CN106916043A - Solvent-free acid amides synthetic method and its macromolecule antioxidative stabilizer synthesis in apply - Google Patents

Solvent-free acid amides synthetic method and its macromolecule antioxidative stabilizer synthesis in apply Download PDF

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CN106916043A
CN106916043A CN201710217143.1A CN201710217143A CN106916043A CN 106916043 A CN106916043 A CN 106916043A CN 201710217143 A CN201710217143 A CN 201710217143A CN 106916043 A CN106916043 A CN 106916043A
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reaction
solvent
acid amides
sodium
potassium
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毛丽娟
刘树柏
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SHAOXING RUIKANG BIOTECHNOLOGY Co Ltd
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SHAOXING RUIKANG BIOTECHNOLOGY Co Ltd
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Abstract

The present invention discloses solvent-free acid amides synthetic method and its is applied in the synthesis of macromolecule antioxidative stabilizer, synthesize different structure acid amides by 8 reaction expressions and connect thioether high-temperature and long-efficiency antioxidative stabilizer, the target products such as sterically hindered phenol thioether hydridization antioxidant, sterically hindered phenol acid amides kind antioxidant.These acid amides stabilization is bonded different type multifunctional groups hybrid structure antioxidant and is bonded antioxidant comparative structure stabilization with the most carboxylate in market, it is antiacid, alkali resistant, resistant to hydrolysis, environment resistant degradation capability is strong, synergistic antioxidative activities can be good, it is established that performance of new generation more meets the antioxidative stabilizer product of new material development demand.These novel high polymer material antioxidative stabilizer products overcome the similar ester bond in market and connect the ester bond of antioxidative stabilizer and decomposed under acid-base condition, the unstability energy such as facile hydrolysis, the problem that existing market product DSTDP/DLTDP uses release VOCs in the smell and degradable material produced in processing is greatly reducing simultaneously, for novel high polymer material development provides the antioxidative stabilizer provided powerful support for more more options.

Description

Solvent-free acid amides synthetic method and its macromolecule antioxidative stabilizer synthesis in apply
Technical field
The invention belongs to the synthetically prepared field of macromolecule antioxidative stabilizer, more particularly to a kind of solvent-free acid amides synthesis side Method and macromolecule antioxidative stabilizer synthesis in apply.
Background technology
Extensive carboxylic acid amides synthesis mode industrial at this stage is, by carboxylic acyloxy chlorination, then to be reacted with organic amine again, two Step chemical reactive synthesis go out carboxylic acid amides product.Conventional chloride reagent has SOCl2And C2O2Cl2, by urging for DMF or DMAP Change, accelerate the conversion of carboxyl acyl chloride, excessive SOCl in reaction2Or C2O2Cl2The inevitable hydrogen chloride gas of meeting are produced, and unhappy Acyl chlorides smell；Next step carboxyl acyl chloride it is necessary excessive or at least it is quantitative tie up soda acid in the presence of could effectively with organic amine coupling Close reaction and produce carboxylic acid amides product.In this two-step reaction, excess reagent, the smell discharged in reaction, accessory substance etc. is all Although showing that this kind of reaction is effective, cost of material is low, has obvious not chlorine colour circle to protect, cumbersome, three-protection design trouble The shortcomings of.In addition it is also to prepare the another class of carboxylic acid amides generally side that other carboxylic acids are directly reacted by condensation reagent and organic amine Method, common agents have DCC/HOBt, EDCI, BOP, PyBOP, BOP-Cl, FDP, FDPP, DEPBT, PyBr, TBTU, HBPyU, HATU, HAPyU, HDTU, HAPyTU etc., condensation reagent is more expensive in general, and accessory substance is bound to produce simultaneously, to final product Isolate and purify and bring cumbersome.Introduce active group activated carboxyl, then organic amine there is substitution reaction with it and prepare carboxylic acid amides be The conventional preparation method of another carboxylic acid amides, common Acibenzolar has nitro phenyl ester, 2,4,6- trichlorine phenyl esters, pentachlorophenyl ester, five Fluorobenzene ester (PfOH), N-hydroxy-succinamide (HOSu) ester and N- hydroxybenzotriazoles ester (HOBt) etc..General operation step Suddenly it is first to prepare and isolated Acibenzolar, then acid amides, two-step reaction is obtained with amine reaction, it is desirable to which effectively follow-up accessory substance is separated Purification step, high cost.
