CN112358410A - Preparation method of carboxyl-terminated diamide - Google Patents
Preparation method of carboxyl-terminated diamide Download PDFInfo
- Publication number
- CN112358410A CN112358410A CN202011216562.1A CN202011216562A CN112358410A CN 112358410 A CN112358410 A CN 112358410A CN 202011216562 A CN202011216562 A CN 202011216562A CN 112358410 A CN112358410 A CN 112358410A
- Authority
- CN
- China
- Prior art keywords
- carboxyl
- organic solvent
- reaction
- terminated diamide
- dibasic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 44
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 41
- 150000004985 diamines Chemical class 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000047 product Substances 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000706 filtrate Substances 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000376 reactant Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 17
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims 5
- 229920000728 polyester Polymers 0.000 abstract description 37
- 238000002156 mixing Methods 0.000 abstract description 17
- 239000006227 byproduct Substances 0.000 abstract description 12
- 239000003607 modifier Substances 0.000 abstract description 11
- 150000003863 ammonium salts Chemical class 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- -1 Amide salts Chemical class 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- 150000001408 amides Chemical class 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000010976 amide bond formation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
Abstract
The invention relates to a preparation method of carboxyl-terminated diamide, which comprises the steps of mixing diamine diacid salt, dibasic acid (aliphatic dibasic acid or aromatic dibasic acid) and a nonpolar organic solvent, reacting, carrying out azeotropic distillation at the temperature higher than the boiling point of the nonpolar organic solvent, and removing water in a product to prepare carboxyl-terminated diamide; the molar ratio of the diamine diacid salt to the dibasic acid is 1: 1-2. The preparation method of the carboxyl-terminated diamide has the advantages of simple process and mild conditions; the activity of naked ammonium radicals in organic ammonium salts is slowed down, and the carboxyl-terminated diamide can be used as a modifier for polyester reaction, so that the color change phenomenon caused by the reaction with byproducts in the polyester copolymerization process is avoided.
Description
Technical Field
The invention belongs to the technical field of preparation of amide monomers, relates to a preparation method of carboxyl-terminated diamide, and particularly relates to a method for preparing carboxyl-terminated diamide by reacting diamine diacid salt with aliphatic dibasic acid or aromatic dibasic acid.
Background
Amide salts are stable, can be transported without any special precautions and are easy to store, are widely used as industrially important substances, and are also important research directions for the synthesis of polyesters as hydrophilic modifiers. However, the use of amide salts is greatly affected by the phenomenon that naked ammonium groups in organic ammonium salts are susceptible to side reactions during the copolymerization of polyesters and cause color changes. Protection of ammonium groups with carboxylate groups and development of amide bond formation by reaction are very necessary synthetic techniques, but there are few studies at present.
Common preparation methods of amides include: (1) carboxylic acid and its derivatives (acyl chloride, acid amine and ester) and amines are prepared by condensation acylation; (2) a condensing agent condensation process, which requires the reaction of excess condensing agent, base and solvent. The above method consumes a large amount of metal catalyst and produces chemically toxic by-products, which is not environmentally friendly. For example: patent US 2009/0062565 discloses a fatty acid amide prepared from the corresponding carboxylic acid and amine using a two reactor system, the water formed being distilled off together with the amine, and the amine being recycled by the introduced acid to produce the amide product. However, this process requires an excess of amine, the reaction product contains toxic substances and is disadvantageous for small-scale production and discontinuous processes. Patent CN108610226 discloses a method for preparing amide compounds by using manganese oxide to catalyze amine oxidation, in the invention, an organic solvent is added into a pressure container, an organic amine substrate and a catalyst are uniformly mixed, oxygen is charged, a C ═ O double bond is formed on alpha carbon of the organic amine substrate, and then an amide group is obtained, and finally the amide compounds are obtained. However, the reaction process is complicated and there is a consumption of catalyst. Patent CN103922955 discloses a method for preparing amide by using dicarbonyl compound as acylating agent, in the invention, amine compound and symmetrical dicarbonyl compound must react under normal pressure in the presence of metal element salt to obtain target product.
