CN117820220A - Preparation method of high-content rubber antioxidant TMQ - Google Patents
Preparation method of high-content rubber antioxidant TMQ Download PDFInfo
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 98
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000003377 acid catalyst Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 18
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000539 dimer Substances 0.000 claims abstract description 11
- FEQIKDBPUQIQKY-UHFFFAOYSA-N n-phenyl-n-propan-2-ylaniline Chemical compound C=1C=CC=CC=1N(C(C)C)C1=CC=CC=C1 FEQIKDBPUQIQKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 230000003712 anti-aging effect Effects 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 11
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 8
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 claims description 4
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 17
- 150000003141 primary amines Chemical class 0.000 abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 4
- -1 aromatic sulfonic acid series Chemical class 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
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- ZZXDRXVIRVJQBT-UHFFFAOYSA-N 2,3-dimethylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-N 0.000 description 1
- MNURPFVONZPVLA-UHFFFAOYSA-N 2-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1Cl MNURPFVONZPVLA-UHFFFAOYSA-N 0.000 description 1
- IQOJIHIRSVQTJJ-UHFFFAOYSA-N 3-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(Cl)=C1 IQOJIHIRSVQTJJ-UHFFFAOYSA-N 0.000 description 1
- JDQDSEVNMTYMOC-UHFFFAOYSA-N 3-methylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1 JDQDSEVNMTYMOC-UHFFFAOYSA-N 0.000 description 1
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 1
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- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
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- OATNQHYJXLHTEW-UHFFFAOYSA-N benzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C=C1 OATNQHYJXLHTEW-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a high-content rubber antioxidant TMQ, which relates to the field of fine chemical engineering; the high-content rubber antioxidant TMQ is obtained by performing one-step polycondensation reaction on aniline and acetone under the action of a compound acid catalyst, neutralizing and separating reaction liquid, and distilling oil phase; the compound acid catalyst is prepared from hydrogen chloride and aromatic sulfonic acid series substances according to the mole ratio of 1: (6-20), the conversion rate of aniline under the catalyst can reach more than 95%, the dimer content of the product can reach 66.5%, the dimer content of the second, third and fourth polymers can reach 91%, the primary amine content is not more than 0.35%, and the isopropyl diphenylamine content is not more than 0.3%; the composite acid catalyst adopted by the method is an inexpensive industrial product, and the prepared catalyst has low cost and is suitable for industrial production of the high-content rubber catalyst TMQ.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a preparation method of a high-content rubber antioxidant TMQ.
Background
The 2, 4-trimethyl-1, 2-dihydroquinoline is mainly used for producing an anti-aging agent TMQ, wherein the anti-aging agent TMQ is a di, tri and tetra polymer of 2, 4-trimethyl-1, 2-dihydroquinoline, also called an anti-aging agent RD, is a ketoamine anti-aging agent, is light yellow to ruin poise particles or flakes, is mainly used as a rubber anti-aging agent, has the annual requirement of 10 ten thousand tons at home, is one of the most demanded rubber anti-aging agent products in the market at home and abroad,
the main raw materials for synthesizing the anti-aging agent TMQ are aniline and acetone (or derivatives thereof), and the process can be roughly divided into a one-step method or a two-step method. The process of the one-step method comprises the following steps: and (3) performing condensation and polymerization reaction on aniline and acetone under the action of a catalyst to directly obtain an anti-aging agent TMQ polycondensation liquid containing two, three and four polymers of 2, 4-trimethyl-1, 2-dihydroquinoline, and neutralizing the TMQ polycondensation liquid by liquid alkali, separating water, distilling and the like to obtain TMQ. The process of the two-step method is as follows: and (3) performing condensation reaction on aniline and acetone under the action of a catalyst, distilling or rectifying the reaction liquid or the neutralized reaction liquid to obtain 2, 4-trimethyl-1, 2-dihydroquinoline, namely TMQ monomer, performing polymerization reaction on the TMQ monomer under the action of the catalyst to obtain di-, tri-and tetra-polymers of the 2, 4-trimethyl-1, 2-dihydroquinoline, and neutralizing, water splitting and distilling to obtain the anti-aging agent TMQ. In order to accelerate the reaction process, solvents such as toluene, xylene, and cyclohexane are added to the reaction, so the TMQ synthesis method can be classified into "solvent method" or "solvent-free method" and the like.
