WO2019233017A1

WO2019233017A1 - Modified polyphenylene ether foam bead, preparation method and application thereof

Info

Publication number: WO2019233017A1
Application number: PCT/CN2018/111453
Authority: WO
Inventors: 冯云平
Original assignee: 广东奔迪新材料科技有限公司
Priority date: 2018-06-06
Filing date: 2018-10-23
Publication date: 2019-12-12
Also published as: CN109054337A

Abstract

Disclosed is a formula of a modified polyphenylene ether foam bead, and a preparation method and an application thererof. The formula comprises the following components, in parts by weight: 30-90 parts of polyphenylene ether, 30-90 parts of modified polymer, 5-30 parts of a compatibilizer, 5-30 parts of a toughening agent, 5-20 parts of a flame retardant, 1-5 parts of an antioxidant, 1-5 parts of a secondary antioxidant, 1-3 parts of a lubricant, 1-3 parts of a coupling agent, 1-10 parts of a dispersant, and 2-6 parts of an inorganic nano-nucleating agent material. The invention can be used to produce a foam bead that is uniformly foamed, having large magnification, a high closed-cell ratio, uniform and fine cells, and that is not easy to shrink and collapse. The production of the modified polyphenylene ether foam bead is completed using fast, safe, energy-efficient pre-foaming equipment and processing.

Description

[Name of invention formulated by ISA according to Rule 37.2] A modified polyphenylene ether foaming bead, preparation method and application thereof

Technical field

The invention relates to the technical field of polymer materials, in particular to a formula, a preparation method and applications of modified polyphenylene ether foamed beads.

Background technique

In the past 20 years, automobile manufacturers of various countries have attached great importance to the lightweighting of automobiles, invested a lot of manpower and funds for research, and achieved significant achievements in automotive lightweighting, mainly due to scientific and technological progress in the field of materials engineering. The first is the development of many high-strength lightweight materials and their application in automobile manufacturing, which has replaced many traditional steel parts; the second is the new forming process, which continues to emerge, optimizes the workpiece structure, and greatly reduces material consumption. The realization of lightweighting of automobiles mainly depends on the upgrading of materials and the innovation of processing technology. Knowledge of new materials can update the processing technology and create new processing technologies to achieve the purpose.

Compared with other countries, China's research in this area is not advanced enough, and more efforts should be invested to develop this process, that is, changing the manufacturing materials of automobiles, and changing some parts and structural designs of automobiles, combining technology and materials. To promote the development of lightweight vehicles.

The battery box of an electric vehicle is a key component of the power battery box assembly as a load-bearing and protection device for the battery pack of a pure electric vehicle. Pure electric vehicles are equipped with a large number of power batteries to meet the requirements of electric vehicle mileage. Often, the total achievement of the power battery box accounts for 30% -40% of the total mass of the vehicle. The major battery manufacturers currently use heavy box-type battery boxes to load power batteries, which virtually increases the overall quality of pure electric vehicles. Therefore, on the basis of meeting the basic requirements of battery box dynamic and static performance, waterproofness, and collision safety, the battery box structure of pure electric vehicles needs to be optimized to achieve its lightweight design. Rapid development is of great significance.

The battery box of an electric vehicle as a power source carried by an electric vehicle is a key component of an electric vehicle. The performance of the battery box will have a significant impact on the application prospects of electric vehicles. The power battery environment is generally poor. The battery box is used as The protective parts of power batteries need to meet many functional requirements. In the design of the cabinet structure, the following factors need to be considered: vibration resistance and fatigue durability; impact resistance, which requires that the outside and inside of the cabinet undergo shock without mechanical damage, deformation and loosening of the fastening parts; collision safety performance , Effective protection measures taken by the vehicle during the frontal collision, side collision, and rear collision that may cause crush damage to the battery box; sealing performance, the battery is located below the body floor, outside the body, and close to the road, Its waterproof and dustproof sealing requirements are indispensable; anti-corrosion performance, the location of the battery is very easy to stick to rain, mud, is a severely corroded area, its anti-corrosion performance requirements should be high; heat resistance, high battery performance during work Heat, the material of the protective box must have high temperature resistance and light weight. Considering the excessive consumption of vehicle energy and atmospheric pollution, the lighter the battery box, the better. Therefore, the existing traditional method is to use an easily formed metal box (such as an aluminum alloy) and copolymerize PP and m-PPE high-strength plastic materials.