In conclusion, the prior art for preparing amide has the disadvantages of complex process, high production cost and large amount of three wastes (waste water, waste gas and solid waste). In view of this, the invention provides an amide preparation technology with simple reaction flow, mild conditions, low energy consumption and low material consumption, and avoids the color change caused by the reaction of the naked ammonium salt in the reaction product and the by-product in the copolymerization process.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a preparation method of carboxyl-terminated diamide. According to the preparation method of the carboxyl-terminated diamide, the diamine diacid salt and the dibasic acid are reacted in the nonpolar organic solvent, and water in a product is removed in the reaction process, so that the reaction process is simple, the conditions are mild, a catalyst is not required in the reaction, a chemical toxic byproduct is not generated, and the problem of environmental pollution is not caused; the activity of naked ammonium radicals in organic ammonium salts is slowed down, the prepared carboxyl-terminated diamide can be used as a modifier for polyester reaction, and the color change phenomenon caused by the reaction with byproducts (acetaldehyde and the like) in the polyester copolymerization process is avoided.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of carboxyl-terminated diamide is characterized by mixing diamine diacid salt, dibasic acid and a nonpolar organic solvent for reaction, reacting the diamine diacid salt with the dibasic acid for dehydration, and removing generated water through azeotropic distillation to prepare the carboxyl-terminated diamide;
the nonpolar organic solvent is more than one of toluene, xylene and trimethylbenzene, the three organic solvents of toluene, xylene and trimethylbenzene are not mutually soluble with water, and the density is less than that of water;
the dibasic acid is aliphatic dibasic acid or aromatic dibasic acid;
the structural formula of the diamine diacid salt is shown as
The structural formula of the aliphatic dibasic acid is shown in the specification
The structural formula of the aromatic dibasic acid is shown as
m is a positive integer of 4-8, n1 is a positive integer of 4-10, and n2 is a positive integer of 4-10;
the temperature of the azeotropic distillation is higher than the boiling point of the non-polar organic solvent;
the molar ratio of the diamine diacid salt to the dibasic acid is 1: 1-2, and the mass spectrum result shows that in the range, as the molar ratio of the dibasic acid to the diamine diacid salt is increased, the by-products are increased, and the proportion of the carboxyl-terminated diamide monomer in the product is reduced;
since the liberation of the charged substance is not facilitated in the nonpolar solvent, the formation of an amide bond can be promoted. This reaction is an equilibrium reaction, and the presence of water inhibits the stable amide salt from dehydrating the diacid to form the amide covalent bond, i.e., removal of the product water facilitates dehydration of the amide salt to form the amide bond. And (2) performing azeotropic distillation at a temperature higher than the boiling point of the nonpolar organic solvent, continuously and circularly taking out the product water, separating the water from the reactant due to the fact that the content of the terminal carboxyl is higher than 2 times of that of the terminal amino, further promoting the generation of amido bond, and generating stable amido covalent bond by the ionic bond in the amide salt, so that the content of the terminal carboxyl diamide monomer in the obtained target product is high in specific gravity, and the specific gravity of the dimer, the trimer and the polymer is very low.
The preparation method of the carboxyl-terminated diamide slows down the activity of exposed ammonium radicals in organic ammonium salt, the prepared carboxyl-terminated diamide can be used as a modifier for polyester reaction to protect the exposed ammonium radicals, thereby avoiding the color change phenomenon caused by the reaction with the byproduct (such as acetaldehyde) in the polyester copolymerization process (for example, the amide 56 salt can generate color reaction with the acetaldehyde due to the reaction of the ammonium group of the amide 56 salt with the acetaldehyde, and the ammonium group reacts with acid after the end capping to generate amido bond which protects the ammonium group and cannot react with the acetaldehyde), and the existence of the hydrophilic group containing amino effectively improves the hydrophilicity of the polyester (the polyester lacks hydrophilic groups, molecular chain arrangement is regular and compact, so the hydrophilicity is poor, the wearing comfort is greatly reduced, and the improvement of the hydrophilic performance is one of important directions for developing the functions of the polyester fiber).
