CN106316877A - Preparation method of dicyclohexylterephthalamide - Google Patents
Preparation method of dicyclohexylterephthalamide Download PDFInfo
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Abstract
The invention relates to the field of amide nucleating agents, and discloses a preparation method of N,N'-dicyclohexylterephthalamide. The method is characterized in that dimetyl terephthalate reacts with cyclohexylamine in the presence of anhydrous potassium carbonate and pyridine to generate N,N'-dicyclohexylterephthalamide represented by formula (I). The N,N'-dicyclohexylterephthalamide represented by formula (I), prepared through the method, has the advantages of easiness in separation, high yield, good purity, environment protection facilitation, and suitableness 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 '-two hexamethylene
The preparation method of base terephthalamide.
Background technology
In recent years, the tough-increased and reinforced modification of polypropylene (PP) has become as and makes Engineering of Polypropylene, function
The important means change, become more meticulous.PP can form α, β, γ, δ and plan six side etc. no at different conditions
Isomorphism.Alpha-crystal form is monoclinic form, is the most stable a kind of crystal formation being easily formed most, in generally processing
In the case of be substantially this crystal formation.Beta crystal is thermodynamically metastable crystal formation, only specific
Crystallization condition under or beta nucleater in the presence of could generate, and stability can not show a candle to alpha-crystal form.
But, Beta-crystalline polyacrylic makes obscurity boundary due to the structure that its β spherocrystal is special, and platelet is by spherocrystal center
Or parallel set forms bundle, the most outside branched growth or helical form are to outgrowth, the most branched, so β
There is no obvious interface between spherocrystal, thus beta-crystal polypropylene has preferably toughness and draftability.If
Alpha-crystal form in PP is completely or partially transformed into beta crystal, it is likely that overcome alpha-crystal form PP to exist
The problem that impact property is poor, heat distortion temperature is low.Research finds, β crystalline phase PP has preferable room temperature
And impact strength at low temperature, demonstrate higher toughness and ductility, make PP manufacture anti-impact engineering plastics
On have certain application prospect, along with the development of modification technology, Beta-crystalline polyacrylic is increasingly by people
Attention.Therefore, prepare the PP goods of high beta-crystalline form content, become polymeric material field in recent years
One important problem, the application prospect of Beta-crystalline polyacrylic promotes research and the development of beta nucleater.
The method that can obtain β-PP being currently known mainly has 3 kinds: (1) temperature gradient method；(2)
Shear orientation；(3) beta nucleater is added.First two method limitation in actual production process is big, difficult
To implement, the specially good effect nucleator adding energy inductive formation beta crystal is to obtain high level beta crystal the most may be used
The approach of row.
It has recently been found that some amides compound can be as β-crystalline substance nucleator and have and well induce effect
Really.As N, N '-dicyclohexyl terephthalamide can prepare high beta-crystal polypropylene as β-crystalline substance nucleator.
And be the active component of important polypropylene processing aid-beta nucleater.Diamide nucleator has conjunction
Become convenient, good with the PP compatibility, the advantages such as purified, Heat stability is good can be obtained, be not only convenient for
Study mechanism and new nucleator MOLECULE DESIGN, and homopolymerization PP and copolymerization PP are all shown good β
Nucleator toughening effect, therefore has broad application prospects and development potentiality.
Patent US6235823B1 discloses is prepared amide-type polypropylene beta crystalline substance by dicarboxylic acids and monoamine
The method of type nucleator, the method is included in atent solvent, at a temperature of about 60-200 DEG C, makes two
Unit carboxylic acid and monoamine react 2-8 hour, in the reaction use activator phosphorus pentoxide, polyphosphoric acid,
Triphenyl phosphites etc. accelerate reaction, but, it is found through experiments, uses above-mentioned patented method to prepare
Amide-type polypropylene beta crystal nucleating agent need react (at more than 1MPa) under elevated pressure conditions,
Thus production equipment is had the highest requirement, thus large-scale industrial production can not be carried out, Er Qiexu
Want expensive catalysts and solvents, economical not.It addition, the method activator to be used phosphorus pentoxide,
Polyphosphoric acid, triphenyl phosphite etc., be unfavorable for separating, be also unfavorable for environmental protection.
