CN106810687A - Diamine dicarboxylates, copolymers and process for their preparation - Google Patents
Diamine dicarboxylates, copolymers and process for their preparation Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000004985 diamines Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 230000008569 process Effects 0.000 title description 9
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 3
- 241000764238 Isis Species 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 30
- 230000008018 melting Effects 0.000 abstract description 30
- 238000005336 cracking Methods 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 8
- 230000000704 physical effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 61
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 239000001361 adipic acid Substances 0.000 description 17
- 235000011037 adipic acid Nutrition 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 14
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 14
- 229920002292 Nylon 6 Polymers 0.000 description 13
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229940125904 compound 1 Drugs 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000004566 IR spectroscopy Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229940126214 compound 3 Drugs 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 0 CC(C)C*(C)C(c1ccc(C*(CC(*)*)=C)cc1C)=* Chemical compound CC(C)C*(C)C(c1ccc(C*(CC(*)*)=C)cc1C)=* 0.000 description 4
- QAOWNCQODCNURD-ZSJDYOACSA-N Sulfuric acid-d2 Chemical compound [2H]OS(=O)(=O)O[2H] QAOWNCQODCNURD-ZSJDYOACSA-N 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004687 Nylon copolymer Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BNOVGRANWPZASU-DCAQKATOSA-N CC[F][C@](C)(CC[C@H](C)[IH][C@H](C)N)[IH]C Chemical compound CC[F][C@](C)(CC[C@H](C)[IH][C@H](C)N)[IH]C BNOVGRANWPZASU-DCAQKATOSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ULCGAWLDXLEIIR-UHFFFAOYSA-N bis(2-hydroxyethyl) benzene-1,3-dicarboxylate Chemical compound OCCOC(=O)C1=CC=CC(C(=O)OCCO)=C1 ULCGAWLDXLEIIR-UHFFFAOYSA-N 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/78—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/14—Adipic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/20—Sebacic acid
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a diamine dicarboxylates, a copolymer and a preparation method thereof. The copolymer is the reaction product of a composition comprising a first monomer and a second monomer, wherein the first monomer has the structure shown in formula (I)Wherein n is a positive integer independently selected from 2 to 6; and the second monomer has a structure represented by formula (II)Wherein A is- (CH)2)m-、m is a positive integer selected from 2 to 12, and R1Is H, C1-8Alkyl, or C1-6Alkanol group (alkanol group). The copolymer has two physical properties of high-uniformity sequence distribution and high melting point, and the melting point is not higher than the cracking point, so that the subsequent processing procedure is facilitated.
Description
Technical Field
The invention relates to diamine dicarboxylates, copolymers and preparation methods thereof.
Background
Currently, nylon 6(nylon 6) fibers are widely used in daily life, such as clothes, home furnishings, or other fields. However, nylon 6 has a lower melting point, softening point, heat resistance, and mechanical strength than nylon 66(nylon 66). These unfavorable physical properties have long limited the scope of development of downstream applications for nylon 6. The industry has attempted to produce differentiated nylon 6 by chemical synthesis in the hope of increasing the added value of nylon 6. However, in the current nylon 6 modification technology, nylon 6 products with high uniformity sequence distribution and high melting point physical properties cannot be obtained. In addition, the melting point of the nylon 6 modified product cannot be higher than the cracking point, otherwise, the subsequent processing procedure is not easy to be carried out.
Disclosure of Invention
It is an object of the present invention to provide a novel modified nylon 6 which is expected to have both high uniformity of sequence distribution and high melting point.
It is another object of the present invention to provide a novel modified nylon 6 having a melting point not higher than its cracking point, which is expected to facilitate subsequent processing.
Still another object of the present invention is to provide a process for producing the modified nylon 6.
Still another object of the present invention is to provide an intermediate for producing the modified nylon 6.
According to an embodiment of the present invention, a copolymer is disclosed. The copolymer is the reaction product of a composition comprising a first monomer and a second monomer, wherein the first monomer has the structure shown in formula (I)
Wherein n is a positive integer independently selected from 2 to 6;
and the second monomer has a structure represented by formula (II)
Wherein,wherein A is- (CH)2)m-、m is a positive integer selected from 2 to 12, and R1Is H, C1-8Alkyl, or C1-6Alkanol group (alkanol group).
