CN108250562B - Low-odor low-emission polypropylene composite material and preparation method thereof - Google Patents
Low-odor low-emission polypropylene composite material and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a low-odor low-emission polypropylene composite material and a preparation method thereof, wherein the polypropylene composite material comprises the following components: 60-80 parts of polypropylene; 17-23 parts of an inorganic filler; 0.1-3 parts of ethanol, wherein the weight content of iron element is 10ppm-200ppm based on the total weight of the low-odor low-emission polypropylene composite material, and the preparation method of the polypropylene composite material comprises the following steps: adding polypropylene, an iron-containing compound and ethanol into a high-speed mixer, mixing, adding into a double-screw extruder, adding an inorganic filler into the double-screw extruder from a side feed, performing melt extrusion, bracing, water cooling, granulation, drying and bagging, placing in a drying tank for drying, and turning over the materials every 2-4 hours, wherein the double-screw extruder is designed in a three-vacuum mode, the vacuum degree is controlled to be less than or equal to-0.05 bar, and a filter screen is arranged at the head of the double-screw extruder to remove large-particle impurities. The low-odor diffusion characteristic is obviously improved, and meanwhile, the mechanical property and the heating property can be kept well, so that the low-odor diffusion material can be widely applied to automotive upholsteries.
Description
Technical Field
The invention relates to the field of high polymer materials and molding processing thereof, in particular to a low-odor low-emission polypropylene composite material and a preparation method thereof.
Background
The automobile air conditioner shell is an extremely important functional part under an automobile engine cover, the temperature change of the working environment is large, circulating gas directly flows through the space in an automobile, and the automobile air conditioner shell has higher requirements on mechanical strength, particularly high requirements on heat resistance, odor property and diffusion property.
Currently, the automobile industry in China is developing vigorously with a large stride gesture, and the demands of consumers on the comfort and health of automobiles are increasing day by day. The national GB/T27630-2011 'evaluation guidance for quality of air in a passenger car' clearly stipulates the upper limit value of benzene and aldehyde ketone organic volatile matters, and the odor property of the air in the car visually reflects the concentration of the organic volatile matters. And each joint venture brand and independent brand host factory establish corresponding evaluation standards of the smell in the passenger car, and aim to respond policies and improve the industry competitiveness.
The improvement of the air quality in the vehicle is a comprehensive system engineering, and parts such as textile fabrics, leather, artificial leather, instrument boards, door protection plates, stand columns, seat protection plates, air conditioner shells and the like in the vehicle contribute to organic volatile matters and odor performance of the air in the vehicle to different degrees, so that the material of each part can meet the requirement to ensure that the indoor air quality of the whole vehicle meets the requirement. The air conditioner shell material is an important link for improving the quality of air in a vehicle, and each host factory puts strict requirements on the air conditioner shell material, so that the air conditioner shell material not only needs to meet high strength and high modulus and molding processability, but also needs to have excellent thermal oxidation aging resistance, low diffusion and low odor. The traditional air conditioner shell material is formed by injection molding of a composite material of polypropylene, talcum powder, a thermoplastic elastomer and an antioxidant, so that basic mechanical strength and injection molding requirements are easily met, but the composite material can emit strong odor of organic volatile matters, even if porous minerals are added into the raw materials of the air conditioner shell to serve as an adsorbent, the effect is still poor, and the quality of air in a vehicle still cannot meet the standard of GB/T27630-2011' evaluation guideline for quality of air in a vehicle.
Therefore, how to develop a low-odor low-emission polypropylene composite material is a problem to be solved urgently today.
Disclosure of Invention
The object of the present invention is to provide a low odor, low emission polypropylene composite having significantly improved emission characteristics.
The invention also aims to provide a preparation method of the polypropylene composite material.
In order to realize the purpose, the following technical scheme is adopted:
the low-odor and low-emission polypropylene composite material comprises the following components in parts by weight:
60-80 parts of polypropylene;
b, 17-23 parts of inorganic filler;
c. 0.1-3 parts of ethanol.
Wherein the weight content of the iron element is 10ppm to 200ppm based on the total weight of the low-odor low-emission polypropylene composite material.
The weight content of the iron element in the low-odor low-emission polypropylene composite material is tested by adopting a microwave digestion-ICP-OES method: weighing 0.1g of crushed sample, placing the crushed sample into a microwave digestion tank, adding 5mL of nitric acid to completely immerse the sample, slowly dripping 1.0mL of hydrogen peroxide, reacting for 2min, covering a cover, sealing the digestion tank, placing the digestion tank into a microwave digestion furnace for digestion, cooling to room temperature, filtering the solution in the digestion tank by using a 0.45-micrometer filter membrane, transferring the solution to a volumetric flask, diluting the solution to 50mL by using distilled water, and testing by using ICP-OES.
