CN110845387B - 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
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- 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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Abstract
The invention discloses a bis (citraconimido) hydrocarbon, a preparation method thereof and application thereof as an anti-reversion agent, wherein the molecule of the bis (citraconimido) hydrocarbon contains two structures of citraconimido and methylene chain segments, can play roles of resisting reversion and enhancing the anti-buckling flexibility of sizing materials, is a good anti-reversion agent, and effectively solves the defects of reducing the anti-buckling property and chipping of rubber caused by PK900. The preparation method disclosed by the invention is simple in process and easy to operate, the obtained product is high in yield and purity, odorless and free from frosting, the direction and the requirements of developing low-odor or odorless tires in the future can be met and complied with, and the preparation method has good economic and social benefits and a broad market prospect.
Description
Technical Field
The invention relates to a bis (citraconimido) hydrocarbon, a preparation method of the bis (citraconimido) hydrocarbon and application of the bis (citraconimido) hydrocarbon as an anti-reversion agent.
Background
Reversion is a phenomenon that a vulcanized rubber cross-linked net is cracked and then the performance of 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. The service life of the tire and other rubber products is shortened, safety accidents are caused, and personal safety is seriously affected. The reversion resistance auxiliary agent is used as an auxiliary agent for keeping a vulcanization network stable, can effectively reduce or eliminate adverse effects caused by reversion, and is widely applied to rubber processing technology.
pk900 is a commonly used reversion inhibitor which reduces reversion but does not participate in the rubber vulcanization reaction and only acts upon thermal degradation without affecting the vulcanization characteristics and physical properties of the compound. Although pk900 can effectively reduce reversion of rubber, it also reduces the anti-flexing property of rubber, which is easy to cause the collapse of rubber. Therefore, it is necessary to develop an anti-reversion agent which can reduce the reversion degree and effectively improve the anti-flex property of rubber.
Disclosure of Invention
The invention aims to provide the bis (citraconimido) hydrocarbon which has the functions of enhancing the flexibility of rubber materials and resisting reversion and has good application prospect.
Another object of the present invention is to provide a method for preparing the above bis (citraconimido) hydrocarbon, which has a simple process, is easy to operate, and is convenient for industrial production.
Another object of the present invention is to provide the use of the above bis (citraconimido) hydrocarbon as an anti-reversion agent, which has both an anti-reversion effect and an effect of enhancing the anti-flex property of a rubber compound, well solving the disadvantages of PK900 and having an effect superior to PK900.
The bis (citraconimido) hydrocarbon provided by the invention has a structural formula shown in the following formula:
wherein R is a substituted or unsubstituted C2-C20 alkylene group (i.e., an alkylene group having 2 to 20 carbon atoms).
Further, the unsubstituted C2-C20 alkylene group means a straight chain alkylene group or a branched chain alkylene group, and does not contain a substituent other than an alkyl group.
Further, the substituted C2-C20 alkylene means that the above-mentioned straight or branched unsubstituted C2-C20 alkylene further comprises at least one non-alkyl substituent, which 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 dehydration cyclization of the biscitraconimido acid, wherein the reaction formula is as follows, and the selection of R is consistent with the above:
further, the dehydration cyclization of the biscitraconazole amic acid is carried out at 80-90 ℃ for 4-6 hours.
Further, the biscitraconazole amic acid is prepared by reacting citraconic anhydride with an amino substituted hydrocarbon according to the following formula, wherein R is selected in accordance with the foregoing:
further, in the preparation of biscitraconazole acid, the molar ratio of citraconic anhydride to amino substituted hydrocarbon is 1.9-2.1:1, preferably the reaction is carried out according to the theoretical molar ratio.
Further, in the preparation of biscitraconazole acid, the reaction of citraconic anhydride with amino substituted hydrocarbon is carried out in the presence of a catalyst, the catalyst used being any catalyst disclosed in the prior art which can catalyze the reaction of anhydride with amino, 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 used may be selected in accordance with the disclosure in the prior art.
