CN114989480B

CN114989480B - EPP composite material with optimized high-temperature-resistant flame-retardant performance and preparation method thereof

Info

Publication number: CN114989480B
Application number: CN202210640748.2A
Authority: CN
Inventors: 王泽云; 丁寅; 张亮; 王梦捷
Original assignee: Yixing Taiyu Automobile Parts Co ltd
Current assignee: Yixing Taiyu Automobile Parts Co ltd
Priority date: 2022-06-07
Filing date: 2022-06-07
Publication date: 2023-06-06
Anticipated expiration: 2042-06-07
Also published as: CN114989480A

Abstract

The invention relates to the technical field of flame-retardant composite materials, in particular to an EPP composite material with optimized high-temperature-resistant flame-retardant performance and a preparation method thereof.

Description

EPP composite material with optimized high-temperature-resistant flame-retardant performance and preparation method thereof

Technical Field

The invention relates to the technical field of flame-retardant composite materials, in particular to an EPP composite material with optimized high-temperature resistance and flame retardance and a preparation method thereof.

Background

The polypropylene plastic foaming material (Expanded polypropylene, EPP for short) is a high-crystallization polymer/gas composite material with excellent performance, and becomes the fastest growing environment-friendly novel compression-resistant buffer heat insulation material at present according to the unique and excellent performance. The product prepared from the EPP material has excellent shock resistance and energy absorption performance, high recovery rate after deformation, heat resistance, chemical resistance, oil resistance and heat insulation, and is light in weight, and the weight of the product can be greatly reduced. EPP composites have been widely used in various fields, for example: the IT field is used for manufacturing packaging materials, and the automobile field is used for preparing accessory materials such as automobile side shockproof cores.

Along with the continuous expansion of the application field of EPP composite materials, the demand for EPP composite materials is higher and higher, and the requirements for various properties of EPP composite materials are higher and higher, so that a great deal of research technology about EPP composite materials appears in the prior art, for example: patent No. 200680032637.2 discloses a method of preparing a flame retardant composite and the resulting material, particularly for composite performance improvement studies, particularly by providing foamed polymeric beads, applying a coating to the beads, forming the thus coated beads into the composite, the coating being an aqueous gel-forming composition comprising 5-40% by weight aluminosilicate, 0-10% by weight of an organic liquid that enhances film integrity, and the organic liquid being substantially immiscible with water, the balance being water and one or more optional other ingredients. The foam polymer is foam polypropylene, and the organic liquid is polyhydroxy alcohol, mineral oil, liquid paraffin oil, glycol ether, silicone oil or a mixture thereof. Also included are metal oxides or corresponding metals to aid in protecting the integrity of the film, the metal oxides being selected from the group consisting of zinc oxide, silicon oxide, aluminum oxide, and mixtures of two or more oxides, such that the solubility of the film formed by application of the composition to the foamed polymer by coating or other means is reduced. And from example 4, example 5, whether zinc oxide was added or not, it was found that: the addition of a small amount of zinc oxide can improve the water resistance; meanwhile, through the experiments carried out in accordance with DIN4102B2, the composite materials prepared in accordance with example 8, example 9 and example 10 and example 11 have corresponding properties such that the weight loss after drying is less than 5%, and the effect comparable to that of the flame retardant EPS is achieved.

For another example: the patent number 201510057496.0 discloses a TPO automobile instrument panel skin material and a manufacturing method thereof, and discloses a study on the application of the EPP material, in particular to the EPP material which consists of a TPO surface layer and EPP foam plastic adhered with the TPO surface layer, wherein the EPP foam plastic is expandable polypropylene foam plastic, and the expansion ratio is 22-30 times. In the method for producing TPO surface layer and backing layer and compounding EPP foam layer, EPP foam plastic is directly led in from the position between upper roller and middle roller of three-roller calender, and the molten TPO material is firmly adhered to EPP foam layer. The properties of the outer layer of the obtained TPO skin, such as tensile strength, elongation at break and tear strength, are greatly improved.

