CN110885520B - High-hardness oil-resistant heat-resistant PVC material - Google Patents
High-hardness oil-resistant heat-resistant PVC material Download PDFInfo
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- 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
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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
- 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
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Abstract
The invention discloses a high-hardness oil-resistant heat-resistant PVC material which comprises the following components in parts by weight: 100 parts of PVC resin, 2-10 parts of heat stabilizer, 8-15 parts of MBS, 2-15 parts of ACR, 0-10 parts of CPE, 3-15 parts of filler and 1-5 parts of lubricant; the polymerization degree of the PVC resin is 700-1300. The PVC material disclosed by the invention adopts PVC resin with the polymerization degree of 700-1300, and is added with MBS, ACR and CPE as toughening agent materials, so that the high-hardness oil-resistant heat-resistant PVC material can be prepared.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-hardness oil-resistant heat-resistant PVC material.
Background
The wire harness protection sleeve is a hard sleeve for wrapping wires in an automobile, mainly plays a role in protecting the automobile wire harness, and in addition, because automobile parts can contact solvents such as engine oil and the like, the wire harness protection sleeve needs to have an oil-resistant function, and meanwhile, the inside of the automobile has a certain temperature, so that the heat-resistant function needs to be considered. At a certain temperature, after the material is soaked in oil, the performance needs to be kept at a higher level, namely the problem of performance retention rate mentioned in the patent. At present, most of PVC wires and cables are soft or semi-soft systems, and the hardness is too low, the heat resistance is low, and the PVC wires and cables cannot be used as wire harness protective sleeves.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a high-hardness oil-resistant heat-resistant PVC material.
In order to achieve the purpose, the invention adopts the technical scheme that: a high-hardness oil-resistant heat-resistant PVC material comprises the following components in parts by weight: 100 parts of PVC resin, 2-10 parts of heat stabilizer, 8-15 parts of MBS (methyl methacrylate, butadiene and styrene terpolymer), 2-15 parts of ACR (acrylic resin), 0-10 parts of CPE (chlorinated polyethylene resin), 3-15 parts of filler and 1-5 parts of lubricant; the polymerization degree of the PVC resin is 700-1300.
The inventor finds that when the polymerization degree of the PVC resin exceeds 1300, the oil resistance and heat resistance effect cannot be achieved below 700, and the PVC resin cannot be processed and molded into products required by customers. When the toughening agent adopts the MBS, ACR and CPE and is compounded according to the proportion, the oil-resistant and heat-resistant effects are better. Therefore, the PVC material disclosed by the invention adopts PVC resin with the polymerization degree of 700-1300, and is added with MBS, ACR and CPE as toughening agent materials, so that the high-hardness oil-resistant heat-resistant PVC material can be prepared.
Preferably, the MBS is 8-12 parts, and the ACR is 8-12 parts. The MBS toughening agent and the ACR toughening agent have better oil resistance and heat resistance when being compounded according to the mixture ratio. More preferably, the MBS is 10 parts and the ACR is 10 parts. Particularly, when the two toughening agents are compounded according to the proportion, the oil resistance and the heat resistance are optimal.
Preferably, the filler is ground calcium carbonate.
Preferably, the filler is 3-8 parts. The oil-resistant and heat-resistant performance of the PVC material is affected by too much or too little adding amount of the filler, and the PVC material can have the oil-resistant and heat-resistant performance by adopting the adding amount. More preferably, the filler is 5 parts.
Preferably, the lubricant is at least one of polyethylene wax, stearic acid, and paraffin wax.
Preferably, the heat stabilizer is an organic tin heat stabilizer and/or a calcium-zinc composite heat stabilizer.
The invention also aims to provide a preparation method of the high-hardness oil-resistant heat-resistant PVC material, which comprises the following steps:
(1) weighing PVC resin, a heat stabilizer, MBS, ACR, CPE and a lubricant according to the proportion, placing the mixture in a high-speed kneader, heating the mixture to 103-106 ℃, mixing the mixture, weighing the filler according to the proportion, and stirring the mixture;
(2) when the temperature of the mixed material is 110-120 ℃, discharging the mixed material into a cooling cylinder with a circulating cooling water device, and obtaining a mixed material after the temperature reaches 50-60 ℃;
(3) extruding the mixture obtained in the step (2) by a conical double-screw extruder for material manufacturing, and drying for 12-48 h to obtain the high-hardness oil-resistant heat-resistant PVC material.
