CN108178878A - A kind of odor adsorption type functional agglomerate and preparation method and the automotive trim PP composite material being made from it - Google Patents
A kind of odor adsorption type functional agglomerate and preparation method and the automotive trim PP composite material being made from it Download PDFInfo
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- CN108178878A CN108178878A CN201711447902.XA CN201711447902A CN108178878A CN 108178878 A CN108178878 A CN 108178878A CN 201711447902 A CN201711447902 A CN 201711447902A CN 108178878 A CN108178878 A CN 108178878A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K7/00—Use of ingredients characterised by shape
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Abstract
The invention discloses a kind of odor adsorption type functional agglomerate and preparation method and the automotive trim PP composite materials being made from it, and count in parts by weight, including following component：35 75 parts of polypropylene, 20 50 parts of diatomite, 2 20 parts of adsorbent, 0.2 2 parts of surface conditioning agent, 0.2 2 parts of antioxidant.The characteristics of present invention is using diatomite porosity height, large specific surface area, with adsorbent by chelating aldoketones molecule, generate synergistic sorption effect, the small-molecule substance that polypropylene can be decomposed to generation during high-temperature fusion is adsorbed in diatomaceous hole so that odor adsorption type functional agglomerate obtained has excellent odor adsorption effect；The odor adsorption type functional agglomerate obtained is added in the automotive trim PP composite material being made from it, can not only reduce the smell of material, improves the problem that distributes of material, while the heat resistance of material is also obviously improved.
Description
Technical field
The present invention relates to polymer modifications and processing technique field, and in particular to a kind of odor adsorption type functional agglomerate and its
Preparation method also relates to the automotive trim PP composite material being made of the odor adsorption type functional agglomerate.
Background technology
As one kind in general-purpose plastics, polypropylene is because with preferable moulding processability and excellent chemically-resistant, resistance to
The advantages that corrosion, at the same it is light inexpensive, it is widely used in the industries such as inner and outer decorative parts of automobile, household electrical appliance and electronic component, is
The most fast universal thermoplastic of growth rate at present.But since polypropylene is in molding process, by thermal history and
The shearing course of screw rod can degrade and generate aldoketones small-molecule substance；The auxiliary agent added in simultaneously can also be gone through in thermal history and shearing
Small-molecule substance is given out under Cheng Zuoyong.During automotive upholstery is prepared, if these small-molecule substances are with the shape that dissociates
State is present in product, and with the raising of temperature, these small-molecule substances can evaporate, and interior air environment is caused very
Big influence endangers the health of driver and passenger.In addition, polypropylene glass transition temperature is higher, material thermal resistance is poor, limits
Its application in many fields.
In current main engine plants both domestic and external, smell for interior trim parts and more and more tighter, the country's mark that distributes requirement
Also the emission of some substance emittings is clearly defined in standard.In field of polypropylene modification, improve grain by the way of baking material
It the smell of son and distributes content and has become a direction instantly.It is made as United States Patent (USP) USP.5,109,056 is squeezed out using high temperature
The method of grain, and during extrusion by the way of vacuumizing, high-temperature baking finally is carried out to the particle made again, with
This removes remaining small-molecule substance.This method technics comparing is complicated, and cost is higher, and in the mistake that particle former is product
Cheng Zhong also suffers from secondary thermal history, so as to influence the smell of product and distribute content.Also there are some additions in formula at present
The application of odor adsorption agent, but odor adsorption effect is limited, the problems such as existing simultaneously adsorption equilibrium and compatibility, persistence.
Such as 200510024840.2 high-performance low-odour polypropylene dedicated for automobile dashboard of Chinese patent and preparation method thereof, pass through addition
Sorbent molecule sieves the smell to reduce material.20081002332.5 low-emanation automobile inner fitting special-purpose material of Chinese patent and
Preparation method uses addition organic matter expellent such as isopropanol/water to reduce the smell of material.
Therefore, it is necessary to find a kind of method for fully balancing above-mentioned various aspects factor so that material has comprehensive and lasting
The low method of high-performing car interior trim PP Pipe Compound distributed of low smell.Diatomite is a kind of something lost by unicellular water plant diatom
The aqueous noncrystalline SiO that bones of the body deposition is formed2, high porosity, bigger serface, strong absorption caused by peculiar microcellular structure
Ability is not available for other inorganic fillers.In addition, diatomite also has small, good, sound-insulating and heat-insulating of chemical stability of density etc.
