CN103571054A - Low VOC polypropylene composite material and preparation and application thereof - Google Patents
Low VOC polypropylene composite material and preparation and application thereof Download PDFInfo
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- CN103571054A CN103571054A CN201310505314.2A CN201310505314A CN103571054A CN 103571054 A CN103571054 A CN 103571054A CN 201310505314 A CN201310505314 A CN 201310505314A CN 103571054 A CN103571054 A CN 103571054A
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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
- C08L23/14—Copolymers of propene
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three 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
- 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
Abstract
The invention discloses a low VOC polypropylene composite material and a preparation method and an application thereof. The material is prepared by polypropylene, a filling agent, a smell removing agent, a scraping-proof agent, an antioxygen, a weather-proof agent and a lubricating agent according to part by weight, wherein the smell removing agent is a water-based solution of a polymer surfactant which is adsorbed on a polypropylene carrier; the used smell removing agent is a novel smell removing agent, the melting point of the smell removing agent is 160 DEG C, the boiling point is higher than 100 DEG C; the smell removing agent has the characteristic that the dispersion is uniform, lots of foam of the fused smell removing agent is generated in an extrusion mixing process, the vacuum devolatilization is clean, residue is not generated and the like. The prepared low VOC polypropylene composite material has the characteristics of being UV resistant, scraping resistant, light in smell, less in the VOC residual volume and the like, and is mainly used on automotive trim materials such as an instrument desk, a door plate and a stand column of an automobile.
Description
Technical field
The present invention relates to the material modified field of automobile, is specifically related to a kind of low VOC polypropylene composite material and preparation and application thereof.
Background technology
Polypropylene modified material, because having good physical and mechanical property and processing characteristics, is widely used in automotive upholstery, comprises major-minor dashboard, door-plate and column etc.But polypropylene modified material is synthetic at starting material, can produce the volatile organic matters such as benzene class, aldehydes and amine (being called for short VOC) in machine-shaping and use weathering process, is detrimental to health.Therefore,, in order to reduce the VOC content in automotive trim PP Pipe Compound, need to control from starting material and complete processing aspect.
Patent CN101691435B has prepared a kind of PP composite material with low VOC and high performance specially used for automotive upholsteries by selecting the hydrogen of low VOC to telomerize propylene, but it has limited the application of polypropylene material, is also unfavorable for eliminating the VOC producing in preparation process.Patent CN101817953B adds a kind of inorganic porous odor adsorption agent and prepares a kind of low modified polypropylene composite material distributing, but these class methods exist the problem of parsing and balance to be also unfavorable for the elimination of VOC.Patent CN101255252B discloses a kind of low-emanation automobile interior trim PP Pipe Compound, uses low molecular carbon Barbiturates to do organism expellent, but it is very difficult compatible with acrylic resin, and VOC removes poor.Patent CN102875895A discloses a kind of low type polypropylene material and its production and use that distributes, and uses lower boiling VOC washing composition and N
2air lift agent, because boiling point is lower, mixing time is shorter, makes washing composition in mixing process, be difficult to reach evenly, is unfavorable for the elimination of VOC.
Summary of the invention
For overcoming the deficiencies in the prior art, object of the present invention is started with from formulating of recipe and two aspects of complete processing simultaneously, and a kind of low VOC polypropylene composite material and preparation method thereof is provided.
The 3rd object of the present invention is to provide the application of above-mentioned low VOC polypropylene composite material on automotive trim.
Technical scheme of the present invention is: a kind of preparation of low VOC polypropylene composite material and application, be prepared from by weight by following raw materials according:
Polypropylene 50-95 part
Toughner 5-15 part
Weighting agent 0-30 part
Smell remover 0.5-2 part
Scratch resistance liniment 1.5-2.5 part
Oxidation inhibitor 0.2-0.8 part
Photostabilizer 0.2-0.4 part
Lubricant 0.3-0.8 part.
Described smell remover is the aqueous solution that is adsorbed on the polymer surfaces active substance in polypropylene carrier.Mainly select the BYK-P 4200 of Bi Ke company, its fusing point is that 160 ℃, boiling point are 200 ℃.
