阅读说明：本技术 一种低摩擦聚苯乙烯复合材料及其制备方法 (Low-friction polystyrene composite material and preparation method thereof ) 是由 赵书敏 于 2021-01-13 设计创作，主要内容包括：本发明公开一种低摩擦聚苯乙烯复合材料及其制备方法；该低摩擦聚苯乙烯复合材料按质量份组分组成为：30-60份低摩擦聚苯乙烯嵌段共聚物,1.5-3份玻璃纤维,0.3-0.6份增韧剂,30-60份有机硅乳液,3-6份分散剂；本发明通过在聚苯乙烯分子链上嵌段具有低摩擦性能作用的聚合物,使聚苯乙烯材料具有耐磨性,且耐磨剂分子以共价键的形式与聚苯乙烯结合,不存在耐磨剂与聚合物相容性差和耐磨剂易流失的问题。(The invention discloses a low-friction polystyrene composite material and a preparation method thereof; the low-friction polystyrene composite material comprises the following components in parts by mass: 30-60 parts of low-friction polystyrene block copolymer, 1.5-3 parts of glass fiber, 0.3-0.6 part of toughening agent, 30-60 parts of organosilicon emulsion and 3-6 parts of dispersing agent; according to the invention, the polymer with low friction performance is blocked on the polystyrene molecular chain, so that the polystyrene material has wear resistance, and the wear-resistant agent molecules are combined with the polystyrene in a covalent bond manner, so that the problems of poor compatibility of the wear-resistant agent and the polymer and easy loss of the wear-resistant agent are solved.)

1. The low-friction polystyrene composite material is characterized by comprising the following components in parts by mass: 30-60 parts of low-friction polystyrene block copolymer, 1.5-3 parts of glass fiber, 0.3-0.6 part of toughening agent, 30-60 parts of organosilicon emulsion and 3-6 parts of dispersing agent; wherein the low-friction polystyrene block copolymer has a structure represented by formula (I):

in the formula, the value of n is 50-100, and the value of m is 5-10.

2. The low friction polystyrene composite material as claimed in claim 1, wherein the preparation method of the low friction polystyrene block copolymer comprises the following steps:

(1) with tetrahydroFuran as solvent, RAFT reagent (i.e. reverse addition-fragmentation chain transfer reagent) 4-cyano-4- (thiobenzoyl) pentanoic acid and SOCl₂Performing acyl chlorination reaction to obtain 4-cyano-4- (thiobenzoyl) valeryl chloride, and performing esterification reaction on hydroxyl polystyrene at one end and 4-cyano-4- (thiobenzoyl) valeryl chloride by using toluene as a solvent and pyridine as an acid-binding agent to obtain a polystyrene macromolecule transfer agent;

(2) reacting for 2-8 hours at 70-80 ℃ under the conditions of no water, no oxygen and nitrogen protection by using dioxane as a solvent, a wear-resisting agent as a monomer, a polystyrene macromolecular chain transfer agent as a chain transfer agent and azodiisobutyronitrile as an initiator to obtain the low-friction polystyrene block copolymer.

3. The low friction polystyrene composite of claim 2, wherein the low friction polystyrene block copolymer is prepared by reacting 4-cyano-4- (thiobenzoyl) pentanoic acid with SOCl in step (1)₂The molar ratio of the single-end hydroxyl polystyrene is 1:1: 5.

4. The low-friction polystyrene composite material as claimed in claim 2, wherein in the step (2), the anti-wear agent has the following structure:

5. the low-friction polystyrene composite material as claimed in claim 2, wherein in the step (2), the molar ratio of the polystyrene macromolecular chain transfer agent, the azobisisobutyronitrile and the wear-resisting agent is 1:10: 1000.

6. The low-friction polystyrene composite material as claimed in claim 2, wherein in the step (2), the concentration of the anti-wear agent is 1 mol/L.

7. The low friction polystyrene composite of claim 1, wherein said toughening agent is an acrylonitrile-butadiene-styrene copolymer.

8. The low friction polystyrene composite of claim 1, wherein the silicone oil content of the silicone emulsion is 10-15%.

9. The low friction polystyrene composite of claim 1, wherein said dispersant is a sodium salt of a polycarboxylic acid.

10. The method for preparing a low friction polystyrene composite material according to claim 1, comprising the steps of:

30-60 parts by mass of low-friction polystyrene block copolymer and 1.5-3 parts by mass of toughening agent are crushed until the particle size is 200-300 meshes, then the materials are uniformly mixed and sent into a double-screw extruder, the rotation number of a screw is controlled to be 300r/min, then 0.3-0.6 part by mass of glass fiber, 30-60 parts by weight of organosilicon emulsion and 3-6 parts by mass of dispersing agent are fed into the extruder in a lateral feeding manner, and the wear-resistant polystyrene composite material is obtained by extrusion in the extruder.

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a low-friction polystyrene composite material and a preparation method thereof.

