride used in the following example of the present invention and nano-silicon nitride are purchased from Nanjing
Guan Ye Chemical Co., Ltd..
Spray carbon black used in the following example of the present invention, zinc oxide, zinc stearate, promotion
Agent TMTD, altax, anti-aging agent RD and antioxidant MB are purchased from Guangzhou this rubber of power
Collagen material trade Co., Ltd.
Trithiocyanuric acid used in the following example of the present invention is purchased from Shanghai, and to grind minister industry limited
Company.
Embodiment 1
In polyvinyl chloride emulsion, by 3～8% addition cross-linking radiation auxiliary agents of dry glue weight
TMPTA, then carries out cross-linking radiation, contains ultra-fine after irradiated crosslinking in polyvinyl chloride emulsion
Vulcanized polyvinyl chloride particle, is then spray-dried, and obtains ultra-fine sulfide powder polyvinyl chloride.
Prepare nitrile rubber/polyvinyl chloride composite materials, prepare raw material and parts by weight such as table 1 thereof
Shown in.
Table 1 high-performance nitrile rubber/polyvinyl chloride composite materials prepare raw material and parts by weight thereof
Embodiment 2
A kind of preparation method of high-performance nitrile rubber/polyvinyl chloride composite materials, this material by with
Prepared by the raw material of lower parts by weight: superelevation nitrile nitrile rubber 70 parts, middle high nitrile nitrile rubber 30
Part, polyvinyl chloride 35 parts, porous ceramics 5 parts, nm-class boron nitride 10 parts, nano-silicon nitride
10 parts, spray carbon black 30 parts, 8 parts of zinc oxide, stearic acid 4 parts, zinc stearate 1 part,
Plasticizer DOP 5 parts, trithiocyanuric acid 0.7 part, ultra-fine form of finely divided powder, mehtod polyvinyl chloride 10
Part, Vulcanization accelerator TMTD 0.5 part, altax 1 part, anti-aging agent RD 2 parts, age resistor
MB 2 parts.
The preparation method of described high-performance nitrile rubber/polyvinyl chloride composite materials is as follows:
1) superelevation nitrile nitrile rubber, middle high nitrile nitrile rubber and polyvinyl chloride are put into banbury
In, it is heated to 80 DEG C, plasticate 15 minutes；
2) it is warming up to 110 DEG C, add porous ceramics, nm-class boron nitride, nano-silicon nitride, spray
Mist carbon black, zinc oxide, stearic acid, zinc stearate, plasticizer DOP, anti-aging agent RD, anti-
Old agent MB, kneads 15 minutes, discharge, and cooling parks 24 hours；
3) above-mentioned elastomeric compound is put in mill, add trithiocyanuric acid, ultra-fine full sulfuration powder
End polyvinyl chloride, Vulcanization accelerator TMTD, altax, thin logical 6 times, obtain high-performance fourth
Nitrile rubber/polyvinyl chloride composite materials.
Embodiment 3
A kind of preparation method of high-performance nitrile rubber/polyvinyl chloride composite materials, this material by with
Prepared by the raw material of lower parts by weight: superelevation nitrile nitrile rubber 70 parts, middle high nitrile nitrile rubber 30
Part, polyvinyl chloride 35 parts, porous ceramics 5 parts, nm-class boron nitride 15 parts, nano-silicon nitride
15 parts, spray carbon black 20 parts, 8 parts of zinc oxide, stearic acid 4 parts, zinc stearate 1 part,
Plasticizer DOP 5 parts, trithiocyanuric acid 1 part, ultra-fine form of finely divided powder, mehtod polyvinyl chloride 10 parts,
Vulcanization accelerator TMTD 1 part, altax 1.5 parts, anti-aging agent RD 2 parts, antioxidant MB
2 parts.
