CN108219270B - Antistatic PP modified material and preparation method thereof - Google Patents

Antistatic PP modified material and preparation method thereof Download PDF

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CN108219270B
CN108219270B CN201711274877.XA CN201711274877A CN108219270B CN 108219270 B CN108219270 B CN 108219270B CN 201711274877 A CN201711274877 A CN 201711274877A CN 108219270 B CN108219270 B CN 108219270B
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antistatic
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CN108219270A (en
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叶根林
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Starway International Home Living Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

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Abstract

The invention belongs to the technical field of modification and processing of high polymer materials, and relates to an antistatic PP (polypropylene) modified material and a preparation method thereof. The antistatic PP modified material comprises a polypropylene material and an auxiliary agent, wherein the auxiliary agent comprises an antistatic agent, medium alkali glass fiber, an antioxidant and a halogen absorbent, the polypropylene material and the auxiliary agent are blended to prepare the antistatic PP modified material, the antistatic agent used in the antistatic PP modified material has a good antistatic effect, and the two antistatic agents can generate a synergistic effect when used simultaneously, so that the antistatic PP modified material has better antistatic capability compared with the prior art, and the preparation method disclosed by the invention is simple in process flow, convenient to operate, high in production efficiency and easy to apply to large-scale industrial production.

Description

Antistatic PP modified material and preparation method thereof
Technical Field
The invention belongs to the technical field of modification and processing of high polymer materials, and relates to an antistatic PP (polypropylene) modified material and a preparation method thereof.
Background
Polypropylene is a thermoplastic resin, abbreviated as PP, produced by the polymerization of propylene. The polypropylene is a thermoplastic plastic, has light specific gravity, large surface hardness of finished products and high elasticity, has good heat resistance, can be used for sterilizing and disinfecting products at the temperature of over 100 ℃, does not deform at 150 ℃ under the condition of no external force, has good chemical stability, can be corroded by concentrated sulfuric acid and concentrated nitric acid, is more stable to other chemical reagents, is suitable for manufacturing various chemical pipelines and accessories, has good corrosion resistance effect and higher dielectric coefficient, can be used for manufacturing heated electrical appliance insulating products along with the rise of temperature, has good voltage resistance and arc resistance, has high breakdown voltage, and is suitable for being used as electrical appliance accessories and the like. Therefore, polypropylene is widely applied to the fields of automobile parts, household appliances and the like, but the antistatic effect of polypropylene is not ideal.
People also explore and research the problem in long-term production and living practices, for example, the Chinese patent application discloses an antistatic PP modified material and a preparation method thereof [ application number: 201510862583.3], the invention application provides an antistatic PP modified material, which comprises the following raw materials in parts by weight: 60-95 parts of PP resin, 5-15 parts of antistatic agent, 5-15 parts of POE resin, 0.05-0.15 part of PETS, 0.1-0.3 part of diffusion oil, 1-1.5 parts of zinc stearate and 0.2-1.5 parts of antioxidant; wherein the antistatic agent is prepared from carbon black with the particle size of 10-50nm and carbon fiber with the monofilament diameter of 50-100nm according to the weight ratio of 1.4-2.2: 1, in a mixture of the components.
The antistatic PP modified material provided by the invention is not ideal enough in antistatic effect and poor in strength, and the application range of the material is limited.
Disclosure of Invention
The invention aims to solve the problems and provide an antistatic PP modified material, and the invention also aims to provide a preparation method of the antistatic PP modified material. In order to achieve the purpose, the invention adopts the following technical scheme:
the antistatic PP modified material comprises a polypropylene material and an auxiliary agent, wherein the auxiliary agent comprises an antistatic agent, medium-alkali glass fiber, an antioxidant and a halogen absorbent, and the polypropylene material and the auxiliary agent are blended to prepare the antistatic PP modified material.
In the antistatic PP modified material, the antistatic agent is a material with long-chain alkyl R1Quaternary ammonium salt and/or polyethylene glycol monomethyl ether butyrate of (1), wherein R1Is a straight chain alkyl group having 12 or more carbon atoms.
