CN110845387A - Bis (citraconimido) hydrocarbon, preparation method thereof and application thereof as anti-reversion agent - Google Patents
Bis (citraconimido) hydrocarbon, preparation method thereof and application thereof as anti-reversion agent Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
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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
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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Abstract
The invention discloses a bis (citraconimido) hydrocarbon, a preparation method thereof and application thereof as an anti-reversion agent, wherein the bis (citraconimido) hydrocarbon molecule contains two structures of citraconimido and methylene chain segment, can simultaneously play roles in anti-reversion and enhancing the anti-bending flexibility of rubber materials, is a good anti-reversion agent, and effectively solves the defects that PK900 causes the anti-bending property of rubber to be reduced and flowers and blocks to fall off. The preparation method has simple process and easy operation, the obtained product has high yield, high purity, no odor and no frost spraying, can meet and conform to the direction and the requirement of developing low-odor or odorless tires in the future, and has good economic and social benefits and wide market prospect.
Description
Technical Field
The invention relates to bis (citraconimido) hydrocarbon, and also relates to a preparation method and application of the bis (citraconimido) hydrocarbon as an anti-reversion agent.
Background
Reversion is the phenomenon that the vulcanized rubber crosslinked network is cracked and then the performance of the vulcanized rubber is reduced due to high vulcanization temperature and overlong vulcanization time in the rubber processing process. This phenomenon also occurs due to the heat accumulation effect during the use of rubber products such as tires. This phenomenon can lead to shortened service life of tires and other rubber products, cause safety accidents and seriously affect personal safety. The anti-reversion auxiliary agent is used as an auxiliary agent for keeping the stability of a vulcanization network, can effectively reduce or eliminate adverse effects caused by reversion, and is widely applied to rubber processing technology.
pk900 is a commonly used anti-reversion agent, can reduce the reversion degree, does not participate in rubber vulcanization reaction, can only act when thermal degradation occurs, and has no influence on the vulcanization characteristic and physical property of rubber materials. Although pk900 can effectively reduce rubber reversion, the rubber flex resistance is reduced, and rubber chipping and chipping are easily caused. Therefore, there is a need to develop an anti-reversion auxiliary which can reduce the degree of reversion and effectively improve the anti-flex property of rubber.
Disclosure of Invention
The invention aims to provide bis (citraconimido) hydrocarbon which has the functions of enhancing the yield resistance and reversion resistance of rubber materials and has good application prospect.
The invention also aims to provide a preparation method of the bis (citraconimido) hydrocarbon, which has the advantages of simple process, easy operation and convenient industrial production.
The invention also aims to provide the application of the bis (citraconimido) hydrocarbon as the anti-reversion agent, which has the anti-reversion effect and the effect of enhancing the anti-flex property of rubber materials, well overcomes the defects of PK900 and has better effect than the PK 900.
The invention provides bis (citraconimido) hydrocarbon, which has a structural formula shown in the following formula:
wherein R is substituted or unsubstituted C2-C20 alkylene (i.e. alkylene with 2-20 carbon atoms).
Further, the unsubstituted C2-C20 alkylene group means a linear alkylene group or a branched alkylene group, and does not contain a substituent other than an alkyl group.
Further, the substituted C2-C20 alkylene group means that the linear or branched unsubstituted C2-C20 alkylene group further contains at least one substituent other than alkyl, and the substituent may be aryl, halogen, aralkyl or pyridyl.
Further, the R is preferably a substituted or unsubstituted C2-C10 alkylene group, preferably an unsubstituted C2-C10 linear alkylene group, more preferably a hexylene group, i.e., - (CH)2）6-。
The invention also provides a preparation method of the bis (citraconimido) hydrocarbon, which is obtained by dehydrating and cyclizing the biscitraconimido acid, and the reaction formula is as follows, wherein the selection of R is consistent with the above:
further, the dehydration cyclization of the biscitraconazole is carried out at 80-90 ℃ for 4-6 h.
Further, the biscitraconamic acid is obtained by reacting citraconic anhydride with an amino-substituted hydrocarbon according to the following reaction scheme, wherein R is selected in accordance with the foregoing:
further, in the preparation of biscitraconamic acid, the molar ratio of citraconic anhydride to amino-substituted hydrocarbon is 1.9 to 2.1:1, and the reaction is preferably carried out in the theoretical molar ratio.
