CN106674591B - A kind of long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered and its application - Google Patents

A kind of long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered and its application Download PDF

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CN106674591B
CN106674591B CN201611160817.0A CN201611160817A CN106674591B CN 106674591 B CN106674591 B CN 106674591B CN 201611160817 A CN201611160817 A CN 201611160817A CN 106674591 B CN106674591 B CN 106674591B
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long
sulfide
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high temperatures
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CN106674591A (en
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毛丽娟
刘树柏
丁轶凡
尹奇伟
罗瑞王刚
竺梦晓
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SHAOXING RUIKANG BIOTECHNOLOGY Co Ltd
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Abstract

The invention belongs to novel high polymer material antioxidative stabilizer additive agent fields, including four class general formulas.The beneficial technical effect of the present invention lies in can prevent color set by Degradation of Polymer Materials, protection high molecular material, keep its original function; the selection of the anti-oxidant stabilization additives of a variety of novel long-life, high-temperatures is provided for high molecular material; the present invention is applied to plastics; rubber; fiber; coating, in paint and the series of products such as petroleum.

Description

A kind of long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered and its application
Technical field
The invention belongs to macromolecule antioxidative stabilizers to be synthetically prepared field, in particular to a kind of Sulfide-containing Hindered is long-acting resistant to high temperatures Antioxidative stabilizer and its application.
Background technique
Antioxidative stabilizer is also known as antioxidant, is that one kind can help to capture and neutralize free radical, to dispel free radical Substance.The anti-oxidant stabilization additives selling market in the whole world is very huge, and the consumption of the unitary plastic antioxidant whole world just reaches hundreds of thousands Ton.The demand of material against oxidative stabilization additives and production are transferred to the emerging city in Asia from the U.S., West Europe and Japan successively Field, especially the nations of China and India.The consumption of country's antioxidant increases very fast at present.But a small number of big international suppliers are still Material against oxidative stabilizer world market price so is controlled, the market supply of its patented product is controlled, so that field of new materials Develop unbalanced all over the world.
Most polymers material need 200 DEG C or more at a temperature of processed or handled, and since it is continuous It is subjected in high temperature and strong light environment, usual material will appear reduced service life, and color is easy to be destroyed, strength reduction or material The problems such as expecting surface embrittlement cracking.However, these influences can prevent and subtract by introducing specific anti-oxidant stabilization additives Few material damage, extends the materials'use service life, keeps beautiful, durable, reduces cost, reduces waste material yield, protects environment.
Extensive used anti-oxidant stabilization additives such as DSTDP, DLTDP currently on the market, molecular weight is small, volatile, Ester bond connects degradable loss, and effect is unevenly distributed in the material, and generates rotten-egg odour under high temperature, so that material be made to handle Or be especially under the conditions of high temperature and strong illumination during use, it being damaged, causes service life short, color is destroyed, The problems such as strength reduction or embrittlement cracking.
Summary of the invention
It is an object of the present invention to provide a kind of stability is more preferable, more efficient Sulfide-containing Hindered high temperature resistant long acting is oxidation resistant to be added Add agent.It has the characteristics that prevent Degradation of Polymer Materials, protection high molecular material color, keeps its original function, in particular High molecular material provides the selection of a variety of novel antioxidant stabilization additives.
In order to achieve the above objectives, the specific technical solution of the utility model is as follows, a kind of long-acting antioxygen resistant to high temperatures of Sulfide-containing Hindered Change stabilizer, it is characterised in that including with flowering structure:
Wherein R is H, Me, Et, Pr, Bu, Bz；
R1For C1~C8Alkyl, R2For C2~C3Alkyl, R3For C8~C12Alkyl；
Target product (I) of the present invention is prepared by following reaction, and reaction equation is as follows:
Wherein R is H, Me, Et, Pr, Bu, Bz；R1For C1~C8Alkyl, R2For C2~C3Alkyl, R3For C8~C12Alkyl, R4 For methyl or ethyl.
R=H, group shown in R1, R2, R3 represent compound through MS,1H-NMR confirms structure, as shown in table 1.
Table 1:
Note: (1) the 1H NMR detection of all compounds is all to test to complete on Bruker 400MHz NMR instrument.
(2) compound 1HNMR test is identical as (1) condition of annotation in following table or product.
