阅读说明：本技术 一种基于互穿网络结构的改性塑料及其制备方法 (Modified plastic based on interpenetrating network structure and preparation method thereof ) 是由 原亮 周乐宁 于 2021-02-04 设计创作，主要内容包括：本发明公开了一种基于互穿网络结构的改性塑料,所述改性塑料由以下重量份数的原料组成：50～80份聚苯乙烯、20～30份六氟双酚A二丙烯酸酯、1～10份偶氮引发剂、40～60份多元醇、5～10份脂肪族异氰酸酯、20～40份羟基丙烯酸酯、0.5～5.5份催化剂、1.2～3.6份无机填料、1.5～5.5份添加剂和0.1～1份紫外线吸收剂。本发明的基于互穿网络结构的改性塑料,不仅具有优异的力学性能,而且提高了聚苯乙烯塑料的耐低温、抗静电、阻燃、耐老化和疏水性等性能,可满足不同严苛条件下的材料使用要求。本发明还公开了一种基于互穿网络结构的改性塑料的制备方法。(The invention discloses a modified plastic based on an interpenetrating network structure, which is prepared from the following raw materials in parts by weight: 50-80 parts of polystyrene, 20-30 parts of hexafluorobisphenol A diacrylate, 1-10 parts of azo initiator, 40-60 parts of polyol, 5-10 parts of aliphatic isocyanate, 20-40 parts of hydroxyl acrylate, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorber. The modified plastic based on the interpenetrating network structure has excellent mechanical properties, improves the low temperature resistance, antistatic property, flame retardance, aging resistance, hydrophobicity and other properties of polystyrene plastic, and can meet the material use requirements under different severe conditions. The invention also discloses a preparation method of the modified plastic based on the interpenetrating network structure.)

1. The modified plastic based on the interpenetrating network structure is characterized by comprising the following raw materials in parts by weight: 50-80 parts of polystyrene, 20-30 parts of hexafluorobisphenol A diacrylate, 1-10 parts of azo initiator, 40-60 parts of polyol, 5-10 parts of aliphatic isocyanate, 20-40 parts of hydroxyl acrylate, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorber.

2. The modified plastic based on interpenetrating network structure of claim 1, wherein the aliphatic isocyanate is hexamethylene diisocyanate and/or isophorone diisocyanate.

3. The modified plastic based on interpenetrating network structure of claim 1, wherein the azo initiator is at least one of azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, and azobisisobutyronitrile formamide.

4. The modified plastic based on interpenetrating network structure of claim 1, wherein the polyol is a combination of ethylene glycol and polyhydroxy cage silsesquioxane.

5. The modified plastic based on interpenetrating network structure of claim 1, wherein the hydroxy acrylate is at least one of 6-hydroxyhexyl acrylate, 2, 3-dihydroxypropyl acrylate, and 2-hydroxybutyl acrylate.

6. The modified plastic based on interpenetrating network structure of claim 1, wherein the catalyst is at least one of zinc iso-octoate, dibutyltin dilaurate, tetrabutylammonium bromide.

7. The modified plastic based on interpenetrating network structure of claim 1, wherein the inorganic filler is at least one of nano calcium carbonate, nano zinc oxide, nano cerium dioxide and nano titanium dioxide.

8. The modified plastic based on the interpenetrating network structure of claim 1, wherein the additive is modified graphene, and the modification method of the modified graphene is as follows: weighing 20-30 parts by weight of quaternary phosphonium salt compound, adding the quaternary phosphonium salt compound into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate for carrying out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: 1-3, weighing 20-50 mg of ionic liquid and carboxyl graphene in total, dissolving the ionic liquid and the carboxyl graphene in 30-50 ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 3-8 h, and removing impurities to obtain the modified graphene.

9. The modified plastic based on interpenetrating network structure of claim 8, wherein the quaternary phosphonium salt compound is at least one of tetrakis (hydroxymethyl) phosphonium bromide, tetrakis (hydroxymethyl) phosphonium iodide, tris (hydroxymethyl) phosphonium chloride.