As a modified engineering plastic polyphenylene ether (m-PPE), its specific gravity is 1.07g / cm3; its molecular structure determines its good thermal properties. Its glass transition temperature (Tg) can reach 210 ° C. In the temperature range, it can maintain excellent mechanical properties, electrical properties, thermal insulation properties, flame retardant properties, and has good resistance to hot water and water vapor.

As a basic material, high-performance polyphenylene ether resin has a strength of about 70 MPa, about three times that of polyethylene, an elastic modulus of more than 2000 MPa, and an impact resistance of the material greater than 430 J / m (Izod test method). The heat distortion temperature is as high as 120 ℃, and the linear expansion coefficient is about 1.0--2.0X106 ℃, which is lower than that of polyethylene and polypropylene. Therefore, the size of the product is stable and its creep resistance is the best among the five engineering plastics. The strength has high reliability, the polyphenylene ether material also has intrinsic flame retardancy, and is a low-smoke, halogen-free and environmentally friendly flame retardant. The resin itself is acid and alkali resistant, water resistant, and has good hygienic performance.

However, the high-performance polyphenylene ether resin has large molecular bonds, high glass transition temperature, difficult orientation, high residual internal stress in the product, poor melt fluidity, difficult processing, and high price. Therefore, PPE is usually modified by alloying methods such as blending, and by adding a foaming agent, a modified polyphenylene ether foam material is produced.

Invention patent CN1041165A discloses a foamable polymer made of polyphenylene ether and vinyl aromatic compound, and a preparation method and application thereof. The invention is a method for preparing a foamable polymer by a one-step method, that is, it is added in the polymerization process. Foaming agent. Water was placed in a sealed autoclave with a stirrer, and a suspending agent was dissolved therein, and polyphenylene ether and styrene containing dissolved peroxybenzoic acid and t-butyl perbenzoate were added to the mixture. The reaction mixture was heated with stirring and then heated to a certain temperature, at which time pentane was added under a certain pressure. After a certain period of time, the suspended polymer is sieved and dried. The pentane content of the dry beads is 6-7%. This was pre-foamed with steam to obtain a bulk density of 40 g / l. A foam material prepared from the foamed polymer is preferably used for a thermal insulation material. The method is to add a foaming agent in the polymerization process, and is a one-step method for preparing a foamable polymer. The method is complicated in process, it is difficult to control the particle size and gas content of the beads, and the particle size distribution is not uniform.

Summary of the Invention

The purpose of the present invention is to provide a formula, a preparation method and an application of a modified polyphenylene ether foamed bead, so as to solve the problems raised in the background art described above.

To achieve the above objective, the present invention provides the following technical solutions:

A formula of modified polyphenylene ether foam beads; made of the following components by weight: 30-90 parts of polyphenylene ether, 30-90 parts of modified polymer, 5-30 parts of compatibilizer, 5-30 parts of toughener, 5-20 parts of flame retardant, 1-5 parts of antioxidant, 1-5 parts of auxiliary antioxidant, 1-3 parts of lubricant, 1-3 parts of coupling agent, dispersion 1-10 parts of agent, 2-6 parts of inorganic nano nucleating agent material.

A method for preparing modified polyphenylene ether foamed beads, including the following steps:

Step 1: material modification, using polyphenylene ether material as the base material, adding modified polymer, compatibilizer, inorganic nano material and related auxiliary agents, mixing and heating, and extruding to obtain foamed modified polyphenylene ether material;

Step 2: Underwater pelletizing: Add the materials according to the formula and mix them evenly in a high-speed mixer. Put in twin or three-screw extrusion mixing equipment to melt the materials at high temperature. Use the underwater pelletizing equipment to perform underwater pelletization to make the pellets cut out. Uniform particle size, particle size 0.3 ~ 6mm, high roundness of particle shape, smooth surface;