According to another embodiment of the present invention, there is provided a bis-amine bis-carboxylate salt, which is a compound having a structure represented by formula (VI):
wherein D is2+Is thatOr a combination of the above, i is a positive integer independently selected from 2 to 6, n is a positive integer independently selected from 2 to 6, A is- (CH)2)m-、And m is a positive integer selected from 2 to 12.
According to another embodiment of the present invention, there is provided a method for preparing a copolymer, comprising: forming a composition into a bis-amine bis-carboxylate salt; and heating the diamine dicarboxylates to obtain the copolymer, wherein the composition comprises a first monomer and a second monomer, and the first monomer has a structure shown in formula (I)
Wherein n is a positive integer independently selected from 2 to 6;
and the second monomer has a structure represented by formula (II)
Wherein A is- (CH)2)m-、m is a positive integer selected from 2 to 12, and R1Is H, C1-8Alkyl, or C1-6Alkanol group (alkanol group).
The invention has the advantages that: on one hand, EDA (or BDA) and DMI are synthesized into diamine monomers, and the diamine monomers and dicarboxylic acid monomers (AA or SA) are subjected to copolymerization reaction, so that a cross-type (alternating) polymer with optimal sequence distribution can be obtained, and the physical properties of the copolymer, such as symmetry, high sequence distribution, high melting point and the like, are improved; on the other hand, the invention uses the meta-phenyl compound with the disubstituted functional group as the reaction monomer, so that the rigidity of the copolymer can be reduced, the melting point of the copolymer is prevented from being higher than the cracking temperature (>280 ℃), and the problem that the copolymer obtained by using the para-phenyl compound with the disubstituted functional group as the starting material can not be processed is solved; in another aspect, the present invention can also be used to control the melting point of the resulting copolymer by adding a di-substituted functional meta-phenyl compound as a reactive monomer and mixing with a di-substituted functional para-phenyl compound; in yet another aspect, the present invention can reduce the melting point of the resulting copolymer by increasing the molar ratio of the di-substituted functional group meta-phenyl compound to the di-substituted functional group para-phenyl compound, and avoid the copolymer having a melting point higher than its cracking temperature.
In order to make the aforementioned and other objects, features, and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below:
Detailed Description
In accordance with an embodiment of the present invention, there is provided a copolymer that is the reaction product of a composition. The composition may comprise a first monomer and a second monomer, wherein the molar ratio of the first monomer to the second monomer may be between 1.2:1 and 1:1.2, for example 1:1. Wherein the first monomer can have a structure shown in formula (I)
Wherein n is a positive integer independently selected from 2 to 6;
and the second monomer may have a structure represented by formula (II)
Wherein A is- (CH)2)m-、m is a positive integer selected from 2 to 12, and R1Is H, C1-8Alkyl, or C1-6Alkanol group (alkanol group).
For example, the first monomer can be And the second monomer can be
According to an embodiment of the present invention, the copolymer may have a repeating unit having a structure as shown in formula (IV)
Wherein n is a positive integer independently selected from 2 to 6, e.g., 2, 3, 4, 5, or 6, A is- (CH)2)m-、 And m is a positive integer selected from 2-12, for example 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
According to an embodiment of the present invention, in order to adjust the structural rigidity and melting point of the obtained copolymer, the composition further comprises a third monomer, wherein the third monomer has a structure represented by formula (III)
Wherein i is a positive integer independently selected from 2 to 6, for example 2, 3, 4, 5, or 6. According to an embodiment of the present invention, the molar ratio of the first monomer to the third monomer may be between 1:9 and 9: 1. In addition, increasing the molar ratio of the first monomer to the third monomer can lower the melting point of the copolymer, or prevent the melting point of the copolymer from being higher than the cracking temperature, so that the subsequent processing process is easier to perform. Furthermore, the ratio of the sum of the moles of the first monomer and the third monomer to the moles of the second monomer may be between 1:1.2 and 1.2: 1. The copolymer can have repeating units with structures shown as formulas (IV) and (V)
Wherein i is a positive integer independently selected from 2 to 6, n is a positive integer independently selected from 2 to 6, A is-(CH2)m-、And m is a positive integer selected from 2 to 12.
