阅读说明：本技术 共聚物与其形成方法 (Copolymers and methods of forming the same ) 是由 王惠民 陈俊智 刘弘仁 高信敬 于 2021-03-30 设计创作，主要内容包括：共聚物的形成方法包括：取与反应形成盐类,取x摩尔份的盐类与y摩尔份的反应形成共聚物其中m＝4-10,n是4-6,以及x:y＝1:9至4:6。共聚物的相对粘度可为1.5至4.0。(The method of forming the copolymer comprises: get And reacting to form salts, taking x mol parts of the salts and y mol parts of the salts Reacting to form a copolymer)

1. A copolymer having the structure:

wherein m is 4-10 of the total weight of the compound,

n is 4-6, and

x: y ═ 1:9 to 4: 6.

2. The copolymer of claim 1, wherein m-5-7 and n-5.

3. The copolymer of claim 1, wherein m-6 and n-5.

4. The copolymer of claim 1, wherein the copolymer has a relative viscosity of 1.5 to 4.0.

5. A method of forming a copolymer, comprising:

getAndreacting to form a salt, taking x mol parts of the salt and y mol parts of the saltReacted to form a copolymer

Wherein m is 4-10 of the total weight of the compound,

n is 4-6, and

x: y ═ 1:9 to 4: 6.

6. The method of forming a copolymer according to claim 5, wherein m-5-7 and n-5.

7. The method of forming the copolymer of claim 5, wherein the relative viscosity of the copolymer is 1.5 to 4.0.

8. The method of claim 5, wherein the salt has the structure

9. The method of claim 5, wherein the salt is formed at a temperature of 25 ℃ to 100 ℃ and a pressure of 0.9atm to 1.1 atm.

10. The method of forming a copolymer as claimed in claim 5, wherein the temperature at which the copolymer is formed is 250 ℃ to 290 ℃, and the pressure is 0.9atm to 1.1 atm.

Technical Field

Embodiments of the present disclosure relate to copolymers and methods of forming the same.

Background

In recent years, with the development of energy saving, light weight and other trends, engineering plastics are gradually replacing original metal materials in many application products. However, nylon 6 and nylon 66 are generally commercially available with poor weather and UV resistance, which limits their outdoor applications. In view of the above, there is a need for new polymers to improve the problems of poor weather resistance, insufficient strength, poor processability, etc. of nylon. In addition, it is also desirable to develop a polymer process that can be performed at atmospheric pressure.

Disclosure of Invention

It is an object of the present invention to provide a novel copolymer which substantially improves the problems of poor weather resistance, insufficient strength, poor processability, etc. of the prior art nylons.

It is another object of the present invention to provide a process for forming the copolymer which is carried out at atmospheric pressure.

The present disclosure provides a copolymer, which has the following structure:wherein m is 4-10, n is 4-6, and x: y is 1:9 to 4: 6.

In some embodiments, m-5-7 and n-5. In some embodiments, m is 6 and n is 5.

In some embodiments, the relative viscosity of the copolymer is 1.5 to 4.0.

An embodiment of the present disclosure provides a method for forming a copolymer, including: getAndreacting to form salts, taking x mol parts of the salts and y mol parts of the saltsReacting to form a copolymerWherein m is 4-10, n is 4-6, and x is 1:9 to 4: 6.

In some embodiments, m-5-7 and n-5. In some embodiments, m is 6 and n is 5.

In some embodiments, the relative viscosity of the copolymer is 1.5 to 4.0.

In some embodiments, the salt is of the structure

In some embodiments, the temperature at which the salt is formed is from 25 ℃ to 100 ℃ and the pressure is from 0.9atm to 1.1 atm.

In some embodiments, the temperature at which the copolymer is formed is 250 ℃ to 290 ℃, and the pressure is 0.9atm to 1.1 atm.

Compared with the prior art, the copolymer provided by the invention has the advantages that the problems of poor weather resistance, insufficient strength, poor processability and the like of nylon in the prior art are solved; also, the polymerization process of the copolymer of the present invention may be carried out under normal pressure.

Detailed Description

The disclosed embodiments provide a method for forming a copolymer as follows. Firstly, getAndreacting to form salts. For example, the salt has the structureThe molar ratio of diacid to diamine can be 1:1 to 1.2: 1. If the proportion of diacids is too high, the salts formed may be bis (diacid) diamine saltsOr tris (diacid) bis (diamine) saltsIf the proportion of diamine is too high, the salts formed may be di (diamine) diacid saltsOr di (diacid) tri (diamine) saltThen taking x mole parts of salt and y mole parts ofReacting to form a copolymerWherein m is 4-10, n is 4-6, and x: y is 1:9 to 4: 6. In some embodiments, m-5-7 and n-5. In some embodiments, m is 6 and n is 5. For example,can be used as the raw material of hexamethylene diamine,can be aminocaproic acid, andmay be caprolactam such as

In some embodiments, the relative viscosity of the copolymer is 1.5 to 4.0. The relative viscosity of the copolymer is positively correlated with the weight average molecular weight. If the relative viscosity of the copolymer is too low or too high, subsequent processing and application will be difficult.