(3) Mass Spectrometer Method is completed on 6400 instrument of Agilent LC-MS.
Or
Wherein n:0,1,2,3,4,5,6,7,8,9,10,11,12,12,14,15,16,17,18；
M:1,2,3,4,5；
R:H, Me, Et, Pr, Bu, OH, O- alkyl；
R3: C8~C12Alkyl.
Target product (II) of the present invention is prepared by following reaction, and reaction equation is as follows:
Wherein n:0,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18；m:1,2,3,4,5；R:H, Me, Et, Pr, Bu, OH, O- alkyl；R3: C8~C12Alkyl；X is methyl or ethyl.R=H, n, m, R3The compound of shown group Through MS,1HNMR structural confirmation is as shown in table 2.
Table 2:
Or
Wherein n:2,3,4,5,6；
m:1,2,3,4,5；h:6,7,8,9,10,11,12,13,14,15,16,17,18；
R:H, Me, Et, Pr, Bu, OH, O- alkyl；
R3:C8~C12Alkyl；
Target product (III) of the present invention is prepared by following reaction, and reaction equation is as follows:
Wherein n:2,3,4,5,6；m:1,2,3,4,5；h:6,7,8,9,10,11,12,13,14,15,16,17,18；
R:H, Me, Et, Pr, Bu, OH, O- alkyl；R3:C8~C12Alkyl；X is methyl or ethyl.The chemical combination of shown group Object through MS,1HNMR structural confirmation is as shown in table 3.
Table 3:
Or
Wherein n:0,1,2,3,4,5,6,7,8,9,10,11,12；
M:1,2,3,4,5；h:2,3,4,5,6,7,8,9,10,11；
R:H, C1-C6Alkyl；
R1: C2-C12Alkyl；
Target product (IV) of the present invention is prepared by following reaction, and reaction equation is as follows:
n:5,6,7；m:2-20
R:H, Me, Et, Pr, Bu, OH, OC1-8 alkyl；R1:C2-18 alkyl
The compound of shown group through MS,1HNMR structural confirmation is as shown in table 4.
Table 4:
Preferably, a kind of long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered is one of following below formula:
R=R1:H, CH3, Et, Pr, Bu, OH, OR,Wherein OR is O alkyl (similarly hereinafter).
Or
R:CH3,Et,Pr,Bu,OH,OR,
Or
R:H, CH3, Et, Pr, Bu, OH, OR,
Or
R:H.CH3, Et, Pr, Bu, OH, O alkylR1: the alkyl containing 3-8 carbon
The Sulfide-containing Hindered functionalizing closes application of the object as long-life, high-temperature antioxidative stabilizer.
The Sulfide-containing Hindered function base antioxidative stabilizer is produced in the series such as plastics, rubber, fiber, coating, paint and petroleum Application in product.
The present invention can be added directly applied in high molecular material, and effect is to prevent Degradation of Polymer Materials, protection high Molecular material color keeps its original function, provides the selection of a variety of novel antioxidant stabilization additives for high molecular material, Present invention can apply to plastics, rubber, fiber, coating, in the series of products such as paint and petroleum.
Existing anti-oxidant stabilization additives such as DSTDP, DLTDP used, molecular weight is small, volatile, ester bond connection easily drop Solution loss, effect is unevenly distributed in the material, and generates rotten-egg odour under high temperature, to keep material special during processing or use It is not to be damaged under the conditions of high temperature and strong illumination, causes service life short, color is destroyed, strength reduction or crisp The problems such as changing cracking.Problem above can prevent and reduce material damage by introducing specific anti-oxidant stabilization additives, prolong Long material service life keeps beautiful, durable, reduces cost, reduces waste material yield, protects environment.So the present invention can also be The use of additive escorts, and improves the stability of additive.
The present invention designs the antioxidative stabilizer and preparation method thereof of research and development, enables corresponding material under the high temperature conditions It keeps stable property and odorless generates, have the characteristics that environmentally protective.
The present invention is further elaborated below by way of specific embodiment.
Specific embodiment
Embodiment 1
The preparation of ten disulfide ethamine
115g 2- chloroethene is added in the 1000ml there-necked flask equipped with mechanical agitator, thermometer and nitrogen protection device Amine hydrochlorate, 300ml ethyl alcohol, appropriate sodium hydroxide, 202g n- dodecyl mereaptan is added under cryostat, and then maintaining reaction temperature is 20 It~55 DEG C, until fully reacting, is removed under reduced pressure ethyl alcohol, is recrystallized in methylene chloride petroleum ether mixed solvent, obtains white solid 240g, Obtained solid i.e. ten disulfide ethamine.
