CN104650448A - High/low-temperature resisting ethylene acrylic acid copolymer and preparation method thereof - Google Patents
High/low-temperature resisting ethylene acrylic acid copolymer and preparation method thereof Download PDFInfo
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- CN104650448A CN104650448A CN201510067598.0A CN201510067598A CN104650448A CN 104650448 A CN104650448 A CN 104650448A CN 201510067598 A CN201510067598 A CN 201510067598A CN 104650448 A CN104650448 A CN 104650448A
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/00—Use of organic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/17—Amines; Quaternary ammonium compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a high/low-temperature resisting ethylene acrylic acid copolymer which comprises the following raw materials in parts by weight: 80-120 parts of an ethylene acrylic acid copolymer, 40-80 parts of carbon black, 8-12 parts of a compound ether ester plasticizer, 1-2 parts of hexamethylendiamine carbamate, 3-5 parts of an active amino accelerator, 1-3 parts of an anti-aging agent KY-405, 1-3 parts of stearic acid and 0.3-0.5 part of octadecylamine. The invention further discloses a preparation method of the high/low-temperature resisting ethylene acrylic acid copolymer. The high/low-temperature resisting ethylene acrylic acid copolymer disclosed by the invention is excellent in high temperature resistance and low temperature resistance, low in pressure deformation and excellent in engine oil resistance, crankshaft box mixed gas resistance and ozone aging resistance, and can be used in high temperature as high as 185 DEG C and low temperature as low as minus 45 DEG C, and the service life can be prolonged.
Description
Technical field
The present invention relates to field of rubber technology, particularly relate to a kind of high-low temperature resistant ethylene acrylic acid co polymer and preparation method thereof.
Background technology
In recent years, along with the high speed development of automobile industry scientific and technological level, world's various brands automobile industry is all using turbosupercharged engine energetically, reduces energy consumption with this, improve the service efficiency of engine, but turbo charged extensive popularization, also encounters a lot of technical barrier simultaneously, as long-term in hot air aging environment, cause common rubber item to occur be full of cracks, the phenomenons such as embrittlement are one of evil backstage manipulators behind the scenes of many automobile vendors " Defective vehicle recall " in recent years.Learnt by the understanding of many automakers, because turbine increases systematic difference, cause the cleaned air pipe of automobile air inlet system to be heated significantly to promote, conventional elastomeric material can not meet the use of turbosupercharged engine, and therefore develop a kind ofly has the ethylene acrylic acid co polymer of excellent in performance more and more important under high and low temperature.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes a kind of high-low temperature resistant ethylene acrylic acid co polymer and preparation method thereof, there is excellent high temperature resistant and resistance to low temperature, increase the service life, can use for a long time in the low temperature of the high temperature up to 185 DEG C and-45 DEG C, and pressure step-down, also there is outstanding resistance to engine oil, the mixed gas of resistance to crankcase, ozone-resistant aging property.
A kind of high-low temperature resistant ethylene acrylic acid co polymer that the present invention proposes, its raw material comprises by weight: ethylene acrylic acid co polymer 80-120 part, carbon black 40-80 part, mixed ether lipid plasticizer A-8100 8-12 part, hexyl diamino carbamate 1-2 part, reactive amines promotor 3-5 part, anti-aging agent KY-405 1-3 part, stearic acid 1-3 part, stearylamine 0.3-0.5 part.
In above-mentioned high-low temperature resistant ethylene acrylic acid co polymer raw material, the weight part of ethylene acrylic acid co polymer can be 80 parts, 83 parts, 85 parts, 87 parts, 90 parts, 92 parts, 95 parts, 98 parts, 100 parts, 104 parts, 105 parts, 106 parts, 110 parts, 111 parts, 115 parts, 119 parts, 120 parts, the weight part of carbon black can be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, the weight part of mixed ether lipid plasticizer A-8100 can be 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, the weight part of hexyl diamino carbamate can be 1 part, 1.2 part, 1.4 part, 1.5 part, 1.6 part, 1.8 part, 1.9 part, 2 parts, the weight part of reactive amines promotor can be 3 parts, 3.5 part, 4 parts, 4.5 part, 5 parts, the weight part of anti-aging agent KY-405 can be 1 part, 1.3 part, 1.6 part, 2 parts, 2.3 part, 2.7 part, 3 parts, stearic weight part can be 1 part, 1.3 part, 1.7 part, 2 parts, 2.3 part, 2.6 part, 3 parts, the weight part of stearylamine can be 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part.
