CN107337853B - Preparation method of low-fogging value, low-volatility and low-odor polypropylene composition for automotive interior - Google Patents

Preparation method of low-fogging value, low-volatility and low-odor polypropylene composition for automotive interior Download PDF

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CN107337853B
CN107337853B CN201710598670.1A CN201710598670A CN107337853B CN 107337853 B CN107337853 B CN 107337853B CN 201710598670 A CN201710598670 A CN 201710598670A CN 107337853 B CN107337853 B CN 107337853B
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polypropylene
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CN107337853A (en
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杨治
谭江梅
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Sichuan Guangya New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B29B2009/168—Removing undesirable residual components, e.g. solvents, unreacted monomers; Degassing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Abstract

The invention discloses a preparation method of a low-fogging value, low-volatility and low-odor polypropylene composition for automotive interior, wherein the polypropylene composition is composed of polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant, and the preparation method comprises high-speed mixing, extrusion granulation and homogenization circulation. The low-VOC resin is selected and reasonably compatible with other auxiliary agents, two sections of water injection are used for washing, extracting and devolatilizing, no molecular sieve adsorbent is needed to be added, and the prepared automotive interior material has the advantages of low atomization value, low volatility and low odor, and good forming appearance; the invention pumps the produced granular material into a three-component homogenizing tank, and sweeps the surface of the particles by hot air, so that the residual volatile organic compounds in the particles are thoroughly devolatilized under the action of heating circulation; the preparation method has the advantages of controllable process, stable quality, simplicity, feasibility, mature process, wide raw material source and low production cost, and is suitable for industrial large-scale production.

Description

Preparation method of low-fogging value, low-volatility and low-odor polypropylene composition for automotive interior
Technical Field
The invention belongs to the field of processing of high polymer materials, and particularly relates to a preparation method of a low-fogging value, low-volatility and low-odor polypropylene composition for automotive interior trim.
Background
Along with the development trend of light weight and environmental protection of automobiles and convenient recovery of materials, the modified polypropylene material is widely applied to automobile interior systems due to easy molding, good heat resistance and high cost performance. Along with the continuous improvement of the air quality requirement of the interior of the automobile by consumers, in 2012, the national environmental protection department issues a guidance on seeking the national environmental protection standard 'air quality evaluation guidance in passenger cars', and revises the recommended standard into a mandatory standard, in 2012, each automobile host factory strengthens the standard of Volatile Organic Compounds (VOCs) in the automobile, and simultaneously sets the odor level in the automobile as an important control index and sets up corresponding enterprise standards. VOC is an important cause of affecting the quality of air in vehicles. The main components of the compound comprise alkane, alkene, aromatic hydrocarbon, aldehyde or ketone, etc., and the compound has special pungent odor, and part of the compound is listed as carcinogenic substances, such as chloroethylene, benzene, polycyclic aromatic hydrocarbon, etc., and part of VOC also has destructive effect on an ozone layer, such as chlorofluorocarbon and hydrochlorofluorocarbon, when the VOC concentration is too high, acute poisoning is easily caused, and the mild people can have headache, dizziness, cough, nausea and vomiting; in severe cases, convulsions occur and can damage the liver, kidneys, brain and nervous system of a human.
The Total Volatile Organic Compounds (TVOC) of the automotive interior polypropylene product exceed the standard, the smell is large, and the main reasons are as follows: firstly, because the catalyst or the regulator is not fully volatilized in the process of synthesizing the polypropylene resin, the catalyst or the regulator is remained in the resin, so that the Total Volatile Organic Compound (TVOC) is high in content and large in smell; and secondly, because the polypropylene has more tertiary carbon atoms, the polypropylene is easy to degrade under the conditions of high temperature, illumination and shearing, aldehyde and ketone substances are generated, VOC and odor are influenced, and therefore the quality of air in the vehicle is influenced, and the health of passengers is damaged. At present, the VOC content and odor of polypropylene materials are mainly reduced by two methods: firstly, improving a synthesis process, fully devolatilizing, and removing residual catalyst, solvent, regulator and the like; and secondly, optimizing a processing technology in the processing process, and adding a heat stabilizer, a devolatilization agent, an adsorbent and the like.