With the implementation of TMQ new national standard GB/T8826-2019 in China 2020, TMQ is classified into common TMQ and high-content TMQ, wherein the content requirement of an effective body of the high-content TMQ is more than or equal to 70.0%, the content requirement of primary amine is less than or equal to 1.0%, the content requirement of the effective body of the common TMQ is more than or equal to 40.0%, the content of primary amine is not required, the high-content TMQ is more environment-friendly and is high-efficiency in application, and the TMQ becomes a trend of the development of the TMQ industry in the future.
CN103467372a describes a method for the joint production of TMQ and an anti-aging agent FR: adding catalyst into the front cut fraction in the distillation process of the anti-aging agent TMQ finished product to react, and obtaining the anti-aging agent FR finished product through neutralization, water washing and distillation. Although this method can obtain TMQ in a high content, the yield is limited by the yield of TMQ in a normal form and its front-end.
CN112142657a describes reacting a front cut with acetone in the presence of a catalyst to obtain a low primary amine TMQ reaction solution; and neutralizing the low primary amine TMQ reaction liquid by using liquid alkali, separating water, and distilling an oil phase to obtain the low primary amine TMQ. Although the method reduces the primary amine content, the effective body content is not obviously improved to more than 70%.
Disclosure of Invention
The invention aims to provide a preparation method of a high-content rubber antioxidant TMQ, wherein the conversion rate of aniline in a reactant is more than 95% by improving the proportion and the preparation process of a catalyst, and the high-content rubber antioxidant is prepared by one-step method; in addition, the content of 2, 4-trimethyl-1, 2-dihydroquinoline dimer with the best ageing resistance in the product can reach 66.5%, the effective physical energy content can reach 91.0%, and the service performance of the rubber anti-ageing agent TMQ is effectively improved.
In order to achieve the above purpose, the present invention proposes the following technical scheme: a preparation method of a high-content rubber antioxidant TMQ comprises the following steps: performing one-step polycondensation reaction on aniline and acetone under the action of a compound acid catalyst, neutralizing and separating water from the reaction solution, and distilling an oil phase to obtain a high-content rubber anti-aging agent TMQ;
the reaction temperature of the polycondensation reaction is 90-250 ℃, and the molar ratio of the reactants aniline to acetone is 1: (2-10), wherein the mass ratio of the reactant aniline to the composite acid catalyst is 1 (0.01-0.5); wherein the compound acid catalyst comprises hydrogen chloride and aromatic sulfonic acid, and the molar ratio of the hydrogen chloride to the sulfuric acid to the aromatic sulfonic acid is 1: (6-20).
Further, the dimer content of the 2, 4-trimethyl-1, 2-dihydroquinoline in the high-content rubber antioxidant TMQ is not less than 53.0%, and the effective body content is not less than 81.5%.
Further, the compound acid catalyst also comprises sulfuric acid, and the molar ratio of the hydrogen chloride to the sulfuric acid in the compound acid catalyst is 1:0.3 to 0.5.
Further, the aromatic sulfonic acid is one or a mixture of more of benzenesulfonic acid, monoalkylbenzenesulfonic acid, dialkylbenzenesulfonic acid, polyalkylbenzenesulfonic acid, monohalobenzenesulfonic acid and polyhalobenzenesulfonic acid, and the aromatic benzene ring can be monosulfonic acid substituted, disulfonic acid substituted or trisulfonic acid substituted.
Further, the compound acid catalyst also comprises one or more solvents of aniline, acetone, mesityl oxide, diphenylamine and isopropyl diphenylamine, and the molar ratio of the compound acid catalyst to the solvents is 1: (0.1-1).
Further, the water content of the composite acid catalyst is less than 5%, and the molar ratio of the hydrogen chloride to the aromatic sulfonic acid in the composite acid catalyst is 1: (10-15).
Further, the molar ratio of aniline and acetone reactants in the polycondensation reaction is 1: (4-6), the mass ratio of the reactant aniline to the composite acid catalyst is 1 (0.05-0.25).
Further, the specific process of performing one-step polycondensation reaction on the aniline and the acetone under the action of the composite acid catalyst is as follows: aniline, acetone and a compound acid catalyst are completed in one step in a reaction tower, the temperature of the reaction tower is maintained at 120-180 ℃, and the residence time of materials in the tower is 0.001-0.05 h; the residence time is calculated as the time for the acetone to pass through the reaction column at the maintenance temperature.