In the antistatic PP-modified material, the quaternary ammonium salt having a long chain alkyl group is prepared by the following steps:
the method comprises the following steps: a halogenated hydrocarbon R1Mixing the X with water, stirring, introducing trimethylamine into the mixed solution, observing the mixed solution, and stopping introducing the trimethylamine until an organic layer basically disappears;
step two: standing for layering, extracting the water layer with ethyl acetate for several times, and mixing the ethyl acetate extractive solutions;
step three: adding poor solvent of long-chain alkyl quaternary ammonium salt into ethyl acetate extract, stirring, filtering after solid is completely separated out, and drying to obtain long-chain alkyl quaternary ammonium salt.
In the antistatic PP modified material, the poor solvent is petroleum ether or diethyl ether with the distillation range of 30-60 ℃ and halogenated hydrocarbon R1X in X is Cl or Br.
In the antistatic PP modified material, the polyethylene glycol monomethyl ether butyrate is prepared by the following steps:
the method comprises the following steps: adding polyethylene glycol monomethyl ether and n-butyric acid into DMF, adding polymerization inhibitor, DMAP and DCC, heating to 50-70 ℃ under stirring, and reacting for 12-24 h;
step two: and (3) flushing the reaction solution into water, stirring for 0.5-1h, adjusting the pH value to 8-9, filtering, washing the obtained solid with water for multiple times, and drying to obtain the polyethylene glycol monomethyl ether butyrate.
In the antistatic PP modified material, the molecular weight of the polyethylene glycol monomethyl ether is 2000-10000.
In the antistatic PP modified material, the polypropylene material comprises 70-90 parts by mass of PP, and the auxiliary agent comprises 2-8 parts by mass of antistatic agent, 10-30 parts by mass of medium alkali glass fiber, 0.05-0.5 part by mass of antioxidant and 0.05-0.5 part by mass of halogen absorbent.
In the antistatic PP modified material, the polypropylene material comprises 80 parts by mass of PP, and the auxiliary agent comprises 5 parts by mass of antistatic agent, 20 parts by mass of medium alkali glass fiber, 0.3 part by mass of antioxidant and 0.2 part by mass of halogen absorbent.
The preparation method of the antistatic PP modified material comprises the following steps:
the method comprises the following steps: taking a certain weight of PP, placing the PP in a vacuum drying oven, and carrying out vacuum drying for 2-4h at the temperature of 70-80 ℃ to obtain dried PP;
step two: taking 70-90 parts of dried PP, 2-8 parts of antistatic agent, 10-30 parts of medium alkali glass fiber, 0.05-0.5 part of antioxidant and 0.05-0.5 part of halogen absorbent, adding into a mixer, mixing for 10-20min, transferring into a double-screw extruder, heating at the temperature of 230 plus materials for melting and mixing, extruding and granulating after 1-2h, wherein the extrusion temperature is 260 plus materials, the screw rotating speed is 250 plus materials for 350r/min, and granulating after cooling an extruded sample strip to obtain the antistatic PP modified material.
In the preparation method of the antistatic PP modified material, the cooling temperature of the extruded sample strip in the second step is 30-50 ℃.
Compared with the prior art, the invention has the advantages that:
1. the antistatic agent used in the invention has a good antistatic effect, and the two antistatic agents can generate a synergistic effect when used simultaneously, so that the antistatic PP modified material has better antistatic capability compared with the prior art.
2. The preparation method has the advantages of simple process flow, convenient operation and high production efficiency, and is easy to be applied to large-scale industrial production.
3. According to the invention, the conductive path is formed in the PP material by adding the medium alkali glass fiber, so that the strength of the PP material is improved, and the antistatic capability of the PP material is further improved.
4. The halogen absorbent is added in the invention, and can be used for neutralizing residual halogen in each component for preparing the high polymer material, preventing the halogen from corroding equipment in the processing process, and greatly prolonging the service life of the processing equipment.