Feature.Therefore, using diatomite porous characteristic and the ability of deodorant absorption smell, a kind of synergistic sorption effect is formed,
There to be actual application value.
Invention content
For overcome the deficiencies in the prior art, primary and foremost purpose of the invention, which is to provide, a kind of to be had low smell, low distributes effect
The odor adsorption type functional agglomerate of fruit.
It is a further object of the present invention to provide the preparation methods of above-mentioned odor adsorption type functional agglomerate.
Another object of the present invention is to provide the purposes of above-mentioned odor adsorption type functional agglomerate.
It is yet another object of the invention to provide the automotive trim polypropylene composite materials for including above-mentioned odor adsorption type functional agglomerate
Material.
Above-mentioned purpose that the invention is realized by the following technical scheme：
A kind of odor adsorption type functional agglomerate, is configured to by the raw material of following weight percent：
Preferably, a kind of odor adsorption type functional agglomerate, is configured to by the raw material of following weight percent：
Wherein, for the polypropylene under 230 DEG C, 2.16kg loading condictions, melt flow rate (MFR) is 20~60g/10min.
The polypropylene is homo-polypropylene or block copolymerization propylene；The crystallinity of the homo-polypropylene more than 70%, etc.
Normality is more than 99%；The comonomer of the block copolymerization propylene is ethylene, vinyl monomer repetitive unit molar content for 4~
10%.
The diatomite main component is SiO2, grain size is 5~40 μm, and density is 1.9~2.3g/cm3, and pore volume is
0.55~0.95m3/g。
The adsorbent is ricinoleic acid salt deodorant, is white powder.
The surface conditioning agent is silane coupling agent, one or more mixed in titanate coupling agent, aluminate coupling agent
Close object.
The antioxidant includes primary antioxidant and auxiliary anti-oxidant, and primary antioxidant is hindered phenol or sulphur ester antioxidant；It is auxiliary anti-
Oxygen agent is phosphorite kind antioxidant.
The primary antioxidant is one or more of 3114,1010 and DSTP mixing；During auxiliary anti-oxidant is 618 and 168
One or two.
Odor adsorption type functional agglomerate disclosed by the invention, the total weight based on functional agglomerate further include 0-2 parts other
Auxiliary agent；Other auxiliary agents are selected from one or more of stearates, amides, silicone, metal soap.
A kind of preparation method of above-mentioned odor adsorption type functional agglomerate, includes the following steps：
(1) after weighing diatomite, adsorbent and surface conditioning agent by weight according to proportioning, through ultrasound in ethanol solution
Wavelength-division dissipates 3~5 minutes, is dried for standby in 100 DEG C of baking ovens；
(2) by treated mixture and polypropylene, antioxidant, after being weighed according to proportioning, in super mixer
Mixing 3~5 minutes；
(3) raw material for being uniformly mixed step (2) is added in double screw extruder, is granulated by melting extrusion postcooling,
Its technique is：One 180~190 DEG C of area, two 190~200 DEG C of areas, three 200~210 DEG C of areas, four 205~215 DEG C of areas；Screw speed
For 200-500r/min；The residence time of entire extrusion is 1~2 minute.
The invention also discloses application of the above-mentioned odor adsorption type functional agglomerate in automotive trim PP composite material.
The invention also discloses the automotive trim PP composite material for including above-mentioned odor adsorption type functional agglomerate, by weight
Amount includes following component：2-15 parts of odor adsorption type functional agglomerates, 48-90 parts of polypropylene, 0-35 parts of talcum powder, 6-15 parts of elasticity
Body POE.
The preparation method of automotive trim PP composite material comprising above-mentioned odor adsorption type functional agglomerate, including as follows
Step：
After weighing polypropylene, talcum powder, elastomer POE, odor adsorption type functional agglomerate according to proportioning, it is added at a high speed
It mixes 3~5 minutes, is added in double screw extruder in mixer, is granulated by melting extrusion postcooling, technique is：One
190~200 DEG C of area, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 205~215 DEG C of areas；Screw speed is 450-
1000r/min；The residence time of entire extrusion is 1~2 minute, and pressure is 12~18MPa, purging vacuum degree reaches 5~
20kPa。
Compared with prior art, the present invention it has the following advantages that：
1st, using diatomite porosity height, large specific surface area the characteristics of, with adsorbent by chelating aldoketones molecule, generates
Synergistic sorption effect, the small-molecule substance that polypropylene can be decomposed to generation during high-temperature fusion are adsorbed in diatomaceous hole
In gap so that odor adsorption type functional agglomerate obtained has excellent odor adsorption effect；
2nd, the odor adsorption type functional agglomerate obtained is added to the automotive trim PP composite material being made from it
In, the smell of material can be not only reduced, improves the problem that distributes of material, while the heat resistance of material also has and significantly carries
It rises.