Further, in the preparation of biscitraconamic acid, the reaction of citraconic anhydride with an amino-substituted hydrocarbon is carried out in the presence of a catalyst, which is any catalyst disclosed in the art that can catalyze the reaction of an anhydride with an amino group, such as an acid catalyst. The acid catalyst may be an organic acid catalyst such as benzenesulfonic acid, acetic acid, etc., or an inorganic acid catalyst such as hydrochloric acid, sulfuric acid, etc. The amount of catalyst may be selected according to the disclosure in the prior art.
Further, in the preparation of biscitraconamic acid, the reaction of citraconic anhydride with the amino-substituted hydrocarbon is carried out in a solvent which serves to provide a reaction medium and which is an organic solvent, such as benzene, toluene, and the like.
Further, in the preparation of the biscitraconazole, the amino-substituted hydrocarbon is added dropwise. First mixing citraconic anhydride, solvent and catalyst homogeneously, raising the temperature to reaction temperature, and then dropping amino substituted hydrocarbon slowly for reaction.
Further, in the preparation of biscitraconamic acid, the reaction temperature of citraconic anhydride and amino-substituted hydrocarbon is 80 to 90 ℃. The citraconic anhydride and the amino-substituted hydrocarbon have high reaction speed, react in the dropping process of the amino-substituted hydrocarbon, and basically realize complete reaction after the dropping is finished. If the reaction is not completed after the completion of the dropwise addition, the reaction can be kept for a certain time until the reaction is completed.
Further, when the biscitraconazole is prepared, the dripping time of the amino-substituted hydrocarbon is 2-10 min.
Further, in a specific embodiment of the present invention, a specific method for preparing biscitraconic acid is provided, which comprises the steps of mixing citraconic anhydride, toluene as a solvent and acetic acid as a catalyst, heating to 80-90 ℃, stirring uniformly, and slowly adding dropwise amino-substituted hydrocarbon for reaction to obtain the biscitraconic acid. Wherein the mol ratio of citraconic anhydride to toluene to acetic acid is 2: 6-16: 3-4.
Further, the citraconic anhydride can be purchased as it is or can be prepared by a method disclosed in the prior art. In a specific embodiment of the present invention, a method for preparing citraconic anhydride is disclosed, comprising the following steps: mixing itaconic acid, 1,2, 4-trimethylbenzene and an organic acid-base catalyst according to the weight ratio of 2-15: 20-30:1, heating to 135-160 ℃ for reaction for 2-4h, continuously removing generated water during the reaction, and removing the solvent and the catalyst after the reaction to obtain citraconic anhydride. Wherein the organic acid-base catalyst is pyridinium p-toluenesulfonate and the like. The pyridinium p-toluenesulfonate, also known as pyridinium p-toluenesulfonate or pyridinium p-toluenesulfonate, is a white crystal and powder in appearance, has a molecular formula of C7H8O 3S. C5H5N, and can be purchased from the market.
The obtained bis (citraconimido) hydrocarbon contains two structures of citraconimido and methylene chain segment, has the effects of resisting reversion and enhancing the bending resistance and flexibility of rubber materials, and is a good anti-reversion agent. Therefore, the application of the product as the anti-reversion agent is also within the protection scope of the invention.
The invention has the following beneficial effects:
1. the bis (citraconimido) hydrocarbon molecule contains two structures of citraconimido and methylene chain segment, can simultaneously play roles in resisting reversion and enhancing the bending resistance and flexibility of rubber materials, is a good reversion resistant agent, and effectively overcomes the defects that PK900 enables the bending resistance of rubber to be reduced and flowers and blocks to fall off;
2. the preparation method has simple process and easy operation, the obtained product has high yield, high purity, no odor and no frost spraying, can meet and conform to the direction and the requirement of developing low-odor or odorless tires in the future, and has good economic and social benefits and wide market prospect.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be purely exemplary and are not intended to be limiting.