Further, in the preparation of biscitraconazole acid, the reaction of citraconic anhydride with amino substituted hydrocarbon is carried out in a solvent, wherein the solvent is used for providing a reaction medium, and the solvent is an organic solvent, such as benzene, toluene and the like.
Further, in the preparation of biscitraconazole acid, the amino-substituted hydrocarbon is added in the form of dropwise addition. The citraconic anhydride, the solvent and the catalyst are mixed homogeneously, raised to the reaction temperature and then the amino substituted hydrocarbon is dropped slowly to react.
Further, in the preparation of biscitraconazole acid, the reaction temperature of citraconic anhydride and amino substituted hydrocarbon is 80-90 ℃. The reaction speed of citraconic anhydride and amino substituted hydrocarbon is high, and the citraconic anhydride and the amino substituted hydrocarbon react during the dripping process, so that complete reaction can be realized basically after the dripping is completed. If the reaction is not completed after the completion of the dripping, the temperature can be kept for a certain time until the reaction is complete.
Further, when the biscitraconazole amic acid is prepared, the dropwise adding time of the amino substituted hydrocarbon is 2-10min.
Further, in a specific embodiment of the present invention, a specific method for preparing biscitraconazole amic acid is provided, which comprises the steps of mixing citraconic anhydride, solvent toluene and catalyst acetic acid, heating to 80-90 ℃, stirring uniformly, and then slowly dropwise adding amino-substituted hydrocarbon for reaction to obtain biscitraconazole amic acid. Wherein, the molar ratio of citraconic anhydride, toluene and acetic acid is 2:6-16:3-4.
Further, the citraconic anhydride can be purchased directly from commercial sources or can be prepared by methods disclosed in the prior art. In a specific embodiment of the invention, a preparation method of 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 reacting for 2-4 hours, 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 is also called pyridine p-toluenesulfonate or pyridine p-toluenesulfonate, is white crystal and powder with the molecular formula of C7H28O3S.C5H25N, and can be purchased from the market.
The bis (citraconimido) hydrocarbon obtained by the invention contains two structures of citraconimido and methylene chain segments, has the effects of resisting reversion and enhancing the anti-buckling flexibility of sizing materials, and is a good anti-reversion agent. Therefore, the application of the product as an anti-reversion agent is also within the protection scope of the invention.
The invention has the following beneficial effects:
1. the bi (citraconimido) hydrocarbon molecule contains two structures of citraconimido and methylene chain segments, can play roles of resisting reversion and enhancing the anti-buckling flexibility of sizing materials, is a good anti-reversion agent, and effectively solves the defects that PK900 leads the anti-buckling property of rubber to be reduced and blocks to collapse;
2. the preparation method disclosed by the invention is simple in process and easy to operate, the obtained product is high in yield and purity, odorless and free from frosting, the direction and the requirements of developing low-odor or odorless tires in the future can be met and complied with, and the preparation method has good economic and social benefits and a broad market prospect.
Detailed Description
The invention is further illustrated by the following specific examples, which are given by way of illustration only and are not limiting in any way.
The invention provides a preparation method of bis (citraconimido) hydrocarbon, which is prepared from itaconic acid serving as a raw material, and comprises the following specific steps:
step 1, preparation of citraconic anhydride: mixing itaconic acid and 1,2, 4-trimethylbenzene in a weight ratio of 2-15:20-30:1, adding the mixture into a reaction kettle, heating to a 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, preparation of biscitraconazole acid: adding citraconic anhydride, toluene and 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 citraconic anhydride is prepared according to the mass ratio of the materials: slowly dropwise adding the amino-substituted hydrocarbon into the mixture according to the ratio of the amino-substituted hydrocarbon to the mixture of 1.9-2.1:1 to prepare biscitraconazole amic acid;
step 3, preparation of bis (citraconimido) hydrocarbon: refluxing the biscitraconazole amic acid obtained in the step 2 for 4-6 hours at a constant temperature of 80-90 ℃ and dehydrating and cyclizing to obtain the bis (citraconimido) hydrocarbon.