Described polypropylene is at least one in Co-polypropylene, homo-polypropylene.
Described toughner is at least one in ethylene-octene copolymer, terpolymer EP rubber/propylene-alpha olefin multipolymer, propylene-alpha olefin multipolymer, styrene-ethylene-propylene-styrene segmented copolymer.
At least one in described weighting agent talcum powder, calcium carbonate, barium sulfate, wollastonite, mica.
Described scratch resistance liniment is silicone scratch resistance liniment, has scraping and wiping resistance performance excellence, good weatherability, the features such as odorlessness.
Described oxidation inhibitor is at least one in Hinered phenols, monothioester class, phosphorous acid ester type thermal stabilizing agent, Hinered phenols is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), monothioester class is thio-2 acid 2 stearyl ester (oxidation inhibitor DSTP), phosphorous acid esters are tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (irgasfos 168).
Described photostabilizer is hindered amine light stabilizer, the hindered amine light stabilizer CYASORB UV-3808 PP5 or the CYASORB UV-V680 that mainly select Qing Te company to produce.
Described lubricant is selected from least one in polyethylene wax, stearate, ethylene bis stearamide, grafting ethylene bis stearamide.
Another object of the present invention is to provide the preparation method of above-mentioned low VOC polypropylene composite material, comprises the following steps:
(1) by proportioning, take polypropylene, toughner, weighting agent, smell remover, scratch resistance liniment, oxidation inhibitor, photostabilizer and lubricant, add together high mixer high speed to mix 2-10 minute;
(2) mixed material is dropped into melting in parallel double-screw extruder, extruding pelletization, make modified polypropylene composite material; Wherein the barrel zone temperature of forcing machine is 180-230 ℃, and screw speed is 400-600r/min, and melt pressure is 1.5-2.5MPa, and vacuum tightness is-0.04～0.1MPa.
Further, for smell remover is played one's part to the full, front 2 sections of temperature of forcing machine vacuum port will be higher than 200 ℃.And guarantee that vacuum tightness is at-0.04～0.1MPa.
The 3rd object of the present invention is to provide the application of above-mentioned low VOC polypropylene composite material, and it can be used for making in automotive upholstery as dashboard, door-plate, column polypropylene composite material.
Beneficial effect of the present invention:
1, the present invention, by adding smell remover, regulates temperature and the vacuum tightness of forcing machine, reaches the low VOC automotive trim polypropylene composite material of preparation, and technique is simple, workable;
2, the present invention adds smell remover, it is a kind of aqueous solution that is adsorbed on the polymer surfaces active substance in polypropylene carrier, normal temperature is solid powder, fusing point is at 160 ℃, 100 ℃ of boiling point >, have and be uniformly dispersed, after melting, in extruding mixing process, foam is abundant, the features such as vacuum volatilization is clean, noresidue;
3, the polypropylene composite material that the present invention is prepared by adding smell remover, oder levels meets inside gadget >=6 grade requirement, meet≤2mg of the atomization composition of low molecular compound, VOC content is lower, at 120-130 ug/g.Can meet the physical property requirement to polypropylene composite material of dashboard in automotive upholstery, door-plate and column.
Embodiment
For better understanding the present invention, below in conjunction with embodiment, the invention will be further described, but embodiments of the present invention are not limited to this.
The preparation method of embodiment is below as follows:
(1) by proportioning, take polypropylene, toughner, weighting agent, smell remover, scratch resistance liniment, oxidation inhibitor, photostabilizer and lubricant, add together high mixer high speed to mix 2-10 minute;
(2) mixed material is dropped into melting in parallel double-screw extruder, extruding pelletization, make modified polypropylene composite material; Wherein the barrel zone temperature of forcing machine is 180-230 ℃, and screw speed is 400-600r/min, and melt pressure is 1.5-2.5MPa, and vacuum tightness is-0.04～0.1MPa.