The content of the invention
Carry out condensation reaction and form the invention reside in methyl esters and organic amine under one kind is catalyzed by solvent-free carboxylate is provided Solvent-free acid amides synthetic method, it has high conversion rate, the characteristics of easy to operate, particularly suitable for environmental protection produce, be mesh Before untill most economical, most convenient, the most environmentally friendly production conversion process for preparing carboxylic acid amides.
To reach above-mentioned purpose, concrete scheme of the invention is as follows：
Solvent-free acid amides synthetic method, the solvent-free acid amides synthetic method synthesizes formula and is：
Wherein, X：S, O, CH2...；
n:2,3,4,5,6,7,8,9,10,11,12,13,14,15,16；
m:2,3,4,5,6...；h:2,3,4,5,6...；
k:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16...；
Cat. sodium formate, sodium acetate, sodium propionate, potassium formate, potassium acetate, potassium propionate, sodium methoxide；
R：H, CH3, Et, n-Pr, n-Bu, t-Bu, Bz...；
Or
Wherein, X, n, m are identical with formula 1；
R1：H, Me, Et, n-Pr, n-Bu, i-Bu, t-Bu,Bz；
R：
R2：With R1It is identical；
Or
(formula 3)；
Wherein, n:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16；
m:2,3,4,5,6,7；
h:0,1,2,3,4,5,6,7,8,9,10,11,12；
X:S,O,CH2；
R:H,Me,Et,Pr,n-Bu,i-Bu,Bz
Or
Wherein, m:1,2,3,4,5；n:0,1,2,3,4,5,67；h:2,3,4,5,6,7；
k:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16；
X:S,O,CH2；
R1:H,Me,Et,n-Pr,n-Bu,i-Bu,
R:OH,Me,Et,i-Pr,t-Bu；
Or
Wherein, n:2,3,4,5,6；m:2,3,4,5,6；
h:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16...；
X:S,O,CH2；R:Me,Et,n-Pr,i-Pr,n-Bu,i-Bu,Bz；
Or
Wherein, n:2,3,4,5,6；
m:2,3,4,5,6；h:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16...；
X:S,O,CH2；
R:Me,Et,n-Pr,i-Pr,n-Bu,i-Bu,Bz；
Or
Wherein, X：S, O, CH2；
m:1,2,3,4,5,6,7,8...；
n:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19...；
R:Me, Et, Pr, Bu, other alkyl；
R1：Me, Et, Pr, Bu, other alkyl, O, OH, O- other chain alkyls,
Or
X：S, O, CH2；
m:1,2,3,4,5,6,7,8...；
n:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19...；
R:Me, Et, Pr, Bu, other alkyl；
R1：Me, Et, Pr, Bu, other alkyl, O, OH, O- other chain alkyls,
Specifically
The first step, methyl acrylate is with mercaptan in solvent-free sodium formate or potassium formate or carboxylic acid sodium or carboxylic acid potassium or sodium methoxide Under catalytic condition beta- thioether methyl esters is obtained by Michael Isosorbide-5-Nitraes-addition reaction；
Second step, organic amine and beta- thioethers methyl ester intermediate are reacted, organic amine carboxylate or it is sodium methoxide catalyzed under, Reaction is completed；
First step reaction temperature control in 0-75 degree Celsius ranges preferably, the reaction time at 1-48 hours preferably. The second step reaction condition temperature control for room temperature to 170 degrees Celsius preferably, solvent-free reaction condition is critically important.
Or
Catalyst sodium formate or sodium acetate or potassium formate or potassium acetate or sodium methoxide are added in carboxylate methyl ester, is protected in nitrogen Shield is lower to add organic amine.After organic amine is added, reaction is heated up and reaches the maximum temperature that reaction is required, second is added after the completion of reaction Alcohol solution or petroleum ether and water mixed liquid, cold filtration obtain solid product.
Or
Beta-12 alkyl (or 8 alkyl) thioether methyl propionate is added in reaction bulb, catalyst sodium formate is subsequently adding Or sodium acetate or potassium formate or potassium acetate or sodium methoxide, hexamethylene diamine, intensification heating stirring 1-7 days, TLC are added under nitrogen protection Or GC monitoring reaction process is until reaction is complete.
