CN1240787A - Process for preparing lower amide containing shielding phenol - Google Patents
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- CN1240787A CN1240787A CN 98102725 CN98102725A CN1240787A CN 1240787 A CN1240787 A CN 1240787A CN 98102725 CN98102725 CN 98102725 CN 98102725 A CN98102725 A CN 98102725A CN 1240787 A CN1240787 A CN 1240787A
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Abstract
A process for preparing lower amide containing shielding phenol features use of the lower acid ester containing shielding phenol and polyamine whose molecule contains at least 2 amino linked to H as raw materials, use of organotin compound as catalyst, and reaction at 100-180 deg.C for 2-6 hr in hydrocarbon solvent. Its advantages are short reaction time and high yield and purity of product. Said lower amide can be used as antioxidizing agent or thermal stabilizer of high-molecular compounds.
Description
The invention belongs to the preparation method of aromatic carboxylic acid's acid amides of hydroxyl, specifically, is the preparation method who contains the lower amide that shields phenol who can be used as oxidation inhibitor.
Contain the lower amide that shields phenol and can be used as oxidation inhibitor and thermo-stabilizer, be mainly used in polymeric amide, also can be used for polyolefine, acetal, polyester, urethane, synthetic or natural rubber amine and other macromolecular compound the thermooxidative degradation sensitivity.Contain shielding phenol and two kinds of antioxidant groups of amine in their molecule; Thereby have the double effects that shields phenolic antioxidant and amine antioxidants, and have good consistency, advantages such as the anti-property separated out, thermostability and radioresistance with macromolecular compound, thereby be a kind of very promising oxidation inhibitor.
Containing the lower amide compounds that shields phenol mainly contains: N, [3-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) propionyl] quadrol, N, [3-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, N, N '-dimethyl-N, [3-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) propionyl] quadrol, N, N '-two [3-(3-methyl-4 hydroxyls-5-tert-butyl-phenyl) propionyl] hexanediamine, N, [2-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) isobutyryl] hexanediamine and N, N '-two [2-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] quadrol etc.This compounds generally is to carry out ammonolysis reaction and make by containing the ester that shields phenol or acyl chlorides and polyamines.
GB1299591 discloses a kind of synthesis method, is will contain the propionic acid that shields phenol earlier to react with sulfur oxychloride in benzene solvent, makes acyl chlorides, adds hexanediamine again and carries out ammonolysis reaction.Complicated procedures of forming such as aftertreatment must be through washing, alkali cleaning, pickling, wash, evaporate, dry recrystallization just can obtain product, thereby product yield is lower, is about 50%.US3,584,047 disclose other two kinds of synthetic methods, and first method is to react contain the methyl propionate and the hexanediamine that shield phenol to 3h at 150～155 ℃, separate the methyl alcohol that generates simultaneously, at 160～190 ℃ of reaction 1.5h, this moment, transformation efficiency reached 86%, reacted 2.5h at last under 200 ℃, 5～10mmHg again, then product is poured in the benzene and solidified, filtration, recrystallization, this method temperature of reaction height, long reaction time; Second method is to be dissolved in the benzene containing the propionyl chloride that shields phenol, pours in the solution that contains polyamines, salt of wormwood and water that is cooled to 0～5 ℃ in advance reaction 15h again into.This method reaction times is longer.Above several method is not owing to all use catalyzer, thereby all has long reaction time, the defective that reaction process is loaded down with trivial details, productive rate is low to some extent.
The objective of the invention is to based on prior art, provide a kind of and contain the method for the lower amide that shields phenol by the preparation of using catalyzer to relax reaction conditions, raising productive rate.
The preparation method who contains the lower amide that shields phenol provided by the invention, be that to have the polyamines of two amino that link to each other with H at least in the low-carbon ester that shields phenol and the molecule be raw material to contain, at varsol and consumption be raw material weight 0.2～3.0% organotin catalysts in the presence of, starvation, in 100～180 ℃ of reaction 2～6h, separated product.
Exactly, the preparation method is as follows: will contain the low-carbon ester, polyamines, organotin catalysts and the varsol that shield phenol and mix, then starvation, at 100～180 ℃, preferred 120～160 ℃ are reacted 2～6h down, preferred 3～5 hours, separate methyl alcohol or the ethanol that generates in the reaction simultaneously.After having reacted, cooled off, leave standstill 5～10 hours, and made the product crystallization complete, suction filtration, oven dry then obtains the product of purity about 98%.If obtain the higher product of purity, product can be dissolved in and carry out recrystallization in chloroform, ethanol or the benzene according to a conventional method.Wherein, the consumption of organotin catalysts is that raw material is 0.2～3.0%, preferred 0.8～2.0% of low-carbon ester and a polyamines gross weight.In two kinds of raw materials, low-carbon ester determines that according to the number of the amino that links to each other with H in the polyamines suppose that it is n, then mixing mol ratio is n: 1 with the blending ratio of polyamines.More complete for the reaction that makes low-carbon ester, polyamines can excessive 10～50%.The mode of starvation can be to feed rare gas element such as nitrogen, also can be decompression vacuum pumping or other similar maintenance anoxybiotic mode.