The preparation method of described high-performance nitrile rubber/polyvinyl chloride composite materials is as follows:
1) superelevation nitrile nitrile rubber, middle high nitrile nitrile rubber and polyvinyl chloride are put into banbury
In, it is heated to 85 DEG C, plasticate 15 minutes；
2) it is warming up to 120 DEG C, add porous ceramics, nm-class boron nitride, nano-silicon nitride, spray
Mist carbon black, zinc oxide, stearic acid, zinc stearate, plasticizer DOP, anti-aging agent RD, anti-
Old agent MB, kneads 15 minutes, discharge, and cooling parks 24 hours；
3) above-mentioned elastomeric compound is put in mill, add trithiocyanuric acid, ultra-fine full sulfuration powder
End polyvinyl chloride, Vulcanization accelerator TMTD, altax, thin logical 6 times, obtain high-performance fourth
Nitrile rubber/polyvinyl chloride composite materials.
Embodiment 4
A kind of preparation method of high-performance nitrile rubber/polyvinyl chloride composite materials, this material by with
Prepared by the raw material of lower parts by weight: superelevation nitrile nitrile rubber 70 parts, middle high nitrile nitrile rubber 30
Part, polyvinyl chloride 50 parts, porous ceramics 5 parts, nm-class boron nitride 10 parts, nano-silicon nitride
10 parts, spray carbon black 30 parts, 8 parts of zinc oxide, stearic acid 4 parts, zinc stearate 2 parts,
Plasticizer DOP 10 parts, trithiocyanuric acid 1.2 parts, ultra-fine form of finely divided powder, mehtod polyvinyl chloride 15
Part, Vulcanization accelerator TMTD 1.5 parts, altax 2 parts, anti-aging agent RD 5 parts, age resistor
MB 5 parts.
The preparation method of described high-performance nitrile rubber/polyvinyl chloride composite materials is as follows:
1) superelevation nitrile nitrile rubber, middle high nitrile nitrile rubber and polyvinyl chloride are put into banbury
In, it is heated to 90 DEG C, plasticate 18 minutes；
2) it is warming up to 130 DEG C, add porous ceramics, nm-class boron nitride, nano-silicon nitride, spray
Mist carbon black, zinc oxide, stearic acid, zinc stearate, plasticizer DOP, anti-aging agent RD, anti-
Old agent MB, kneads 18 minutes, discharge, and cooling parks 24 hours；
3) above-mentioned elastomeric compound is put in mill, add trithiocyanuric acid, ultra-fine full sulfuration powder
End polyvinyl chloride, Vulcanization accelerator TMTD, altax, thin logical 8 times, obtain high-performance fourth
Nitrile rubber/polyvinyl chloride composite materials.
Embodiment 5
A kind of preparation method of high-performance nitrile rubber/polyvinyl chloride composite materials, this material by with
Prepared by the raw material of lower parts by weight: superelevation nitrile nitrile rubber 80 parts, middle high nitrile nitrile rubber 20
Part, polyvinyl chloride 50 parts, porous ceramics 10 parts, nm-class boron nitride 15 parts, nano-silicon nitride
15 parts, spray carbon black 20 parts, 8 parts of zinc oxide, stearic acid 4 parts, zinc stearate 2 parts,
Plasticizer DOP 10 parts, trithiocyanuric acid 1.2 parts, ultra-fine form of finely divided powder, mehtod polyvinyl chloride 15
Part, Vulcanization accelerator TMTD 2 parts, altax 2.5 parts, anti-aging agent RD 5 parts, age resistor
MB 5 parts.
The preparation method of described high-performance nitrile rubber/polyvinyl chloride composite materials is as follows:
1) superelevation nitrile nitrile rubber, middle high nitrile nitrile rubber and polyvinyl chloride are put into banbury
In, it is heated to 85 DEG C, plasticate 20 minutes；
2) it is warming up to 120 DEG C, add porous ceramics, nm-class boron nitride, nano-silicon nitride, spray
Mist carbon black, zinc oxide, stearic acid, zinc stearate, plasticizer DOP, anti-aging agent RD, anti-
Old agent MB, kneads 20 minutes, discharge, and cooling parks 24 hours；
3) above-mentioned elastomeric compound is put in mill, add trithiocyanuric acid, ultra-fine full sulfuration powder
End polyvinyl chloride, Vulcanization accelerator TMTD, altax, thin logical 8 times, obtain high-performance fourth
Nitrile rubber/polyvinyl chloride composite materials.