5. According to the invention, the PP material is modified by adopting a method of internally mixing the PP material and the antistatic agent, so that the prepared antistatic PP modified material has a lasting antistatic effect.
Detailed Description
The reagents used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.
Example 1
The embodiment provides an antistatic PP modified material, and specifically, the antistatic PP modified material comprises 70 parts by mass of PP, 8 parts by mass of an antistatic agent, 10 parts by mass of medium alkali glass fiber, 0.5 part by mass of an antioxidant and 0.05 part by mass of a halogen absorbent.
The antistatic agent is long-chain alkyl quaternary ammonium salt with linear alkyl of more than 12 carbon atoms, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant is 0.3 part by mass of antioxidant 1010, the auxiliary antioxidant is 0.2 part by mass of antioxidant 168, and the halogen absorbent is calcium stearate.
The specific synthetic steps of the long-chain alkyl quaternary ammonium salt used as the antistatic agent are as follows, wherein R1For long-chain alkyl radicals on long-chain alkyl quaternary ammonium salts：
The method comprises the following steps: a halogenated hydrocarbon R1Mixing the X with water, stirring, introducing trimethylamine into the mixed solution, observing the mixed solution, and stopping introducing the trimethylamine until an organic layer basically disappears;
step two: standing for layering, extracting the water layer with ethyl acetate for several times, and mixing the ethyl acetate extractive solutions;
step three: adding poor solvent of long-chain alkyl quaternary ammonium salt into ethyl acetate extract, stirring, filtering after solid is completely separated out, and drying to obtain long-chain alkyl quaternary ammonium salt.
From the viewpoint of cost, the halogenated hydrocarbon R1The halogen in X is preferably Cl or Br, a halogenated hydrocarbon R1Mixing X with water, introducing trimethylamine under stirring, and attacking the halogenated hydrocarbon R with lone pair electrons on N atom in the trimethylamine1And C atoms of halogen are connected in the X, so that the halogen is removed to form long-chain alkyl quaternary ammonium salt, the formed long-chain alkyl quaternary ammonium salt is dissolved in water, so that the gradual disappearance of an organic layer in the mixed solution can be observed, the introduction of trimethylamine is stopped after the organic layer is basically disappeared, the mixed solution is kept stand and layered, a water layer is extracted for multiple times by using ethyl acetate, ethyl acetate extraction liquid is combined, the long-chain alkyl quaternary ammonium salt generated by the reaction is extracted into the ethyl acetate extraction liquid, and the long-chain alkyl quaternary ammonium salt can be gradually separated out after a poor solvent of the long-chain alkyl quaternary ammonium salt is added into the ethyl acetate extraction liquid, wherein the poor solvent of the long-chain alkyl quaternary ammonium salt can be petroleum ether or diethyl ether.
The glass fiber is an inorganic non-metallic material with excellent performance, has the advantages of good insulativity, strong heat resistance, good corrosion resistance, high mechanical strength and the like, but has the defects of brittleness and poor wear resistance. The novel hair-dyeing and-weaving process is characterized in that glass balls or waste glass is used as a raw material and is manufactured through processes of high-temperature melting, wire drawing, winding, weaving and the like, the diameter of each monofilament ranges from several micrometers to twenty micrometers, the diameter of each monofilament is equivalent to 1/20-1/5 of one hair, and each fiber strand consists of hundreds of monofilaments and even thousands of monofilaments.
Glass fibers are generally used as reinforcing materials in composite materials, and the reinforcing effect of the glass fibers on plastics is very obvious because the modulus of the glass fibers is very high, the glass fibers grow along the inside of a machine body, external force is diffused when external force is applied to the glass fibers and the whole material, and the impact resistance and the bending performance are improved.
