CN113045749A

CN113045749A - Synthesis method of long carbon chain polyamide material

Info

Publication number: CN113045749A
Application number: CN202110406160.6A
Authority: CN
Inventors: 安江波; 贺炳博; 张小林
Original assignee: Henan Huaying New Material Co ltd
Current assignee: Henan Huaying New Material Co ltd
Priority date: 2021-04-15
Filing date: 2021-04-15
Publication date: 2021-06-29
Anticipated expiration: 2041-04-15
Also published as: CN113045749B

Abstract

The invention provides a synthesis method of a long carbon chain polyamide material, which takes a compound formed by hypophosphite, transition metal salt and triphenylphosphine as a catalyst, and can improve the synthesis efficiency, shorten the synthesis time and reduce the production cost in the synthesis process of polyamide taking water as a dispersion medium. The use of the composite catalyst has a faster synthesis speed than the use of only hypophosphite, and the molecular weight and molecular weight distribution of the product are also satisfactory.

Description

Synthesis method of long carbon chain polyamide material

Technical Field

The invention belongs to the field of synthesis of polyamide materials, and particularly relates to a high-temperature-resistant polyamide material and a synthesis method thereof.

Background

Polyamide is a high molecular material which enters the life at the earliest, and is developed and industrialized by Carothers in the 30 th century. The commonly used PA6 and PA66 have high water absorption, thereby causing great changes of the product size and the performance, and limiting the application and development of nylon. In order to reduce the water absorption rate of the polyamide material, a method for increasing the hydrophobicity by growing a carbon chain is developed successfully, and materials such as PA1010, PA11, PA12 and PA1212 are subsequently introduced into the market. The polyamide material with long carbon chains is called long carbon chain polyamide, and has the general properties of common polyamide, such as lubricity, wear resistance, compression resistance, easy processability and the like, and also has the characteristics of good toughness and flexibility, low water absorption, good dimensional stability, excellent dielectric property, good wear resistance, low density and the like.

However, the long-chain polyamide is difficult to be rapidly salified by using a traditional salt formation method in the aqueous phase synthesis process due to the long carbon chain, and the production is also hidden by using organic solvents such as methanol and ethanol. Therefore, in the polyamide synthesis method of the long carbon chain polyamide material with water as a dispersion medium, research hotspots are made on how to rapidly form salt and improve synthesis efficiency.

Disclosure of Invention

The invention aims to provide a synthesis method of a long carbon chain polyamide material, which takes a compound formed by hypophosphite, transition metal salt and triphenylphosphine as a catalyst and can improve the synthesis efficiency in the synthesis process of polyamide taking water as a dispersion medium.

In order to achieve the purpose, the invention provides a synthesis method of a long carbon chain polyamide material, which takes a composite catalyst containing a transition metal salt as a catalyst.

The composite catalyst comprises hypophosphite, a transition metal salt and triphenylphosphine.

The hypophosphite is one or more of sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite and calcium hypophosphite.

The transition metal salt is one or more of soluble salt of a tenth group element, soluble salt of an eleventh group element and soluble salt of a twelfth group element.

The element of the tenth group is one or more of Ni, Pd and Pt.

The eleventh group element is one or more of Cu, Ag and Au.

The twelfth group element is one or more of Zn, Cd and Hg.

The soluble salt is one or more of chloride, sulfate, nitrate, phosphate, phosphite and hypophosphite.

In a preferred embodiment, the mole ratio of the hypophosphite, the transition metal salt and the triphenylphosphine is (25-40): 1, (0.7-1).

In a preferred embodiment, the feeding amount of the catalyst is 0.01-0.1% of the total mass of the diamine and the diacid.

In a preferred embodiment, the long carbon chain polyamide is PA1010, PA1111, PA1212 and copolymers thereof.

The synthesis method of the long-carbon-chain polyamide material comprises the following steps: (1) adding diamine and dibasic acid into a polymerization reaction kettle, adding a catalyst and water, sealing and stirring, and replacing with non-reactive gas, wherein the set gas pressure is 10-100 kPa. (2) And (3) heating the temperature in the kettle to 100-150 ℃, and preserving the temperature for 1-3 hours until the raw materials are completely salified. (3) And continuously heating the polymerization reaction kettle, releasing water vapor when the pressure in the kettle reaches a set value, and maintaining the pressure for 1-3 hours. And continuously heating to 280-300 ℃, keeping the pressure constant for 1-3 hours, and discharging after aeration to obtain the long carbon chain polyamide.