The test knot obtaining after related physical performance test is carried out to above example gained sample
Fruit is shown in Table 2.
The different Example formulations of table 2 sample quantitative measurement
From Table 2, it can be seen that nitrile rubber/polyvinyl chloride prepared by the embodiment of the present invention is combined
Material has good mechanical performance.
The explanation of above example is only intended to help to understand that the method for the present invention and core thereof are thought
Think.It should be pointed out that, for those skilled in the art, without departing from this
On the premise of bright principle, the present invention can also be carried out some improve and modify, these improve and
Modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of
Or the use present invention.Those skilled in the art are come by the multiple modifications to these embodiments
Saying and will be apparent from, generic principles defined herein can be without departing from the present invention's
In the case of spirit or scope, realize in other embodiments.Therefore, the present invention will not be by
It is limited to the embodiments shown herein, and be to fit to and principles disclosed herein and new
The consistent scope the widest of grain husk feature.
Claims (10)
1. nitrile rubber/polyvinyl chloride composite materials, it is characterised in that prepared by following raw material:
Superelevation nitrile nitrile rubber 70-80 weight portion, middle high nitrile nitrile rubber 20-30 weight portion, polyvinyl chloride
35-50 weight portion, porous ceramics 5-10 weight portion, nm-class boron nitride 10-15 weight portion, nano-silicon nitride
10-15 weight portion, spray carbon black 20-30 weight portion, zinc oxide 4-8 weight portion, stearic acid 2-4 weight
Part, zinc stearate 1-2 weight portion, plasticizer DOP 5-10 weight portion, trithiocyanuric acid 0.7-1.2 weight
Part, ultra-fine form of finely divided powder, mehtod polyvinyl chloride 10-15 weight portion, Vulcanization accelerator TMTD 0.5-2 weight portion, promote
Enter agent DM 1-2.5 weight portion, anti-aging agent RD 2-5 weight portion, antioxidant MB 2-5 weight portion, described
Superelevation nitrile nitrile rubber bound acrylonitrile amount is 42%, and described middle high nitrile nitrile rubber bound acrylonitrile amount is
31-35%.
2. nitrile rubber/polyvinyl chloride composite materials according to claim 1, it is characterised in that institute
State ultra-fine form of finely divided powder, mehtod polyvinyl chloride to be prepared as follows:
In polyvinyl chloride emulsion, by 3～8% addition cross-linking radiation auxiliary agent TMPTA of dry glue weight, so
After carry out cross-linking radiation, obtain ultra-fine form of finely divided powder, mehtod polyvinyl chloride after spray drying.
3. the preparation method of nitrile rubber/polyvinyl chloride composite materials, it is characterised in that include following
Step:
Step a) is by high nitrile nitrile rubber in 70-80 weight portion superelevation nitrile nitrile rubber, 20-30 weight portion
Put in banbury with 35-50 weight portion polyvinyl chloride, be heated to 80～90 DEG C, plasticate 10～30 minutes,
Described superelevation nitrile nitrile rubber bound acrylonitrile amount is 42%, described middle high nitrile nitrile rubber bound acrylonitrile
Amount is 31-35%；
Step b) is warming up to 110～130 DEG C, adds 5-10 weight portion porous ceramics, 10-15 weight portion to receive
Rice boron nitride, 10-15 weight portion nano-silicon nitride, 20-30 weight portion spray carbon black, the oxidation of 4-8 weight portion
Zinc, 2-4 weight portion stearic acid, 1-2 weight portion zinc stearate, 5-10 parts by weight of plasticizer DOP, 2-5
Weight portion anti-aging agent RD and 2-5 weight portion antioxidant MB, knead 10～30 minutes, cools down after discharge,
Obtain elastomeric compound；
Described elastomeric compound is put in mill by step c), addition 0.7-1.2 weight portion trithiocyanuric acid,
10-15 weight portion ultra-fine form of finely divided powder, mehtod polyvinyl chloride, 0.5-2 weight portion Vulcanization accelerator TMTD and 1-2.5
Weight portion altax, thin logical after obtain nitrile rubber/polyvinyl chloride composite materials.