The invention also aims to provide an automobile wire harness protective sleeve material which comprises the high-hardness oil-resistant heat-resistant PVC material.
The invention has the beneficial effects that: the invention provides a high-hardness oil-resistant heat-resistant PVC material, which is prepared by adopting PVC resin with the polymerization degree of 700-1300 and adding MBS, ACR and CPE as toughening agent materials.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Each raw material in examples and comparative examples was purchased from the market, wherein a PVC resin having a degree of polymerization of 450 was purchased from japan koyun chemical industry corporation and the model number thereof was PVC resin powder S400; the PVC resin with the polymerization degree of 700 is purchased from Tianjin Lejin Staphylum chemical Co., Ltd, and the model is PVC TL-700; the PVC resin with the polymerization degree of 1000 is purchased from Tianjin Lejin Staphylum chemical Co., Ltd, and the model is PVC TL-1000; the PVC resin with the polymerization degree of 1300 is purchased from Tosoh corporation of Japan, and the model is PVC TG-1300; the PVC resin with the polymerization degree of 1800 is purchased from Taiwan plastic industry Co., Ltd, and the model is PVC S-80;
the organic tin heat stabilizer is purchased from Singapore Sanyi chemical industry and has the model of SAK MT 9001;
MBS is available from Lomhas corporation, USA, and is model No. BTA 717;
ACR was purchased from Dow chemical company under the model KM 355P;
CPE was purchased from Weifang Yaxing chemical Co., Ltd, model number WEIPREN 6000;
the polyethylene wax is HONEYWELL 617A;
stearic acid is purchased from Guangzhou Jinchangsheng science and technology limited, and the model is 1801;
paraffin wax was purchased from Sanyo chemical industries, Inc. (Shanghai) under the model LOXIOL 2050;
the particle size of the ground calcium carbonate was 0.7 μm or less, when D50 was used.
The preparation method of the high-hardness oil-resistant heat-resistant PVC material in the examples and the comparative examples comprises the following steps:
(1) weighing PVC resin, a heat stabilizer, MBS, ACR, CPE and a lubricant according to the proportion, placing the mixture in a high-speed kneader, heating the mixture to 103-106 ℃, mixing the mixture, weighing the filler according to the proportion, and stirring the mixture;
(2) when the temperature of the mixed material is 110-120 ℃, discharging the mixed material into a cooling cylinder with a circulating cooling water device, and obtaining a mixed material after the temperature reaches 50-60 ℃;
(3) extruding the mixture obtained in the step (2) by a conical double-screw extruder for material manufacturing, and drying for 12-48 h to obtain the high-hardness oil-resistant heat-resistant PVC material.
The formulations of the high-hardness oil-resistant heat-resistant PVC materials described in examples 1-12 and comparative examples 1-9 are shown in tables 1 and 2.
TABLE 1
TABLE 2
The high-hardness oil-resistant heat-resistant PVC materials in the examples and the comparative examples are subjected to performance tests, and the test methods are as follows:
hardness was measured according to JIS K7215;
odor rating was tested according to VDA 270;
the method for the heat resistance test comprises the following steps: the test specimen was heated at 70 ℃ for 120 hours, and its tensile strength was measured according to JIS K711 and its elongation at break was measured according to JIS K7161.
The oil resistance test method comprises the following steps: the test specimens were immersed in a 50 ℃ mixed oil of lamp oil and lubricating oil for internal combustion engines (mass ratio 1:1) for 20 hours, tested for tensile strength according to JIS K711 and for elongation at break according to JIS K7161;
the tensile strength retention rate and the elongation at break retention rate were calculated, the retention rate being the tensile strength/original tensile strength of the heat or oil resistance test 100%, and the elongation at break retention rate being the elongation at break/original elongation at break of the heat or oil resistance test 100%.
The test results are shown in tables 3 and 4.