As a preferred technical scheme:
in the above-described method for producing a carboxyl-terminated diamide, the mass ratio of the carboxyl-terminated diamide in the reaction product is 85% or more.
In the preparation method of the carboxyl-terminated diamide, the reaction temperature is 10-30 ℃ higher than the boiling point of the nonpolar organic solvent.
The preparation method of the carboxyl-terminated diamide has the advantages that the reaction temperature is 130-180 ℃ (130-150 ℃ when the nonpolar organic solvent is toluene, 150-170 ℃ when the nonpolar organic solvent is xylene, 160-180 ℃ when the nonpolar organic solvent is trimethylbenzene) and the reaction time is 12-20 hours.
According to the preparation method of the carboxyl-terminated diamide, azeotropic distillation and condensation reaction are carried out simultaneously, and because the product water is incompatible with the nonpolar organic solvent and the density of the water is greater than that of the nonpolar organic solvent, an oil-water separation device is adopted in the azeotropic distillation, the product water is continuously and circularly taken out by the organic solvent, the water is separated from the reactant, the reaction is further promoted, and the carboxyl-terminated diamide monomer is prepared, wherein the azeotropic distillation time is 12-24 hours.
In the method for preparing the carboxyl-terminated diamide, the ratio of the volume of the nonpolar organic solvent to the mass of the diamine diacid salt is 1-10: 1(mL/g), and the addition amount of the nonpolar organic solvent is required to meet the requirement of refluxing after the oil-water separation device is filled.
In the preparation method of the carboxyl-terminated diamide, after the reaction is finished, the product is purified by using an alcohol organic solvent.
In the above method for preparing carboxyl-terminated diamide, the alcohol organic solvent is one or more of methanol, ethanol and propanol.
The preparation method of the carboxyl-terminated diamide, which uses the alcohol organic solvent to purify the product, comprises the following specific steps: firstly, mixing a product after the reaction with an alcohol organic solvent at the temperature of 60-80 ℃, cooling to normal temperature (25 ℃) and precipitating a reactant insoluble in the alcohol organic solvent, filtering to obtain a filtrate I, then putting the filtrate I into the environment of 0 ℃ to precipitate the reactant soluble in the alcohol organic solvent, filtering to obtain a filtrate II, finally carrying out rotary evaporation on the filtrate II to obtain a product, drying, sealing and storing.
Has the advantages that:
(1) the preparation method of the carboxyl-terminated diamide has the advantages of simple reaction process, mild conditions, low energy consumption and low material consumption in the reaction process;
(2) according to the preparation method of the carboxyl-terminated diamide, a catalyst is not used in the reaction process, no chemical toxic by-product is generated, and the preparation method is environment-friendly;
(3) the preparation method of the carboxyl-terminated diamide slows down the activity of naked ammonium radicals in organic ammonium salt, and the carboxyl-terminated diamide can be used as a modifier of polyester reaction to reduce the color change phenomenon caused by the reaction with byproducts in the polyester copolymerization process.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
In the reaction formula 1 and the reaction formula 2, m is a positive integer of 4-8, n1 is a positive integer of 4-10, and n2 is a positive integer of 4-10.
A preparation method of carboxyl-terminated diamide, as shown in reaction formula 1 or reaction formula 2, diamine diacid salt (structural formula I), dibasic acid (structural formula II or IV) and nonpolar organic solvent (more than one of toluene, xylene and trimethylbenzene) are mixed and then react, and azeotropic distillation is carried out while the reaction is carried out to remove generated water, so as to prepare carboxyl-terminated diamide; wherein the molar ratio of the diamine diacid salt to the dibasic acid is 1: 1-2, the ratio of the volume of the nonpolar organic solvent to the mass of the diamine diacid salt is 1-10: 1(mL/g), the reaction temperature is 10-30 ℃ higher than the boiling point of the nonpolar organic solvent, the reaction time is 12-20 h, an oil-water separation device is adopted for azeotropic distillation, the temperature of the azeotropic distillation is higher than the boiling point of the nonpolar organic solvent, and the azeotropic distillation time is 12-24 h;
after the reaction is finished, alcohol organic solvent (more than one of methanol, ethanol and propanol) is used for purification, and the specific process comprises the following steps: firstly, mixing a reacted mixture with an alcohol organic solvent at the temperature of 60-80 ℃, cooling to normal temperature, precipitating insoluble reactants, filtering to obtain a filtrate I, then putting the filtrate I into the environment of 0 ℃ to precipitate the reactants dissolved in the alcohol organic solvent, filtering to obtain a filtrate II, finally carrying out rotary evaporation on the filtrate II to obtain a product, drying, sealing and storing.
