WO2022057182A1 - Polyolefin material and method for preparation thereof - Google Patents

Abstract

Provided are a polyolefin material and method for preparation thereof, comprising the components: 90-99.9 parts of reinforcing-fiber masterbatch; 0.1-10 parts of foaming masterbatch. By means of adding both reinforcing fibers and hollow microspheres to the reinforcing fiber masterbatch, the effectiveness of the two is synergistically enhanced, and the reinforcing fiber masterbatch thus prepared is blended with the foaming masterbatch, not only significantly reducing the density of the material and increasing the wave permeability of the material, but also increasing the strength and heat resistance of the material, such that the material has the advantages of low density, good impact, and high wave permeability.

Description

A kind of polyolefin material and preparation method thereof technical field

The invention belongs to the field of polymer materials, in particular to a polyolefin material and a preparation method thereof.

Background technique

Polyolefin materials are the most widely used in real life due to their abundant raw materials, low price, easy processing and molding, and excellent comprehensive performance.

At present, the reinforcement method of conventional polyolefin mainly uses glass fiber as the reinforcement medium, and uses the high strength and high rigidity of glass fiber to improve the strength and heat resistance of the product. However, using this method, the glass fiber reinforced polyolefin after adding glass fiber has defects such as high density, poor wave transmission performance (large dielectric constant and dielectric loss), and poor toughness, which cannot meet the requirements of weight or wave transmission performance. Use in high places.

In order to improve the wave-transmitting properties of polyolefin materials, a method of adding low-dielectric glass fibers or quartz fibers has been studied. Although this method can achieve better wave-transmitting properties, it also has the defects of high density and high cost.

Therefore, it has a good market prospect to study a polyolefin material with low density, good impact and high wave transmittance.

SUMMARY OF THE INVENTION

In order to overcome the above-mentioned shortcomings of the prior art, the primary purpose of the present invention is to provide a polyolefin material, which has the advantages of low density, good impact and high wave transmittance.

Another object of the present invention is to provide a method for preparing the above-mentioned polyolefin material.

The present invention is achieved through the following technical solutions:

A polyolefin material, by weight, comprising the following components:

Reinforcing fiber masterbatch 90-99.9 copies;

Foaming masterbatch 0.1-10 parts.

The reinforcing fiber masterbatch, in parts by weight, comprises the following components:

Described foaming master batch, by weight, comprises the following components:

Polyolefin resin 10-99 parts;

Foaming agent 0.1-50 parts.

Preferably, the polyolefin resin is selected from one or a mixture of polypropylene, polyethylene and polybutene.

Preferably, the compatibilizer is a graft polymer of a polar monomer and a polyolefin, wherein the polar monomer is selected from one or more mixtures of maleic anhydride, acrylic acid, and acrylate derivatives, The polyolefin is selected from one or a mixture of polypropylene and polyethylene.

Preferably, the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers, and basalt fibers, preferably glass fibers with an average diameter of 5-20 μm.

The hollow microspheres of the invention contain air, have strong wave-transmitting ability, low density, light weight, higher hardness than glass, and stronger pressure resistance. Preferably, the hollow microspheres are selected from one or more mixtures of hollow mullite microspheres and hollow glass microspheres; the particle size D50 is 10-50 microns, preferably 15-30 microns, and the density is 0.2- 0.9g/cm ³ , preferably 0.3-0.5g/cm ³ , the bearing pressure is 5000PSI-50000PSI, preferably 10000-30000PSI; if the bearing pressure is too poor, it will be easily broken during the extrusion process. The compressive strength of the hollow mullite microspheres was measured by the water isostatic pressure testing method. Preferably, in the reinforcing fiber masterbatch, hollow microspheres account for 0.5-50 parts. Preferably, the mass ratio of the reinforcing fibers to the hollow microspheres is 1:5-5:1, preferably 1:2-2:1.

