CN117659686A - Nylon composite material and preparation method and application thereof - Google Patents

Abstract

The invention relates to a nylon composite material and its preparation method and application. The nylon composite material includes the following components: PA resin, toughening agent, benzenesulfonamide plasticizer, inorganic metal salt and other auxiliaries. The nylon composite material is added with a benzene sulfonate plasticizer and a specific inorganic metal salt. The resulting nylon composite material has high elongation at break, high notch impact strength, low flexural modulus, and low hardness. The nylon composite material is suitable for preparing products such as cable protective sheaths.

Description

Nylon composite material and preparation method and application thereof

Technical field

The present invention relates to the technical field of polymer materials, and more specifically, to a nylon composite material and its preparation method and application.

Background technique

Nylon material has excellent properties such as good wear resistance, self-lubrication and chemical corrosion resistance, and is suitable for various molding processing methods such as injection molding and extrusion. Therefore, it is widely used in automotive engineering plastics, spinning, electrical appliances and Electronic materials and other fields. Pure nylon materials also have shortcomings such as notch sensitivity and high hardness, which also results in certain limitations in their applications. For example, nylon's wear resistance and chemical corrosion resistance are suitable for cable sheathing, but the cable sheath material has flexibility requirements and needs to overcome the shortcomings of nylon materials such as notch sensitivity and high hardness. To this end, it is necessary to Nylon materials are modified to improve their elongation at break and notched impact resistance, and reduce their hardness. Generally speaking, the elongation at break is required to reach ≥150%, the notched impact strength is ≥80KJ/m ² , and the flexural modulus is ≤ 500MPa and hardness ≤70HD are suitable for preparing cable sheaths.

Patent CN115594966A discloses a polyamide composite material. Its components mainly include polyamide 6, long carbon chain aliphatic polyamide, impact modifier, hydroxybenzoate plasticizer, and end groups with hydroxyl and carboxyl groups. Hyperbranched polyester, the resulting polyamide composite material has high tensile fracture toughness, but still has high crystallinity, resulting in the composite material still showing high rigidity (flexural modulus), hardness, and flexibility Insufficient and cannot meet the requirements for cable sheathing.

To this end, it is necessary to develop a nylon material with high toughness, low rigidity and low hardness.

Contents of the invention

The primary purpose of the present invention is to overcome the problem that nylon composite materials in the current technology cannot meet the requirements of high elongation at break, high notched impact strength and low rigidity and low hardness, and provide a nylon composite material. The nylon composite material is added with a benzene sulfonate plasticizer and a specific inorganic metal salt, and the resulting nylon composite material has high flexibility (high elongation at break, high notched impact strength, and low flexural modulus) and low hardness. The nylon composite material is suitable for preparing products such as cable protective sheaths.

A further object of the present invention is to provide a method for preparing the above-mentioned nylon composite material.

A further object of the present invention is to provide the application of the above nylon composite material in preparing cable protective sheaths.

The above objects of the present invention are achieved through the following technical solutions:

A nylon composite material, including the following components by weight:

The inorganic metal salt is a metal halide and is at least one of lithium salt, calcium salt or zinc salt;

The mass ratio of the benzenesulfonamide plasticizer to the inorganic metal salt is ≤7.

In the present invention, PA resin is used as the main resin, and its mass ratio in the nylon composite material is at least 45%.

The inventor of the present invention found through research that adding benzene sulfonamide plasticizer to PA resin has good compatibility because the benzene sulfonamide plasticizer has similar polarity to the PA resin macromolecules. In the amorphous region of the PA resin, the benzene sulfonate plasticizer is distributed around the PA resin macromolecules, which can reduce the van der Waals force between the PA resin macromolecules and play an intermolecular lubrication effect, making the polyamide molecular chain segments The degree of freedom of movement is increased and the resistance is reduced. Macroscopically, the elongation at break and notched impact strength of the material are increased. However, benzenesulfonamide plasticizers have limited effect on intermolecular hydrogen bonds in the crystallization region of PA resin, and the material still exhibits relatively high rigidity and hardness macroscopically.

