CN106316877B - A kind of preparation method of dicyclohexyl terephthalamide - Google Patents
A kind of preparation method of dicyclohexyl terephthalamide Download PDFInfo
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Abstract
The present invention relates to amide-type nucleator field, disclose a kind of N, the preparation method of N ' dicyclohexyl terephthalamides, wherein, this method is included in the presence of Anhydrous potassium carbonate and pyridine, dimethyl terephthalate (DMT) and cyclohexylamine are reacted, generate the N shown in formula (I), N ' dicyclohexyl terephthalamides；N shown in formula (I) prepared by the inventive method, N ' dicyclohexyl terephthalamides, easily separated, yield is higher, and purity is good, is advantageous to environmental protection, suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the preparation method of amide-type nucleator, in particular it relates to a kind of N, N '-dicyclohexyl terephthaldehyde
The preparation method of acid amides.
Background technology
In recent years, the tough-increased and reinforced modification of polypropylene (PP), which has become, makes Engineering of Polypropylene, functionalization, becomes more meticulous
Important means.PP can form α, β, γ, δ and intend the different crystal forms such as six sides at different conditions.Alpha-crystal form is monoclinic form, is most
A kind of stable crystal formation also most easily formed, it is this crystal formation substantially in the case of usual processing.Beta crystal is thermodynamically accurate
Stable crystal formation, could be generated only under specific crystallization condition or in the presence of beta nucleater, and stability is remote not
Such as alpha-crystal form.But Beta-crystalline polyacrylic, because the special structure of its β spherocrystal makes obscurity boundary, platelet is by spherocrystal center or parallel
Assemble bunchy, then outwards branched growth or helical form are then branched to outgrowth, so not having obvious boundary between β spherocrystals
Face, thus beta-crystal polypropylene has preferable toughness and draftability.If the alpha-crystal form in PP is completely or partially transformed into β crystalline substances
Type, it is likely that overcome the problem of impact property existing for alpha-crystal form PP is poor, heat distortion temperature is low.Research finds that β crystalline phases PP has
There are preferable room temperature and impact strength at low temperature, show higher toughness and ductility, make PP on manufacture anti-impact engineering plastics
There is certain application prospect, with the development of modification technology, Beta-crystalline polyacrylic is increasingly valued by people.Therefore, prepare
The PP products of high beta-crystalline form content, turn into one important problem of polymeric material field in recent years, the application of Beta-crystalline polyacrylic
Prospect promotes the research and development of beta nucleater.
The method that can obtain β-PP being currently known mainly has 3 kinds：(1) temperature gradient method；(2) shearing orientation；(3) add
Enter beta nucleater.First two method limitation in actual production process is big, it is difficult to implements, the spy of addition energy inductive formation beta crystal
Effect nucleator is to obtain high level beta crystal approach the most feasible.
It has recently been found that some amides compounds can be used as β-brilliant nucleator and have good inducing effect.Such as N,
N '-dicyclohexyl terephthalamide can prepare high beta-crystal polypropylene as β-brilliant nucleator.And it is important polypropylene processing
The active component of auxiliary agent-beta nucleater.Diamide nucleator has synthesis conveniently, good with PP compatibilities, can be purified
Thing, the advantages that heat endurance is good, study mechanism and new nucleator MOLECULE DESIGN are not only convenient for, and it is equal to homopolymerization PP and copolymerization PP
Good beta nucleater toughening effect is shown, therefore is had broad application prospects and development potentiality.
Patent US6235823B1 discloses prepares amide-type polypropylene beta crystal nucleating agent by dicarboxylic acids and monoamine
Method, this method are included in atent solvent, at a temperature of about 60-200 DEG C, make dicarboxylic acids and monoamine reaction 2-8 small
When, accelerate to react using activator phosphorus pentoxide, polyphosphoric acid, triphenyl phosphite etc. in the reaction, however, passing through reality
Issue after examination and approval it is existing, the amide-type polypropylene beta crystal nucleating agent for using above-mentioned patented method to prepare need under elevated pressure conditions (1MPa with
On) reacted, thus there is very high requirement to production equipment, and so as to which large-scale industrial production can not be carried out, Er Qiexu
Expensive catalysts and solvents are wanted, it is not economical enough.In addition, this method will use activator phosphorus pentoxide, polyphosphoric acid, phosphorous acid
Triphenylmethyl methacrylate etc., it is unfavorable for separating, is also unfavorable for environmental protection.