Preferably, carbon black is one or more the composition in carbon black N550, carbon black N330, carbon black N660, carbon black N539.
Preferably, the weight ratio of ethylene acrylic acid co polymer, carbon black and stearylamine is 90-100:50-70:0.35-0.45.
Preferably, the weight ratio of ethylene acrylic acid co polymer, hexyl diamino carbamate and reactive amines promotor is 90-100:1.2-1.8:3.5-4.5.
Preferably, its raw material comprises by weight: ethylene acrylic acid co polymer 90-100 part, carbon black 50-70 part, mixed ether lipid plasticizer A-8100 9-10 part, hexyl diamino carbamate 1.2-1.8 part, reactive amines promotor 3.5-4.5 part, anti-aging agent KY-405 1.6-2.3 part, stearic acid 1.7-2.6 part, stearylamine 0.35-0.45 part.
Above-mentioned mixed ether lipid plasticizer A-8100 is produced by Hallsgar company.
The present invention also proposes the preparation method of above-mentioned high-low temperature resistant ethylene acrylic acid co polymer, obtains mixture by mixing in ethylene acrylic acid co polymer, carbon black, mixed ether lipid plasticizer A-8100, hexyl diamino carbamate, reactive amines promotor, anti-aging agent KY-405, stearic acid and stearylamine feeding Banbury mixer; Sent into by mixture in mill and carry out opening the type of being smelt, the forming mould being then placed in vulcanizing equipment carries out sulfuration and obtains high-low temperature resistant ethylene acrylic acid co polymer.
Preferably, mixture is obtained by mixing in ethylene acrylic acid co polymer, carbon black, mixed ether lipid plasticizer A-8100, hexyl diamino carbamate, reactive amines promotor, anti-aging agent KY-405, stearic acid and stearylamine feeding Banbury mixer, wherein the hardness of mixture is 75 ± 3 degree, intensity >=the 10MPa of mixture, elongation >=150% of mixture; Sent into by mixture in mill and carry out opening the type of being smelt, the forming mould being then placed in vulcanizing equipment carries out sulfuration and obtains high-low temperature resistant ethylene acrylic acid co polymer.
Preferably, mixture is obtained by mixing in ethylene acrylic acid co polymer, carbon black, mixed ether lipid plasticizer A-8100, hexyl diamino carbamate, reactive amines promotor, anti-aging agent KY-405, stearic acid and stearylamine feeding Banbury mixer, wherein the hardness of mixture is 75 ± 3 degree, intensity>=the 10MPa of mixture, elongation>=150% of mixture; Sent into by mixture in mill and carry out opening the type of being smelt, the forming mould sulfuration 300-480s being then placed in vulcanizing equipment obtains high-low temperature resistant ethylene acrylic acid co polymer, and sulfide stress is 140-160Kgf/cm
2, curing temperature is 170-180 DEG C.
Preferably, mixture is obtained by mixing in ethylene acrylic acid co polymer, carbon black, mixed ether lipid plasticizer A-8100, hexyl diamino carbamate, reactive amines promotor, anti-aging agent KY-405, stearic acid and stearylamine feeding Banbury mixer, wherein the hardness of mixture is 75 ± 3 degree, intensity>=the 10MPa of mixture, elongation>=150% of mixture; Sent into by mixture in mill and carry out opening the type of being smelt, the forming mould being then placed in vulcanizing equipment carries out a sulfuration and obtains the first material, and the pressure of a sulfuration is 140-160Kgf/cm
2, the temperature of a sulfuration is 170-180 DEG C, and the time of a sulfuration is 300-480s; First material is carried out post cure and obtains high-low temperature resistant ethylene acrylic acid co polymer, the temperature of post cure is 170-180 DEG C, and the time of post cure is 3-5h.