Further, the specific process of performing one-step polycondensation reaction on the aniline and the acetone under the action of the composite acid catalyst is as follows: the aniline, the acetone and the compound acid catalyst are completed in one step in a reaction kettle, the temperature of the reaction kettle is maintained at 80-180 ℃, and the reaction time is 1-10 h.
Further, the specific process of performing one-step polycondensation reaction on the aniline and the acetone under the action of the composite acid catalyst is as follows: the aniline, the acetone and the compound acid catalyst are completed in one step in a micro-reactor, the temperature of the micro-reactor is maintained at 80-180 ℃, and the reaction time is 0.01-20 min; the microreactor is a micro-flow field reactor or a micro-channel reactor.
According to the technical scheme, the following beneficial effects are achieved:
the invention discloses a preparation method of a high-content rubber antioxidant TMQ, which is obtained by performing one-step polycondensation reaction on aniline, acetone and a compound acid catalyst in a reaction tower, a reaction kettle or a microreactor, neutralizing reaction liquid, separating water and distilling an oil phase; wherein the water content of the composite acid catalyst is less than 1%, and the molar ratio of the hydrogen chloride to the aromatic sulfonic acid is 1: (6-20), the conversion rate of aniline under the catalyst can reach more than 95%, the dimer content of the product can reach 66.5%, the dimer content of the second, third and fourth polymers can reach 91%, the primary amine content is not more than 0.35%, and the isopropyl diphenylamine content is not more than 0.3%; the invention prepares high-content TMQ through a one-step reaction, and greatly improves the service performance of TMQ by improving the dimer content with the best ageing resistance to more than 60 percent.
In addition, the composite acid catalyst adopted by the method is composed of cheap industrial products, and the prepared composite catalyst has low cost and is suitable for industrial production of the high-content rubber catalyst TMQ.
It should be understood that all combinations of the foregoing concepts, as well as additional concepts described in more detail below, may be considered a part of the inventive subject matter of the present disclosure as long as such concepts are not mutually inconsistent.
The foregoing and other aspects, embodiments, and features of the present teachings will be more fully understood from the following description in conjunction with the accompanying examples. Other additional aspects of the invention, such as features and/or advantages of the exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of the embodiments according to the teachings of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The terms "first," "second," and the like in the description and in the claims, are not used for any order, quantity, or importance, but are used for distinguishing between different elements. Also, unless the context clearly indicates otherwise, singular forms "a," "an," or "the" and similar terms do not denote a limitation of quantity, but rather denote the presence of at least one. The terms "comprises," "comprising," or the like are intended to cover a feature, integer, step, operation, element, and/or component recited as being present in the element or article that "comprises" or "comprising" does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. "up", "down", "left", "right" and the like are used only to indicate a relative positional relationship, and when the absolute position of the object to be described is changed, the relative positional relationship may be changed accordingly.
Based on the application and implementation of a new national standard of TMQ, high-content TMQ with high performance and environmental protection characteristics becomes an industry development trend; however, the existing preparation method of the high-content TMQ can obtain a product, but the yield or the effective body content of the product can not be synchronously improved due to the limitation of the adopted method; therefore, the invention provides a preparation method of the high-content rubber antioxidant TMQ, which not only can industrially produce the high-content TMQ, but also can greatly improve the content of effective substances in the product.
The preparation method of high-content rubber antioxidant TMQ comprises the steps of performing one-step polycondensation reaction on aniline and acetone in a reaction tower, a reaction kettle or a microreactor under the action of a composite acid catalyst, neutralizing and separating reaction liquid, and distilling an oil phase to obtain the high-content rubber antioxidant TMQ; the conditions of the polycondensation reaction are: the reaction temperature is 90-250 ℃; the molar ratio of the reactants aniline and acetone is 1: (2-10), preferably 1: (4-6); the mass ratio of the reactant aniline to the composite acid catalyst is 1 (0.01-0.5), preferably 1 (0.05-0.25); wherein the water content of the complex acid catalyst is less than 5%, preferably less than 1%, comprising hydrogen chloride and aromatic sulfonic acid, and the molar ratio of hydrogen chloride to aromatic sulfonic acid is 1: (6 to 20), preferably 1: (10-15); the aromatic sulfonic acid is one or a mixture of more of benzenesulfonic acid, monoalkylbenzenesulfonic acid, dialkylbenzenesulfonic acid, polyalkylbenzenesulfonic acid, monohalobenzenesulfonic acid and polyhalobenzenesulfonic acid, and the aromatic benzene ring can be monosulfonic acid substituted, disulfonic acid substituted or trisulfonic acid substituted; for example, in addition to benzenesulfonic acid, one or more of toluenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, p-toluenesulfonic acid, dimethylbenzenesulfonic acid, p-chlorobenzenesulfonic acid, o-chlorobenzenesulfonic acid, m-chlorobenzenesulfonic acid, p-phenylene disulfonic acid, o-phenylene disulfonic acid, and m-phenylene disulfonic acid may be selected.
