CN108203526A - A kind of halogen-free flameproof TPO elastomeric materials and preparation method thereof - Google Patents
A kind of halogen-free flameproof TPO elastomeric materials and preparation method thereof Download PDFInfo
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- CN108203526A CN108203526A CN201611187019.7A CN201611187019A CN108203526A CN 108203526 A CN108203526 A CN 108203526A CN 201611187019 A CN201611187019 A CN 201611187019A CN 108203526 A CN108203526 A CN 108203526A
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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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Abstract
The invention discloses a kind of halogen-free flameproof TPO elastomeric materials, are made of the raw material for including following parts by weight：15 45 parts of LLDPE, 8 15 parts of homopolymerization PPs, 15 30 parts of SEBS, 30 45 parts of white oils, 10 20 parts of MCA, 25 portions of triphenyl phosphates, 25 parts of hypo-aluminum orthophosphates, 0.1 0.5 parts of antioxidant and 0.2 1 parts of coupling agents.The invention also discloses the preparation methods of above-mentioned halogen-free flameproof TPO elastomeric materials.The halogen-free flameproof TPO elastomeric materials of the present invention, using the SEBS through LLDPE and homopolymerization PP modification as matrix, it had not only had the elastic property of rubber, but also the thermoplastic property with plastics, manufacture easy to process, and leftover pieces are recyclable reuses, simultaneously in the case where adding in small amount halogen-free flame retardants, higher limit oxygen index is realized, it is at low cost, and it is easy to process, auto industry and civilian field of sealing technology can be widely used in.
Description
Technical field
The invention belongs to TPO elastomeric material technical fields, more particularly to a kind of halogen-free flameproof TPO elastomeric materials and its
Preparation method.
Background technology
Thermoplastic elastomer (TPE) be it is a kind of not only there is rubber performance, but also the molding high molecular material of plasticization, have concurrently rubber and
The characteristics of plastics.Thermoplastic elastomer (TPE) mainly includes six major class：Polyolefins thermoplastic elastomer (TPO)；Polyurethanes thermoplastic
Property elastomer；Styrene analog thermoplastic elastomer；Polyvinyl chloride analog thermoplastic elastomer；Polyester-type thermoplastic elastomer；Polyamides
Amine thermoplastic elastomer (TPE).
TPO has excellent weather-proof, UV resistant and good temperature tolerance, impact resistance, can be moulded with common thermoplastic
Expect process equipment carry out processing and forming and it is reusable the advantages of, quickly grow, it has also become increase most in thermoplastic elastomer (TPE)
A fast kind is widely used in automobile, electric, the industrial and fields such as civilian.
TPO production methods are divided into two kinds：Composite type and reaction type.Composite type include again mechanical blending method and
Dynamic vulcanization process, mechanical blending method are most ripe TPO production technologies, and the method is by double screw extruder by elastomer or rubber
Blending extrusion is carried out with polyolefin, it is simple for process, at low cost；Meanwhile in the filling of TPO systems a certain amount of oily (paraffine base crude oil, ring
Alkyl oil) improve processability, and greatly reduce cost, but due in system each component be all combustible material, greatly limit
The use scope of TPO is made.
Chinese patent CN104387681A discloses a kind of ageing-resistant weather-proof waterproof TPO material and preparation method thereof, passes through
The method of twin-screw extrusion adds vinyl elastomer, light stabilizer to realize in PP, and the material which provides has low
Warm bending performance and tearing toughness, and have excellent ageing-resistant performance and weather-proof water resistance.
Chinese patent CN105670116A discloses a kind of polypropylene blend and preparation method thereof, by leading in screw rod
Enter postcritical carbon dioxide, approach the viscosity of polypropylene and thermoplastic elastic body, improve rubber or thermoplasticity
Dispersion of the elastomer in polypropylene matrix, obtains excellent in mechanical performance polyacrylic polymer.