The said structural formula that contains the low-carbon ester that shields phenol is:
Wherein, R
1, R
2Be C
1～C
8Alkyl or cycloalkyl, as methyl, ethyl, sec.-propyl, sec-butyl, the tertiary butyl, isopentyl, iso-octyl, uncle's octyl group, Alpha-Methyl cyclohexyl etc.R
1And R
2In preferably have one at least for the tertiary butyl, preferably have an ortho position that is positioned at hydroxyl at least.X is 1～3 positive integer, then-and C
xH
2x-can be-CH
2-,-CH
2CH
2-,-CH
2CH
2CH
2-or-CH
2(CH
3) CH-or-(CH
3) CH-CH
2-.Y is 1 or 2, promptly-and C
yH
2y+1-be-CH
3Or-CH
2CH
3Thereby to contain the low-carbon ester that shields phenol can be 3-(3-methyl-4 hydroxyls-5-tert-butyl-phenyl) methyl propionate, 3-(3,5-dimethyl-4-hydroxy phenyl) methyl propionate, 2-(3, the 5-di-tert-butyl-hydroxy phenyl) ethyl isobutyrate, 3,5-di-tert-butyl-hydroxy phenyl ethyl acetate and 2-(3, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate etc.
The said low-carbon ester that shields phenol that contains can be buied from market, also can be according to FR 1,343,301 or JP81,135, the self-control of 443 disclosed methods, concrete grammar is as follows: in the four-hole bottle that dropping funnel, stirring rod, thermometer and nitrogen conduit are housed, add 2,6-DI-tert-butylphenol compounds or other shielding phenol and weight for the potassium hydroxide of shielding phenol 4～5% or sodium methylate as catalyzer, from dropping funnel, splash into and shield the equimolar low-carbon ester of phenol, as methyl propionate, methyl isobutyrate, ethyl propionate etc.After dripping off, dropping funnel is removed the reconfiguration vacuum pump, hierarchy of control vacuum tightness is 10～20mmHg, is warming up to 80～120 ℃, reacts 6～9 hours, and separated product gets final product.
Said polyamines is the polyamines that has two amino that link to each other with H in the molecule at least, can have following structure, NH
2(C
mH
2mNH
2)
KH, m are 0～12 integer, and k is 1～4 positive integer, as hydrazine, quadrol, 1,3-diaminopropanes, 1,6-diamino-2,2-dimethylhexane, hexanediamine, butanediamine, pentamethylene diamine, octamethylenediamine, decamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine etc.Also can have following structure: (NH
2C
mH
2m)
3N, m is 2～6 positive integer, as (NH
2CH
2CH
2)
3N.Perhaps has following structure: [NH
2(CH
2)
m]
2-N-(CH
2)
m-N-[(CH
2)
mNH
2]
2, m is 2～6 positive integer, as [NH
2CH
2CH
2]
2-N-CH
2CH
2-N-[CH
2CH
2NH
2]
2In addition, said polyamines can also be alicyclic ring polyamines such as two dimethylamine, or 1, the polysubstituted alkane of aliphatic cyclic amine such as 3-bipyridyl propane.
Said organotin catalysts can have following structure: R
1R
2R
3R
4Sn, wherein R
1, R
2, R
3, R
4Be identical or different C
1～C
30, preferred C
2～C
20Alkyl, alkoxyl group, alkylthio, halogen atom, hydroxyl, sulfydryl or acyloxy, preferred R
1～R
4In at least one substituent carbonatoms greater than 2, preferably four substituent the total number of carbon atoms are at least 8, and at least one substituent non-carbon atom directly links to each other with tin atom in four substituting groups.Said organotin catalysts also can have following structure: R
5R
6Sn=O, wherein R
5, R
6Be C
1～C
30, preferred C
2～C
20Alkyl, alkoxyl group, alkylthio, halogen atom, hydroxyl, sulfydryl or acyloxy, preferred R
5, R
6In at least one substituent carbonatoms greater than 2, best two substituent the total number of carbon atoms are at least 8.For example, said organotin catalysts can be: fentin chloride, dioctyltin oxide, dihexyl stannic oxide, di-n-butyltin dilaurate, dihexyl undecyl tin chloride, two (butyl maleate) dioctyltin, the trioctylphosphine stannic hydroxide, triethylbenzene methanoyl tin, the dibenzyl tindichloride, triethyl acetoxyl group tin, two (methyl propionate) tindichloride, lauric acid toxilic acid dibutyl tin, the Dodecyl Mercaptan di-n-butyl tin, the β-Qiu Jibingsuan dioctyltin, S, S '-two (isooctyl thioglycollate) two (methoxycarbonyl ethyl) tin etc.