CN102040532 overcomes and prepares polypropylene beta crystal nucleating agent in prior art and need under high pressure to enter
Row reaction, discloses the preparation method of a kind of polypropylene beta crystal nucleating agent at ambient pressure, and the method includes
In the presence of catalysts and solvents, catalyst exist under conditions of, dicarboxylic acids is contacted with amine into
Row condensation reaction, described amine is primary amine or secondary amine, uses the method can make primary amine or secondary amine at ambient pressure
Can fully react, with prepared amide-type polypropylene beta crystal nucleating agent.But the method needs use
Catalyst be still phosphorus pentoxide, polyphosphoric acid, triphenyl phosphite one or more, and catalyst
Consumption is big, close to the consumption of reactant amine.Such as: reactant amine is 1 with the mol ratio of catalyst:
0.8-1.2, reactant amine is 2-3.5:1 with the mol ratio of reactant dicarboxylic acids.This is unfavorable for product
Separate, be also unfavorable for environmental conservation.
CN101948401 mentions and being dissolved in organic solvent by paraphthaloyl chloride, then in stirring and cooling
Lower in this solution, drip sodium hydrate aqueous solution and the mixture of cyclohexylamine, drip to finish and be stirred for 30min,
Finally filtering, washing filter cake obtains target product.The method have compared with additive method do not use organic
Acid binding agent, amine need not excess or excess seldom and yield advantages of higher, but reactant paraphthaloyl chloride
There is corrosivity, and facile hydrolysis becomes p-phthalic acid and hydrogen chloride, is unfavorable for environmental conservation.
Therefore, how the preparation of environmental protection ground can be still urgently as the amides compound of beta crystal-type nucleater
The problem of research and development.
Summary of the invention
The invention aims to solve prior art and prepare N, N '-dicyclohexyl terephthalamide product
The problem that product exist, such as, use a large amount of phosphorus pentoxides, polyphosphoric acid, Asia with p-phthalic acid for raw material
The activators such as triphenyl phosphate, thus cause isolated and purified during relatively costly and inadequate environmental protection ask
Topic, and for raw material, there is corrosivity with paraphthaloyl chloride, and facile hydrolysis becomes p-phthalic acid and chlorine
The problem changing hydrogen, it is provided that a kind of new N, the preparation method of N '-dicyclohexyl terephthalamide.
To achieve these goals, the present invention provides the system of a kind of N, N '-dicyclohexyl terephthalamide
Preparation Method, wherein, the method is included in the presence of Anhydrous potassium carbonate and pyridine, by p-phthalic acid two
Methyl ester reacts with cyclohexylamine, generates the N shown in formula (I), N '-dicyclohexyl terephthalamide；
The preparation of the N that structural formula is (I), N ' provided by the present invention-dicyclohexyl terephthalamide
Method, it is not necessary to use the activators such as phosphorus pentoxide, polyphosphoric acid, triphenyl phosphite to accelerate benzene two
The reaction of formic acid dimethyl ester and cyclohexylamine, the most isolated and purified product, reduce cost, or without
Use the steady of the Butyltriphenylphosphonium chloride with corrosivity, facile hydrolysis, beneficially production safety and product quality
Fixed.The inventive method product is easily separated, is conducive to protecting environment, is suitable to large-scale industrial production.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of N, N '-dicyclohexyl terephthalamide, wherein, be somebody's turn to do
Method is included in the presence of Anhydrous potassium carbonate and pyridine, is carried out with cyclohexylamine by dimethyl terephthalate (DMT)
Reaction, generates the N shown in formula (I), N '-dicyclohexyl terephthalamide；
According to the present invention, carry out reacting preferably at Anhydrous potassium carbonate by dimethyl terephthalate (DMT) and cyclohexylamine
Carry out with in the presence of pyridine, and described dimethyl terephthalate (DMT) is thrown with the initial of described Anhydrous potassium carbonate
The mol ratio of doses can be 1:0.07-0.2, preferably 1:0.1-0.15.