Invention content
The first object of the present invention is to provide a kind of halogen-free flameproof TPO elastomeric materials, with through LLDPE (linea low densities
Polyethylene) and the modified SEBS (hydrogenated styrene-butadiene block copolymer) of homopolymerization PP (polypropylene) be matrix so that the base
Body not only have rubber performance, but also with plastics thermoplastic property and add in it is less amount of by MCA (melamine cyanurates
Salt), triphenyl phosphate and hypo-aluminum orthophosphate composition halogen-free flame retardants in the case of, realize the TPO elastomeric materials have compared with
High limit oxygen index, while SEBS is also utilized with good oil-filled property, a certain amount of white oil is added in system, is changed significantly
It has been apt to processability and has reduced cost.
The present invention the and purpose is to provide a kind of preparation method of above-mentioned halogen-free flameproof TPO elastomeric materials, with warp
SEBS (the hydrogenated styrene-butadiene block copolymerizations that LLDPE (linear low density polyethylene) and homopolymerization PP (polypropylene) are modified
Object) be matrix so that the matrix not only have rubber performance, but also with plastics thermoplastic property and add in it is less amount of by
In the case of the halogen-free flame retardants of MCA (melamine cyanurate), triphenyl phosphate and hypo-aluminum orthophosphate composition, this is realized
TPO elastomeric materials have higher limit oxygen index, while also utilize SEBS with good oil-filled property, are added in system
A certain amount of white oil substantially improves processability and reduces cost.
Technical scheme is as follows：
A kind of halogen-free flameproof TPO elastomeric materials, are made of the raw material for including following parts by weight：
Wherein, the total amount of the LLDPE, the homopolymerization PP, the SEBS and the white oil is 100 weight
Part.
Preferably, the LLDPE is 20-30 parts；Or the homopolymerization PP is 10-12 parts；Or the SEBS is 20-
25 parts；Or the white oil is 35-40 parts.
Preferably, the MCA is 15 parts；Or the triphenyl phosphate is 4 parts；Or the hypo-aluminum orthophosphate is 4 parts；
Or the antioxidant is 0.3 part；Or the coupling agent is 0.5 part.
Preferably, the LLDPE melt index are 2-20g/10min, more preferably 5g/10min.
Preferably, the melt index of the homopolymerization PP is 5-20g/10min, more preferably 10g/10min.
Preferably, the white oil is one or both of naphthenic base white oil or paraffinic base white oil.
Preferably, the antioxidant is Hinered phenols antioxidant and the compound system of phosphite ester kind antioxidant.
Preferably, compound system of the antioxidant for antioxidant 1010 and irgasfos 168, the antioxidant 1010
Mass ratio with irgasfos 168 is 2: 1.
Preferably, the coupling agent is one kind in KH550, KH-560 or KH-570.
The invention also discloses a kind of preparation methods of above-mentioned halogen-free flameproof TPO elastomeric materials, include the following steps：
(1) parts by weight of above-mentioned each raw material are weighed respectively, for use；The white oil is first separated into several pieces, and portionwise
It is added in the SEBS, adds mixing after the white oil every time；It is stood after adding, obtains mixture；
(2) into the mixture, the LLDPE, the homopolymerization PP, the MCA, the phosphoric acid are added in
Triphenylmethyl methacrylate, the hypo-aluminum orthophosphate, the antioxidant and the coupling agent, mixing；Then it is squeezed out with double screw extruder
It is granulated to get to the halogen-free flameproof TPO elastomeric materials.
Compared with prior art, beneficial effects of the present invention are as follows：
First, a kind of halogen-free flameproof TPO elastomeric materials of the invention, by the LLDPE and for selecting particular melt index
Poly- PP is modified SEBS, and obtained matrix had not only had the elastic property of rubber, but also the thermoplastic property with plastics, was convenient for
Processing and manufacturing, and leftover pieces are recyclable reuses；
2nd, a kind of halogen-free flameproof TPO elastomeric materials of the invention, add in less amount of into the matrix of modified SEBS
The halogen-free flame retardants being made of MCA (melamine cyanurate), triphenyl phosphate and hypo-aluminum orthophosphate realizes TPO elasticity
Body material has higher limit oxygen index, has the advantages that simple and practicable, small investment, efficient, has significant economic effect
Benefit；
3rd, a kind of halogen-free flameproof TPO elastomeric materials of the invention, also using SEBS has good oil-filled property,
System adds in a certain amount of white oil, substantially improves processability and reduces cost.