Preferably, the foaming agent is azodicarbonamide, azobisisobutyronitrile, azodiisoheptanenitrile, diisopropyl azodicarboxylate, barium azodicarboxylate, azodicarboxylate Diethyl ester, diethyl azodicarboxylate, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, dinitrosopentamethylenetetramine, benzenesulfonic acid Hydrazide, p-toluenesulfonylhydrazide, 4,4'-bisphenylsulfonylhydrazide, 3,3'-disulfonylhydrazide, diphenylsulfone, 1,3-benzenedisulfonylhydrazide, p-toluenesulfonyl semicarbazide , 4,4'-oxobis(benzenesulfonyl semicarbazide), trihydrazine triazine, 5-phenyltetrazole, calcium carbonate, magnesium carbonate or sodium bicarbonate one or more mixtures.

The present invention also provides a method for preparing the above-mentioned polyolefin material, comprising the following steps:

(1) According to the proportion, mix the polyolefin resin and compatibilizer, add it to the main feeding system of the extruder, and add the reinforcing fibers and hollow microspheres to the side feeding system at the same time. All components are mixed and extruded by the extruder. granules to obtain reinforced fiber masterbatch;

(2) adding the polyolefin resin and the foaming agent to the main feeding system of the extruder according to the proportioning, mixing, extruding and granulating to obtain the foaming master batch;

(3) Blending the reinforcing fiber masterbatch and the foaming masterbatch to obtain a polyolefin material.

The present invention also provides the application of the above-mentioned polyolefin material in the fields of household appliances, automobiles or communications.

Compared with the prior art, the present invention has the following beneficial effects:

In the present invention, reinforcing fibers and hollow microspheres are added to the reinforcing fiber master batch at the same time, and the two synergistically synergize, and the prepared reinforcing fiber master batch is blended with the foaming master batch, and the addition of the foaming master batch can reduce the molding time. It can greatly improve the retention length of the glass fiber and keep the hollow microspheres from being damaged, which can not only significantly reduce the density of the material, improve the wave-transmitting performance of the material, but also improve the strength and heat resistance of the material. The material combines the advantages of low density, good impact and high wave transmission.

detailed description

The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

The raw materials used in the present invention are all derived from commercially available, and the raw materials used in Examples and Comparative Examples are now described as follows, but are not limited to these materials:

Polypropylene resin: PP SP179;

Polyethylene resin: HDPE 5000S;

Compatibilizer: PP-g-MAH, HDPE-g-MAH;

Reinforcing fibers:

Glass fiber 1: the average diameter is 8 μm;

Glass fiber 2: the average diameter is 25 μm;

Basalt fiber, quartz fiber;

Hollow mullite microspheres: particle size 30 microns, density 0.3 g/cm ³ , pressure 15000 PSI;

Hollow glass microbeads: particle size 15 microns, density 0.6g/cm ³ , pressure 25000PSI;

Foaming agent: azodicarbonamide, benzenesulfonyl hydrazide, sodium bicarbonate, all from the market.

The relevant performance test standards or methods are as follows:

Density: tested according to ISO1183 standard;

Dielectric constant and dielectric loss: Test frequency according to GB12636: 10GHz;

Bending strength: tested according to ISO178;

-40 degree notched impact strength: tested according to ISO 180/1A; test temperature -40 degrees;

Heat distortion temperature: ISO75-2 test, test condition 1.82MPa.

【Preparation of Reinforcing Fiber Masterbatch】

According to the ratio in Table 1, the polyolefin resin and compatibilizer are mixed and added to the main feeding system of the extruder. At the same time, the reinforcing fibers and hollow microspheres are added to the side feeding system. All components are mixed and extruded by the extruder. granules to obtain reinforced fiber masterbatches.

Table 1 The distribution ratio of each component in the reinforced fiber masterbatch (parts by weight)

【Preparation of Foaming Masterbatch】

According to the ratio in Table 2, the polyolefin resin and the foaming agent are added to the main feeding system of the extruder, mixed and extruded for granulation to obtain the foamed master batch.

Table 2 The proportion of each component in the foamed masterbatch (parts by weight)

	C1	C2	C3
Polypropylene resin PP SP179	90
Polyethylene resin HDPE 5000S		99	50
azodicarbonamide	10
Benzenesulfonylhydrazide			25
sodium bicarbonate		50

Example 1-8 Comparative Example 1-2:

According to the ratio in Table 3, the reinforcing fiber masterbatch and the foamed masterbatch are blended to obtain a polyolefin material. The performance test results are shown in Table 4.

