阅读说明：本技术 复合填料增强尼龙的制备方法 (Preparation method of composite filler reinforced nylon ) 是由 丁玉婕 何大方 史小军 于 2021-01-22 设计创作，主要内容包括：本发明涉及尼龙制备方法领域,尤其是复合填料增强尼龙的制备方法。该制备方法的步骤为：A、钛酸盐用端氨基硅烷偶联剂进行氨基化改性后,用1～2mol/L的酸性溶液调节pH 3～4,超声搅拌制得均匀的钛酸盐分散液；B、将钛酸盐分散液加入氧化石墨烯水溶液,制得石墨烯/钛酸盐复合材料粉体；该发明通过构筑氧化石墨烯包覆钛酸盐结构,借助氧化石墨烯表面丰富的羧基和羟基,使得它能够与尼龙的端基基团形成共价键,从而能够形成连续的网络胶粘点,提高尼龙的稳定性,解决尼龙材料耐热性差以及耐冲击强度低的缺点。(The invention relates to the field of nylon preparation methods, in particular to a preparation method of composite filler reinforced nylon. The preparation method comprises the following steps: A. carrying out amination modification on titanate by using an amino-terminated silane coupling agent, adjusting the pH value to 3-4 by using 1-2 mol/L acid solution, and carrying out ultrasonic stirring to obtain uniform titanate dispersion liquid; B. adding titanate dispersion liquid into a graphene oxide aqueous solution to prepare graphene/titanate composite material powder; according to the invention, by constructing the graphene oxide coated titanate structure and by means of rich carboxyl and hydroxyl on the surface of graphene oxide, the graphene oxide coated titanate structure can form a covalent bond with a terminal group of nylon, so that a continuous network adhesive point can be formed, the stability of nylon is improved, and the defects of poor heat resistance and low impact strength of a nylon material are overcome.)

1. A preparation method of composite filler reinforced nylon is characterized by comprising the following steps:

A. carrying out amination modification on titanate by using an amino-terminated silane coupling agent, adjusting the pH value to 3-4 by using 1-2 mol/L acid solution, and carrying out ultrasonic stirring to obtain uniform titanate dispersion liquid;

B. adding titanate dispersion liquid into a graphene oxide aqueous solution to prepare graphene/titanate composite material powder;

C. ultrasonically mixing graphene/titanate composite material powder and diamine in an aqueous solution, performing suction filtration and washing after complete mixing, and finally placing in a vacuum drying oven for drying treatment to obtain ammonium carboxylate;

D. dissolving glutaric acid and adipic acid in water solution, reacting to obtain salt solution, and placing the salt solution in a high-pressure reaction kettle at the reaction temperature of 230 ℃ and 250 ℃ and the reaction pressure of 1.5-3.5 Mpa; reacting for 1-2 hours to obtain a prepolymer of the nylon material;

and (3) performing polycondensation on the dried ammonium carboxylate and the prepolymer of the nylon material in a high-pressure reaction kettle, extruding and drying after the polycondensation is completed, and obtaining the nylon resin.

2. The preparation method of the composite filler reinforced nylon according to claim 1, wherein the nylon comprises the following components in parts by weight: 1 part of titanate dispersion liquid, 0.1-0.2 part of graphene oxide aqueous solution, 2-3 parts of diamine and 3-6 parts of dibasic acid.

3. The method of claim 1, wherein the diamine is at least one of pentamethylenediamine and hexamethylenediamine.

4. The method for preparing the composite filler reinforced nylon according to claim 1, wherein the dibasic acid is at least one of adipic acid, oxalic acid, succinic acid, sebacic acid and dodecanedioic acid.

5. The method for preparing the composite filler reinforced nylon according to claim 1, wherein the titanate is any one of potassium titanate, sodium iron titanate and potassium magnesium titanate.

6. The method for preparing the composite filler reinforced nylon according to claim 1, wherein the temperature of the ultrasonic mixing in the step C is 40-60 ℃.

7. The method for preparing the composite filler reinforced nylon according to claim 1, wherein in the step C, the concentration obtained by ultrasonically mixing the graphene/titanate composite material powder and the diamine in the aqueous solution is 30-50 wt%.