10. The preparation method of the modified plastic based on the interpenetrating network structure according to any one of claims 1 to 9, wherein the preparation method comprises the following steps:

s1: weighing 50-80 parts by weight of polystyrene, 20-30 parts by weight of hexafluorobisphenol A diacrylate and 1-10 parts by weight of azo initiator, uniformly stirring and mixing by magnetic force, maintaining the temperature at 50-100 ℃, reacting for 0.5-3.5 h, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;

s2: weighing 70-110 parts of the polystyrene polymer modified in the step S1, adding 20-40 parts of hydroxyl acrylate, swelling for 0.5-2.5 h, adding 5-10 parts of aliphatic isocyanate, and continuing to swell for 0.5-2.5 h to obtain a uniformly dissolved mixed solution;

s3: and (3) adding 40-60 parts of polyol, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorbent into the mixed solution swelled in the step S2, uniformly mixing by magnetic stirring, maintaining the temperature at 30-70 ℃, and reacting for 3-8 hours to obtain the modified plastic based on the interpenetrating network structure.

Technical Field

The invention relates to the technical field of modified plastics, in particular to a modified plastic based on an interpenetrating network structure and a preparation method thereof.

Background

The plastic is a high molecular compound polymerized by addition polymerization or polycondensation reaction using monomer as raw material, and is composed of synthetic resin, filler, plasticizer, stabilizer, lubricant, pigment and other additives. With the continuous development of industry, plastics are widely applied to various industries such as electronics, electrics, automobiles, buildings, household appliances, office equipment, electric power, transportation and the like.

Different plastics such as polyethylene, polypropylene, polyamide, polyformaldehyde, polycarbonate, ABS and the like exist, each plastic has the advantages and disadvantages in performance, the different performances of the plastic determine the application of the plastic in life and industry, and with the progress of technology, researches on the modification of the plastic, including antistatic performance, heat conduction performance, low temperature resistance, hydrophobicity and the like, have not been stopped. The existing heat-conducting and antistatic materials are mostly made of metal or metal-containing materials, and have the defects of poor compatibility with plastic materials, uneven dispersion, easy oxidation corrosion, short service life, high manufacturing cost, complex preparation process and the like; the plastic added with non-metallic materials such as graphite has the problems of low-temperature brittle deformation, reduced impact toughness and thermal stability and the like at low temperature, and the produced product is easy to break in winter storage and transportation, and particularly has a series of problems of glue shortage, gas decomposition mark, workpiece embrittlement and the like when a large workpiece or a thin-wall workpiece is molded.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide the modified plastic based on the interpenetrating network structure so as to solve the comprehensive problem of poor performances of low temperature resistance, impact resistance, static resistance, heat conduction, hydrophobicity and the like of the conventional plastic.

In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:

the modified plastic based on the interpenetrating network structure is prepared from the following raw materials in parts by weight: 50-80 parts of polystyrene, 20-30 parts of hexafluorobisphenol A diacrylate, 1-10 parts of azo initiator, 40-60 parts of polyol, 5-10 parts of aliphatic isocyanate, 20-40 parts of hydroxyl acrylate, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorber.

Preferably, the aliphatic isocyanate is hexamethylene diisocyanate and/or isophorone diisocyanate.

Preferably, the azo initiator is at least one of azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride and azobisisobutyronitrile formamide.

Preferably, the polyol is a combination of ethylene glycol and a polyhydroxy cage silsesquioxane.

Preferably, the hydroxy acrylate is at least one of 6-hydroxyhexyl acrylate, 2, 3-dihydroxypropyl acrylate and 2-hydroxybutyl acrylate.

Preferably, the catalyst is at least one of zinc isooctanoate, dibutyltin dilaurate and tetrabutylammonium bromide.

Preferably, the inorganic filler is at least one of nano calcium carbonate, nano zinc oxide, nano cerium dioxide and nano titanium dioxide.