Chinese patent publication No. CN103044771A discloses a preparation method of polypropylene material with low volatile organic compounds, which is characterized in that a water-soluble surfactant is added, the water-soluble surfactant generates a large amount of micro bubbles in the process of twin-screw high-temperature extrusion, adsorbs volatile organic compounds in polypropylene melt, and discharges VOC substances in the micro bubbles under the action of vacuum, the method is simple and easy to implement, but because a large amount of steam is generated, the defect of material return is easily formed at a discharge port, and the productivity is influenced; patent 1727389a discloses a low odor and low volatile polypropylene composite material, which is prepared by adding fine-pore silica gel to suppress VOC in melt so as to meet the requirement of low odor; chinese patent publication No. CN101691435A discloses a low-VOC high-performance PP composite material for automotive upholstery and a method for preparing the same, wherein the low-VOC polypropylene composite material is produced by using a specific hydrogen blending polypropylene, but there is a risk of volatile matter generation during material processing.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor.
The purpose of the invention is realized by the following technical scheme: a preparation method of a polypropylene composition with low fogging value, low volatility and low odor for automobile interior decoration, wherein the polypropylene composition is composed of polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant, and the preparation method comprises the following steps:
s1, high-speed mixing: adding polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant into a high-speed mixer for mixing for 2-7 min, wherein the rotating speed of the high-speed mixer is 1000-1500 rad/min;
s2, extruding and granulating: adding the high-speed mixed material into a double-screw extruder with a liquid injection system in a double vacuum, wherein the length-diameter ratio of the extruder is 44-56: 1, a thread element of an injection section is designed into a groove reverse rotation type mixing block, the melt block passing through the section is cut to be small, high-pressure water is pumped to wash low-molecular organic matters in the melt, the low-molecular organic matters are separated from the melt, then the low-molecular organic matters are extracted under negative pressure of-0.6 to-0.1 MPa by using a vacuum pump, and the low-molecular organic matters are subjected to melt blending extrusion granulation, wherein the temperature of the extruder is set to 160-195 ℃, and the rotating speed of a screw is 400-600 rpm;
s3 homogenization cycle: and (5) pumping the granular material extruded and granulated in the step S2 into a three-component homogenizing tank, setting the temperature to be 80-135 ℃, and performing homogenization circulation for 3-6 hours to obtain the low-atomization-value, low-volatility and low-odor polypropylene composition for automotive interiors.
Further, the polypropylene composition is prepared from the following raw materials in parts by weight:
polypropylene resin: 50-90; polyethylene resin: 3-10;
and (3) toughening: 0 to 20; reinforcing agent: 0 to 30 parts by weight;
thermal stabilizer: 0.3 to 0.8; light stabilizer: 0.4 to 1;
lubricant: 0.3 to 1.
Preferably, the polypropylene composition is prepared from the following raw materials in parts by weight:
polypropylene resin: 58; polyethylene resin: 7;
and (3) toughening: 10; reinforcing agent: 20;
thermal stabilizer: 05, carrying out a reaction; light stabilizer: 0.7;
lubricant: 0.6.
Furthermore, the total carbon volatilization amount of the polypropylene resin is less than or equal to 80ugC/g, and the total carbon volatilization amount of the polyethylene resin is less than or equal to 80 ugC/g.
Further, the toughening agent is one or a combination of ethylene-butene copolymer or ethylene-octene copolymer, the density is less than or equal to 0.87g/cm, and the total carbon volatilization amount is less than or equal to 80 ugC/g.
Further, the reinforcing agent is silicate mineral, is in the shape of one or two of sheet or needle, has a particle size of 0.5-15 um, has a silicon content of less than or equal to 60 percent, and has a burning vector of less than 10 percent at 1000 ℃ for 1 hour.
Further, the heat stabilizer is one or more of amide, thioester or thiophenol of hindered phenol.
Further, the light stabilizer is one or a mixture of triazine hindered phenol or piperidyl hindered amine.
Further, the lubricant is one or more of synthetic polyethylene wax, metal soap and amide.
The automotive interior part product has high requirements on atomization value, volatile organic compounds and smell, and the raw materials of the automotive interior part product are subjected to two processing procedures, namely, the raw materials are subjected to high-temperature melting, extrusion and granulation, and the plastic particles are subjected to high-temperature melting, injection molding and forming to obtain the product. The polypropylene material can be degraded under high-temperature shearing to generate volatile organic compounds, and to obtain a product with a low atomization value, a low TVOC (total volatile organic compound) and a low odor, plastic particles are required to meet the three indexes firstly, and the plastic particles are required to have a heat-resistant effect in the injection molding process, so that the plastic particles can be ensured not to generate the overproof volatile organic compounds in the second process.