The invention provides a preparation method of bis (citraconimido) hydrocarbon, which is prepared by taking itaconic acid as a raw material and comprises the following specific steps:
step 1, preparation of citraconic anhydride: mixing itaconic acid, 1,2, 4-trimethylbenzene and an organic acid-base catalyst according to the weight ratio of 2-15: 20-30:1, adding the mixture into a reaction kettle, heating to the normal pressure reflux temperature of 135-160 ℃, reacting for about 2-4 hours, dehydrating, and removing a solvent and the catalyst to obtain liquid citraconic anhydride, wherein the reaction formula is as follows:
step 2, preparing the dicitrakoamic acid: adding the citraconic anhydride, the toluene and the acetic acid obtained in the step 1 into a reaction kettle according to the mass ratio of 2: 6-16: 3-4, heating to 80-90 ℃, and uniformly stirring, wherein the mass ratio of citraconic anhydride: slowly dripping amino-substituted hydrocarbon according to the proportion of the amino-substituted hydrocarbon =1.9-2.1:1 to prepare the biscitraconazole;
step 3, preparation of bis (citraconimido) hydrocarbon: refluxing the biscitraconimido acid obtained in the step 2 at a constant temperature of 80-90 ℃ for 4-6h, and dehydrating and cyclizing to obtain the bis (citraconimido) hydrocarbon.
Several preferred examples of the present invention are listed below in order that those skilled in the art can better understand the present invention. In the following examples, all raw materials were purchased from the market.
Example 1
Preparation of 1, 6-bis (citraconimido) hexane, comprising the following steps:
1. 200g of itaconic acid, 600g of 1,2, 4-trimethylbenzene solvent and 20g of p-toluenesulfonic acid pyridinium salt catalyst are added into a 1000ml four-neck flask connected with a water separator, a condenser pipe, a thermometer and a stirrer, the temperature is rapidly raised to 140 ℃ after stirring and mixing, the temperature is kept for reaction for about 3 hours, the removed water is continuously carried out by 1,2, 4-trimethylbenzene during the reaction, the heating is stopped after the theoretical water yield reaches 27.5g, and the mixed solution of citraconic anhydride, 1,2, 4-trimethylbenzene and the catalyst is obtained. The mixed solution in the three-neck flask is continuously heated to 180 ℃, 1,2, 4-trimethylbenzene is removed by distillation under normal pressure, the temperature is reduced to room temperature, and the catalyst of pyridinium p-toluenesulfonate is removed by filtration, thereby obtaining 170g of citraconic anhydride.
2. 170g of citraconic anhydride prepared in the step 1, 700ml of toluene and 180g of acetic acid are added into a 1000ml flask connected with a condenser, a thermometer and a stirrer, the flask is opened and heated to 90 ℃ rapidly, the mixture is stirred uniformly, 88g of 1, 6-hexanediamine is weighed and added into the flask dropwise, and the dropwise addition is completed within 5min to prepare the reaction liquid containing the 1, 6-bisningosamide acid.
3. And (3) preserving the temperature of the reaction liquid obtained in the step (2) and refluxing for 5h, dehydrating and cyclizing to generate 1, 6-bis (citraconimido) hexane, cooling to 5-10 ℃ after the reaction is finished, crystallizing for 2h, filtering and drying to obtain 220g of white powder, namely the finished product of the 1, 6-bis (citraconimido) hexane. The yield was 95% based on hexamethylenediamine and the purity was 99.8% by HPLC.
Example 2
Preparation of 1, 2-bis (citraconimido) ethane comprising the following steps:
1. 100g of itaconic acid, 400g of 1,2, 4-trimethylbenzene solvent and 15g of p-toluenesulfonic acid pyridinium salt catalyst are added into a 1000ml four-neck flask connected with a water separator, a condenser pipe, a thermometer and a stirrer, the temperature is rapidly raised to 150 ℃ after stirring and mixing, the temperature is kept for reaction for about 3 hours, the removed water is continuously taken out by 1,2, 4-trimethylbenzene during the reaction, the heating is stopped after the theoretical water yield reaches 13.8g, and the mixed solution of citraconic anhydride, 1,2, 4-trimethylbenzene and the catalyst is obtained. The mixed solution in the three-necked flask was further heated to 180 ℃ and distilled under normal pressure to remove 1,2, 4-trimethylbenzene, and after cooling to room temperature, the p-toluenesulfonate pyridinium salt catalyst was removed by filtration to obtain 86.2g of citraconic anhydride.
2. Adding 86.2g of citraconic anhydride prepared in the step 1, 570ml of toluene and 70g of acetic acid into a 1000ml flask connected with a condenser, a thermometer and a stirrer, opening, heating, quickly raising the temperature to 80 ℃, stirring, weighing 23g of ethylenediamine, dropwise adding into the flask, and dropwise adding within 4min to obtain the reaction liquid containing 1, 2-biscitraconinic acid.