The mass ratio of the carboxyl-terminated diamide in the reaction product is more than 85%.
Example 1
A method for preparing carboxyl-terminated diamide, diamine is preparedAcid salt (structural formula is
) Dibasic acid (structural formula is
) Mixing with a nonpolar organic solvent (dimethylbenzene), reacting while performing azeotropic distillation to remove generated water to obtain carboxyl-terminated diamide; wherein the molar ratio of the diamine diacid salt to the dibasic acid is 1:1.5, the ratio of the volume of the nonpolar organic solvent to the mass of the diamine diacid salt is 6:1(mL/g), the reaction temperature is 160 ℃, the reaction time is 18h, an oil-water separation device is adopted for azeotropic distillation, the temperature of the azeotropic distillation is 160 ℃, and the time of the azeotropic distillation is 18 h;
after the reaction is finished, an alcohol organic solvent (ethanol) is used for purification, and the specific process is as follows: firstly, mixing a reacted mixture with an alcohol organic solvent at the temperature of 65 ℃, cooling to normal temperature, precipitating an insoluble reactant, filtering to obtain a filtrate I, then putting the filtrate I into the environment of 0 ℃ to precipitate the reactant dissolved in the alcohol organic solvent, filtering to obtain a filtrate II, finally carrying out rotary evaporation on the filtrate II to obtain a product, drying, sealing and storing.
The mass ratio of the carboxyl-terminated diamide in the reaction product was 87%.
The color value of the prepared modified polyester is improved by taking the prepared carboxyl-terminated diamide as a modifier for Polyester (PET) reaction, and the b value of the modified polyester is reduced to 6-9 from the original value of 15-17.
Comparative example 1
The same as example 1 except that the diamine diacid salt (structural formula
) Dibasic acid (structural formula is
) Mixing with a nonpolar organic solvent (dimethylbenzene) and then reacting, wherein azeotropic distillation is not carried out in the reaction process; due to the presence of water in the resultantThe ionic bond of the diamine diacid salt is more stable, stable amido bond is not easy to generate, and the mass percentage of the carboxyl-terminated diamide in the reaction product is only 20%.
Comparative example 2
Essentially the same as example 1 except that the molar ratio of the diamine diacid salt to the diacid is 1: 2.5; due to the excessive increase of the dibasic acid, the by-products in the product are increased, the ratio of the carboxyl-terminated diamide monomer in the product is reduced, and the mass ratio of the carboxyl-terminated diamide in the reaction product is 68%.
Comparative example 3
Essentially the same as example 1 except that the molar ratio of diamine diacid salt to diacid is 1: 0.5; due to the reduction of the addition amount of the dibasic acid, and the addition ratio of the acid to the amine is less than 2:1, partial diamine diacid salt can not participate in the reaction, so that the yield is reduced, and the diamine diacid salt generates byproducts at a certain temperature, so that the byproducts in the products are increased, namely the ratio of the carboxyl-terminated diamide monomer in the products is reduced, and the mass ratio of the carboxyl-terminated diamide in the reaction products is 68%.