Optionally, the composite acid catalyst further comprises sulfuric acid and a solvent, wherein the solvent is one or more of aniline, acetone, mesityl oxide, diphenylamine and isopropyl diphenylamine, and the adding ratio is that the molar ratio of hydrogen chloride to sulfuric acid is 1:0.3 to 0.5, the mol ratio of the composite acid catalyst to the solvent is 1: (0.1 to 1); wherein, aniline, acetone, mesityl oxide, diphenylamine or isopropyl diphenylamine are added to improve the fluidity of the composite catalyst, sulfuric acid is added to act with hydrochloric acid in a synergistic way, and the polymerization reaction time is shortened; preferably, in order to facilitate the preparation of high-content TMQ, the components added in the compound catalyst formula are aniline or acetone, so that the compound catalyst is convenient to use.
The preparation method of the high-content rubber antioxidant TMQ disclosed by the invention is further specifically described below by combining specific examples.
Example 1
Adding 80 g of 10mol of aniline and a composite acid catalyst (containing 2% of hydrogen chloride, 96% of p-toluenesulfonic acid and 2% of aniline, wherein the molar ratio of the hydrogen chloride to the p-toluenesulfonic acid is 1:10) into a reaction kettle, stirring and heating to a reaction temperature of 130 ℃, continuously introducing 50mol of acetone for reaction within 8 hours, and removing reaction water while reacting; after the reaction is finished, maintaining the reaction temperature for 0.5h, and detecting that the aniline content is 1.0%; then adding liquid alkali with the mass concentration of 20% for neutralization, adjusting the pH value to 10, separating water, distilling an oil phase, and removing unreacted acetone, water, aniline and 2, 4-trimethyl-1, 2-dihydroquinoline monomers to obtain 148.1g of high-content TMQ product; the dimer content is detected to be 63.5 percent, the dimer content is detected to be 89.3 percent, the tetramer content is detected to be 0.20 percent, the isopropyl diphenylamine content is detected to be 0.04 percent, the softening point is detected to be 94.4 ℃, and all indexes meet the national standard.
Example 2
The reaction conditions and the operation procedures were the same as in example 1 except that the composition of the complex acid catalyst was changed to (3% hydrogen chloride, 94% benzenesulfonic acid, 3% aniline, and the molar ratio of hydrogen chloride to benzenesulfonic acid was 1:7), and the aniline content in the polycondensation reaction liquid was detected to be 1.7%. 153.0g of a high-content TMQ product was obtained. Detecting that the dimer content is 61.5%, the dimer content, the tetramer content and the tetramer content are 88.5%, the primary amine content is 0.34%, the content of isopropyl diphenylamine is 0.15%, the softening point is 90.4 ℃, and various indexes meet national standards.
Examples 3 to 13 the experimental procedure of example 1 was used to examine the quality of high-content TMQ by changing the catalyst composition and the operating conditions for preparing TMQ, with other conditions unchanged, and the results are shown in Table 1 below:
TABLE 1 reaction conditions and product quality for examples 3 to 13
The invention provides a new catalyst, which strictly controls the proportion of hydrogen chloride and aromatic sulfonic acid in the composition, obviously improves the content of TMQ effective bodies of products, especially improves the content of 2, 4-trimethyl-1, 2-dihydroquinoline dimer while controlling the products not to generate high polymers, and prepares the high-content TMQ by one-step method; the method not only can industrially produce high-quality high-content TMQ with low cost, but also has environment-friendly preparation process.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art to which the present invention pertains will appreciate that numerous modifications and variations can be made without departing from the spirit and scope of the invention; for example, such as varying TMQ preparation acid catalyst type and reaction temperature/time, different reaction modes such as batch and continuous, and the like; acetone derivatives, aniline derivatives, reaction intermediates of aniline and acetone, and the like are used. Accordingly, the scope of the invention is defined by the appended claims.
