CN103589072B - A kind of low VOC polypropylene composite material for automotive upholstery and preparation method thereof - Google Patents
A kind of low VOC polypropylene composite material for automotive upholstery and preparation method thereof Download PDFInfo
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- 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
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- 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
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- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
The present invention and a kind of low VOC polypropylene composite material for automotive upholstery and preparation method thereof, low VOC polypropylene composite material is by polypropylene, high-density polyethylene resin, weighting agent, toughner, odour absorbents, oxidation inhibitor, lubricant, photostabilizer by weight through mixing, the granulation of two vacuum parallel double-screw extruder, and pellet being put into baking oven, to carry out ovens dry obtained.The VOC content of the polypropylene composite material that the present invention obtains is low, meets the technical requirements of in-car air quality evaluation guide, is applicable to use on automotive upholstery, improves its use range, and reduces automobile production cost, meets its light-weighted requirement.
Description
Technical field
The present invention relates to technical field of macromolecules, be specifically related to a kind of low VOC polypropylene composite material for automotive upholstery and preparation method thereof.
Background technology
Polypropylene due to synthetic method simple, and have abundant raw material source, cheap, have good physical and mechanical property and processing characteristics, thus become one of the fastest kind of plastics increase of production, its output accounts for the 3rd in five large general-purpose plastics.
Good Heat-resistance, the flexural fatigue resistance of polypropylene (PP) are good, price is low, is widely used in automobile industry.But the shortcomings such as PP impelling strength is low and creep resistance is poor, molding shrinkage is large, dimensional stability is bad; Particularly polypropylene composite material is generally also containing certain smell, and smell source is mainly from the micromolecular compound that the thermal-oxidative degradation in the dissolvent residual added in catalyst residue, monomeric compound production process in polymerization process and the course of processing produces.It has had a strong impact on in-car air quality, seriously prosperously can injure the healthy of officer and passenger inside the vehicle.Above-mentioned shortcoming limits the use of polypropylene composite material, considerably limit the use of polypropylene on the goods that odor profiles requirement is higher, particularly to long-term use of placing out of doors on goods and automobile product, therefore must improve polyacrylic odor properties and just can widen polyacrylic range of application.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of low VOC polypropylene composite material for automotive upholstery and preparation method thereof.The polypropylene composite material of preparation has the features such as low VOC, scrape resistant, weathering, mechanical property are strong, and the feature such as comprehensive cost is excellent.
Technical scheme of the present invention is: a kind of low VOC polypropylene composite material, is made up of by weight following raw materials according:
PP resin 49.6-93.1 part
High-density polyethylene resin (HDPE) 5.0-8.0 part
Toughner 0-15 part
Weighting agent 0-20 part
Oxidation inhibitor 0.2-1 part
Odour absorbents 1.0-5.0 part
Lubricant 0.5-1 part
Photostabilizer 0.2-0.4 part.
The preferred version of such scheme is, described PP resin 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 block copolymer.
At least one in described weighting agent talcum powder, calcium carbonate, barium sulfate, wollastonite, mica
At least one in described odour absorbents gac, porous silica, porous alumina, porous molecular screen
Described oxidation inhibitor is at least one in Hinered phenols, monothioester class, phosphorous acid ester type thermal stabilizing agent.Wherein 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 lubricant is selected from polyethylene wax (PE wax), stearate comprises calcium stearate (CaSt), at least one in Zinic stearas (ZnSt), ethylene bis stearamide (EBS), grafting ethylene bis stearamide (TAF).
Described photostabilizer is hindered amine light stabilizer, mainly selects Qing Te company CYASORBUV-3808PP5 or CYASORBUV-V680.
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) take PP resin, toughner, odour absorbents, weighting agent, oxidation inhibitor, lubricant and photostabilizer by proportioning, add high mixer high speed mixing 2-10 minute together;
(2) mixed material is dropped into melting in two vacuum parallel double-screw extruder, extruding pelletization; Wherein the barrel zone temperature of forcing machine is 180-230 DEG C, and screw speed is 400-600r/min, and melt pressure is 1.5-2.5MPa, and vacuum tightness is-0.04 ~ 0.1MPa;
(3) pellet in (2) is put into baking oven, bake out temperature is 85 ± 5 DEG C, and the time is 3 ± 0.2h, obtains low VOC modified polypropylene composite material.
Low VOC polypropylene composite material of the present invention has following beneficial effect relative to prior art:
1, the present invention adopts gac, porous silica, porous alumina or porous molecular screen physics odour absorbents to prepare polypropylene composite material, polypropylene composite material is made to have low distribution performance, polyacrylic Application Areas can be widened, the use especially on automotive field.
2, preparation method of the present invention is simple, cost is low, high efficiency.
