CN112708260A

CN112708260A - Nylon 6 composite material, preparation method and application

Info

Publication number: CN112708260A
Application number: CN201911022538.1A
Authority: CN
Inventors: 邵静波; 张师军; 张�浩; 高达利; 董穆; 初立秋
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2019-10-25
Filing date: 2019-10-25
Publication date: 2021-04-27

Abstract

The invention discloses a nylon 6 composite material, a preparation method and application. The composite material is prepared by blending the following raw materials: 6100 parts of nylon; 5-40 parts by weight of fully vulcanized powdered rubber; 0.1-2 parts of oil. The preparation method comprises the following steps: the nylon 6 composite material is prepared by melting and blending the components according to the using amount. The high-performance nylon 6 material obtained by the invention not only keeps the performance of the original material, but also greatly improves the toughness of the material and the friction performance of the material. The method is suitable for 3D printing.

Description

Nylon 6 composite material, preparation method and application

Technical Field

The invention relates to the technical field of high molecular polymer processing, in particular to a nylon 6 composite material, a preparation method and application.

Background

The 3D printing (3D pirnitgn) technology is also called Rapid Prototyping, Rapid Prototyping (RPM), and additive Manufacturing, and is a high and new Manufacturing technology based on a material stacking method. The technology is a technology for constructing an object by using a bondable material such as powdered metal or plastic and the like and printing layer by layer on the basis of a digital model file, integrates mechanical engineering, CAD (computer aided design), reverse publicity technology, layered manufacturing technology, numerical control technology and material science, and is called as manufacturing technology with industrial revolution significance. The technique of forming layer by layer is realized by melting and sintering material powder laid on a worktable or a part in advance selectively layer by layer through high-intensity laser irradiation. The 3D technology has high design flexibility, can produce accurate models and prototypes, can form directly usable parts with reliable structures, and has a short production cycle and a simple process, thus being particularly suitable for the development of new products. The molding materials are widely available, including polymers, paraffins, metals, ceramics and their composites. However, the properties and properties of the molding material are important factors for the success of technical sintering, and the molding speed, the molding precision, and the physical and chemical properties and the comprehensive properties of the molded part are directly influenced. Although the variety of applicable molding materials is wide, the polymer powder raw materials which can be directly applied to automobile parts and 3D technology and successfully manufacture molded products with small dimensional errors, regular surfaces and low porosity are few at present. The 3D forming mainly comprises various 3D printing technologies including Fused Deposition Modeling (FDM), Selective Laser Sintering (SLS), three-dimensional light solidification modeling (SLA) and the like, so that the material forming method is greatly expanded, and particularly for materials which cannot be formed through fusion processing, the 3D printing forming is a good solution. The most common 3D printing materials in the market at present comprise various materials such as PP, PE, ABS, PLA and the like, along with the popularization of 3D printing technology, the 3D printing technology is more and more complex, the requirements on aviation, electronics, automobiles and the like are more and more high, the nylon 6 material is widely applied due to the unique performance of the nylon 6 material, and the nylon 6 material is important in the use and maintenance of equipment due to the existence of friction and wear in practical application, and the nylon material effectively reduces the friction and wear by adding a lubricating material and is the main direction in the material modification and processing processes.

The PA6 material is prepared by hydrolyzing caprolactam monomer at high temperature to obtain aminocaproic acid and then polymerizing at high temperature, is semitransparent or opaque milky-white particles, and has the characteristics of thermoplasticity, light weight, good toughness, chemical resistance, good durability and the like. The melting point of nylon 6 is low, and the process temperature range is wide. It has better impact resistance and dissolution resistance than nylon 66 plastic, but also has stronger hygroscopicity. Since many of the quality characteristics of the plastic parts are affected by moisture absorption, this is considered sufficient when designing products using nylon 6. In order to improve the mechanical properties of nylon 6, various modifiers are often added. Glass fiber is the most common additive, and sometimes synthetic rubbers such as EPDM and SBR are added to improve impact resistance. For the product without the additive, the shrinkage of the nylon 6 plastic raw material is between 1% and 1.5%. The addition of the glass fiber additive reduced the shrinkage to 0.3% (but somewhat higher in the direction perpendicular to the flow path). Shrinkage of the molded assembly is mainly affected by material crystallinity and moisture absorption. The actual shrinkage is also a function of the plastic design, wall thickness and other process parameters. The nylon 6 injection drying treatment is particularly noticeable because nylon 6 easily absorbs moisture, and thus drying before processing is particularly noticeable. If the material is supplied packaged with a waterproof material, the container should remain closed.