Step 3: Pre-expanded particles: Add supercritical fluid (carbon dioxide, nitrogen) to the pre-expanded bead molding equipment, and cut the particles that are cut out underwater under high-frequency heating at a temperature of 120-250 ° C under high pressure. Sprayed into the pre-expanded bead molding equipment, through the processes of gas infiltration and dissolution, pressure release, cooling and cooling, etc., the production of modified polyphenylene ether foamed beads is completed with high-efficiency and energy-saving pre-expanded processing equipment and processes. , Foaming ratio of 3-30 times, making foaming beads suitable for uniform foaming, large magnification, high closed cell ratio, uniform and fine cells, and not easy to shrink and collapse; make it reach the required foaming ratio of foamed particles .

Application of a modified polyphenylene ether foamed bead in a lightweight power battery box; using high-frequency heating molding equipment with high efficiency, pre-foamed foamed particles with a certain expansion ratio are blown into a mold and foamed After the particles are filled in the mold, the heating temperature is high through high-frequency heating, and the foamed beads are heated uniformly from the inside to the outside to ensure the quality of the foamed products. After the foamed particles are heated and welded, they are quickly cooled and molded to obtain the plastic of the electric vehicle. Foam beads are molded into lithium battery box products; the molding temperature needs to be 150 ° C, and the pressure needs to be 0.25 MPa.

As a further solution of the present invention, the modified polymer is manufactured by mixing ABS, PE, PPS, PA, HIPS, PP, BS and GPPS according to equal weight.

As a further solution of the present invention, the compatibilizer is made of PP-g-MAH, SEBS-g-MAH, PE-g-MAH, EPDM, and POE-g-GMA according to equal weight.

As a still further solution of the present invention, the toughening agent is made by mixing SBS, SEBS, polybutene, LCP, EPDM, and polyolefin elastomer according to equal weight.

As a still further solution of the present invention, the flame retardant is prepared by mixing phosphate ester flame retardant and inorganic nano flame retardant in equal weight; the inorganic nano flame retardant: nano aluminum hydroxide , Nano-magnesium hydroxide, red phosphorus, zinc borate, nano-antimony oxide, nano-molybdenum compound, layered silicate and anhydrous magnesium carbonate are mixed and produced according to equal weight.

As a further solution of the present invention: the antioxidant is antioxidant 1010; the auxiliary antioxidant is auxiliary antioxidant 168; the lubricant is liquid paraffin; and the coupling agent is a silane coupling agent and a titanate coupling agent. The cross-linking agent and the aluminate coupling agent are produced by mixing at equal weights. The dispersant is produced by mixing polyolefin-based hyperdispersants, polyether-based hyperdispersants, and polyacrylate-based hyperdispersants at equal weights.

Compared with the prior art, the present invention has the beneficial effects that the present invention can produce foamed beads suitable for uniform foaming, large magnification, high closed cell ratio, uniform and fine cells, and difficult to shrink and collapse; fast, safe and efficient Energy-saving pre-foaming processing equipment and processes to complete the production of foamed modified polyphenylene ether foam beads; according to the relatively high softening temperature of foamed beads, innovatively develop heating and high-efficiency high-frequency technical equipment to change the existing Steam is the heating method of the heating medium, the forming pressure is low, and the production is safe and fast.

Detailed ways

The technical solution of the present invention will be further described in detail in combination with specific embodiments below.

Example 1

A formula of modified polyphenylene ether foam beads; made of the following components by weight: 30-90 parts of polyphenylene ether, 90 parts of modified polymer, 30 parts of compatibilizer, and 30 of toughening agent Parts, 20 parts flame retardants, 5 parts antioxidants, 5 parts auxiliary antioxidants, 3 parts lubricants, 3 parts coupling agents, 10 parts dispersants, 6 parts inorganic nucleating agent materials.