The iron element is preferably present in an amount of 20ppm to 160ppm by weight, more preferably 30ppm to 80ppm by weight, based on the total weight of the low odor low emission polypropylene composite.
The iron element is derived from an iron-containing compound, and the iron-containing compound is selected from one or more of ferrous oxide, ferrous sulfate, ferric sulfate, ammonium ferrous sulfate, ferrous nitrate, ferric nitrate, ferrous chloride, ferric oxide or ferroferric oxide.
The melt flow rate of the polypropylene is 0.3-100 g/10min according to ISO 1133 standard under the conditions of 230 ℃ of temperature and 2.16kg of load.
The inorganic filler is selected from one or more of talcum powder, wollastonite, mica powder, calcium carbonate or kaolin.
The low-odor low-emission polypropylene composite material also comprises 2-10 parts of a toughening agent, wherein the toughening agent is one or more of polyethylene, an ethylene-vinyl acetate copolymer, a hydrogenated ethylene-butadiene-styrene copolymer, a styrene-butadiene-styrene triblock copolymer, a hydrogenated styrene-butadiene-styrene triblock copolymer, an ethylene-octene copolymer, ethylene propylene diene monomer rubber or polyurethane, and the melt flow rate of the toughening agent is 0.3-50 g/10min under the conditions of 190 ℃ and 2.16 kg.
The low-odor low-emission polypropylene composite material also comprises 0.2-1 part of lubricant, 0.2-0.8 part of antioxidant and 1-2 parts of adsorbent, wherein the lubricant is selected from one or more of low molecular esters, metal soaps, stearic acid composite esters or amides; the antioxidant is selected from one or more of phenols, amines, phosphites or semi-hindered phenols; the adsorbent is selected from one or two of zeolite or diatomite.
The lubricant can effectively reduce the friction among partial molecules in the melt, between the melt and a screw, and between the melt and the inner wall of the extruder, so that the chain scission degradation of polypropylene is reduced from the source, and the content of small molecule organic volatile matter residues is reduced.
The introduction of the adsorbent plays a role in adsorbing organic matters in the melt extrusion stage, but because most residual micromolecules are extracted in the double-vacuum devolatilization process, the adsorbent does not reach a saturated adsorption state, the volatilization of micromolecule residues can be inhibited in the use process of the material, and the effects of long-acting low emission and low odor are kept.
A preparation method of a low-odor low-emission polypropylene composite material comprises the following steps:
a) adding polypropylene, a toughening agent and ethanol into a high-speed mixer, and mixing for 3-5 minutes, wherein the rotating speed of the high-speed mixer is controlled to be 250-350 r/min;
b) b, putting the material obtained in the step a into a double-screw extruder from a main feeding port, wherein the double-screw extruder is designed in a three-vacuum mode, the vacuum degree is controlled to be less than or equal to-0.05 bar, the length-diameter ratio is 40-60, the temperature of each section is 190-230 ℃, the rotating speed of a screw is controlled to be 300-1000 rpm, the total feeding is controlled to be 100-1000 kg/h, a filter screen is arranged at the head of the double-screw extruder to remove large-particle impurities, and the filter screen is replaced every 6-12 h;
c) adding inorganic filler, a lubricant, an antioxidant, an adsorbent and an iron-containing compound into a double-screw extruder from a side feeding port, performing melt extrusion, bracing, water cooling, granulation, drying and bagging, then placing in a drying tank for drying, setting the temperature at 100-130 ℃, and turning over the materials every 2-4 hours to obtain the composite material.
The filter screen avoids the introduction of large-particle impurities, ensures that the mechanical strength of the material is not reduced, and can effectively avoid thermal oxidation aging failure caused by the impurities; the three-section vacuumizing device greatly improves the devolatilization effect of the organic volatile matters; and in the material drying stage, residual small-molecule volatile matters can be further removed, and the emission characteristic and the odor grade of the material are reduced.