For another example: the patent application number is: 202110363321.8 the preparation process of composite heat insulating core material with nanometer mesoporous mineral includes the following steps: 1) Preparing a high molecular organic material; 2) And (3) coating a high-molecular organic material: uniformly mixing phenolic resin, nano zinc oxide and nano silicon oxide to obtain a flame-retardant adhesive; placing the mixture and EPP foaming particles into a mold box for uniform stirring, adding a flame-retardant adhesive, and uniformly mixing; 3) Preparing inorganic powder mineral slurry: adding the powder mineral into a reaction kettle, and fully and uniformly stirring and adding water into the reaction kettle to form thick inorganic powder mineral slurry; 4) Mixing and stirring: mixing the foaming particles coated in the step 2) with inorganic powder mineral slurry, injecting into a mixing box, and adding nano mesoporous mineral for stirring; 5) Curing and shaping: pressurizing and curing the mixture obtained in the step 4) at normal temperature; demolding to form blocks, and cooling; the heat preservation core material prepared has a heat value less than 20, a K value less than or equal to 0.040w/m.k, an oxygen index more than 30 and a hydrophobicity rate more than 99%.

Therefore, in the prior art, a great deal of EPP composite material performance improvement research and application research have been carried out, but the raw materials adopted by the preparation are relatively high in selection, the cost is high, and the comprehensive performance improvement of the EPP composite material is still not ideal. Therefore, the researchers combine the long-term production and research practice of the composite material, develop the EPP composite material research, realize the optimization of the high temperature resistance and the flame retardance of the EPP composite material, and provide a new product for the EPP composite material.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention provides the EPP composite material with optimized high-temperature resistance and flame retardance and the preparation method thereof.

The method is realized by the following technical scheme:

one of the objects of the present invention is to provide an EPP composite material with optimized high temperature resistance and flame retardance, comprising an EPP polymer and a modifier for modifying the EPP polymer, wherein the EPP polymer is particles with a particle diameter of 0.5-1.0mm, and the EPP polymer can be expanded by foaming; the modifier is suspension prepared from inorganic mineral tailing powder, and comprises, by weight, 3-7% of inorganic mineral tailing powder, 20% of silicone oil and the balance of water; the mass ratio of the EPP polymer to the modifier is 1:0.15-0.3.

After the inorganic mineral tailing powder is selected to prepare the suspension modifier, EPP polymer particles are poured into the stirring and mixing device, so that the modifier is coated and mixed on the surfaces of the EPP polymer particles, the film-forming flame retardant property of the surfaces of the EPP polymer is improved, and the cost of modification treatment of the EPP polymer particles is reduced.

In order to avoid excessive modifier components which form more dust in the composite material and consequently affect the tensile properties of the composite material, it is preferred that the mass ratio of the EPP polymer to the modifier is 1:0.2.

In order to improve the flame retardancy of the EPP composite and to ensure the tensile properties of the EPP composite, it is preferable that the EPP polymer is capable of foaming to a particle size of between 4 and 6 mm.

More preferably, the modifier is suspension prepared from inorganic mineral tailing powder, which comprises 4% by weight of inorganic mineral tailing powder, 20% by weight of silicone oil and the balance of water.

Preferably, the inorganic mineral tailing powder is a mixture formed by mixing powder which is ball-milled by fluorite tailing and screened by a 600-mesh sieve with powder which is ball-milled by ash of a zinc smelting plant and screened by the 600-mesh sieve according to the equal mass ratio.

The second object of the invention is to provide a preparation method of the EPP composite material with optimized high temperature resistance and flame retardance, which comprises the following steps:

(1) Preparing an expanded EPP polymer;

(2) Preparing a modifier;

(3) Mixing the expanded EPP polymer and the modifier in the step (1), stirring uniformly, and transferring into a casting film for molding; the mass ratio of the EPP polymer to the modifier is 1:0.15-0.3; the EPP polymer is particles having a particle diameter of 0.5-1.0mm, and the EPP polymer can be expanded by foaming; the modifier is suspension prepared from inorganic mineral tailing powder, and comprises, by weight, 3-7% of inorganic mineral tailing powder, 20% of silicone oil and the balance of water.

The preparation process of the EPP composite material is simplified, the flame retardant property of the EPP composite material can be ensured, and the tensile resistance of the EPP composite material is improved.

