CN110330744B - Methanol-resistant and high-wear-resistant valve oil seal fluororubber material and preparation method thereof - Google Patents
Methanol-resistant and high-wear-resistant valve oil seal fluororubber material and preparation method thereof Download PDFInfo
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- CN110330744B CN110330744B CN201910546903.2A CN201910546903A CN110330744B CN 110330744 B CN110330744 B CN 110330744B CN 201910546903 A CN201910546903 A CN 201910546903A CN 110330744 B CN110330744 B CN 110330744B
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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
- C08L27/12—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 fluorine atoms
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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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- 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
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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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- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a methanol-resistant high-wear-resistant valve oil seal fluororubber material and a preparation method thereof, and solves the problems that in the prior art, after methanol permeates into common rubber materials, the rubber performance is influenced, the surface of a valve oil seal is damaged after long-term use, and potential safety hazards exist. The invention relates to a methanol-resistant high-wear-resistance valve oil seal fluororubber material which is prepared from the following raw materials in parts by weight: 95-105 parts of fluororubber, 5-30 parts of engineering plastic, 5-20 parts of acid absorbent, 10-50 parts of reinforcing filler and 1-5 parts of processing aid. The valve oil seal fluororubber material has the advantages of scientific design and reasonable formula, has good comprehensive performance, and not only has methanol swelling resistance, but also has unexpected high wear resistance.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a methanol-resistant high-wear-resistance valve oil seal fluororubber material and a preparation method thereof.
Background
Methanol is used as a clean energy source, has the advantages of complete combustion, high efficiency and less pollution discharge due to high oxygen content, and is considered to be a vehicle alternative fuel with good performance. But methanol is used as a good solvent, has small molecular weight and simple structure, and is easier to permeate into automobile parts such as rubber and the like compared with gasoline. The rubber mainly plays a sealing role in automobiles, once methanol permeates into the rubber, the rubber swells, the performance of the rubber is affected, and vehicle fuel is leaked to cause loss and even accidents. In addition, the valve oil seal can rub with the valve cover in the using process, the surface of the valve oil seal can be damaged due to long-term friction, and the valve oil seal fails after serious abrasion. Therefore, the research and development of the valve oil seal fluororubber material with excellent methanol resistance and high wear resistance has great significance.
Disclosure of Invention
The technical problem solved by the invention is as follows: the valve oil seal fluororubber material is resistant to methanol and high in wear resistance, and solves the problems that in the prior art, after a common rubber material permeates methanol, the rubber performance is influenced, the surface of a valve oil seal is damaged after long-term use, and potential safety hazards exist.
The invention also provides a preparation method of the fluororubber material.
The technical scheme adopted by the invention is as follows:
the invention relates to a methanol-resistant high-wear-resistance valve oil seal fluororubber material which is prepared from the following raw materials in parts by weight: 95-105 parts of fluororubber, 5-30 parts of engineering plastic, 5-20 parts of acid absorbent, 10-50 parts of reinforcing filler and 1-5 parts of processing aid.
Further, the feed is prepared from the following raw materials in parts by weight: 100 parts of fluororubber, 7-20 parts of engineering plastics, 5-15 parts of acid absorbent, 15-25 parts of reinforcing filler and 1-5 parts of processing aid.
Further, the feed is prepared from the following raw materials in parts by weight: 100 parts of fluororubber, 10 parts of engineering plastics, 8 parts of acid absorbent, 22 parts of reinforcing filler and 3 parts of processing aid.
Further, the fluororubber is ternary polymerization fluororubber, and the fluorine content is more than or equal to 70 wt%.
Further, the fluororubber is terpolymer fluororubber G-621.
Further, the engineering plastic is superfine polyimide micro powder.
Further, the acid acceptor is selected from one or two of magnesium oxide and calcium hydroxide.
Further, the reinforcing filler is selected from any one or more of barium sulfate, diatomite and carbon black.
The invention relates to a preparation method of a methanol-resistant high-wear-resistance valve oil seal fluororubber material, which comprises the following steps:
step 1, preparing raw materials in parts by weight;
step 2, putting the fluororubber and the engineering plastic into an internal mixer for mixing, then discharging rubber, tabletting, air cooling and collecting rubber to obtain pre-mixed rubber;
step 3, putting the premixed rubber prepared in the step 2 into an internal mixer, then putting the other raw materials, mixing, and then discharging rubber;
and step 4, turning and tabletting: adjusting the roll spacing of the open mill, pouring the rubber compound discharged in the step 3 onto the open mill, turning the rubber, then adjusting the roll spacing of the open mill to be small, thinly passing for 2-4 times, finally adjusting the roll spacing of the open mill to be large, and discharging sheets;
step 5, air cooling, and collecting rubber when the mixing degree of the rubber compound is less than 40 ℃;
and 6, standing the mixed rubber obtained in the step 5 for 1-5 days, and repeating the step 4 and the step 5 to obtain the valve oil seal fluororubber material.
