CN109369908A - A kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine - Google Patents
A kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine Download PDFInfo
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- CN109369908A CN109369908A CN201810982101.1A CN201810982101A CN109369908A CN 109369908 A CN109369908 A CN 109369908A CN 201810982101 A CN201810982101 A CN 201810982101A CN 109369908 A CN109369908 A CN 109369908A
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- dimethylamine
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- synthetic method
- paraphenylene terephthalamide
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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
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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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
- C08G69/04—Preparatory processes
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Polyamides (AREA)
Abstract
The polycondensation synthetic method of a kind of poly- paraphenylene terephthalamide p dimethylamine disclosed by the invention, it is characterised in that including paraphenylene terephthalamide's preparation step, p dimethylamine's preparation step and polycondensation synthesis step.The beneficial effects of the present invention are: that the present invention is directed to is then the poly- paraphenylene terephthalamide p dimethylamine of a new varieties-in aromatic polyamide family, from structure, the characteristics of structure of poly- paraphenylene terephthalamide p dimethylamine has both fatty polyamide and fully aromatic polyamide has the characteristics that amide group is connected with phenyl ring, aliphatic.Therefore the polymer still has preferable heat resistance, while making moderate progress in the flexibility of material.Polycondensation synthetic method preparation process of the present invention is simple, and reaction substrate is easy to get, and has good industrial reproducibility.
Description
Technical field
The present invention relates to polymeric material fields, more particularly, to the condensation polymerization of poly- paraphenylene terephthalamide p dimethylamine a kind of
At method.
Background technique
Polyamide (polyamide, PA) is commonly referred to as nylon (Nylon), it is in polymer macromolecule chain containing weight
The heterochain polymer general name of complex structure unit amide group (NHCO-), mainly by binary acid and diamine or amino acid lactams
It is obtained through polycondensation or autohemagglutination, is to develop earliest, the maximum thermoplastic engineering plastic of usage amount.
Polyamide kind is more, and it is poly- to be divided into fatty polyamide, semiaromatic polyamide composition, all aromatic by backbone structure
Amide, polyamide containing heteroaromatic and alicyclic polyamide.In fully aromatic polyamide, phenyl ring is intensive with amide group,
And symmetrical configuration, therefore fusing point is very high, and it is not easy to be processed, it is at high cost to be not easy to industrialize.Current most successful fully aromatic polyamide
It is poly(p-phenylene terephthalamide) (PPTA), belongs to Lyotropic Liquid Crystalline Polymer, can be processed into fiber, referred to as Kevlar.
But in practical applications, it is not suitable for operating since the processing temperature of full aramid fiber is too high, so general in the market
It is promoted using semi-aromatic nylon as main species.New varieties of the semi-aromatic nylon as nylon, remain the excellent of nylon
Characteristic, and improving the certain insufficient aspects of full aramid fiber.Therefore for the related product in aromatic polyamide family
The further exploitation of kind is just very significant.
Summary of the invention
In order to solve defect of the existing technology, the purpose of the present invention is to provide a kind of poly- paraphenylene terephthalamides to benzene two
The polycondensation synthetic method of methylamine.
In order to realize above-mentioned purpose of the present invention, the technical scheme adopted by the invention is that a kind of poly- paraphenylene terephthalamide is to benzene two
The polycondensation synthetic method of methylamine, includes the following steps:
(1) chlorination lithium powder and N-methyl pyrrolidone solution are added in the reaction vessel, mixed solvent is made in stirring；
(2) solvent obtained by part steps (1) is taken, and p dimethylamine is added, is stirred, solution is made in dissolution；
(3) acid binding agent is added in the solution obtained by step (2)；
(4) solvent obtained by part steps (1) is separately taken, paraphthaloyl chloride is added, is mixed into solution；
(5) solution obtained in step (4) is divided into two parts, is added sequentially in the reaction vessel of step (2), during which between
Every certain time, it is kept stirring；
(6) continue to be stirred to react a period of time, distilled water is added, stop reaction, generate white depositions；
(7) with water step (6) are cleaned multiple times obtained by sediment, drying, obtain product.
In a preferred embodiment of the invention, which is characterized in that in step (1), the content of the lithium chloride is 3
~10%.
In a preferred embodiment of the invention, which is characterized in that in step (1), the N-methyl pyrrolidones
Mass percent is 97~90%, and the mass percent of chlorination lithium powder is 3~10%.