The invention has the following advantages:
(1) the low-VOC resin is selected and reasonably compatible with other auxiliary agents, two sections of water injection are used for washing, extracting and devolatilizing, no molecular sieve adsorbent is needed to be added, and the prepared automotive interior material has the advantages of low atomization value, low volatility and low odor, and good forming appearance;
(2) the invention pumps the produced granular material into a three-component homogenizing tank, and sweeps the surface of the particles by hot air, so that the residual volatile organic compounds in the particles are thoroughly devolatilized under the action of heating circulation;
(3) the preparation method has the advantages of controllable process, stable quality, simplicity and feasibility, mature process and wide source because the adopted resin is a domestic raw material, has the selling price far lower than that of imported low-VOC polypropylene resin, obviously reduces the production cost, and is suitable for industrial large-scale production.
Detailed Description
The invention is further described below with reference to examples, without limiting the scope of the invention to the following:
example 1: a preparation method of a polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor comprises the following raw materials in parts by weight:
polypropylene resin: 50; polyethylene resin: 3;
thermal stabilizer: 0.3; light stabilizer: 0.4;
lubricant: 0.3.
The total carbon volatilization amount of the polypropylene resin is less than or equal to 80ugC/g, the polypropylene resin is prepared by a gas phase synthesis method, metallocene is used as a catalyst and a hydrogen regulation method, the molecular weight distribution is narrow, and the content of low molecular polypropylene is low. The blending and matching of the copolymerization polypropylene and the homopolymerization polypropylene are preferred, which is beneficial to the adjustment of the rigidity-toughness balance of the composition; the total carbon volatilization amount of the polyethylene resin is less than or equal to 80ugC/g, a gas phase synthesis method is adopted, and metallocene is used as a catalyst. The polyethylene resin prepared by the process can better alleviate the stress whitening problem of automotive upholstery; the toughening agent is an ethylene-butene copolymer, the density is less than or equal to 0.87g/cm, the total carbon volatilization is less than or equal to 80ugC/g, and preferably the elastomer with the melt flow rate of 2-15g/10mim is obtained under the test condition of 190 ℃ x 2.16 kg; the reinforcing agent is silicate mineral, is sheet-shaped, has the particle size of 0.5-15 um, has the silicon content of less than or equal to 60 percent, and has the burning vector of less than 10 percent at 1000 ℃ for 1 hour; the thermal stabilizer is CHINOX 1024; the light stabilizer is CHISORB 5411; the lubricant is synthetic polyethylene wax.
The preparation method comprises the following steps:
s1, high-speed mixing: adding polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant into a high-speed mixer for mixing for 2min, wherein the rotating speed of the high-speed mixer is 1000 rad/min;
s2, extruding and granulating: adding the high-speed mixed material into a double-screw extruder with a liquid injection system in a double vacuum, wherein the length-diameter ratio of the extruder is 44:1, a thread element of an injection section is designed into a groove reverse rotation type mixing block, the melt block passing through the section is cut to be small, high-pressure water is pumped to wash low-molecular organic matters in the melt, the low-molecular organic matters are separated from the melt, then the low-molecular organic matters are extracted under negative pressure of-0.6 MPa by using a vacuum pump, the melt blending extrusion granulation is carried out, the temperature of the extruder is set to be 160 ℃, and the rotating speed of a screw is 400 rpm;
s3 homogenization cycle: and (3) pumping the granular material extruded and granulated in the step S2 into a three-component homogenizing tank, setting the temperature to be 80 ℃, and performing homogenization circulation for 3 hours to obtain the low-atomization-value, low-volatility and low-odor polypropylene composition for automotive interiors.
Example 2: a preparation method of a polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor comprises the following raw materials in parts by weight:
polypropylene resin: 90, respectively; polyethylene resin: 10;
and (3) toughening: 20; thermal stabilizer: 0.8;
light stabilizer: 1; lubricant: 1.
