CN107286545B - Cross-linkable thermoplastic low-oil-permeability elastomer material - Google Patents
Cross-linkable thermoplastic low-oil-permeability elastomer material Download PDFInfo
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- CN107286545B CN107286545B CN201710589605.2A CN201710589605A CN107286545B CN 107286545 B CN107286545 B CN 107286545B CN 201710589605 A CN201710589605 A CN 201710589605A CN 107286545 B CN107286545 B CN 107286545B
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- 239000000463 material Substances 0.000 title claims abstract description 34
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 13
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 13
- 229920001971 elastomer Polymers 0.000 title claims description 19
- 239000000806 elastomer Substances 0.000 title claims description 19
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000013536 elastomeric material Substances 0.000 claims abstract 2
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000007794 irritation Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- C08L29/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- 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
-
- 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
- C08L2207/04—Thermoplastic elastomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention aims to provide a crosslinkable thermoplastic low oil-permeable elastomeric material. The material consists of 40-60 parts of POE resin, 40-60 parts of silane grafted POE, 40-80 parts of polyvinyl alcohol fiber and 5-15 parts of POE-MAH. The material has the advantages of good oil resistance, low oil permeability, high strength, low creep, low density, simple forming process, low manufacturing cost, nontoxic and harmless raw materials, no irritation to human body, natural degradation, safety and environmental protection. The product formed by the material of the invention can generate an oil-resistant product with a cross-linking structure after certain temperature and humidity adjustment, and is suitable for manufacturing oil-contacting parts such as oil conveying pipe fittings, oil seals and the like.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and relates to a crosslinkable thermoplastic low-oil-permeability elastomer material.
Background
The low oil-leakage elastomer material is mainly applied to oil line sealing structures of oil pipes, oil seals and the like, has the characteristics of oil resistance, low permeability and the like, and is generally prepared from materials such as polytetrafluoroethylene, silicon rubber, fluororubber and the like in the prior art. The materials are expensive, the melt viscosity is extremely high, the materials can be formed only by adopting low-efficiency forming modes such as die pressing, sintering and the like, the forming time is long, and the process cost is high. Meanwhile, the material waste treatment can generate toxic and harmful gases, and the environmental hazard is large. The oil seal material prepared by the thermoplastic elastomer has the advantage of high-efficiency forming, but has poor oil resistance and high oil seepage rate. Therefore, it is necessary to develop a low oil permeability elastomer material which can be rapidly formed and is environment-friendly.
Disclosure of Invention
The invention aims to provide a crosslinkable thermoplastic low-oil-permeability elastomer material. The invention adopts POE resin as a matrix, adds polyvinyl alcohol fiber and silane graft polymer, and disperses and compatibilizes the polyvinyl alcohol fiber in the matrix resin in a net structure. The material can be molded by high-efficiency molding modes such as injection or extrusion. The formed product is adjusted under a certain temperature and humidity environment to generate a low-oil-permeability product with a certain crosslinking degree, and the low-oil-permeability product has the characteristics of good oil resistance, low oil permeability, good rebound resilience and the like.
The invention realizes the technical aim through the following scheme:
the crosslinkable thermoplastic low-oil-permeability elastomer material is composed of 40-60 parts of POE resin, 40-60 parts of silane grafted POE, 40-80 parts of polyvinyl alcohol fiber and 5-15 parts of POE-MAH.
Wherein the POE resin is an ethylene-octene copolymer, and the melting temperature of the POE resin is not higher than 90 ℃.
Wherein the melting temperature of the silane grafted POE is not higher than 90 ℃, and the silane grafting content is 2-3%.
Wherein the water soluble substance of the polyvinyl alcohol fiber is more than 90%, and the fiber length is 1-5 mm, preferably 3 mm.
Wherein, the POE-MAH is maleic anhydride graft modified POE resin, the melting temperature is not higher than 90 ℃, and the MAH graft content is 0.8-1.2%.