In a preferred embodiment of the invention, which is characterized in that in step (2), the terephthaldehyde of the addition
The amount of amine is the 0.5~10% of solvent.
In a preferred embodiment of the invention, which is characterized in that in step (3), the acid binding agent is pyridine, 2-
The mixing of any one or two kinds in picoline, additional amount are the 0.5~20% of solvent.
In a preferred embodiment of the invention, which is characterized in that in step (4), the terephthaldehyde of the addition
The molar ratio of p dimethylamine is 0.095~1.005:1 in the amount of acyl chlorides and step (2).
In a preferred embodiment of the invention, which is characterized in that in step (5), two parts of solution being divided into account for respectively
Volume ratio be 40~60% and 60%~40%, reaction temperature control be -5~10 DEG C, the dosing intervals time be 3~10min.
In a preferred embodiment of the invention, which is characterized in that in step (6), the reaction time is 10~40min,
Reaction temperature control is -5~10 DEG C.
In a preferred embodiment of the invention, which is characterized in that in step (7), products therefrom yield be 45~
95%.
Beneficial effects of the present invention are as follows:
The present invention is directed the poly- paraphenylene terephthalamide p dimethylamine of a new varieties-in aromatic polyamide family,
From structure, the structure of poly- paraphenylene terephthalamide p dimethylamine has both the spy of fatty polyamide and fully aromatic polyamide
Point has the characteristics that amide group is connected with phenyl ring, aliphatic.Therefore the polymer still has preferable heat resistance, simultaneously
It makes moderate progress in the flexibility of material.
Polycondensation synthetic method preparation process of the present invention is simple, and reaction substrate is easy to get, and has good industry can
Replicability.
Detailed description of the invention
Fig. 1 is variation schematic diagram of 1 yield of the embodiment of the present invention with reaction temperature.
Specific embodiment
The present invention is further illustrated by the following examples, but these embodiments must not be used to explain to the present invention
Limitation.
Embodiment 1
6.0g lithium chloride and 194.0g N-methyl pyrrolidones are added in four-hole boiling flask I, is mixed, it is saturating to obtain clarification
Bright LiCl/NMP solvent.The LiCl/NMP solvent of 90mL is poured into four-hole boiling flask II, and 5.4476g terephthaldehyde is added
Amine, stirring obtain PXD-LiCl/NMP solution I to dissolving.20mL pyridine is then added in solution I.In four-hole boiling flask III
The LiCl/NMP solvent of 90mL is added, and 8.1614g paraphthaloyl chloride is added, stirring obtains TPC-LiCl/NMP to dissolving
Solution II.Solution II is divided into two parts, first 40% solution II is poured into four-hole boiling flask II, is stirred to react 3min.Then add
Enter remaining 60% solution II, the reaction was continued 10min, control reaction temperature is 0 DEG C.Add water to stop reaction, it is heavy to generate white
Starch.Sediment is cleaned multiple times with water, dries, obtains product, yield 91%.
According to above-described embodiment 1, by reaction temperature be set separately -15 DEG C, -10 DEG C, -5 DEG C, 15 DEG C, 10 DEG C, 5 DEG C into
Row reaction, it is seen that reaction temperature is controlled at 0 DEG C, and yield is highest.As a result referring to Fig. 1.
Embodiment 2
10.0g lithium chloride and 190.0g N-methyl pyrrolidones are added in four-hole boiling flask I, is mixed, is clarified
Transparent LiCl/NMP solvent.The LiCl/NMP solvent of 80mL is poured into four-hole boiling flask II, and 4.1757g terephthaldehyde is added
Amine, stirring obtain PXD-LiCl/NMP solution I to dissolving.10mL pyridine is then added in solution I.In four-hole boiling flask III
The LiCl/NMP solvent of 80mL is added, and 6.0910g paraphthaloyl chloride is added, stirring obtains TPC-LiCl/NMP to dissolving
Solution II.Solution II is divided into two parts, first 50% solution II is poured into four-hole boiling flask II, is stirred to react 15min.Then add
Enter remaining 40% solution II, the reaction was continued 15min, control reaction temperature is -5 DEG C.Add water to stop reaction, it is heavy to generate white
Starch.Sediment is cleaned multiple times with water, dries, obtains product, yield 85%.