8. The method for preparing the composite filler reinforced nylon according to claim 1, wherein in the step D, a high-pressure reaction kettle in which the prepolymer of the ammonium carboxylate and the nylon material is arranged is divided into two temperature zones: the reaction temperature of the front temperature zone is controlled to be 230-250 ℃ for 0.5-1 h, and the pressure in the reaction kettle is 1-3 MPa; and (3) releasing the pressure of the reaction kettle to normal pressure in the later temperature zone for 2-3 h, and gradually increasing the temperature to 280 ℃.

Technical Field

The invention relates to the field of nylon preparation methods, in particular to a preparation method of composite filler reinforced nylon.

Background

The most important varieties of engineering plastics, nylon, has a great vitality in improving its performance after modification. With the acceleration of light weight and miniaturization, industries such as automobiles, communication, electronic appliances and the like all put forward more stringent requirements on products. The nylon material has good comprehensive performance, high fatigue resistance and rigidity strength, good heat resistance and good chemical stability, but has higher sensitivity to temperature and humidity, thereby causing the poor dimensional stability and low-temperature impact strength of the nylon material. To improve the tensile strength, impact strength, modulus, abrasion resistance and dimensional stability of nylon, reinforcing agents are often added to the nylon matrix. The traditional nylon reinforcing mode improves the performance of nylon in a physical blending mode by adding metal particles, inorganic filler and carbon materials. Conventional reinforcing fillers suffer from two major drawbacks: on the one hand, the addition amount is usually higher, which leads to the reduction of other properties of the nylon per se; secondly, the physical mixing is easy to cause uneven distribution, so that the material has poor system fluidity and uneven flow during manufacturing, and the filler is easy to expose. Titanate series new materials and graphene both have excellent wear resistance and mechanical properties. But because both are difficult to uniformly disperse in organic matrices, they have greatly reduced their use properties, thereby limiting their applications.

Disclosure of Invention

In order to overcome the defect of poor performance of the existing nylon, the invention provides a preparation method of composite filler reinforced nylon.

The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of composite filler reinforced nylon comprises the following steps:

A. carrying out amination modification on titanate by using an amino-terminated silane coupling agent, adjusting the pH value to 3-4 by using 1-2 mol/L acid solution, and carrying out ultrasonic stirring to obtain uniform titanate dispersion liquid;

B. adding titanate dispersion liquid into a graphene oxide aqueous solution to prepare graphene/titanate composite material powder;

C. ultrasonically mixing graphene/titanate composite material powder and diamine in an aqueous solution, performing suction filtration and washing after complete mixing, and finally placing in a vacuum drying oven for drying treatment to obtain ammonium carboxylate;

D. dissolving glutaric acid and adipic acid in water solution, reacting to obtain salt solution, and placing the salt solution in a high-pressure reaction kettle at the reaction temperature of 230 ℃ and 250 ℃ and the reaction pressure of 1.5-3.5 Mpa; reacting for 1-2 hours to obtain a prepolymer of the nylon material;

and (3) performing polycondensation on the dried ammonium carboxylate and the prepolymer of the nylon material in a high-pressure reaction kettle, extruding and drying after the polycondensation is completed, and obtaining the nylon resin.

According to another embodiment of the invention, the nylon further comprises the following components in parts by weight: 1 part of titanate dispersion liquid, 0.1-0.2 part of graphene oxide aqueous solution, 2-3 parts of diamine and 3-6 parts of dibasic acid.

According to another embodiment of the present invention, it further comprises that the diamine is at least one of pentanediamine and hexanediamine.

According to another embodiment of the present invention, it further comprises that the dibasic acid is at least one of adipic acid, oxalic acid, succinic acid, sebacic acid, and dodecanedioic acid.

According to another embodiment of the present invention, it is further included that the titanate is any one of potassium titanate, sodium iron titanate, and potassium magnesium titanate.

According to another embodiment of the present invention, further comprising the step of C, the temperature of the ultrasonic mixing is 40-60 ℃.

According to another embodiment of the invention, in the step C, the concentration obtained by ultrasonically mixing the graphene/titanate composite material powder and the diamine in the aqueous solution is 30wt% to 50 wt%.

