CN113087657A - Improved process of aldehyde amine accelerant DHP - Google Patents
Improved process of aldehyde amine accelerant DHP Download PDFInfo
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- CN113087657A CN113087657A CN202110385391.3A CN202110385391A CN113087657A CN 113087657 A CN113087657 A CN 113087657A CN 202110385391 A CN202110385391 A CN 202110385391A CN 113087657 A CN113087657 A CN 113087657A
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- accelerator
- heptaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K5/3432—Six-membered rings
Abstract
The invention provides an improved process of an aldehyde amine accelerant DHP, which comprises the following specific synthetic steps: (1) adding heptaldehyde and organic acid into a reactor, and stirring and mixing; (2) controlling the temperature, dropwise adding aniline, and keeping the temperature for reaction after dropwise adding; (3) and (4) distilling under reduced pressure, removing water generated in the system, recovering heptaldehyde, and obtaining a residual liquid as a product. The product content is not less than 50%, the product smell is small, and the color is light.
Description
Technical Field
The invention relates to the field of rubber vulcanization accelerators, in particular to an improved process of an aldehyde amine accelerator DHP.
Background
The aldehyde amine vulcanized rubber accelerator has the vulcanization critical temperature of 120 ℃, is most suitable for a thiadiazole vulcanization system of chlorinated polyethylene rubber CM, and is particularly suitable for obviously improving the strength, ageing resistance, heat resistance, oil resistance and flame retardance of the vulcanized rubber. In addition, the aldehyde amine accelerator can be used for vulcanizing natural rubber, synthetic rubber and latex, and can also be used as an activator of an acid accelerator to be widely applied to vulcanizing chloroprene rubber, styrene-butadiene rosin rubber, butadiene rubber and the like. The aldehyde amine accelerator is used as a secondary accelerator together with thiuram, guanidine and thiazole accelerators to increase the activity of the accelerator and obtain tough and difficult-aging rubber products.
At present, anilino aldehyde amine accelerators mainly comprise accelerators 808, DHP and A-20 in the market, and research on the anilino aldehyde amine accelerators is recently reported at home and abroad. Accelerator 808 was first reported in 1969 by Masuo Funabasl, a research staff in Japan, and in recent years, the process improvement of accelerator 808 and DHP was carried out in Master 'complete synthesis of Saframycin C and process research of aldehyde amine vulcanization accelerator' by Chentao at national tobacco station university. The method comprises the following specific steps:
(1) accelerator 808
The reaction is divided into two steps, wherein in the first step, 2 molecules of n-butyraldehyde are subjected to self-condensation under the catalysis of alkali to obtain 2-ethyl-2-hexenal, and in the second step, 2-ethyl-2-hexenal and aniline are subjected to condensation under the catalysis of p-toluenesulfonic acid to obtain an accelerator 808, and the reaction formula is as follows:
(2)DHP
under the protection of nitrogen, aniline is slowly added into n-butyl aldehyde at 0 ℃, then acetic acid is added, the temperature is rapidly raised to 75 ℃, the temperature is kept for 1h, then the temperature is continuously raised to 100 ℃ for reaction for 1h, and the DHP product is obtained by washing and rectifying, wherein the yield is 60 percent, and the purity is 90 percent. The specific reaction formula is as follows:
since the synthesis raw material of the product is basically the same as the promoter 808, and the self-condensation reaction of aldehyde also occurs when acid is used as a catalyst, the promoter 808 and the Schiff base product of aniline and one molecule of aldehyde (or two molecules of aldehyde) are also generated in the process. During the subsequent rectification of the product, the product generally has a greater odor due to the smaller difference in boiling points between the product and the by-products, etc. In addition, although the reaction is carried out under the protection of nitrogen in the improved scheme, in fact, aniline cannot be completely converted in the process, so that the appearance color of the product can be continuously deepened in the subsequent rectification and storage processes.
(3)A20
A20 is the condensate of heptaldehyde and aniline, and its synthesis method is to mix the same molar ratio of aniline and heptaldehyde, then add 5% sulfur, heat to 140 deg.C and react until all water is evaporated. The reaction formula is as follows:
the accelerator 808, DHP and A20 products and by-products thereof have relatively large odor, and a small amount of residual aniline and butyraldehyde with relatively high volatility in the products cause the odor of the products to be more complicated and unpleasant, thereby severely limiting the practical application of the products. However, the rubber is a strong promoter in natural rubber and latex, can endow the product with good mechanical properties, and has an irreplaceable effect. Therefore, it is very important to develop an aldamine accelerator which has a small odor and can be widely used.
