CN110498869B - Preparation method of high-performance hydrogenated rubber elastomer - Google Patents
Preparation method of high-performance hydrogenated rubber elastomer Download PDFInfo
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Abstract
The invention relates to a catalyst, a high-performance hydrogenated rubber elastomer and a preparation method of the high-performance hydrogenated rubber elastomer, wherein the catalyst is carbon black, and the specific surface area of the carbon black is 500-600 cm2(ii)/g, the particle size is 10-15 nm; wherein the unsaturated rubber emulsion is SBR emulsion or NBR emulsion. The new catalyst adopted by the invention provides a new preparation method for preparing the high-performance hydrogenated rubber elastomer, and the prepared hydrogenated rubber elastomer material has potential application value in the field of high-performance rubber. The invention prepares the high-performance hydrogenated styrene-butadiene rubber elastomer by carrying out emulsion hydrogenation on unsaturated carbon-carbon double bonds on a styrene-butadiene rubber molecular chain under the action of a novel catalyst. The HSBR elastomer prepared by the invention has excellent heat resistance and good mechanical property.
Description
Technical Field
The invention relates to the field of rubber elastomers, in particular to a preparation method of a high-performance hydrogenated rubber elastomer.
Background
Styrene butadiene rubber is an elastomer obtained from butadiene and styrene by emulsion polymerization. Has good wear resistance, but has poor high temperature resistance and thermal oxygen aging resistance due to the existence of carbon-carbon unsaturated double bonds in molecular chains. In order to improve the high temperature resistance and the thermal-oxidative aging resistance, the unsaturated carbon-carbon double bond can be hydrogenated and modified.
The hydrogenation of solutions using RhCl (PPh) has been studied3)3The hydrogenation degree can reach more than 95% after 12h of reaction time, and the catalyst has good hydrogenation activity and good selectivity. However, high-pressure hydrogen and a noble metal catalyst RhCl (PPh) are still required to be used in the reaction3)3The safety is poor and the cost is high. The method which adopts emulsion hydrogenation and is relatively mature only comprises hydrogen peroxide/hydrazine hydrate/Cu+The hydrogenation system, although obtaining hydrogenated styrene-butadiene rubber with higher hydrogenation degree, can affect the purity of the product due to the existence of the metal particle catalyst, so that the rubber is hardened, thereby affecting the processing and using performances of the product. Therefore, there is a need to provide a new emulsion hydrogenation catalyst and a method for hydrogenating and modifying rubber thereof.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a high-performance hydrogenated rubber elastomer.
Specifically, the invention aims to provide a hydrogenation catalyst for unsaturated rubber emulsion, wherein the catalyst is carbon black, and the specific surface area of the carbon black is 500-600 cm2(ii)/g, the particle size is 10-15 nm; wherein the unsaturated rubber emulsion is SBR emulsion or NBR emulsion. The new catalyst adopted by the invention provides a new preparation method for preparing the high-performance hydrogenated rubber elastomer, and the prepared hydrogenated rubber elastomer material has potential application value in the field of high-performance rubber. The invention prepares the high-performance hydrogenated styrene-butadiene rubber elastomer by carrying out emulsion hydrogenation on unsaturated carbon-carbon double bonds on a styrene-butadiene rubber molecular chain under the action of a novel catalyst. The HSBR elastomer prepared by the invention has excellent heat resistance and good mechanical property.
Another object of the present invention is to provide a process for preparing a hydrogenated rubber elastomer using the catalyst, preferably, comprising the steps of: the unsaturated rubber latex, the carbon black and the hydrazine compound are used as raw materials and are prepared by hydrogenation reaction. The invention prepares the high-performance hydrogenated styrene-butadiene rubber elastomer by carrying out emulsion hydrogenation on unsaturated carbon-carbon double bonds on a styrene-butadiene rubber molecular chain under the action of a novel catalyst. The HSBR elastomer prepared by the invention has excellent heat resistance and good mechanical property. The method provided by the invention is simple in process flow, convenient to operate, green and environment-friendly, and high in safety. In addition, the new catalyst adopted by the invention provides a new preparation method for preparing the high-performance HSBR elastomer, and the prepared HSBR elastomer material has potential application value in the field of high-performance rubber.
According to some preferred embodiments of the present invention, the carbon black is a high pigment carbon black; preferably, the specific surface area of the carbon black is 560cm2(ii)/g, particle size 13 nm; the carbon black and the unsaturated carbon-carbon double bond [ -C ═ C-]The mass ratio of (a) to (b) is 17:1 to 2:1, preferably 11: 1.