CN102040532 overcomes to be prepared polypropylene beta crystal nucleating agent and needs to be reacted under high pressure in the prior art, public
A kind of preparation method of polypropylene beta crystal nucleating agent at ambient pressure has been opened, this method is included in the presence of catalysts and solvents,
Under the conditions of existing for catalyst, dicarboxylic acids is contacted with amine and carries out condensation reaction, the amine is primary amine or secondary amine, using this
Method can be such that primary amine or secondary amine fully reacts at ambient pressure, so that amide-type polypropylene beta crystal nucleating agent is made.But should
The catalyst that method needs to use is still the one or more of phosphorus pentoxide, polyphosphoric acid, triphenyl phosphite, and catalyst
Dosage is big, close to the dosage of reactant amine.Such as：The mol ratio of reactant amine and catalyst is 1：0.8-1.2, reactant amine with
The mol ratio of reactant dicarboxylic acids is 2-3.5：1.This is unfavorable for the separation of product, is also unfavorable for environmental protection.
CN101948401, which is referred to, is dissolved in paraphthaloyl chloride in organic solvent, then molten to this under stirring and cooling
The mixture of sodium hydrate aqueous solution and cyclohexylamine is added dropwise in liquid, drop, which finishes, is stirred for 30min, finally filters, and washing filter cake obtains
Target product.This method has compared with other method does not have to excessive or excessive seldom and yield without using organic acid binding agent, amine
The advantages that high, but reactant paraphthaloyl chloride has corrosivity, and facile hydrolysis is into terephthalic acid (TPA) and hydrogen chloride, and it is unfavorable
In environmental protection.
Therefore, preparing how environmentally friendlyly can be still urgently to study and send out as the amides compound of beta crystal-type nucleater
The problem of exhibition.
The content of the invention
The invention aims to solve prior art to prepare N, existing for N '-dicyclohexyl terephthalamide product
Problem, such as the activators such as a large amount of phosphorus pentoxides, polyphosphoric acid, triphenyl phosphite are used by raw material of terephthalic acid (TPA), from
And the higher and inadequate environmental issue of the cost during isolating and purifying is caused, and there is corrosion by raw material of paraphthaloyl chloride
Property, and the problem of facile hydrolysis is into terephthalic acid (TPA) and hydrogen chloride, there is provided a kind of new N, N '-dicyclohexyl terephthalamide
Preparation method.
To achieve these goals, a kind of N of present invention offer, the preparation method of N '-dicyclohexyl terephthalamide, its
In, this method is included in the presence of Anhydrous potassium carbonate and pyridine, and dimethyl terephthalate (DMT) and cyclohexylamine are reacted, raw
Into the N shown in formula (I), N '-dicyclohexyl terephthalamide；
N by structural formula provided by the invention for (I), the preparation method of N '-dicyclohexyl terephthalamide, without
Accelerate the anti-of dimethyl terephthalate (DMT) and cyclohexylamine using activators such as phosphorus pentoxide, polyphosphoric acid, triphenyl phosphites
Should, be advantageous to isolate and purify product, reduce cost, or without using the Butyltriphenylphosphonium chloride with corrosivity, facile hydrolysis,
Be advantageous to the stabilization of production safety and product quality.The inventive method product is easily separated, is advantageous to environmental protection, suitable for extensive
Industrial production.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of N, the preparation method of N '-dicyclohexyl terephthalamide, wherein, this method is included in
In the presence of Anhydrous potassium carbonate and pyridine, dimethyl terephthalate (DMT) and cyclohexylamine are reacted, generate the N shown in formula (I),
N '-dicyclohexyl terephthalamide；
According to the present invention, dimethyl terephthalate (DMT) and cyclohexylamine are reacted preferably in Anhydrous potassium carbonate and pyridine
In the presence of carry out, and the mol ratio of the initial charge of the dimethyl terephthalate (DMT) and the Anhydrous potassium carbonate can be 1：
0.07-0.2, preferably 1：0.1-0.15.
According to the present invention, dimethyl terephthalate (DMT) and cyclohexylamine are reacted preferably in Anhydrous potassium carbonate and pyridine
In the presence of carry out, and the mol ratio of the initial charge of the dimethyl terephthalate (DMT) and the pyridine can be 1：2-12,
Preferably 1：2-7.
According to the present invention, dimethyl terephthalate (DMT) and cyclohexylamine are reacted preferably in Anhydrous potassium carbonate and pyridine
In the presence of carry out, and the mol ratio of the initial charge of the dimethyl terephthalate (DMT) and cyclohexylamine can be 1：2-10, it is excellent
Elect 1 as:2-5.