Compared with the prior art, the invention has the following beneficial effects:
the invention discovers that a low-odor and low-emission polypropylene composite material is obtained by adding 0.1-3 parts of ethanol and 10-200ppm of iron element based on the total weight of the polypropylene composite material into 60-80 parts of polypropylene and 17-23 parts of inorganic filler, the emission characteristic of the polypropylene composite material is obviously improved, and the excellent mechanical property and heating property of the polypropylene composite material can be maintained.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
Polypropylene grade: PP H-Z30S, manufacturer: performing petrochemical processing on the Jingmen, and controlling the temperature to be 230 ℃ and the load to be 30.3 g/10min according to the ISO 1133 standard under the condition of 2.16 kg;
toughener, ethylene-octene copolymer, grade: DF610, manufacturer: chemical of three wells;
inorganic filler, talc powder, grade: TYT-777A, manufacturer: the north sea;
antioxidant:
phenolic antioxidants, hindered phenolic antioxidants, designations: 1010, manufacturer: yixing angel synthetic chemistry in the city;
phosphite antioxidant, grade: 168, manufacturer: yixing angel synthetic chemistry in the city;
lubricants, amides, designations: EBS P400, manufacturer: moistening the tip;
adsorbent, diatomaceous earth, trade mark: 535, manufacturer: CELITE;
both ethanol and iron-containing compounds were obtained commercially.
Preparation of polypropylene composites for examples 1-16 and comparative examples 1-3:
weighing polypropylene, a toughening agent and ethanol according to the proportion in the table 1, adding the mixture into a high-speed mixer, and mixing for 3-5 minutes, wherein the rotating speed of the high-speed mixer is controlled to be 250-350 r/min; putting the mixture into a double-screw extruder from a main feeding port, feeding an inorganic filler, an iron-containing compound, a lubricant, an antioxidant and an adsorbent into the double-screw extruder from a side feeding port, performing melt extrusion, bracing, water cooling and granulation, then placing the mixture into a drying tank for drying, setting the temperature to be 100-130 ℃, and turning over the material every 2-4 hours to obtain the low-odor low-emission polypropylene composite material; the double-screw extruder is designed in a triple vacuum mode, the vacuum degree is controlled to be less than or equal to-0.05 bar, the length-diameter ratio is 40-60, the temperature of each section is 190-230 ℃, the rotating speed of a screw is controlled to be 300-1000 rpm, the total feed is controlled to be 100-1000 kg/h, a filter screen is arranged at the head of the double-screw extruder to remove large-particle impurities, and the filter screen is replaced every 6-12 h; the weight content of the iron element is controlled by changing the adding amount of the iron-containing compound.
And (3) performance testing:
(1) density: testing according to ISO 1183;
(2) melt flow rate: testing according to ISO 1133, wherein the temperature is 230 ℃, and the weight is 2.16 kg;
(3) tensile strength: testing according to ISO 527/2, at 23 deg.C, and stretching speed of 50 mm/min;
(4) bending strength: testing according to ISO 178 at 23 deg.C and bending rate of 2 mm/min;
(5) flexural modulus: testing according to ISO 178 at 23 deg.C and bending rate of 2 mm/min;
(6) 23 ℃ notched impact strength: testing according to ISO 180;
(7) unnotched impact strength at 23 ℃: testing according to ISO 180;
(8) heat distortion temperature: the load is 0.45MPa according to ISO 75/2 test;
(9) the content of iron element: and (3) testing by a microwave digestion-ICP-OES method: weighing 0.1g of crushed sample, placing the crushed sample into a microwave digestion tank, adding 5mL of nitric acid to completely immerse the sample, slowly dripping 1.0mL of hydrogen peroxide, reacting for 2min, covering a cover, sealing the digestion tank, placing the digestion tank into a microwave digestion furnace for digestion, cooling to room temperature, filtering the solution in the digestion tank by using a 0.45-micrometer filter membrane, transferring the solution into a volumetric flask, diluting the solution to 50mL by using distilled water, and testing by using ICP-OES; (10) odor grade: testing according to PV 3900, 50g of particles, baking for 2h at 80 ℃, and evaluating at 65 ℃;
(11) VOC: the number of the cells is SJ-NW-39, SJ-NW-42 and SJ-NW-43.
TABLE 1 ingredient ratios (parts by weight) and results of performance tests for examples 1 to 16 and comparative examples 1 to 2
TABLE 1
TABLE 2 VOC test results (. mu.g/m) of examples 1 to 16 and comparative examples 1 to 23）
As can be seen from the data in Table 2, the addition of 0.1 to 3 parts of ethanol and 10ppm to 200ppm of iron element based on the total weight of the low odor polypropylene composite to 60 to 80 parts of polypropylene and 17 to 23 parts of inorganic filler resulted in a low odor polypropylene composite having a significantly reduced VOC content of volatile organic compounds referred to as TVOC of less than 5700 μ g/m3The test data in table 1 shows that the polypropylene composite material has obviously improved emission characteristics and can maintain excellent mechanical properties and heating properties. Compared with the comparative example 1, the weight content of the iron element is less than 10ppm, the weight part of the ethanol is less than 0.1 part, the weight content of the iron element is more than 200ppm, the weight part of the ethanol is more than 3 parts, the VOC content of the volatile organic compounds is obviously reduced and obviously increased, and the indoor organic gaseous substance named as TVOC is more than 7000 mu g/m3The emission characteristics are poor.