4. preparation method according to claim 3, it is characterised in that described ultra-fine form of finely divided powder, mehtod
Polyvinyl chloride is prepared as follows:
In polyvinyl chloride emulsion, by 3～8% addition cross-linking radiation auxiliary agent TMPTA of dry glue weight, so
After carry out cross-linking radiation, obtain ultra-fine form of finely divided powder, mehtod polyvinyl chloride after spray drying.
5. preparation method according to claim 3, it is characterised in that described zinc oxide is 8 weight
Part.
6. preparation method according to claim 3, it is characterised in that described stearic acid is 4 weight
Part.
7. preparation method according to claim 3, it is characterised in that the time of plasticating is 15～20 points
Clock.
8. preparation method according to claim 3, it is characterised in that mixing time is 15～20 points
Clock.
9. preparation method according to claim 3, it is characterised in that cool time is 20～30 little
When.
10. preparation method according to claim 3, it is characterised in that thin logical number of times is 6～8 times.
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| CN107011558B (en) * | 2017-05-25 | 2019-03-05 | 马成耀 | A kind of power generator yielding rubber and preparation method thereof |
| CN107474441B (en) * | 2017-09-18 | 2020-10-02 | 台州市恒辰塑业有限公司 | Modified polyvinyl chloride material |
| CN107987430B (en) * | 2017-12-27 | 2020-08-28 | 武汉工程大学 | Oil-resistant high-temperature-resistant modified polyvinyl chloride composite material and preparation method thereof |
| CN111849045A (en) * | 2020-07-19 | 2020-10-30 | 长沙市国发橡塑有限公司 | Wear-resistant corrosion-resistant elastomer material |
| CN112048113A (en) * | 2020-09-11 | 2020-12-08 | 九江学院 | Heat-resistant anti-aging cable insulation material and preparation method and application thereof |
| CN112659431B (en) * | 2020-11-16 | 2022-10-04 | 元氏县金亨塑胶制品有限公司 | Preparation process of polyvinyl chloride-butadiene-acrylonitrile rubber composite gloves |
| CN115232370B (en) * | 2022-08-03 | 2023-11-17 | 江苏多肯新材料有限公司 | Rubber sealing material for vehicle and preparation method thereof |
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|---|---|---|---|---|
| CN101353451A (en) * | 2007-07-25 | 2009-01-28 | 比亚迪股份有限公司 | Oil resistant low temperature resistant rubber composition |
| CN103146173A (en) * | 2013-02-28 | 2013-06-12 | 谭贤志 | Airtight tyre material prepared by blending ecichloro-hydrin rubber with poly vinyl alcohol and preparation method of aright tyre material |
| CN103249772A (en) * | 2011-01-14 | 2013-08-14 | 东海橡塑工业株式会社 | Rubber composition and automobile fuel system part using same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353451A (en) * | 2007-07-25 | 2009-01-28 | 比亚迪股份有限公司 | Oil resistant low temperature resistant rubber composition |
| CN103249772A (en) * | 2011-01-14 | 2013-08-14 | 东海橡塑工业株式会社 | Rubber composition and automobile fuel system part using same |
| CN103146173A (en) * | 2013-02-28 | 2013-06-12 | 谭贤志 | Airtight tyre material prepared by blending ecichloro-hydrin rubber with poly vinyl alcohol and preparation method of aright tyre material |
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