Or
Methyl stearate or 16 carbon carboxylate methyl esters (1.0 equivalent) are added in reaction bulb, sodium formate or second is subsequently adding Sour sodium or potassium formate or potassium acetate or sodium methoxide, stir under nitrogen protection temperature control, add 2,2,6,6- tetramethyl -4- ammonia Phenylpiperidines.Heated up after adding and continue to stir 10-96 hours.TLC or GC-MS tracking reaction process is complete until reaction.Add stone Oily ether/water mixed solvent, filters white solid, and vacuum drying provides white solid product.
The product that a kind of solvent-free acid amides synthetic method is made, as the application of macromolecular material antioxidant.
The product that a kind of solvent-free acid amides synthetic method is made is in construction material, organic electronic, plastics, rubber, oil Application in paint, petroleum series product, coating or fiber.
The present invention has synthesized different structure acid amides and has connected thioether high-temperature and long-efficiency antioxygen by 8 reaction expressions listed above Change the target products such as stabilizer, sterically hindered phenol thioether hydridization antioxidant, sterically hindered phenol acid amides kind antioxidant.These acid amides stabilization is bonded not Same type multifunctional groups hybrid structure antioxidant is bonded antioxidant comparative structure and stablizes with the most carboxylate in market, antiacid, alkali resistant, Resistant to hydrolysis, environment resistant degradation capability is strong, and synergistic antioxidative activities can be good, it is established that performance of new generation more meets new material development need The antioxidative stabilizer product asked.It is even anti-that these novel high polymer material antioxidative stabilizer products overcome the similar ester bond in market The unstability energy of oxidation stabilizers, to greatly reducing and discharge VOCs in existing market product DSTDP/DLTDP smells and material Problem, provided powerful support for and the antioxidative stabilizer of more more options for novel high polymer material development is provided.With carboxylate methyl ester The method for preparing carboxylic acid amides with organic amine reaction as initiation material also has been reported that all such reaction all applies different catalysis Agent, enzymatic, metal alkyl highly basic (as PrMgCl, t-BuOK, NaOMe etc.), organic amine directly replaces in big polar solvent Methyl esters is reacted (as DMF, MeOH etc.).Method mentioned above, the gentle yield of enzyme-catalyzed reaction condition is high, other method temperature Height, conversion ratio is different with structure difference, and especially strong base catalyst brings corrosion to reactor.All these methods are all molten Completed in agent medium.Invention reaction carboxylate dislocation catalyst, solvent-free reaction, high conversion rate is simple to operate, Three wastes are produced, and are current environmental protection production optimum conditions.
The present invention is further elaborated below by way of specific embodiment.
Specific embodiment
Embodiment 1
The reaction equation of monoamine and diamine and methyl esters：
n：Natural number；
R:H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, t-Bu, chain alkyl
RCO2Na：HCO2Na, CH3CO2Na etc..It is an important factor that the embodiment computer heating control heats up, and is reacted in length Can turn yellow under time high-temperature condition, product quality declines, and corresponding reaction condition is see following table：Beta- thioethers methyl esters and unitary With binary organic amine condensation reaction under carboxylate catalysis
Annotation：N.a. mean and be not applied to this (not applicable)
Synthesis example methyl acrylate is raw material：
The first step：Methyl acrylate is anti-by Michael Isosorbide-5-Nitraes-addition under solvent-free carboxylate catalytic condition with mercaptan Beta- thioether methyl esters should be obtained, reaction needs to control temperature, stirs at 1-24 hours or so preferably.Second step：Organic amine and sulphur Ether methyl ester intermediate is reacted, and organic amine can be the first amine, the second amine；Organic amine can be an amine, diamines, triamine etc.；It is organic Amine is completed under carboxylate catalysis under the conditions of heating solvent-free reaction, reacts deadline and catalytic amount, and reaction temperature has Close, reaction in optimum temperature range, optimum reacting time conversion ratio up to 85-99%, if methyl esters excess or organic amine mistake Quantitative response can be quantified and completed.Organic multicomponent amine (for example, butanediamine, hexamethylene diamine, triamine etc.) reacts with thioether methyl esters, thioether methyl esters It is preferably excessive, if conversely selection polyamine excess, fully and completely makes troubles to reaction, the partial reaction product amount of polyamine Increase, separates to the complete product of polyamine and brings difficulty.