Specifically, when the composite material is subjected to an external force, either a transverse force or a longitudinal force, or a tensile force or a compressive force, a stress is generated in the composite material. When the glass fiber is added into the composite material, the stress is well dispersed by virtue of the excellent interface bonding force between the matrix phase of the composite material and the glass fiber, so that the fiber with excellent performance bears most of the stress, thereby improving the comprehensive performance of the composite material. The existing experiment results can show that when the composite material is subjected to a force along the longitudinal direction of the glass fiber, stress is concentrated at two ends of the glass fiber, and an oval area with stress lower than the average stress exists around the glass fiber, so that the glass fiber achieves the reinforcing effect by reducing the average stress of the matrix phase of the composite material; when the composite material is subjected to a force along the transverse direction of the glass fibers, the matrix of the composite material deforms under the influence of an external force, the modulus of the matrix is smaller than that of the glass fibers, and the matrix and the glass fibers are combined tightly, so that the deformation of the matrix is restricted by the glass fibers and the load is transmitted to the glass fibers, the load is born by the matrix and the glass fibers together, and the mechanical property of the material is improved due to the fact that the rigidity and the strength of the glass fibers are far higher than those of the matrix.
The glass fiber can be divided into alkali-free glass fiber, medium-alkali glass fiber and high-alkali glass fiber according to the content of alkali metal oxide, the alkali-free glass fiber has better electrical insulation property due to lower content of the metal oxide, is not suitable for being added into the antistatic PP modified material, the national production of the high-alkali glass fiber is forbidden, and after the medium-alkali glass fiber is added into the antistatic PP modified material, a conductive path can be formed in the PP material, so that the antistatic capability of the PP material can be further improved while the strength of the PP material is improved.
Antioxidants are mainly classified into two major classes, one is a main antioxidant, and the other is a hindered phenol antioxidant which can continuously play an antioxidant role for a long time by capturing free radicals generated in the degradation process of plastics; one is an auxiliary antioxidant, mainly phosphite and thioester antioxidants, which achieves the purpose of antioxidation by decomposing peroxide generated by further degrading plastics and mainly provides thermal processing stability. The primary antioxidant and the secondary antioxidant can be used together to produce a synergistic effect.
The antioxidant 1010 is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (CAS: 6683-19-8), and can effectively prevent the polymer material from thermal oxidative degradation in the long-term use process.
The antioxidant 168 is tris [2, 4-di-tert-butylphenyl ] phosphite (CAS: 31570-04-4), which can effectively prevent the thermal degradation of the alloy material in the basic injection molding process and provide extra long-term protection for the polymer.
The calcium stearate is added into the PP material as a halogen absorbent, and the main function of the halogen absorbent is to neutralize residual halogen in each component for preparing the high polymer material and prevent the halogen from corroding equipment in the processing process. Calcium stearate has good long-term absorption of halogen ions, and reacts with the halogen ions to generate calcium halide and stearic acid, wherein the reaction equation is as follows:
Ca(C17H35COO)2+2H++2X-→CaX2+2C17H35COOH
example 2
The embodiment provides an antistatic PP modified material, and specifically, the antistatic PP modified material comprises 90 parts by mass of PP, 2 parts by mass of an antistatic agent, 30 parts by mass of medium alkali glass fiber, 0.05 part by mass of an antioxidant and 0.5 part by mass of a halogen absorbent.
The antistatic agent is long-chain alkyl quaternary ammonium salt with straight-chain alkyl of more than 12 carbon atoms, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant is 0.03 part by mass of antioxidant 1076, the auxiliary antioxidant is 0.02 part by mass of antioxidant 168, and the halogen absorbent is hydrated talcum powder.
The specific synthesis procedure of the long-chain alkyl quaternary ammonium salt as the antistatic agent is completely the same as that in example 1, and thus the detailed description is omitted.
The antioxidant 1076 is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS: 2082-79-3), and can effectively inhibit thermal degradation and oxidative degradation of the polymer.