According to an embodiment of the present invention, there is provided a bisamine dicarboxylates, which is a compound having a structure represented by formula (VI):
wherein D is2+Is thatOr a combination of the foregoing, i is a positive integer independently selected from 2 to 6, n is a positive integer independently selected from 2 to 6, e.g., 2, 3, 4, 5, or 6, A is- (CH)2)m-、And m is a positive integer selected from 2-12, for example 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
According to an embodiment of the present invention, D2+Can be And isAndthe equivalent ratio of (a) may be 1:99 to 99:1, for example 1:9 to 9:1, or 1:5 to 5: 1.
According to an embodiment of the present invention, there is provided a method of preparing a copolymer to form the above copolymer. The preparation method comprises the following steps: reacting a composition at 60-120 ℃ for 6-16 hours to form a bis-amine bis-carboxylate salt; and, performing a heating reaction (e.g. a melting process or a solution process) on the diamine dicarboxylates, e.g. at 180-260 ℃ for 4-16 hours, and drying to obtain the copolymer. In one embodiment, the heating reaction is a stepwise increase in temperature from an initial temperature (e.g., 180 ℃) to 5-20 ℃ at intervals (e.g., 30 minutes-2 hours) to complete the reaction, the reaction temperature not exceeding 260 ℃. The composition comprises a first monomer and a second monomer, wherein the first monomer has a structure shown in formula (I)
Wherein n is a positive integer independently selected from 2 to 6;
and the second monomer has a structure represented by formula (II)
Wherein A is- (CH)2)m-、m is a positive integer selected from 2 to 12, and R1Is H, C1-8Alkyl, or C1-6Alkanol group (alkanol group). In addition, the composition may further comprise a third monomer, wherein the third monomer has a structure represented by formula (III)
Wherein i is a positive integer independently selected from 2 to 6.
The following examples and comparative examples are provided to further illustrate the technical features of the present invention by illustrating the preparation of the monomer, diamine dicarboxylate and copolymer of the present invention.
Preparation of the first monomer
Preparation example 1: preparation of Compound 1 with EDA and DMI
A reaction flask was provided, into which 36g of Ethylene Diamine (EDA), 19.4g of dimethyl isophthalate (DMI), and 100ml of Ethylene Glycol (EG) were charged. The flask was then slowly warmed to 90 ℃ under nitrogen. After 24 hours of reaction, it was cooled to room temperature and filtered. Then, the solid was collected, the obtained solid was washed with water and methanol, and the washed solid was dried in an oven at 80 ℃ to obtain compound 1. The reaction formula of the above reaction is shown below:
nuclear Magnetic Resonance (NMR) spectroscopic analysis was performed on Compound 1, and the results were as follows:
1HNMR(D2SO4，ppm)＝8.7(1H、s)；8.5(2H、s)；8.4(1H、s)；4.4-4.3(4H、m)；4.0(4H、m)。
preparation example 2: preparation of Compound 1 with EDA and BHEI
A reaction flask was provided, and 6g of Ethylenediamine (EDA), 2.54g of bis (2-hydroxyethyl) isophthalate (BHEI) and 20ml of Ethylene Glycol (EG) were added thereto. Next, 0.06g of sodium acetate was added to the reaction flask. The flask was then slowly warmed to 110 ℃ under nitrogen. After 24 hours of reaction, it was cooled to room temperature and filtered. Then, the solid was collected, the obtained solid was washed with water and methanol, and the washed solid was dried in an oven at 80 ℃ to obtain compound 1. The reaction formula of the above reaction is shown below:
nuclear Magnetic Resonance (NMR) spectrum analysis was performed on Compound 1, and the results were the same as those in preparation example 1.