According to the present invention, dimethyl terephthalate (DMT) and the condition that cyclohexylamine is reacted are included：In normal pressure or pressing
Under the conditions of power is 0.1-0.2MPa, the heating medium temperature of reaction can be 65-170 DEG C；Preferably, it is in normal pressure or in pressure
Under the conditions of 0.1-0.11MPa, the heating medium temperature of reaction is 127 DEG C -140 DEG C.Specifically, in the present invention, when will be to benzene
When dicarboxylic acid dimethyl ester is reacted with cyclohexylamine, it is to be ensured that the temperature of reaction is more than or equal in course of reaction the methanol generated
Boiling point.According to the present invention, " heating medium temperature of reaction " is equal to " reaction temperature ", i.e. in the present invention, example
Such as, when the heating medium temperature of reaction is 100 DEG C, it can be understood as the reaction temperature of the reaction is also 100 DEG C；Therefore, instead
The temperature answered can be 65-170 DEG C.
And when the heating medium temperature of reaction reaches more than the boiling point (that is, 65 DEG C) of methanol, it is necessary to add entrainer, this
When, it is necessary to make reaction temperature be more than or equal to the entrainer boiling point.Therefore, in the present invention, in practical operation, reaction
Temperature with during the course of the reaction remove dereaction generation lower boiling by-product alcohol HOR1(such as the boiling point bp65 of methanol
DEG C) and increase；In the present invention, it is preferred to the reaction is carried out under the conditions of simple distillation or rectifying, to remove during the course of the reaction
Remove the methanol of generation.
According to the present invention, the entrainer can be the solvent that boiling point is 80-176 DEG C；Preferably, the entrainer is selected from
One or more in pyridine, cyclohexylamine, trimethylbenzene, dimethylbenzene, toluene, benzene and N,N-dimethylformamide；It is highly preferred that institute
State entrainer and be selected from pyridine and/or cyclohexylamine；Wherein, the boiling point of the pyridine is 115.2 DEG C, and the boiling point of the cyclohexylamine is
134 DEG C, the trimethylbenzene can be mesitylene and/or pseudocumene, and the boiling point of the mesitylene can be 164-165
DEG C, the boiling point of the pseudocumene can be 169.4 DEG C, the dimethylbenzene include paraxylene, ortho-xylene, meta-xylene and
The dimethylbenzene of conventional mixed isomers, wherein, the boiling point of paraxylene is 138 DEG C, 143-145 DEG C of the boiling point of ortho-xylene,
138-139 DEG C of the boiling point of meta-xylene, 137-140 DEG C of the boiling point of the dimethylbenzene of conventional mixed isomers, the boiling of the toluene
Point is 110.6 DEG C, and the boiling point of the benzene is 80.1 DEG C, and the boiling point of the DMF is 152.8 DEG C.In addition,
In the present invention, when the entrainer is pyridine and/or cyclohexylamine, then in the reaction, the pyridine and cyclohexylamine being firstly added
As the accelerator that can accelerate reaction, when pyridine is as accelerator, the used in amounts of pyridine will be according to above-mentioned " described to benzene two
The mol ratio of formic acid dimethyl ester and the initial charge of the pyridine can be 1：2-12, preferably 1：2-7 " is limited to add；
When cyclohexylamine is as accelerator, the used in amounts of cyclohexylamine will according to it is above-mentioned " dimethyl terephthalate (DMT) and cyclohexylamine
The mol ratio of initial charge can be 1：2-10, preferably 1:2-5 " is limited to add；And ought add during the course of the reaction
When pyridine and cyclohexylamine are used as entrainer, addition, feed postition and the addition time of the entrainer are referring particularly to following
Description carry out.
According to the present invention, dimethyl terephthalate (DMT) and the reactor that cyclohexylamine is reacted are not particularly limited, can
The conventional selection of those skilled in the art is thought, it is for instance possible to use conventional glass flask is as reactor；And in this hair
In bright, the thermal source required for controlling the reaction temperature of reaction is not particularly limited, can be with known to those skilled in the art
Various methods, for example, in the present invention, the reactor can be carried out in medium such as water-bath or oil bath is heated, and work as water-bath
Or the temperature of oil bath can make reaction temperature control in 65 DEG C to azeotropic point of temperature when being 65-170 DEG C, preferably 127-140 DEG C
Degree, for example, 65-100 DEG C of temperature range can be provided by water vapour bath or oil bath heating, 100-170 DEG C of temperature range
It can be provided by pressurized steam bath or oil bath heating.