Or
With carboxylate methyl ester as raw material：
Carboxylate methyl ester is added in reaction bulb, then adds people's sodium formate or sodium acetate or potassium formate or potassium acetate or methyl alcohol Sodium, is dividedly in some parts organic amine under nitrogen protection, controls heating-up temperature.After organic amine is added, in the lowest temperature that reaction is required Degree stirring 3-10 hours, then heats up and reaches the maximum temperature that reaction is required (see each reaction condition form).TLC or GC-MS with Track reaction process, adds ethanol water or petroleum ether and water mixed liquid after the completion of reaction is confirmed, stirring, cooled and filtered is obtained To solid product.Yield：75-99%.
Embodiment 2
3,3'- thioether dipropionic acid methyl esters and unitary and binary organic amine reaction equation
The preparation method of disulfide adipamide：
Beta-12 alkyl (or 8 alkyl) thioether methyl propionate (1 equivalent) is added in reaction bulb, formic acid is subsequently adding Sodium or sodium acetate catalyst, add hexamethylene diamine (0.45-0.49 equivalents) under nitrogen protection, and then heat up heating, TLC or GC- MS tracks reaction process, until reaction is complete.Ethanol water or methanol aqueous solution are added, is recrystallized, cold filtration obtains white Color solid, yield 85-99%.
A. alkyl-beta- disulfide adipamides the m.p. of product two -12:The 133-137 DEG C of alkyl beta- sulphur of product 2 12 Ether adipamide1HNMR tests are completed in NMR instruments Bruker, 400MHz,1H NMR in CD3OD(δ,ppm)：0.87-0.93 (m,6H),1.28-1.35(m,40H),1.35-1.46(m,8H),2.47(t,4),2.55(t,4H),2.78(t,4H),3.23 (t,4H),3.33(bm,CH3OH in CD3OD),4.89(b,H2O in CD3OD)
Mass spectrum (ESI, MS+)：629.51(M+1)+
B. the carbon alkyl-beta- disulfide adipamides m.p. of product two -8:139-141 DEG C of carbon alkyl of product two-8- Beta- disulfide adipamides1HNMR tests are completed in NMR instruments Bruker, 400MHz,1H NMR in CD3OD(δ,ppm)： 0.89-0.95(m,6H),1.30-1.35(m,20H),1.37-1.45(m,8H),2.49(t,4),2.57(t,4H),2.77(t, 4H),3.25(t,4H),3.33(bm,CH3OH in CD3OD),4.89(b,H2O in CD3OD)
Mass spectrum (ESI, MS+)：517.38(M+1)+
Embodiment 3
Dimethyl dicarboxylate and organic mono amine or thioether monoamine reaction equation：
The synthesis condition of the present embodiment：
Embodiment 4
The synthetic reaction equation of the unitary acid amides of amine light stabilizer containing tetramethyl piperidine：
The synthesis condition of the present embodiment：
2,2,6,6- tetramethyl piperidine amine amides of stearic 2,2,6,6- tetramethyl piperidine amine amides or 16 carbon carboxylic acids Preparation method：
Methyl stearate or 16 carbon carboxylate methyl esters (1.0 equivalent) are added in reaction bulb, sodium formate or second is subsequently adding Sour sodium or potassium formate or potassium acetate or sodium methoxide, add 2,2,6,6- tetramethyl -4- amino piperidines under nitrogen protection.After adding 30-160 DEG C of stirring is gradually heating to, TLC or GC-MS tracking reaction process is complete until reaction.Add petroleum ether/water mixing molten Agent necessity can heating stirring 20-90 minutes, cold filtration white solid, vacuum drying, yield 85-97%.