According to another embodiment of the present invention, in step D, the high pressure reaction kettle in which the prepolymer of the ammonium carboxylate and the nylon material is located is divided into two temperature zones: the reaction temperature of the front temperature zone is controlled to be 230-250 ℃ for 0.5-1 h, and the pressure in the reaction kettle is 1-3 MPa; and (3) releasing the pressure of the reaction kettle to normal pressure in the later temperature zone for 2-3 h, and gradually increasing the temperature to 280 ℃.

The preparation method has the beneficial effects that through the construction of the graphene oxide coated titanate structure, the graphene oxide coated titanate structure can form a covalent bond with a terminal group of nylon by virtue of rich carboxyl and hydroxyl on the surface of the graphene oxide, so that continuous network adhesive points can be formed, the stability of the nylon is improved, and the defects of poor heat resistance and low impact strength of a nylon material are overcome.

Detailed Description

A preparation method of composite filler reinforced nylon comprises the following steps:

A. carrying out amination modification on titanate by using an amino-terminated silane coupling agent, adjusting the pH value to 3-4 by using 1-2 mol/L acid solution, and carrying out ultrasonic stirring to obtain uniform titanate dispersion liquid;

B. adding titanate dispersion liquid into a graphene oxide aqueous solution to prepare graphene/titanate composite material powder;

C. ultrasonically mixing graphene/titanate composite material powder and diamine in an aqueous solution, performing suction filtration and washing after complete mixing, and finally placing in a vacuum drying oven for drying treatment to obtain ammonium carboxylate;

D. dissolving glutaric acid and adipic acid in water solution, reacting to obtain salt solution, and placing the salt solution in a high-pressure reaction kettle at the reaction temperature of 230 ℃ and 250 ℃ and the reaction pressure of 1.5-3.5 Mpa; reacting for 1-2 hours to obtain a prepolymer of the nylon material;

and (3) performing polycondensation on the dried ammonium carboxylate and the prepolymer of the nylon material in a high-pressure reaction kettle, extruding and drying after the polycondensation is completed, and obtaining the nylon resin.

The nylon comprises the following components in parts by weight: 1 part of titanate dispersion liquid, 0.1-0.2 part of graphene oxide aqueous solution, 2-3 parts of diamine and 3-6 parts of dibasic acid. The diamine is at least one of pentanediamine and hexanediamine. The dibasic acid is at least one of adipic acid, oxalic acid, succinic acid, sebacic acid and dodecanedioic acid. The titanate is any one of potassium titanate, sodium iron titanate and potassium magnesium titanate. In the step C, the temperature of the ultrasonic mixing is 40-60 ℃. In the step C, the concentration of the graphene/titanate composite material powder and diamine obtained by ultrasonic mixing in an aqueous solution is 30-50 wt%. In the step D, a high-pressure reaction kettle in which the prepolymer of the ammonium carboxylate and the nylon material is located is divided into two temperature zones: the reaction temperature of the front temperature zone is controlled to be 230-250 ℃ for 0.5-1 h, and the pressure in the reaction kettle is 1-3 MPa; and (3) releasing the pressure of the reaction kettle to normal pressure in the later temperature zone for 2-3 h, and gradually increasing the temperature to 280 ℃.

Example 1:

A. carrying out amination modification on 5g of titanate by using 0.0125g of terminal aminosilane coupling agent, adjusting the pH value to 3-4 by using 1mol/L of acid solution, and carrying out ultrasonic stirring to obtain uniform titanate dispersion liquid;

B. adding 5g of titanate dispersion liquid into 0.5g of graphene oxide aqueous solution to prepare graphene/titanate composite material powder;

C. ultrasonically mixing 5g of graphene/titanate composite material powder and 1g of pentamethylene diamine in an aqueous solution, and mixing completely

Carrying out suction filtration, washing with water, and finally placing in a vacuum drying oven for drying treatment to obtain ammonium carboxylate; the temperature of ultrasonic mixing was 30 c,