Preferably, the additive is modified graphene, and the modification method of the modified graphene comprises the following steps: weighing 20-30 parts by weight of quaternary phosphonium salt compound, adding the quaternary phosphonium salt compound into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate for carrying out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: 1-3, weighing 20-50 mg of ionic liquid and carboxyl graphene in total, dissolving the ionic liquid and the carboxyl graphene in 30-50 ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 3-8 h, and removing impurities to obtain the modified graphene. The graphene modified by the ionic liquid has excellent performances of the ionic liquid and the graphene. The ionic liquid has good compatibility with organic and inorganic components in the plastic, improves the dispersion performance of the graphene, prevents the graphene from agglomerating, and further enhances the antistatic, heat-resistant and flame-retardant performances of the modified plastic.

Preferably, the quaternary phosphonium salt compound is at least one of tetrakis (hydroxymethyl) phosphonium bromide, tetrakis (hydroxymethyl) phosphonium iodide, and tris (hydroxymethyl) phosphonium chloride.

Another aspect of the present invention is to provide a method for preparing the modified plastic based on the interpenetrating network structure, the method comprising the following steps:

s1: weighing 50-80 parts by weight of polystyrene, 20-30 parts by weight of hexafluorobisphenol A diacrylate and 1-10 parts by weight of azo initiator, uniformly stirring and mixing by magnetic force, maintaining the temperature at 50-100 ℃, reacting for 0.5-3.5 h, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;

s2: weighing 70-110 parts of the polystyrene polymer modified in the step S1, adding 20-40 parts of hydroxyl acrylate, swelling for 0.5-2.5 h, adding 5-10 parts of aliphatic isocyanate, and continuing to swell for 0.5-2.5 h to obtain a uniformly dissolved mixed solution;

s3: and (3) adding 40-60 parts of polyol, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorbent into the mixed solution swelled in the step S2, uniformly mixing by magnetic stirring, maintaining the temperature at 30-70 ℃, and reacting for 3-8 hours to obtain the modified plastic based on the interpenetrating network structure.

The invention has the beneficial effects that:

the invention relates to a modified plastic based on interpenetrating network structure and a preparation method thereof, wherein polystyrene is used as a main plastic component, hexafluorobisphenol A diacrylate is modified firstly, then aliphatic isocyanate and hydroxy acrylate are swelled in sequence to enable the aliphatic isocyanate and the hydroxy acrylate to permeate into the network structure of a modified polystyrene polymer, polyol and catalyst are added, the aliphatic isocyanate, the hydroxy acrylate and the polyol are subjected to cross-linking reaction to form the modified plastic with the interpenetrating network structure, and meanwhile, inorganic filler, additive and ultraviolet absorbent are added as auxiliary additives, so that the modified plastic not only has the advantages of modified polystyrene and rubber, but also improves the mechanical property and the processing property of the polystyrene plastic, and further improves the antistatic property, the flame retardance, the UV absorption property and the processing property of the modified plastic, Aging resistance, hydrophobicity and the like.

The modified plastic based on the interpenetrating network structure can meet the use requirements of long-term severe conditions in important fields of automobile industry, consumer goods, electronic and electric appliances, building industry and the like.

The preparation method of the modified plastic based on the interpenetrating network structure has the advantages of low production cost, flexibility and controllability, and can realize large-scale production.

Detailed Description

The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.

Example 1

The modified plastic based on the interpenetrating network structure of the embodiment is composed of the following raw materials in parts by weight: 50 parts of polystyrene, 20 parts of hexafluorobisphenol A diacrylate, 1 part of azobisisobutyramidine hydrochloride, 40 parts of polyol, 5 parts of hexamethylene diisocyanate, 20 parts of 6-hydroxyhexyl acrylate, 0.5 part of dibutyltin dilaurate, 1.2 parts of nano calcium carbonate, 1.5 parts of an additive and 0.1 part of an ultraviolet absorber.

The polyhydric alcohol is a composition of ethylene glycol and polyhydroxy cage type silsesquioxane, and the mass ratio of the ethylene glycol to the polyhydroxy cage type silsesquioxane is 3: 1.

the additive is modified graphene, and the modification method of the modified graphene comprises the following steps: weighing 20 parts by weight of tetrakis (hydroxymethyl) phosphonium bromide, adding the weighed tetrakis (hydroxymethyl) phosphonium bromide into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate for carrying out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: 1, weighing 20mg of ionic liquid and carboxyl graphene in total, dissolving the ionic liquid and the carboxyl graphene in 30ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 5 hours, and removing impurities to obtain the modified graphene.