The total carbon volatilization amount of the polypropylene resin is less than or equal to 80ugC/g, the polypropylene resin is prepared by a gas phase synthesis method, metallocene is used as a catalyst and a hydrogen regulation method, the molecular weight distribution is narrow, and the content of low molecular polypropylene is low. The blending and matching of the copolymerization polypropylene and the homopolymerization polypropylene are preferred, which is beneficial to the adjustment of the rigidity-toughness balance of the composition; the total carbon volatilization amount of the polyethylene resin is less than or equal to 80ugC/g, a gas phase synthesis method is adopted, and metallocene is used as a catalyst. The polyethylene resin prepared by the process can better alleviate the stress whitening problem of automotive upholstery; the toughening agent is one or a combination of ethylene-octene copolymer, has a density of less than or equal to 0.87g/cm and a total carbon volatilization amount of less than or equal to 80ugC/g, and is preferably an elastomer with a melt flow rate of 2-15g/10mim under the test condition of 190 ℃ multiplied by 2.16 kg; the reinforcing agent is a silicate mineral, is needle-shaped, has a particle size of 0.5-15 um, has a silicon content of less than or equal to 60 percent, and has a burning vector of less than 10 percent at 1000 ℃ for 1 hour; the thermal stabilizer is a mixture of CHINOX1325 and 1790; the light stabilizer is CHISORB T2164 and CHISORB 622; the lubricant is a metal soap.
The preparation method comprises the following steps:
s1, high-speed mixing: adding polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant into a high-speed mixer for mixing for 7min, wherein the rotating speed of the high-speed mixer is 1500 rad/min;
s2, extruding and granulating: adding the high-speed mixed material into a double-screw extruder with a liquid injection system in a double vacuum, wherein the length-diameter ratio of the extruder is 56:1, a thread element of an injection section is designed into a groove reverse rotation type mixing block, the melt block passing through the section is cut to be small, high-pressure water is pumped to wash low-molecular organic matters in the melt, the low-molecular organic matters are separated from the melt, then the low-molecular organic matters are extracted under negative pressure of-0.1 MPa by using a vacuum pump, the melt blending extrusion granulation is carried out, the temperature of the extruder is set to 195 ℃, and the rotating speed of a screw is 600 rpm;
s3 homogenization cycle: and (4) pumping the granular material extruded and granulated in the step S2 into a three-component homogenizing tank, setting the temperature to be 135 ℃, and performing homogenization circulation for 6 hours to obtain the low-atomization-value, low-volatility and low-odor polypropylene composition for automobile interiors.
Example 3: a preparation method of a polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor comprises the following raw materials in parts by weight:
polypropylene resin: 60, adding a solvent to the mixture; polyethylene resin: 4;
and (3) toughening: 1; reinforcing agent: 8;
thermal stabilizer: 0.5; light stabilizer: 0.5;
lubricant: 0.4.
The total carbon volatilization amount of the polypropylene resin is less than or equal to 80ugC/g, the polypropylene resin is prepared by a gas phase synthesis method, metallocene is used as a catalyst and a hydrogen regulation method, the molecular weight distribution is narrow, and the content of low molecular polypropylene is low. The blending and matching of the copolymerization polypropylene and the homopolymerization polypropylene are preferred, which is beneficial to the adjustment of the rigidity-toughness balance of the composition; the total carbon volatilization amount of the polyethylene resin is less than or equal to 80ugC/g, a gas phase synthesis method is adopted, and metallocene is used as a catalyst. The polyethylene resin prepared by the process can better alleviate the stress whitening problem of automotive upholstery; the toughening agent is a combination of an ethylene-butene copolymer and an ethylene-octene copolymer, the density is not more than 0.87g/cm, the total carbon volatilization is not more than 80ugC/g, and the elastomer with the melt flow rate of 2-15g/10mim is preferably selected under the test condition of 190 ℃ multiplied by 2.16 kg; the reinforcing agent is silicate mineral, is sheet-shaped and needle-shaped, has a particle size of 0.5-15 um, has a silicon content of less than or equal to 60 percent, and has a burning vector of less than 10 percent at 1000 ℃ for 1 hour; the heat stabilizer is a mixture of CHINOX626, PS1589 and 3520; the light stabilizer is a mixture of CHISORB T2164, CHISORB622 and CHISORB 944; the lubricant is a mixture of synthetic polyethylene wax and metal soap.