Preparation example 3: preparation of Compound 2 from BDA and DMI
A reaction flask was provided, and 22.6g of butanediamine (1,4-butylene diamine, BDA), 5g of dimethyl isophthalate (DMI), and 100ml of Ethylene Glycol (EG) were added thereto. The flask was then slowly warmed to 90 ℃ under nitrogen. After 24 hours of reaction, it was cooled to room temperature and filtered. Then, the solid was collected, the obtained solid was washed with water and methanol, and the washed solid was dried in an oven at 80 ℃ to obtain compound 2. The reaction formula of the above reaction is shown below:
nuclear Magnetic Resonance (NMR) spectroscopic analysis was performed on Compound 2, and the results were as follows:
1HNMR(D2SO4，ppm)＝8.7(1H、s)；8.5(2H、s)；8.4(1H、s)；4.4-4.3(4H、m)；4.0(4H、m)；2.5-2.4(8H、m)。
preparation example 4: preparation of Compound 3 from EDA and DMT
A reaction flask was provided, into which 36g of Ethylene Diamine (EDA), 19.4g of dimethyl terephthalate (DMT) and 100ml of Ethylene Glycol (EG) were added. The flask was then slowly warmed to 90 ℃ under nitrogen. After 24 hours of reaction, it was cooled to room temperature and filtered. Then, the solid was collected, the obtained solid was washed with water and methanol, and the washed solid was dried in an oven at 80 ℃ to obtain compound 3. The reaction formula of the above reaction is shown below:
preparation of diamine dicarboxylates
Example 1
0.25g of Compound 1 obtained in production example 1, 0.146g of Adipic Acid (AA), and 5ml of water were charged into a reaction flask. Then, the reaction flask was heated to 90 ℃ and reacted for 8 hours. Then, it was cooled to room temperature and filtered, and the resulting solid was washed with water and methanol. And drying the washed solid in an oven at 80 ℃ to obtain the diamine dicarboxylates 1. The reaction formula of the above reaction is shown below:
the Nuclear Magnetic Resonance (NMR) spectrum of the bisamine biscarboxylate 1 was measured, and the results were as follows:
1HNMR(D2SO4，ppm)＝8.7(1H、s)；8.5(2H、s)；8.4(1H、s)；4.4-4.3(4H、m)；4.2-4.1(4H、m)；3.3-3.2(4H、m)；2.1-1.9(4H、m)。
example 2
0.50g of Compound 1 obtained in production example 1, 0.41g of sebacic acid (sebasic acid, SA), and 5ml of water were charged into a reaction flask. Then, the reaction flask was heated to 90 ℃ and reacted for 8 hours. Then, it was cooled to room temperature and filtered, and the resulting solid was washed with water and methanol. And drying the washed solid in an oven at 80 ℃ to obtain the diamine dicarboxylates 2. The reaction formula of the above reaction is shown below:
the Nuclear Magnetic Resonance (NMR) spectrum of the bisamine biscarboxylate 2 was measured, and the results were as follows:
1HNMR(D2SO4，ppm)＝8.7(1H、s)；8.5(2H、s)；8.4(1H、s)；4.4-4.3(4H、m)；4.2-4.1(4H、m)；3.3-3.2(4H、m)；2.1-2.0(4H、m)；1.8-1.7(8H、m)。
example 3
5g of Compound 2 obtained in production example 3, 2.4g of Adipic Acid (AA), and 10ml of water were charged into a reaction flask. Then, the reaction flask was heated to 90 ℃ and reacted for 8 hours. Then, it was cooled to room temperature and filtered, and the resulting solid was washed with water and methanol. And drying the washed solid in an oven at 80 ℃ to obtain the diamine dicarboxylates 3. The reaction formula of the above reaction is shown below:
the Nuclear Magnetic Resonance (NMR) spectrum of the bisamine biscarboxylate 3 was measured, and the results were as follows:
1HNMR(D2SO4，ppm)＝8.7(1H、s)；8.5(2H、s)；8.4(1H、s)；4.4-4.3(4H、m)；4.2-4.0(4H、m)；3.3-3.2(4H、m)；2.4-2.2(4H、m)；2.1-2.0(4H、m)。
example 4
0.5g of Compound 1 obtained in production example 1, 2.0g of Compound 3 obtained in production example 4, 1.46g of adipic acid (adipic acid, AA) and 150ml of water were added to a reaction mixtureIn a bottle. Then, the reaction flask was heated to 90 ℃ and reacted for 8 hours. Then, it was cooled to room temperature and filtered, and the resulting solid was washed with water and methanol. Drying the cleaned solid in an oven at 80 ℃ to obtain diamine dicarboxylates 4: (Cation andthe molar ratio of cations was 1: 4). The reaction formula of the above reaction is shown below:
the Nuclear Magnetic Resonance (NMR) spectrum of the bisamine biscarboxylate 4 was measured, and the results were as follows:
1H NMR(D2SO4,ppm)＝8.7(1H、s、meta-aromatic)；8.5(2H、s、meta-aromatic)；8.4(1H、s、meta-aromatic)；8.5(16H、s、para-aromatic)；4.4-4.3(20H、m)；4.2-4.1(20H、m)；3.3-3.2(20H、m)；2.1-1.9(20H、m)。
example 5
2.0g of Compound 1 obtained in production example 1, 0.5g of Compound 3 obtained in production example 4, 1.46g of adipic acid (adipic acid, AA), and 150ml of water were put into a reaction flask. Then, the reaction flask was heated to 90 ℃ and reacted for 8 hours. Then, it was cooled to room temperature and filtered, and the resulting solid was washed with water and methanol. Drying the cleaned solid in an oven at 80 ℃ to obtain diamine dicarboxylates 5: (Cation andcationic polymerMolar ratio of subunits 4: 1). The reaction formula of the above reaction is shown below:
the Nuclear Magnetic Resonance (NMR) spectrum of the bisamine biscarboxylate 5 was measured, and the results were as follows:
1H NMR(D2SO4,ppm)＝8.7(4H、s、meta-aromatic)；8.5(8H、s、meta-aromatic)；8.4(4H、s、meta-aromatic)；8.5(4H、s、para-aromatic)；4.4-4.3(20H、m)；4.2-4.0(20H、m)；3.3-3.2(20H、m)；2.1-1.9(20H、m)。
comparative example 1
0.25g of Compound 3 obtained in production example 4, 0.146g of Adipic Acid (AA), and 5ml of water were charged into a reaction flask. Then, the reaction flask was heated to 90 ℃ and reacted for 8 hours. Then, it was cooled to room temperature and filtered, and the resulting solid was washed with water and methanol. And drying the washed solid in an oven at 80 ℃ to obtain the diamine dicarboxylates 6. The reaction formula of the above reaction is shown below:
the Nuclear Magnetic Resonance (NMR) spectrum of the bisamine biscarboxylate 6 was measured, and the results were as follows:
1HNMR(D2SO4，ppm)＝8.5(4H、s)；4.4-4.3(4H、m)；4.2-4.1(4H、m)；3.3-3.2(4H、m)；2.1-2.0(4H、m)。
preparation of the copolymer
Example 6
0.4g of the solution obtained in example 1 was addedThe diamine dicarboxylates 1 were placed in a reaction flask and connected to a rotary heating device. After evacuation for 5 minutes, nitrogen was added and the above procedure was repeated 3 times. Then, the reaction was carried out under nitrogen gas with heating at 180 ℃ for 1 hour, at 200 ℃ for 1 hour, at 220 ℃ for 1 hour, at 240 ℃ for 1 hour, and at 250 ℃ for 1 hour. Finally, the resulting product was dried at 80 ℃ for 24 hours. After cooling, copolymer 1 (havingRepeat unit), the yield was 93%.
Copolymer 1 was measured with a differential scanning calorimeter (differential scanning calorimeter) and found to have a melting temperature (Tm) of 251 c (highest peak), a glass transition temperature (Tg) of between about 91 c and 92 c, and a relative viscosity (R.V.) of 2.4. The relative viscosity (R.V.) of the copolymer was analyzed by placing 0.25g of the nylon copolymer in an analyzing glass bottle, adding concentrated sulfuric acid (97 wt% concentration) to prepare a 50ml solution, and analyzing the relative viscosity (R.V.) at 25 ℃. The copolymer 1 was analyzed by nmr spectroscopy and ir spectroscopy, and the spectral information obtained was as follows:
1HNMR(D2SO4，ppm)＝8.7(1H、s)；8.5(2H、s)；8.4(1H、s)；4.3(4H、m)；4.0-3.9(4H、m)；2.4-2.3(4H、m)；2.1-2.0(4H、m)。
example 7
0.4g of the bisamine biscarboxylate 2 from example 2 was placed in a reaction flask and the rotary heating device was turned on. After evacuation for 5 minutes, nitrogen was added and the above procedure was repeated 3 times. Then, the reaction was carried out under nitrogen gas with heating at 180 ℃ for 1 hour, at 200 ℃ for 1 hour, at 220 ℃ for 1 hour, at 240 ℃ for 1 hour, and at 250 ℃ for 1 hour. Finally, the resulting product was dried at 80 ℃ for 24 hours. After cooling, a copolymer is obtainedObject 2 (with)Repeat unit), the yield was 93%.
