CN110872402B - Method for enhancing temperature resistance of nitrile rubber by using nano zeolite powder - Google Patents
Method for enhancing temperature resistance of nitrile rubber by using nano zeolite powder Download PDFInfo
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- CN110872402B CN110872402B CN201911245870.4A CN201911245870A CN110872402B CN 110872402 B CN110872402 B CN 110872402B CN 201911245870 A CN201911245870 A CN 201911245870A CN 110872402 B CN110872402 B CN 110872402B
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- C08L9/02—Copolymers with acrylonitrile
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Abstract
The invention discloses a method for enhancing the temperature resistance of nitrile rubber by using nano zeolite powder, which relates to the technical field of rubber materials and comprises the following steps: s1, compounding polycarboborane methyl siloxane on the nano zeolite powder to obtain the nano zeolite powder compounded polycarboborane methyl siloxane; s2, plasticating and mixing nitrile butadiene rubber, nano zeolite powder composite polycarboborane methyl siloxane, a vulcanizing agent and an accelerant, and finally vulcanizing to obtain the nitrile butadiene rubber and nano zeolite powder composite polycarboborane methyl siloxane rubber; the nano zeolite powder prepared by the method enhances the temperature resistance of the nitrile rubber, and can greatly improve the temperature resistance of the nitrile rubber.
Description
Technical Field
The invention belongs to the technical field of rubber materials, and particularly relates to a method for enhancing the temperature resistance of nitrile rubber by using nano zeolite powder.
Background
The nitrile rubber is polar unsaturated carbon chain rubber, has the common property of unsaturated rubber, has middle and lower heat resistance, has slightly higher heat resistance than natural rubber, styrene butadiene rubber and butadiene rubber, but has poor heat resistance compared with fluorine rubber and silicon rubber, the nitrile rubber product can work for a long time at the temperature of 100 ℃, the service life of the nitrile rubber product only reaches about 40 days, and when the nitrile rubber product works at the temperature of 150 ℃, the service life is only 3 days, so that the high temperature resistance of the nitrile rubber product is poor, and the application field of the nitrile rubber product is greatly limited.
The prior art is as follows: "201910604985.1 a nanometer aramid fiber modified nitrile rubber and a preparation method thereof", wherein the modified nitrile rubber is prepared by mixing the following raw materials, the raw materials comprise nitrile rubber, modified aramid fiber-nitrile rubber masterbatch, sulfur, an activating agent and an accelerating agent, and the modified aramid fiber in the modified nitrile rubber is well dispersed in the nitrile rubber, so that the tensile strength and the stress at definite elongation of the nitrile rubber are improved, but the heat resistance of the nitrile rubber is not improved.
Disclosure of Invention
The invention aims to provide a method for enhancing the temperature resistance of nitrile rubber by using nano zeolite powder aiming at the existing problems.
The invention is realized by the following technical scheme:
a method for enhancing the temperature resistance of nitrile rubber by using nano zeolite powder is characterized by comprising the following steps:
s1, carrying out composite polycarboborane methyl siloxane on nano zeolite powder to obtain the composite polycarboborane methyl siloxane of the nano zeolite powder, wherein the preparation method of the composite polycarboborane methyl siloxane of the nano zeolite powder comprises the following steps:
(1) Uniformly dispersing nano zeolite powder into acetone to prepare an acetone dispersion liquid of the nano zeolite powder, wherein the mixing mass ratio of the nano zeolite powder to the acetone is 1;
(2) Adding nitrile rubber with the mass of 1.5-2% into the acetone dispersion liquid of the nano zeolite powder obtained in the step (1), heating to 120 ℃, and stirring at the rotating speed of 500r/min for 40min to obtain a mixed liquid;
(3) Adding 3-4% of polycarboborane methyl siloxane and 1.0-1.2% of organic acid into the mixed liquid obtained in the step (2), stirring for 2 hours at the rotating speed of 1000r/min, preserving heat for 30min at 100 ℃, and then carrying out rotary evaporation on the solvent, and drying to constant weight to obtain the organic acid, wherein the organic acid is selected from one or more of C1-C18 organic carboxylic acids, preferably formic acid, acetic acid, n-butyric acid and stearic acid.