The hydrated talcum powder is added into a PP material as a halogen absorbent, has obvious anion exchange characteristic, and carbonate ions in the hydrated talcum powder are easy to exchange with halogen ions, so that the halogen ions are adsorbed and fixed in a stable crystal structure, and the reaction equation is as follows:
Mg4.5Al2(OH)13CO3·3.5H2O+2H++2X-→Mg4.5Al2(OH)13X2·3.5H2O+H2O+CO2
example 3
The embodiment provides an antistatic PP modified material, and specifically, the antistatic PP modified material comprises 80 parts by mass of PP, 5 parts by mass of an antistatic agent, 20 parts by mass of medium alkali glass fiber, 0.3 part by mass of an antioxidant and 0.2 part by mass of a halogen absorbent.
The antistatic agent is long-chain alkyl quaternary ammonium salt with straight-chain alkyl of more than 12 carbon atoms, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant is 0.1 part by mass of antioxidant 1076 and 0.1 part by mass of antioxidant 1010, the auxiliary antioxidant is 0.1 part by mass of antioxidant 168, and the halogen absorbent is calcium stearate.
The specific synthesis procedure of the long-chain alkyl quaternary ammonium salt as the antistatic agent is completely the same as that in example 1, and thus the detailed description is omitted.
Example 4
The embodiment provides an antistatic PP modified material, and specifically, the antistatic PP modified material comprises 70 parts by mass of PP, 8 parts by mass of an antistatic agent, 10 parts by mass of medium alkali glass fiber, 0.5 part by mass of an antioxidant and 0.05 part by mass of a halogen absorbent.
The antistatic agent is polyethylene glycol monomethyl ether butyrate, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant is 0.3 part by mass of antioxidant 1010, the auxiliary antioxidant is 0.2 part by mass of antioxidant 168, and the halogen absorbent is calcium stearate.
The specific synthetic steps of the polyethylene glycol monomethyl ether butyrate serving as the antistatic agent are as follows:
the method comprises the following steps: adding polyethylene glycol monomethyl ether and n-butyric acid into DMF, adding polymerization inhibitor, DMAP and DCC, heating to 50-70 ℃ under stirring, and reacting for 12-24 h;
step two: and (3) flushing the reaction solution into water, stirring for 0.5-1h, adjusting the pH value to 8-9, filtering, washing the obtained solid with water for multiple times, and drying to obtain the polyethylene glycol monomethyl ether butyrate.
One of the raw materials for preparing the methoxypolyethylene glycol butyrate is methoxypolyethylene glycol, wherein the polymerization degree of polyethylene glycol has great influence on the antistatic effect of the methoxypolyethylene glycol butyrate, the physical state and the physical parameters of the methoxypolyethylene glycol, so the antistatic effect of the prepared product and the operation convenience degree in the preparation process are comprehensively considered, the methoxypolyethylene glycol with the molecular weight of 2000-10000 is selected as a reaction raw material, the methoxypolyethylene glycol and n-butyric acid are added into a solvent DMF, a polymerization inhibitor, a catalyst DMAP and a dehydrating agent DCC are added, the mixture is stirred and uniformly mixed, the mixture is heated to 50-70 ℃ for reaction for 12-24h, after the reaction is finished, a reaction solution is flushed into water, a large amount of solid can be observed to be separated out, the mixture is stirred for 0.5-1h, the pH value is adjusted to 8-9, the filtration is carried out, the obtained, drying to obtain polyethylene glycol monomethyl ether butyrate.
Example 5
The embodiment provides an antistatic PP modified material, and specifically, the antistatic PP modified material comprises 90 parts by mass of PP, 2 parts by mass of an antistatic agent, 30 parts by mass of medium alkali glass fiber, 0.05 part by mass of an antioxidant and 0.5 part by mass of a halogen absorbent.
The antistatic agent is polyethylene glycol monomethyl ether butyrate, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant is 0.03 part by mass of antioxidant 1076, the auxiliary antioxidant is 0.02 part by mass of antioxidant 168, and the halogen absorbent is hydrated talcum powder.
The specific procedure for the synthesis of methoxypolyethylene glycol butyrate as an antistatic agent is exactly the same as in example 4 and is not repeated here.