Dimethyl malenate and ten disulfide ethamine
It weighs 13.2g (0.1mol) dimethyl malenate and ten disulfide ethamine of 50g is added in reaction flask, nitrogen protection Lower addition carboxylate (carboxylic acid potassium or carboxylic acid sodium or potassium formate or sodium formate or sodium methoxide), heating reaction 3-7 days, is added 95% second Alcohol reflux is cooled to room temperature filtering, obtains white solid 50g, yield 93%.
1H NMR is on Bruker 400MHz NMR instrument in CD3(δ, ppm) is tested in OD: 0.92 (t, 6H), 1.28- 1.37(m,36H),1.55-1.67(m,4H),2.56(t,4H),2.66(t,4H),3.19(s,2H),3.31-3.37(bs, CH3OH in CD3OD),3.40(t,4H),4.90(bs,H2O in CD3OD)
Mass Spectrometer Method is completed on 6400 instrument of Agilent LC-MS, MS-ESI:M+559.32,659.94.
Embodiment 2
Dimethyl sebacate is reacted with ten disulfide ethamine
23.3g (0.1mol) dimethyl sebacate is weighed, ten disulfide ethamine of 50g is put into reaction flask, under nitrogen protection It is added catalyst carboxylate (carboxylic acid potassium or carboxylic acid sodium or potassium formate or sodium formate or sodium methoxide), reacts heating stirring 4-8 days, TLC or GC tracks reaction process, and 95% alcohol reflux of 120ml is added after completion of the reaction, and cold filtration obtains white solid 60.4g, yield 91%.
1H NMR is on Bruker 400MHz NMR instrument in CDCl3Middle test (δ, ppm): 0.87 (t, 6H), 1.21- 1.42(m,44H),1.52-1.66(m,8H),2.81(t,4H),2.52(t,4H),2.66(t,4H),3.44(m,4H),6.87 (sb,2H),7.26(s,CHCl3in CDCl3)
Mass Spectrometer Method is completed on 6400 instrument of Agilent LC-MS, MS-ESI:MS+657.21。
Embodiment 3
The preparation of pungent thioether propylamine
130g 3- chlorine third is added in the 1000ml there-necked flask equipped with mechanical agitator, thermometer and nitrogen protection device Amine hydrochlorate, 300ml ethyl alcohol, appropriate sodium hydroxide or potassium hydroxide, are added 146g n-octyl mercaptan, and reaction temperature is 10~55 DEG C Preferably, TLC or GC tracking reaction process until the reaction is complete, remove alcohol solvent, in DCM petroleum ether in the mixed solvent weight to range Crystallization, cold filtration obtain white solid 200g, obtained solid, that is, pungent thioether propylamine.Dimethyl malenate and pungent thioether propylamine
13.3g (0.1mol) dimethyl malenate is weighed, the pungent thioether propylamine of 42.6g is put into reaction flask, under nitrogen protection It is added carboxylate catalyst (carboxylic acid potassium or carboxylic acid sodium or potassium formate or sodium formate or sodium methoxide), reacts heating stirring 2-7 days, add Enter 95% ethyl alcohol, be cooled to room temperature filtering, obtains white solid 44g, yield 93%,
1H NMR is on Bruker 400MHz NMR instrument in CDCl3Middle test (δ, ppm): 0.88 (t, 6H), 1.22- 1.42(m,20H),1.51-1.66(m,4H),1.82(t,4H),2.51(m,8H),3.16(s,2H),3.37(t,4H),6.93 (sb,2H 7.26(s,CHCl3in CDCl3)
Mass Spectrometer Method is completed on 6400 instrument of Agilent LC-MS, MS-ESI:MS+474.80。
Embodiment 4
14.6g (0.1mol) dimethyl succinate is weighed, the pungent thioether propylamine of 42.6g is put into reaction flask, under nitrogen protection Carboxylate catalyst is added, heating stirring is reacted 2-6 days, and 95% ethyl alcohol is added, and cold filtration obtains white solid 45g, yield 94%.