Disclosure of Invention
An improved process for preparing aldehyde-amine promoter DHP features that heptaldehyde and phenylamine are used as raw materials, and after reaction under the catalysis of organic acid, the product is obtained by distillation. The structural formula of the compound is similar to that of butyraldehyde-based DHP, and the compound is as follows:
the reaction equation is as follows:
the invention uses heptaldehyde to replace butyraldehyde in the original DHP product, and because the molecular weight of heptaldehyde is far larger than that of butyraldehyde, the difference of molecular weight is larger after condensation reaction. After the molecular weight of the product is increased and the difference is more obvious, the boiling points of the by-products and the product in the synthesis process are greatly improved, and the difference of the boiling points is larger. This allows for the subsequent removal of residual heptanal and aniline by simple distillation, resulting in a product with a low odor. Meanwhile, the organic acid catalyst with lower boiling point can be removed in the distillation process, so that the organic acid catalyst does not need to be removed by alkali washing and then water washing.
When the synthesis of the heptaldehyde DHP is carried out, if the operation is carried out according to the existing butyraldehyde DHP process, the obtained heptaldehyde DHP has extremely low purity. The reason is that the heptaldehyde has larger steric hindrance effect and poorer reaction activity than the butyraldehyde and the aniline, so the aniline and the heptaldehyde are directly mixed and reacted, the heptaldehyde is optimized to react with the aniline to generate Schiff base, and the generated Schiff base cannot be continuously reacted with the heptaldehyde to generate a product.
According to the invention, by optimizing reaction parameters, an organic acid catalyst is added into a system in advance, so that the heptaldehyde is subjected to a self-condensation reaction firstly, and although a two-molecule heptaldehyde condensate and a three-molecule heptaldehyde condensate are generated in the system in the process, the heptaldehyde DHP generated by the reaction of the three-molecule heptaldehyde condensate and aniline has better stability, so that the aniline preferentially reacts with the three-molecule heptaldehyde condensate to generate the heptaldehyde DHP. Therefore, a DHP product with higher heptaldehyde group content is obtained, and the conversion rate of aniline is higher than that of the butyraldehyde DHP, so that the aniline can be converted basically and completely.
The specific synthesis steps are as follows:
(1) adding heptaldehyde and organic acid into a reactor, and stirring, mixing and reacting;
(2) controlling the temperature, dropwise adding aniline, and reacting for 1-10 h under the condition of heat preservation after dropwise adding;
(3) and (4) distilling under reduced pressure, removing water generated in the system, recovering heptaldehyde, and obtaining a residual liquid as a product.
The organic acid is formic acid, acetic acid, propionic acid and the like or a mixture thereof, and the dosage of the organic acid is 5 to 20 percent of the weight of aniline;
the temperature of the dropwise adding aniline is 0-40 ℃.
The aniline of the invention: the molar ratio of heptanal is 1: 4-5.
The reduced pressure distillation is to vacuumize the system by an oil pump, remove water at 40-50 ℃, and recover heptaldehyde at 110-120 ℃.
The content of effective components of the heptaldehyde DHP is more than or equal to 50%.
The invention also claims the aldehyde-amine promoter DHP prepared by the improved process, wherein the aldehyde-amine promoter DHP is heptaldehyde DHP.
The invention further claims a vulcanized rubber complex, the formula of which comprises natural rubber, zinc oxide, sulfur and stearic acid, and the heptaldehyde DHP prepared by the invention is used as a vulcanization accelerator.
The invention has the beneficial effects that:
the reaction is carried out under mild conditions, and nitrogen protection is not needed, so the operation is simplified; the conversion rate of the aniline is improved, the residue of the aniline in the product is greatly reduced, and the product is yellow clear liquid; the excess heptanal is subsequently recovered by simple distillation. The content of the heptaldehyde DHP synthesized by the method is more than or equal to 50%, and the heptaldehyde DHP has the advantages of light appearance color, light smell and the like, and has higher market application value.
Drawings
FIG. 1 is a graph showing the vulcanization curves of examples of the present invention and comparative examples.
FIG. 2 shows the vulcanization curves of example 2 and three comparative examples (with respect to FIG. 1, the more effective example 2 is selected to compare with the comparative example in order to more clearly show the difference between the vulcanization curves of the example and the comparative example).
Detailed Description
The following detailed description is presented in conjunction with specific embodiments of the invention, but it should be understood that the scope of the invention is not limited by the specific embodiments.