Through further research, the inventor of the present invention found that on the basis of adding benzene sulfonic acid amide plasticizer to PA resin, and then adding the inorganic metal salt of the present invention, this kind of inorganic metal salt can be used as Lewis acid and PA resin macromolecules. The polar amide group on the PA resin undergoes a complexation reaction to prevent the formation of intermolecular hydrogen bonds in the PA resin, thus reducing the crystallinity of the PA resin and increasing the proportion of amorphous regions, making it easier for benzene sulfonic acid amide plasticizers to enter the polymer In the amide molecular chain, the toughening effect is more obvious, the material is more flexible and the hardness is reduced, showing a certain synergistic promotion effect.

That is, the present invention adds benzene sulfonate plasticizer and specific inorganic metal salt, and the obtained nylon composite material has high flexibility (high elongation at break, high notched impact strength, low flexural modulus) and low hardness. The nylon composite material is suitable for preparing products such as cable protective sheaths.

Optionally, the relative viscosity of the PA resin is 2.0 to 3.0.

In the present invention, the relative viscosity of PA resin can be measured according to ISO 307:2007.

Preferably, the relative viscosity of the PA resin is 2.5 to 2.8. If the PA resin is selected within this range, the resulting nylon composite material will have higher notched impact strength.

Optionally, the PA resin is a short carbon chain PA resin.

It should be understood that short carbon chain PA resin means that the repeating units of the PA resin are derived from aliphatic diamines with a carbon number of 6 or less and aliphatic diacids with a carbon number of 6 or less.

Optionally, the PA resin is at least one of PA6 resin, PA66 resin or PA56 resin.

Preferably, the PA resin is PA6 resin.

Alternatively, the benzene sulfonamide plasticizer is N-butylbenzenesulfonamide, N-ethyl o-p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N,N-diethylbenzene At least one of sulfonamide, N,N-diethyl p-toluenesulfonamide, N,N-dibutylbenzenesulfonamide, N-octylbenzenesulfonamide or N-phenylbenzenesulfonamide.

Preferably, the benzene sulfonamide plasticizer is N-butylbenzenesulfonamide. By selecting this benzene sulfonamide plasticizer, the obtained nylon composite material has better properties and is more suitable for manufacturing. into a cable protective sleeve.

Optionally, the inorganic metal salt is at least one of lithium chloride, calcium chloride or zinc chloride.

Preferably, the inorganic metal salt is calcium chloride. By selecting this inorganic metal salt, the obtained nylon composite material has better properties and is more suitable for making a cable protective sheath.

Usually, the mass ratio of the benzene sulfonamide plasticizer and the inorganic metal salt is 1: (0.15~0.5); specifically, it can be 1:0.15, 1:0.16, 1:0.17, 1:0.18, 1:0.19 , 1:0.20, 1:0.25, 1:0.305, 1:0.35, 1:0.40, 1:0.45, 1:0.50.

Toughening agents commonly used in this field can be used in the present invention.

Optionally, the toughening agent is at least one of maleic anhydride-grafted POE or maleic anhydride-grafted EPDM.

Optionally, the other auxiliary agent is at least one of an antioxidant, a lubricant or a weathering agent.

Optionally, the antioxidants include, but are not limited to, hindered phenolic antioxidants or phosphite antioxidants.

Optionally, the lubricant includes but is not limited to ester lubricant.

Optionally, the weathering agent includes, but is not limited to, an anti-ultraviolet agent.

Preferably, the nylon composite material includes the following components by weight:

The preparation method of the above-mentioned nylon composite material includes the following steps: mix each component except the benzenesulfonic acid amide plasticizer to obtain a mixture; add the mixture from the main feeding port of the extruder, add the benzenesulfonic acid The amide plasticizer is added from the side feed port of the extruder, melted, extruded, and granulated to obtain the nylon composite material.

Preferably, the mixing is performed in a mixing mixer, the mixing speed is 100-300 r/min, and the mixing time is 10-15 min.

Preferably, the melt extrusion temperature is 200-235°C.

The application of the above-mentioned nylon composite materials in preparing cable protective sheaths is also within the protection scope of the present invention.

Compared with the prior art, the beneficial effects of the present invention are:

The present invention adds benzene sulfonamide plasticizer and specific inorganic metal salt, and the obtained nylon composite material has high flexibility (high elongation at break, high notch impact strength, low bending modulus) and low hardness. The nylon composite material is suitable for preparing products such as cable protective sheaths.

Detailed ways

In order to describe the technical solutions of the present invention more clearly and completely, the present invention is further described in detail below through specific embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention. Various changes can be made within the scope defined by the rights of the present invention.