The preparation method of the modified plastic based on the interpenetrating network structure comprises the following steps:

s1: weighing 50 parts of polystyrene, 20 parts of hexafluorobisphenol A diacrylate and 1 part of azodiisobutyl amidine hydrochloride by weight parts, uniformly mixing by magnetic stirring, maintaining the temperature at 60 ℃, reacting for 1 hour, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;

s2: weighing 70 parts of the polystyrene polymer modified in the step S1, adding 20 parts of 6-hydroxyhexyl acrylate, swelling for 1 hour, adding 5 parts of hexamethylene diisocyanate, and continuing to swell for 2 hours to obtain a uniformly dissolved mixed solution;

s3: and (4) adding 40 parts of polyol, 0.5 part of dibutyltin dilaurate, 1.2 parts of nano calcium carbonate, 1.5 parts of additive and 0.1 part of ultraviolet absorbent into the mixed solution swelled in the step S2, uniformly stirring and mixing by magnetic force, maintaining the temperature at 30 ℃, and reacting for 8 hours to obtain the modified plastic based on the interpenetrating network structure.

Example 2

The modified plastic based on the interpenetrating network structure of the embodiment is composed of the following raw materials in parts by weight: 65 parts of polystyrene, 25 parts of hexafluorobisphenol A diacrylate, 5 parts of azobisisobutyrimidazoline hydrochloride, 50 parts of polyol, 7 parts of hexamethylene diisocyanate, 30 parts of 2, 3-dihydroxypropyl acrylate, 3.5 parts of tetrabutylammonium bromide, 2.5 parts of nano cerium dioxide, 3 parts of an additive and 0.4 part of an ultraviolet absorber.

The polyhydric alcohol is a composition of ethylene glycol and polyhydroxy cage type silsesquioxane, and the mass ratio of the ethylene glycol to the polyhydroxy cage type silsesquioxane is 5: 1.

the additive is modified graphene, and the modification method of the modified graphene comprises the following steps: weighing 25 parts by weight of tetrakis (hydroxymethyl) phosphonium iodide into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate to carry out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: 2, weighing 30mg of ionic liquid and carboxyl graphene in total, dissolving the ionic liquid and the carboxyl graphene in 40ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 6 hours, and removing impurities to obtain the modified graphene.

The preparation method of the modified plastic based on the interpenetrating network structure comprises the following steps:

s1: weighing 65 parts of polystyrene, 25 parts of hexafluorobisphenol A diacrylate and 5 parts of azobisisobutyrimidazoline hydrochloride according to parts by weight, uniformly mixing by magnetic stirring, maintaining the temperature at 70 ℃, reacting for 2 hours, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;

s2: weighing 90 parts of the polystyrene polymer modified in the step S1, adding 30 parts of 2, 3-dihydroxypropyl acrylate, swelling for 1.5h, adding 7 parts of hexamethylene diisocyanate, and continuing to swell for 1.5h to obtain a uniformly dissolved mixed solution;

s3: and (3) adding 50 parts of polyol, 3.5 parts of tetrabutylammonium bromide, 2.5 parts of nano cerium dioxide, 3 parts of additive and 0.4 part of ultraviolet absorbent into the mixed solution swelled in the step S2, uniformly stirring and mixing by magnetic force, maintaining the temperature at 50 ℃, and reacting for 6 hours to obtain the modified plastic based on the interpenetrating network structure.

Example 3

The modified plastic based on the interpenetrating network structure of the embodiment is composed of the following raw materials in parts by weight: 80 parts of polystyrene, 30 parts of hexafluorobisphenol A diacrylate, 10 parts of azoisobutyryl cyanoformamide, 60 parts of polyol, 10 parts of isophorone diisocyanate, 40 parts of 2-hydroxybutyl acrylate, 5.5 parts of dibutyltin dilaurate, 3.6 parts of nano titanium dioxide, 5.5 parts of an additive and 1 part of an ultraviolet absorber.