Background

The styrene polymer can be classified into atactic polystyrene, isotactic polystyrene and syndiotactic polystyrene (sPS for short), wherein the atactic polystyrene is a general-purpose plastic but has poor heat resistance and chemical resistance. Syndiotactic polystyrene is a new type of polystyrene, different from atactic polystyrene, and has high melting point, excellent heat and chemical resistance, high crystallinity, controllable crystallization temperature in a wide range, and is suitable for conventional plastic processing and forming process.

To change the polystyrene material and its brittleness disadvantage, it is generally modified by adding some additives. However, the wear resistance of the polystyrene material is poor due to the addition of a large amount of substances for changing the brittleness of the polystyrene; based on the above, the invention provides a low-friction polystyrene composite material and a preparation method thereof.

Disclosure of Invention

In order to solve the defects of the prior art, the invention provides a low-friction polystyrene composite material and a preparation method thereof, wherein a polymer with a low-friction performance function is blocked on a polystyrene molecular chain, so that the polystyrene material has wear resistance, and wear-resistant agent molecules are combined with polystyrene in a covalent bond mode, so that the problems of poor compatibility of the wear-resistant agent and the polymer and easy loss of the wear-resistant agent are solved.

The invention aims to provide a low-friction polystyrene composite material.

The invention also aims to provide a preparation method of the low-friction polystyrene composite material.

The above purpose of the invention is realized by the following technical scheme:

the preparation method of the low-friction polystyrene composite material comprises the following steps:

30-60 parts by mass of low-friction polystyrene block copolymer and 1.5-3 parts by mass of toughening agent are crushed until the particle size is 200-300 meshes, then the materials are uniformly mixed and sent into a double-screw extruder, the rotation number of a screw is controlled to be 300r/min, then 0.3-0.6 part by mass of glass fiber, 30-60 parts by weight of organosilicon emulsion and 3-6 parts by mass of dispersing agent are fed into the extruder in a lateral feeding manner, and the wear-resistant polystyrene composite material is obtained by extrusion in the extruder.

The structural formula of the low-friction polystyrene block copolymer is shown as the following formula (I):

in the formula, the value of n is 50-100, and the value of m is 5-10.

The reaction process and the preparation method of the low-friction polystyrene block copolymer are as follows:

the preparation method of the low-friction polystyrene block copolymer comprises the following steps:

(1) and (3) preparing a polystyrene macromolecular chain transfer agent.

Using tetrahydrofuran as solvent, RAFT reagent (i.e. reverse addition-fragmentation chain transfer reagent) 4-cyano-4- (thiobenzoyl) valeric acid and SOCl₂Performing acyl chlorination reaction to obtain 4-cyano-4- (thiobenzoyl) valeryl chloride, and performing esterification reaction on hydroxyl polystyrene at one end and 4-cyano-4- (thiobenzoyl) valeryl chloride by using toluene as a solvent and pyridine as an acid-binding agent to obtain the polystyrene macromolecule transfer agent.

Wherein the 4-cyano-4- (thiobenzoyl) pentanoic acid is reacted with SOCl₂The molar ratio of the single-end hydroxyl polystyrene is 1:1: 5.

(2) Preparation of low-friction polystyrene block copolymer.

Reacting for 2-8 hours at 70-80 ℃ under the conditions of no water, no oxygen and nitrogen protection by using dioxane as a solvent, a wear-resisting agent as a monomer, a polystyrene macromolecular chain transfer agent as a chain transfer agent and azodiisobutyronitrile as an initiator to obtain the low-friction polystyrene block copolymer.

Wherein the anti-wear agent has the following structure:

wherein the molar ratio of the polystyrene macromolecular chain transfer agent, the azobisisobutyronitrile and the wear-resisting agent is 1:10: 1000.

Wherein the concentration of the anti-wear agent is 1 mol/L.

Wherein the toughening agent is acrylonitrile-butadiene-styrene copolymer.

Wherein the silicone oil content of the silicone emulsion is 10-15%.

Wherein the dispersant is a sodium polycarboxylate salt.

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

(1) the invention provides a low-friction polystyrene composite material, which leads polystyrene molecules to have the performance of a wear-resistant agent by blocking the wear-resistant agent on a polystyrene molecular chain.

(2) The invention provides a low-friction polystyrene composite material, wherein molecules of a wear-resistant agent and covalent bonds are combined with polystyrene, so that the problems of poor compatibility of the wear-resistant agent and a polymer and easy loss of the wear-resistant agent are solved by adding the wear-resistant agent into a polystyrene base material by a physical mixing method.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of a low friction polystyrene block copolymer.

FIG. 2 is an infrared spectrum of a low friction polystyrene block copolymer.

Detailed Description

The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Example 1

Adding 4-cyano-4- (thiobenzoyl) valeric acid (5.0mmol) into a 50ml bottle with stirrer, adding 20ml anhydrous tetrahydrofuran THF with syringe, and slowly adding thionyl chloride SOCl dropwise under stirring₂(50.0mmol), the oil bath temperature was raised to 75 ℃ and refluxed for 2.5h, after the reaction was complete, SOCl was removed by distillation under reduced pressure₂And THF to give a yellow oily product, which was dissolved in an appropriate amount of toluene solution.