3rd, preparation process of the invention is simple, at low cost, can be widely applied in automotive interior material.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.The scope of the present invention is not by these embodiments
Limitation, the scope of the present invention propose in detail in the claims.
The embodiment of the present invention and comparative example are not limited only to these raw materials using the following raw material：
Polypropylene is the copolymer polypropylene of Shanghai Petrochemical Co. Ltd.'s production, and trade name M2600R melts
Body flow rate is 25g/10min (test conditions：230℃×2.16kg).
Diatomite is the microfine diatomaceous after calcining, and mesh number is 2000 mesh.
Adsorbent is zinc ricinate, white powdered.
Surface conditioning agent is Silane coupling agent KH550.
Primary antioxidant be BASF AG production 3114, product designation Irganox 3114, chemical name 3, bis- uncles of 5-
Butyl -4- hydroxybenzyl phosphates diethylester and DSTP, the product designation Negonox DSTP of the production of ICE companies of Britain, chemistry
Entitled thio-2 acid octadecyl ester.
Auxiliary anti-oxidant is the 168 of BASF AG's production, and product designation Irgafos 168, chemical name is three (2,4- bis- uncles
Butyl phenyl) phosphite ester.
Talcum powder, mesh number are 1250 mesh, and average grain diameter is 10 μm.
Elastomer POE is ethylene-octene copolymer Engage8150, the density 0.868g/cm3 of DOW companies, melts
Melt index as 0.5g/10min (test conditions：190℃×2.16kg).
Other auxiliary agents used include a variety of colors additive, light stabilizer, various esters or fatty acid lubricant etc..
The test method of each performance indicator：
Tensile property is tested：It is carried out by ISO 527-2 standards, specimen size is 170 × 10 × 4mm, and tensile speed is
50mm/min；
Bending property is tested：It is carried out by 178 standards of ISO, specimen size is 80 × 10 × 4mm, rate of bending 2mm/
Min, span 64mm；
Notch impact strength is tested：It is carried out by ISO 179-1 standards, specimen size is 80 × 10 × 4mm, and notch depth is
/ 3rd of sample thickness, test temperature are 23 DEG C；
Smell is tested：It is carried out according to public PV3900 standards, using 50g models, 1L odor bottles.Sample is placed on odor bottle
In, odor bottle is put into the baking oven of (80 ± 2) DEG C after storage 2h ± 10min, after odor bottle is cooled to 60 ± 5 DEG C, then into
Row is judged；
Condensed components are tested：It is carried out according to public PV3015 standards, specimen size is 80 × 2mm of Φ, judges mode as examination
Test the quality of condensed material on front and rear aluminium foil；
Total carbon emitting value is tested：It is tested according to public PV3341 standards, sample weight 1.2g, the mode of judge is total
Carbon emission value size；
Heat resistance is tested：According to the heat distortion temperature of ISO52 Standards for Testing Materials, specimen size is 80 × 10 × 4mm,
Sample is kept flat, load 0.45MPa.
Embodiment A1-A8 and comparative example B1-B3：The preparation of odor adsorption type functional agglomerate
Diatomite and adsorbent, the antioxidant and/or other auxiliary agents after polypropylene, surface treatment are existed by the proportioning of table 1
Melting mixing in double screw extruder is added in super mixer after mixing to disperse, up to odor adsorption after cooling granulation
Type functional agglomerate.Its technique is：One 180~190 DEG C of area, two 190~200 DEG C of areas, three 200~210 DEG C of areas, four areas 205~215
℃；Screw speed is 200-500r/min；The residence time of entire extrusion is 1~2 minute.