3. And (3) preserving the temperature of the reaction liquid obtained in the step (2) and refluxing for 5h, dehydrating and cyclizing to generate 1, 6-bis (citraconimido) hexane, cooling to 10-20 ℃ after the reaction is finished, crystallizing for 2.5h, filtering and drying to obtain 87g of white powder, namely the finished product of the 1, 6-bis (citraconimido) ethane. The yield was 91% based on ethylenediamine, and the purity was 99.0% by HPLC.
Example 3
The preparation of 1, 8-bis (citraconimido) octane comprises the following steps:
1. 150g of itaconic acid, 300g of 1,2, 4-trimethylbenzene solvent and 10g of p-toluenesulfonic acid pyridinium salt catalyst are added into a 1000ml four-neck flask connected with a water separator, a condenser pipe, a thermometer and a stirrer, the temperature is rapidly raised to 135 ℃ after stirring and mixing, the temperature is kept for reaction for about 3 hours, the removed water is continuously taken out by 1,2, 4-trimethylbenzene during the reaction, the heating is stopped after the theoretical water yield reaches 20.5g, and the mixed solution of citraconic anhydride, 1,2, 4-trimethylbenzene and the catalyst is obtained. The mixed solution in the three-neck flask is continuously heated to 180 ℃, 1,2, 4-trimethylbenzene is removed by distillation under normal pressure, the temperature is reduced to room temperature, and the catalyst of pyridinium p-toluenesulfonate is removed by filtration, thereby obtaining 125g of citraconic anhydride.
2. 125g of citraconic anhydride prepared in the step 1 and 400ml of toluene are added into a 1000ml flask connected with a condensing tube, a thermometer and a stirrer, 117g of acetic acid is started to be heated and quickly heated to 85 ℃, stirred, 80.4g of 1, 8-octanediamine is weighed and added into the flask dropwise, and the dropwise addition is finished within 10min to prepare the reaction liquid containing 1, 8-biscitraconic acid.
3. And (3) carrying out heat preservation and reflux on the reaction liquid obtained in the step (2) at the temperature of 90 ℃ for 5h, dehydrating and cyclizing to generate 1, 8-bis (citraconimido) octane, cooling to 0-10 ℃ after the reaction is finished, crystallizing for 2h, filtering and drying to obtain 173g of white powder, namely the finished product of the 1, 8-bis (citraconimido) octane. The yield was 92% based on octanediamine and the purity was 99.9% by HPLC.
Example 4
Preparation of 1, 4-bis (citraconimido) butane, comprising the following steps:
1. 50g of itaconic acid, 400g of 1,2, 4-trimethylbenzene solvent and 20g of p-toluenesulfonic acid pyridinium salt catalyst are added into a 1000ml four-neck flask connected with a water separator, a condenser pipe, a thermometer and a stirrer, the temperature is rapidly raised to 140 ℃ after stirring and mixing, the temperature is kept for reaction for about 2 hours, the removed water is continuously taken out by 1,2, 4-trimethylbenzene during the reaction, the heating is stopped after the theoretical water yield reaches 6.92g, and the mixed solution of citraconic anhydride, 1,2, 4-trimethylbenzene and the catalyst is obtained. The mixed solution in the three-neck flask is continuously heated to 180 ℃, 1,2, 4-trimethylbenzene is removed by distillation under normal pressure, the temperature is reduced to room temperature, and the p-toluenesulfonic acid pyridinium salt catalyst is removed by filtration, so that 42g of citraconic anhydride is obtained.
2. 42g of citraconic anhydride prepared in the step 1, 300ml of toluene and 40.5g of acetic acid are added into a 1000ml flask which is connected with a condenser tube, a thermometer and a stirrer, the flask is opened and heated to quickly rise the temperature to 90 ℃, stirred, 16.5g of 1, 4-butanediamine is weighed and added into the flask dropwise, and the dropwise addition is completed within 5min, so that the reaction solution containing 1, 4-biscitrainstance is prepared.