According to the present invention, carry out reacting preferably at Anhydrous potassium carbonate by dimethyl terephthalate (DMT) and cyclohexylamine
Carry out with in the presence of pyridine, and the initial charge of described dimethyl terephthalate (DMT) and described pyridine
Mol ratio can be 1:2-12, preferably 1:2-7.
According to the present invention, carry out reacting preferably at Anhydrous potassium carbonate by dimethyl terephthalate (DMT) and cyclohexylamine
Carry out with in the presence of pyridine, and the rubbing of the initial charge of described dimethyl terephthalate (DMT) and cyclohexylamine
Your ratio can be 1:2-10, preferably 1:2-5.
According to the present invention, the condition that dimethyl terephthalate (DMT) and cyclohexylamine carry out reacting is included: often
Press or under the conditions of pressure is 0.1-0.2MPa, the heating medium temperature of reaction can be 65-170 DEG C；
Preferably, at normal pressure or under the conditions of pressure is 0.1-0.11MPa, the heating medium temperature of reaction is 127
℃-140℃.Specifically, in the present invention, when dimethyl terephthalate (DMT) is reacted with cyclohexylamine
Time, it is to be ensured that the temperature of reaction is more than or equal to the boiling point of the methanol generated in course of reaction.According to this
Bright, described " heating medium temperature of reaction " is equal to " reaction temperature ", i.e. in the present invention,
Such as, when reaction heating medium temperature be 100 DEG C time it can be understood as the reaction temperature of this reaction also
It it is 100 DEG C；Therefore, the temperature of reaction 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, need to add
Add entrainer, at this time, it may be necessary to make reaction temperature be more than or equal to the boiling point of described entrainer.Therefore, exist
In the present invention, in practical operation, the temperature of reaction is along with removing the low of reaction generation in course of reaction
The by-product alcohol HOR of boiling point1(boiling point of such as methanol bp65 DEG C) and increase；In the present invention, excellent
Described reaction is selected to carry out under the conditions of simple distillation or rectification, to remove the first of generation in course of reaction
Alcohol.
According to the present invention, described entrainer can be boiling point be the solvent of 80-176 DEG C；Preferably, described
Entrainer is selected from pyridine, cyclohexylamine, trimethylbenzene, dimethylbenzene, toluene, benzene and N,N-dimethylformamide
In one or more；It is highly preferred that described entrainer is selected from pyridine and/or cyclohexylamine；Wherein, described
The boiling point of pyridine is 115.2 DEG C, and the boiling point of described cyclohexylamine is 134 DEG C, and described trimethylbenzene can be equal three
Toluene and/or pseudocumene, and the boiling point of described sym-trimethylbenzene. can be 164-165 DEG C, described inclined front three
The boiling point of benzene can be 169.4 DEG C, and described dimethylbenzene includes xylol, o-Dimethylbenzene, meta-xylene
With the dimethylbenzene of conventional mixed isomers, wherein, the boiling point of xylol is 138 DEG C, o-Dimethylbenzene
Boiling point 143-145 DEG C, the boiling point of meta-xylene 138-139 DEG C, the dimethylbenzene of conventional mixed isomers
Boiling point 137-140 DEG C, the boiling point of described toluene is 110.6 DEG C, and the boiling point of described benzene is 80.1 DEG C, institute
The boiling point stating N,N-dimethylformamide is 152.8 DEG C.It addition, in the present invention, when described entrainer
During for pyridine and/or cyclohexylamine, the most in the reaction, the pyridine being firstly added and cyclohexylamine are as adding
The accelerator of speed reaction, when pyridine is as accelerator, the used in amounts of pyridine will be according to above-mentioned " described right
Dimethyl phthalate can be 1:2-12 with the mol ratio of the initial charge of described pyridine, is preferably
1:2-7 " limit add；When cyclohexylamine is as accelerator, the used in amounts of cyclohexylamine will be according to above-mentioned
" described dimethyl terephthalate (DMT) can be 1:2-10 with the mol ratio of the initial charge of cyclohexylamine,
Be preferably 1:2-5 " limit add；And when the pyridine added in course of reaction and cyclohexylamine are used as altogether
During boiling agent, the addition of this entrainer, feed postition and joining day are referring particularly to description given below
Carry out.