The crosslinkable thermoplastic low-oil-permeability elastomer material is prepared by the following steps:
firstly, mixing POE resin and POE-MAH in an internal mixer at 90-100 ℃ for 2-3 min;
and step two, adding silane grafted POE and polyvinyl alcohol fibers, continuously mixing for 10-12 min under the protection of nitrogen, and discharging. The mixing temperature is 120-130 ℃.
The invention has the following beneficial effects:
the invention provides a low oil-permeability elastomer material. Compared with the prior art, the invention has the following beneficial effects:
the material provided by the invention has the advantages of good oil resistance, low oil permeability, high strength, low creep, simple forming process, low manufacturing cost and the like.
2 the raw materials used in the invention are nontoxic and harmless, and the used fiber materials have no irritation to human bodies and can be naturally degraded, thereby being safe and environment-friendly.
3, the material provided by the invention has small specific gravity and meets the development requirement of light weight of equipment.
Detailed Description
The present invention will be described in detail with reference to examples.
The test medium for the soluble content reference GB/T24282-;
the ethanol gasoline permeability is tested by reference GB/T21529-;
the melt flow rate is tested according to GB/T3682-;
the tensile strength was measured according to GB/T1040-.
The preparation process of the sample is injection molding, the temperature of an injection machine is 130-160 ℃, the injection pressure is 45-55 bar, and the temperature of a mold is 30-35 ℃. The sample conditioning environment is as follows: the temperature is 35-40 ℃, the humidity is 75-95%, and the adjusting time is 168 h.
Example 1
In this embodiment, the low oil permeability elastomer material is composed of 40 parts of POE resin, 60 parts of silane grafted POE, 40 parts of polyvinyl alcohol fiber, and 5 parts of POE-MAH.
The crosslinkable thermoplastic low-oil-permeability elastomer material is prepared by the following steps:
firstly, mixing POE resin and POE-MAH in an internal mixer at 90-100 ℃ for 2-3 min;
and step two, adding silane grafted POE and polyvinyl alcohol fibers, continuously mixing for 10-12 min under the protection of nitrogen, and discharging. The mixing temperature is 120-130 ℃.
Example 2
In this embodiment, the low oil permeability elastomer material is composed of 60 parts of POE resin, 40 parts of silane grafted POE, 80 parts of polyvinyl alcohol fiber, and 15 parts of POE-MAH.
The preparation steps are the same as above.
Example 3
In this example, the low oil permeability elastomer material is composed of 50 parts of POE resin, 50 parts of silane grafted POE, 60 parts of polyvinyl alcohol fiber, and 10 parts of POE-MAH.
The preparation steps are the same as above.
Example 4
In this example, the low oil permeability elastomer material is composed of 50 parts of POE resin, 50 parts of silane grafted POE, 70 parts of polyvinyl alcohol fiber, and 12 parts of POE-MAH.
The preparation steps are the same as above.
Example 5
In this embodiment, the low oil permeability elastomer material is composed of 50 parts of POE resin, 50 parts of silane grafted POE, 80 parts of polyvinyl alcohol fiber, and 15 parts of POE-MAH.
The preparation steps are the same as above.
Comparative example 1
In this comparative example, the material consisted of 100 parts POE resin, 80 parts polyvinyl alcohol fiber and 15 parts POE-MAH.
The preparation steps are the same as above.
The biggest difference between the comparative example and the examples is that no silane-grafted POE is present in the components.
Comparative example 2
In the comparative example, the material consisted of 50 parts of POE resin, 50 parts of silane grafted POE, 80 parts of polyvinyl alcohol fiber and 15 parts of POE-MAH.
The preparation steps are the same as above.
The greatest difference between this comparative example and the examples is that the length of the polyvinyl alcohol fiber is 8mm to 10 mm.
Comparative example 3
In the comparative example, the material consisted of 50 parts of POE resin, 50 parts of silane-grafted POE, and 80 parts of polyvinyl alcohol fiber.
The preparation steps are the same as above.
The biggest difference between the comparative example and the example is that POE-MAH is not contained in the components.
Comparative example 4
In the comparative example, the material consisted of 50 parts of POE resin, 50 parts of silane grafted POE, and 15 parts of POE-MAH.