1 embodiment A1-A8 of table and comparative example B1-B3 each group distribution ratios (weight %)
Embodiment 1-8 and comparative example 1-3：The preparation of automotive trim PP composite material
Odor adsorption type functional agglomerate as shown in the proportioning of table 2 by polypropylene, talcum powder, elastomer POE, table 1 and/or
Other auxiliary agents after mixing, are added to melting mixing in double screw extruder and disperse, after cooling granulation in super mixer
Up to automotive trim PP composite material.Its technique is：One 190~200 DEG C of area, two 200~210 DEG C of areas, three areas 200~
210 DEG C, four 205~215 DEG C of areas；Screw speed is 450-1000r/min；The residence time of entire extrusion is 1~2 point
Clock, pressure are 12~18MPa, and purging vacuum degree reaches 5~20kPa.
The mechanical property of gained automotive trim PP composite material, smell and distribution performance test result are as shown in table 2.
2 embodiment 1-8 of table and comparative example 1-3 material prescriptions and performance table
It can be seen that from the performance test results of embodiment 1-8 and comparative example 1-3 and smell introduced in composite system
After absorbent-type functional agglomerate, the smell and distribution performance of composite material have obvious improvement, and oder levels can reach 3 grades,
Condensed components and total carbon emitting amount reduce significantly simultaneously.Meanwhile the comprehensive mechanical property of composite material compares the range of decrease
Less, but heat resistance has promotion by a relatively large margin.
Claims (14)
1. a kind of odor adsorption type functional agglomerate, it is characterised in that：It is configured to by the raw material of following weight percent：
2. a kind of odor adsorption type functional agglomerate according to claim 1, it is characterised in that：By following weight percent
Raw material is configured to：
3. a kind of odor adsorption type functional agglomerate according to claim 1 or 2, it is characterised in that：The polypropylene is 230
DEG C, under 2.16kg loading condictions, melt flow rate (MFR) is 20~60g/10min.
4. a kind of odor adsorption type functional agglomerate according to claim 1 or 2, it is characterised in that：The polypropylene is equal
Polypropylene or block copolymerization propylene；For the crystallinity of the homo-polypropylene more than 70%, isotacticity is more than 99%；The block
The comonomer of co-polypropylene is ethylene, and vinyl monomer repetitive unit molar content is 4~10%.
5. a kind of odor adsorption type functional agglomerate according to claim 1 or 2, it is characterised in that：The diatomite is main
Ingredient is SiO2, grain size is 5~40 μm, and density is 1.9~2.3g/cm3, and pore volume is 0.55~0.95m3/g。
6. a kind of odor adsorption type functional agglomerate according to claim 1 or 2, it is characterised in that：The adsorbent is castor
Sesame oil Barbiturates deodorant is white powder.
7. a kind of odor adsorption type functional agglomerate according to claim 1 or 2, it is characterised in that：The surface conditioning agent
For one or more mixtures in silane coupling agent, titanate coupling agent, aluminate coupling agent.
8. a kind of odor adsorption type functional agglomerate according to claim 1 or 2, it is characterised in that：The antioxidant includes
Primary antioxidant and auxiliary anti-oxidant, primary antioxidant are hindered phenol or sulphur ester antioxidant；Auxiliary anti-oxidant resists for phosphorite class
Oxygen agent.
9. a kind of odor adsorption type functional agglomerate according to claim 1 or 2, it is characterised in that：The primary antioxidant is
3114th, one or more of 1010 and DSTP mixing；Auxiliary anti-oxidant is one or both of 618 and 168.
10. a kind of odor adsorption type functional agglomerate according to claim 1 or 2, it is characterised in that：Further include 0-2 parts
Other auxiliary agents；Other auxiliary agents are selected from one or more of stearates, amides, silicone, metal soap.
11. the preparation method of odor adsorption type functional agglomerate described in claims 1 or 2, it is characterised in that：Include the following steps：
(1) after weighing diatomite, adsorbent and surface conditioning agent by weight according to proportioning, through ultrasonic wavelength-division in ethanol solution
It dissipates 3~5 minutes, is dried for standby in 100 DEG C of baking ovens；
(2) by treated mixture and polypropylene, antioxidant, after being weighed according to proportioning, 3 are mixed in super mixer
~5 minutes；
(3) raw material for being uniformly mixed step (2) is added in double screw extruder, is granulated by melting extrusion postcooling, work
Skill is：One 180~190 DEG C of area, two 190~200 DEG C of areas, three 200~210 DEG C of areas, four 205~215 DEG C of areas；Screw speed is
200-500r/min；The residence time of entire extrusion is 1~2 minute.