The preparation method comprises the following steps:
s1, high-speed mixing: adding polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant into a high-speed mixer for mixing for 3min, wherein the rotating speed of the high-speed mixer is 1100 rad/min;
s2, extruding and granulating: adding the high-speed mixed material into a double-screw extruder with a liquid injection system in a double vacuum, wherein the length-diameter ratio of the extruder is 46:1, a thread element of an injection section is designed into a groove reverse rotation type mixing block, the melt block passing through the section is cut to be small, high-pressure water is pumped to wash low-molecular organic matters in the melt, the low-molecular organic matters are separated from the melt, then the low-molecular organic matters are extracted under negative pressure of-0.7 MPa by using a vacuum pump, the melt blending extrusion granulation is carried out, the temperature of the extruder is set to be 165 ℃, and the rotating speed of a screw;
s3 homogenization cycle: and (4) pumping the granular material extruded and granulated in the step S2 into a three-component homogenizing tank, setting the temperature to be 90 ℃, and performing homogenization circulation for 3-6 hours to obtain the low-atomization-value, low-volatility and low-odor polypropylene composition for automotive interiors.
Example 4: a preparation method of a polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor comprises the following raw materials in parts by weight:
polypropylene resin: 50; polyethylene resin: 3;
and (3) toughening: 5; reinforcing agent: 10;
thermal stabilizer: 0.3; light stabilizer: 0.4;
lubricant: 0.3.
The total carbon volatilization amount of the polypropylene resin is less than or equal to 80ugC/g, the polypropylene resin is prepared by a gas phase synthesis method, metallocene is used as a catalyst and a hydrogen regulation method, the molecular weight distribution is narrow, and the content of low molecular polypropylene is low. The blending and matching of the copolymerization polypropylene and the homopolymerization polypropylene are preferred, which is beneficial to the adjustment of the rigidity-toughness balance of the composition; the total carbon volatilization amount of the polyethylene resin is less than or equal to 80ugC/g, a gas phase synthesis method is adopted, and metallocene is used as a catalyst. The polyethylene resin prepared by the process can better alleviate the stress whitening problem of automotive upholstery; the toughening agent is an ethylene-butylene copolymer, the density is less than or equal to 0.87g/cm, and the total carbon volatilization amount is less than or equal to 80 ugC/g; the reinforcing agent is silicate mineral, is sheet-shaped, has the particle size of 0.5-15 um, has the silicon content of less than or equal to 60 percent, and has the burning vector of less than 10 percent at 1000 ℃ for 1 hour; the thermal stabilizer is a mixture of CHINOX1024, 1325, 1790 and 626; the light stabilizer is a mixture of CHISORB5411, CHISORB T2164, CHISORB622 and CHISORB 944; the lubricant is a mixture of synthetic polyethylene wax, metal soaps and amides.
The preparation method comprises the following steps:
s1, high-speed mixing: adding polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant into a high-speed mixer for mixing for 6min, wherein the rotating speed of the high-speed mixer is 1200 rad/min;
s2, extruding and granulating: adding the high-speed mixed material into a double-screw extruder with a liquid injection system in a double vacuum, wherein the length-diameter ratio of the extruder is 50:1, a thread element of an injection section is designed into a groove reverse rotation type mixing block, the melt block passing through the section is cut to be small, high-pressure water is pumped to wash low-molecular organic matters in the melt, the low-molecular organic matters are separated from the melt, then the low-molecular organic matters are extracted under negative pressure of-0.9 MPa by using a vacuum pump, the melt blending extrusion granulation is carried out, the temperature of the extruder is set to 190 ℃, and the rotating speed of a screw is 520 rpm;
s3 homogenization cycle: and (3) pumping the granular material extruded and granulated in the step S2 into a three-component homogenizing tank, setting the temperature to be 120 ℃, and performing homogenization circulation for 3.5 hours to obtain the low-atomization-value, low-volatility and low-odor polypropylene composition for automotive interiors.
Example 5: a preparation method of a polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor comprises the following raw materials in parts by weight:
polypropylene resin: 75; polyethylene resin: 10;
and (3) toughening: 20; reinforcing agent: 30, of a nitrogen-containing gas;
thermal stabilizer: 0.8; light stabilizer: 1;
lubricant: 1.