Example 6
The embodiment provides an antistatic PP modified material, and specifically, the antistatic PP modified material comprises 80 parts by mass of PP, 5 parts by mass of an antistatic agent, 20 parts by mass of medium alkali glass fiber, 0.3 part by mass of an antioxidant and 0.2 part by mass of a halogen absorbent.
The antistatic agent is polyethylene glycol monomethyl ether butyrate, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant is 0.1 part of antioxidant 1076 and 0.1 part of antioxidant 1010 in parts by weight, the auxiliary antioxidant is 0.1 part of antioxidant 168 in parts by weight, and the halogen absorbent is calcium stearate.
The specific procedure for the synthesis of methoxypolyethylene glycol butyrate as an antistatic agent is exactly the same as in example 4 and is not repeated here.
Example 7
The embodiment provides an antistatic PP modified material, and specifically, the antistatic PP modified material comprises 70 parts by mass of PP, 8 parts by mass of an antistatic agent, 10 parts by mass of medium alkali glass fiber, 0.5 part by mass of an antioxidant and 0.05 part by mass of a halogen absorbent.
The antistatic agent is a mixture formed by mixing long-chain alkyl quaternary ammonium salt with linear alkyl of more than 12 carbon atoms and polyethylene glycol monomethyl ether butyrate according to the mass ratio of 3:1, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant is 0.3 part by mass of an antioxidant 1010, the auxiliary antioxidant is 0.2 part by mass of an antioxidant 168, and the halogen absorbent is calcium stearate.
The specific steps for synthesizing the long-chain alkyl quaternary ammonium salt serving as the antistatic agent are completely the same as those in example 1, and the specific steps for synthesizing the polyethylene glycol monomethyl ether butyrate are completely the same as those in example 4, so that the details are not repeated herein.
Example 8
The embodiment provides an antistatic PP modified material, and specifically, the antistatic PP modified material comprises 90 parts by mass of PP, 2 parts by mass of an antistatic agent, 30 parts by mass of medium alkali glass fiber, 0.05 part by mass of an antioxidant and 0.5 part by mass of a halogen absorbent.
The antistatic agent is a mixture formed by mixing long-chain alkyl quaternary ammonium salt with linear alkyl of more than 12 carbon atoms and polyethylene glycol monomethyl ether butyrate according to the mass ratio of 3:1, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant is 0.03 part by mass of antioxidant 1076, the auxiliary antioxidant is 0.02 part by mass of antioxidant 168, and the halogen absorbent is hydrated talcum powder.
The specific steps for synthesizing the long-chain alkyl quaternary ammonium salt serving as the antistatic agent are completely the same as those in example 1, and the specific steps for synthesizing the polyethylene glycol monomethyl ether butyrate are completely the same as those in example 4, so that the details are not repeated herein.
Example 9
The embodiment provides an antistatic PP modified material, and specifically, the antistatic PP modified material comprises 80 parts by mass of PP, 5 parts by mass of an antistatic agent, 20 parts by mass of medium alkali glass fiber, 0.3 part by mass of an antioxidant and 0.2 part by mass of a halogen absorbent.
The antistatic agent is a mixture formed by mixing long-chain alkyl quaternary ammonium salt with linear alkyl of more than 12 carbon atoms and polyethylene glycol monomethyl ether butyrate according to the mass ratio of 3:1, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant is 0.1 part by mass of antioxidant 1076 and 0.1 part by mass of antioxidant 1010, the auxiliary antioxidant is 0.1 part by mass of antioxidant 168, and the halogen absorbent is calcium stearate.
The specific steps for synthesizing the long-chain alkyl quaternary ammonium salt serving as the antistatic agent are completely the same as those in example 1, and the specific steps for synthesizing the polyethylene glycol monomethyl ether butyrate are completely the same as those in example 4, so that the details are not repeated herein.