Said reaction solvent is that boiling point is 80～180 ℃ a varsol, as benzene, toluene, ethylbenzene, dimethylbenzene, trimethylbenzene, light naphtha gasoline etc.The consumption of solvent is as the criterion with complete dissolving raw material, generally is 2～5 times of raw material weight, preferred 2～3 times.
The preparation method who contains the lower amide that shields phenol provided by the invention, owing to adopted organotin catalysts, improved speed of reaction, relaxed reaction conditions, make the reaction times shorten to 2～6 hours, product yield is brought up to greater than 90%, and the product purity height, without recrystallization, purity also can be higher than 90%.
The N that accompanying drawing 1 makes for example 1, the infrared spectrum of N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine.
The N that accompanying drawing 2 makes for example 1, N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine
1The H-NMR spectrogram.
The N that accompanying drawing 3 makes for example 1, N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine
13The C-NMR spectrogram.
The invention will be further described below by embodiment.
The organotin catalysts that uses in the example be the Chongqing chemical industry product, chemical pure.
Agitator is being housed, thermometer, the cool pipe (magnetic tape trailer gas delivery pipe) that coagulates refluxes, add 1170 gram β-(3 in the 1000ml four-hole bottle of nitrogen conduit, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate (is pressed FR1,343,301 method self-control), the diamines 25.5 restrain oneself, 310 gram dioctyltin oxide and 350ml ethylbenzene, feed nitrogen, start stirrer after system is stable, the heating of electricity consumption heating jacket makes its dissolving, slowly be warming up to 130 ℃, reacted 3 hours, stop heating, close source of the gas, cooling was left standstill 8 hours, the suction filtration oven dry obtains product 124.8 grams, yield is 98%, the gas chromatography method analyze purity 98%.156～161 ℃ of product fusing points, the outward appearance powder that is white in color shows slightly crystalline.
Agitator is being housed, thermometer, the cool pipe (magnetic tape trailer gas delivery pipe) that coagulates refluxes, add 122.6 gram β-(3 in the 1000ml four-hole bottle of nitrogen conduit, the 5-di-tert-butyl-hydroxy phenyl) methyl isobutyrate (is pressed JP81,135, the self-control of 443 methods), 12.6 gram quadrol, 2.0 two (single-ethylhexyl maleate) dioctyltins of gram and 400ml dimethylbenzene, feed nitrogen, start stirrer after system is stable, the heating of electricity consumption heating jacket makes its dissolving, slowly be warming up to 120 ℃, reacted 4 hours, stop heating, close source of the gas, cooling was left standstill 8 hours, the suction filtration oven dry, obtain product 143.1 grams, yield is 94%, purity is 96%, and the outward appearance powder that is white in color shows slightly crystalline.
Agitator is being housed, thermometer, the cool pipe (band exhaust pipe) that coagulates refluxes, add 183.9 gram β-(3 in the 1000ml four-hole bottle of nitrogen conduit, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate (is pressed JP81,135, the self-control of 443 methods), 20.6 gram diethylenetriamine (Yang Xi chemical plant, Yixing, Jiangsu, chemical pure), 3.0 gram di-n-butyltin dilaurate and 400ml toluene, feed nitrogen, start stirrer after system is stable, the heating of electricity consumption heating jacket makes its dissolving, slowly be warming up to 140 ℃, reacted 5 hours, stop heating, close source of the gas, cooling was left standstill 8 hours, the suction filtration oven dry obtains product 202.2 grams, yield is 92%%, and purity is 94%, the outward appearance powder that is white in color shows slightly crystalline.
Embodiment 4
Agitator is being housed, thermometer, the cool pipe (magnetic tape trailer gas delivery pipe) that coagulates refluxes, add 102.6 gram β-(3-methyl-5-tert-butyl-hydroxy phenyl) methyl propionates in the 1000ml four-hole bottle of nitrogen conduit and (press JP81,135, the self-control of 443 methods), 28.4 two dimethylamine (Changzhou petroleum chemical plant products of gram, chemical pure), 2.6 gram dihexyl tin chloride and 400ml dimethylbenzene, feed helium, start stirrer after system is stable, the heating of electricity consumption heating jacket makes its dissolving, slowly be warming up to 110 ℃, reacted 3.5 hours, stop heating, close source of the gas, cooling was left standstill 8 hours, the suction filtration oven dry, obtain product 138.8 grams, yield is 94%, purity is 97%, and the outward appearance powder that is white in color shows slightly crystalline.