Step 2: Underwater pelletizing: Add the materials according to the formula and mix them evenly in a high-speed mixer. Put in twin or three-screw extrusion mixing equipment to melt the materials at high temperature. Use the underwater pelletizing equipment to perform underwater pelletization to make the pellets cut out. Uniform particle size, particle diameter 6mm, high roundness of particle shape, smooth surface;

Step 3: Pre-expanded particles: Supercritical fluid (carbon dioxide, nitrogen) is added to the pre-expanded bead molding equipment, and the particles cut out underwater are sprayed under high pressure at a temperature of 250 ° C by high-frequency heating. In the pre-expanded bead molding equipment, through the processes of gas infiltration and dissolution, pressure release, cooling and cooling, etc., the production of modified polyphenylene ether foamed beads is completed with efficient and energy-saving pre-expanded processing equipment and processes. The foaming ratio is 30 times, and the foaming beads suitable for uniform foaming, large magnification, high closed cell ratio, uniform and fine cells, and difficult to shrink and collapse are produced;

Application of a modified polyphenylene ether foamed bead in a lightweight power battery box; using high-frequency heating molding equipment with high efficiency, pre-foamed foamed particles with a certain expansion ratio are blown into a mold and foamed After the particles are filled in the mold, the heating temperature is high through high-frequency heating, and the foamed beads are heated uniformly from the inside to the outside to ensure the quality of the foamed products. After the foamed particles are heated and welded, they are quickly cooled and molded to obtain the plastic of the electric vehicle Foam beads are molded into lithium battery box products; the molding temperature needs to be 150 ° C, and the pressure needs to be 0.25 MPa.

Example 2

A formula of modified polyphenylene ether foam beads; made of the following components by weight: 30 parts polyphenylene ether, 30 parts modified polymer, 5 parts compatibilizer, 5 parts toughener, 5 parts flame retardant, 1 part antioxidant, 1 part auxiliary antioxidant, 1 part lubricant, 1 part coupling agent, 1 part dispersant, and 2 parts inorganic inorganic nucleating agent material.

Step 2: Underwater pelletizing: Add the materials according to the formula and mix them evenly in a high-speed mixer. Put in twin or three-screw extrusion mixing equipment to melt the materials at high temperature. Use the underwater pelletizing equipment to perform underwater pelletization to make the pellets cut out. Uniform particle size, particle size 0.3, high roundness of particle shape, smooth surface;

Step 3: Pre-expanded particles: Supercritical fluid (carbon dioxide, nitrogen) is added to the pre-expanded bead molding equipment, and the particles cut out underwater are sprayed under high pressure at a temperature of 120 ° C by means of high-frequency heating. In the pre-expanded bead molding equipment, through the processes of gas infiltration and dissolution, pressure release, cooling and cooling, etc., the production of modified polyphenylene ether foamed beads is completed with efficient and energy-saving pre-expanded processing equipment and processes. The foaming ratio is 3 times, and the foaming beads suitable for uniform foaming, large magnification, high closed cell ratio, uniform and fine cells, and difficult to shrink and collapse are produced;

Example 3

A formula of modified polyphenylene ether foam beads; made of the following components by weight: 30-90 parts of polyphenylene ether, 60 parts of modified polymer, 18 parts of compatibilizer, and 17 of toughening agent Parts, 13 parts flame retardant, 3 parts antioxidant, 3 parts auxiliary antioxidant, 2 parts lubricant, 2 parts coupling agent, 6 parts dispersant, and 4 parts inorganic inorganic nucleating agent material.

Step 2: Underwater pelletizing: Add the materials according to the formula and mix them evenly in a high-speed mixer. Put in twin or three-screw extrusion mixing equipment to melt the materials at high temperature. Use the underwater pelletizing equipment to perform underwater pelletization to make the pellets cut out. Uniform particle size, particle size 2mm, high roundness of particle shape, smooth surface;

Step 3: Pre-expanded particles: Add supercritical fluid (carbon dioxide, nitrogen) to the pre-expanded bead molding equipment, and use high-frequency heating at a temperature of 135 ° C to inject the particles cut out underwater under high pressure. In the pre-expanded bead molding equipment, through the processes of gas infiltration and dissolution, pressure release, cooling and cooling, etc., the production of modified polyphenylene ether foamed beads is completed with efficient and energy-saving pre-expanded processing equipment and processes. The foaming ratio is 16 times, and the foaming beads suitable for uniform foaming, large magnification, high closed cell ratio, uniform and fine cells, and difficult to shrink and collapse are produced;

Technical indicators of tested products:

Heat resistance: load 0.2MPa, cross-sectional area 13mm × 6mm, support distance 64mm, temperature 105 ° C, foaming rate 5 (cc / g), deformation ≤ 0.34mm. Product forming dimension tolerance: 0.2 ～ 0.7%.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments, and within the scope of knowledge possessed by a person of ordinary skill in the art, various embodiments can be made without departing from the spirit of the present invention. Kind of change.