The total carbon volatilization amount of the polypropylene resin is less than or equal to 80ugC/g, the polypropylene resin is prepared by a gas phase synthesis method, metallocene is used as a catalyst and a hydrogen regulation method, the molecular weight distribution is narrow, and the content of low molecular polypropylene is low. The blending and matching of the copolymerization polypropylene and the homopolymerization polypropylene are preferred, which is beneficial to the adjustment of the rigidity-toughness balance of the composition; the total carbon volatilization amount of the polyethylene resin is less than or equal to 80ugC/g, a gas phase synthesis method is adopted, and metallocene is used as a catalyst. The polyethylene resin prepared by the process can better alleviate the stress whitening problem of automotive upholstery; the toughening agent is the combination of an ethylene-butene copolymer and an ethylene-octene copolymer, the density is less than or equal to 0.87g/cm, and the total carbon volatilization amount is less than or equal to 80 ugC/g; the reinforcing agent is a silicate mineral, is needle-shaped, has a particle size of 0.5-15 um, has a silicon content of less than or equal to 60 percent, and has a burning vector of less than 10 percent at 1000 ℃ for 1 hour; the thermal stabilizer is a mixture of CHINOX1024, 1325, 1790, 626 and 3520; the light stabilizer is a mixture of chiSORB5411 and chiSORB T2164; the lubricant is an amide.
The preparation method comprises the following steps:
s1, high-speed mixing: adding polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant into a high-speed mixer for mixing for 4min, wherein the rotating speed of the high-speed mixer is 1300 rad/min;
s2, extruding and granulating: adding the high-speed mixed material into a double-screw extruder with a liquid injection system in a double vacuum, wherein the length-diameter ratio of the extruder is 48:1, a thread element of an injection section is designed into a groove reverse rotation type mixing block, the melt block passing through the section is cut to be small, high-pressure water is pumped to wash low-molecular organic matters in the melt, the low-molecular organic matters are separated from the melt, then the low-molecular organic matters are extracted under negative pressure of-0.7 MPa by using a vacuum pump, the melt blending extrusion granulation is carried out, the temperature of the extruder is set to be 170 ℃, and the rotating speed of a screw is 500 rpm;
s3 homogenization cycle: and (4) pumping the granular material extruded and granulated in the step S2 into a three-component homogenizing tank, setting the temperature to be 95 ℃, and performing homogenization circulation for 4.5 hours to obtain the low-atomization-value, low-volatility and low-odor polypropylene composition for automotive interiors.
Example 6: a preparation method of a polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor comprises the following raw materials in parts by weight:
polypropylene resin: 58; polyethylene resin: 7;
and (3) toughening: 10; reinforcing agent: 20;
thermal stabilizer: 05, carrying out a reaction; light stabilizer: 0.7;
lubricant: 0.6.
The total carbon volatilization amount of the polypropylene resin is less than or equal to 80ugC/g, the polypropylene resin is prepared by a gas phase synthesis method, metallocene is used as a catalyst and a hydrogen regulation method, the molecular weight distribution is narrow, and the content of low molecular polypropylene is low. The blending and matching of the copolymerization polypropylene and the homopolymerization polypropylene are preferred, which is beneficial to the adjustment of the rigidity-toughness balance of the composition; the total carbon volatilization amount of the polyethylene resin is less than or equal to 80ugC/g, a gas phase synthesis method is adopted, and metallocene is used as a catalyst. The polyethylene resin prepared by the process can better alleviate the stress whitening problem of automotive upholstery; the toughening agent is one or a combination of ethylene-octene copolymer, has a density of less than or equal to 0.87g/cm and a total carbon volatilization amount of less than or equal to 80ugC/g, and is preferably an elastomer with a melt flow rate of 2-15g/10mim under the test condition of 190 ℃ multiplied by 2.16 kg; the reinforcing agent is silicate mineral, is sheet-shaped and needle-shaped, has a particle size of 0.5-15 um, has a silicon content of less than or equal to 60 percent, and has a burning vector of less than 10 percent at 1000 ℃ for 1 hour; the heat stabilizer is a mixture of CHINOX1024, 1325, 1790, 626, PS1589 and 3520; the light stabilizer is CHISORB 944; the lubricant is synthetic polyethylene wax.