Compared with the prior art, the invention has the following beneficial effects:
the valve oil seal fluororubber material has the advantages of scientific design and reasonable formula, and has good comprehensive performance, unexpected methanol swelling resistance and high wear resistance.
The method is simple and is easy and convenient to operate, the fluororubber and the engineering plastic are firstly mixed to prepare the pre-mixed rubber, and then the rest raw materials are added for mixing to prepare the mixed rubber, so that all the materials can be fully mixed, and the performance of the obtained valve oil seal fluororubber material is better.
Detailed Description
The technical solutions of the present invention are described below with specific examples, but the scope of the present invention is not limited to the described examples.
The materials used in the examples of the present invention are all commercially available products.
The fluororubber G-621 in the example of the invention was a terpolymer fluororubber produced by Japan Dajin industries, Ltd., having a fluorine content of 70.5 wt%;
fluororubber G-752 was a binary polymerized fluororubber produced by Japan Daiki Industrial Co., Ltd., and had a fluorine content of 66.5 wt%;
diatomaceous earth (model MV25) was supplied by EP first grade minerals in the united states;
diatomaceous earth (model AKTSIL Q) is supplied by hoffman in germany;
the WAX (model WAX) was carnauba WAX;
wax (model WS280) was supplied by Struktol corporation, USA.
Example 1
The embodiment provides a raw material formula table of the methanol-resistant high-wear-resistant valve oil seal fluororubber material, which is specifically shown in table 1.
TABLE 1 raw material formula table of methanol-resistant highly wear-resistant valve oil seal fluororubber material
Example 2
The embodiment discloses a preparation method of a methanol-resistant high-wear-resistance valve oil seal fluororubber material, which comprises the following steps:
step 1, preparing raw materials in parts by weight;
step 2, controlling the temperature of the internal mixer to be less than 65 ℃, adding fluororubber and superfine polyimide micropowder for mixing, wherein the rotating speed of a rotor is 30rpm, mixing for 30S after the temperature reaches 170 ℃, discharging rubber, tabletting, air-cooling for 5-30min, and collecting rubber when the temperature of the premixed rubber is less than 40 ℃ to prepare premixed rubber;
and 3, putting the obtained premixed rubber prepared in the step 2 into an internal mixer for mixing for 30S, then putting the rest raw materials, and mixing for 80S, wherein the rotating speed of a rotor is 25 rpm. And then opening the upper top bolt, cleaning the powder of the gland and the feeding door, and reducing the mixing time of the upper top bolt for 60S, wherein the rotating speed of a rotor is 25 rpm. Opening the upper top bolt, cleaning powder on the edge of the rotor chamber, reducing the mixing time of the upper top bolt for 80-140S, controlling the rotating speed of a rotor to be 25rpm, and then discharging rubber at the temperature of 100 +/-5 ℃;
step 4, turning and tabletting, namely adjusting the roller spacing of the open mill to be 1.5-2.5mm, pouring the mixed rubber discharged in the step 3 onto the open mill, turning the rubber for 200 +/-20 seconds, adjusting the roller spacing of the open mill to be 0.2-0.5mm, thinly passing for 3 times, adjusting the roller spacing of the open mill to be 3-4mm, and discharging the tablets;
step 5, air cooling for 5-30min, and collecting the rubber when the mixing degree of the rubber compound is less than 40 ℃;
and 6, standing the mixed rubber obtained in the step 5 for 1-5 days, and repeating the step 4 and the step 5 to obtain the valve oil seal fluororubber material.
Example 3
The embodiment provides preparation of a methanol-resistant high-wear-resistant valve oil seal fluororubber material, which is prepared by adopting the raw material composition of formula 1 in the table 1 and adopting the method of the embodiment 2, and the obtained valve oil seal fluororubber material is marked as A1. In step 6, the standing time of the rubber compound is 3 days.
Example 4
The embodiment provides preparation of a methanol-resistant high-wear-resistant valve oil seal fluororubber material, which is prepared by adopting the raw material composition of formula 2 in table 1 according to the method of the embodiment 2, and the obtained valve oil seal fluororubber material is marked as A2. In step 6, the standing time of the rubber compound is 1 day.
Example 5
The embodiment provides preparation of a methanol-resistant high-wear-resistant valve oil seal fluororubber material, which is prepared by adopting the raw material composition of formula 3 in table 1 and adopting the method of the embodiment 2, and the obtained valve oil seal fluororubber material is marked as A3. In step 6, the standing time of the rubber compound is 5 days.
Example 6
The embodiment provides preparation of a methanol-resistant high-wear-resistant valve oil seal fluororubber material, which is prepared by adopting the raw material composition of formula 4 in table 1 and by the method of the embodiment 2, and the obtained valve oil seal fluororubber material is marked as A4. In step 6, the standing time of the rubber compound is 4 days.