The following are preferred examples of the present invention to provide a better understanding of the present invention to those skilled in the art. In the examples below, all starting materials are commercially available.
Example 1
The preparation of 1, 6-bis (citraconimido) hexane comprises the steps of:
1. 200g of itaconic acid, 600g of 1,2, 4-trimethylbenzene solvent and 20g of pyridinium p-toluenesulfonate 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 quickly raised to 140 ℃ after stirring and mixing, the reaction is carried out for 3 hours, the water removed in the process is continuously carried out by 1,2, 4-trimethylbenzene, the theoretical water yield is 27.5g, and the heating is stopped to obtain the citraconic anhydride, 1,2, 4-trimethylbenzene and catalyst mixed solution. Continuously heating the mixed solution in the three-neck flask to 180 ℃, distilling under normal pressure to remove 1,2, 4-trimethylbenzene, cooling to room temperature, and filtering to remove the pyridinium p-toluenesulfonate catalyst to obtain 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 tube, a thermometer and a stirrer, the temperature is quickly raised to 90 ℃ by opening heating, the mixture is stirred uniformly, 88g of 1, 6-hexamethylenediamine is weighed and added into the flask dropwise, and the reaction solution containing 1, 6-biningkanamic acid is prepared after the dropwise addition is completed within 5 min.
3. And (3) carrying out heat preservation and reflux on the reaction liquid obtained in the step (2) for 5 hours at 90 ℃, dehydrating and cyclizing to generate 1, 6-bis (citraconimido) hexane, cooling to 5-10 ℃ after the reaction is finished, crystallizing for 2 hours, and filtering and drying to obtain 220g of white powder, namely a finished product of the 1, 6-bis (citraconimido) hexane. The yield was 95% and the purity was 99.8% by HPLC based on hexamethylenediamine.
Example 2
The preparation of 1, 2-bis (citraconimido) ethane comprises the steps of:
1. 100g of itaconic acid, 400g of 1,2, 4-trimethylbenzene solvent and 15g of pyridinium p-toluenesulfonate 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 quickly raised to 150 ℃ after stirring and mixing, the reaction is carried out for 3 hours, the water removed in the process is continuously carried out by 1,2, 4-trimethylbenzene, the theoretical water yield is 13.8g, and the heating is stopped to obtain the citraconic anhydride, 1,2, 4-trimethylbenzene and catalyst mixed solution. The mixed solution in the three-neck flask was continuously heated to 180℃and distilled under normal pressure to remove 1,2, 4-trimethylbenzene, and after cooling to room temperature, the pyridinium p-toluenesulfonate catalyst was removed by filtration to obtain 86.2g of citraconic anhydride.
2. 86.2g of citraconic anhydride prepared in the step 1, 570ml of toluene and 70g of acetic acid are added into a 1000ml flask connected with a condenser, a thermometer and a stirrer, the temperature is quickly raised to 80 ℃ by opening heating, stirring is carried out, 23g of ethylenediamine is weighed and added into the flask dropwise, and the reaction solution containing 1, 2-biscitraconic amic acid is prepared after the dropwise addition is completed within 4 min.
3. And (3) carrying out heat preservation and reflux on the reaction liquid obtained in the step (2) for 5 hours at the temperature of 80 ℃, dehydrating and cyclizing to generate 1, 6-bis (citraconimido) hexane, cooling to 10-20 ℃ after the reaction is finished, crystallizing for 2.5 hours, and filtering and drying to obtain 87g of white powder, namely a finished product of 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 steps of:
1. 150g of itaconic acid, 300g of 1,2, 4-trimethylbenzene solvent and 10g of pyridinium p-toluenesulfonate 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 quickly raised to 135 ℃ after stirring and mixing, the reaction is carried out for 3 hours, the water removed in the process is continuously carried out by 1,2, 4-trimethylbenzene, the theoretical water yield is 20.5g, and the heating is stopped to obtain the citraconic anhydride, 1,2, 4-trimethylbenzene and catalyst mixed solution. And continuously heating the mixed solution in the three-neck flask to 180 ℃, distilling under normal pressure to remove 1,2, 4-trimethylbenzene, cooling to room temperature, and filtering to remove the pyridinium p-toluenesulfonate catalyst to obtain 125g of citraconic anhydride.