According to some preferred embodiments of the present invention, the carbon black is selected from one or more of hibblack 900L, XPB235, hibblack 600L, hibblack 50L, MTH200, M900 and Cabot M1300 high pigment carbon blacks. The invention adopts a novel catalyst to carry out catalytic hydrogenation on the styrene-butadiene rubber emulsion under the normal pressure condition. On one hand, unsaturated carbon-carbon double bonds in the butadiene styrene latex are hydrogenated into carbon-carbon single bonds, so that the butadiene styrene latex becomes the HSBR elastomer material with high heat resistance; on the other hand, the catalyst exists in the HSBR elastomer without being separated and recycled, and can be further used as a reinforcing filler of the HSBR elastomer, so that the mechanical property of the HSBR elastomer can be improved.
According to some preferred embodiments of the present invention, the unsaturated rubber emulsion is NBR emulsion or SBR emulsion, preferably selected from any one of butylbenzene latex, carboxybutylbenzene latex and butylbenzene pyridine latex; preferably, the solid content of the unsaturated rubber emulsion is 6-50%, and preferably 10-30%.
According to some preferred embodiments of the present invention, the hydrazine compound is selected from hydrazine hydrate, sulfonic acid group hydrazine hydrate or any combination thereof; preferably, the amount ratio of the hydrazine compound to the unsaturated carbon-carbon double bond [ -C ═ C- ] on the molecular chain in the unsaturated rubber emulsion is 6:1 to 1:1, preferably 4: 1.
According to some preferred embodiments of the present invention, the method further comprises a post-treatment step, wherein the reaction product of the hydrogenation reaction is obtained by precipitation with a precipitant, washing and drying; preferably, the precipitating agent is selected from one or more of methanol, ethanol and isopropanol.
According to some preferred embodiments of the invention, the carbon black is added into the unsaturated rubber emulsion, then the hydrazine compound is dropwise added, hydrogenation reaction is carried out for 6-16h at the reaction temperature of 20-120 ℃ under the stirring condition, and the unsaturated rubber emulsion is prepared by precipitation with the precipitant, washing and drying.
According to some preferred embodiments of the invention, the conditions of the hydrogenation reaction are: the hydrogenation reaction is carried out for 6 to 16 hours under the conditions of normal pressure environment, the reaction temperature of 20 to 120 ℃, the stirring speed of 100 and 500 r/min. The method adopts the action of the novel catalyst and hydrazine hydrate to hydrogenate unsaturated double bonds in the SBR rubber, and is green, environment-friendly and pollution-free. The reaction is carried out at normal temperature and normal pressure, the equipment is not strictly required, high-pressure hydrogen is not used, and potential safety hazards caused by high temperature and high pressure are eliminated. Has the advantages of low cost, high safety factor and simple preparation process.
The invention also aims to provide the hydrogenated rubber elastomer prepared by the method. The HSBR elastomer prepared by the invention has excellent heat resistance and good mechanical property.
The invention has the beneficial effects that: the invention adopts a new SBR emulsion hydrogenation catalyst; the styrene butadiene rubber elastomer is used for hydrogenation of SBR emulsion to obtain hydrogenated styrene butadiene rubber elastomer, and on the other hand, the heat resistance of the HSBR is endowed, the aging resistance and the mechanical property of the HSBR are improved, and the application field of the styrene butadiene rubber is further widened. The heat-resistant high-performance hydrogenated styrene-butadiene rubber elastomer material prepared by the invention can be used in a harsher environment, meets the requirements of heat resistance, aging resistance, oxygen resistance and the like, provides a novel emulsion hydrogenation method, and has important application value in the field of hydrogenated rubber preparation. The method provided by the invention is simple in process flow, convenient to operate, green and environment-friendly, and high in safety. In addition, the new catalyst adopted by the invention provides a new preparation method for preparing the high-performance HSBR elastomer, and the prepared HSBR elastomer material has potential application value in the field of high-performance rubber.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of HSBR-90.3% and SBR in example 23 of the present invention.
FIG. 2 is an IR spectrum of HSBR-90.3% and SBR of example 23 of the present invention.
FIG. 3 is a thermogravimetric analysis chart of HSBR-90.3% and SBR in example 23 of the present invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not specify particular techniques or conditions, according to techniques or conditions described in the literature in the field or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer. In the following examples, 1502 styrene-butadiene latex (10% solids) was used as the SBR emulsion, and M1300, a specific table, was used as the high-pigment carbon blackThe area is 560cm2(ii)/g, particle diameter is 13 nm.