Some of the reagents selected for each embodiment and comparative example of the present invention are described below:

PA resin 1#: PA6, brand name HY2800A, Haiyang Chemical Fiber Group, relative viscosity 2.8;

PA resin 2#: PA6, brand name HY2500A, Haiyang Chemical Fiber Group, relative viscosity 2.5;

PA resin 3#: PA6, brand name HY2000A, Haiyang Chemical Fiber Group, relative viscosity 2.0;

PA resin 4#: PA66, brand name EP-158, Zhejiang Huafeng New Materials Co., Ltd., relative viscosity 2.7;

Benzenesulfonamide plasticizer #1: N-butylbenzenesulfonamide, Suzhou Jinzhong Chemical Co., Ltd.;

Benzenesulfonamide plasticizer 2#: N-ethyl o-p-toluenesulfonamide, Suzhou Jinzhong Chemical Co., Ltd.;

Other plasticizers: tributyl citrate, Jinan Jinbang Environmental Protection Technology Co., Ltd.;

Inorganic metal salt 1#: calcium chloride, purity ≥99%, commercially available;

Inorganic metal salt 2#: zinc chloride, purity ≥99%, commercially available;

Inorganic metal salt 3#: lithium chloride, purity ≥99%, commercially available;

Inorganic metal salt 4#: potassium chloride, purity ≥99%, commercially available;

Toughening agent: maleic anhydride grafted POE, brand N406, Ningbo Nengzhiguang New Material Technology Co., Ltd.;

Antioxidant: Obtained by mixing hindered amine antioxidant and phosphite antioxidant at a mass ratio of 1:1, in which the hindered amine antioxidant is N,N'-bis-(3-(3,5-ditert. Butyl-4-hydroxyphenyl)propionyl)hexanediamine, and the phosphite antioxidant is bis(2,4-dicumylphenyl)pentaerythritol diphosphite, both of which are commercially available products;

Lubricant: calcium stearate, commercially available.

Unless otherwise specified, the components (such as antioxidants, lubricants) selected in each parallel example and comparative example are all the same commercially available products.

The performance of the nylon composite materials provided in each embodiment and comparative example of the present invention is measured according to the following test methods:

(1) Elongation at break: Tensile test is conducted according to ISO 527-2:2012, the span is 115mm, the tensile rate is 50mm/min, and the test temperature is 23°C;

(2) Flexural modulus: Conduct bending test according to ISO 178:2019, span 64mm, test speed 2mm/s, test temperature 23℃;

(3) Izod notched impact strength: The Izod notched impact test is carried out according to ISO 180:2019. The notched impact specimen is type A, 2mm deep, and the test temperature is 23°C;

(4) Shore D hardness: tested according to ISO 868:2003, the test temperature is 23°C;

The nylon composite materials of the examples and comparative examples of the present invention are prepared by the following preparation methods:

Weigh each component according to the formula; weigh the other components except the plasticizer and mix them evenly in a high mixer to obtain a mixture; then add the mixture into the twin-screw extruder from the main feeding port; add the plasticizer The agent is placed in a container and placed in a 90-degree water bath. Use a metering pump to add it to the twin-screw extruder from the second feeding port of the twin-screw extruder. After melting, extrusion, water cooling, and pelletizing, the nylon composite is obtained. Material. Among them, the rotation speed of the high mixer is 100r/min and the mixing time is 15min; the melt extrusion temperature of the twin-screw extruder is 200~235℃.

Examples 1 to 13

Examples 1 to 13 provide a series of nylon composite materials, the formulations of which are shown in Tables 1 and 2.

Table 1 Formulas of Examples 1 to 7 (parts by weight)

Table 2 Formulas of Examples 8 to 13 (parts by weight)

Comparative example 1

This comparative example provides a nylon composite material, the preparation method and formula of which are basically the same as those of Example 1, except that the benzenesulfonamide plasticizer #1 is not added.

Comparative example 2

This comparative example provides a nylon composite material, the preparation method and formula of which are basically the same as those of Example 1, except that inorganic metal salt 1# is not added.

Comparative example 3

This comparative example provides a nylon composite material. Its preparation method and formula are basically the same as those in Example 1. The difference is that benzenesulfonamide plasticizer #1 and inorganic metal salt #1 are not added.