Preferably, the step (2) is to adjust the water content of the fluorite tailing slag to be less than 5wt%, send the fluorite tailing slag into a ball mill for ball milling, and pass through a 600 mesh sieve to obtain fluorite tailing slag powder; adjusting the ash of a zinc smelting plant to a water content of 1-5wt%, then sending the ash into a ball mill for ball milling, and sieving the ash with a 600-mesh sieve to obtain zinc-containing ash powder; mixing fluorite tailing slag powder and zinc-containing ash powder according to the equal mass ratio to form inorganic mineral tailing powder; and adding the inorganic mineral tailing powder, the silicone oil and the water in sequence, and stirring for 10min at a stirring speed of 1000r/min to form a suspension.

More preferably, step (1) is to expand EPP polymer particles having a particle diameter of between 0.5 and 1.0mm to a particle diameter of between 4 and 6mm under a pressure of 0.18 Pa.

Compared with the prior art, the invention has the technical effects that:

(1) The raw materials are easy to obtain, the cost of the raw materials is low, waste materials are changed into valuable materials, solid waste resources are fully utilized, and the cost for improving the performance of the composite material is reduced.

(2) The preparation process is simple, the direct stirring and mixing process can be adopted to realize the surface coating of the EPP particles with the modifier, and the EPP polymer particles are fully foamed and expanded, so that the flame retardance of the composite material is greatly improved, and the tensile resistance of the composite material is ensured.

Detailed Description

The technical scheme of the present invention is further defined below in conjunction with the specific embodiments, but the scope of the claimed invention is not limited to the description.

In certain embodiments, a high temperature resistant flame retardant performance optimized EPP composite comprises an EPP polymer and a modifier for modifying the EPP polymer, the EPP polymer is a particle having a particle size between 0.5 and 1.0mm, and the EPP polymer is capable of foaming to expand; the modifier is suspension prepared from inorganic mineral tailing powder, and the inorganic mineral tailing powder accounts for 3-7% by weight, for example: 3%,4%,4.5%,5%,5.5%,6%,7% and the like, silicone oil 20% and the balance being water; the mass ratio of the EPP polymer to the modifier is 1:0.15-0.3, for example: 1:0.15,1:0.20,1:0.27,1:0.30, etc.

In certain embodiments, the EPP polymer can be foamed and expanded to a particle size of between 4 and 6mm, such that the EPP polymer can be sufficiently foamed while maintaining the property properties of the EPP polymer, enhancing the tensile strength of the resulting EPP composite.

In some embodiments, the inorganic mineral tailings powder is a mixture of powder ball milled and sieved by 600 meshes of fluorite tailings powder and powder ball milled and sieved by 600 meshes of zinc smelter soot powder according to the equal mass ratio. The fluorite tailing slag is utilized, so that the silicon dioxide component in the fluorite tailing slag is fully utilized, the plasticity of the fluorite tailing slag is utilized, the multi-metal oxide component such as zinc oxide component is contained in the zinc smelting plant ash, the waste solid component is changed into valuable, the metal oxide component is supplemented, the EPP polymer particles are modified after the suspension is formed, the flame retardance of the EPP composite material is enhanced, and the tensile resistance of the EPP composite material is improved.

In certain embodiments, the method for preparing the EPP composite material with optimized high temperature resistance and flame retardant performance comprises the following steps:

(1) Preparing an expanded EPP polymer;

(2) Preparing a modifier;

(3) Mixing the expanded EPP polymer and the modifier in the step (1), stirring uniformly, and transferring into a casting film for molding; the mass ratio of the EPP polymer to the modifier is 1:0.15-0.3; the EPP polymer is particles having a particle diameter of 0.5-1.0mm, and the EPP polymer can be expanded by foaming; the modifier is suspension prepared from 3-7% of inorganic mineral tailing powder, 20% of silicone oil and the balance of water in parts by weight.

The process has simple steps and easy operation, and the obtained EPP composite material has excellent flame retardant property and tensile resistance.

In some embodiments, the step (2) is to adjust the water content of the fluorite tailing slag to be less than 5wt%, send the fluorite tailing slag into a ball mill for ball milling, and pass through a 600-mesh sieve to obtain fluorite tailing slag powder; adjusting the ash of a zinc smelting plant to a water content of 1-5wt%, then sending the ash into a ball mill for ball milling, and sieving the ash with a 600-mesh sieve to obtain zinc-containing ash powder; mixing fluorite tailing slag powder and zinc-containing ash powder according to the equal mass ratio to form inorganic mineral tailing powder; and adding the inorganic mineral tailing powder, the silicone oil and the water in sequence, and stirring for 10min at a stirring speed of 1000r/min to form a suspension.