Patent CN101195707A discloses a glass fiber reinforced nylon 6-polypropylene alloy material, which is characterized in that nylon 6 and polypropylene are used as matrix resin, and the mechanical properties of the glass fiber reinforced nylon 6 can reach and be superior to those of single reinforced nylon 6 without adding polypropylene under the condition that the content of a toughening agent (anhydride grafted elastomer and polyethylene or polypropylene polymer) is not changed. But the toughness of the material is greatly reduced after the glass fiber is added.

Patent CN103540013A discloses a nylon 6/polypropylene plastic alloy and a preparation method thereof, which comprises polypropylene, nylon 6, a compatibilizer (one or more of polypropylene grafted maleic anhydride, ethylene propylene diene monomer grafted maleic anhydride, polyolefin elastomer grafted maleic anhydride, ethylene-vinyl acetate copolymer grafted maleic anhydride or polypropylene grafted hyperbranched polyester), an antioxidant, a lubricant and a light stabilizer. The alloy makes up the defects of high nylon water absorption and difficult molding, and takes the polypropylene as the main resin, thereby reducing the material cost. In the actual material preparation, we find that the melting of the nylon material and the polypropylene material also causes the material performance to be obviously lower because the materials are seriously layered and can not be effectively melted.

Disclosure of Invention

The invention provides a nylon 6 composite material, a preparation method and application in order to solve the problem of poor performance of the nylon 6 composite material in the prior art. The high-performance nylon 6 material obtained by the invention not only keeps the performance of the original material, but also greatly improves the toughness of the material and the friction performance of the material. The method is suitable for 3D printing.

One of the objects of the present invention is to provide a nylon 6 composite.

Is prepared by blending the following raw materials:

the components are calculated according to the parts by weight,

6100 parts by weight of nylon;

5-40 parts by weight of fully vulcanized powdered rubber; preferably 5 to 10 parts by weight;

0.1-2 parts by weight of oil; preferably 0.5 to 1 part by weight.

The oil is silicone oil, preferably methyl silicone oil;

the silicone oil is added into the nylon 6 material, so that the friction resistance of the nylon material can be improved, and the wear resistance of the material is mainly improved.

The fully vulcanized powdered rubber can be all fully vulcanized powdered rubbers in the prior art. In the invention, one or a combination of fully vulcanized powdered nitrile rubber, fully vulcanized powdered butadiene-styrene-pyridine rubber and fully vulcanized powdered butadiene-styrene rubber can be preferably selected.

The gel content of the fully vulcanized powder rubber is 60% by weight or more, 80% by weight or more in terms of weight ratio; more preferably 90% by weight or more.

The particle diameter of the fully vulcanized powder rubber is below 100 nanometers.

The fully vulcanized powdered rubber is well combined with a nylon material chain segment, so that the effects of compatibilization and toughening are well achieved, and the compound of the rubber powder and the silicone oil well achieves the effect of dispersing the rubber powder in the material.

The raw material of the nylon 6 composite material also comprises an antioxidant. The antioxidant can be any conventional antioxidant in the art, such as 1010, 168, 1098, etc., and the amount thereof is conventional and can be adjusted by the skilled person according to the actual situation.

The second purpose of the invention is to provide a preparation method of the nylon 6 composite material.

The method comprises the following steps:

the nylon 6 composite material is prepared by melting and blending the components according to the using amount.

Among them, preferred are:

the melting temperature is 210-220 ℃.