1H NMR is on Bruker 400MHz NMR instrument in CDCl3Middle test (δ, ppm): 0.88 (t, 6H), 1.22- 1.41(m,20H),1.53-1.61(m,4H),1.75-1.83(m,4H),2.47-2.58(m,12H),3.32-3.38(m,4H), 7.26(s,CHCl3in CDCl3)
Mass Spectrometer Method is completed on 6400 instrument of Agilent LC-MS, MS-ESI:M+489.27,589.95
Embodiment 5
N=4, m=3, R3=C12 alkyl
(1) preparation of dodecyl thio-methyl propionate
202g n- dodecyl mereaptan and 86g methyl acrylate are added in reaction flask, N2Catalyst (DMAP is added under protection Or carboxylate or sodium hydroxide or potassium hydroxide), 5-50 degrees Celsius of stirring, TLC obtains GC tracking reaction process, after purification 12 Alkylthio methyl propionate.
The preparation of (2) two (dodecyl propane thioic acid) succinamides
8.8g 1,4-Diaminobutane and 57.6g (0.2mol) dodecyl thio-methyl propionate are put into reaction flask, It is added carboxylate catalyst (carboxylic acid potassium or carboxylic acid sodium or potassium formate or sodium formate or sodium methoxide), N2The lower reaction heating of protection is stirred It mixes, until end of reaction ethanol water is added, cold filtration is dry, obtains 55g white solid in TLC or GC tracking reaction process Powder.
1H NMR is on Bruker 400MHz NMR instrument in CDCl3Middle test (δ, ppm): 0.93 (t, 6H), 1.25- 1.37(m,36H),1.53-1.59(m,4H),1.64-1.70(t,4H),2.42-2.49(t,4H),2.52-2.59(t,4H), 2.69-2.73(t,4H),3.24(t,4H),3.25-3.50(m,CH3OH in CD3OD),4.56-4.90(H2O in CD3OD)
Mass Spectrometer Method is completed on 6400 instrument of Agilent LC-MS, MS-ESI:M+601.39。
Embodiment 6
N=8, m=2, R3=C12 alkyl
By 14.4g 1, in 8- diamino-octane and 57.6g dodecyl thio-methyl propionate investment reaction flask, N2Protection Lower addition carboxylate catalyst (carboxylic acid potassium or carboxylic acid sodium or potassium formate or sodium formate or sodium methoxide), reaction heating stirring is until anti- It should finish, ethanol water is added, cold filtration is dry, obtains 62g white solid powder.
1H NMR is on Bruker 400MHz NMR instrument in CDCl3Middle test (δ, ppm): 0.92 (t, 6H), 1.23- 1.47(m,44H),1.54-1.67(m,8H),2.41-2.45(t,4H),2.53-2.57(t,4H),2.70-2.74(t,4H), 3.18-3.23(m,4H),3.29-3.33(bs,CH3OH in CD3OD),4.87(bs,H2O in CD3OD)
Mass Spectrometer Method is completed on 6400 instrument of Agilent LC-MS, MS-ESI:M+657.49,655.46.
Embodiment 7
M=2, n=2, h=11, R=H, R3=C12 alkyl
The preparation of (1) ten disulfide ethamine (n=2, h=11)
115g 2- chloroethene is added into the 1000ml there-necked flask equipped with mechanical agitator, thermometer and nitrogen protection device 202g n- dodecyl mereaptan, control is added in amine hydrochlorate and alcohol solvent, appropriate DMAP or carboxylate or sodium hydroxide or potassium hydroxide The lower stirring of reaction temperature control processed until the reaction is complete, is removed under reduced pressure ethyl alcohol, recrystallizes in DCM and petroleum ether, cold filtration, Obtain white solid 240g, obtained solid i.e. ten disulfide ethamine.
(2) dodecyl thio-methyl propionate (m=2, R3=-C12H25) preparation
202g n- dodecyl mereaptan and 86g methyl acrylate are added in reaction flask, catalyst (DMAP or carboxylic acid potassium are added Or carboxylic acid sodium or potassium formate or sodium formate or sodium methoxide), N2Protect lower temperature control at 5-50 degrees Celsius preferably, stir TLC or GC tracks reaction process until the reaction is complete, obtains dodecyl thio-methyl propionate 288g.