Example 1
58.86g of n-heptanal and 1.40g of acetic acid are added into a 200ml flask, stirred and reacted for 1h, the temperature is reduced to 0 ℃, the temperature is controlled to be 0-5 ℃, 9.31g of aniline is slowly dripped, and heat preservation is continued for 10h after dripping is finished. Starting an oil pump to keep the system at a negative pressure, starting heating, and distilling water at 30-60 ℃; and continuously heating to 110-120 ℃, recovering n-heptaldehyde, cooling to obtain 51.13g of a product, wherein the product is yellow clear liquid, the content of DHP (dehydroepiandrosterone) of heptaldehyde groups is 60.52% through gas chromatography, and residual heptaldehyde and aniline are not detected.
Example 2
58.86g of n-heptanal and 1.40g of acetic acid are added into a 200ml flask, stirred and reacted for 1h, the temperature is controlled to be 20-30 ℃, 9.31g of aniline is slowly dripped, and heat preservation is continued for 5h after dripping is finished. Starting an oil pump to keep the system at a negative pressure, starting heating, and distilling water at 30-60 ℃; and continuously heating to 110-120 ℃, recovering n-heptanal, cooling to obtain 51.03g of a product, wherein the product is a yellow clear liquid, the content of DHP (dehydroepiandrosterone) in heptaldehyde groups is detected by gas chromatography to be 63.21%, and residual heptaldehyde and aniline are not detected.
Example 3
58.86g of n-heptanal and 1.40g of acetic acid are added into a 200ml flask, stirred and reacted for 1h, the temperature is controlled to be 30-40 ℃, 9.31g of aniline is slowly dripped, and heat preservation is continued for 4h after dripping is finished. Starting an oil pump to keep the system at a negative pressure, starting heating, and distilling water at 30-60 ℃; and continuously heating to 110-120 ℃, recovering n-heptaldehyde, cooling to obtain 51.06g of a product, wherein the product is yellow clear liquid, the content of DHP (dehydroepiandrosterone) of heptaldehyde groups is 63.13% through gas chromatography, and residual heptaldehyde and aniline are not detected.
Example 4
58.86g of n-heptanal and 0.47g of formic acid are added into a 200ml flask, stirred and reacted for 1 hour, the temperature is controlled to be 30-40 ℃, 9.31g of aniline is slowly dripped, and heat preservation is continued for 1 hour after dripping is finished. Starting an oil pump to keep the system at a negative pressure, starting heating, and distilling water at 30-60 ℃; and continuously heating to 110-120 ℃, recovering n-heptaldehyde, cooling to obtain 51.36g of a product, wherein the product is a yellow clear liquid, the content of DHP (dehydroepiandrosterone) in the heptaldehyde groups is detected by a gas chromatography, and residual heptaldehyde and aniline are not detected.
Example 5
58.86g of n-heptanal and 1.86g of propionic acid are added into a 200ml flask, stirred and reacted for 1h, the temperature is controlled to be 30-40 ℃, 9.31g of aniline is slowly dripped, and heat preservation is continued for 6h after dripping is finished. Starting an oil pump to keep the system at a negative pressure, starting heating, and distilling water at 30-60 ℃; and continuously heating to 110-120 ℃, recovering n-heptaldehyde, cooling to obtain 51.16g of a product, wherein the product is yellow clear liquid, the content of DHP (dehydroepiandrosterone) of heptaldehyde groups is 60.48% through gas chromatography, and residual heptaldehyde and aniline are not detected.
Example 6
Adding 52.97g of n-heptanal and 1.40g of acetic acid into a 200ml flask, stirring and reacting for 1h, controlling the temperature to be 30-40 ℃, slowly dropwise adding 9.31g of aniline, and continuously preserving the temperature for 4h after dropwise adding is finished. Starting an oil pump to keep the system at a negative pressure, starting heating, and distilling water at 30-60 ℃; and continuously heating to 110-120 ℃, recovering n-heptanal, cooling to obtain 49.86g of a product, wherein the appearance of the product is yellow clear liquid, the content of DHP (dehydroepiandrosterone) of heptaldehyde groups is detected by gas chromatography to be 55.02%, and heptaldehyde and aniline residues are not detected.
Example 7
Adding 47.09g of n-heptanal and 1.40g of acetic acid into a 200ml flask, stirring and reacting for 1h, controlling the temperature to be 30-40 ℃, slowly dropwise adding 9.31g of aniline, and continuously preserving the temperature for 4h after dropwise adding is finished. Starting an oil pump to keep the system at a negative pressure, starting heating, and distilling water at 30-60 ℃; and continuously heating to 110-120 ℃, recovering n-heptanal, cooling to obtain 48.97g of a yellow clear liquid, detecting the content of DHP (dehydroepiandrosterone) of the heptaldehyde groups by using a gas chromatography, wherein the content of the DHP of the heptaldehyde groups is 52.32%, the content of aniline is 0.02%, and no heptaldehyde residue is detected.