Embodiment 3
6.0g lithium chloride and 194.0g N-methyl pyrrolidones are added in four-hole boiling flask I, is mixed, it is saturating to obtain clarification
Bright LiCl/NMP solvent.The LiCl/NMP solvent of 80mL is poured into four-hole boiling flask II, and 5.4476g terephthaldehyde is added
Amine, stirring obtain PXD-LiCl/NMP solution I to dissolving.10mL pyridine is then added in solution I.In four-hole boiling flask III
The LiCl/NMP solvent of 80mL is added, and 8.1614g paraphthaloyl chloride is added, stirring obtains TPC-LiCl/NMP to dissolving
Solution II.Solution II is divided into two parts, first 40% solution II is poured into four-hole boiling flask II, is stirred to react 20min.Then add
Enter remaining 60% solution II, the reaction was continued 30min, control reaction temperature is 10 DEG C.Add water to stop reaction, it is heavy to generate white
Starch.Sediment is cleaned multiple times with water, dries, obtains product, yield 45%.
Claims (9)
1. a kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine, which comprises the steps of:
(1) chlorination lithium powder and N-methyl pyrrolidone solution are added in the reaction vessel, mixed solvent is made in stirring；
(2) solvent obtained by part steps (1) is taken, and p dimethylamine is added, is stirred, solution is made in dissolution；
(3) acid binding agent is added in the solution obtained by step (2)；
(4) solvent obtained by part steps (1) is separately taken, paraphthaloyl chloride is added, is mixed into solution；
(5) solution obtained in step (4) is divided into two parts, is added sequentially in the reaction vessel of step (2), during which interval one
It fixes time, is kept stirring；
(6) continue to be stirred to react a period of time, distilled water is added, stop reaction, generate white depositions；
(7) with water step (6) are cleaned multiple times obtained by sediment, drying, obtain product.
2. a kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine as described in claim 1, which is characterized in that step
Suddenly in (1), the content of the lithium chloride is 3~10%.
3. a kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine as described in claim 1, which is characterized in that step
Suddenly in (1), the N-methyl pyrrolidones mass percent is 97~90%, the mass percent of chlorination lithium powder is 3~
10%.
4. a kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine as described in claim 1, which is characterized in that step
Suddenly in (2), the amount of the p dimethylamine of the addition is the 0.5~10% of solvent.
5. a kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine as described in claim 1, which is characterized in that step
Suddenly in (3), the acid binding agent is the mixing of pyridine, any one or two kinds in 2- picoline, and additional amount is solvent
0.5~20%.
6. a kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine as described in claim 1, which is characterized in that step
Suddenly in (4), in the amount of the paraphthaloyl chloride of the addition and step (2) molar ratio of p dimethylamine be 0.095~
1.005:1。
7. a kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine as described in claim 1, which is characterized in that step
Suddenly in (5), volume ratio that two parts of solution being divided into account for respectively is 40~60% and 60%~40%, reaction temperature control for -5~
10 DEG C, the dosing intervals time is 3~10min.
8. a kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine as described in claim 1, which is characterized in that step
Suddenly in (6), the reaction time is 10~40min, and reaction temperature control is -5~10 DEG C.
9. a kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine as described in claim 1, which is characterized in that step
Suddenly in (7), products therefrom yield is 45~95%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810982101.1A CN109369908A (en) | 2018-08-27 | 2018-08-27 | A kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine |
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| CN201810982101.1A CN109369908A (en) | 2018-08-27 | 2018-08-27 | A kind of polycondensation synthetic method of poly- paraphenylene terephthalamide p dimethylamine |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814659A (en) * | 2006-01-17 | 2006-08-09 | 东华大学 | Method for synthesizing poly-terephthalyl-acyl P-pheny lene diamine |
| CN105801844A (en) * | 2016-04-14 | 2016-07-27 | 南华大学 | Poly(m-phenylene) terephthamide and solution polycondensation preparing method thereof |
-
2018
- 2018-08-27 CN CN201810982101.1A patent/CN109369908A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814659A (en) * | 2006-01-17 | 2006-08-09 | 东华大学 | Method for synthesizing poly-terephthalyl-acyl P-pheny lene diamine |
| CN105801844A (en) * | 2016-04-14 | 2016-07-27 | 南华大学 | Poly(m-phenylene) terephthamide and solution polycondensation preparing method thereof |
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