Comparative example 4

This comparative example provides a nylon composite material, the preparation method and formula of which are basically the same as those in Example 1, except that the benzenesulfonamide plasticizer #1 is replaced with other plasticizers.

Comparative example 5

This comparative example provides a nylon composite material, the preparation method and formula of which are basically the same as those of Example 1, except that the inorganic metal salt 1# is replaced by the inorganic metal salt 4#.

Comparative example 6

This comparative example provides a nylon composite material, the preparation method and formula of which are basically the same as those in Example 6, except that the amount of inorganic metal salt is 2 parts by weight.

The properties of the nylon composite materials of each example and comparative example were measured according to the above-mentioned test methods. The test results are shown in Table 3.

Table 3 Nylon composite material performance test results of each embodiment and comparative example

It can be seen from Table 3:

The elongation at break of the nylon composite materials of Examples 1 to 13 are all ≥150%, the flexural modulus is ≤500MPa, the notched impact strength is ≥80KJ/m ² , and the hardness is ≤70HD, indicating that the nylon composite material of the present invention has an elongation at break. It has high length and notch impact strength, low flexural modulus and low hardness, which meets the requirements for preparing cable sheaths.

Comparative Example 1 does not add benzene sulfonamide plasticizer, and the properties of the nylon composite material do not meet the requirements for preparing cable sheaths. Comparative Example 2 does not add specific inorganic metal salts, and the flexural modulus of its nylon composite material is high and does not meet the requirements. Comparative Example 3 does not add benzene sulfonamide plasticizer and specific inorganic metal salt, and the properties of the nylon composite material do not meet the requirements for preparing cable sheaths. The plasticizer selected in Comparative Example 4 is inappropriate. The flexural modulus of the nylon composite material is too high and the notched impact strength is too low, which does not meet the requirements for preparing cable sheaths. The inorganic metal salt selected in Comparative Example 5 is inappropriate. The flexural modulus of the nylon composite material is too high, the notched impact strength is low, and the hardness is high. It also does not meet the requirements for preparing cable sheaths. The mass ratio of the benzene sulfonamide plasticizer and the inorganic metal salt added in Comparative Example 6 is inappropriate, and the flexural modulus of the nylon composite material is high.

Obviously, the above-mentioned embodiments of the present invention are only examples to clearly illustrate the present invention, and are not intended to limit the implementation of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. An exhaustive list of all implementations is neither necessary nor possible. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the claims of the present invention.

Claims (10)

1. The nylon composite material is characterized by comprising the following components in parts by weight:

the inorganic metal salt is a metal halide and is at least one of a lithium salt, a calcium salt or a zinc salt;

the mass ratio of the benzenesulfonic acid amide plasticizer to the inorganic metal salt is less than or equal to 7.

2. The nylon composite of claim 1, wherein the PA resin is at least one of PA6 resin, PA66 resin, or PA56 resin.

3. The nylon composite of claim 1, wherein the benzenesulfonamide plasticizer is at least one of N-butylbenzenesulfonamide, N-ethyl ortho-para-toluenesulfonamide, N-ethyl para-toluenesulfonamide, N-diethylbenzenesulfonamide, N-diethylpara-toluenesulfonamide, N-dibutylbenzenesulfonamide, N-octylbenzenesulfonamide, or N-phenylbenzenesulfonamide.

4. The nylon composite of claim 1, wherein the inorganic metal salt is at least one of lithium chloride, calcium chloride, or zinc chloride.

5. The nylon composite of claim 1 wherein the PA resin has a relative viscosity of 2.0 to 3.0.

6. The nylon composite of claim 1, wherein the toughening agent is at least one of maleic anhydride grafted POE or maleic anhydride grafted EPDM.

7. The nylon composite of claim 1, wherein the other auxiliary agent is at least one of an antioxidant, a lubricant, or a weathering agent.

8. The nylon composite of claim 1, wherein the nylon composite comprises the following components in parts by weight:

9. the method for preparing the nylon composite material according to any one of claims 1 to 8, which is characterized by comprising the following steps: mixing the components except the benzenesulfonic acid amide plasticizer to obtain a mixture; adding the mixture from a main feeding port of an extruder, adding benzenesulfonamide plasticizer from a side feeding port of the extruder, performing melt extrusion, and granulating to obtain the nylon composite material.

10. Use of a nylon composite according to any one of claims 1 to 8 for the preparation of a cable protective sheath.