CN106243483B - A kind of zero VOC polypropylene material and its preparation process - Google Patents

A kind of zero VOC polypropylene material and its preparation process Download PDF

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Publication number
CN106243483B
CN106243483B CN201610767743.0A CN201610767743A CN106243483B CN 106243483 B CN106243483 B CN 106243483B CN 201610767743 A CN201610767743 A CN 201610767743A CN 106243483 B CN106243483 B CN 106243483B
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polypropylene
preparation process
voc
supercritical fluid
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CN106243483A (en
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胡林
张奎
李荣群
徐剑
汪鹏程
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Orinko Advanced Plastics 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
    • 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
    • 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
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • 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
    • 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
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • 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
    • C08L2207/066—LDPE (radical process)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of zero VOC polypropylene material and its preparation process, material is made of the raw material of following parts by weight：60-65 parts of polypropylene, 10-15 parts of toughener, 20-25 parts of talcum powder, 0.5-0.8 parts of antioxidant, 0.3-0.5 parts of light stabilizer, 2-4 parts of scratch resistance liniment, 0.2-0.4 parts of lubricant, 1-3 parts of toner；Supercritical fluid is introduced in preparation process as reaction carriers, by its powerful infiltration and solvability, the volatile small molecule in fluid-absorbent.Meanwhile using domestic raw materials formula system, instead of currently used extensive import formula for raw stock system.Under the premise of ensureing material smell and VOC performances, cost is reduced, the competitiveness of product is improved.It is discharged by vaccum exhaust outlet.Nontoxic, there are no pollution to the environment, has huge popularization potential quality.