3, the present invention adopts HDPE, makes polypropylene composite material have good rigidity-toughness balanced performance, has better improvement to the moulding process of polypropylene composite material and outward appearance.
4, the present invention adopts two vacuum parallel double-screw extruder to carry out extruding pelletization, and pellet is put into baking oven again and dry, make the VOC content of the polypropylene composite material obtained low, meet the technical requirements of in-car air quality evaluation guide, be applicable to use on automotive upholstery, improve its use range, and reduce automobile production cost, meet its light-weighted requirement.
Embodiment
Embodiment 1:
Low VOC polypropylene composite material in this example is made up of by weight following raw materials according:
Co-polypropylene 78.1 parts
Homo-polypropylene 15 parts
High-density polyethylene resin (HDPE) 5 parts
Antioxidant 1076 0.3 part
Irgasfos 168 0.2 part
Gac 1.0 parts
Ethylene bis stearamide 0.5 part
CYASORBUV-3808PP5 0.3 part
Concrete preparation method comprises the following steps:
(1) the above-mentioned raw material that measures is added high mixer high speed together and mixes 5 minutes;
(2) mixed material is dropped into melting in two vacuum parallel double-screw extruder, extruding pelletization, obtained modified polypropylene composite material; Wherein the barrel zone temperature of forcing machine is 220 DEG C, and screw speed is 450r/min, and melt pressure is 2.0MPa, and vacuum tightness is 0.05MPa.
(3) particle good for extruding pelletization is passed through vacuum drying oven, under temperature is 85 DEG C of conditions, dries 3h.
Comparative example 1: raw material is with embodiment 1, and difference is only that forcing machine does not carry out drying and processing by vacuum drying oven after extruding.
Embodiment 2:
Low VOC polypropylene composite material in this example is made up of by weight following raw materials according:
Co-polypropylene 49.6 parts
High-density polyethylene resin (HDPE) 8.0 parts
Ethylene-octene copolymer 15 parts
Talcum powder 15 parts
Irgasfos 168 0.2 part
Porous silica 2.0 parts
Calcium stearate 0.8 part
CYASORBUV-3808PP5 0.2 part
Concrete preparation method comprises the following steps:
(1) the above-mentioned each raw material measured is added high mixer high speed together and mix 8 minutes;
(2) mixed material is dropped into melting in two vacuum parallel double-screw extruder, extruding pelletization, obtained modified polypropylene composite material; Wherein the barrel zone temperature of forcing machine is 180 DEG C, and screw speed is 400r/min, and melt pressure is 1.5MPa, and vacuum tightness is 0.01MPa
(3) particle good for extruding pelletization is passed through vacuum drying oven, be 80 DEG C in temperature, the time is dry under 2.8h condition.
Embodiment 3:
Low VOC polypropylene composite material in this example is made up of by weight following raw materials according:
Co-polypropylene 40 parts
Co-polypropylene 20 parts
High-density polyethylene resin (HDPE) 7 parts
Terpolymer EP rubber/propylene-alpha olefin copolymer 10 part
Wollastonite 10 parts
10 parts, mica
Antioxidant 1076 0.3 part
Irgasfos 168 0.2 part
Porous molecular screen 3.0 parts
Polyethylene wax 0.5 part
CYASORBUV-V680 0.4 part
Concrete preparation method comprises the following steps:
(1) the above-mentioned each raw material measured is added high mixer high speed together and mix 2 minutes;
(2) mixed material is dropped into melting in two vacuum parallel double-screw extruder, extruding pelletization, obtained modified polypropylene composite material; Wherein the barrel zone temperature of forcing machine is 230 DEG C, and screw speed is 500r/min, and melt pressure is 2.0MPa, and vacuum tightness is-0.04MPa
(3) particle good for extruding pelletization is passed through vacuum drying oven, be 85 DEG C in temperature, the time is dry under 3h condition.
Embodiment 4:
Low VOC polypropylene composite material in this example is made up of by weight following raw materials according:
PP resin (Co-polypropylene) 25 parts
PP resin (Co-polypropylene) 30 parts
High-density polyethylene resin (HDPE) 7 parts
Ethylene-octene copolymer 10 parts
Propylene-alpha olefin multipolymer 5 parts
20 parts, barium sulfate
Oxidation inhibitor DSTP 0.5 part
Irgasfos 168 0.5 part
Porous silica 3.0 parts
Porous alumina 2.0 parts
Calcium stearate 0.5 part
Zinic stearas 0.5 part
CYASORBUV-V680 0.4 part
Concrete preparation method comprises the following steps:
(1) the above-mentioned each raw material measured is added high mixer high speed together and mix 10 minutes;
(2) mixed material is dropped into melting in two vacuum parallel double-screw extruder, extruding pelletization, obtained modified polypropylene composite material; Wherein the barrel zone temperature of forcing machine is 200 DEG C, and screw speed is 600r/min, and melt pressure is 2.5MPa, and vacuum tightness is 0.1MPa.