Wherein, to select homo-polypropylene and Co-polypropylene be the mixture of 1:4 by weight proportion to polypropylene used;
Toughner is selected ethylene-octene copolymer, terpolymer EP rubber/propylene-alpha olefin multipolymer, propylene-alpha olefin multipolymer or styrene-ethylene-propylene-styrene segmented copolymer;
Smell remover is selected the BYK-P 4200 of Bi Ke company;
Scratch resistance liniment is selected silicone;
Oxidation inhibitor is selected antioxidant 1010 and irgasfos 168 mixture or the oxidation inhibitor DSTP of 1:1 by weight proportion;
Photostabilizer is selected the CYASORB UV-3808 PP5 of hindered amines ，Qing Te company or CYASORB UV-V680;
Lubricant is selected stearate, polyethylene wax, stearate, ethylene bis stearamide or grafting ethylene bis stearamide;
Weighting agent is selected talcum powder, calcium carbonate, barium sulfate, wollastonite or mica.
Preparation Example 1-4 according to the method described above, its composition of raw materials is in Table 1:
Table 1 composition of raw materials (unit: weight part)
| Component/% | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| PP resin | 95 | 77.9 | 63.9 | 50 |
| Toughner | 5 | 8 | 12 | 15 |
| Weighting agent | 0 | 10 | 20 | 30 |
| Smell remover | 1 | 1.5 | 2 | 0.5 |
| Scratch resistance liniment | 1.5 | 2 | 2.5 | 2.5 |
| Oxidation inhibitor | 0.2 | 0.4 | 0.8 | 0.4 |
| Photostabilizer | 0.4 | 0.3 | 0.2 | 0.3 |
| Lubricant | 0.4 | 0.3 | 0.4 | 0.8 |
Material prepared by above-described embodiment carries out injection moulding, and preparation test bars, tests its performance, be shown in Table 2, wherein:
1) tensile strength: according to ISO 527 tests, speed of experiment 50mm/min;
2) flexural strength and modulus: according to ISO 178 tests, speed of experiment 2mm/min;
3) socle girder notched Izod impact strength: according to ISO 180 tests;
4) smell test: according to GMW 3205 tests;
5) atomization measure: according to GMW 3235 tests;
6) scrape resistant test: test according to GMW 14688-10N;
7) VOC test: according to GMW 15634 tests.
Table 2 embodiment 1-4 the performance test results
| Physicals | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength MPa | 19 | 18 | 17 | 17 |
| Flexural strength MPa | 23 | 23 | 22 | 23 |
| Modulus in flexure MPa | 2000 | 1950 | 1800 | 1800 |
| The strong KJ/m of socle girder notch shock 2 | 15 | 20 | 30 | 30 |
| Smell | 6.5 | 6 | 6 | 6.5 |
| Atomization mg | 1.3 | 1.4 | 1.4 | 1.1 |
| Scrape resistant dL | 1.0 | 1.1 | 1.2 | 1.3 |
| VOC ug/g | 123 | 125 | 130 | 120 |
Test result by table 2 embodiment 1-4 can find out, the oder levels of polypropylene composite material prepared by the present invention meets inside gadget >=6 grade requirement, meet≤2mg of the atomization composition of low molecular compound, and VOC content is lower.Talc ratio increases, and reduces the distribution of smell remover on polypropylene matrix material, but little on the result impact of VOC.Above embodiment all can meet the physical property requirement to polypropylene composite material of dashboard in automotive upholstery, door-plate and column.