Description

A kind of zero VOC polypropylene material and its preparation process
Technical field
The invention belongs to automotive interior material domain technology fields, and in particular to a kind of zero VOC polypropylene material and its Preparation process.
Background technology
Currently, the environmental protection of automotive material is the popular direction of auto manufacturing.Wherein, orthodox car material exists easy The problems such as volatile organic compounds discharge capacity is larger, and in-vehicle air is poor limits the popularization of automotive interior material.Meanwhile it is volatile Organic matter can have toxic and harmful gas, have very big harm to the health of people.With constantly carrying for people's environmental consciousness Height, the low VOC polypropylene of automobile is increasingly by the concern and application of major main engine plants.
Currently, the related research result about the low VOC polypropylene materials of automobile has very much.Publication No.
The patent of CN104403204.A discloses a kind of preparation method of low VOC polypropylene materials, and the preparation method is poly- Polypropylene formulations introduce molecular sieve, by the adsorption capacity of molecular sieve, remove small molecule volatile matter.Publication No. CN The patent of 103304893.A discloses a kind of low VOC polypropylene composition and preparation method thereof, which matches in polypropylene Fully sulfurized silicon rubber powder and Benzopyranone kind free radical scavenger are added in side, inhibits polypropylene to exist by the two components Because of heat, the small molecule volatile matter of oxygen and mechanical degradation generation in process.The patent of Publication No. CN 102049823.A is public A kind of low preparation method for distributing polypropylene and its complex particle is opened.The preparation method mixes complex particle with water, Heating rotation is carried out in closed rotary funace, and the small molecule volatile matter in material is made to exclude in water, to prepare It is low to distribute polypropylene material.
But currently, in the prior art automotive trim with low VOC polypropylene materials generally existing production technology complexity, cost It is higher, the problems such as efficiency is low and product stability is poor.Therefore, it is necessary to by other methods come reduce the manufacturing of product at This, improves production efficiency and stable prod performance.
Invention content
The present invention proposes a kind of zero VOC polypropylene material and its preparation process, introduces supercritical fluid as anti- Carrier is answered, by its powerful infiltration and solvability, the volatile small molecule in fluid-absorbent.Meanwhile using domestic former material Material formula system, instead of currently used extensive import formula for raw stock system.In the premise for ensureing material smell and VOC performances Under, cost is reduced, the competitiveness of product is improved.It is discharged by vaccum exhaust outlet.Nontoxic, there are no pollution to the environment, With huge popularization potential quality.
The invention discloses a kind of zero VOC polypropylene materials, are made of the raw material of following parts by weight：Polypropylene 60-65 Part, 10-15 parts of toughener, 20-25 parts of talcum powder, 0.5-0.8 parts of antioxidant, 0.3-0.5 parts of light stabilizer, scratch resistance liniment 2-4 Part, 0.2-0.4 parts of lubricant, 1-3 parts of toner.
Preferably, it is made of the raw material of following parts by weight：61-64 parts of polypropylene, 12-14 parts of toughener, talcum powder 22- 24 parts, 0.6-0.7 parts of antioxidant, 0.35-0.45 parts of light stabilizer, 2.5-3.5 parts of scratch resistance liniment, 0.25-0.35 parts of lubricant, 1.5-2.5 parts of toner.
Any of the above-described scheme is preferably, and the polypropylene is at least one of copolymer polypropylene, high impact resistance polypropylene. Manufacturer is Yanshan Petrochemical, Yangtze petrochemical industry, Maoming Petrochemical etc..
Any of the above-described scheme is preferably, and the toughener is at least one of POE, EPDM, HDPE, LDPE.
Any of the above-described scheme is preferably, and the mesh number of the talcum powder is 3000-5000 mesh.
Any of the above-described scheme is preferably, and the antioxidant is in Hinered phenols, thioesters, phosphite ester kind antioxidant At least one.
Any of the above-described scheme is preferably, and the light stabilizer is hindered amine light stabilizer.
Any of the above-described scheme is preferably, the hindered amine light stabilizer be 3808PP5, V680 and V703 at least It is a kind of.
Any of the above-described scheme is preferably, and the liniment of scraping is that silicone scrapes liniment.
Any of the above-described scheme is preferably, the silicone scrape liniment be DOW CORNING MB50-001 and LYSI-306 in extremely Few one kind
Any of the above-described scheme is preferably, and the lubricant is polyethylene wax, stearate, ethylene bis stearamide, connects At least one of branch ethylene bis stearamide.
Any of the above-described scheme is preferably, and the toner is inorganic toner.
Invention additionally discloses a kind of preparation processes of zero VOC polypropylene material described above, which is characterized in that including Following steps：
Step (1) according to formula rate by polypropylene, toughener, talcum powder, antioxidant, light stabilizer, scratch resistance liniment, Lubricant, toner are added to high speed mixing smelting machine high speed and mix 5-10 minutes together.