TABLE 3
TABLE 4
As can be seen from tables 3 and 4, the PVC resin with the polymerization degree of 700-1300 has higher oil resistance and heat resistance; when the adding amount of the filler is 3-15 parts, the oil resistance and the heat resistance can be better, but when the adding amount of the filler is more than 5 parts, the oil resistance and the heat resistance are reduced, when the adding amount of the filler is more than 8 parts, the oil resistance and the heat resistance are reduced quickly, and when the adding amount of the filler is more than 15 parts, the tensile strength retention rate or the breaking elongation retention rate is lower than 80 percent in an oil resistance or heat resistance test, so that the requirements are difficult to meet; when the toughening agent is prepared by combining MBS, ACR and CPE, the oil resistance and heat resistance are better, especially when the MBS and ACR are combined, the oil resistance and heat resistance are better, and the cost can be reduced by adding the CPE, so that the MBS, ACR and CPE can be added by comprehensively considering the oil resistance, heat resistance and cost. The oil resistance and the heat resistance are good when the addition amounts of the MBS 8-12 parts and the ACR 8-12 parts, and the oil resistance and the heat resistance are optimal when the addition amounts of the MBS10 parts and the ACR 10 parts.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The high-hardness oil-resistant heat-resistant PVC material is characterized by comprising the following components in parts by weight: 100 parts of PVC resin, 2-10 parts of heat stabilizer, 8-12 parts of MBS, 8-12 parts of ACR, 0-10 parts of CPE, 3-15 parts of filler and 1-5 parts of lubricant; the polymerization degree of the PVC resin is 700-1300.
2. The high-hardness oil-resistant heat-resistant PVC material according to claim 1, wherein MBS is 10 parts, and ACR is 10 parts.
3. The high-hardness oil-resistant heat-resistant PVC material according to claim 1, wherein the filler is ground calcium carbonate.
4. The PVC material with high hardness, oil resistance and heat resistance as claimed in claim 1, wherein the filler is 3-8 parts.
5. The high-hardness oil-resistant heat-resistant PVC material according to claim 1, wherein the filler is 5 parts.
6. The high-hardness oil-resistant heat-resistant PVC material according to claim 1, wherein the lubricant is at least one of polyethylene wax, stearic acid and paraffin wax.
7. The high-hardness oil-resistant heat-resistant PVC material according to claim 1, wherein the heat stabilizer is an organotin heat stabilizer and/or a calcium-zinc composite heat stabilizer.
8. A preparation method of the high-hardness oil-resistant heat-resistant PVC material as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
(1) weighing PVC resin, a heat stabilizer, MBS, ACR, CPE and a lubricant according to the proportion, placing the mixture in a high-speed kneader, heating the mixture to 103-106 ℃, mixing the mixture, weighing the filler according to the proportion, and stirring the mixture; (2) when the temperature of the mixed material is 110-120 ℃, discharging the mixed material into a cooling cylinder with a circulating cooling water device, and obtaining a mixed material after the temperature reaches 50-60 ℃;
(3) extruding the mixture obtained in the step (2) by a conical double-screw extruder for material manufacturing, and drying for 12-48 h to obtain the high-hardness oil-resistant heat-resistant PVC material.
9. A protective sheath material for automobile wire harness, characterized by comprising the high-hardness oil-resistant heat-resistant PVC material according to any one of claims 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911322208.4A CN110885520B (en) | 2019-12-20 | 2019-12-20 | High-hardness oil-resistant heat-resistant PVC material |
| PCT/CN2020/125092 WO2021120884A1 (en) | 2019-12-20 | 2020-10-30 | High hardness oil-resistant heat-resistant pvc material |
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| CN201911322208.4A CN110885520B (en) | 2019-12-20 | 2019-12-20 | High-hardness oil-resistant heat-resistant PVC material |
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| CN110885520B (en) * | 2019-12-20 | 2022-01-14 | 金发科技股份有限公司 | High-hardness oil-resistant heat-resistant PVC material |
| CN114516997B (en) * | 2022-03-28 | 2023-08-22 | 金发科技股份有限公司 | High heat-resistant flame-retardant PVC alloy composition and preparation method and application thereof |
| CN114806030B (en) * | 2022-04-18 | 2023-11-24 | 镇江中佳电器有限公司 | Heat-resistant moisture-resistant insulating cable material and preparation process thereof |
| CN115232415A (en) * | 2022-07-28 | 2022-10-25 | 苏州国宇碳纤维科技有限公司 | HPVC modified material for protective tube and preparation method of HPVC cable protective tube |
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| WO2021120884A1 (en) | 2021-06-24 |
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