According to the present invention, the reactor carrying out reacting by dimethyl terephthalate (DMT) and cyclohexylamine is the most concrete
Limit, can be the conventional selection of those skilled in the art, it is for instance possible to use the glass flask of routine
As reactor；And in the present invention, control the thermal source required for the reaction temperature of reaction the most concrete
Limit, various methods that can be known to those skilled in the art, such as, in the present invention, described
Reactor can be carried out in adding thermal medium such as water-bath or oil bath, when the temperature of water-bath or oil bath is
65-170 DEG C, when preferably 127-140 DEG C, reaction temperature can be made to control the temperature at 65 DEG C to azeotropic point,
Such as, the temperature range of 65-100 DEG C can be bathed by water vapour or oil bath heating provides, 100-170 DEG C
Temperature range can be bathed by pressurized steam or oil bath heating provides.
In accordance with the present invention it is preferred that, at normal pressure or under the conditions of pressure is 0.1-0.11MPa, reaction
Heating medium temperature is at 127 DEG C～140 DEG C, reaches the boiling point (that is, 65 DEG C) of methanol in reaction temperature
Add entrainer time above, or after described reaction is carried out 5-7 hour, in reactant liquor, add entrainer,
And by the way of distillation or azeotropic distillation, remove the methanol that reaction generates, can enter under this preferred version
One step improves the structural formula yield that is the product N, N ' shown in (I)-dicyclohexyl terephthalamide and pure
Degree.
In accordance with the present invention it is preferred that, described entrainer divides 5-7 addition, and adjacent twice addition time
Between be spaced apart 1-6 hour, preferably 3-6 hour, more preferably 4-5 hour, and rub relative to 1
Your dimethyl terephthalate (DMT), the addition of described entrainer can be 60mL/ time-600mL/ time,
Increase each addition of entrainer and be conducive to improving structural formula for product N, N '-two hexamethylene shown in (I)
The yield of base terephthalamide and purity.
According to the present invention, another kind adds the optimal way of entrainer and is, reaction begins to use simple distillation to fill
Putting or rectifier unit, after reacting 5-7 hour under the conditions of simple distillation or rectification, entrainer is simply
Under the conditions of distillation or rectification, continuously stream is added in reactant liquor, when starting relative to reaction 1 mole to benzene two
Formic acid dimethyl ester, flow acceleration is 10-200mL/ hour, and it is 10-30 hour that stream adds the time.
It will be understood by those skilled in the art that, after adding entrainer, the temperature controlling reaction is more than
Or the boiling point equal to entrainer, add fashionable by several times, when adding entrainer, can not lower the temperature, it is also possible to
It is cooled to, under the boiling point of entrainer, add entrainer by the temperature of reaction, preferably lowers the temperature at laboratory
To the boiling point of entrainer, the time needed for general cooling is little less than half an hour, preferably 0.1-0.5
Time；Flowing the added-time continuously, reaction should be formed at the alcohol of the boiling point of entrainer and entrainer and reaction generation
Carrying out between the boiling point of azeotropic mixture, flow acceleration can come according to response speed, the kind of entrainer and consumption
Regulation.The entrainer mode that continuous stream is added to reactant liquor under the conditions of simple distillation or rectification is particularly suitable for greatly
Large-scale production.
According to the present invention, in order to enable the most lasting being carried forward of above-mentioned preferred version, instead
Upper end should be begun to use as simple distillation device, described " liquor separator " equipped with " liquor separator " of condensing tube
Dean and Stark apparatus (the Dean and Stark apparatus with a of piston switch is had bottom finger
stopcock at the lower end)。
According to the present invention, it will be understood by those skilled in the art that the structure higher in order to obtain purity
Formula is the N, N ' shown in (I)-dicyclohexyl terephthalamide, and the inventive method is preferably also included in instead
After should terminating, including carrying out the dimethylbenzene of addition distilling post processing, in order to be (I) institute by structural formula
The N shown, N '-dicyclohexyl terephthalamide is separated gained mixture after reaction, wherein,
In the present invention, described dimethylbenzene can be xylol, o-Dimethylbenzene, meta-xylene or mixing isomery
The dimethylbenzene of body.By structural formula for the N, N ' shown in (I)-dicyclohexyl terephthalamide from reaction after
The method separated in gained mixture, including by the Anhydrous potassium carbonate in reaction gained mixture, pyrrole
Pyridine, unreacted cyclohexylamine and and a small amount of intermediate product, remove from reaction gained mixture, right
In the method removed without particular/special requirement, the thinkable various methods of those skilled in the art can be used,
In the present invention, the method preferably first passing through simple distillation, rectification, more preferably add xylenes agent and steam
The method evaporated, by volatile compounds such as the methanol of reaction generation, pyridine, unreacted cyclohexylamine from instead
Answer in gained mixture and remove, then by washing, filter, the method for centrifugation or extraction is by anhydrous carbon
Acid potassium, pyridine remove, finally by the method for recrystallization, in a small amount of from reaction gained mixture
Between product remove from product.