3. And (3) preserving the temperature of the reaction liquid obtained in the step (2) and refluxing for 5h, dehydrating and cyclizing to generate 1, 4-bis (citraconimido) butane, cooling to 0-10 ℃ after the reaction is finished, crystallizing for 3h, filtering and drying to obtain 47g of white powder, namely the finished product of the 1, 4-bis (citraconimido) butane. The yield was 91% based on butanediamine and the purity was 98.8% by HPLC.
Example 5
The preparation of 2-methyl-1, 5-bis (citraconimido) pentane comprises the following steps:
1. 100g of itaconic acid, 150g of 1,2, 4-trimethylbenzene solvent and 7g of p-toluenesulfonic acid pyridinium salt catalyst are added into a 1000ml four-neck flask connected with a water separator, a condenser pipe, a thermometer and a stirrer, the temperature is rapidly raised to 140 ℃ after stirring and mixing, the temperature is kept for reaction for about 2 hours, the removed water is continuously taken out by 1,2, 4-trimethylbenzene during the reaction, the heating is stopped after the theoretical water yield reaches 13.8g, and the mixed solution of citraconic anhydride, 1,2, 4-trimethylbenzene and the catalyst is obtained. The mixed solution in the three-neck flask is continuously heated to 180 ℃, 1,2, 4-trimethylbenzene is removed by distillation under normal pressure, the temperature is reduced to room temperature, and the p-toluenesulfonic acid pyridinium salt catalyst is removed by filtration, so that 86g of citraconic anhydride is obtained.
2. Adding 86g of citraconic anhydride prepared in the step 1, 400ml of toluene and 70g of acetic acid into a 1000ml flask connected with a condenser tube, a thermometer and a stirrer, opening, heating to quickly rise the temperature to 90 ℃, stirring, weighing 44.5g of 2-methylpentamethylenediamine, dropwise adding into the flask, and obtaining the reaction liquid containing 2-methyl-1, 5-biscitraconinic acid within 8 min.
3. And (3) preserving the temperature of the reaction liquid obtained in the step (2) and refluxing for 5h, dehydrating and cyclizing to generate 2-methyl-1, 5-bis (citraconimido) pentane, cooling to 5-10 ℃ after the reaction is finished, crystallizing for 4h, filtering and drying to obtain 110g of white powder, namely a finished product of the 2-methyl-1, 5-bis (citraconimido) pentane, wherein the yield is 94% in terms of 2-methylpentamethylenediamine, and the purity is 99.6% by HPLC.
Example 6
Preparation of 2,2, 4-trimethyl-1, 6-bis (citraconimido) hexane, comprising the following steps:
1. 300g of itaconic acid, 600g of 1,2, 4-trimethylbenzene solvent and 20g of p-toluenesulfonic acid pyridinium salt catalyst are added into a 2000ml four-neck flask connected with a water separator, a condenser pipe, a thermometer and a stirrer, the temperature is rapidly raised to 160 ℃ after stirring and mixing, the temperature is kept for reaction for about 3 hours, the removed water is continuously carried out by 1,2, 4-trimethylbenzene during the reaction, the heating is stopped after the theoretical water yield reaches 41.5g, and the mixed solution of citraconic anhydride, 1,2, 4-trimethylbenzene and the catalyst is obtained. The mixed solution in the three-neck flask is continuously heated to 180 ℃, 1,2, 4-trimethylbenzene is removed by distillation under normal pressure, the temperature is reduced to room temperature, and the catalyst of pyridinium p-toluenesulfonate is removed by filtration, thus obtaining 258g of citraconic anhydride.
2. 258g of citraconic anhydride prepared in the step 1, 900ml of toluene and 270g of acetic acid are added into a 2000ml flask connected with a condenser tube, a thermometer and a stirrer, the temperature is quickly raised to 90 ℃ after the heating is started, the mixture is stirred, 181g of 2,2, 4-trimethylhexamethylenediamine is weighed and added into the flask dropwise, and the dropwise addition is completed within 10min to prepare the reaction liquid containing 2,2, 4-trimethyl-1, 6-biscitrainstance.
3. And (3) preserving the temperature of the reaction liquid obtained in the step (2) and refluxing for 5h, dehydrating and cyclizing to generate 2,2, 4-trimethyl-1, 6-bis (citraconimido) hexane, cooling to 0-5 ℃ after the reaction is finished, crystallizing for 4h, filtering and drying to obtain 370g of white powder, namely the finished product of the 2,2, 4-trimethyl-1, 6-bis (citraconimido) hexane. The yield was 93% based on 2,2, 4-trimethylhexamethylenediamine and the purity was 96.6% by HPLC.