In some embodiments, the temperature at which the salt is formed is from 25 ℃ to 100 ℃ and the pressure is from 0.9atm to 1.1 atm. If the temperature at which the salt is formed is too low, the salt may not react to form. If the temperature at which the salt is formed is too high, the molar ratio of the negative ion corresponding to the diacid to the positive ion corresponding to the diamine in the salt formed is not 1: 1.

In some embodiments, the temperature at which the copolymer is formed is 250 ℃ to 290 ℃, and the pressure is 0.9atm to 1.1 atm. If the temperature for forming the copolymer is too low, the copolymer cannot be melted and polymerized. If the temperature at which the copolymer is formed is too high, it may crack during melt polymerization. If the pressure for forming the copolymer is too low, unreacted materials are easily withdrawn, resulting in an imbalance in the reaction ratio and a low molecular weight of the polymer. If the pressure at which the copolymer is formed is too high, water as a by-product of the reaction cannot be taken out, so that the internal temperature is too low to polymerize a high molecular weight polymer.

The above copolymers may be used alone or blended with other polymers. In addition, the above-mentioned copolymer may be mixed with other inorganic materials such as carbon materials, silicon oxide, glass fibers, or other suitable inorganic materials to form a composite material. The copolymer, blend or composite has good weather resistance and can be used for outdoor products.

In order to make the aforementioned and other objects, features, and advantages of the present disclosure more comprehensible, embodiments accompanied with figures are described in detail below:

[ examples ]

In the following examples, the relative viscosity of the copolymer was measured by ASTM D789. The melting point (Tm), glass transition temperature (Tg), and cold crystallization temperature (Tc) of the copolymer are measured by Differential Scanning Calorimetry (DSC). In addition, the tensile strength of the material is measured according to ASTM D638.

Example 1

5.2g (0.03mol) of 1, 4-cyclohexanedicarboxylic acid (CHDA), 3.5g (0.03mol) of Hexamethylenediamine (HMDA) and 20ml of ethanol were put into a reaction flask, and the reaction was carried out for 8 hours after the temperature was raised to 50 ℃. After cooling to room temperature, the solid was washed with methanol and then dried in an oven at 80 ℃ to obtain CHDA-HMDA as a white solid powder. To be provided with¹H NMR confirmed this product with a CHDA to HMDA molar ratio of 1: 1. The above reaction is shown below:

example 2

4.32g (15mmol) of CHDA-HMDA and 11.15g (85mmol) of Aminocaproic acid (Aminocaproic acid, ACA) were taken under nitrogen, heated to 250 ℃ and reacted for 3 hours. After cooling, copolymer 1 was obtained, which had a relative viscosity of 2.24, a melting point (Tm) of 188 ℃, a glass transition temperature (Tg) of 60 ℃ and a cold crystallization temperature (Tc) of 135 ℃. The above reaction is as follows:

60 parts by weight of copolymer 1 and 40 parts by weight of glass fibers (from Dobule HP3540) were mixed by a screw and then thermally extruded to give a sheet. The sheet had a tensile strength of 175 MPa. The sheet had a tensile strength of 94MPa seven days after the sheet was placed in an environment of 80 ℃ and 95% relative humidity and containing 500ppm ozone (equivalent to 20 years of placing the sheet outdoors). After the weather resistance test, the tensile strength maintenance rate of the sheet was 53.7%.

Example 3

4.86g (22.5mmol) of CHDA-HMDA and 7.63g (77.5mmol) of aminocaproic acid (ACA) were taken under nitrogen, heated to 250 ℃ and reacted for 3 hours. After cooling, copolymer 2 was obtained, which had a relative viscosity of 2.37, a Tm of 220 ℃, a Tg of 70 ℃ and a Tcc of 170 ℃. The above reaction is as follows:

60 parts by weight of copolymer 2 and 40 parts by weight of glass fibers (from Dobule HP3540) were mixed by a screw and then thermally extruded to give a sheet. The tensile strength of the sheet was 188 MPa. The sheet had a tensile strength of 103MPa seven days after the sheet was placed in an environment of 80 ℃ and 95% relative humidity and containing 500ppm ozone (equivalent to 20 years of placing the sheet outdoors). After the weather resistance test, the tensile strength maintenance rate of the sheet is 54.8%.