12. a kind of odor adsorption type functional agglomerate according to claim 1 or 2, it is characterised in that：The odor adsorption type
Application of the functional agglomerate in automotive trim PP composite material.
13. a kind of automotive trim PP composite material for including odor adsorption type functional agglomerate described in claims 1 or 2,
It is characterized in that：By weight, including following component：2-15 parts of odor adsorption type functional agglomerates, 48-90 parts of polypropylene, 0-35
Part talcum powder, 6-15 parts of elastomer POE.
14. the preparation side of the automotive trim PP composite material comprising odor adsorption type functional agglomerate described in claim 13
Method, it is characterised in that：Include the following steps：
After polypropylene, talcum powder, elastomer POE, odor adsorption type functional agglomerate being weighed according to proportioning, be added to mixed at high speed
It mixes 3~5 minutes, is added in double screw extruder in device, is granulated by melting extrusion postcooling, technique is：One area 190
~200 DEG C, two 200~210 DEG C of areas, three 200~210 DEG C of areas, four 205~215 DEG C of areas；Screw speed is 450-1000r/min；
The residence time of entire extrusion is 1~2 minute, and pressure is 12~18MPa, and purging vacuum degree reaches 5~20kPa.
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Cited By (7)
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| CN109776957A (en) * | 2018-12-27 | 2019-05-21 | 联泓(江苏)新材料研究院有限公司 | A kind of taste removal master batch and its preparation method and application |
| CN110964260A (en) * | 2019-12-13 | 2020-04-07 | 天津金发新材料有限公司 | Low-odor low-TVOC polypropylene composite material and preparation method thereof |
| CN112574440A (en) * | 2020-12-17 | 2021-03-30 | 武汉金发科技有限公司 | Adsorption type low-odor master batch for polypropylene and preparation method thereof |
| CN112625347A (en) * | 2020-12-15 | 2021-04-09 | 上海普利特复合材料股份有限公司 | Low-odor, high-performance and environment-friendly polypropylene composite material and preparation method thereof |
| CN112961430A (en) * | 2021-02-02 | 2021-06-15 | 中国第一汽车股份有限公司 | Low-odor polypropylene and preparation method thereof |
| CN114196109A (en) * | 2021-12-08 | 2022-03-18 | 武汉金发科技有限公司 | Polypropylene odor adsorption master batch and preparation method thereof |
| CN114773638A (en) * | 2021-06-25 | 2022-07-22 | 安徽星贝达新材料科技有限公司 | Composite odor removal master batch and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776957A (en) * | 2018-12-27 | 2019-05-21 | 联泓(江苏)新材料研究院有限公司 | A kind of taste removal master batch and its preparation method and application |
| CN109776957B (en) * | 2018-12-27 | 2021-09-28 | 联泓(江苏)新材料研究院有限公司 | Odor removing master batch and preparation method and application thereof |
| CN110964260A (en) * | 2019-12-13 | 2020-04-07 | 天津金发新材料有限公司 | Low-odor low-TVOC polypropylene composite material and preparation method thereof |
| CN110964260B (en) * | 2019-12-13 | 2022-06-14 | 天津金发新材料有限公司 | Low-odor low-TVOC polypropylene composite material and preparation method thereof |
| CN112625347A (en) * | 2020-12-15 | 2021-04-09 | 上海普利特复合材料股份有限公司 | Low-odor, high-performance and environment-friendly polypropylene composite material and preparation method thereof |
| CN112574440A (en) * | 2020-12-17 | 2021-03-30 | 武汉金发科技有限公司 | Adsorption type low-odor master batch for polypropylene and preparation method thereof |
| CN112961430A (en) * | 2021-02-02 | 2021-06-15 | 中国第一汽车股份有限公司 | Low-odor polypropylene and preparation method thereof |
| CN114773638A (en) * | 2021-06-25 | 2022-07-22 | 安徽星贝达新材料科技有限公司 | Composite odor removal master batch and application thereof |
| CN114196109A (en) * | 2021-12-08 | 2022-03-18 | 武汉金发科技有限公司 | Polypropylene odor adsorption master batch and preparation method thereof |
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Application publication date: 20180619 |