Carbon black in the present invention is carbon black N550, carbon black N330, carbon black N660, one or more composition in carbon black N539, can greatly improve mechanical property of the present invention, and ethylene acrylic acid co polymer, carbon black, stearylamine and mixed ether lipid plasticizer A-8100 cooperatively interact, the present invention is made to be easy to processing, and adopt hexyl diamino carbamate and reactive amines promotor as vulcanization system, significantly improve crosslinking degree of the present invention, thus improve high temperature resistant and resistance to low temperature of the present invention, and stearic acid, stearylamine and mixed ether lipid plasticizer A-8100 cooperatively interact, carbon black degree of scatter in ethylene acrylic acid co polymer can be promoted, make property retention of the present invention balanced.The present invention has excellent high temperature resistant and resistance to low temperature by mixing postcure, and adopt the mode of twice sulfuration, make resistance to elevated temperatures of the present invention up to 185 DEG C, resistance to low temperature can reach-45 DEG C, the present invention simultaneously presses step-down, but also has outstanding resistance to engine oil, the mixed gas of resistance to crankcase, ozone-resistant aging property.
Embodiment
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A kind of high-low temperature resistant ethylene acrylic acid co polymer that the present invention proposes, its raw material comprises by weight: ethylene acrylic acid co polymer 80 parts, carbon black 40 parts, mixed ether fat plasticizer A-8,100 8 parts, hexyl diamino carbamate 1 part, reactive amines promotor 3 parts, anti-aging agent KY-405 1 part, stearic acid 1 part, stearylamine 0.3 part.
The present invention also proposes the preparation method of above-mentioned high-low temperature resistant ethylene acrylic acid co polymer, above-mentioned raw materials is sent into and mixingly in Banbury mixer obtains mixture, wherein the hardness of mixture is 73 degree, and the intensity of mixture is 11.7MPa, and the elongation of mixture is 215%; Sent into by mixture in mill and carry out opening the type of being smelt, the temperature opening the type of being smelt is 60 DEG C, and the forming mould being then placed in vulcanizing equipment carries out a sulfuration and obtains the first material, and the pressure of a sulfuration is 140Kgf/cm
2, the temperature of a sulfuration is 175 DEG C, and the time of a sulfuration is 360s; First material is carried out post cure and obtains high-low temperature resistant ethylene acrylic acid co polymer, the temperature of post cure is 170 DEG C, and the time of post cure is 5h.
Embodiment 2
A kind of high-low temperature resistant ethylene acrylic acid co polymer that the present invention proposes, its raw material comprises by weight: ethylene acrylic acid co polymer 100 parts, carbon black 60 parts, mixed ether lipid plasticizer A-8,100 10 parts, hexyl diamino carbamate 1.5 parts, reactive amines promotor 4 parts, anti-aging agent KY-405 2 parts, stearic acid 2 parts, stearylamine 0.4 part.
The present invention also proposes the preparation method of above-mentioned high-low temperature resistant ethylene acrylic acid co polymer, above-mentioned raw materials is sent into and mixingly in Banbury mixer obtains mixture, wherein the hardness of mixture is 75 degree, and the intensity of mixture is 12.8MPa, and the elongation of mixture is 210%; Sent into by mixture in mill and carry out opening the type of being smelt, opening refining mold temperature is 65 DEG C, and the forming mould being then placed in vulcanizing equipment carries out a sulfuration and obtains the first material, and the pressure of a sulfuration is 150Kgf/cm
2, the temperature of a sulfuration is 170 DEG C, and the time of a sulfuration is 420s; First material is carried out post cure and obtains high-low temperature resistant ethylene acrylic acid co polymer, the temperature of post cure is 175 DEG C, and the time of post cure is 4h.