Example 4

8.65g (30mmol) of CHDA-HMDA and 9.18g (70mmol) of aminocaproic acid (ACA) were taken under nitrogen, heated to 250 ℃ and reacted for 3 hours. After cooling, copolymer 3 was obtained, which had a relative viscosity of 2.50, a Tm of 236 ℃, a Tg of 79 ℃ and a Tcc of 200 ℃. The above reaction is as follows:

60 parts by weight of copolymer 3 and 40 parts by weight of glass fibers (available from Dobule-Producer HP3540) were mixed by a screw and then thermally extruded to give a sheet. The tensile strength of the sheet was 184 MPa. The sheet had a tensile strength of 108MPa after being placed in an environment of 80 ℃ and 95% relative humidity and containing 500ppm ozone for seven days (equivalent to 20 years of placing the sheet outdoors). After the weather resistance test, the tensile strength maintenance rate of the sheet is 57.7%.

Comparative example 1

1.44g (5mmol) of CHDA-HMDA and 12.5g (95mmol) of aminocaproic acid (ACA) were taken under nitrogen, heated to 250 ℃ and reacted for 3 hours. After cooling, copolymer 4 was obtained, which had a relative viscosity of 2.60, a Tm of 202 ℃, a Tg of 45 ℃ and a Tcc of 140 ℃. The above reaction is as follows:

60 parts by weight of copolymer 4 and 40 parts by weight of glass fibers (available from Dobule-Producer HP3540) were mixed by a screw and then thermally extruded to give a sheet. The sheet had a tensile strength of 120 MPa. The sheet was placed at 80 ℃ in an atmosphere containing 95% relative humidity and 500ppm ozone for seven days (equivalent to 20 years of the sheet placed outdoors), and the tensile strength of the sheet was 60 MPa. After the weather resistance test, the tensile strength maintenance rate of the sheet is 50.0%.

Comparative example 2

14.4g (50mmol) of CHDA-HMDA and 6.56g (50mmol) of aminocaproic acid (ACA) were taken under nitrogen, heated to 250 ℃ and reacted for 3 hours. After cooling, copolymer 5 was obtained, which had a relative viscosity of 1.15 and a Tg of 89 deg.C (Tm and Tcc were not measured). The above reaction is as follows:

60 parts by weight of copolymer 5 and 40 parts by weight of glass fibers (from the general HP3540) were mixed in a screw and hot pressed into a sheet because the molecular weight was too low.

Comparative example 3

3.87g (22.5mmol) of CHDA, 2.61g (22.5mmol) of HMDA and 10.17g (77.5mmol) of aminocaproic acid (ACA) were taken under nitrogen, heated to 250 ℃ and reacted for 3 hours. After cooling, copolymer 6 was obtained, which had a relative viscosity of 2.12, a Tm of 217 ℃, a Tg of 67 ℃ and a Tcc of 170 ℃. The above reaction is as follows:

in the above formula, x + m is 0.225, and xy + n is 0.775. 60 parts by weight of copolymer 6 and 40 parts by weight of glass fibers (available from Dobule-Producer HP3540) were mixed in a screw and then thermally extruded to give a sheet. The sheet had a tensile strength of 145 MPa. The sheet was placed at 80 ℃ in an atmosphere containing 95% relative humidity and 500ppm ozone for seven days (equivalent to 20 years of the sheet placed outdoors), and the tensile strength of the sheet was 79 MPa. After the weather resistance test, the tensile strength maintenance rate of the sheet is 54.4%.

Comparative example 4

6.5g (22.5mmol) of CHDA-HMDA and 5.8g (77.5mmol) of glycine (Gly) were placed under nitrogen, heated to 250 ℃ and reacted for 3 hours. After cooling, a cleaved copolymer 7 is obtained having a Tm of 247 ℃, a thermal cleavage temperature (Td) of 234 ℃ and a Tg of 103 ℃. Since the thermal cracking temperature is lower than the melting point, it is cracked in melt polymerization. The above reaction is as follows:

comparative example 5

12.5g (95mmol) of aminocaproic acid (ACA) were taken under nitrogen, heated to 250 ℃ and reacted for 3 hours. After cooling, a polymer was obtained with a relative viscosity of 2.60, a Tm of 220 ℃, a Tg of 45 ℃ and a Tcc of 170 ℃. The above reaction is as follows:

in the above formula, 1.00 refers to the proportion of repeating units (100%) rather than the number of repeats. 60 parts by weight of the polymer and 40 parts by weight of glass fibers (from the general HP3540) were mixed in a screw and thermally extruded into a sheet. The sheet had a tensile strength of 136 MPa. The sheet was placed at 80 ℃ under an atmosphere containing ozone at a relative humidity of 95% and 500ppm for seven days (equivalent to 20 years of the sheet placed outdoors), and the tensile strength of the sheet was 66 MPa. After the weather resistance test, the tensile strength maintenance rate of the sheet is 48.5%.

Although the present disclosure has been described with reference to a number of preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure, and the scope of the disclosure should be limited only by the appended claims.