D. dissolving 10g of pentanediamine and 14.3g of adipic acid in an aqueous solution, reacting to obtain a salt solution, and placing the salt solution in a high-pressure reaction kettle at the reaction temperature of 240 ℃ and the reaction pressure of 2.5 Mpa; the prepolymer of the nylon material is obtained after the reaction is carried out for 1.5 hours. And (3) performing polycondensation on the dried 5g of ammonium carboxylate and 200g of the prepolymer of the nylon material in a high-pressure reaction kettle, extruding and drying after the polycondensation is completed, and thus obtaining the nylon resin. The reaction temperature is controlled at 230 ℃ for 0.5h in the front temperature zone of a high-pressure reaction kettle in which the prepolymer of the ammonium carboxylate and the nylon material is positioned, and the pressure in the reaction kettle is 1 MPa; the pressure of the reaction kettle is released to normal pressure in the later temperature zone for 2.5h, and the temperature is gradually increased to 280 ℃.

The nylon prepared in example 1 was tested to have a tensile strength of 83MPa, a flexural strength of 92MPa and a compressive strength of 125 MPa.

Example 2:

A. carrying out amination modification on 5g of magnesium titanate by using 0.025g of terminal amino silane coupling agent, adjusting the pH value to 3-4 by using 1mol/L of acid solution, and carrying out ultrasonic stirring to prepare uniform titanate dispersion liquid;

B. adding 5g of titanate dispersion liquid into 0.5g of graphene oxide aqueous solution to prepare graphene/titanate composite material powder;

C. ultrasonically mixing 5g of graphene/titanate composite material powder and 1.2g of pentamethylene diamine in an aqueous solution, and mixing completely

Then carrying out suction filtration, washing with water, and finally placing in a vacuum drying oven for drying treatment to obtain ammonium carboxylate; the temperature of ultrasonic mixing was 30 c,

D. dissolving 15g of pentanediamine and 21.45g of adipic acid in an aqueous solution, reacting to obtain a salt solution, and placing the salt solution in a high-pressure reaction kettle at the reaction temperature of 240 ℃ and the reaction pressure of 3 Mpa; the prepolymer of the nylon material is obtained after the reaction is carried out for 1.5 hours. And (3) performing polycondensation on the dried 5g of ammonium carboxylate and the dried prepolymer of the 250g of nylon material in a high-pressure reaction kettle, extruding and drying after the polycondensation is completed, and thus obtaining the nylon resin. The reaction temperature is controlled at 230 ℃ for 0.5h in the front temperature zone of a high-pressure reaction kettle in which the prepolymer of the ammonium carboxylate and the nylon material is positioned, and the pressure in the reaction kettle is 1 MPa; the pressure of the reaction kettle is released to normal pressure in the later temperature zone for 2.5h, and the temperature is gradually increased to 280 ℃.

The nylon prepared in example 2 was tested to have a tensile strength of 85MPa, a flexural strength of 92MPa and a compressive strength of 132 MPa.

Example 3:

A. carrying out amination modification on 5g of sodium iron titanate by using 0.025g of terminal amino silane coupling agent, adjusting the pH value to 3-4 by using 1mol/L of acid solution, and carrying out ultrasonic stirring to prepare uniform titanate dispersion liquid;

B. adding 5g of titanate dispersion liquid into 0.5g of graphene oxide aqueous solution to prepare graphene/titanate composite material powder;

C. ultrasonically mixing 5g of graphene/titanate composite material powder and 1.5g of hexamethylenediamine in an aqueous solution, and mixing completely

Then carrying out suction filtration, washing with water, and finally placing in a vacuum drying oven for drying treatment to obtain ammonium carboxylate; the temperature of ultrasonic mixing is 50 ℃;

D. dissolving 23g of hexamethylenediamine and 28.6g of adipic acid in an aqueous solution, reacting to obtain a salt solution, and placing the salt solution in a high-pressure reaction kettle at the reaction temperature of 230 ℃ and the reaction pressure of 1.8 Mpa; the prepolymer of the nylon material is obtained after the reaction is carried out for 1.5 hours. And (3) performing polycondensation on the dried 5g of carboxylic acid ammonium salt and the prepolymer of 300g of the nylon material in a high-pressure reaction kettle, extruding and drying after the polycondensation is completed, and thus obtaining the nylon resin. The reaction temperature is controlled to be 250 ℃ in a front temperature zone 1h of a high-pressure reaction kettle in which the prepolymer of the ammonium carboxylate and the nylon material is positioned, and the pressure in the reaction kettle is 1 MPa; the pressure of the reaction kettle is released to normal pressure in the later temperature zone for 2.5h, and the temperature is gradually increased to 280 ℃.