In a preferred embodiment, the dibasic acid in step (1) is one or more of sebacic acid, undecanedioic acid and dodecanedioic acid.

In a preferred embodiment, the diamine in step (1) is one or more of decamethylenediamine, undecanediamine, and dodecanediamine.

In a preferred embodiment, the diacid and diamine are dosed in step (1) in equivalent amounts, which may comprise an error of less than 1%, preferably an error of less than 0.5%, further preferably an error of less than 0.1%. An excess of diamine is preferred.

In a preferred embodiment, the non-reactive gas in step (1) is one or more of nitrogen, carbon dioxide, helium, neon and argon.

In a preferred embodiment, the air pressure in the step (1) is preferably 10 to 50kPa, and more preferably 50 kPa.

In a preferred embodiment, the temperature in the kettle in the step (2) is increased to 110-130 ℃, preferably 110-120 ℃, and more preferably 120 ℃.

In a preferred embodiment, the temperature keeping time in the step (2) is 1-2 hours, preferably 2 hours.

In a preferred embodiment, the pressure set value in the step (3) is 1 to 3MPa, preferably 2 to 3MPa, and more preferably 3 MPa.

In a preferred embodiment, the pressure maintaining time in the step (3) is 1 to 2 hours, preferably 1 hour.

In a preferred embodiment, the temperature for further raising the temperature in the step (3) is 280-300 ℃, preferably 285-295 ℃, and further preferably 290 ℃.

In a preferred embodiment, the constant pressure time in step (3) is 1-2 hours, preferably 1 hour.

Compared with the prior art, the invention has the following beneficial effects.

(1) The invention takes the compound formed by sodium hypophosphite, transition metal salt and triphenylphosphine as a catalyst, can improve the synthesis efficiency, shorten the synthesis time and reduce the production cost in the polyamide synthesis process taking water as a dispersion medium.

(2) The preparation method disclosed by the invention is simple in process, adopts a one-pot polymerization method, does not need to spatially separate the steps of salt, prepolymerization and solid-phase tackifying, can complete all the steps by adopting one polymerization kettle, and is convenient to produce.

Detailed Description

The following embodiments of the present invention are further described in conjunction with the detailed description, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein.

Before the present embodiments are further described, it is to be understood that the scope of the present invention includes, but is not limited to, the following specific embodiments. In general, the terminology used in the examples herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. The test methods in the following examples, in which specific conditions are not specified, are generally carried out under conventional conditions or conditions recommended by the respective manufacturers.

When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.

Preparation example 1

A general method for preparing the composite catalyst is as follows: mixing 25.80g of sodium hypophosphite, 1.36g of zinc chloride and 1.83g of triphenylphosphine in a test tube, adding 30g of mixed solvent (V/V1:1) of DMSO and water, and dissolving in ultrasound to obtain a homogeneous solution, namely the composite catalyst, until an oil phase of the triphenylphosphine disappears.

Example 1

(1) Putting 1mol of decanediamine and 1mol of sebacic acid into a polymerization reaction kettle, adding 0.19g (calculated by solid matters) of composite catalyst, uniformly mixing, injecting 100mL of deionized water, sealing the polymerization kettle, starting stirring at the stirring speed of 100rpm, and adding N₂The gas was replaced three times, and the pressure in the autoclave was set to 50 kPa.

And (3) raising the temperature in the kettle to 120 ℃ and preserving the temperature for 1 hour until the sebacic acid and the decanediamine are completely salified.

And continuously heating the polymerization reaction kettle, opening the pressure release valve to release the generated water vapor when the pressure in the kettle reaches 3MPa, and keeping the pressure in the kettle at constant pressure for 1 hour. Then continuously heating to 290 ℃ at the speed of 5 ℃/min, keeping the pressure constant for 1 hour, and filling N into the kettle₂And discharging to obtain the long carbon chain polyamide.

And (3) testing molecular weight: GPC measurements were carried out using 0.05M potassium trifluoroacetate-stabilized hexafluoroisopropanol as solvent, 1g/L sample concentration, and PMMA calibration curve.