The preparation method comprises the following steps:
s1, high-speed mixing: adding polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant into a high-speed mixer for mixing for 5min, wherein the rotating speed of the high-speed mixer is 1400 rad/min;
s2, extruding and granulating: adding the high-speed mixed material into a double-screw extruder with a liquid injection system in a double vacuum, wherein the length-diameter ratio of the extruder is 50:1, a thread element of an injection section is designed into a groove reverse rotation type mixing block, the melt block passing through the section is cut to be small, high-pressure water is pumped to wash low-molecular organic matters in the melt, the low-molecular organic matters are separated from the melt, then the low-molecular organic matters are extracted under negative pressure of-0.6 MPa by using a vacuum pump, the melt blending extrusion granulation is carried out, the temperature of the extruder is set to 195 ℃, and the rotation speed of a screw is;
s3 homogenization cycle: and (4) pumping the granular material extruded and granulated in the step S2 into a three-component homogenizing tank, setting the temperature at 130 ℃, and performing homogenization circulation for 6 hours to obtain the low-atomization-value, low-volatility and low-odor polypropylene composition for automobile interiors.
The following experiments illustrate the beneficial effects of the present invention:
1. the experimental formula is as follows: as shown in table 1:
table 1: component proportion of polypropylene composition for automobile interior decoration with low atomization value, low volatility and low odor
Name of raw material Experimental example 1 Experimental example 2 Experimental example 3 Experimental example 4 Experimental example 5
Polypropylene 90 79 72 65 61
Polyethylene 3 6 5 7 4
Toughening agent 7 10 13 12 15
Reinforcing agent 0 5 10 20 30
Heat stabilizer 0.4 0.6 0.6 0.7 0.8
Light stabilizers 0.5 0.7 0.8 0.9 0.7
Lubricant agent 0.5 0.6 0.8 0.9 1.0
2. The preparation method comprises the following steps: the preparation method comprises the following steps:
s1, high-speed mixing: adding polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant into a high-speed mixer for mixing for 4min, wherein the rotating speed of the high-speed mixer is 1200 rad/min;
s2, extruding and granulating: adding the high-speed mixed material into a double-screw extruder with a liquid injection system in a double vacuum, wherein the length-diameter ratio of the extruder is 48:1, a thread element of an injection section is designed into a groove reverse rotation type mixing block, the melt block passing through the section is cut to be small, high-pressure water is pumped to wash low-molecular organic matters in the melt, the low-molecular organic matters are separated from the melt, then the low-molecular organic matters are extracted under negative pressure of-0.7 MPa by using a vacuum pump, the melt blending extrusion granulation is carried out, the temperature of the extruder is set to be 170 ℃, and the rotating speed of a screw is 500 rpm;
s3 homogenization cycle: and (4) pumping the granular material extruded and granulated in the step S2 into a three-component homogenizing tank, setting the temperature to be 95 ℃, and performing homogenization circulation for 4.5 hours to obtain the low-atomization-value, low-volatility and low-odor polypropylene composition for automotive interiors.
3. The detection method comprises the following steps: the polypropylene compositions for automobile interiors, which have low fogging values, low volatility and low odor and are obtained in the experimental examples 1 to 5, are subjected to relevant data tests by adopting a traditional preparation method, and the detection data are obtained according to the following test standards:
(1) the tensile yield strength and the tensile breaking strain are measured according to ISO 527/GB/T1040;
(2) the flexural strength and the elastic modulus were measured according to ISO 178/GB/T9341;
(3) the notched Izod impact strength was measured according to ISO 180/GB/T1843;
(4) the melt flow rate is determined according to ISO 1133/GB/T3682;
(5) the fogging value is determined according to DIN 75201B haze characteristics;
(6) odor test 50 cm was tested according to VDA 270 method3The plastic article of (2) was placed in a closed 1L glass bottle and heated at 80 ℃ for 2 hours, and five persons evaluated according to the rule of Table 2.
Table 2: odor evaluation rules
Grade Level 1 Stage 2 Grade 3 4 stage Grade 5 Grade 6
Standard of merit Is not easy to feel Can feel without irritation Can be obviously sensed without stimulation Thorn nose Very pungent Is intolerable
Note: when the rating is between the two, the result is required to be half-graded to illustrate the odor
(7) Testing of VOCs and TVOC contents was performed with reference to japanese standard JASP MO 902: 2007, using a 10L bag method:
7.1 placing the sample in a sampling bag, and sealing the sampling bag;
7.2 after the sampling bag is repeatedly cleaned, 5L of high-purity nitrogen is filled in the sampling bag;
7.3 placing the sampling bag in a thermostat at 65 ℃ for 2H;
7.4 simultaneously using a DNPH column and a TENAX tube to carry out online adsorption on the gas in the sampling bag;
7.5 the DNPH column is used for testing the aldehyde ketone series VOCs by a High Performance Liquid Chromatograph (HPLC) after being eluted by an acetonitrile solvent; the TENAX tube is directly applied to a thermal desorption-gas chromatography-mass spectrometer for testing benzene series VOCs and TVOC. The types of instruments used were: the model of the high performance liquid chromatograph is LC-20A; the model of the thermal desorption-gas chromatography-mass spectrometer is TD-20, GCMS-QP 2010.