Copolymer 2 was measured with a differential scanning calorimeter (differential scanning calorimeter) and found to have a melting temperature (Tm) of 220 ℃ (highest peak), a glass transition temperature (Tg) of between about 91 ℃ and 92 ℃, and a relative viscosity (R.V.) of 1.6. The copolymer 2 was analyzed by nmr spectroscopy and ir spectroscopy, and the spectral information obtained was as follows:
1HNMR(D2SO4，ppm)＝8.7(1H、s)；8.5(2H、s)；8.4(1H、s)；4.4-4.3(4H、m)；4.1-3.9(4H、m)；3.3-3.2(4H、m)；2.3-2.2(4H、m)；1.8-1.7(8H、m)。
example 8
0.4g of the bisamine biscarboxylate 3 from example 3 was placed in a reaction flask and the rotary heating device was turned on. After evacuation for 5 minutes, nitrogen was added and the above procedure was repeated 3 times. Then, the reaction was carried out under nitrogen gas with heating at 180 ℃ for 1 hour, at 200 ℃ for 1 hour, at 220 ℃ for 1 hour, at 240 ℃ for 1 hour, and at 250 ℃ for 1 hour. Finally, the resulting product was dried at 80 ℃ for 24 hours. After cooling, copolymer 3 (havingRepeat unit), the yield was 91%.
Copolymer 3 was measured with a differential scanning calorimeter (differential scanning calorimeter) and found to have a melting temperature (Tm) of 230 ℃ (highest peak), a glass transition temperature (Tg) of between about 87 ℃ and 88 ℃, and a relative viscosity (R.V.) of 2.1. The copolymer 3 was analyzed by nmr spectroscopy and ir spectroscopy, and the spectral information obtained was as follows:
1HNMR(D2SO4，ppm)＝8.7(1H、s)；8.5(2H、s)；8.4(1H、s)；4.3(4H、m)；4.0-3.9(4H、m)；3.3-3.2(4H、m)；2.4-2.3(4H、m)；2.1-2.0(4H、m)。
example 9
2g of the bisamine biscarboxylate 4 from example 4 were placed in a reaction flask and the heating device was rotated upward. After evacuation for 5 minutes, nitrogen was added and the above procedure was repeated 3 times. Then, the reaction was carried out under nitrogen gas with heating at 180 ℃ for 1 hour, at 200 ℃ for 1 hour, at 220 ℃ for 1 hour, at 240 ℃ for 1 hour, and at 250 ℃ for 1 hour. Finally, the resulting product was dried at 80 ℃ for 24 hours. After cooling, copolymer 4 (havingRepeat unit), yield 94%.
Copolymer 4 was measured with a differential scanning calorimeter (differential scanning calorimeter) and found to have a melting temperature (Tm) of 271 ℃ and 279 ℃ (peak), a glass transition temperature (Tg) of between about 89 ℃ and 92 ℃, and a relative viscosity (R.V.) of 2.3. The copolymer 4 was analyzed by nmr spectroscopy and ir spectroscopy, and the spectral information obtained was as follows:
1H NMR(D2SO4,ppm)＝8.7(1H、s、meta-aromatic)；8.5(2H、s、meta-aromatic)；8.4(1H、s、meta-aromatic)；8.5(16H、s、para-aromatic)；4.4-4.3(20H、m)；4.0-3.9(20H、m)；3.3-3.2(20H、m)；2.1-1.9(20H、m)。
example 10
2g of the bisamine biscarboxylate 5 from example 5 were placed in a reaction flask and the heating device was rotated upward. After evacuation for 5 minutes, nitrogen was added and the above procedure was repeated 3 times. Then, a heating reaction is carried out under nitrogen gas under the condition thatHeating at 180 ℃ for 1 hour, at 200 ℃ for 1 hour, at 220 ℃ for 1 hour, at 240 ℃ for 1 hour, and at 250 ℃ for 1 hour. Finally, the resulting product was dried at 80 ℃ for 24 hours. After cooling, copolymer 5 (havingRepeat unit), yield was 92%.