Comparative example 1

Example 1 was repeated, except that the constant pressure time of 290 ℃ was set to 20min on the basis of example 1, and the other conditions were not changed.

Comparative example 2

Example 1 was repeated, except that the constant pressure time of 290 ℃ was set to 3 hours on the basis of example 1, and the other conditions were not changed.

Comparative example 3

Example 1 was repeated, except that the catalyst was replaced with equal mass of sodium hypophosphite on the basis of example 1, and the other conditions were not changed.

Comparative example 4

Example 1 was repeated, except that on the basis of example 1 the catalyst was replaced by phosphorous acid of equal quality, and the other conditions were unchanged.

The molecular weight tests of example 1 and comparative examples 1 to 4 are as follows

	Number average molecular weight	Molecular weight distribution
			Example 1	19442	2.2
Comparative example 1	7391	2.9
			Comparative example 2	20137	2.3
Comparative example 3	15733	2.8
			Comparative example 4	16492	3.1

Example 2

Example 1 was repeated, except that zinc chloride was replaced by copper chloride on the basis of example 1, and the other conditions were not changed.

Example 3

Example 1 was repeated, except that zinc chloride was replaced by nickel chloride on the basis of example 1, and the other conditions were not changed.

Comparative example 5

Example 1 was repeated, except that zinc chloride was replaced by ferrous chloride on the basis of example 1, and other conditions were not changed.

Comparative example 6

Example 1 was repeated, except that zinc chloride was replaced by cobalt chloride on the basis of example 1, and the other conditions were not changed.

Example 4

Example 1 was repeated, except that zinc chloride was replaced with zinc sulfate on the basis of example 1, and other conditions were not changed.

The molecular weight tests of examples 2 to 4 and comparative examples 5 to 6 are as follows

The composite catalyst comprises hypophosphite, transition metal salt and triphenylphosphine, and is obtained through long-term experiments, wherein the hypophosphite is a catalyst commonly used in the polyamide polymerization process, and is matched with a complex formed by the transition metal salt and the triphenylphosphine, so that the amide polymerization can be accelerated, the synthesis speed is higher when the composite catalyst is used than when only the hypophosphite is used in the same synthesis time, and the molecular weight distribution of a product are satisfactory.

All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims

1. The composite catalyst for synthesizing long carbon chain polyamide includes hypophosphite, transition metal salt and triphenyl phosphine.

2. The composite catalyst of claim 1, wherein the transition metal salt is one or more of a soluble salt of a group ten element, a soluble salt of a group eleventh element, and a soluble salt of a group twelfth element.

3. The composite catalyst according to claim 2, wherein the group ten element is one or more of Ni, Pd, Pt; the eleventh group element is one or more of Cu, Ag and Au; the twelfth group element is one or more of Zn, Cd and Hg.

4. The composite catalyst according to claim 1, wherein the molar ratio of the hypophosphite, the transition metal salt and the triphenylphosphine is (25-40): 1, (0.7-1).

5. A process for synthesizing a long carbon chain polyamide, characterized by using the composite catalyst according to any one of claims 1 to 4 as a catalyst.

6. The method for synthesizing long carbon chain polyamide according to claim 5, comprising the steps of:

(1) putting diamine and dibasic acid into a polymerization reaction kettle, adding a composite catalyst and water, sealing and stirring, replacing with non-reactive gas, and setting the gas pressure to be 10-100 kPa;

(2) heating the temperature in the kettle to 100-150 ℃, and preserving the heat for 1-3 hours until the raw materials are completely salified;

(3) continuously heating the polymerization reaction kettle, releasing water vapor when the pressure in the kettle reaches a set value, and maintaining the pressure for 1-3 hours; and continuously heating to 280-300 ℃, keeping the pressure constant for 1-3 hours, and discharging after aeration to obtain the long carbon chain polyamide.

7. The method for synthesizing long carbon chain polyamide according to claim 6, wherein the non-reactive gas in step (1) is one or more of nitrogen, carbon dioxide, helium, neon and argon.

8. The method for synthesizing long carbon chain polyamide according to claim 5, wherein the long carbon chain polyamide is PA1010, PA1111, PA1212 and their copolymers.

9. A long carbon chain polyamide obtainable by a synthesis process according to any one of claims 5 to 8.