3. The experimental results are as follows: the results of the experiment are shown in table 3.
Table 3: results of Performance test
Figure RE-GDA0001398519090000101
Note: the atomization value is required to be less than or equal to 2mg, the TVOC is required to be less than or equal to 50ugC/g, the N.D. representative data is lower than the detection limit value, and the benzene series is 10ug/m3The aldehyde ketone acetaldehyde, acrolein and acetone are 15ug/m3The formaldehyde is 30ug/m3。
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (4)

1. A preparation method of a polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor is characterized in that the polypropylene composition is composed of polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant, and the preparation method comprises the following steps:
s1, high-speed mixing: adding polypropylene resin, polyethylene resin, a toughening agent, a reinforcing agent, a heat stabilizer, a light stabilizer and a lubricant into a high-speed mixer for mixing for 2-7 min, wherein the rotating speed of the high-speed mixer is 1000-1500 rad/min;
s2, extruding and granulating: adding the high-speed mixed material into a double-screw extruder with a liquid injection system in a double vacuum, wherein the length-diameter ratio of the extruder is 44-56: 1, a thread element of an injection section is designed into a groove reverse rotation type mixing block, the melt block passing through the section is cut to be small, high-pressure water is pumped to wash low-molecular organic matters in the melt, the low-molecular organic matters are separated from the melt, then the low-molecular organic matters are extracted under negative pressure of-0.6 to-0.1 MPa by using a vacuum pump, and the low-molecular organic matters are subjected to melt blending extrusion granulation, wherein the temperature of the extruder is set to 160-195 ℃, and the rotating speed of a screw is 400-600 rpm;
s3, homogenizing circulation: pumping the granular material extruded and granulated in the step S2 into a three-component homogenizing tank, setting the temperature to be 80-135 ℃, and performing homogenization circulation for 3-6 hours to obtain the polypropylene composition for the automotive interior with low atomization value, low volatility and low odor,
the polypropylene resin is prepared by blending copolymerization and homopolymerization polypropylene, wherein the total carbon volatilization of the polypropylene resin is less than or equal to 80ugC/g, and the polypropylene resin is prepared by a gas phase synthesis method, metallocene serving as a catalyst and a hydrogen regulation method; the total carbon volatilization amount of the polyethylene resin is less than or equal to 80ugC/g, and the polyethylene resin is prepared by a low pressure method; the heat stabilizer is one or more of amide, thioester or thiophenol of hindered phenol; the lubricant is one or a combination of more of synthetic polyethylene wax, metal soaps and amides; the light stabilizer is triazine hindered phenol;
the polypropylene composition is prepared from the following raw materials in parts by weight:
polypropylene resin: 50-90; polyethylene resin: 3-10;
a toughening agent: 0 to 20; reinforcing agent: 0 to 30 parts by weight;
thermal stabilizer: 0.3 to 0.8; light stabilizer: 0.4 to 1;
lubricant: 0.3 to 1.
2. The preparation method of the polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor as claimed in claim 1, wherein the polypropylene composition is prepared from the following raw materials in parts by weight:
polypropylene resin: 58; polyethylene resin: 7;
a toughening agent: 10; reinforcing agent: 20;
thermal stabilizer: 05, carrying out a reaction; light stabilizer: 0.7;
lubricant: 0.6.
3. the method for preparing the polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor as claimed in claim 1 or 2, wherein the toughening agent is one or more of ethylene-butene copolymer or combination of ethylene-octene copolymer, and the density is less than or equal to 0.87g/cm3The total carbon volatilization is less than or equal to 80 ugC/g.
4. The preparation method of the polypropylene composition for automobile interior decoration with low fogging value, low volatility and low odor as claimed in claim 2, wherein the reinforcing agent is silicate mineral, is in the shape of one or two of sheet or needle, has a particle size of 0.5-15 um, a silicon content of 60% or less, and has a burning vector of less than 10% at 1000 ℃ for 1 hour.
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