Embodiment 3
A kind of high-low temperature resistant ethylene acrylic acid co polymer that the present invention proposes, its raw material comprises by weight: ethylene acrylic acid co polymer 120 parts, carbon black 80 parts, mixed ether lipid plasticizer A-8,100 12 parts, hexyl diamino carbamate 2 parts, reactive amines promotor 5 parts, anti-aging agent KY-405 3 parts, stearic acid 3 parts, stearylamine 0.5 part.
The present invention also proposes the preparation method of above-mentioned high-low temperature resistant ethylene acrylic acid co polymer, above-mentioned raw materials is sent into and mixingly in Banbury mixer obtains mixture, wherein the hardness of mixture is 77 degree, and the intensity of mixture is 13.4MPa, and the elongation of mixture is 177%; Sent into by mixture in mill and carry out opening the type of being smelt, opening refining mold temperature is 70 DEG C, and the forming mould being then placed in vulcanizing equipment carries out a sulfuration and obtains the first material, and the pressure of a sulfuration is 150Kgf/cm
2, the temperature of a sulfuration is 180 DEG C, and the time of a sulfuration is 480s; First material is carried out post cure and obtains high-low temperature resistant ethylene acrylic acid co polymer, the temperature of post cure is 180 DEG C, and the time of post cure is 3h.
Resistance to elevated temperatures and resistance to low temperature detection are carried out to embodiment 1-3, in prior art with ECO and AEM as a control group.
Wherein resistance to elevated temperatures contrast is as follows:
| ECO | AEM | Embodiment 1-3 mean value | |
| Life-time service temperature | 130℃ | 160℃ | 175℃ |
| Ultimate-use temperature | 140℃ | 175℃ | 185℃ |
Wherein resistance to low temperature contrast is as follows:
| ECO | AEM | Embodiment 1-3 mean value | |
| Life-time service temperature | -35℃ | -35℃ | -40℃ |
| Ultimate-use temperature | -40℃ | -40℃ | -45℃ |
Proceed Performance Detection to embodiment 1-3, in prior art with the obtained cleaned air pipe of AEM as a control group, its result is as follows:
From above-mentioned Data Comparison, technical indicator of the present invention meets the technical standards completely, under high/low temperature condition, be obviously better than prior art.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (9)
1. a high-low temperature resistant ethylene acrylic acid co polymer, it is characterized in that, its raw material comprises by weight: ethylene acrylic acid co polymer 80-120 part, carbon black 40-80 part, mixed ether lipid plasticizer A-8100 8-12 part, hexyl diamino carbamate 1-2 part, reactive amines promotor 3-5 part, anti-aging agent KY-405 1-3 part, stearic acid 1-3 part, stearylamine 0.3-0.5 part.
2. high-low temperature resistant ethylene acrylic acid co polymer according to claim 1, it is characterized in that, carbon black is one or more the composition in carbon black N550, carbon black N330, carbon black N660, carbon black N539.
3. high-low temperature resistant ethylene acrylic acid co polymer according to claim 1 or 2, is characterized in that, the weight ratio of ethylene acrylic acid co polymer, carbon black and stearylamine is 90-100:50-70:0.35-0.45.
4. high-low temperature resistant ethylene acrylic acid co polymer according to any one of claim 1-3, is characterized in that, the weight ratio of ethylene acrylic acid co polymer, hexyl diamino carbamate and reactive amines promotor is 90-100:1.2-1.8:3.5-4.5.
5. high-low temperature resistant ethylene acrylic acid co polymer according to any one of claim 1-4, it is characterized in that, its raw material comprises by weight: ethylene acrylic acid co polymer 90-100 part, carbon black 50-70 part, mixed ether lipid plasticizer A-8100 9-10 part, hexyl diamino carbamate 1.2-1.8 part, reactive amines promotor 3.5-4.5 part, anti-aging agent KY-405 1.6-2.3 part, stearic acid 1.7-2.6 part, stearylamine 0.35-0.45 part.