Claims

A formula of modified polyphenylene ether foamed beads, which is characterized by being composed of the following components by weight: 30-90 parts of polyphenylene ether, 30-90 parts of modified polymer, and compatibilizer 5 -30 parts, toughener 5-30 parts, flame retardant 5-20 parts, antioxidants 1-5 parts, auxiliary antioxidants 1-5 parts, lubricants 1-3 parts, coupling agent 1-- 3 parts, dispersant 1--10 parts, inorganic nano-nucleating agent material 2-6 parts.
The formulation of a modified polyphenylene ether foamed bead according to claim 1, wherein the modified polymer is made of ABS, PE, PPS, PA, HIPS, PP, BS, and GPPS according to Made by mixing weights.
The compatibilizer is made by mixing PP-g-MAH, SEBS-g-MAH, PE-g-MAH, EPDM and POE-g-GMA according to equal weight.
The toughening agent is made by mixing SBS, SEBS, polybutene, LCP, EPDM, and polyolefin elastomer according to equal weight.
The flame retardant is prepared by mixing a phosphate ester flame retardant and an inorganic nano flame retardant in an equal weight; the inorganic nano flame retardant: nano aluminum hydroxide, nano magnesium hydroxide, and red phosphorus , Zinc borate, nano antimony oxide, nano molybdenum compound, layered silicate and anhydrous magnesium carbonate are mixed and produced according to equal weight.
The antioxidant is antioxidant 1010; the auxiliary antioxidant is auxiliary antioxidant 168; the lubricant is liquid paraffin; and the coupling agent is a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. The dispersant is made by mixing the same weight, and the dispersant is made by mixing the polyolefin type super dispersant, the polyether type super dispersant and the polyacrylate type super dispersant according to the same weight.
A method for preparing a modified polyphenylene ether foamed bead according to any one of claims 1-6, comprising the following steps:

Step 1: material modification, using polyphenylene ether material as the base material, adding modified polymer, compatibilizer, inorganic nano material and related auxiliary agents, mixing and heating, and extruding to obtain foamed modified polyphenylene ether material;

Step 2: Underwater pelletizing: Add the materials according to the formula and mix them evenly in a high-speed mixer. Put in twin or three-screw extrusion mixing equipment to melt the materials at high temperature. Use the underwater pelletizing equipment to perform underwater pelletization to make the pellets cut out. Uniform particle size, particle size 0.3 ~ 6mm, high roundness of particle shape, smooth surface;

Step 3: Pre-expanded particles: Add supercritical fluid (carbon dioxide, nitrogen) to the pre-expanded bead molding equipment, and cut the particles that are cut out underwater under high-frequency heating at a temperature of 120-250 ° C under high pressure. Sprayed into the pre-expanded bead molding equipment, through the processes of gas infiltration and dissolution, pressure release, cooling and cooling, etc., the production of modified polyphenylene ether foamed beads is completed with high-efficiency and energy-saving pre-expanded processing equipment and processes. , Foaming ratio of 3-30 times, making foaming beads suitable for uniform foaming, large magnification, high closed cell ratio, uniform and fine cells, and not easy to shrink and collapse; make it reach the required foaming ratio of foamed particles .
The use of a modified polyphenylene ether foamed bead as claimed in claim 7 in a lightweight power battery box, characterized in that high-frequency heating molding equipment using efficient heating is used to pre-foam a certain amount of hair. The foaming rate of the foamed particles is sent into the mold by wind. After the foamed particles are filled in the mold, the heating temperature is high and the foamed beads are heated uniformly from the inside to the outside to ensure the quality of the foamed products; the foamed particles are heated After welding, the product was quickly cooled and molded to obtain an electric vehicle plastic foam bead molded lithium battery box product. The molding temperature was 150 ° C and the pressure was 0.25 MPa.