In certain embodiments, step (1) is to expand EPP polymer particles having a particle size of between 0.5 and 1.0mm to a particle size of between 4 and 6mm at a pressure of 0.18 Pa. For specific pressure expansion reference may be made to, for example: the intermittent expander disclosed in example 8 of 200680032637.2 is used for expansion treatment, and the expansion pressure is controlled to be 0.18 Pa.

Example 1

Adjusting the water content of the fluorite tailing slag to be less than 5%, sending the fluorite tailing slag into a ball mill for ball milling, and sieving the fluorite tailing slag with a 600-mesh sieve to obtain fluorite tailing slag powder; adjusting the ash of a zinc smelting plant to a water content of 1-5%, then sending the ash into a ball mill for ball milling, and sieving the ash with a 600-mesh sieve to obtain zinc-containing ash powder; mixing fluorite tailing slag powder and zinc-containing ash powder according to the equal mass ratio to form inorganic mineral tailing powder; and then adding 3% of inorganic mineral tailing powder, 20% of silicone oil and the balance of water in percentage by mass, and stirring for 10min at a stirring speed of 1000r/min to form a modifier suspension.

And expanding EPP polymer particles with the particle size of 0.5-1.0mm to the particle size of 4-6mm under the pressure of 0.18Pa to obtain the expanded EPP polymer.

And (3) mixing the expanded EPP polymer and the modifier according to the mass ratio of 1:0.15, stirring uniformly, and transferring into a casting film for molding to obtain the modified EPP polymer.

Example 2

Adjusting the water content of the fluorite tailing slag to be less than 5%, sending the fluorite tailing slag into a ball mill for ball milling, and sieving the fluorite tailing slag with a 600-mesh sieve to obtain fluorite tailing slag powder; adjusting the ash of a zinc smelting plant to a water content of 1-5%, then sending the ash into a ball mill for ball milling, and sieving the ash with a 600-mesh sieve to obtain zinc-containing ash powder; mixing fluorite tailing slag powder and zinc-containing ash powder according to the equal mass ratio to form inorganic mineral tailing powder; and then adding 7% of inorganic mineral tailing powder, 20% of silicone oil and the balance of water in percentage by mass, and stirring for 10min at a stirring speed of 1000r/min to form a modifier suspension.

And (3) mixing the expanded EPP polymer and the modifier according to the mass ratio of 1:0.3, stirring uniformly, and transferring into a casting film for molding to obtain the modified EPP polymer.

Example 3

Adjusting the water content of the fluorite tailing slag to be less than 5%, sending the fluorite tailing slag into a ball mill for ball milling, and sieving the fluorite tailing slag with a 600-mesh sieve to obtain fluorite tailing slag powder; adjusting the ash of a zinc smelting plant to a water content of 1-5%, then sending the ash into a ball mill for ball milling, and sieving the ash with a 600-mesh sieve to obtain zinc-containing ash powder; mixing fluorite tailing slag powder and zinc-containing ash powder according to the equal mass ratio to form inorganic mineral tailing powder; and adding 6% of inorganic mineral tailing powder, 20% of silicone oil and the balance of water in percentage by mass, and stirring at a stirring speed of 1000r/min for 10min to form modifier suspension.

And (3) mixing the expanded EPP polymer and the modifier according to the mass ratio of 1:0.2, stirring uniformly, and transferring into a casting film for molding to obtain the modified EPP polymer.

Example 4

On the basis of example 1, fluorite tailing slag powder was replaced with equal mass of silica powder, and the procedure of example 1 was followed.

Example 5

Based on example 1, zinc-containing soot powder was replaced with equal mass of zinc oxide powder, and all other materials were prepared according to the procedure of example 1.

Example 6

The silicone oil was replaced with equal mass of water based on example 1, except that the same as in example 1 was used.

EPP composite materials prepared in examples 1 to 6 were used as samples, and heat resistance (. Degree.C.) and density (kg/m) were examined ³ ) Tensile strength (MPa), elongation at break (%),tear Strength (N/mm), the results are shown in Table 1 below:

TABLE 1 EPP composite Performance test results

Remarks: the heat resistance is detected by referring to GB/T1035-1970; density measurements were performed in accordance with GB/T1033-1986.