Hereinafter will be described the present invention by embodiment.In following example, infrared spectrum divides
Analyzer is Nicolet Nexus 470 purchased from company of U.S. Thermo Fisher Scintific company model, uses
In ester carbonyl group and product N, the N '-dicyclohexyl terephthalamide of analyzing raw material dimethyl terephthalate (DMT)
Amidocarbonylation；
Raw material dimethyl terephthalate (DMT) (chemical pure), pyridine (analytical pure), cyclohexylamine (analytical pure),
Dimethylbenzene (analytical pure, mixed isomers) etc. is purchased from the commercially available of Chemical Reagent Co., Ltd., Sinopharm Group
Reagent product；Potassium carbonate (chemical pure) is purchased from the commercial reagent of Tianjin recovery fine chemistry industry institute company
Product；DMF (analytical pure) is purchased from the commercial reagent product of Beijing Chemical Plant.
Embodiment 1
This embodiment is for illustrating the N that the present invention provides, the preparation side of N '-dicyclohexyl terephthalamide
Method, in this embodiment, accelerates reaction with pyridine and potassium carbonate, and with pyridine and cyclohexylamine as common
Boiling agent.
At ambient pressure, band condenser, liquor separator, agitator 100mL three neck round bottom flask in add
Enter 9.42g dimethyl terephthalate (DMT), 22.52g cyclohexylamine, 25mL pyridine and 0.69g potassium carbonate；So
After to control the temperature of oil bath in heating medium oil bath be 127 DEG C, react 30h, distillation collected by liquor separator
The fraction gone out；
Wherein, in course of reaction, add entrainer pyridine and ring when reaction temperature reaches more than 65 DEG C
Hexylamine, and point add pyridine 6 times, add 5mL every time, add cyclohexylamine 6 times simultaneously, add every time
About 21g, the time interval that adjacent twice adds pyridine or cyclohexylamine is 5 hours；After reaction terminates, take out
Filter, water washing and precipitating, dry, the N, N ' of result acquisition 12.6g-dicyclohexyl terephthalamide, receives
Rate is 79.1 weight %, and purity good (seeing below infrared spectrum analysis), is beneficial in whole preparation process
Environmental protection；And
IR (KBr tabletting, 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
Preparing N, N '-dicyclohexyl terephthalamide according to method same as in Example 1, institute is different
Part is, the consumption of potassium carbonate is 0.17g；
The N, N ' of result acquisition 7.86g-dicyclohexyl terephthalamide, yield is 56.4 weight %.
Comparative example 1-2
Preparing N, N '-dicyclohexyl terephthalamide according to method same as in Example 1, institute is different
Part is, the consumption of potassium carbonate is 0.34g；
The N, N ' of result acquisition 7.86g-dicyclohexyl terephthalamide, yield is 54.1 weight %.
Comparative example 1-3
Preparing N, N '-dicyclohexyl terephthalamide according to method same as in Example 1, institute is different
Part is, the consumption of potassium carbonate is 1.04g；
The N, N ' of result acquisition 7.60g-dicyclohexyl terephthalamide, yield is 47.7 weight %.
Comparative example 1-4
Preparing N, N '-dicyclohexyl terephthalamide according to method same as in Example 1, institute is different
Part is, the consumption of dimethyl terephthalate (DMT) is 9.09g, and the consumption of potassium carbonate is 0.34g；
In course of reaction, divide and add pyridine 9 times, add 5mL every time, add cyclohexylamine 9 times simultaneously,
Add about 20g every time；
The N, N ' of result acquisition 7.86g-dicyclohexyl terephthalamide, yield is 51.1 weight %.