In accordance with the present invention it is preferred that in normal pressure or under the conditions of pressure is 0.1-0.11MPa, the heating medium temperature of reaction
Spend at 127 DEG C~140 DEG C, entrainer is added when reaction temperature reaches more than the boiling point (that is, 65 DEG C) of methanol, or described
Reaction carries out adding entrainer in 5-7 hours backward reaction solution, and except dereaction generates by way of distillation or azeotropic distillation
Methanol, structural formula can be further improved under the preferred scheme as product N, N '-dicyclohexyl terephthaldehyde shown in (I)
The yield and purity of acid amides.
In accordance with the present invention it is preferred that the entrainer divides 5-7 addition, and the adjacent time interval added twice is 1-6
Hour, preferably 3-6 hours, more preferably 4-5 hours, and relative to 1 mole of dimethyl terephthalate (DMT), the azeotropic
The addition of agent can be 60mL/ times -600mL/ times, and it is (I) that each addition of increase entrainer, which is advantageous to improve structural formula,
The yield and purity of shown product N, N '-dicyclohexyl terephthalamide.
According to the present invention, the preferred embodiment of another kind plus entrainer is that reaction begins to use simple distillation device or rectifying
Device, after reacting 5-7 hours under the conditions of simple distillation or rectifying, entrainer continuous stream under the conditions of simple distillation or rectifying
It is added in reaction solution, 1 mole of dimethyl terephthalate (DMT) when starting relative to reaction, flow acceleration is 10-200mL/ hours,
It it is 10-30 hours between the stream added-time.
It will be understood by those skilled in the art that after entrainer is added, the temperature of reaction is controlled to be more than or equal to altogether
The boiling point of agent is boiled, when adding by several times, when adding entrainer, can not cool, the temperature of reaction can also be cooled to azeotropic
Under the boiling point of agent, add entrainer, be preferably cooled in laboratory under the boiling point of entrainer, needed for general cooling when
Between be no more than half an hour, preferably 0.1-0.5 hours；The continuous stream added-time, reaction should entrainer boiling point and entrainer with it is anti-
Carried out between the boiling point for the azeotropic mixture that the alcohol that should be generated is formed, flow acceleration can be according to reaction speed, the species of entrainer and use
Measure to adjust.The mode that entrainer continuous stream under the conditions of simple distillation or rectifying is added to reaction solution is particularly suitable for extensive life
Production.
According to the present invention, in order that above-mentioned preferred scheme preferably steadily lasting can be carried forward, reaction starts to make
By the use of " knockout " of the upper end equipped with condenser pipe as simple distillation device, " knockout ", which refers to bottom, the enlightening of piston switch
Amp- Stark apparatus (Dean and Stark apparatus with a stopcock at the lower end).
According to the present invention, it will be understood by those skilled in the art that in order to obtain the higher structural formula of purity as (I) institute
The N shown, N '-dicyclohexyl terephthalamide, after the inventive method is preferably also included in reaction terminating, including two by addition
Toluene carries out distillation post processing, so as to by structural formula be (I) shown in N, N '-dicyclohexyl terephthalamide institute after reaction
Obtain and separated in mixture, wherein, in the present invention, the dimethylbenzene can be paraxylene, ortho-xylene, meta-xylene
Or the dimethylbenzene of mixed isomers.It is the N shown in (I) by structural formula, N '-dicyclohexyl terephthalamide is obtained by after reaction
The method separated in mixture, including Anhydrous potassium carbonate, pyridine, the unreacted cyclohexylamine that will be reacted in gained mixture
With and a small amount of intermediate product, from reaction gained mixture in remove, for removing method without particular/special requirement, can use
The thinkable various methods of those skilled in the art institute, in the present invention, the method that preferably first passes through simple distillation, rectifying is more excellent
The method that choosing adds xylenes agent distillation, the volatility chemical combination such as the methanol, pyridine, unreacted cyclohexylamine of generation will be reacted
Thing removes from reaction gained mixture, then the method by washing, filtering, centrifuging or extracting is by Anhydrous potassium carbonate, pyrrole
Pyridine is removed from reaction gained mixture, and finally by the method for recrystallization, a small amount of intermediate product is removed from product.