6. the preparation method of a high-low temperature resistant ethylene acrylic acid co polymer as described in any one of claim 1-5, it is characterized in that, obtain mixture by mixing in ethylene acrylic acid co polymer, carbon black, mixed ether lipid plasticizer A-8100, hexyl diamino carbamate, reactive amines promotor, anti-aging agent KY-405, stearic acid and stearylamine feeding Banbury mixer; Sent into by mixture in mill and carry out opening the type of being smelt, the forming mould being then placed in vulcanizing equipment carries out sulfuration and obtains high-low temperature resistant ethylene acrylic acid co polymer.
7. the preparation method of high-low temperature resistant ethylene acrylic acid co polymer according to claim 6, it is characterized in that, mixture is obtained by mixing in ethylene acrylic acid co polymer, carbon black, mixed ether lipid plasticizer A-8100, hexyl diamino carbamate, reactive amines promotor, anti-aging agent KY-405, stearic acid and stearylamine feeding Banbury mixer, wherein the hardness of mixture is 75 ± 3 degree, intensity >=the 10MPa of mixture, elongation >=150% of mixture; Sent into by mixture in mill and carry out opening the type of being smelt, the forming mould being then placed in vulcanizing equipment carries out sulfuration and obtains high-low temperature resistant ethylene acrylic acid co polymer.
8. the preparation method of high-low temperature resistant ethylene acrylic acid co polymer according to claim 6 or 7, it is characterized in that, mixture is obtained by mixing in ethylene acrylic acid co polymer, carbon black, mixed ether lipid plasticizer A-8100, hexyl diamino carbamate, reactive amines promotor, anti-aging agent KY-405, stearic acid and stearylamine feeding Banbury mixer, wherein the hardness of mixture is 75 ± 3 degree, intensity>=the 10MPa of mixture, elongation>=150% of mixture; Sent into by mixture in mill and carry out opening the type of being smelt, the forming mould sulfuration 300-480s being then placed in vulcanizing equipment obtains high-low temperature resistant ethylene acrylic acid co polymer, and sulfide stress is 140-160Kgf/cm
2, curing temperature is 170-180 DEG C.
9. the preparation method of high-low temperature resistant ethylene acrylic acid co polymer according to claim 6 or 7, it is characterized in that, mixture is obtained by mixing in ethylene acrylic acid co polymer, carbon black, mixed ether lipid plasticizer A-8100, hexyl diamino carbamate, reactive amines promotor, anti-aging agent KY-405, stearic acid and stearylamine feeding Banbury mixer, wherein the hardness of mixture is 75 ± 3 degree, intensity>=the 10MPa of mixture, elongation>=150% of mixture; Sent into by mixture in mill and carry out opening the type of being smelt, the forming mould being then placed in vulcanizing equipment carries out a sulfuration and obtains the first material, and the pressure of a sulfuration is 140-160Kgf/cm
2, the temperature of a sulfuration is 170-180 DEG C, and the time of a sulfuration is 300-480s; First material is carried out post cure and obtains high-low temperature resistant ethylene acrylic acid co polymer, the temperature of post cure is 170-180 DEG C, and the time of post cure is 3-5h.
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Citations (3)
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| CN101812210A (en) * | 2009-12-07 | 2010-08-25 | 天津鹏翎胶管股份有限公司 | Formula of ethylene-acrylate rubber of fuel hose for automobiles |
| CN102408655A (en) * | 2011-08-22 | 2012-04-11 | 安徽中鼎密封件股份有限公司 | Sealing gasket and preparation method thereof |
| CN102766295A (en) * | 2012-07-12 | 2012-11-07 | 安徽中鼎密封件股份有限公司 | Clean air tube and preparation method thereof |
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2015
- 2015-02-09 CN CN201510067598.0A patent/CN104650448A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812210A (en) * | 2009-12-07 | 2010-08-25 | 天津鹏翎胶管股份有限公司 | Formula of ethylene-acrylate rubber of fuel hose for automobiles |
| CN102408655A (en) * | 2011-08-22 | 2012-04-11 | 安徽中鼎密封件股份有限公司 | Sealing gasket and preparation method thereof |
| CN102766295A (en) * | 2012-07-12 | 2012-11-07 | 安徽中鼎密封件股份有限公司 | Clean air tube and preparation method thereof |
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