Comparative example 1-5
Preparing N, N '-dicyclohexyl terephthalamide according to method same as in Example 1, institute is different
Part is, the consumption of dimethyl terephthalate (DMT) is 9.78g, and the consumption of potassium carbonate is 1.37g；
In course of reaction, divide and add pyridine 10 times, add 5mL every time, add cyclohexylamine 10 times simultaneously,
Add about 22g every time；
The N, N ' of result acquisition 7.86g-dicyclohexyl terephthalamide, yield is 46.7 weight %.
Embodiment 2
This embodiment is for illustrating the N that the present invention provides, the preparation side of N '-dicyclohexyl terephthalamide
Method, in this embodiment, accelerates reaction, with cyclohexylamine as entrainer with pyridine and potassium carbonate.
Under 0.1MPa, band condenser, liquor separator, agitator 100mL three neck round bottom flask in
Add 9.42g dimethyl terephthalate (DMT), 22.52g cyclohexylamine, 12mL pyridine and 0.69g potassium carbonate；
Then the temperature controlling oil bath in heating medium oil bath is 140 DEG C, reacts 30h, and liquor separator is collected and steamed
The fraction distillated；
Wherein, in course of reaction, after reaction 5 hours, divide and add cyclohexylamine 6 times, mend every time
Adding about 21g, the time interval that adjacent twice adds cyclohexylamine is about 4.2 hours；After reaction terminates, take out
Filter, water washing and precipitating, dry, the N, N ' of result acquisition 12.7g-dicyclohexyl terephthalamide, receives
Rate is 79.8 weight %, and purity good (seeing below infrared spectrum analysis), is beneficial in whole preparation process
Environmental protection；And
IR (KBr tabletting, 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
Preparing N, N '-dicyclohexyl terephthalamide according to method same as in Example 2, institute is different
Part is, the consumption of pyridine is 25mL；
The N, N ' of result acquisition 8.37g-dicyclohexyl terephthalamide, yield is 52.5 weight %.
Comparative example 2-2
Preparing N, N '-dicyclohexyl terephthalamide according to method same as in Example 2, institute is different
Part is, the consumption of pyridine is 25mL；In course of reaction, divide and add cyclohexylamine 4 times, mend every time
Add about 21g；
The N, N ' of result acquisition 8.37g-dicyclohexyl terephthalamide, yield is 54.4 weight %.
Embodiment 3
This embodiment is for illustrating the N that the present invention provides, the preparation side of N '-dicyclohexyl terephthalamide
Method, in this embodiment, accelerates reaction with pyridine and potassium carbonate, with cyclohexylamine as entrainer, reaction
With the method separation product adding xylenes agent distillation after end.
At ambient pressure, band condenser, liquor separator, agitator 100mL three neck round bottom flask in add
Enter 9.42g dimethyl terephthalate (DMT), 22.52g cyclohexylamine, 25mL pyridine and 0.69g potassium carbonate；So
After to control the temperature of oil bath in heating medium oil bath be 135 DEG C, react 30h, distillation collected by liquor separator
The fraction gone out；
In course of reaction, point add cyclohexylamine for 6 times, and in the temperature 135 DEG C of oil bath by partial reaction
Liquid distills, and adds about 21g every time, is about 4 hours between the time that adjacent twice adds cyclohexylamine；
After reacting 30 hours, add dimethylbenzene, and oil bath temperature 140 DEG C by partial reaction liquid distill
Out, divide and add dimethylbenzene 2 times, add 50mL, between the time that adjacent twice adds dimethylbenzene every time
Every about 5 hours；
After reaction terminates, decompression and solvent recovery, add water, sucking filtration, water washing and precipitating, to dry, result obtains
The N of 14.08g, N '-dicyclohexyl terephthalamide, yield is 88.4 weight %, and purity good (see
Infrared spectrum analysis below), whole preparation process is beneficial to environmental protection；And
IR (KBr tabletting, 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
Preparing N, N '-dicyclohexyl terephthalamide according to method same as in Example 3, institute is different
Part is, is added without potassium carbonate；After reacting 30 hours, point add for 4 times dimethylbenzene (analytical pure,
Mixed isomers), add 25mL every time, the time interval that adjacent twice adds dimethylbenzene is 2.5 hours；
The N, N ' of result acquisition 11.50g-dicyclohexyl terephthalamide, yield is about 72.2 weight %,
Purity is not so good as embodiment 1 (seeing below infrared spectrum analysis)；And
IR (KBr tabletting, cm-1): consistent with embodiment 3, but there is ester at 1718 (υ-OC=O)
Carbonyl characteristic absorption small peak, its peak height is about the 8.8% of amidocarbonylation (υ-HNC=O) peak height.