The present invention will be described in detail by way of examples below.In following examples, infrared spectrometric analyzer is purchased from
Company of Thermo Fisher Scintific companies of U.S. model Nicolet Nexus 470, for analyzing raw material to benzene two
The ester carbonyl group of formic acid dimethyl ester and the amidocarbonylation of product N, N '-dicyclohexyl terephthalamide；
Raw material dimethyl terephthalate (DMT) (chemistry is pure), pyridine (analysis is pure), cyclohexylamine (analysis is pure), dimethylbenzene (analysis
Pure, mixed isomers) etc. be purchased from the commercial reagent product of Chemical Reagent Co., Ltd., Sinopharm Group；Potassium carbonate (chemistry is pure) is purchased from
The commercial reagent product of Tianjin company of recovery fine chemistry industry research institute；DMF (analysis is pure) is purchased from the commercial reagent of Beijing Chemical Plant
Product.
Embodiment 1
The embodiment is used to illustrate N provided by the invention, the preparation method of N '-dicyclohexyl terephthalamide, at this
In embodiment, accelerate reaction with pyridine and potassium carbonate, and be used as entrainer by the use of pyridine and cyclohexylamine.
At ambient pressure, with condenser, knockout, agitator 100mL three neck round bottom flask in add 9.42g to benzene two
Formic acid dimethyl ester, 22.52g cyclohexylamine, 25mL pyridines and 0.69g potassium carbonate；Then oil bath is controlled in medium oil bath is heated
Temperature is 127 DEG C, reacts 30h, and knockout collects the cut distilled out；
Wherein, during the course of the reaction, entrainer pyridine and cyclohexylamine are added when reaction temperature reaches more than 65 DEG C, and is divided
Add pyridine 6 times, add 5mL every time, while add cyclohexylamine 6 times, add about 21g every time, it is adjacent to add pyridine or ring twice
The time interval of hexylamine is 5 hours；After reaction terminates, filter, water washing and precipitating, drying, as a result obtain 12.6g N, the rings of N '-two
Hexyl terephthalamide, yield is 79.1 weight %, and purity is good (seeing below infrared spectrum analysis), in whole preparation process
Beneficial to environmental protection；And
IR (KBr tablettings, cm-1)：3318 (υ NH), 3080-3020 (υ Ф-H), 2937,2852,1626 (υ-HNC=O),
1540,1501,1447,865,843.
Comparative example 1-1
N, N '-dicyclohexyl terephthalamide are prepared according to method same as Example 1, institute's difference is,
The dosage of potassium carbonate is 0.17g；
As a result 7.86g N is obtained, N '-dicyclohexyl terephthalamide, yield is 56.4 weight %.
Comparative example 1-2
N, N '-dicyclohexyl terephthalamide are prepared according to method same as Example 1, institute's difference is,
The dosage of potassium carbonate is 0.34g；
As a result 7.86g N is obtained, N '-dicyclohexyl terephthalamide, yield is 54.1 weight %.
Comparative example 1-3
N, N '-dicyclohexyl terephthalamide are prepared according to method same as Example 1, institute's difference is,
The dosage of potassium carbonate is 1.04g；
As a result 7.60g N is obtained, N '-dicyclohexyl terephthalamide, yield is 47.7 weight %.
Comparative example 1-4
N, N '-dicyclohexyl terephthalamide are prepared according to method same as Example 1, institute's difference is,
The dosage of dimethyl terephthalate (DMT) is 9.09g, and the dosage of potassium carbonate is 0.34g；
In course of reaction, divide 9 times and add pyridine, add 5mL every time, while add cyclohexylamine 9 times, add about 20g every time；
As a result 7.86g N is obtained, N '-dicyclohexyl terephthalamide, yield is 51.1 weight %.
Comparative example 1-5
N, N '-dicyclohexyl terephthalamide are prepared according to method same as Example 1, institute's difference is,
The dosage of dimethyl terephthalate (DMT) is 9.78g, and the dosage of potassium carbonate is 1.37g；
In course of reaction, divide 10 times and add pyridine, add 5mL every time, while add cyclohexylamine 10 times, add every time about
22g；
As a result 7.86g N is obtained, N '-dicyclohexyl terephthalamide, yield is 46.7 weight %.
Embodiment 2
The embodiment is used to illustrate N provided by the invention, the preparation method of N '-dicyclohexyl terephthalamide, at this
In embodiment, accelerate reaction with pyridine and potassium carbonate, entrainer is used as by the use of cyclohexylamine.