Example 7
The embodiment is a comparative example, compared with the embodiment 3, the fluororubber G-621 is replaced by the fluororubber G-752 in the raw materials of the embodiment, the rest conditions are the same, and the obtained door oil seal fluororubber material is marked as D1.
Example 8
This example is a comparative example, and compared with example 3, the raw material of this example does not contain ultrafine polyimide micropowder, and the rest conditions are the same, and the obtained valve oil seal fluororubber material is marked as D2.
Example 9
The embodiment discloses various performance measurement results of a valve oil seal fluororubber material, which are specifically shown in table 2:
TABLE 2 valve oil seal fluororubber material property measurement results
As can be seen from the table above, the fluororubber material for the valve oil seal has good comprehensive performance, and has good methanol swelling resistance and wear resistance.
Compared with the fluororubber material without adding superfine polyimide micropowder, the fluororubber material for the valve oil seal has better performances, in particular friction coefficient, thermal ageing resistance and methanol resistance. The superfine polyimide powder added in the invention has the unexpected effect of improving the methanol swelling resistance, the thermal aging resistance and the wear resistance of the door oil seal fluororubber material.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The methanol-resistant high-wear-resistance valve oil seal fluororubber material is characterized by being prepared from the following raw materials in parts by weight: 95-105 parts of fluororubber, 5-30 parts of superfine polyimide micro powder, 5-20 parts of acid absorbent, 10-50 parts of reinforcing filler and 1-5 parts of processing aid.
2. The valve oil seal fluororubber material with methanol resistance and high wear resistance as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 100 parts of fluororubber, 7-20 parts of superfine polyimide micropowder, 5-15 parts of acid absorbent, 15-25 parts of reinforcing filler and 1-5 parts of processing aid.
3. The valve oil seal fluororubber material with methanol resistance and high wear resistance as claimed in claim 2, which is prepared from the following raw materials in parts by weight: 100 parts of fluororubber, 10 parts of superfine polyimide micropowder, 8 parts of acid acceptor, 22 parts of reinforcing filler and 3 parts of processing aid.
4. The valve oil seal fluororubber material with methanol resistance and high wear resistance according to any one of claims 1-3, wherein the fluororubber is terpolymer fluororubber with fluorine content of 70wt% or more.
5. The valve oil seal fluororubber material with methanol resistance and high wear resistance as claimed in claim 4, wherein the fluororubber is terpolymer fluororubber G-621.
6. The valve oil seal fluororubber material with methanol resistance and high wear resistance according to claim 5, wherein the acid absorbent is selected from one or two of magnesium oxide and calcium hydroxide.
7. The valve oil seal fluororubber material with methanol resistance and high wear resistance according to claim 6, wherein the reinforcing filler is selected from any one or more of barium sulfate, diatomite and carbon black.
8. The preparation method of the methanol-resistant high-wear-resistant valve oil seal fluororubber material according to any one of claims 1 to 7, characterized by comprising the following steps:
step 1, preparing raw materials in parts by weight;
step 2, putting the fluororubber and the superfine polyimide micropowder into an internal mixer for mixing, then discharging rubber, tabletting, air cooling and collecting rubber to obtain pre-mixed rubber;
step 3, putting the premixed rubber prepared in the step 2 into an internal mixer, then putting the other raw materials, mixing, and then discharging rubber;
and step 4, turning and tabletting: adjusting the roll spacing of the open mill, pouring the rubber compound discharged in the step 3 onto the open mill, turning the rubber, then adjusting the roll spacing of the open mill to be small, thinly passing for 2-4 times, finally adjusting the roll spacing of the open mill to be large, and discharging sheets;
step 5, air cooling, and collecting rubber when the temperature of the mixed rubber is lower than 40 ℃;
and 6, standing the mixed rubber obtained in the step 5 for 1-5 days, and repeating the step 4 and the step 5 to obtain the valve oil seal fluororubber material.
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| CN201910546903.2A CN110330744B (en) | 2019-06-24 | 2019-06-24 | Methanol-resistant and high-wear-resistant valve oil seal fluororubber material and preparation method thereof |
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| CN201910546903.2A CN110330744B (en) | 2019-06-24 | 2019-06-24 | Methanol-resistant and high-wear-resistant valve oil seal fluororubber material and preparation method thereof |
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| CN110330744B true CN110330744B (en) | 2021-01-26 |
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| CN113122006A (en) * | 2021-04-27 | 2021-07-16 | 浙江吉利控股集团有限公司 | Methanol engine valve oil seal material, structure and automobile |
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2019
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| CN102731942A (en) * | 2012-06-13 | 2012-10-17 | 浙江大学 | Preparation method of talc filled PTFE composite material |
| CN103102625A (en) * | 2012-12-27 | 2013-05-15 | 上海长园电子材料有限公司 | Fluorine plastic and fluorine plastic sleeve |
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