Agitator is being housed, thermometer, the cool pipe (magnetic tape trailer gas delivery pipe) that coagulates refluxes, add 146.2 gram β-(3 in the 1000ml four-hole bottle of nitrogen conduit, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, 20.0 gram tetraethylene pentamine (Yang Xi chemical plant, Yixing, Jiangsu product, chemical pure), 3.3 gram lauric acid toxilic acid dibutyl tin and 450ml toluene, feed nitrogen, start stirrer after system is stable, the heating of electricity consumption heating jacket makes its dissolving, slowly be warming up to 150 ℃, reacted 3.5 hours, stop heating, close source of the gas, cooling was left standstill 8 hours, the suction filtration oven dry, obtain product 143.2 grams, yield is 96%, product purity 97%, the outward appearance powder that is white in color shows slightly crystalline.
Agitator is being housed, thermometer, the cool pipe (magnetic tape trailer gas delivery pipe) that coagulates refluxes, add 117.0 gram β-(3 in the 1000ml four-hole bottle of nitrogen conduit, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, 37.9 restrain 1,10-decamethylene diamine (Shanghai reagent one factory's product, chemical pure), 1.3 gram β-Qiu Jibingsuan dioctyltin and 450ml toluene, feed nitrogen, start stirrer after system is stable, the heating of electricity consumption heating jacket makes its dissolving, slowly be warming up to 150 ℃, reacted 3 hours, stop heating, close source of the gas, cooling was left standstill 8 hours, suction filtration is dissolved in product then and carries out the recrystallization oven dry in the chloroform, refilters, oven dry, obtain product 124.7 grams, yield is 90%, purity 99.9%, the outward appearance powder that is white in color shows slightly crystalline.
Comparative Examples 1
According to US3, the method for 584,047 examples 1, in the 2000ml four-hole bottle that stirring product, thermometer, reflux condensing tube (magnetic tape trailer gas delivery pipe), nitrogen conduit are housed, add 128.6 gram β-(3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate and 23.2 diamines of restraining oneself feeds nitrogen and opens stirrer after stable, is heated to 150～155 ℃, kept 3.5 hours, and then be warmed up to 160～190 ℃, kept 1.5 hours, under 5～10mmHg pressure, be heated to 200 ℃, reacted 2.5 hours.To be dissolved in the 550ml benzene after the product cooling, can get solid phase prod 115.6 grams, yield is about 50%.Product appearance is slightly yellow, 155～162 ℃ of fusing points.
By contrast as can be seen, preparation method provided by the invention has relaxed reaction conditions owing to adopted organotin catalysts, has shortened the reaction times, has improved product yield and product purity.
Claims (14)
1. the preparation method who contains the lower amide that shields phenol, be that to have the polyamines of two amino that link to each other with H at least in the low-carbon ester that shields phenol and the molecule be raw material to contain, in varsol and under the condition of starvation, react, it is characterized in that be consumption be raw material weight 0.2～3.0% organotin catalysts in the presence of, at 100～180 ℃ of reaction 2～6h, separated product, the said low-carbon ester that shields phenol that contains has following structure:
R wherein
1, R
2Be C
1～C
8Alkyl or cycloalkyl, X is 1～3 positive integer, Y is 1 or 2.
2. according to the described preparation method of claim 1, it is characterized in that in the said low-carbon ester structure R
1, R
2In have one at least for the tertiary butyl, and have an ortho position that is positioned at hydroxyl at least.
3. according to the described preparation method of claim 1, it is characterized in that said polyamines has following structure: NH
2(C
mH
2mNH)
kH, m are 0～12 positive integer, and K is 1～4.
4. according to claim 1 or 3 described preparation methods, it is characterized in that said polyamines is selected from one of quadrol, propylene diamine, hexanediamine, butanediamine, pentamethylene diamine, heptamethylene diamine, octamethylenediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine.
5. according to the described preparation method of claim 1, it is characterized in that said polyamines is to dimethylamine.
6. according to the described preparation method of claim 1, it is characterized in that said organotin catalysts has following structure: R
1R
2R
3R
4Sn, wherein R
1, R
2, R
3, R
4Be identical or different C
1～C
30Alkyl, alkoxyl group, alkylthio, halogen atom, hydroxyl, sulfydryl or acyloxy.