Under 0.1MPa, with condenser, knockout, agitator 100mL three neck round bottom flask in add 9.42g to benzene
Dicarboxylic acid dimethyl ester, 22.52g cyclohexylamine, 12mL pyridines and 0.69g potassium carbonate；Then oil bath is controlled in medium oil bath is heated
Temperature be 140 DEG C, react 30h, knockout collects the cut that distills out；
Wherein, during the course of the reaction, after reaction 5 hours, divide 6 times and add cyclohexylamine, add about 21g every time, it is adjacent
The time interval for adding cyclohexylamine twice is about 4.2 hours；After reaction terminates, filter, water washing and precipitating, drying, as a result obtain
12.7g N, N '-dicyclohexyl terephthalamide, yield are 79.8 weight %, and purity is good (sees below infrared spectrum point
Analysis), environmental protection is beneficial in whole preparation process；And
IR (KBr tablettings, cm-1)：3318 (υ NH), 3080-3020 (υ Ф-H), 2937,2850,1626 (υ-HNC=O),
1540,1501,1447,865,843.
Comparative example 2-1
N, N '-dicyclohexyl terephthalamide are prepared according to method same as Example 2, institute's difference is,
The dosage of pyridine is 25mL；
As a result 8.37g N is obtained, N '-dicyclohexyl terephthalamide, yield is 52.5 weight %.
Comparative example 2-2
N, N '-dicyclohexyl terephthalamide are prepared according to method same as Example 2, institute's difference is,
The dosage of pyridine is 25mL；In course of reaction, divide 4 times and add cyclohexylamine, add about 21g every time；
As a result 8.37g N is obtained, N '-dicyclohexyl terephthalamide, yield is 54.4 weight %.
Embodiment 3
The embodiment is used to illustrate N provided by the invention, the preparation method of N '-dicyclohexyl terephthalamide, at this
In embodiment, accelerate reaction with pyridine and potassium carbonate, by the use of cyclohexylamine as entrainer, reaction is used after terminating and adds xylenes
The method separation product of agent distillation.
At ambient pressure, with condenser, knockout, agitator 100mL three neck round bottom flask in add 9.42g to benzene two
Formic acid dimethyl ester, 22.52g cyclohexylamine, 25mL pyridines and 0.69g potassium carbonate；Then oil bath is controlled in medium oil bath is heated
Temperature is 135 DEG C, reacts 30h, and knockout collects the cut distilled out；
During the course of the reaction, divide 6 times and add cyclohexylamine, and distill partial reaction liquid in 135 DEG C of the temperature of oil bath,
About 21g is added every time, about 4 hours between the adjacent time for adding cyclohexylamine twice；
After reaction 30 hours, dimethylbenzene is added, and distills partial reaction liquid in 140 DEG C of the temperature of oil bath, is divided 2 times
Dimethylbenzene is added, adds 50mL every time, the adjacent time interval for adding dimethylbenzene twice is about 5 hours；
After reaction terminates, solvent is recovered under reduced pressure, adds water, filters, water washing and precipitating, the N of drying, as a result acquisition 14.08g, N '-
Dicyclohexyl terephthalamide, yield is 88.4 weight %, and purity is good (seeing below infrared spectrum analysis), entirely prepares
It is beneficial to environmental protection in journey；And
IR (KBr tablettings, cm-1)：3318 (υ NH), 3080-3020 (υ Ф-H), 2937,2851,1626 (υ-HNC=O),
1540,1501,1447,865,843.
Comparative example 3-1
N, N '-dicyclohexyl terephthalamide are prepared according to method same as Example 3, institute's difference is,
It is added without potassium carbonate；After reaction 30 hours, divide 4 times and add dimethylbenzene (analyzing pure, mixed isomers), add 25mL, phase every time
The adjacent time interval for adding dimethylbenzene twice is 2.5 hours；
As a result 11.50g N is obtained, N '-dicyclohexyl terephthalamide, yield is about 72.2 weight %, and purity is not so good as
Embodiment 1 (sees below infrared spectrum analysis)；And
IR (KBr tablettings, cm-1)：It is consistent with embodiment 3, but have ester carbonyl group characteristic absorption small in 1718 (υ-OC=O)
Peak, its peak height are about the 8.8% of amidocarbonylation (υ-HNC=O) peak height.
Comparative example 3-2
N, N '-dicyclohexyl terephthalamide are prepared according to method same as Example 3, institute's difference is,
It is added without pyridine；After reaction 30 hours, divide 4 times and add dimethylbenzene, add 25mL, the adjacent time for adding dimethylbenzene twice every time
At intervals of 2-3 hours；
As a result 11.79g N is obtained, N '-dicyclohexyl terephthalamide crude product, purity is poor, infrared spectrum analysis
(KBr tablettings, cm-1) containing impurity ester carbonyl group characteristic absorption peak in the crude product, its peak height 1718 (υ-OC=O) is about amidocarbonylation
1626 (υ-HNC=O) 28 weight %, yield are less than 73 weight %.