Example 1
The embodiment relates to a synthesis method of high-performance hydrogenated styrene-butadiene rubber, which comprises the following steps:
1) firstly, adding 50g of SBR emulsion into a round bottom flask, adding 5g of high-pigment carbon black, stirring for 30min, fully mixing uniformly, then adding 10g of hydrazine hydrate, stirring at the normal pressure environment and at the rotation speed of 200r/min, wherein the reaction temperature is 40 ℃, and stirring and hydrogenating for 8 h; obtaining reaction stock solution;
2) the reaction stock solution is prepared by precipitating with absolute ethyl alcohol, washing and drying at 50 ℃ for 24h, wherein the mass ratio of hydrazine hydrate to unsaturated carbon-carbon double bond [ -C ═ C- ] in the above embodiment is 2: 1. The hydrogenation degree is detected to be 12.2%.
Examples 2 to 5
The same as in example 1, except that the reaction temperatures were 50 ℃ C., 60 ℃ C., 70 ℃ C., and 80 ℃ C., respectively. The hydrogenation degree is detected to be 40.2%, 34.9%, 32.1% and 29.0% respectively.
Example 6
The embodiment relates to a synthesis method of high-performance hydrogenated styrene-butadiene rubber, which comprises the following steps:
1) firstly, adding 50g of SBR emulsion into a round bottom flask, adding 5g of high-pigment carbon black, stirring for 30min, fully mixing uniformly, then adding 10g of hydrazine hydrate, stirring at the normal pressure environment and the rotation speed of 200r/min, wherein the reaction temperature is 60 ℃, and stirring and hydrogenating for 8 h; obtaining reaction stock solution;
2) the reaction stock solution is prepared by precipitating with absolute ethyl alcohol, washing and drying at 50 ℃ for 24h, wherein the mass ratio of hydrazine hydrate to unsaturated carbon-carbon double bond [ -C ═ C- ] in the above embodiment is 2: 1. The degree of hydrogenation was found to be 40.2%.
Examples 7 to 12
The same as in example 6, except that the amount ratios of the high-color carbon black to the carbon-carbon double bond were 5:1, 7:1, 9:1, 11:1, 15:1, and 17:1, respectively. The hydrogenation degree is detected to be 25.7%, 27.5%, 32.6%, 41.5%, 38.5% and 38.2% respectively.
Example 13
The embodiment relates to a synthesis method of high-performance hydrogenated styrene-butadiene rubber, which comprises the following steps:
1) adding 50g of SBR emulsion into a round bottom flask, adding high pigment carbon black, stirring for 30min, fully mixing uniformly, then adding 5g of hydrazine hydrate, stirring at the normal pressure and at the rotating speed of 200r/min, stirring and hydrogenating for 8h, wherein the mass ratio of the SBR emulsion to carbon-carbon double bond substances is 11: 1; obtaining reaction stock solution;
2) the reaction stock solution is prepared by precipitating with absolute ethyl alcohol, washing and drying at 50 ℃ for 24h, wherein the mass ratio of hydrazine hydrate to unsaturated carbon-carbon double bond [ -C ═ C- ] in the above embodiment is 1: 1. The degree of hydrogenation was found to be 31.8%.
Examples 14 to 18
The same as example 13, except that the amounts of hydrazine hydrate and unsaturated carbon-carbon double bond were 2:1, 3:1, 4:1, 5:1, and 6:1, respectively. The hydrogenation degree is respectively detected to be 30.5%, 41.5%, 50.1%, 36.8% and 36.5%.
Example 19
The embodiment relates to a synthesis method of high-performance hydrogenated styrene-butadiene rubber, which comprises the following steps:
1) adding 50g of SBR emulsion into a round-bottom flask, adding high-pigment carbon black, stirring for 30min, fully mixing uniformly, then adding hydrazine hydrate and substances with unsaturated carbon-carbon double bonds (C-) in a quantity ratio of 4:1, stirring at a reaction temperature of 60 ℃ in a normal pressure environment at a rotation speed of 200r/min, and stirring for hydrogenation reaction for 4 h; obtaining reaction stock solution;
2) precipitating the reaction stock solution with absolute ethyl alcohol, washing, and drying at 50 ℃ for 24 h. The degree of hydrogenation was found to be 34.8%.
Examples 20 to 23
The same as example 19, except that the reaction times were 6h, 8h, 12h and 16h, respectively. The hydrogenation degree is respectively 38.2%, 50.1%, 73.7% and 90.3%.