From table 1, it is known that: the fluorite tailing slag is adopted to replace a silicon dioxide component, and meanwhile, the zinc-containing ash powder is adopted to replace zinc oxide powder, so that the fluorite tailing slag powder and the zinc-containing ash powder are compounded to prepare inorganic mineral tailing powder, the inorganic mineral tailing powder, silicone oil and water are utilized to prepare suspension, and the suspension is used as a modifier to be uniformly mixed with EPP polymer particles to prepare the EPP composite material.

The invention is implemented by conventional technical means, for example, by referring to the prior art or common general knowledge known to the person skilled in the art, in other cases: and (5) detecting tensile resistance.

The sample piece prepared by the casting mould in the test process is a piece with the specification of 10cm multiplied by 0.5cm, and is prepared by pressurizing at normal temperature, curing and shaping, demoulding and cooling, wherein the curing temperature is controlled to be about 90 ℃, the curing time is at least 10 hours, and the compression ratio is up to 40% when the sample piece is pressurized at normal temperature. The invention has simple integral preparation process, easily obtained raw materials, low cost, optimized flame retardance and improved stretch resistance.

The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims

1. An EPP composite material with optimized high temperature resistance and flame retardant properties, characterized by comprising an EPP polymer and a modifier for modifying the EPP polymer, wherein the EPP polymer is particles with a particle size of 0.5-1.0mm, and the EPP polymer can be expanded by foaming; the modifier is suspension prepared from inorganic mineral tailing powder, and comprises, by weight, 3-7% of inorganic mineral tailing powder, 20% of silicone oil and the balance of water; the mass ratio of the EPP polymer to the modifier is 1:0.15-0.3;

the inorganic mineral tailing powder is a mixture formed by mixing powder which is ball-milled by fluorite tailing slag and screened by a 600-mesh sieve with powder which is ball-milled by ash of a zinc smelting plant and screened by the 600-mesh sieve according to the equal mass ratio.

2. The EPP composite material with optimized high temperature resistance and flame retardant property according to claim 1, wherein the modifier is suspension prepared from inorganic mineral tailing powder, and the suspension comprises, by weight, 4% of inorganic mineral tailing powder, 20% of silicone oil and the balance of water.

3. The high temperature resistant flame retardant optimized EPP composite material according to claim 1, wherein the mass ratio of the EPP polymer to the modifier is 1:0.2.

4. The high temperature resistant flame retardant optimized EPP composite material according to claim 1 wherein said EPP polymer is capable of foaming to a particle size between 4 and 6 mm.

5. The method for preparing the EPP composite material with optimized high temperature resistance and flame retardant property according to any one of claims 1 to 4, comprising the following steps:

(1) Preparing an expanded EPP polymer;

(2) Preparing a modifier;

(3) Mixing the expanded EPP polymer and the modifier in the step (1), stirring uniformly, and transferring into a casting film for molding; the mass ratio of the EPP polymer to the modifier is 1:0.15-0.3; the EPP polymer is particles having a particle diameter of 0.5-1.0mm, and the EPP polymer can be expanded by foaming; the modifier is suspension prepared from inorganic mineral tailing powder, and comprises, by weight, 3-7% of inorganic mineral tailing powder, 20% of silicone oil and the balance of water;

the step (2) is to adjust the water content of the fluorite tailing slag to be less than 5wt percent, send the fluorite tailing slag into a ball mill for ball milling, and pass through a 600-mesh sieve to obtain fluorite tailing slag powder; adjusting the ash of a zinc smelting plant to a water content of 1-5wt%, then sending the ash into a ball mill for ball milling, and sieving the ash with a 600-mesh sieve to obtain zinc-containing ash powder; mixing fluorite tailing slag powder and zinc-containing ash powder according to the equal mass ratio to form inorganic mineral tailing powder; and adding the inorganic mineral tailing powder, the silicone oil and the water in sequence, and stirring for 10min at a stirring speed of 1000r/min to form a suspension.

6. The method for preparing the EPP composite material with optimized high temperature resistance and flame retardant property according to claim 5, wherein the step (1) is to expand EPP polymer particles with the particle size of 0.5-1.0mm to the particle size of 4-6mm under the pressure of 0.18 Pa.