Comparative example 3-2
Preparing N, N '-dicyclohexyl terephthalamide according to method same as in Example 3, institute is different
Part is, is added without pyridine；After reacting 30 hours, divide and add dimethylbenzene 4 times, add 25mL every time,
The time interval that adjacent twice adds dimethylbenzene is 2-3 hour；
The N, N ' of result acquisition 11.79g-dicyclohexyl terephthalamide crude product, purity is poor, infrared
Spectrum analysis (KBr tabletting, cm-1) in this crude product containing impurity ester carbonyl group characteristic absorption peak, its peak height
1718 (υ-OC=O) are about 28 weight % of amidocarbonylation 1626 (υ-HNC=O), and yield is less than
73 weight %.
Embodiment 4
This embodiment is for illustrating the N that the present invention provides, the preparation side of N '-dicyclohexyl terephthalamide
Method, in this embodiment, uses DMF (DMF) solvent, with pyridine and carbonic acid
Potassium accelerates reaction, with pyridine and cyclohexylamine as entrainer.
At ambient pressure, band condenser, liquor separator, agitator 100mL three neck round bottom flask in add
Enter 14.13g dimethyl terephthalate (DMT), 33.78g cyclohexylamine, 12mL pyridine and 1.03g potassium carbonate,
Add 5mL DMF.Then the temperature controlling oil bath in heating medium oil bath is 140 DEG C, reaction
30h, the fraction distilled out collected by liquor separator；
Wherein, in course of reaction, after reaction 7 hours, divide and add cyclohexylamine 6 times, mend every time
Adding about 32g, the time interval that adjacent twice adds cyclohexylamine is about 4.5 hours；Mend after reacting 18 hours
Add 6mL pyridine 1 time；
After reaction terminates, decompression and solvent recovery, obtain crude product 23.8g, add water, sucking filtration, water washing and precipitating,
Drying, the N, N ' of result acquisition 17.34g-dicyclohexyl terephthalamide, yield is 70.4 weight %,
And purity is good, whole preparation process is beneficial to environmental protection.
Embodiment 5
This embodiment is for illustrating the N that the present invention provides, the preparation side of N '-dicyclohexyl terephthalamide
Method, in this embodiment, uses DMF (DMF) solvent, with pyridine and carbonic acid
Potassium accelerates reaction, with cyclohexylamine as entrainer.
At ambient pressure, band condenser, liquor separator, agitator 100mL three neck round bottom flask in add
Enter 14.13g dimethyl terephthalate (DMT), 33.78g cyclohexylamine, 12mL pyridine and 1.03g potassium carbonate,
Add 5mL DMF.Then the temperature controlling oil bath in heating medium oil bath is 140 DEG C, reaction
30h, the fraction distilled out collected by liquor separator；
In course of reaction, after reaction 5 hours, divide and add cyclohexylamine 6 times, add about 32g every time,
The time interval that adjacent twice adds cyclohexylamine is about 5 hours；
After reaction terminates, decompression and solvent recovery, obtain crude product 23.8g, add water, sucking filtration, water washing and precipitating,
Drying, the N, N ' of result acquisition 17.34g-dicyclohexyl terephthalamide, yield is 72.6 weight %,
And purity is good, whole preparation process is beneficial to environmental protection.
Embodiment 6
This embodiment is for illustrating the N that the present invention provides, the preparation side of N '-dicyclohexyl terephthalamide
Method, in this embodiment, uses DMF (DMF) solvent, with pyridine and carbonic acid
Potassium accelerates reaction, with cyclohexylamine and DMF as entrainer.