Table 3 The proportion of each component of the polyolefin material of the embodiment and the comparative example (parts by weight)

Table 4: Performance Test Results

It can be seen from Comparative Example 1 that only adding reinforced fiber masterbatch, the density of the material is high, and the wave transmission performance is poor. In Comparative Example 2, only hollow mullite microspheres were added to the reinforced fiber masterbatch. Although its density decreased and its wave-transmitting performance was significantly improved, its strength was poor. It can be seen from the examples that in the present invention, by adding reinforcing fibers and hollow microspheres to the reinforcing fiber masterbatch at the same time, the two synergistically synergize, and blending the prepared reinforcing fiber masterbatch and foaming masterbatch, not only can It can significantly reduce the density of the material, improve the wave transmission performance of the material, and at the same time improve the strength and heat resistance of the material, so that the material has the advantages of low density, good impact and high wave transmission.

Claims (10)

1. A polyolefin material is characterized in that, by weight, comprises the following components:

   Reinforcing fiber masterbatch 90-99.9 parts;

   Foaming masterbatch 0.1-10 copies;

   The reinforcing fiber masterbatch, in parts by weight, comprises the following components:

   

   Described foaming master batch, by weight, comprises the following components:

   10-99 parts of polyolefin resin;

   Foaming agent 0.1-50 parts.
2. The polyolefin material according to claim 1, characterized in that, in the reinforcing fiber masterbatch, hollow microspheres account for 0.5-50 parts.
3. The polyolefin material according to claim 1, wherein the compatibilizer is a graft polymer of a polar monomer and a polyolefin, wherein the polar monomer is selected from maleic anhydride, acrylic acid, and acrylates A mixture of one or more derivatives, the polyolefin is selected from one or a mixture of polypropylene and polyethylene.
4. The polyolefin material according to claim 1, wherein the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers, and basalt fibers, preferably glass fibers with an average diameter of 5-20 μm .
5. The polyolefin material according to claim 1, wherein the hollow microspheres are selected from one or more mixtures of hollow mullite microspheres and hollow glass microspheres; the particle size D50 thereof is 10-50 Micron, preferably 15-30 microns, density is 0.2-0.9g/cm ³ , preferably 0.3-0.5g/cm ³ , pressure is 5000PSI-50000PSI, preferably 10000-30000PSI.
6. The polyolefin material according to claim 1, wherein the mass ratio of the reinforcing fibers to the hollow microspheres is 1:5-5:1, preferably 1:2-2:1.
7. The polyolefin material according to claim 1, wherein the polyolefin resin is selected from one or a mixture of polypropylene, polyethylene and polybutene.
8. The polyolefin material according to claim 1, wherein the foaming agent is azodicarbonamide, azobisisobutyronitrile, azodiisoheptanenitrile, diisopropyl azodicarboxylate, Barium azodicarboxylate, diethyl azodicarboxylate, diethyl azodicarboxylate, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, dinitrosophthalamide Nitrosopentamethylenetetramine, benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, 4,4'-bisphenylsulfonylhydrazide, 3,3'-disulfonylhydrazide diphenylsulfone, 1,3- Benzenedisulfonyl hydrazide, p-toluenesulfonyl semicarbazide, 4,4'-oxobis(benzenesulfonyl semicarbazide), trihydrazinotriazine, 5-phenyltetrazole, calcium carbonate, magnesium carbonate or bicarbonate One or a mixture of sodium.
9. The preparation method of polyolefin material according to any one of claims 1-8, is characterized in that, comprises the steps:

   (1) According to the proportion, mix the polyolefin resin and compatibilizer, add it to the main feeding system of the extruder, and add the reinforcing fibers and hollow microspheres to the side feeding system at the same time. All components are mixed and extruded by the extruder. granules to obtain reinforced fiber masterbatch;

   (2) adding the polyolefin resin and the foaming agent to the main feeding system of the extruder according to the proportioning, mixing, extruding and granulating to obtain the foaming master batch;

   (3) Blending the reinforcing fiber masterbatch and the foaming masterbatch to obtain a polyolefin material.
10. Application of the polyolefin material according to any one of claims 1 to 8 in the fields of household appliances, automobiles or communications.