The preparation steps are the same as above.
The biggest difference between this comparative example and the examples is that there is no polyvinyl alcohol fiber in the composition.
The results of the performance tests of the examples and comparative examples are shown in Table 1.
TABLE 1
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions, such as adding certain processing aids like anti-aging agents and pigments, or using other commonly used melt-mixing equipment, can be made without departing from the method of the present invention, and these modifications and additions should also be considered as the protection scope of the present invention.
Claims (5)
1. The crosslinkable thermoplastic low-oil-permeability elastomer material is characterized by comprising the following raw materials of 40-60 parts of POE resin, 40-60 parts of silane grafted POE, 40-80 parts of polyvinyl alcohol fiber and 5-15 parts of POE-MAH;
the preparation method comprises the following steps:
firstly, mixing POE resin and POE-MAH in an internal mixer at 90-100 ℃ for 2-3 min;
heating to the temperature of 120-;
wherein, the length of the polyvinyl alcohol fiber is 1-5 mm.
2. A crosslinkable thermoplastic oil-impermeable elastomer material according to claim 1, characterized in that the POE resin is an ethylene-octene copolymer having a melting temperature not higher than 90 ℃.
3. A crosslinkable thermoplastic oil-impermeable elastomer material according to claim 1, characterized in that the silane-grafted POE has a melting temperature not higher than 90 ℃ and a silane-grafting content of 2 to 3%.
4. A crosslinkable thermoplastic oil-impermeable elastomeric material according to claim 1, characterized in that the polyvinyl alcohol fibers have a water solubles of more than 90%.
5. The crosslinkable thermoplastic oil-impermeable elastomer material as claimed in claim 1, wherein the POE-MAH is a maleic anhydride graft-modified POE resin having a melting temperature of not higher than 90 ℃ and a MAH graft content of 0.8% to 1.2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710589605.2A CN107286545B (en) | 2017-07-10 | 2017-07-10 | Cross-linkable thermoplastic low-oil-permeability elastomer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710589605.2A CN107286545B (en) | 2017-07-10 | 2017-07-10 | Cross-linkable thermoplastic low-oil-permeability elastomer material |
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| Publication Number | Publication Date |
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| CN107286545A CN107286545A (en) | 2017-10-24 |
| CN107286545B true CN107286545B (en) | 2020-11-13 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070880A1 (en) * | 2000-03-17 | 2001-09-27 | Uniroyal Chemical Company, Inc. | Thermoplastic elastomer blends |
| WO2007136460A1 (en) * | 2006-05-23 | 2007-11-29 | Exxonmobil Chemical Patents Inc. | Elastomeric modifier and process for manufacture |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8410215B2 (en) * | 2006-08-23 | 2013-04-02 | Jsr Corporation | Thermoplastic resin composition and molded article obtained from the same |
| CN103205074A (en) * | 2012-01-11 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Yoga mat making method |
| CN103242612A (en) * | 2013-05-28 | 2013-08-14 | 上海博疆新材料科技有限公司 | Polyvinyl alcohol composition and application thereof |
| CN104262883A (en) * | 2014-10-13 | 2015-01-07 | 无锡杰科塑业有限公司 | Low-smoke halogen-free flame-retardant silane crosslinked cable material capable of being crosslinked at room temperature and preparation method of cable material |
| CN105885173B (en) * | 2016-05-23 | 2018-03-02 | 江苏德威新材料股份有限公司 | A kind of special color masterbatch of silane crosslinked insulating material and preparation method thereof |
| CN106188795A (en) * | 2016-07-08 | 2016-12-07 | 贵州省材料产业技术研究院 | In-situ fibrillation strengthens thermoplastic elastomer films material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070880A1 (en) * | 2000-03-17 | 2001-09-27 | Uniroyal Chemical Company, Inc. | Thermoplastic elastomer blends |
| WO2007136460A1 (en) * | 2006-05-23 | 2007-11-29 | Exxonmobil Chemical Patents Inc. | Elastomeric modifier and process for manufacture |
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