Test example 1
The hydrogenated styrene-butadiene rubbers of examples 1, 9, 21, 22 and 23 with different degrees of hydrogenation were compared in their properties; testing the mechanical property according to GB/T5282009; the same batch of sample bars are placed in a thermal oxidation aging oven at 100 ℃ for aging for 72h, the mechanical property is tested according to GB/T5282009, and the retention rate is calculated, wherein the retention rate is equal to the performance index after aging/before aging multiplied by 100%, see Table 1.
TABLE 1 test results
According to the test results in the above table 1, it can be seen that the hydrogenated styrene butadiene rubber provided by the present invention has high tensile strength and good aging resistance, and fig. 1 to fig. 3 are the nuclear magnetic spectrum, the infrared spectrum and the thermogravimetric analysis chart of the HSBR-90.3% and the SBR in example 23 of the present invention, respectively. The thermogravimetric analysis result of fig. 3 shows that the hydrogenated styrene-butadiene rubber has good heat resistance.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (14)
1. A method for preparing a hydrogenated rubber elastomer, comprising the steps of: the catalyst is prepared by taking unsaturated rubber emulsion, carbon black and a hydrazine compound as raw materials through hydrogenation reaction, a catalyst is taken as the carbon black, and the specific surface area of the carbon black is 500-600 cm2(ii)/g, the particle size is 10-15 nm; wherein the unsaturated rubber emulsion is SBR emulsion, and the carbon black is high-pigment carbon black.
2. The method according to claim 1, wherein M1300 is used as the high pigment carbon black.
3. The production method according to claim 1, wherein the carbon black has a specific surface area of 560cm2(ii)/g, particle size 13 nm; the carbon black and the unsaturated carbon-carbon double bond [ -C = C ] on the molecular chain in the unsaturated rubber emulsion]The mass ratio of (a) to (b) is 17:1 to 2: 1.
4. The production method according to claim 3, characterized in that the mass ratio of the carbon black to the unsaturated carbon-carbon double bond [ -C = C- ] on the molecular chain in the unsaturated rubber emulsion is 11: 1.
5. The method according to claim 1, wherein the unsaturated rubber emulsion is selected from any one of styrene-butadiene latex, carboxylated styrene-butadiene latex and styrene-butadiene-pyridine latex.
6. The method according to claim 5, wherein the unsaturated rubber emulsion has a solid content of 6 to 50%.
7. The method according to claim 6, wherein the unsaturated rubber emulsion has a solid content of 10 to 30%.
8. The preparation method according to any one of claims 1 to 4, wherein the hydrazine compound is selected from hydrazine hydrate, sulfonic acid hydrazine hydrate, or any combination thereof.
9. The preparation method according to claim 8, wherein the amount ratio of the hydrazine compound to the substance having an unsaturated carbon-carbon double bond [ -C = C- ] on a molecular chain in the unsaturated rubber emulsion is 6:1 to 1: 1.
10. The method of claim 9, wherein the mass ratio of the hydrazine-based compound to the unsaturated carbon-carbon double bond [ -C = C- ] on the molecular chain in the unsaturated rubber emulsion is 4: 1.
11. The preparation method according to any one of claims 1 to 4, further comprising a post-treatment step of precipitating, washing and drying the reaction product of the hydrogenation reaction by using a precipitant.
12. The method of claim 11, wherein the precipitating agent is selected from one or more of methanol, ethanol, and isopropanol.
13. The preparation method according to any one of claims 1 to 4, characterized in that the carbon black is added into the unsaturated rubber emulsion, then the hydrazine compound is dropwise added, the hydrogenation reaction is carried out for 6 to 16 hours at the reaction temperature of 20 to 120 ℃ under the stirring condition, and the product is prepared by precipitation with a precipitator, washing and drying.
14. The production method according to any one of claims 1 to 4, wherein the conditions of the hydrogenation reaction are: the hydrogenation reaction is carried out for 6 to 16 hours under the conditions of normal pressure environment, the reaction temperature of 20 to 120 ℃, the stirring speed of 100 and 500 r/min.
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| CN102911293B (en) * | 2012-11-13 | 2014-06-25 | 北京化工大学 | Method for normal-pressure hydrogenation of unsaturated polymer using magnetic nano ferroferric oxide catalyst |
| CN109718808B (en) * | 2019-01-09 | 2022-04-15 | 山东玉皇化工有限公司 | Selective hydrogenation catalyst, method for preparing hydrogenated petroleum resin, hydrogenated petroleum resin prepared by method, and hot-melt pressure-sensitive adhesive |
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