Example 2
A method for preparing carboxyl-terminated diamide from diamine diacid salt (structural formula is shown in the specification)
) Dibasic acid (structural formula is
) Mixing with a nonpolar organic solvent (toluene) and then reacting, and removing generated water by azeotropic distillation while reacting to prepare carboxyl-terminated diamide; wherein the molar ratio of the diamine diacid salt to the dibasic acid is 1:1.4, the ratio of the volume of the nonpolar organic solvent to the mass of the diamine diacid salt is 6:1(mL/g), the reaction temperature is 150 ℃, the reaction time is 16h, an oil-water separation device is adopted for azeotropic distillation, the temperature of the azeotropic distillation is 150 ℃, and the time of the azeotropic distillation is 16 h;
after the reaction is finished, an alcohol organic solvent (ethanol) is used for purification, and the specific process is as follows: firstly, mixing a reacted mixture with an alcohol organic solvent at the temperature of 65 ℃, cooling to normal temperature, precipitating an insoluble reactant, filtering to obtain a filtrate I, then putting the filtrate I into the environment of 0 ℃ to precipitate the reactant dissolved in the alcohol organic solvent, filtering to obtain a filtrate II, finally carrying out rotary evaporation on the filtrate II to obtain a product, drying, sealing and storing.
The mass ratio of the carboxyl-terminated diamide in the reaction product was 85%.
The color value of the prepared modified polyester is improved by taking the prepared carboxyl-terminated diamide as a modifier for Polyester (PET) reaction, and the b value of the modified polyester is reduced to 6-9 from the original value of 15-17.
Example 3
A method for preparing carboxyl-terminated diamide from diamine diacid salt (structural formula is shown in the specification)
) Dibasic acid (structural formula is
) Mixing with a nonpolar organic solvent (dimethylbenzene), reacting while performing azeotropic distillation to remove generated water to obtain carboxyl-terminated diamide; wherein the molar ratio of the diamine diacid salt to the dibasic acid is 1:1, the ratio of the volume of the nonpolar organic solvent to the mass of the diamine diacid salt is 2:1(mL/g), the reaction temperature is 155 ℃, the reaction time is 15h, an oil-water separation device is adopted for azeotropic distillation, the temperature of the azeotropic distillation is 150 ℃, and the time of the azeotropic distillation is 15 h;
after the reaction is finished, an alcohol organic solvent (propanol) is used for purification, and the specific process comprises the following steps: firstly, mixing a reacted mixture with an alcohol organic solvent at the temperature of 80 ℃, cooling to normal temperature, precipitating an insoluble reactant, filtering to obtain a filtrate I, then putting the filtrate I into the environment of 0 ℃ to precipitate the reactant dissolved in the alcohol organic solvent, filtering to obtain a filtrate II, finally carrying out rotary evaporation on the filtrate II to obtain a product, drying, sealing and storing.
The mass ratio of the carboxyl-terminated diamide in the reaction product was 85%.
The color value of the prepared modified polyester is improved by taking the prepared carboxyl-terminated diamide as a modifier for Polyester (PET) reaction, and the b value of the modified polyester is reduced to 6-9 from the original value of 15-17.
Example 4
A method for preparing carboxyl-terminated diamide from diamine diacid salt (structural formula is shown in the specification)
) Dibasic acid (structural formula is
) Mixing with a nonpolar organic solvent (toluene) and then reacting, and removing generated water by azeotropic distillation while reacting to prepare carboxyl-terminated diamide; wherein the molar ratio of the diamine diacid salt to the dibasic acid is 1:2, the ratio of the volume of the nonpolar organic solvent to the mass of the diamine diacid salt is 3:1(mL/g), the reaction temperature is 130 ℃, the reaction time is 20h, an oil-water separation device is adopted for azeotropic distillation, the temperature of the azeotropic distillation is 130 ℃, and the time of the azeotropic distillation is 20 h;
after the reaction is finished, an alcohol organic solvent (ethanol and propanol with the volume ratio of 1: 1) is used for purification, and the specific process is as follows: firstly, mixing a reacted mixture with an alcohol organic solvent at the temperature of 75 ℃, cooling to normal temperature, precipitating an insoluble reactant, filtering to obtain a filtrate I, then putting the filtrate I into the environment of 0 ℃ to precipitate the reactant dissolved in the alcohol organic solvent, filtering to obtain a filtrate II, finally carrying out rotary evaporation on the filtrate II to obtain a product, drying, sealing and storing.
The mass ratio of the carboxyl-terminated diamide in the reaction product was 89%.