S2, plasticating the nitrile rubber, the nano zeolite powder compounded polycarboborane methyl siloxane, a vulcanizing agent and an accelerator, wherein the plasticating is carried out by adopting a double-screw extruder, the temperature zones in the double-screw extruder are respectively 100-105 ℃, 105-110 ℃, 115-120 ℃ and 120-130 ℃, the pitch-diameter ratio of a screw of the double-screw extruder is 48, the rotating speed of the screw is 45r/min, the plasticating time is 5-8min, mixing is carried out in the mixing roll for 10-13min, and finally vulcanization is carried out in a flat vulcanizing machine, the vulcanizing time is 15min, and the vulcanizing temperature is 185 ℃; the mixing mass ratio of the nitrile rubber, the nano zeolite powder composite polycarboborane methyl siloxane, the vulcanizing agent and the accelerant is 78-85: 2-2.5:1.3-1.6, the vulcanizing agent is sulfur, and the accelerator is any one of zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate and zinc dimethyldithiocarbamate, preferably zinc dibutyldithiocarbamate.
Has the advantages that: the nanometer zeolite powder prepared by the method enhances the temperature resistance of the nitrile rubber, can greatly improve the temperature resistance of the nitrile rubber, and the nanometer zeolite powder is added with the compound polycarboborane methyl siloxane, so that the nanometer zeolite powder can form a stable chemical cross-linked network with the compound polycarboborane methyl siloxane and the nitrile rubber, the bond energy between the molecular chains of the nitrile rubber is greatly improved, and the heat resistance is improved by combining the preparation method of the invention.
Drawings
FIG. 1 is a graph of the thermal aging resistance of nitrile rubber at different times.
Detailed Description
Example 1
A method for enhancing the temperature resistance of nitrile rubber by using nano zeolite powder is characterized by comprising the following steps:
s1, carrying out composite polycarboborane methyl siloxane on nano zeolite powder to obtain the composite polycarboborane methyl siloxane of the nano zeolite powder, wherein the preparation method of the composite polycarboborane methyl siloxane of the nano zeolite powder comprises the following steps:
(1) Uniformly dispersing nano zeolite powder into acetone to prepare an acetone dispersion liquid of the nano zeolite powder, wherein the mixing mass ratio of the nano zeolite powder to the acetone is 1;
(2) Adding nitrile rubber with the mass of 1.5% into the acetone dispersion liquid of the nano zeolite powder obtained in the step (1), heating to 120 ℃, and stirring at the rotating speed of 500r/min for 40min to obtain a mixed liquid;
(3) And (3) adding 3% of polycarboborane methyl siloxane and 1.0% of organic acid by mass into the mixed liquid obtained in the step (2), stirring at the rotating speed of 1000r/min for 2 hours, preserving the heat at 100 ℃ for 30min, then performing rotary evaporation on the solvent, and drying to constant weight to obtain the organic acid, namely n-butyric acid.
S2, plasticating the nitrile rubber, the nano zeolite powder compounded polycarboborane methyl siloxane, a vulcanizing agent and an accelerator, wherein the plasticating is carried out by adopting a double-screw extruder, the temperature zones in the double-screw extruder are respectively 100 ℃, 105-110 ℃, 105 ℃, 115 ℃ and 120 ℃, the screw pitch-diameter ratio of the double-screw extruder is 48, the screw rotating speed is 45r/min, the plasticating time is 5min, mixing is carried out in a mixing roll, the mixing time is 10min, and finally, vulcanization is carried out in a flat plate vulcanizing machine, the vulcanization time is 15min, and the vulcanization temperature is 185 ℃; the mixing mass ratio of the nitrile rubber, the nano zeolite powder composite polycarboborane methyl siloxane, the vulcanizing agent and the accelerant is 78: 2:1.3, the vulcanizing agent is sulfur, and the accelerator is zinc diethyldithiocarbamate.
Example 2
A method for enhancing the temperature resistance of nitrile rubber by using nano zeolite powder is characterized by comprising the following steps:
s1, carrying out composite polycarboborane methyl siloxane on nano zeolite powder to obtain the composite polycarboborane methyl siloxane of the nano zeolite powder, wherein the preparation method of the composite polycarboborane methyl siloxane of the nano zeolite powder comprises the following steps:
(1) Uniformly dispersing nano zeolite powder into acetone to prepare an acetone dispersion liquid of the nano zeolite powder, wherein the mixing mass ratio of the nano zeolite powder to the acetone is 1;
(2) Adding nitrile rubber with the mass of 2% into the acetone dispersion liquid of the nano zeolite powder obtained in the step (1), heating to 120 ℃, and stirring at the rotating speed of 500r/min for 40min to obtain a mixed liquid;
(3) Adding 4% of polycarboborane methyl siloxane and 1.2% of organic acid by mass into the mixed liquid obtained in the step (2), stirring at the rotating speed of 1000r/min for 2 hours, preserving heat at 100 ℃ for 30min, then performing rotary evaporation on the solvent, and drying to constant weight to obtain the organic acid, namely acetic acid.