Embodiment 4
The embodiment is used to illustrate N provided by the invention, the preparation method of N '-dicyclohexyl terephthalamide, at this
In embodiment, using DMF (DMF) solvent, accelerate reaction with pyridine and potassium carbonate, with pyridine and cyclohexylamine
As entrainer.
At ambient pressure, with condenser, knockout, agitator 100mL three neck round bottom flask in add 14.13g to benzene
Dicarboxylic acid dimethyl ester, 33.78g cyclohexylamine, 12mL pyridines and 1.03g potassium carbonate, add 5mL DMF.Then in heating medium
The temperature that oil bath is controlled in oil bath is 140 DEG C, reacts 30h, and knockout collects the cut distilled out；
Wherein, during the course of the reaction, after reaction 7 hours, divide 6 times and add cyclohexylamine, add about 32g every time, it is adjacent
The time interval for adding cyclohexylamine twice is about 4.5 hours；Reaction adds 6mL pyridines 1 time after 18 hours；
After reaction terminates, solvent is recovered under reduced pressure, obtains crude product 23.8g, add water, filter, water washing and precipitating, drying, as a result obtain
17.34g N, N '-dicyclohexyl terephthalamide, yield is 70.4 weight %, and purity is good, sharp in whole preparation process
In environmental protection.
Embodiment 5
The embodiment is used to illustrate N provided by the invention, the preparation method of N '-dicyclohexyl terephthalamide, at this
In embodiment, using DMF (DMF) solvent, accelerate reaction with pyridine and potassium carbonate, by the use of cyclohexylamine as altogether
Boil agent.
At ambient pressure, with condenser, knockout, agitator 100mL three neck round bottom flask in add 14.13g to benzene
Dicarboxylic acid dimethyl ester, 33.78g cyclohexylamine, 12mL pyridines and 1.03g potassium carbonate, add 5mL DMF.Then in heating medium
The temperature that oil bath is controlled in oil bath is 140 DEG C, reacts 30h, and knockout collects the cut distilled out；
During the course of the reaction, after reaction 5 hours, divide 6 times and add cyclohexylamine, add about 32g every time, it is adjacent to add twice
The time interval for entering cyclohexylamine is about 5 hours；
After reaction terminates, solvent is recovered under reduced pressure, obtains crude product 23.8g, add water, filter, water washing and precipitating, drying, as a result obtain
17.34g N, N '-dicyclohexyl terephthalamide, yield is 72.6 weight %, and purity is good, sharp in whole preparation process
In environmental protection.
Embodiment 6
The embodiment is used to illustrate N provided by the invention, the preparation method of N '-dicyclohexyl terephthalamide, at this
In embodiment, using DMF (DMF) solvent, accelerate reaction with pyridine and potassium carbonate, made with cyclohexylamine and DMF
For entrainer.
At ambient pressure, with condenser, knockout, agitator 100mL three neck round bottom flask in add 14.13g to benzene
Dicarboxylic acid dimethyl ester, 33.78g cyclohexylamine, 12mL pyridines and 1.03g potassium carbonate, add 5mL DMF；Then in heating medium
The temperature that oil bath is controlled in oil bath is 140 DEG C, reacts 30h, and knockout collects the cut distilled out；
During the course of the reaction, divide 6 times and add cyclohexylamine, add about 32g every time, it is adjacent to add twice between the time of cyclohexylamine
Every about 5 hours；Reaction adds 10mL DMF 1 time after 8 hours；
After reaction terminates, solvent is recovered under reduced pressure, adds water, filters, water washing and precipitating, the N of drying, as a result acquisition 17.34g, N '-
Dicyclohexyl terephthalamide, yield is 71.9 weight %, and purity is good, and environmental protection is beneficial in whole preparation process.