(3) particle good for extruding pelletization is passed through vacuum drying oven, under temperature is 90 DEG C of conditions, dries 3.2h.
Comparative example 2: raw material is with embodiment 4, and difference is only that mixture does not also carry out drying and processing by vacuum drying oven after being extruded by single vacuum parallel double-screw extruder.
Choosing embodiment 1-4 and comparative example 1-2 reports the polypropylene composite material prepared respectively to get one, tests its VOC, specifically see the following form according to Air Quality Evaluation guide in GB_T_27630-2011_ passenger car:
| Physicals (GB) | Embodiment 1 | Comparative example 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 2 |
| Benzene mg/m3 | ND | ND | ND | ND | ND | ND |
| Toluene mg/m3 | ND | 1.4 | 0.9 | ND | ND | ND |
| Ethylbenzene mg/m3 | 0.9 | 2.0 | 0.8 | 0.7 | 0.1 | 0.5 |
| Dimethylbenzene mg/m3 | 0.8 | 1.8 | 0.5 | 0.3 | 0.1 | 23.5 |
| Vinylbenzene mg/m3 | 0.1 | 0.5 | ND | ND | ND | 5 |
| Formaldehyde mg/m3 | ND | 0.13 | 0.08 | ND | ND | 2.5 |
| Acetaldehyde mg/m3 | ND | ND | 0.05 | ND | ND | 3.0 |
| Propenal mg/m3 | ND | ND | ND | ND | ND | ND |
Note: in table, ND represents and do not detect this material.
Contrast from the VOC test result of the embodiment 1-4 in upper table and comparative example 1-2 and find out, the present invention adopts adsorbent to carry out extruding processing at two vacuum extruding equipment, and after the particle extruded is carried out drying and processing, obviously can reduce volatile content and odor properties in polypropylene composite material.
Embodiment 1-4 different from the preparation method of comparative example 1-2 to cause preparing VOC detected result in the polypropylene composite material of gained different, the present invention adopts two vacuum-extruder to carry out extruding pelletization, and then carry out baking material by baking oven, its final polypropylene composite material can reach Air Quality Evaluation guide techniques requirement in GB_T_27630-2011_ passenger car.And use single vacuum or do not dry material process, then the VOC test in polypropylene composite material is for defective.Shown in table specific as follows:
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (9)
1., for a low VOC polypropylene composite material for automotive upholstery, it is characterized in that: be made up of by weight following raw materials according:
PP resin 49.6-93.1 part
High-density polyethylene resin 5.0-8.0 part
Toughner 0-15 part
Weighting agent 0-25 part
Oxidation inhibitor 0.2-1 part
Odour absorbents 1.0-5.0 part
Lubricant 0.5-1 part
Photostabilizer 0.2-0.4 part;
(1) take PP resin, toughner, weighting agent, oxidation inhibitor, odour absorbents, lubricant and photostabilizer by proportioning, add high mixer high speed mixing 2-10 minute together;
(2) mixed material is dropped into melting in two vacuum parallel double-screw extruder, extruding pelletization; Wherein the barrel zone temperature of forcing machine is 180-230 DEG C, and screw speed is 400-600r/min, and melt pressure is 1.5-2.5MPa, and vacuum tightness is-0.04 ~ 0.1MPa;
(3) pellet in (2) is put into baking oven, bake out temperature is 85 ± 5 DEG C, and the time is 3 ± 0.2h, obtains low VOC modified polypropylene composite material.
2. low VOC polypropylene composite material according to claim 1, is characterized in that: described PP resin is at least one in Co-polypropylene, homo-polypropylene.
3. 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 block copolymer.
4. low VOC polypropylene composite material according to claim 1, is characterized in that: described odour absorbents is at least one in gac, porous silica, porous alumina, porous molecular screen.
5. low VOC polypropylene composite material according to claim 1, is characterized in that: described weighting agent is at least one in talcum powder, calcium carbonate, barium sulfate, wollastonite, mica.
6. 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.
7. low VOC polypropylene composite material according to claim 6, is characterized in that: described Hinered phenols is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Monothioester class is monothioester class is thio-2 acid 2 stearyl ester; Phosphorous acid esters are tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
8. 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. low VOC polypropylene composite material according to claim 1, is characterized in that: described photostabilizer is hindered amine light stabilizer.
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| CN104119615A (en) * | 2014-07-23 | 2014-10-29 | 广东聚石化学股份有限公司 | Low-TVOC (Total Volatile Organic Compound) and low-luster polypropylene composite for automotive interior trim and preparation method of low-TVOC and low-luster polypropylene composite |
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