(3) prepared by ten disulfide acetamide of dodecyl propane thioic acid
28.8g dodecyl thio-methyl propionate and ten disulfide ethamine of 24.5g are put into reaction flask, catalyst is added (carboxylic acid potassium or carboxylic acid sodium or potassium formate or sodium formate or sodium methoxide), heating overtime work are reacted up to completely, acetone recrystallization being added, 40g white crystal is obtained,.
1H NMR is on Bruker 400MHz NMR instrument in CDCl3Middle test (δ, ppm): 0.88 (t, 6H), 1.22- 1.43(m,36H),1.55-1.62(m,4H),2.48-2.55(m,4H),2.67(t,2H),2.82(m,4H),3.45(m, 2H),.26(s,CHCl3in CDCl3)
Mass Spectrometer Method is completed on 6400 instrument of Agilent LC-MS, MS-ESI:M+502.47。
Embodiment 8
The polythiaether preparation that diamines is reacted with the thio dimethyl malenate of 3,3'-
(1) thio two dimethyl malenate of 3,3'-
116.28 mMs of sodium hydrosulfide aqueous solutions are added in 244.20 mMs of methyl acrylate methanol solutions, are stirred It mixes until the reaction is complete, methylene chloride is added, three times, combining extraction liquid dries, filters extraction product in anhydrous sodium sulfate, dense Contracting purifying obtains 25.3 grams of title intermediates of colorless oil.
(2) hexamethylene diamine and the thio dimethyl malenate of 3,3'- react the polythiaether to be formed
Restrain oneself diamines and proper catalyst (sodium acetate or acetic acid by 18.20 grams of thio dimethyl malenates of 3,3'-, 10.66 First or sodium formate or formic acid first or sodium methoxide) it is added in reaction flask, nitrogen protection, reaction temperature control is in room temperature to 90 degrees Celsius Range preferably, stirs 1-5 days, and 3-15%12 alkyl thio-methyl propionate is added, and reacts 5-18 hours.Ethanol water is added Catalyst and the raw material for reaction, cold filtration are removed, white or 33.6 grams of thioether of off-white powder product amide are obtained. m.p.:139-195℃
1H NMR is on Bruker 400MHz NMR instrument in CDCl3Middle test (δ, ppm):
0.87(t),1.48-1.52(m),1.52-1.63(m),2.43-2.50(m),2.76-2.87(m),3.23-3.26 (m),7.26(s,CHCl3in CDCl3)
The above is only part embodiment of the invention, is not intended to limit the present invention in any form.It is all Any simple modification, equivalent change and modification to the above embodiments according to the technical essence of the invention, each fall within this hair In bright protection scope.

Claims (4)

1. a kind of long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered, it is characterised in that including with flowering structure:
Wherein R is H, Me, Et, Pr, Bu, Bz；
R1For C1~C8Alkyl, R2For C2~C3Alkyl, R3For C8~C12Alkyl；
Or
Wherein n:1,2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18；
M: 1,2,3,4,5；
R:H, Me, Et, Pr, Bu, OH, O- alkyl；
R3: C8~C12Alkyl；
Or
Wherein n:2,3,4,5,6；
m:1,2,3,4,5；h:6,7,8,9,10,11,12,13,14,15,16,17,18；
R:H, Me, Et, Pr, Bu, OH, O- alkyl；
R3:C8~C12Alkyl；
Or
Wherein n:1,2,3,4,5,6,7,8,9,10,11,12；
M: 1,2,3,4,5；H:2,3,4,5,6,7,8,9,10,11；
R:H, C1-C6Alkyl；
R1: C2-C12Alkyl.
2. a kind of long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered as described in claim 1, it is characterised in that described one kind The long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered is one of following below formula:
R:H, CH3, Et, Pr, Bu, OH, O- alkyl,
Or
R:H, CH3, Et, Pr, Bu, OH, O- alkyl,
Or
R:H, CH3, Et, Pr, Bu, OH, O- alkyl,
Or
R:H, CH3, Et, Pr, Bu, OH, O- alkyl,R1: the alkyl containing 3-8 carbon.
3. the long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered as described in claim 1 is as long-life, high-temperature antioxidative stabilizer Using.
4. the long-acting antioxidative stabilizer resistant to high temperatures of Sulfide-containing Hindered as described in claim 1 plastics, rubber, fiber, coating, paint and Application in petroleum series product.
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