2. 125g of citraconic anhydride prepared in the step 1, 400ml of toluene and 117g of acetic acid were added to a 1000ml flask equipped with a condenser, a thermometer and a stirrer, and the flask was heated to 85℃rapidly by opening the flask, stirred, 80.4g of 1, 8-octanediamine was weighed and added dropwise to the flask, and the reaction solution containing 1, 8-biscitraconazole amic acid was prepared after the dropwise addition was completed within 10 minutes.
3. And (3) carrying out heat preservation and reflux on the reaction liquid obtained in the step (2) for 5 hours at the temperature of 90 ℃, dehydrating and cyclizing to generate 1, 8-bis (citraconimido) octane, cooling to 0-10 ℃ after the reaction is finished, crystallizing for 2 hours, and filtering and drying to obtain 173g of white powder, namely a 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
The preparation of 1, 4-bis (citraconimido) butane comprises the steps of:
1. 50g of itaconic acid, 400g of 1,2, 4-trimethylbenzene solvent and 20g of pyridinium p-toluenesulfonate 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 quickly raised to 140 ℃ after stirring and mixing, the reaction is carried out for about 2 hours under heat preservation, the water removed in the process is continuously carried out by 1,2, 4-trimethylbenzene, the heating is stopped after the theoretical water yield reaches 6.92g, and the citraconic anhydride, 1,2, 4-trimethylbenzene and catalyst mixed solution is obtained. Continuously heating the mixed solution in the three-neck flask to 180 ℃, distilling under normal pressure to remove 1,2, 4-trimethylbenzene, cooling to room temperature, and filtering to remove the pyridinium p-toluenesulfonate catalyst to obtain 42g of citraconic anhydride.
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 connected with a condenser, a thermometer and a stirrer, the temperature is quickly raised to 90 ℃ by opening heating, stirring is carried out, 16.5g of 1, 4-butanediamine is weighed and added into the flask dropwise, and the reaction solution containing 1, 4-biscitraconic amic acid is prepared after the dropwise addition is completed within 5 min.
3. And (3) carrying out heat preservation and reflux on the reaction liquid obtained in the step (2) for 5 hours at the temperature of 80 ℃, dehydrating and cyclizing to generate 1, 4-bis (citraconimido) butane, cooling to 0-10 ℃ after the reaction is finished, crystallizing for 3 hours, and filtering and drying to obtain 47g of white powder, namely a 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 steps of:
1. 100g of itaconic acid, 150g of 1,2, 4-trimethylbenzene solvent, 7g of pyridinium p-toluenesulfonate 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 quickly raised to 140 ℃ after stirring and mixing, the reaction is carried out for about 2 hours under heat preservation, the water removed during the reaction is continuously carried out by 1,2, 4-trimethylbenzene, and after the theoretical water yield reaches 13.8g, the heating is stopped, so as to obtain the citraconic anhydride, 1,2, 4-trimethylbenzene and catalyst mixed solution. And continuously heating the mixed solution in the three-neck flask to 180 ℃, distilling under normal pressure to remove 1,2, 4-trimethylbenzene, cooling to room temperature, and filtering to remove the pyridinium p-toluenesulfonate catalyst to obtain 86g of citraconic anhydride.
2. 86g of citraconic anhydride prepared in the step 1, 400ml of toluene and 70g of acetic acid are added into a 1000ml flask connected with a condenser, a thermometer and a stirrer, the temperature is quickly raised to 90 ℃ by opening heating, the mixture is stirred, 44.5g of 2-methylpentanediamine is weighed and added into the flask dropwise, and the reaction solution containing 2-methyl-1, 5-biscitraconic amic acid is prepared after the dropwise addition is completed within 8 min.