S2, plasticating the nitrile rubber, the nano zeolite powder compounded polycarboborane methyl siloxane, a vulcanizing agent and an accelerator, wherein the plasticating is carried out by adopting a double-screw extruder, the temperature zones in the double-screw extruder are respectively 105 ℃, 110 ℃, 120 ℃ and 130 ℃, the screw pitch-diameter ratio of the double-screw extruder is 48; the mixture mass ratio of the nitrile rubber, the nano zeolite powder composite polycarboborane methyl siloxane, the vulcanizing agent and the accelerant is 85: 21: 2.5: 1.6, the vulcanizing agent is sulfur, and the accelerator is zinc diethyldithiocarbamate.
Example 3
A method for enhancing the temperature resistance of nitrile rubber by using nano zeolite powder is characterized by comprising the following steps:
s1, carrying out composite polycarboborane methyl siloxane on nano zeolite powder to obtain the composite polycarboborane methyl siloxane of the nano zeolite powder, wherein the preparation method of the composite polycarboborane methyl siloxane of the nano zeolite powder comprises the following steps:
(1) Uniformly dispersing nano zeolite powder into acetone to prepare an acetone dispersion liquid of the nano zeolite powder, wherein the mixing mass ratio of the nano zeolite powder to the acetone is 1;
(2) Adding nitrile rubber with the mass of 1.8% into the acetone dispersion liquid of the nano zeolite powder obtained in the step (1), heating to 120 ℃, and stirring at the rotating speed of 500r/min for 40min to obtain a mixed liquid;
(3) And (3) adding 3.5% of polycarboborane methyl siloxane and 1.1% of organic acid by mass into the mixed solution obtained in the step (2), stirring for 2 hours at the rotating speed of 1000r/min, preserving the heat at 100 ℃ for 30min, then performing rotary evaporation on the solvent, and drying to constant weight to obtain the organic acid, wherein the organic acid is preferably stearic acid.
S2, plasticating the nitrile rubber, the nano zeolite powder compounded polycarboborane methyl siloxane, a vulcanizing agent and an accelerator, wherein the plasticating is carried out by adopting a double-screw extruder, the temperature zones in the double-screw extruder are respectively 102 ℃, 108 ℃, 118 ℃ and 128 ℃, the screw pitch-diameter ratio of the double-screw extruder is 48; the mixing mass ratio of the nitrile rubber, the nano zeolite powder composite polycarboborane methyl siloxane, the vulcanizing agent and the accelerant is 81: 2.2:1.5, the vulcanizing agent is sulfur, and the accelerator is zinc dimethyldithiocarbamate.
FIG. 1 is a graph showing the thermal aging resistance of nitrile rubber at different times, wherein a represents example 1, b represents comparative example 1, and c represents comparative example 2, wherein in the comparative example 1, nano zeolite powder in nano zeolite powder composite polycarboborane methyl siloxane is replaced by nano bentonite on the basis of example 1, the preparation method is not changed, and in the comparative example 2, nano zeolite powder composite polycarboborane methyl siloxane is replaced by nano zeolite powder on the basis of example 1; as can be seen from fig. 1, the nitrile rubber prepared in example 1 has a greatly improved heat resistance, and particularly has a process of increasing first and then decreasing when subjected to heat-resistant treatment, because the intermolecular bonds in the nitrile rubber prepared in example 1 are higher in the initial stage of heat-resistant treatment, the chemical bonds between the molecular chains are not broken after the heat treatment in a short time, but rather the molecular chains are further subjected to a crosslinking reaction of double bond addition to a certain extent, so that the tensile strength of the nitrile rubber is rather increased, but after a certain period of time, the chemical bonds between the molecular chains begin to break, so that the tensile strength begins to show a continuous decrease.