In order to show better the low VOC performance of polypropylene matrix material of the present invention, by preparation method of the present invention, prepare comparative example 1-2, in comparative example 1, do not add BYK-P 4200 smell removers, in comparative example 2, add inorganic porous diatomite odor adsorption master batch as smell remover, specifically in Table 3:
Table 3 comparative example formulation weight proportioning (unit: %)
| Component/% | Comparative example 1 | Comparative example 2 |
| PP resin | 71.9 | 69.9 |
| Toughner | 10 | 10 |
| Weighting agent | 15 | 15 |
| Smell remover | 0 | 2 |
| Scratch resistance liniment | 2 | 2 |
| Oxidation inhibitor | 0.4 | 0.4 |
| Photostabilizer | 0.3 | 0.3 |
| Lubricant | 0.4 | 0.4 |
Material prepared by above-mentioned comparative example 1-2 carries out injection moulding, tests its performance as shown in table 4 according to preorder testing method:
Table 4 comparative example test result
| Physicals | Comparative example 1 | Comparative example 2 |
| Tensile strength MPa | 18 | 18 |
| Flexural strength MPa | 23 | 24 |
| Modulus in flexure MPa | 1900 | 1912 |
| The strong KJ/m of socle girder notch shock 2 | 15 | 14 |
| Oder levels | 5 | 5.7 |
| Atomization mg | 4 | 3.4 |
| Scrape resistant dL | 1.1 | 1.0 |
| VOC ug/g | 244 | 216 |
From table 4 comparative example 1-2 test result, can find out, not add BYK-P 4200 smell removers or add VOC and the smell of polypropylene material prepared by inorganic porous diatomite odor adsorption master batch all obviously not to meet the requirement of automotive upholstery to VOC.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. a low VOC polypropylene composite material, is characterized in that: by following raw materials according, be prepared from by weight:
Polypropylene 50-95 part
Toughner 5-15 part
Weighting agent 0-30 part
Smell remover 0.5-2 part
Scratch resistance liniment 1.5-2.5 part
Oxidation inhibitor 0.2-0.8 part
Photostabilizer 0.2-0.4 part
Lubricant 0.3-0.8 part
Described smell remover is the aqueous solution that is adsorbed on the polymer surfaces active substance in polypropylene carrier.
2. a kind of low VOC polypropylene composite material according to claim 1, is characterized in that: described polypropylene is at least one in Co-polypropylene, homo-polypropylene.
3. a kind of low VOC polypropylene composite material according to claim 1, is characterized in that: described toughner is at least one in ethylene-octene copolymer, terpolymer EP rubber/propylene-alpha olefin multipolymer, propylene-alpha olefin multipolymer, styrene-ethylene-propylene-styrene segmented copolymer.
4. a kind of low VOC polypropylene composite material according to claim 1, is characterized in that: at least one in described weighting agent talcum powder, calcium carbonate, barium sulfate, wollastonite, mica.
5. a kind of low VOC polypropylene composite material according to claim 1, is characterized in that: described scratch resistance liniment is silicone scratch resistance liniment.
6. a kind of low VOC polypropylene composite material according to claim 1, is characterized in that: described oxidation inhibitor is at least one in Hinered phenols, monothioester class, phosphorous acid ester type thermal stabilizing agent; Described Hinered phenols is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and monothioester class is thio-2 acid 2 stearyl ester, and phosphorous acid esters are tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
7. a kind of low VOC polypropylene composite material according to claim 1, is characterized in that: described photostabilizer is hindered amine light stabilizer.
8. a kind of low VOC polypropylene composite material according to claim 1, is characterized in that: described lubricant is selected from least one in polyethylene wax, stearate, ethylene bis stearamide, grafting ethylene bis stearamide.
9. a method of preparing the low VOC polypropylene composite material as described in claim 1-8 any one, is characterized in that: comprise the following steps:
(1) by proportioning, take polypropylene, toughner, weighting agent, smell remover, scratch resistance liniment, oxidation inhibitor, photostabilizer and lubricant, add together high mixer high speed to mix 2-10 minute;
(2) mixed material is dropped into melting in parallel double-screw extruder, extruding pelletization, make modified polypropylene composite material; Wherein the barrel zone temperature of forcing machine is 180-230 ℃, and screw speed is 400-600r/min, and melt pressure is 1.5-2.5MPa, and vacuum tightness is-0.04～0.1MPa.
10. an application for a kind of low VOC polypropylene composite material as described in claim 1-9 any one, is characterized in that: described low VOC polypropylene composite material is used for making automotive upholstery.
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