A. product stearic acid piperidines amine amide m.p.:57-61℃
Product stearic acid piperidines amine amide1HNMR tests are completed in NMR instruments Bruker, 400MHz,1H NMR in CDCl3(δ,ppm)：0.89(t,3H),1.15(s,12H),1.20-1.36(m,28H),1.57-1.79(m,4H),1.86(dd, 2H),2.13(t,2H),4.18-4.33(m,1H),5.21-5.27(m,1H),7.27(s,CHCl3in CDCl3)
Mass spectrum (ESI, MS+)：423.43(M+1)+
B. the carbon carboxylic acid piperidin's amine amide m.p. of product 16:65-69℃
The carbon carboxylic acid piperidin's amine amide of product 161H NMR tests are completed in NMR instruments Bruker, 400MHz,1H NMR in CDCl3(δ,ppm)：0.90(t,3H),1.16(s,12H),1.21-1.35(m,24H),1.56-1.77(m,4H),1.86(dd, 2H),2.11(t,2H),4.19-4.30(m,1H),5.20-5.26(m,1H),7.26(s,CHCl3in CDCl3)
Mass spectrum (ESI, MS+)：395.39(M+1)+
Embodiment 5
Synthetic reaction equation containing 2,6- di-t-butyls methyl propionate Yu unitary acid amides：
3- (2, the 6- di-t-butyl -4- phenol) propionic acids or 3- (2, the 6- di-t-butyl -4- benzene of 16 amine of octadecylamine Phenol) propionic acid preparation method：
3- (2,6- di-t-butyl -4- phenol) methyl propionate (1.0 equivalent) is added in reaction bulb, formic acid is subsequently adding Sodium or sodium acetate or potassium formate or potassium acetate or sodium methoxide catalyst and organic amine, rise heating stirring under nitrogen protection, TLC or GC-MS tracks reaction process until reaction is complete.Petroleum ether/water mixed solvent, cold filtration is added to obtain white solid, vacuum is done It is dry, yield 83-96%.
A.3- (2,6- di-t-butyl -4- phenol) propionic acid stearamide m.p.:73-77 DEG C of product 3- (2,6- di-t-butyls- 4- phenol) propionic acid 18- carbon alkane acid amides1HNMR tests are completed in NMR instruments Bruker, 400MHz,1H NMR in CDCl3(δ, ppm)：0.93(t,3H),1.25-1.35(m,48H),1.53-1.57(m,2H),2.49-2.53(t,2H),2.80-2.85(t, 2H),3.19-3.30(t,2H),6.81(s,2H)7.26(s,CHCl3in CDCl3)
Mass spectrum (ESI, MS+)：530.48(M+1)+
B.3- (2,6- di-t-butyl -4- phenol) propionic acid hexadecane acid amides m.p.79-82 DEG C of product 3- (2,6- bis- tertiary fourths Base -4- bydropapacumaric acid 16- carbon alkane acid amides1HNMR tests are completed in NMR instruments Bruker, 400MHz,1H NMR in CDCl3(δ, ppm)：0.95(t,3H),1.27-1.34(m,48H),1.53-1.56(m,2H),2.52(t,2H),2.81(t,2H),3.21 (t,2H),6.82(s,2H),7.27(s,CHCl3in CDCl3)
Mass spectrum (ESI, MS+)：502.47(M+1)+
Embodiment 6
3- (2, the 6- di-t-butyl -4- hydroxyls) benzoic amides or 3- (2, the 6- di-t-butyl -4- benzene of 16 amine of octadecylamine Phenol) propionic acid preparation method：
3- (2,6- di-t-butyl -4- hydroxyl phenols) methyl propionate (1.0 equivalent) is added in reaction bulb, is subsequently adding Sodium formate or sodium acetate or potassium formate or potassium acetate or sodium methoxide catalyst and organic amine, rise heating stirring under nitrogen protection, TLC or GC-MS tracking reaction process is complete until reaction.Methanol/water mixed solvent, cold filtration is added to obtain white solid, very Sky is dried, yield 80-90%.