Claims (10)
1. A preparation method of a high-content rubber antioxidant TMQ is characterized by comprising the following steps: performing one-step polycondensation reaction on aniline and acetone under the action of a compound acid catalyst, neutralizing and separating water from the reaction solution, and distilling an oil phase to obtain a high-content rubber anti-aging agent TMQ;
the reaction temperature of the polycondensation reaction is 90-250 ℃, and the molar ratio of the reactants aniline to acetone is 1: (2-10), wherein the mass ratio of the reactant aniline to the composite acid catalyst is 1 (0.01-0.5); wherein the complex acid catalyst comprises hydrogen chloride and aromatic sulfonic acid, and the molar ratio of the hydrogen chloride to the aromatic sulfonic acid is 1: (6-20).
2. The method for producing a high-content rubber antioxidant TMQ according to claim 1, wherein the dimer content of 2, 4-trimethyl-1, 2-dihydroquinoline in the high-content rubber antioxidant TMQ is not less than 53.0% and the effective body content is not less than 81.5%.
3. The method for preparing the high-content rubber antioxidant TMQ according to claim 1, further comprising sulfuric acid, wherein the molar ratio of hydrogen chloride to sulfuric acid in the composite acid catalyst is 1:0.3 to 0.5.
4. The method for preparing the high-content rubber antioxidant TMQ according to claim 1, wherein the aromatic sulfonic acid is one or more of benzenesulfonic acid, monoalkylbenzenesulfonic acid, dialkylbenzenesulfonic acid, polyalkylbenzenesulfonic acid, monohalobenzenesulfonic acid and polyhalobenzenesulfonic acid, and the aromatic benzene ring is optionally monosulfonic acid substituted, disulfonic acid substituted or trisulfonic acid substituted.
5. The preparation method of the high-content rubber antioxidant TMQ according to claim 1, wherein the compound acid catalyst further comprises one or more solvents selected from aniline, acetone, mesityl oxide, diphenylamine and isopropyl diphenylamine, and the molar ratio of the compound acid catalyst to the solvents is 1: (0.1-1).
6. The preparation method of the high-content rubber antioxidant TMQ according to claim 1, wherein the water content of the composite acid catalyst is less than 5%, and the molar ratio of hydrogen chloride to aromatic sulfonic acid in the composite acid catalyst is 1: (10-15).
7. The method for preparing the high-content rubber antioxidant TMQ according to claim 1, wherein the molar ratio of aniline and acetone which are reactants in the polycondensation reaction is 1: (4-6), the mass ratio of the reactant aniline to the composite acid catalyst is 1 (0.05-0.25).
8. The preparation method of the high-content rubber antioxidant TMQ, as claimed in claim 1, is characterized in that the specific process of performing one-step polycondensation reaction of aniline and acetone under the action of a composite acid catalyst is as follows: aniline, acetone and a compound acid catalyst are completed in one step in a reaction tower, the temperature of the reaction tower is maintained at 120-180 ℃, and the residence time of materials in the tower is 0.001-0.05 h; the residence time is calculated as the time for the acetone to pass through the reaction column at the maintenance temperature.
9. The preparation method of the high-content rubber antioxidant TMQ, as claimed in claim 1, is characterized in that the specific process of performing one-step polycondensation reaction of aniline and acetone under the action of a composite acid catalyst is as follows: the aniline, the acetone and the compound acid catalyst are completed in one step in a reaction kettle, the temperature of the reaction kettle is maintained at 80-180 ℃, and the reaction time is 1-10 h.
10. The preparation method of the high-content rubber antioxidant TMQ, as claimed in claim 1, is characterized in that the specific process of performing one-step polycondensation reaction of aniline and acetone under the action of a composite acid catalyst is as follows: the aniline, the acetone and the compound acid catalyst are completed in one step in a micro-reactor, the temperature of the micro-reactor is maintained at 80-180 ℃, and the reaction time is 0.01-20 min; the microreactor is a micro-flow field reactor or a micro-channel reactor.
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