In particular, the amount of the solvent to be used,

after being dried, the nylon 6 is added with the antioxidant and the fully-vulcanized powdered nitrile rubber powder, is stirred and blended for two minutes at a high speed, and is added into a double-screw extruder for melt extrusion. The silicone oil is quantitatively added into a melting section of the double-screw extruder through a liquid pump, and after being injected into a screw low-pressure interval, the grease is melted with a nylon material, extruded and granulated.

In the preparation process, in order to enable the material to have good processability, the silicone oil is added into a high-speed stirrer, the powder rubber powder well adsorbs the grease material in the particle size, and after the powder rubber powder is mixed with the nylon 6 material, the mixture is melted and extruded for granulation under the process conditions of 210 degrees, 220 degrees.

The invention also provides application of the nylon 6 composite material in 3D printing.

The PA6 material is a translucent or opaque milky white material which has good thermoplasticity, light weight, toughness, chemical resistance and durability. The nylon 6 has low melting point, slow crystallization speed and wide process temperature range. It has better impact resistance and dissolution resistance than nylon 66 plastic, but also has stronger hygroscopicity. Since many of the quality characteristics of the plastic parts are affected by moisture absorption, this is considered sufficient when designing products using nylon 6. In order to improve the mechanical property of the nylon 6 and widen the application field of the nylon 6 material, especially the application in the current 3D market, the physical property of the nylon 6 material is improved by adding auxiliary agents and other means by combining the current application market of the nylon 6, the property of the material is changed, and the original defects of the material are overcome. In the actual operation process, aiming at the self-lubricating effect of the nylon 6 material, the lubricating effect of the material is improved by adding silicone oil, and the friction coefficient and the volume abrasion of the material are obviously improved. The nylon 6 material is taken as a hydrophilic material, has certain limitation in practical application, and a certain amount of silicone oil is added in the preparation of the material, a certain amount of microbeads are uniformly distributed on the surface of the material and in a melt, so that the material absorbs water in the environment and has a certain shielding effect, and the water absorption rate of the material is reduced.

The defect of slow crystallization speed in the processing process of the nylon 6 material is overcome, the molding period of a product is longer, the improvement of the actual production efficiency of the product is not facilitated, the crystallization rate of the product is improved by adding fully vulcanized powdered rubber in the preparation process of the material, the molding time of the product is shortened, the powdered rubber and the nylon material have a good melting effect, and the impact performance of the nylon 6 material is improved by 15%.

The existing nylon 6 material has good strength, but because the material is easy to absorb water and has slow crystallization and other defects, the material is usually worn and has a long processing period when applied to a material part. In order to improve the market of the nylon 6 material and expand the application field of the material, the fully vulcanized powdered rubber is added in the invention, so that the toughness of the material is improved, and the silicone oil is uniformly mixed in the nylon 6 material. Effectively fusing nylon 6, silicone oil and fully vulcanized powdered rubber together. The material with excellent performance is obtained through repeated blending effects of extrusion, melting, blending and the like of a double-screw extruder, the oil-filled nylon 6 material not only keeps the original excellent performance of the nylon material, but also improves the wear resistance of the material on the original basis, and also better improves other properties of the material, and the material can be applied to waterproof nylon 3D printing parts, thereby widening the application field of the nylon material.

The nylon 6 material is mainly used for main parts of automobiles due to excellent performance, particularly more used for gears and shaft sleeves, and the lubricating and wear-resisting properties of the nylon 6 material are fully exerted. The method is suitable for 3D printing.

Drawings

FIG. 1 is a cross-sectional electron micrograph of a nylon 6 composite prepared in example 4.

Detailed Description

While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.

Raw materials:

nylon 6: manufactured by petrochemical holy corporation under the designation BH 1800.

Fully vulcanized nitrile rubber powder: the gel content is more than 80 percent by weight when produced by the China petrochemical Beijing chemical research institute;

the grain diameter is below 100 nm.

Methyl silicone oil: beijing Xinke Australian Corp

Antioxidant: BASF corporation, Germany

Firstly, preparing a nylon 63D material by comparison:

comparative example 1:

100 parts by weight of nylon 6 and silicon powder; adding the antioxidant of the nylon material into a high-speed stirrer, and stirring for 2 minutes at normal temperature to fully and uniformly mix the components. And adding the mixed materials into a double-screw extruder at the temperature of 220-250 ℃ for melt blending, extruding and granulating to obtain the comparative example 1.