The copolymer 5 was measured by a differential scanning calorimeter (differential scanning calorimeter) and found to have a melting temperature (Tm) of 208-. The copolymer 5 was analyzed by nmr spectroscopy and ir spectroscopy, and the spectral information obtained was as follows:
1H NMR(D2SO4,ppm)＝8.7(4H、s、meta-aromatic)；8.5(8H、s、meta-aromatic)；8.4(4H、s、meta-aromatic)；8.5(4H、s、para-aromatic)；4.4-4.3(20H、m)；4.0-3.9(20H、m)；3.3-3.2(20H、m)；2.1-1.9(20H、m)。
comparative example 2
0.4g of the bisamine biscarboxylate 6 from comparative example 1 was placed in a reaction flask and the rotary heating device was turned on. After evacuation for 5 minutes, nitrogen was added and the above procedure was repeated 3 times. Then, the reaction was carried out under nitrogen gas with heating at 180 ℃ for 1 hour, at 200 ℃ for 1 hour, at 220 ℃ for 1 hour, at 240 ℃ for 1 hour, and at 250 ℃ for 1 hour. Finally, the resulting product was dried at 80 ℃ for 24 hours. After cooling, copolymer 6 (havingRepeat unit), yield 94%.
The copolymer 6 was measured with a differential scanning calorimeter (differential scanning calorimeter) and it was found that its melting temperature was higher than the cracking temperature so that the melting point was covered with the cracking temperature. A glass transition temperature (Tg) of between about 91 ℃ and 93 ℃ and a relative viscosity (R.V.) of 2.4. The copolymer 6 was analyzed by nmr spectroscopy and ir spectroscopy, and the spectral information obtained was as follows:
1HNMR(D2SO4，ppm)＝8.5(4H、s)；4.4-4.3(4H、m)；4.2-4.1(4H、m)；3.3-3.2(4H、m)；2.1-2.0(4H、m)。
comparative example 3
According to a general synthesis method of nylon copolymer described in the literature (Rwei, s.p.et al, thermochemical Acta,555, 37-45,2013), Ethylene Diamine (EDA), dimethyl isophthalate (DMI), and Adipic Acid (AA) were melt-copolymerized (molar ratio 1:1:2) to obtain copolymer 7.
Copolymer 7 was measured with a differential scanning calorimeter (differential scanning calorimeter) and found to have a number of distinct peaks in melting temperature (Tm) between 196 ℃ and 240 ℃ and a relative viscosity (R.V.) of 2.1.
TABLE 1
As can be seen from table 1, since the copolymer 6 (comparative example 2) uses a relatively rigid dimethyl terephthalate (DMT) as a reaction initiator (and no dimethyl isophthalate is added), the product melting point is higher than the cracking temperature thereof, and the subsequent processing process cannot be performed, compared to the copolymer 1 (example 6, using dimethyl isophthalate (DMI) as a reaction initiator) described in the present application. The copolymer 7 (comparative example 3) is a commonly used random polymerization (copolymerization using three monomers, EDA, DMI, and AA), which results in the formation of polymer blocks (random copolymer) containing many disordered different compositions, such that the sequence distribution of the monomer components in the copolymer is not good, resulting in poor crystallinity, and thus lowering the melting point, strength, and physical stability of the copolymerization product. Inverse copolymers 1 to 3 (examples 6 to 8) were prepared by synthesizing EDA (or BDA) and DMI into diamine-type monomers, and then copolymerizing the diamine-type monomers with dicarboxylic acid-type monomers (AA or SA) to obtain alternating-type (alternate) polymers having an optimal sequence distribution, thereby improving physical properties such as symmetry, high sequence distribution, and high melting point of the copolymers. In addition, since the meta-phenyl compound having the disubstituted functional group is used as a reaction monomer, the rigidity of the copolymer can be reduced, the melting point of the copolymer is prevented from being higher than the cracking temperature (>280 ℃) thereof, and the problem that the copolymer obtained by using the para-phenyl compound having the disubstituted functional group as a starting material cannot be processed is solved. On the other hand, the application can also be used to control the melting point of the copolymer by adding a di-substituted functional meta-phenyl compound as a reactive monomer and mixing with a di-substituted functional para-phenyl compound. From the copolymers 4 to 5 of the present application (examples 9 to 10), it can be seen that increasing the molar ratio of the meta-phenyl compound having a disubstituted functional group to the para-phenyl compound having a disubstituted functional group can lower the melting point of the resulting copolymer and prevent the copolymer from having a melting point higher than its cracking temperature.