A.3- (2,6- di-t-butyl -4- hydroxyls) benzoic acid stearamide m.p.:81-84 DEG C of product 3- (the tertiary fourth of 2,6- bis- Base -4- hydroxyls) benzoic acid 18- carbon alkane acid amides1HNMR tests are completed in NMR instruments Bruker, 400MHz,1H NMR in CDCl3 (δ,ppm)：0.95(t,3H),1.26-1.36(m,48H),1.54-1.57(m,2H),3.19-3.33(t,2H),7.57(s, 2H)7.26(s,CHCl3in CDCl3)
Mass spectrum (ESI, MS+)：502.45(M+1)+
B.3- (2,6- di-t-butyl -4- hydroxyls) benzoic acid palmitamide m.p.:86-89 DEG C of product 3- (the tertiary fourth of 2,6- bis- Base -4- hydroxyls) benzoic acid 16- carbon alkane acid amides1HNMR tests are completed in NMR instruments Bruker, 400MHz,1H NMR in CDCl3 (δ,ppm)：0.97(t,3H),1.27-1.36(m,48H),1.57-1.61(m,2H),3.18-3.23(t,2H),7.60(s, 2H)7.26(s,CHCl3in CDCl3)
Mass spectrum (ESI, MS+)：474.43(M+1)+
The present invention set up a whole set of using carboxylate methyl ester small carboxylic acid molecules' salt catalysis under with organic amine in solvent-free bar The effective ways of acid amides are prepared under part.Invention can be used for monamide, and the synthesis of diamides and multiamide product, reaction turns Rate is high, and post processing is easy, and environmental protection is suitable to modern industry environmental protection production.The reaction of this class can put effectively as production Big reaction, catalyst amount is small, and catalyst molecule amount is small, and the carboxylate of especially small-molecular-weight is easy to get, the non-non- highly basic of strong acid, price Cheap nontoxic, post processing is easy, is effective environmental protection chemical production mode.Environmental protection synthetic method of the present invention is specifically for use in The synthesis technique of the thioether high-temperature and long-efficiency antioxidant that all kinds of acid amides are bonded, realizes high conversion, simple to operate, almost three wastes Ideal design.Additionally, we report synthesizing amide thioether product Intermediate beta- thioether methyl propionates herein first Preparation method, this middle preparation is still to be catalyzed to complete mercaptan to methyl acrylate by solvent-free carboxylate Michael Isosorbide-5-Nitraes-addition reaction, conversion ratio is good, is directly used in the next step without post processing.
The exploitation that synthetic method of the present invention is specifically for use in different improved structure stable polymer antioxidative stabilizers is closed Into making the method for preparing acid amides with extensive carboxylic acid in this way compare from methyl esters and shorten conjunction for catalytic material prepares carboxylic acid amides Into route steps, synthetic operation is simplified, eliminate or reduce the three wastes, effectively synthesized what different structure was bonded with acid amides stabilization Macromolecule antioxidative stabilizer.This patent design invention with carboxylate methyl ester as raw material, small carboxylic acid molecules' salt catalysis next step system Standby carboxylic acid amides technical operation is simple, and cost is advantageous, and accessory substance only has methyl alcohol, solvent-free reaction, odorlessness release, purifying products It is easy to separate, and this patented technology especially meets the chemical production engineering of environmentally friendly protection.
The above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, those of ordinary skill in the art are to this hair Other modifications or equivalent that bright technical scheme is made, without departing from the spirit and scope of technical solution of the present invention, All should cover in scope of the presently claimed invention.

Claims (9)

1. carboxylate catalysis is solvent-free by carboxylate methyl ester and organic first amine or the second amine condensation reaction carboxylic acid amides synthetic method, It is characterized in that the solvent-free carboxylate catalysis acid amides synthetic method synthesis formula is：
Wherein, X：S, O, CH2；
n:2,3,4,5,6,7,8,9,10,11,12,13,14,15,16；
m:2,3,4,5,6...；h:2,3,4,5,6...；
k:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16...；
Cat. sodium formate, sodium acetate, sodium propionate, sodium carbonate, potassium formate, potassium acetate,
Potassium propionate, potassium carbonate；
R：H, CH3, Et, n-Pr, i-Pr, n-Bu, t-Bu, Bz, OH, OR1 (R1：
Alkyl)；
Or
Wherein, X, n, m are identical with formula 1；
R1：H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, t-Bu,Bz,
OH, OR3(R3：Alkyl)；
R：
R2：With R1It is identical；
Or
Wherein, n:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16；
m:2,3,4,5,6,7；
h:0,1,2,3,4,5,6,7,8,9,10,11,12；
X:S,O,CH2；
R:H,Me,Et,Pr,n-Bu,i-Bu,Bz
Or
Wherein, m:1,2,3,4,5；n:0,1,2,3,4,5,67；h:2,3,4,5,6,7；
k:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16；
X:S,O,CH2；
R1:H,Me,Et,n-Pr,n-Bu,i-Bu,OH, O- alkyl
R:OH,Me,Et,i-Pr,t-Bu；
Or
Wherein, n:2,3,4,5,6；m:2,3,4,5,6；
h:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16...；
X:S,O,CH2；R:Me,Et,n-Pr,i-Pr,n-Bu,i-Bu,Bz；
Or
Wherein, n:2,3,4,5,6；
m:2,3,4,5,6；
h:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16...；
X:S,O,CH2；
R:Me,Et,n-Pr,i-Pr,n-Bu,i-Bu,Bz；
Or
Wherein, X：S, O, CH2；
m:1,2,3,4,5,6,7,8...；
n:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19...；
R:Me, Et, Pr, Bu, other alkyl；
R1：Me, Et, Pr, Bu, other alkyl, O, OH, O- alkyl,O-
Alkyl；
X：S, O, CH2；
m:1,2,3,4,5,6,7,8...；
n:1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19...；
R:Me, Et, Pr, Bu, other alkyl；
R1：Me, Et, Pr, Bu, other alkyl, O, OH, O- alkyl,。
2. solvent-free acid amides synthetic method as claimed in claim 1, it is characterised in that bag
Include following steps：
The first step, methyl acrylate is with mercaptan in solvent-free carboxylic acid sodium or sodium formate or hydroxide
Under the conditions of sodium or potassium hydroxide catalysed beta- thioether methyl esters is obtained by Michael Isosorbide-5-Nitraes-addition reaction；
Second step, organic amine and beta- thioether methyl ester intermediate condensation reactions, under carboxylic acid sodium or the catalysis of carboxylic acid potassium, without molten Reacted under the conditions of agent and completed.