Claims (6)
1. The low-odor and low-emission polypropylene composite material is characterized by comprising the following components in parts by weight:
60-80 parts of polypropylene;
b, 17-23 parts of inorganic filler;
c, 0.7-2.5 parts of ethanol; the iron element content is 20ppm to 160ppm by weight based on the total weight of the low-odor low-emission polypropylene composite material,
the iron element is at least one of ferrous sulfate, ferric sulfate, ammonium ferrous sulfate, ferrous nitrate, ferric nitrate, ferrous chloride and ferric chloride;
0.2-1 part of lubricant, 0.2-0.8 part of antioxidant, 1-2 parts of adsorbent and 2-10 parts of toughening agent;
the low-odor low-emission polypropylene composite material is prepared by a double-screw extruder, wherein an adsorbent and an iron-containing compound are added into the double-screw extruder from a side feeding port;
the weight content of the iron element in the low-odor low-emission polypropylene composite material is tested by adopting a microwave digestion-ICP-OES method: weighing 0.1g of crushed sample, placing the crushed sample into a microwave digestion tank, adding 5mL of nitric acid to completely immerse the sample, slowly dripping 1.0mL of hydrogen peroxide, reacting for 2min, covering a cover, sealing the digestion tank, placing the digestion tank into a microwave digestion furnace for digestion, cooling to room temperature, filtering the solution in the digestion tank by using a 0.45-micrometer filter membrane, transferring the solution to a volumetric flask, diluting the solution to 50mL by using distilled water, and testing by using ICP-OES.
2. The low odor, low emission polypropylene composite of claim 1 wherein the elemental iron is present in an amount of from 30ppm to 80ppm by weight based on the total weight of the low odor, low emission polypropylene composite; the weight portion of the ethanol is 1.2-2 portions.
3. The low odor and low emission polypropylene composite material as claimed in claim 1, wherein the melt flow rate of the polypropylene is 0.3 to 100 g/10min at 230 ℃ and 2.16kg according to ISO 1133.
4. The polypropylene composite material of claim 1, wherein the inorganic filler is selected from one or more of talc, wollastonite, mica powder, calcium carbonate and kaolin.
5. The polypropylene composite material of claim 1, wherein the toughening agent is selected from one or more of polyethylene, ethylene-vinyl acetate copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene-butadiene-styrene triblock copolymer, ethylene-octene copolymer, ethylene propylene diene monomer rubber, and polyurethane, and the melt flow rate of the toughening agent is 0.3-50 g/10min at 190 ℃ under 2.16 kg.
6. The polypropylene composite material as claimed in claim 1, wherein the lubricant is selected from one or more of low molecular esters, metal soaps and amides; the antioxidant is selected from one or more of phenols, amines and phosphites; the adsorbent is selected from one or two of zeolite or diatomite.
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| CN115895210A (en) * | 2022-11-29 | 2023-04-04 | 金发科技股份有限公司 | Low-VOC low-odor biodegradable material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4028480A (en) * | 1975-04-17 | 1977-06-07 | Societe Chimique Des Charbonnages - Cdf Chimie | Photodegradable polymer compositions |
| CN103756135A (en) * | 2013-12-30 | 2014-04-30 | 天津金发新材料有限公司 | Environment-friendly flame retardant low-odor modified polypropylene and preparation method and application of modified polypropylene |
| CN104710689A (en) * | 2008-06-27 | 2015-06-17 | 株式会社自动网络技术研究所 | Flame-retardant composition, covered electric wire, and wiring harness |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4028480A (en) * | 1975-04-17 | 1977-06-07 | Societe Chimique Des Charbonnages - Cdf Chimie | Photodegradable polymer compositions |
| CN104710689A (en) * | 2008-06-27 | 2015-06-17 | 株式会社自动网络技术研究所 | Flame-retardant composition, covered electric wire, and wiring harness |
| CN103756135A (en) * | 2013-12-30 | 2014-04-30 | 天津金发新材料有限公司 | Environment-friendly flame retardant low-odor modified polypropylene and preparation method and application of modified polypropylene |
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