Comparative example 2:

100 parts by weight of nylon 6, 10 parts by weight of EPDM and an antioxidant are added into a high-speed stirrer together, and the mixture is stirred for 2 minutes at normal temperature so that the components are fully and uniformly mixed. And adding the mixed materials into a double-screw extruder at the temperature of 220-250 ℃ for melt blending, extruding and granulating to obtain the comparative example 2.

Secondly, preparing the nylon 6 composite material:

examples 1 to 4

The formulation is shown in table 1: (amounts are in parts by weight)

TABLE 1

The preparation method comprises the following steps:

after being dried, the nylon 6 is added with the antioxidant and the fully-vulcanized powdered nitrile rubber powder, is stirred and blended for two minutes at a high speed, and is added into a double-screw extruder for melt extrusion. And quantitatively adding the methyl silicone oil into a melting section of a double-screw extruder through a liquid pump, and melting, extruding and granulating the grease and the nylon material after the grease is injected into a screw low-pressure interval. The melting temperature is 210-220 ℃.

The mechanical properties of the examples and comparative examples are shown in Table 2, and the abrasion data are shown in Table 3.

TABLE 2

TABLE 3

Name (R)	Coefficient of friction (. mu)	Volume abrasion (mg)
			Comparative example 1	0.28	0.0035
Comparative example 2	0.26	0.0042
			Example 1	0.08	0.0028
Example 2	0.06	0.0021
			Example 3	0.07	0.0018
Example 4	0.12	0.0022

As can be seen from the data in tables 2 and 3, the mechanical property of the nylon 6 composite material prepared by the invention is obviously improved compared with that of the comparative example, meanwhile, the abrasion is greatly reduced, and the abrasion resistance is obviously improved.

As shown in figure 1, the cross-sectional observation of the sample prepared from the material of example 4 by using an electron microscope clearly shows that the rubber powder and the silicone oil can be uniformly dispersed in a nylon 6 matrix, and the uniform distribution effect is the basis for preparing a high-quality 3D printing lubricating material.

Claims

1. The nylon 6 composite material is characterized by being prepared by blending the following raw materials:

the components are calculated according to the parts by weight,

6100 parts by weight of nylon;

5-40 parts by weight of fully vulcanized powdered rubber;

0.1-2 parts of oil.

2. The nylon 6 composite of claim 1, wherein:

the components are calculated according to the parts by weight,

6100 parts by weight of nylon;

5-10 parts of fully vulcanized powdered rubber;

0.5-1 part of oil.

3. The nylon 6 composite of claim 1, wherein:

the raw material of the nylon 6 composite material also comprises an antioxidant.

4. The nylon 6 composite material according to any one of claims 1 to 3, wherein:

the oil is a silicone oil, preferably methyl silicone oil.

5. The nylon 6 composite of claim 4, wherein:

the fully vulcanized powdered rubber is one or a combination of fully vulcanized powdered nitrile rubber, fully vulcanized powdered butadiene-styrene-pyridine rubber and fully vulcanized powdered butadiene-styrene rubber.

6. The nylon 6 composite of claim 5, wherein:

the gel content of the fully vulcanized powdery rubber is 60% by weight or more in terms of weight ratio, and the particle diameter is 100 nm or less.

7. The nylon 6 composite of claim 6, wherein:

the gel content of the fully vulcanized powder rubber is 80% by weight or more in terms of weight ratio;

preferably, the gel content of the fully vulcanized powdery rubber is 90% by weight or more in terms of weight ratio.

8. A method for preparing the nylon 6 composite material as claimed in any one of claims 1 to 7, wherein the method comprises:

9. The method of claim 8, wherein the step of preparing the composition comprises

The melting temperature is 210-220 ℃.

10. Use of a nylon 6 composite as claimed in any of claims 1 to 7 in 3D printing.