The color value of the prepared modified polyester is improved by taking the prepared carboxyl-terminated diamide as a modifier for Polyester (PET) reaction, and the b value of the modified polyester is reduced to 6-9 from the original value of 15-17.
Example 5
A method for preparing carboxyl-terminated diamide from diamine diacid salt (structural formula is shown in the specification)
) Dibasic acid (structure)Is of the formula
) Mixing with a nonpolar organic solvent (trimethylbenzene), reacting, and removing generated water by azeotropic distillation while reacting to prepare carboxyl-terminated diamide; wherein the molar ratio of the diamine diacid salt to the dibasic acid is 1:1.5, the ratio of the volume of the nonpolar organic solvent to the mass of the diamine diacid salt is 4:1(mL/g), the reaction temperature is 180 ℃, the reaction time is 12 hours, an oil-water separation device is adopted for azeotropic distillation, the temperature of the azeotropic distillation is 160 ℃, and the time of the azeotropic distillation is 12 hours;
after the reaction is finished, an alcohol organic solvent (methanol) is used for purification, and the specific process is as follows: firstly, mixing a reacted mixture with an alcohol organic solvent at the temperature of 60 ℃, cooling to normal temperature, precipitating an insoluble reactant, filtering to obtain a filtrate I, then putting the filtrate I into the environment of 0 ℃ to precipitate the reactant dissolved in the alcohol organic solvent, filtering to obtain a filtrate II, finally carrying out rotary evaporation on the filtrate II to obtain a product, drying, sealing and storing.
The mass ratio of the carboxyl-terminated diamide in the reaction product was 75%.
The color value of the prepared modified polyester is improved by taking the prepared carboxyl-terminated diamide as a modifier for Polyester (PET) reaction, and the b value of the modified polyester is reduced to 6-9 from the original value of 15-17.
Example 6
A method for preparing carboxyl-terminated diamide from diamine diacid salt (structural formula is shown in the specification)
) Dibasic acid (structural formula is
) Mixing with nonpolar organic solvent (xylene and trimethylbenzene at volume ratio of 1: 1), reacting, and removing generated water by azeotropic distillation while reacting to obtain carboxyl-terminated diamide; wherein the molar ratio of the diamine diacid salt to the dibasic acid is 1:1.2, the ratio of the volume of the nonpolar organic solvent to the mass of the diamine diacid salt is 5:1(mL/g), and the reaction is carried outThe temperature is 170 ℃, the reaction time is 16h, an oil-water separation device is adopted for azeotropic distillation, the temperature of the azeotropic distillation is 165 ℃, and the time of the azeotropic distillation is 16 h;
after the reaction is finished, an alcohol organic solvent (ethanol) is used for purification, and the specific process is as follows: firstly, mixing a reacted mixture with an alcohol organic solvent at the temperature of 65 ℃, cooling to normal temperature, precipitating an insoluble reactant, filtering to obtain a filtrate I, then putting the filtrate I into the environment of 0 ℃ to precipitate the reactant dissolved in the alcohol organic solvent, filtering to obtain a filtrate II, finally carrying out rotary evaporation on the filtrate II to obtain a product, drying, sealing and storing.
The mass ratio of the carboxyl-terminated diamide in the reaction product was 78%.