The nylon prepared in example 3 was tested to have a tensile strength of 82MPa, a flexural strength of 86MPa and a compressive strength of 118 MPa.

Example 4:

A. carrying out amination modification on 5g of potassium magnesium titanate by using 0.0175g of terminal aminosilane coupling agent, adjusting the pH value to 3-4 by using 1mol/L of acid solution, and carrying out ultrasonic stirring to prepare uniform titanate dispersion liquid;

B. adding 5g of titanate dispersion liquid into 0.5g of graphene oxide aqueous solution to prepare graphene/titanate composite material powder;

C. ultrasonically mixing 5g of graphene/titanate composite material powder and 1.8g of hexamethylenediamine in an aqueous solution, and mixing completely

Then carrying out suction filtration, washing with water, and finally placing in a vacuum drying oven for drying treatment to obtain ammonium carboxylate; the temperature of ultrasonic mixing is 50 ℃;

D. dissolving 28g of hexamethylenediamine and 35.75g of adipic acid in an aqueous solution, reacting to obtain a salt solution, and placing the salt solution in a high-pressure reaction kettle at the reaction temperature of 230 ℃ and the reaction pressure of 2 Mpa; the prepolymer of the nylon material is obtained after the reaction is carried out for 1.5 hours. And (3) performing polycondensation on the dried 5g of ammonium carboxylate and 350g of the prepolymer of the nylon material in a high-pressure reaction kettle, extruding and drying after the polycondensation is completed, and thus obtaining the nylon resin. The reaction temperature is controlled to be 250 ℃ in a front temperature zone 1h of a high-pressure reaction kettle in which the prepolymer of the ammonium carboxylate and the nylon material is positioned, and the pressure in the reaction kettle is 1 MPa; the pressure of the reaction kettle is released to normal pressure in the later temperature zone for 2.5h, and the temperature is gradually increased to 280 ℃.

The nylon prepared in example 4 was tested to have a tensile strength of 87MPa, a flexural strength of 93MPa and a compressive strength of 128 MPa.

Example 5:

A. carrying out amination modification on 5g of potassium magnesium titanate by using 0.0175g of terminal aminosilane coupling agent, adjusting the pH value to 3-4 by using 1mol/L of acid solution, and carrying out ultrasonic stirring to prepare uniform titanate dispersion liquid;

B. adding 5g of titanate dispersion liquid into 0.5g of graphene oxide aqueous solution to prepare graphene/titanate composite material powder;

C. ultrasonically mixing 5g of graphene/titanate composite material powder and 2g of hexamethylenediamine in an aqueous solution, and mixing completely

Then carrying out suction filtration, washing with water, and finally placing in a vacuum drying oven for drying treatment to obtain ammonium carboxylate; the temperature of ultrasonic mixing is 50 ℃;

D. dissolving 34g of hexamethylenediamine and 42.9g of adipic acid in an aqueous solution, reacting to obtain a salt solution, and placing the salt solution in a high-pressure reaction kettle at the reaction temperature of 230 ℃ and the reaction pressure of 2.2 Mpa; the prepolymer of the nylon material is obtained after the reaction is carried out for 1.5 hours. And (3) performing polycondensation on the dried 5g of ammonium carboxylate and 400g of the prepolymer of the nylon material in a high-pressure reaction kettle, extruding and drying after the polycondensation is completed, and thus obtaining the nylon resin. The reaction temperature is controlled to be 250 ℃ in a front temperature zone 1h of a high-pressure reaction kettle in which the prepolymer of the ammonium carboxylate and the nylon material is positioned, and the pressure in the reaction kettle is 1 MPa; the pressure of the reaction kettle is released to normal pressure in the later temperature zone for 2.5h, and the temperature is gradually increased to 280 ℃.

The nylon prepared in example 5 was tested to have a tensile strength of 86MPa, a flexural strength of 98MPa and a compressive strength of 132 MPa.