7. according to the described preparation method of claim 6, it is characterized in that R in the said organotin structure
1, R
2, R
3, R
4Has a substituting group carbonatoms in four substituting groups at least greater than 2.
8. according to claim 6 or 7 described preparation methods, it is characterized in that R in the said organotin structure
1, R
2, R
3, R
4Four substituting group the total number of carbon atoms the total number of carbon atoms are at least 8, and at least one substituent non-carbon atom directly links to each other with tin atom in four substituting groups.
9. according to the described preparation method of claim 1, it is characterized in that said organotin catalysts has following structure: R
5R
6Sn=O, wherein R
5, R
6Be identical or different C
1～C
30Alkyl, alkoxyl group, alkylthio, halogen atom, hydroxyl, sulfydryl or acyloxy.
10. according to the described preparation method of claim 9, it is characterized in that R in the said organotin structure
5, R
6Has a substituting group carbonatoms in two substituting groups at least greater than 2.
11., it is characterized in that R in the said organotin structure according to claim 9 or 10 described preparation methods
5, R
6Two substituting group the total number of carbon atoms are at least 8.
12. according to the described preparation method of claim 1, the consumption that it is characterized in that said organotin catalysts is 0.8～2.0% of a raw material weight.
13., it is characterized in that said varsol is the varsol of 80～180 ℃ of boiling points according to the described preparation method of claim 1.
14. according to the described preparation method of claim 1, it is characterized in that temperature of reaction is 120～160 ℃, the reaction times is 3～5h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102725A CN1070844C (en) | 1998-06-25 | 1998-06-25 | Process for preparing lower amide containing shielding phenol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98102725A CN1070844C (en) | 1998-06-25 | 1998-06-25 | Process for preparing lower amide containing shielding phenol |
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| Publication Number | Publication Date |
|---|---|
| CN1240787A true CN1240787A (en) | 2000-01-12 |
| CN1070844C CN1070844C (en) | 2001-09-12 |
Family
ID=5217532
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98102725A Expired - Lifetime CN1070844C (en) | 1998-06-25 | 1998-06-25 | Process for preparing lower amide containing shielding phenol |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8128886B2 (en) | 2005-08-01 | 2012-03-06 | United Initiators Gmbh & Co. Kg | Reactor for preparing organic peroxides via the intermediate of a solid hydroperoxide |
| CN103508923A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for hindered phenol antioxidant |
| CN106674002A (en) * | 2016-12-28 | 2017-05-17 | 天津利安隆新材料股份有限公司 | Preparation method of hindered phenol antioxidant |
| CN112574053A (en) * | 2020-12-11 | 2021-03-30 | 江苏极易新材料有限公司 | Synthesis process of antioxidant 1098 |
| CN114671777A (en) * | 2022-03-18 | 2022-06-28 | 天津利安隆新材料股份有限公司 | Preparation method of amide antioxidant |
| CN114805105A (en) * | 2022-05-20 | 2022-07-29 | 唐山科澳化学助剂有限公司 | Synthesis process of antioxidant 1098 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3584074A (en) * | 1968-11-01 | 1971-06-08 | Teijin Ltd | Fibrous materials from polyethylene terephthalate polyether copolymer and polyamide |
-
1998
- 1998-06-25 CN CN98102725A patent/CN1070844C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8128886B2 (en) | 2005-08-01 | 2012-03-06 | United Initiators Gmbh & Co. Kg | Reactor for preparing organic peroxides via the intermediate of a solid hydroperoxide |
| CN103508923A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for hindered phenol antioxidant |
| CN103508923B (en) * | 2012-06-27 | 2016-06-29 | 中国石油化工股份有限公司 | A kind of preparation method of Hinered phenols antioxidant |
| CN106674002A (en) * | 2016-12-28 | 2017-05-17 | 天津利安隆新材料股份有限公司 | Preparation method of hindered phenol antioxidant |
| CN112574053A (en) * | 2020-12-11 | 2021-03-30 | 江苏极易新材料有限公司 | Synthesis process of antioxidant 1098 |
| CN114671777A (en) * | 2022-03-18 | 2022-06-28 | 天津利安隆新材料股份有限公司 | Preparation method of amide antioxidant |
| CN114671777B (en) * | 2022-03-18 | 2023-09-19 | 天津利安隆新材料股份有限公司 | Preparation method of amide antioxidant |
| CN114805105A (en) * | 2022-05-20 | 2022-07-29 | 唐山科澳化学助剂有限公司 | Synthesis process of antioxidant 1098 |
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|---|---|
| CN1070844C (en) | 2001-09-12 |
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