Mixed material is added to through main feeding in double screw extruder by step (2) to be melted, and shooting flow is passed through Body, extruding pelletization, and excluded lower-molecular substance by high-vacuum pump；
Step (3) is by step (2) well-mixed raw material through double screw extruder melting, mixing, extrusion, cooling, pelletizing And packaging.
Preferably, supercritical fluid is imported by high-pressure metering pump in the step (2), while ensures the maximum of barrel It bears pressure and is more than or equal to 7MPa, and screw combinations are adjusted, supercritical fluid is made to be filled with melt polypropylene in barrel Divide mixing, adsorbs the small molecule in melt to the greatest extent, detached away finally by high-vacuum pump, to improve polypropylene material The VOC performances of material.
Any of the above-described scheme is preferably, and the supercritical fluid is supercritical carbon dioxide, supercritical nitrogen or super Any one in critical.
Any of the above-described scheme is preferably, and the barrel temperature of double screw extruder is 190-220 DEG C in the step (2), Screw speed is 300-500r/min, vacuum degree 0.08-0.1MPa.
Beneficial effects of the present invention are as follows：A kind of zero VOC polypropylene material and its preparation process are provided,
(1) reduces cost, improves the competitiveness of product under the premise of ensureing material smell and VOC performances；
(2) is discharged by vaccum exhaust outlet；
(3) preparation processes, nontoxic, there are no pollution to the environment, has huge popularization potential quality；
(4) raw material used in is domestic raw materials, is derived from a wealth of sources, cheap, is less than the low VOC former materials of commercially available import Material；
(5) improves the VOC performances of material using supercritical fluid, and improvement is apparent, and the VOC performances of product are low In the standard of mainstream automotive factory, meet the needs of customers.
Specific implementation mode
Following embodiments are further explanations for the content of present invention using as the explaination to the technology of the present invention content, but The present invention substantive content be not limited in described in following embodiments, those skilled in the art can with and should know appoint What simple change or replacement based on true spirit should all belong to protection domain of the presently claimed invention.
Embodiment one
1) by domestic polypropylene：60-65 parts；Toughener：10-15 parts, talcum powder：20-25 parts；Antioxidant：0.5-0.8 Part；Light stabilizer：0.3-0.5 parts；Lubricant：0.2-0.4 parts；2-4 parts of scratch resistance liniment, toner：1-3 parts are added to high speed together Kneading machine high speed mixes 5-10 minutes.
2) mixed material is added to through main feeding in tampered double screw extruder and is melted, be passed through 50m3/h Supercritical fluid, extruding pelletization, and being excluded lower-molecular substance by high-vacuum pump.Wherein, barrel temperature 190-220 DEG C, screw speed 300-500r/min, vacuum degree is：0.08~0.1MPa.Main performance index such as table in embodiment one Shown in one.
Main performance index in one embodiment one of table
Performance comparison Conventional material performance Using special process material property
Smell (grade) 4.5 3.5
Total carbon (ugC/g) 138.3 35.6
Benzene (μ g/m3) ND ND
Toluene (μ g/m3) 133.2 18
Dimethylbenzene (μ g/m3) 331.6 16
Formaldehyde (μ g/m3) 14.9 ND
Acetaldehyde (μ g/m3) 38.3 13
TVOC(μg/m3) 34521 7893
From embodiment as can be seen that using supercritical fluid special process method produce low VOC polypropylene materials, in gas Taste, VOC, total carbon test data in, better than conventional polypropylene material.Meet the management and control requirement of mainstream automotive.
Embodiment two
Invention additionally discloses a kind of preparation processes of zero VOC polypropylene material, include the following steps：
Step (1) according to formula rate by 61-64 parts of copolymer polypropylene, POE12-14 parts, 22-24 parts of talcum powder, phosphorous 0.6-0.7 parts of acid esters kind antioxidant, 0.35-0.45 parts of hindered amine light stabilizer, silicone scrape 2.5-3.5 parts of liniment, poly- second 0.25-0.35 parts of alkene wax, inorganic toner 1.5-2.5 parts are added to high speed mixing smelting machine high speed and mix 5-10 minutes together.Talcum The mesh number of powder is 4000 mesh；
Mixed material is added to through main feeding in double screw extruder by step (2) to be melted, and is passed through overcritical two Carbonoxide, extruding pelletization, and excluded lower-molecular substance by high-vacuum pump；To section, grand 75 machine is improved again, introduces high pressure Metering pump, and it is mounted on the 4th section, supercritical carbon dioxide is imported by high-pressure metering pump.Extruding machine barrel and screw rod are carried out Repacking, improves the bearing capacity of barrel, so that barrel maximum is born pressure and is more than or equal to 7MPa.Meanwhile screw combinations are adjusted It is whole, so that supercritical carbon dioxide is sufficiently mixed with melt polypropylene in barrel, adsorbs the small molecule in melt to the greatest extent, And detached away by high-vacuum pump, to improve the VOC performances of polypropylene material.The barrel temperature of double screw extruder is 190-220 DEG C, screw speed 300-500r/min, vacuum degree is 0.08~0.1MPa；
Step (3) is by step (2) well-mixed raw material through double screw extruder melting, mixing, extrusion, cooling, pelletizing And packaging.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Technical solution, all should be in the protection domain being defined in the patent claims.