Example 10
The embodiment provides a preparation method of an antistatic PP modified material, which specifically comprises the following steps:
the method comprises the following steps: taking a plurality of PP (polypropylene), placing the PP in a vacuum drying oven, and carrying out vacuum drying for 2h at 70 ℃ to obtain dried PP;
step two: taking 70-90 parts of dried PP, 2-8 parts of antistatic agent, 10-30 parts of medium alkali glass fiber, 0.05-0.5 part of antioxidant and 0.05-0.5 part of halogen absorbent, adding into a mixer, mixing for 10min, transferring into a double-screw extruder, heating at 230 ℃, melting and mixing, extruding and granulating after 1h, wherein the extrusion temperature is 240 ℃, the screw rotation speed is 250r/min, and the extruded sample strips are cooled at 30 ℃ and then granulated to obtain the antistatic PP modified material.
The preparation method of the high molecular material can finally affect the regularity, crystallinity, crystallization form and ordering degree of high molecular chains in the product, when the high molecular material is extruded and molded, if the cooling temperature is lower during cooling, for example, the high molecular material is immediately cooled at a temperature lower than the glass transition temperature of the high molecular material, the antistatic agent is difficult to diffuse to the surface of the high molecular material, so that the high molecular material has insufficient antistatic effect, and the high molecular material is cooled at a temperature of 30-50 ℃ after being extruded, so that the movement of the macromolecular chain segments in the high molecular material can help the antistatic agent to diffuse, the high molecular material can present sufficient antistatic effect, and the antistatic effect can be rapidly recovered even if the antistatic agent on the surface is removed by friction or washing with water.
Example 11
The embodiment provides a preparation method of an antistatic PP modified material, which specifically comprises the following steps:
the method comprises the following steps: taking a plurality of PP (polypropylene), placing the PP in a vacuum drying oven, and carrying out vacuum drying for 4h at the temperature of 80 ℃ to obtain dried PP;
step two: taking 70-90 parts of dried PP, 2-8 parts of antistatic agent, 10-30 parts of medium alkali glass fiber, 0.05-0.5 part of antioxidant and 0.05-0.5 part of halogen absorbent, adding into a mixer, mixing for 20min, transferring into a double-screw extruder, heating at 250 ℃, melting and mixing, extruding and granulating after 2h, wherein the extrusion temperature is 260 ℃, the screw rotation speed is 350r/min, and the extruded sample strips are cooled at 50 ℃ and then granulated to obtain the antistatic PP modified material.
Example 12
The embodiment provides a preparation method of an antistatic PP modified material, which specifically comprises the following steps:
the method comprises the following steps: taking a plurality of PP (polypropylene), placing the PP in a vacuum drying oven, and carrying out vacuum drying for 3h at 75 ℃ to obtain dried PP;
step two: taking 70-90 parts of dried PP, 2-8 parts of antistatic agent, 10-30 parts of medium alkali glass fiber, 0.05-0.5 part of antioxidant and 0.05-0.5 part of halogen absorbent, adding into a mixer, mixing for 15min, transferring into a double screw extruder, heating at 240 ℃, melting and mixing, extruding and granulating after 1.5h, wherein the extrusion temperature is 250 ℃, the screw rotation speed is 300r/min, and the extruded sample strip is cooled at 40 ℃ and then granulated to obtain the antistatic PP modified material.
Application example 1
The antistatic PP-modified material composition described in example 1 was used to prepare material 1 by the method described in example 12.
Material 2 was prepared by the method described in example 12, using the antistatic PP-modified composition described in example 2.
Material 3 was prepared by the method described in example 12, using the antistatic PP-modified composition described in example 3.
Material 4 was prepared by the method described in example 12, using the antistatic PP-modified composition described in example 6.
The antistatic PP-modified material composition described in example 9 was used to prepare a material 5 by the method described in example 12.
Flexural strength, tensile strength and surface resistivity of materials 1, 2, 3, 4 and 5, respectively, were measured and the results are shown in the following table:
Figure BDA0001496322760000131
and (4) analyzing results: the experimental data show that the antistatic PP modified material prepared by the invention has small surface resistivity, strong antistatic capability, high bending strength and tensile strength, so that the expected purpose of the invention is achieved.