Single-terminal hydroxypolystyrene (0.8mmol) was charged into a 100mL jar equipped with a stirrer, and after purging nitrogen three times, the mixture was stirred under N₂Adding 30ml of anhydrous toluene in the atmosphere, continuously stirring, slowly heating the oil bath to 70 ℃, adding 1.5ml of pyridine after the polymer is completely dissolved, slowly dropwise adding the yellow oily product dissolved in the toluene solution after 40min, reacting for 3h at 80 ℃, cooling the product to room temperature, continuously dissolving/precipitating with toluene/methanol twice, and drying at 50 ℃ in vacuum to constant weight to obtain the polystyrene macromolecular transfer agent, wherein the yield is 68.5%.

Example 2

The polystyrene macromolecular chain transfer agent (0.1mmol), the wear-resistant agent (10mmol), the AIBN (0.01mmol) and 5mL of dioxane prepared in the example 1 are respectively added into a 10mL Schlenk bottle with a stirrer, the oil bath temperature is set to 75 ℃, after three liquid nitrogen freezing-air extraction-unfreezing cycles, the Schlenk bottle is placed in an oil bath reaction kettle for polymerization reaction, the Schlenk bottle is immediately taken out after the reaction is carried out for 3h and is placed in liquid nitrogen for cooling, a crude product is repeatedly precipitated in anhydrous ether, and precipitates are filtered and dried in vacuum to obtain the low-friction polystyrene block copolymer with the yield of 70.9%.

Example 3

60 parts by mass of low-friction polystyrene block copolymer and 2.5 parts by mass of toughening agent are crushed until the particle size is 200-300 meshes, then the materials are uniformly mixed and sent into a double-screw extruder, the rotation number of a screw is controlled at 300r/min, then 0.5 part by mass of glass fiber, 32 parts by weight of organosilicon emulsion and 5 parts by mass of dispersing agent are fed into the extruder in a lateral feeding manner, and the wear-resistant polystyrene composite material is obtained by extrusion in the extruder.

Example 4

50 parts by mass of low-friction polystyrene block copolymer and 2.5 parts by mass of toughening agent are crushed until the particle size is 200-300 meshes, then the materials are uniformly mixed and sent into a double-screw extruder, the rotation number of a screw is controlled at 300r/min, then 0.5 part by mass of glass fiber, 42 parts by weight of organic silicon emulsion and 5 parts by mass of dispersing agent are fed into the extruder in a lateral feeding manner, and the wear-resistant polystyrene composite material is obtained by extrusion in the extruder.

Example 5

40 parts by mass of low-friction polystyrene block copolymer and 2.5 parts by mass of toughening agent are crushed until the particle size is 200-300 meshes, then the materials are uniformly mixed and sent into a double-screw extruder, the rotation number of a screw is controlled at 300r/min, then 0.5 part by mass of glass fiber, 52 parts by weight of organic silicon emulsion and 5 parts by mass of dispersing agent are fed into the extruder in a lateral feeding manner, and the wear-resistant polystyrene composite material is obtained by extrusion in the extruder.

Comparative example 1

The preparation method comprises the steps of crushing 60 parts by mass of polystyrene and 2.5 parts by mass of a toughening agent until the particle size is 200-300 meshes, uniformly mixing, feeding into a double-screw extruder, controlling the rotation number of a screw to be 300r/min, feeding 0.5 part by mass of glass fiber, 32 parts by weight of organosilicon emulsion and 5 parts by mass of a dispersing agent into the extruder in a lateral feeding manner, and extruding in the extruder to obtain the polystyrene composite material.

Comparative example 2

50 parts by mass of polystyrene and 2.5 parts by mass of a toughening agent are crushed until the particle size is 200-300 meshes, then the materials are uniformly mixed and sent into a double-screw extruder, the rotation number of a screw is controlled at 300r/min, then 0.5 part by mass of glass fiber, 42 parts by weight of organosilicon emulsion and 5 parts by mass of a dispersing agent are fed into the extruder in a lateral feeding manner, and the polystyrene composite material is obtained by extrusion in the extruder.

Comparative example 3

40 parts by mass of polystyrene and 2.5 parts by mass of a toughening agent are crushed until the particle size is 200-300 meshes, then the materials are uniformly mixed and sent into a double-screw extruder, the rotation number of a screw is controlled at 300r/min, then 0.5 part by mass of glass fiber, 52 parts by weight of organosilicon emulsion and 5 parts by mass of a dispersing agent are fed into the extruder in a lateral feeding manner, and the polystyrene composite material is obtained by extrusion in the extruder.

And (3) testing the wear resistance: injection moulding a sample with dimensions of 150 × 100 × 3.2mm, according to test method SAEJ 948: 2003, test conditions: grinding the wheel: CS-10, load: the abrasion and surface whitening of the material after the test were identified at 500 g/wheel for a total of 250 revolutions.

Tensile strength was determined according to standard HG/T2580-.

The bending strength was determined according to the standard GB/T12585-2001.

The impact strength of the beam was tested according to ISO179 standard, with a specimen size of 80X 6X 4mm and a notch depth of one third of the specimen thickness.

Table 1 shows the wear resistance of the low friction polystyrene composite.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.