Claims (2)

1. a kind of preparation process of zero VOC polypropylene material, which is characterized in that include the following steps：
Step（1）According to formula rate by polypropylene, toughener, talcum powder, antioxidant, light stabilizer, scratch resistance liniment, lubrication Agent, toner are added to the mixing of high speed mixing smelting machine high speed together；
Step（2）Mixed material is added to through main feeding in double screw extruder and is melted, be passed through supercritical fluid, Extruding pelletization, and excluded lower-molecular substance by high-vacuum pump；
Step（3）By step（2）Well-mixed raw material is through double screw extruder melting, mixing, extrusion, cooling, pelletizing and packet Dress；The zero VOC polypropylene material, is made of the raw material of following parts by weight：60-65 parts of polypropylene, toughener 10-15 Part, 20-25 parts of talcum powder, 0.5-0.8 parts of antioxidant, 0.3-0.5 parts of light stabilizer, 2-4 parts of scratch resistance liniment, lubricant 0.2- 0.4 part, 1-3 parts of toner.
2. the preparation process of zero VOC polypropylene material according to claim 1, which is characterized in that step（2）In pass through High-pressure metering pump imports supercritical fluid, while ensureing that the maximum of barrel bears pressure and is more than or equal to 7MPa, and to screw combinations It is adjusted, supercritical fluid is made to be sufficiently mixed with melt polypropylene in barrel, adsorb small point in melt to the greatest extent Son detaches away finally by high-vacuum pump, to improve the VOC performances of polypropylene material.
CN201610767743.0A 2016-08-29 2016-08-29 A kind of zero VOC polypropylene material and its preparation process Active CN106243483B (en)

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CN108727660A (en) * 2017-04-20 2018-11-02 中国石化扬子石油化工有限公司 A kind of preparation method of low smell polyethylene composition
CN108727683A (en) * 2017-04-20 2018-11-02 中国石化扬子石油化工有限公司 A kind of preparation method of polypropene composition
CN108727661A (en) * 2017-04-20 2018-11-02 中国石化扬子石油化工有限公司 A kind of preparation method of bottle cap polyethylene composition
CN107090128B (en) * 2017-05-13 2021-01-01 会通新材料股份有限公司 Method for preparing supercritical low-odor low-emission polypropylene material
WO2018218467A1 (en) * 2017-05-29 2018-12-06 Dow Global Technologies Llc Thermoplastic polyolefin compositions useful for aldehyde abatement
CN107558209B (en) * 2017-07-28 2020-05-29 上海工程技术大学 By using supercritical CO2Method for organically modifying aramid fibers by fluid technology
CN107522953A (en) * 2017-09-07 2017-12-29 王虎林 A kind of zero VOC polypropylene material and its preparation technology
CN108822399A (en) * 2018-06-01 2018-11-16 上海加略实业有限公司 PP composite material, the processing unit (plant) of PP composite material and preparation method
CN108891004B (en) * 2018-08-31 2020-05-08 安徽纽麦特新材料科技股份有限公司 Polypropylene composite material extrusion device and use method thereof
WO2020107303A1 (en) * 2018-11-29 2020-06-04 Dow Global Technologies Llc Thermoplastic polyolefin compositions useful for odor reduction
CN112480593A (en) * 2020-11-25 2021-03-12 北方华锦化学工业股份有限公司 Heat-resistant low-odor bulk ABS composite material and preparation method thereof
CN112662114B (en) * 2020-12-18 2023-09-29 金旸（厦门）新材料科技有限公司 Low-odor low-VOC scratch-resistant polypropylene interior material for vehicle and preparation method thereof
CN113754953B (en) * 2021-08-11 2023-10-13 常州福隆科技新材料有限公司 Preparation method and application of clean and odorless polypropylene
CN114479272A (en) * 2022-01-25 2022-05-13 南京聚隆科技股份有限公司 Low-odor automobile interior material and preparation method thereof
CN115431433A (en) * 2022-08-11 2022-12-06 北方华锦化学工业股份有限公司 Device and process for preparing low-VOC-content ABS resin by using water as supercritical fluid

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CN105037955A (en) * 2015-08-19 2015-11-11 绍兴佳华高分子材料股份有限公司 Polypropylene composition with low VOC (volatile organic compounds), scratch resistance and stress whitening resistance and preparation method of polypropylene composition

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