Comparative example 1
58.86g of n-heptanal is added into a 200ml flask to be cooled to 0 ℃, nitrogen is introduced to replace system air, then nitrogen is continuously introduced, 9.31g of aniline is slowly dropped, then 1.40g of acetic acid is added, the temperature is raised to 75 ℃ within 0.5 hour, the temperature is kept for 1 hour, and the reaction is carried out for 1 hour after the temperature is raised to 100 ℃. Cooling to below 30 ℃, removing nitrogen, starting an oil pump to keep the system at negative pressure, heating to 30-60 ℃, and distilling water; and continuously heating to 110-120 ℃, recovering n-heptanal, cooling to obtain 53.29g of a product, wherein the appearance of the product is a red clear liquid, the content of DHP (dehydroepiandrosterone) of heptaldehyde groups is 5.06%, the content of aniline is 1.34%, and heptaldehyde residues are not detected by gas chromatography.
Comparative example 2
Into a 1L three-necked flask equipped with a condenser, a thermometer and a magnetic stirring device, 110g of n-butyraldehyde was charged, and the temperature of the system was lowered to 0 ℃ under a nitrogen atmosphere. 31g of aniline was slowly added dropwise and 5g of acetic acid was slowly added dropwise. The ice-water bath was removed, the temperature of the system was rapidly raised to 75 ℃ and held at this temperature for 1h, and the temperature was raised to 100 ℃ and held for 4 h. 100mL of saturated sodium carbonate was added. And (3) keeping the temperature of the solution for reaction for 1h, transferring the reactant into a 1L separating funnel after the reaction is finished, separating out a water phase, washing an organic phase to be neutral, and drying the organic phase by using anhydrous sodium sulfate to obtain a crude product. The content of the butyraldehyde DHP is 55.24 percent by gas chromatography detection.
And distilling the crude product under reduced pressure, collecting fractions at 110-130 ℃ to obtain 79.96g of product, and detecting the content of butyraldehyde DHP (dehydroepiandrosterone) of 90.26%, the residual content of butyraldehyde of 0.32% and the residual content of aniline of 2.12% by gas chromatography.
The following are the application tests of DHP in each set of examples, comparative examples:
(1) formulation and test method
TABLE-1 parts by weight of the materials of the samples in the test formulations
The test method comprises the following steps:
testing according to GB/T16584-
Testing an instrument: vulcanizer, type: M-3000-FA, high-speed rail inspection instruments (Dongguan), Inc.; and (3) testing temperature: 140 deg.C
And (3) testing results:
Claims (9)
1. an improved process of an aldehyde amine accelerator DHP is characterized in that:
the method comprises the following steps:
(1) adding heptaldehyde and organic acid into a reactor, and stirring, mixing and reacting;
(2) controlling the temperature, dropwise adding aniline, keeping the temperature and reacting for a certain time after dropwise adding;
(3) washing with water, layering, and removing the lower aqueous phase;
(4) and (4) distilling under reduced pressure, removing water generated in the system, recovering heptaldehyde, and obtaining a residual liquid as a product.
2. The improved process of an aldamine accelerator DHP according to claim 1, wherein: the organic acid is formic acid, acetic acid, propionic acid or a mixture thereof, and the dosage of the organic acid is 5 to 20 percent of the weight of the aniline.
3. The improved process of an aldamine accelerator DHP according to claim 1, wherein: the temperature of the dropwise adding aniline is 0-40 ℃.
4. The improved process of an aldamine accelerator DHP according to claim 1, wherein: the heat preservation reaction is carried out for a certain time at 0-40 ℃ for 1-10 h.
5. The improved process of an aldamine accelerator DHP according to claim 1, wherein: the aniline: the molar ratio of heptanal is 1: 4-5.
6. The improved process of an aldamine accelerator DHP according to claim 1, wherein: the reduced pressure distillation is to vacuumize the system and remove water at 40-50 ℃ and 110-120 ℃.
7. The improved process of an aldamine accelerator DHP according to claim 1, wherein: the content of DHP is more than or equal to 50 percent.
8. The aldamine promoter DHP prepared by the improved process of any one of claims 1 to 7, wherein: the aldehyde amine promoter DHP is heptaldehyde DHP.
9. A vulcanized rubber complex comprises natural rubber, zinc oxide, sulfur and stearic acid, and is characterized in that: an aldamine accelerator DHP according to claim 8 as a vulcanization accelerator.
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2021
- 2021-04-09 CN CN202110385391.3A patent/CN113087657A/en active Pending
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| IE910741A1 (en) * | 1991-03-06 | 1992-09-09 | Loctite Ireland Ltd | Air activatable polymerisable compositions |
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Application publication date: 20210709 |