Effects of the embodiment
The products of examples 1-6 of the present invention and Perkalink900 were applied to rubber to test the reversion and flex resistance of the compound.
The test formula comprises (parts by weight): 100 parts of natural rubber NR, 50 parts of carbon black N33050, 2 parts of ZnO-805, 2 parts of stearic acid, 1 part of RD, 40201 parts of anti-aging agent, 801.2 parts of accelerator NS-801, 802 parts of S-802 parts and 2 parts of anti-vulcanization reversion agent (example product or pk 900).
First-stage mixing: adding rubber, carbon black, zinc oxide, stearic acid and an anti-aging agent, mixing to 135 ℃ to lift a weight, and continuously mixing to 155 ℃ to discharge rubber.
And (3) second-stage mixing: mixing a first-stage master batch, sulfur, an accelerator and an anti-vulcanization reversion agent for 30 seconds to lift a weight, and continuously mixing to 105 ℃ for a total mixing time of 130-155 seconds.
The reversion resistance of the obtained rubber compound is detected by a vulcanizer, and the experimental results of the vulcanizer at 150 ℃ are shown in the following table 1.
The fatigue resistance of the compound was measured using a fatigue tensile tester, and the results are shown in table 2 below.
From the above table, it can be seen that the reversion resistance of the product of the invention is comparable to that of Pk900, while the flex damage resistance is significantly better than that of Pk900, with the product of example 1 having the best flex damage resistance.
Claims (10)
1. A bis (citraconimido) hydrocarbon characterized by: has a structural formula shown in the specification, wherein R is substituted or unsubstituted C2-C20 alkylene, preferably substituted or unsubstituted C2-C10 alkylene:
。
2. bis (citraconimido) hydrocarbon according to claim 1, characterized in that: r is an unsubstituted linear or branched alkylene group, preferably an unsubstituted linear alkylene group, more preferably a hexylene group.
3. Bis (citraconimido) hydrocarbon according to claim 1, characterized in that: the substituted C2-C20 alkylene has at least one substituent which is not alkyl, and the substituent is aryl, halogen, aralkyl or pyridyl.
4. A process for the preparation of bis (citraconimido) hydrocarbons as claimed in claim 1,2 or 3, characterized in that: is prepared by dehydrative ring closure of biscitraconamic acid, wherein R is substituted or unsubstituted C2-C20 alkylene:
5. the method according to claim 4, wherein: the dehydration cyclization is carried out at 80-90 ℃ and the reaction time is 4-6 h.
6. The method according to claim 4 or 5, wherein: the biscitraconamic acid is obtained by reacting citraconic anhydride and amino-substituted hydrocarbon, and has the following reaction formula, wherein R is substituted or unsubstituted C2-C20 alkylene:
7. the method of claim 6, wherein: in the preparation of the biscitraconamic acid, the molar ratio of citraconic anhydride to amino-substituted hydrocarbon is 1.9-2.1: 1.
8. The method of claim 6, wherein: preferably, when the biscitraconazole acid is prepared, the amino-substituted hydrocarbon is added in a dropwise manner;
preferably, in the preparation of biscitraconamic acid, the reaction of citraconic anhydride with the amino-substituted hydrocarbon is carried out in the presence of a catalyst, preferably an organic or inorganic acid, more preferably benzenesulfonic acid, acetic acid, hydrochloric acid or sulfuric acid;
preferably, in the preparation of biscitraconamic acid, the reaction of citraconic anhydride with the amino-substituted hydrocarbon is carried out in the presence of a solvent, preferably benzene or toluene.
9. The method according to any one of claims 6 to 8, wherein: citraconic anhydride is prepared by the following method: mixing itaconic acid, 1,2, 4-trimethylbenzene and an organic acid-base catalyst according to the weight ratio of 2-15: 20-30:1, heating to 135 ℃ and 160 ℃, reacting for 2-4h, continuously removing generated water during the reaction, and removing the solvent and the catalyst after the reaction to obtain citraconic anhydride; preferably, the organic acid-base catalyst is pyridinium p-toluenesulfonate.
10. Use of the bis (citraconimido) hydrocarbon according to any one of claims 1 to 3 as an anti-reversion agent for rubber.
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