Can be seen that from above-described embodiment 1-6 and comparative example use the structural formula provided by the invention N for (I), N '-
The preparation method of dicyclohexyl terephthalamide, without using phosphorus pentoxide, polyphosphoric acid, phosphorous acid three in preparation process
The activators such as phenyl ester accelerate the reaction of dimethyl terephthalate (DMT) and cyclohexylamine, are advantageous to isolate and purify product, reduce into
This, or without using the Butyltriphenylphosphonium chloride with corrosivity, facile hydrolysis, is advantageous to the steady of production safety and product quality
Determine, and yield is higher, purity is good, is advantageous to environmental protection, suitable for large-scale industrial production.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. the preparation method of a kind of N, N '-dicyclohexyl terephthalamide, it is characterised in that this method is included in Carbon Dioxide
In the presence of potassium and pyridine, dimethyl terephthalate (DMT) and cyclohexylamine are reacted, generate the N shown in formula (I), the rings of N '-two
Hexyl terephthalamide；
Wherein, the mol ratio of the initial charge of the dimethyl terephthalate (DMT), the Anhydrous potassium carbonate and the pyridine
For 1：0.07-0.2：2-12.
2. according to the method for claim 1, wherein, the dimethyl terephthalate (DMT) feeds intake with the initial of the cyclohexylamine
The mol ratio of amount is 1：2-10.
3. the method according to claim 11, wherein, the dimethyl terephthalate (DMT), the Anhydrous potassium carbonate, the pyrrole
The mol ratio of the initial charge of pyridine and the cyclohexylamine is 1：0.1-0.15：2-7：2-5.
4. according to the method for claim 1, wherein, the condition of the reaction includes：It is 0.1-0.2MPa conditions in pressure
Under, the heating medium temperature of reaction is 65 DEG C -170 DEG C.
5. according to the method for claim 4, wherein, the condition of the reaction includes：It is 0.1-0.11MPa conditions in pressure
Under, the heating medium temperature of the reaction is 127 DEG C -140 DEG C.
6. according to the method for claim 5, wherein, the heating medium temperature that this method is additionally included in reaction reaches methanol
Entrainer is added when more than boiling point, or entrainer is added after the reaction carries out 5-7 hours, and makes to add after entrainer is added
Heat medium temperature is more than or equal to the boiling point of the entrainer.
7. according to the method for claim 6, wherein, the entrainer divides 5-7 addition, and the adjacent time added twice
At intervals of 1-6 hours, and relative to 1 mole of the dimethyl terephthalate (DMT) inventory, the addition of the entrainer
For 60mL/ times -600mL/ times.
8. according to the method for claim 7, wherein, the adjacent time interval added twice is 4-5 hours.
9. according to the method for claim 7, wherein, the entrainer is selected from pyridine, cyclohexylamine, trimethylbenzene, dimethylbenzene, first
One or more in benzene, benzene and N,N-dimethylformamide.
10. according to the method for claim 9, wherein, the entrainer is selected from pyridine and/or cyclohexylamine.
11. according to any described method in claim 1-10, wherein, this method is carried out under conditions of being additionally included in distillation.
12. according to the method described in claim 11, wherein, this method is carried out under conditions of being additionally included in rectifying.
13. the method according to claim 11, wherein, after methods described is additionally included in reaction terminating, by addition to two
Toluene, ortho-xylene, the dimethylbenzene of meta-xylene or mixed isomers carry out distillation post processing, using the N by structural formula as (I),
N '-dicyclohexyl terephthalamide is separated after reaction in the mixture of gained.
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| CN101948401A (en) * | 2010-08-20 | 2011-01-19 | 洛阳市中达化工有限公司 | Synthesis method of N,N-dicyclohexyl terephthalamide |
| CN102898724A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Miniaturization amide type beta-polypropylene nucleating agent, preparation method thereof and polypropylene material |
| WO2014077324A1 (en) * | 2012-11-16 | 2014-05-22 | 日産化学工業株式会社 | Polyglycolic acid resin composition |
| CN104211613A (en) * | 2013-06-03 | 2014-12-17 | 中国石油化工股份有限公司 | Production method for amide nucleating agent |
| JP6279378B2 (en) * | 2014-03-27 | 2018-02-14 | 日野自動車株式会社 | Roof spoiler |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101948401A (en) * | 2010-08-20 | 2011-01-19 | 洛阳市中达化工有限公司 | Synthesis method of N,N-dicyclohexyl terephthalamide |
| CN102898724A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Miniaturization amide type beta-polypropylene nucleating agent, preparation method thereof and polypropylene material |
| WO2014077324A1 (en) * | 2012-11-16 | 2014-05-22 | 日産化学工業株式会社 | Polyglycolic acid resin composition |
| CN104211613A (en) * | 2013-06-03 | 2014-12-17 | 中国石油化工股份有限公司 | Production method for amide nucleating agent |
| JP6279378B2 (en) * | 2014-03-27 | 2018-02-14 | 日野自動車株式会社 | Roof spoiler |
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