The surface resistivity test data is from a surface resistance tester manufactured by Beijing Ellida technologies, Inc., and the bending strength and tensile strength test data is from a universal material tester manufactured by Shanghaineton instruments, Inc.
The above experimental values were averaged in three parallel experiments using the instrument.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (9)

1. An antistatic PP modified material is characterized in that: the antistatic PP modified material is prepared by blending the polypropylene material and the auxiliary agent;
the antistatic agent is a compound with long-chain alkyl R1Quaternary ammonium salts of (A) and methoxypolyethylene glycols butyrate, wherein R1Is a straight chain alkyl group having 12 or more carbon atoms.
2. The antistatic PP-modified material of claim 1, wherein: the quaternary ammonium salt with long-chain alkyl is prepared by the following steps:
the method comprises the following steps: a halogenated hydrocarbon R1Mixing the X with water, stirring, introducing trimethylamine into the mixed solution, observing the mixed solution, and stopping introducing the trimethylamine until an organic layer basically disappears;
step two: standing for layering, extracting the water layer with ethyl acetate for several times, and mixing the ethyl acetate extractive solutions;
step three: adding poor solvent of long-chain alkyl quaternary ammonium salt into ethyl acetate extract, stirring, filtering after solid is completely separated out, and drying to obtain long-chain alkyl quaternary ammonium salt.
3. Such asThe antistatic PP-modified material of claim 2, wherein: the poor solvent is petroleum ether or diethyl ether with distillation range of 30-60 deg.C, and halogenated hydrocarbon R1X in X is Cl or Br.
4. The antistatic PP-modified material of claim 1, wherein: the polyethylene glycol monomethyl ether butyrate is prepared by the following steps:
the method comprises the following steps: adding polyethylene glycol monomethyl ether and n-butyric acid into DMF, adding polymerization inhibitor, DMAP and DCC, heating to 50-70 ℃ under stirring, and reacting for 12-24 h;
step two: and (3) flushing the reaction solution into water, stirring for 0.5-1h, adjusting the pH value to 8-9, filtering, washing the obtained solid with water for multiple times, and drying to obtain the polyethylene glycol monomethyl ether butyrate.
5. The antistatic PP-modified material of claim 4, wherein: the molecular weight of the polyethylene glycol monomethyl ether is 2000-10000.
6. The antistatic PP-modified material of claim 1, wherein: the polypropylene material comprises 70-90 parts by mass of PP, and the auxiliary agent comprises 2-8 parts by mass of antistatic agent, 10-30 parts by mass of medium alkali glass fiber, 0.05-0.5 part by mass of antioxidant and 0.05-0.5 part by mass of halogen absorbent.
7. The antistatic PP-modified material of claim 6, wherein: the polypropylene material comprises 80 parts by mass of PP, and the auxiliary agent comprises 5 parts by mass of antistatic agent, 20 parts by mass of medium alkali glass fiber, 0.3 part by mass of antioxidant and 0.2 part by mass of halogen absorbent.
8. The preparation method of the antistatic PP modified material is characterized by comprising the following steps:
the method comprises the following steps: taking a certain weight of PP, placing the PP in a vacuum drying oven, and carrying out vacuum drying for 2-4h at the temperature of 70-80 ℃ to obtain dried PP;
step two: taking 70-90 parts of dried PP, 2-8 parts of antistatic agent, 10-30 parts of medium alkali glass fiber, 0.05-0.5 part of antioxidant and 0.05-0.5 part of halogen absorbent, adding into a mixer, mixing for 10-20min, transferring into a double-screw extruder, heating, melting and mixing at the temperature of 230-;
the antistatic agent is a compound with long-chain alkyl R1Quaternary ammonium salts of (A) and methoxypolyethylene glycols butyrate, wherein R1Is a straight chain alkyl group having 12 or more carbon atoms.
9. The method for preparing antistatic PP modified material as claimed in claim 8, wherein: the cooling temperature of the extruded sample strip in the second step is 30-50 ℃.
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