3. solvent-free acid amides synthetic method as claimed in claim 2, it is characterised in that：The first step mercaptan and acrylic acid first Ester Isosorbide-5-Nitrae-solvent-free the catalytic reaction of addition, reaction temperature temperature is that 0-75 degree celsius temperatures control reaction, and the reaction time is 1-24 Hour.
4. solvent-free acid amides synthetic method as claimed in claim 2, it is characterised in that：The second step carboxylate methyl ester and first Or second amine solvent-free condensation reaction, condition is sodium formate, potassium formate, sodium acetate, potassium acetate, sodium propionate, potassium propionate, carbonic acid , used as catalyst, preferably, solvent-free condensation is this for heating in reaction temperature 25-180 degree Celsius ranges for one of sodium, potassium carbonate The essential condition of patent protection reaction.
5. solvent-free acid amides synthetic method as claimed in claim 1, it is characterised in that comprise the following steps：
Sodium formate or sodium acetate or potassium formate or potassium acetate or NaOH or potassium hydroxide are added in carboxylate methyl ester, in nitrogen Protection cooling is lower to add organic amine, and after organic amine is added, untill reaction is completely, TLC or GC is tracked intensification heating stirring Reaction process.Ethanol water or petroleum ether (60-90 degrees Celsius of boiling point) and water mixed solvent are added after reaction completely, after cooling It is filtrated to get solid product.
6. solvent-free acid amides synthetic method as claimed in claim 1, it is characterised in that comprise the following steps：
Beta-12 alkyl (or 8 alkyl) thioether methyl propionate is added in reaction bulb, catalyst sodium formate or second is subsequently adding Sour sodium or potassium formate or potassium acetate or sodium methoxide, add hexamethylene diamine, then intensification heating stirring 1-5 under nitrogen protection stirring My god, TLC or GC tracking reaction process is until reaction is complete.
7. solvent-free acid amides synthetic method as claimed in claim 1, it is characterised in that comprise the following steps：
Methyl stearate or 16 carbon carboxylate methyl esters are added in reaction bulb, catalyst sodium formate or sodium acetate or first is subsequently adding Sour potassium or potassium acetate or sodium methoxide, under nitrogen protection, control temperature adds 2,2,6,6- tetramethyl -4- amino piperidines.Add Intensification heating stirring is until reaction is complete afterwards.TLC or GC-MS tracking reaction process.Add petroleum ether/water mixed solvent, cooling White solid is filtrated to get, vacuum drying provides product.
8. the sulfide amide product that a kind of solvent-free acid amides synthetic method as claimed in claim 1 is made, as high score The application of sub- material against oxidative agent.Acid amides steric hindrance amine product prepared by solvent-free catalyzing and condensing is used as macromolecular material light stabilization Agent.Sulfide amide steric hindrance amine product prepared by solvent-free catalyzing and condensing is used as the macromolecular material anti-oxidant stabilization of hydridization function synergic Agent.
9. the product that a kind of solvent-free acid amides synthetic method as claimed in claim 1 is made is in construction material, Organic Electricity Application in son, plastics, rubber, paint, petroleum series product, coating or fiber.
CN201710217143.1A 2016-12-07 2017-04-05 Solvent-free acid amides synthetic method and its macromolecule antioxidative stabilizer synthesis in apply Pending CN106916043A (en)

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