The polyhydric alcohol is a composition of ethylene glycol and polyhydroxy cage type silsesquioxane, and the mass ratio of the ethylene glycol to the polyhydroxy cage type silsesquioxane is 7: 1.

the additive is modified graphene, and the modification method of the modified graphene comprises the following steps: weighing 30 parts by weight of tris (hydroxymethyl) phosphonium chloride, adding the tris (hydroxymethyl) phosphonium chloride into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate for carrying out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: and 3, weighing 50mg of ionic liquid and carboxyl graphene, dissolving the ionic liquid and the carboxyl graphene in 50ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 8 hours, and removing impurities to obtain the modified graphene.

The preparation method of the modified plastic based on the interpenetrating network structure comprises the following steps:

s1: weighing 80 parts by weight of polystyrene, 30 parts by weight of hexafluorobisphenol A diacrylate and 10 parts by weight of azo initiator, uniformly mixing by magnetic stirring, maintaining the temperature at 100 ℃, reacting for 3.5 hours, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;

s2: weighing 110 parts of the polystyrene polymer modified in the step S1, adding 40 parts of 2-hydroxybutyl acrylate, swelling for 2.5h, adding 10 parts of isophorone diisocyanate, and continuing to swell for 2.5h to obtain a uniformly dissolved mixed solution;

s3: and (4) adding 60 parts of polyol, 5.5 parts of dibutyltin dilaurate, 3.6 parts of nano titanium dioxide, 5.5 parts of additive and 1 part of ultraviolet absorbent into the mixed solution swelled in the step S2, magnetically stirring and uniformly mixing, maintaining the temperature at 70 ℃, and reacting for 4 hours to obtain the modified plastic based on the interpenetrating network structure.

Comparative example 1

The raw material composition and the preparation method of the modified plastic based on the interpenetrating network structure of the comparative example are substantially the same as those of example 3, except that the modified graphene additive is not added to the composite material of the comparative example.

Comparative example 2

The raw material composition and the preparation method of the modified plastic based on the interpenetrating network structure of the comparative example are substantially the same as those of example 3, except that the polyhydroxy cage-type silsesquioxane is not added to the composite material of the comparative example.

Comparative example 3

The raw material composition and the preparation method of the modified plastic based on the interpenetrating network structure of the comparative example were substantially the same as those of example 3, except that hexafluorobisphenol a diacrylate was not added to the composite material of the comparative example.

Comparative example 4

The preparation method of the modified plastic based on the interpenetrating network structure of the present comparative example does not undergo the swelling treatment of step S2, and specifically, the preparation method comprises the following steps:

s1: weighing 80 parts by weight of polystyrene, 30 parts by weight of hexafluorobisphenol A diacrylate and 10 parts by weight of azo initiator, uniformly mixing by magnetic stirring, maintaining the temperature at 100 ℃, reacting for 3.5 hours, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;

s2: adding 40 parts of 2-hydroxybutyl acrylate, 10 parts of isophorone diisocyanate, 60 parts of polyol, 5.5 parts of dibutyltin dilaurate, 3.6 parts of nano titanium dioxide, 5.5 parts of additive and 1 part of ultraviolet absorbent, magnetically stirring and uniformly mixing, maintaining the temperature at 70 ℃, and reacting for 4 hours to obtain the modified plastic based on the interpenetrating network structure.

The modified plastics based on the interpenetrating network structure prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to performance tests, and the performance results are shown in table 1:

wherein: and (3) tensile test: the mechanical properties (tensile strength, elongation at break) of the material were tested using a tensile machine.

Notched impact strength: testing was performed as specified in ASTM.

And (3) testing heat resistance, namely performing continuous 168h testing in an accelerated aging box at 150 ℃, and judging the heat resistance of the composite material through the change rate of tensile strength.

And (4) testing the antistatic performance by testing the volume resistivity of the composite material.

Limiting oxygen index test: the volume fraction of oxygen in the oxygen and nitrogen mixture that the test polymer had just supported the polymerization combustion was called the limiting oxygen index (%).

Combustion experiments: the material was burned in air and the burning of the material was recorded and observed (whether there was a drop, whether there was smoke, whether it could be self-extinguished).

TABLE 1

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.