The color value of the prepared modified polyester is improved by taking the prepared carboxyl-terminated diamide as a modifier for Polyester (PET) reaction, and the b value of the modified polyester is reduced to 6-9 from the original value of 15-17.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011216562.1A CN112358410A (en) | 2020-11-04 | 2020-11-04 | Preparation method of carboxyl-terminated diamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011216562.1A CN112358410A (en) | 2020-11-04 | 2020-11-04 | Preparation method of carboxyl-terminated diamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112358410A true CN112358410A (en) | 2021-02-12 |
Family
ID=74513008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011216562.1A Pending CN112358410A (en) | 2020-11-04 | 2020-11-04 | Preparation method of carboxyl-terminated diamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112358410A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994027627A1 (en) * | 1993-05-24 | 1994-12-08 | Smithkline Beecham Corporation | Hemoregulatory peptides |
| CN102234373A (en) * | 2010-04-30 | 2011-11-09 | 北京化工大学 | Method for preparing biodegradable polyesteramide through chain extension |
| CN103881086A (en) * | 2012-12-22 | 2014-06-25 | 北京化工大学 | Biodegradable alternate polyesteramide preparation method |
| CN104710623A (en) * | 2013-12-11 | 2015-06-17 | 北京化工大学 | Preparation method of biodegradable polyesteramide modified polylactic acid |
-
2020
- 2020-11-04 CN CN202011216562.1A patent/CN112358410A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994027627A1 (en) * | 1993-05-24 | 1994-12-08 | Smithkline Beecham Corporation | Hemoregulatory peptides |
| CN102234373A (en) * | 2010-04-30 | 2011-11-09 | 北京化工大学 | Method for preparing biodegradable polyesteramide through chain extension |
| CN103881086A (en) * | 2012-12-22 | 2014-06-25 | 北京化工大学 | Biodegradable alternate polyesteramide preparation method |
| CN104710623A (en) * | 2013-12-11 | 2015-06-17 | 北京化工大学 | Preparation method of biodegradable polyesteramide modified polylactic acid |
Non-Patent Citations (3)
| Title |
|---|
| RACHEL FRIEDMAN OHANA，等: "Deciphering the Cellular Targets of Bioactive Compounds Using a Chloroalkane Capture Tag", 《ACS CHEM. BIOL.》 * |
| 徐元清，等: "《有机化学实验》", 31 December 2017, 河南大学出版社 * |
| 陈召，等: "尼龙66-6T 共聚物的晶体结构与力学性能研究", 《合成纤维工业》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101486639B (en) | Novel method for synthesizing mixed glucose derivative | |
| CN108794400B (en) | A kind of cationic amino acid-containing ionic liquid containing amino acid and preparation method and application thereof | |
| CN108383814A (en) | A kind of preparation method of 2,5- furandicarboxylic acids | |
| CN108558800A (en) | A kind of industrialized process for preparing of the 2,5- furandicarboxylic acids of low cost | |
| KR101125853B1 (en) | Process for preparing of n-methyl pyrrolidone | |
| CN107602619A (en) | A kind of Ru-polypyridine complex sensitising agent and preparation method thereof | |
| CN113527674B (en) | One-step method for synthesizing polyethyleneimine | |
| CN113117748A (en) | Bicyclic guanidine salt eutectic solvent catalyst and preparation method and application thereof | |
| CN114874121B (en) | Method for preparing substance containing monothiocarbonate group and product | |
| CN114605451B (en) | A method for preparing β-boramide based on chitosan functionalized copper material | |
| CN112358410A (en) | Preparation method of carboxyl-terminated diamide | |
| CN114210365B (en) | Catalyst for synthesizing methyl ethyl carbonate and diethyl carbonate and method thereof | |
| CN114516888A (en) | Process and equipment for producing coupling agent | |
| WO1991019696A1 (en) | Process for producing n-substituted aziridine compound | |
| CN1132809C (en) | Process for preparing diethyl carbonate | |
| CN111269158A (en) | Preparation method of α -hydroxy acid ester compound | |
| CN101072748B (en) | Method for producing N, N-Dimethylacetamide (DMAC) | |
| CN101072747A (en) | Method for producing N, N-Dimethylacetamide (DMAC) | |
| CN104591967A (en) | Crude glycerin treatment and applications of the same in epichlorohydrin production | |
| CN111072626B (en) | Preparation method of cyclic methylene disulfonate compound | |
| CN115557928A (en) | Synthetic method of 2-chlorothiophene-5-formic acid | |
| CN114230857A (en) | Method for rapidly degrading PET through high-temperature swelling effect | |
| CN114671810A (en) | Preparation method of imidocarb | |
| CN100412058C (en) | A kind of synthetic method of bis-indole alkyl compound | |
| CN102964195B (en) | Method for preparing second-level and third-level substituted amide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210212 |
|
| RJ01 | Rejection of invention patent application after publication |