3. And (3) carrying out heat preservation reflux on the reaction liquid obtained in the step (2) for 5 hours at 85 ℃, dehydrating and cyclizing to generate 2-methyl-1, 5-bis (citraconimido) pentane, cooling to 5-10 ℃ after the reaction is finished, crystallizing for 4 hours, filtering and drying to obtain 110g of white powder, namely a finished product of 2-methyl-1, 5-bis (citraconimido) pentane, wherein the yield is 94% based on 2-methylpentanediamine, and the purity is 99.6% based on HPLC.
Example 6
The preparation of 2, 4-trimethyl-1, 6-bis (citraconimido) hexane comprises the following steps:
1. 300g of itaconic acid, 600g of 1,2, 4-trimethylbenzene solvent and 20g of pyridinium p-toluenesulfonate 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 quickly raised to 160 ℃ after stirring and mixing, the reaction is carried out for 3 hours, the water removed in the process is continuously carried out by 1,2, 4-trimethylbenzene, the theoretical water yield is 41.5g, and the heating is stopped to obtain the citraconic anhydride, 1,2, 4-trimethylbenzene and catalyst mixed solution. Continuously heating the mixed solution in the three-neck flask to 180 ℃, distilling under normal pressure to remove 1,2, 4-trimethylbenzene, cooling to room temperature, and filtering to remove the pyridinium p-toluenesulfonate catalyst to obtain 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, a thermometer and a stirrer, the temperature is quickly raised to 90 ℃ by opening heating, stirring is carried out, 181g of 2, 4-trimethylhexamethylenediamine is weighed and added into the flask dropwise, and the reaction solution containing 2, 4-trimethyl-1, 6-biscitraconic acid is prepared after the dropwise addition is completed within 10min.
3. And (3) carrying out heat preservation and reflux on the reaction liquid obtained in the step (2) for 5 hours at the temperature of 80 ℃, dehydrating and cyclizing to generate 2, 4-trimethyl-1, 6-bis (citraconimido) hexane, cooling to 0-5 ℃ after the reaction is finished, crystallizing for 4 hours, and filtering and drying to obtain 370g of white powder, namely a finished product of the 2, 4-trimethyl-1, 6-bis (citraconimido) hexane. The yield was 93% based on 2, 4-trimethylhexamethylenediamine and the purity was 96.6% by HPLC.
Effect examples
The products of examples 1 to 6 of the present invention and Perkalink900 were applied to rubber, and the reversion resistance and the flex resistance of the rubber compound were examined.
The test formula comprises the following components in parts by weight: 100 parts of natural rubber NR, 330 parts of carbon black N, 5 parts of ZnO-80, 2 parts of stearic acid, 1 part of RD, 4020 parts of an anti-aging agent, 1.2 parts of an accelerator NS-80, 2 parts of S-80 and 2 parts of an anti-reversion agent (example product or pk 900).
And (3) mixing: adding rubber, carbon black, zinc oxide, stearic acid and an anti-aging agent, mixing to 135 ℃ and lifting a weight, and continuously mixing to 155 ℃ and discharging rubber.
Two-stage mixing: mixing a section of masterbatch, sulfur, an accelerator and an anti-reversion agent for 30s, lifting a pressing weight, and continuing mixing until the temperature reaches 105 ℃, wherein the total mixing time is 130-155s.
The reversion resistance of the obtained rubber was 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 compounds was measured by a fatigue tensile tester, and the results are shown in Table 2 below.
As can be seen from the above table, the reversion resistance of the product of the present invention is equivalent to that of Pk900, and the resistance to flexural failure is significantly better than that of Pk900, wherein the product of example 1 has the best resistance to flexural failure.
Claims (1)
- Use of 2-methyl-1, 5-bis (citraconimido) pentane as an anti-reversion agent for rubber.
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