The foregoing description of the embodiments is provided merely as an aid in understanding the manner and key concepts of the invention, and many modifications of these embodiments will be apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention, and thus, the invention is not to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for enhancing the temperature resistance of nitrile rubber by using nano zeolite powder is characterized by comprising the following steps:
s1, compounding polycarboborane methyl siloxane on nano zeolite powder to obtain the nano zeolite powder compounded polycarboborane methyl siloxane, wherein the mixing mass ratio of the nitrile rubber, the nano zeolite powder compounded polycarboborane methyl siloxane, a vulcanizing agent and an accelerator is 78-85: 2-2.5:1.3-1.6;
s2, plasticating and mixing nitrile butadiene rubber, nano zeolite powder composite polycarboborane methyl siloxane, a vulcanizing agent and an accelerant, and finally vulcanizing to obtain the nitrile butadiene rubber and nano zeolite powder composite polycarboborane methyl siloxane rubber; the preparation method of the nano zeolite powder composite polycarboborane methyl siloxane comprises the following steps:
(1) Uniformly dispersing the nano zeolite powder into acetone to prepare acetone dispersion liquid of the nano zeolite powder;
(2) Adding nitrile rubber with the mass of 1.5-2% into the acetone dispersion liquid of the nano zeolite powder obtained in the step (1), heating to 120 ℃, and stirring at the rotating speed of 500r/min for 40min to obtain a mixed liquid;
(3) And (3) adding 3-4% of polycarboborane methyl siloxane and 1.0-1.2% of organic acid by mass into the mixed liquid obtained in the step (2), stirring at the rotating speed of 1000r/min for 2 hours, preserving the heat at 100 ℃ for 30min, then performing rotary evaporation on the solvent, and drying to constant weight to obtain the catalyst.
2. The method for enhancing the temperature resistance of nitrile rubber by using the nano zeolite powder as claimed in claim 1, wherein the mixing mass ratio of the nano zeolite powder to acetone is 1.
3. The method for enhancing the temperature resistance of nitrile rubber by using the nano zeolite powder as claimed in claim 1, wherein the organic acid is one or more selected from C1-C18 organic carboxylic acids.
4. The method for enhancing the temperature resistance of nitrile rubber by using the nano zeolite powder as claimed in claim 1, wherein the vulcanizing agent is sulfur.
5. The method for enhancing the temperature resistance of nitrile rubber by using the nano zeolite powder as claimed in claim 1, wherein the accelerator is any one of zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate and zinc dimethyldithiocarbamate.
6. The method for enhancing the temperature resistance of nitrile rubber by using nano zeolite powder as claimed in claim 1, wherein the plastication is performed by using a twin-screw extruder for 5-8min.
7. The method for enhancing the temperature resistance of nitrile rubber by using the nano zeolite powder as claimed in claim 1, wherein the mixing is carried out in a mixing mill for 10-13min.
8. The method for enhancing the temperature resistance of nitrile rubber by using the nano zeolite powder as claimed in claim 1, wherein the vulcanization is carried out in a flat vulcanizing press for 15min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185451A (en) * | 2015-09-22 | 2015-12-23 | 晋源电气集团股份有限公司 | Marine anti-aging and corrosion resistant cable |
| CN106800683A (en) * | 2017-02-27 | 2017-06-06 | 合肥中科富华新材料有限公司 | A kind of wear-resistant cable material and preparation method |
| CN107189134A (en) * | 2017-07-17 | 2017-09-22 | 合肥威斯伏新材料有限公司 | A kind of wear-resistant cable material and preparation method |
| CN109111672A (en) * | 2018-06-27 | 2019-01-01 | 武汉工程大学 | A kind of acrylic ester grafted modified zeolite high temperature resistant composite and preparation method thereof |
-
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- 2019-12-07 CN CN201911245870.4A patent/CN110872402B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185451A (en) * | 2015-09-22 | 2015-12-23 | 晋源电气集团股份有限公司 | Marine anti-aging and corrosion resistant cable |
| CN106800683A (en) * | 2017-02-27 | 2017-06-06 | 合肥中科富华新材料有限公司 | A kind of wear-resistant cable material and preparation method |
| CN107189134A (en) * | 2017-07-17 | 2017-09-22 | 合肥威斯伏新材料有限公司 | A kind of wear-resistant cable material and preparation method |
| CN109111672A (en) * | 2018-06-27 | 2019-01-01 | 武汉工程大学 | A kind of acrylic ester grafted modified zeolite high temperature resistant composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 夏征农等."有机硅材料及其他元素有机高分子材料".《大辞海 第37卷 材料科学卷》.上海辞海出版社,2015, * |
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