Although embodiments of the present invention and their advantages have been described above, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification, but it is to be understood that any process, machine, manufacture, composition of matter, means, method and steps, presently existing or later to be developed, that will be obvious to one skilled in the art from this disclosure may be utilized according to the present application as many equivalents of the presently available embodiments of the present application are possible and equivalents may be developed in that way. Accordingly, the scope of the present application includes the processes, machines, manufacture, compositions of matter, means, methods, and steps described above. In addition, each claim constitutes an individual embodiment, and the scope of protection of the present invention also includes combinations of the respective claims and embodiments.
Claims (12)
1. A copolymer that is the reaction product of a composition comprising a first monomer and a second monomer, wherein the first monomer has a structure according to formula (I)
Wherein n is a positive integer independently selected from 2 to 6;
and the second monomer has a structure represented by formula (II)
Wherein A is- (CH)2)m-、m is a positive integer selected from 2 to 12, and R1Is H, C1-8Alkyl, or C1-6And (3) alkanol groups.
2. The copolymer of claim 1, wherein the first monomer is
3. The copolymer of claim 1, wherein the second monomer is
4. The copolymer of claim 1, wherein the copolymer has a repeating unit having a structure as shown in formula (IV)
Wherein n is a positive integer independently selected from 2 to 6, and A is- (CH)2)m-、And m is a positive integer selected from 2 to 12.
5. The copolymer of claim 1, wherein the composition further comprises a third monomer, wherein the third monomer has the structure of formula (III)
Wherein i is a positive integer independently selected from 2 to 6.
6. The copolymer of claim 5, wherein the molar ratio of the first monomer to the third monomer is between 1:9 and 9: 1.
7. The copolymer of claim 5, wherein the third monomer is
8. The copolymer of claim 5, wherein the copolymer has repeating units of the structures shown in formula (IV) and formula (V)
Wherein i is a positive integer independently selected from 2 to 6, n is a positive integer independently selected from 2 to 6, and A is- (CH)2)m-、And m is a positive integer selected from 2 to 12.
9. A bis-amine bis-carboxylate salt which is a compound having the structure shown in formula (VI):
wherein D is2+Is that Or a combination of the above, i is a positive integer independently selected from 2 to 6, n is a positive integer independently selected from 2 to 6, A is- (CH)2)m-、And m is a positive integer selected from 2 to 12.
10. The bis-amine bis-carboxylate salt of claim 9 wherein D2+Is that
And isIs 1:9 to 9: 1.
11. A method of making a copolymer to form the copolymer of claim 1, comprising:
forming a composition into a bis-amine bis-carboxylate salt; and
heating the diamine dicarboxylates to obtain the copolymer, wherein the composition comprises a first monomer and a second monomer, wherein the first monomer has a structure shown in formula (I)
Wherein n is a positive integer independently selected from 2 to 6;
and the second monomer has a structure represented by formula (II)
Wherein A is- (CH)2)m-、m is a positive integer selected from 2 to 12, and R1Is H, C1-8Alkyl, or C1-6And (3) alkanol groups.
12. The method of claim 11, wherein the composition further comprises a third monomer, wherein the third monomer has the structure of formula (III)
Wherein i is a positive integer independently selected from 2 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2371104A (en) * | 1945-03-06 | Rxnhxa | ||
| EP0231545A1 (en) * | 1986-01-04 | 1987-08-12 | Dsm N.V. | Copolyamides and a process for the preparation thereof |
| US5093464A (en) * | 1988-12-01 | 1992-03-03 | Korea Institute Of Science And Technology | Wholly aromatic polyamide from N,N'-bis (4-amino phenyl)-isophthalamide |
| CN1646603A (en) * | 2002-02-21 | 2005-07-27 | 斯地廷荷兰聚合物研究所 | Copolymer containing one or more amide segments |
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| US5393902A (en) * | 1994-04-26 | 1995-02-28 | Lever Brothers Company, Division Of Conopco, Inc. | Process for the preparation of bis(amidocarboxylic acids) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2371104A (en) * | 1945-03-06 | Rxnhxa | ||
| EP0231545A1 (en) * | 1986-01-04 | 1987-08-12 | Dsm N.V. | Copolyamides and a process for the preparation thereof |
| US5093464A (en) * | 1988-12-01 | 1992-03-03 | Korea Institute Of Science And Technology | Wholly aromatic polyamide from N,N'-bis (4-amino phenyl)-isophthalamide |
| CN1646603A (en) * | 2002-02-21 | 2005-07-27 | 斯地廷荷兰聚合物研究所 | Copolymer containing one or more amide segments |
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