At ambient pressure, band condenser, liquor separator, agitator 100mL three neck round bottom flask in add
Enter 14.13g dimethyl terephthalate (DMT), 33.78g cyclohexylamine, 12mL pyridine and 1.03g potassium carbonate,
Add 5mL DMF；Then the temperature controlling oil bath in heating medium oil bath is 140 DEG C, reaction
30h, the fraction distilled out collected by liquor separator；
In course of reaction, divide and add cyclohexylamine 6 times, add about 32g every time, add ring adjacent twice
The time interval of hexylamine is about 5 hours；10mL DMF is added 1 time after reacting 8 hours；
After reaction terminates, decompression and solvent recovery, add water, sucking filtration, water washing and precipitating, to dry, result obtains
The N of 17.34g, N '-dicyclohexyl terephthalamide, yield is 71.9 weight %, and purity is good, whole
Individual preparation process is beneficial to environmental protection.
From above-described embodiment 1-6 and comparative example it can be seen that the structural formula using the present invention to provide is (I)
The preparation method of N, N '-dicyclohexyl terephthalamide, without using five oxidations in preparation process
The activators such as two phosphorus, polyphosphoric acid, triphenyl phosphite accelerate dimethyl terephthalate (DMT) and cyclohexylamine
Reaction, the most isolated and purified product, reduce cost, or without using, there is corrosivity, the Yishui River
Stablizing of the Butyltriphenylphosphonium chloride solved, beneficially production safety and product quality, and yield is higher, pure
Spend, be conducive to protecting environment, be suitable to large-scale industrial production.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the preparation method of a N, N '-dicyclohexyl terephthalamide, it is characterised in that the method
It is included in the presence of Anhydrous potassium carbonate and pyridine, dimethyl terephthalate (DMT) and cyclohexylamine are carried out instead
Should, generate the N shown in formula (I), N '-dicyclohexyl terephthalamide；
Method the most according to claim 1, wherein, described dimethyl terephthalate (DMT), described
The mol ratio of the initial charge of Anhydrous potassium carbonate, described pyridine and described cyclohexylamine is 1:0.07-0.2:
2-12:2-10, preferably 1:0.1-0.15:2-7:2-5.
Method the most according to claim 1, wherein, the condition of described reaction includes: at normal pressure
Or under the conditions of pressure is 0.1-0.2MPa, the heating medium temperature of reaction is 65 DEG C-170 DEG C.
Method the most according to claim 3, wherein, the condition of described reaction includes: at pressure
Under the conditions of 0.1-0.11MPa, the heating medium temperature of described reaction is 127 DEG C-140 DEG C.
5. according to the method described in claim 3 or 4, wherein, the method is additionally included in adding of reaction
Heat medium temperature reaches to add entrainer during more than the boiling point of methanol, or carries out 5-7 hour in described reaction
Rear interpolation entrainer, and make heating medium temperature be more than or equal to described entrainer after adding entrainer
Boiling point.
Method the most according to claim 5, wherein, described entrainer divides 5-7 addition, and
The time interval of adjacent twice addition is 1-6 hour, preferably 4-5 hour, and relative to 1 mole
Described dimethyl terephthalate (DMT) inventory, the addition of described entrainer is 60mL/-600mL/
Secondary.
7. according to the method described in claim 5 or 6, wherein, described entrainer is selected from pyridine, ring
One or more in hexylamine, trimethylbenzene, dimethylbenzene, toluene, benzene and N,N-dimethylformamide.
Method the most according to claim 7, wherein, described entrainer is selected from pyridine and/or hexamethylene
Amine.
9., according to method the most described in claim 1-8, wherein, the method is additionally included in distillation
Or carry out under conditions of rectification.
Method the most according to claim 9, wherein, after described method is additionally included in reaction terminating,
After the dimethylbenzene of the xylol of addition, o-Dimethylbenzene, meta-xylene or mixed isomers is distilled
Process, with N, N '-dicyclohexyl terephthalamide gained after reacting be (I) by structural formula
Mixture is separated.
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