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than restriction protection scope of the present invention.Those skilled in the art change according to what the present invention made in practical applications
Into and adjustment, still fall within protection scope of the present invention.
A kind of halogen-free flameproof TPO elastomeric materials of the present invention, are made of the raw material for including following parts by weight：
Wherein, the total amount of the LLDPE, the homopolymerization PP, the SEBS and the white oil is 100 weight
Part.
The LLDPE is 20-30 parts；Or the homopolymerization PP is 10-12 parts；Or the SEBS is 20-25 parts；Or
The white oil is 35-40 parts；The MCA is 15 parts；Or the triphenyl phosphate is 4 parts；Or the hypo-aluminum orthophosphate
It is 4 parts；Or the antioxidant is 0.3 part；Or the coupling agent is 0.5 part.
The LLDPE melt index are 2-20g/10min；The melt index of the homopolymerization PP is 5-20g/10min.
The white oil is one or both of naphthenic base white oil or paraffinic base white oil.
The antioxidant is Hinered phenols antioxidant and the compound system of phosphite ester kind antioxidant；The antioxidant
For antioxidant 1010 and the compound system of irgasfos 168, the mass ratio of the antioxidant 1010 and irgasfos 168 is 2: 1.
The coupling agent is one kind in KH550, KH-560 or KH-570.
The invention also discloses a kind of preparation methods of above-mentioned halogen-free flameproof TPO elastomeric materials, include the following steps：
(1) parts by weight of above-mentioned each raw material are weighed respectively, for use；The white oil is first separated into several equal portions, and by
Part is added in the SEBS, adds the white oil every time after mixing in high mixer；White oil is stood after all adding, and is obtained
Mixture；
(2) into the mixture, the LLDPE, the homopolymerization PP, the MCA, the phosphoric acid are added in
Triphenylmethyl methacrylate, the hypo-aluminum orthophosphate, the antioxidant and the coupling agent mixing in high mixer；Then it is squeezed with twin-screw
Go out machine extruding pelletization to get to the halogen-free flameproof TPO elastomeric materials.
In order to more preferably illustrate technical scheme of the present invention, below by way of several specific embodiments with embody the present invention skill
Art feature, and relevant performance test is carried out by elastomeric material will be made in embodiment, to illustrate the elastomer of the present invention
Realize the goal of the invention mentioned by the present invention.
Following embodiment is operated according to the extruder technique of table 1, elastomeric material, screw speed is made：
260r/min：
Table 1
Comparative example 1
(1) 20 parts of SEBS and 30 part of paraffinic base white oil is weighed, the white oil weighed is then divided into trisection and is gradually added
Enter in SEBS, add the mixture of SEBS and white oil every time after white oil in high-speed mixer and mixing 5min, after finally mixing
Mixture stand for 24 hours；
(2) weigh homopolymerization PP that LLDPE, 15 parts of melt index that 35 parts of melt index are 5g/10min are 10g/10min,
, 0.5 part of KH550 0.3 part of antioxidant (compound system of antioxidant 1010 and irgasfos 168, mass ratio 2: 1), by itself and step
Suddenly in (1) mixture of SEBS in high-speed mixer and mixing 5min；
(3) extruding pelletization is carried out to the mixture in step (2) with double screw extruder and just obtains halogen-free flameproof TPO elasticity
Body.
Embodiment 1
(1) 20 parts of SEBS and 30 part of paraffinic base white oil is weighed, the white oil weighed is then divided into trisection and is gradually added
Enter in SEBS, add the mixture of SEBS and white oil every time after white oil in high-speed mixer and mixing 5min, after finally mixing
Mixture stand for 24 hours；
(2) weigh homopolymerization PP that LLDPE, 15 parts of melt index that 35 parts of melt index are 5g/10min are 10g/10min,
15 parts of MCA, 4 portions of triphenyl phosphates, 4 parts of hypo-aluminum orthophosphates, 0.3 part of antioxidant (compound ligand of antioxidant 1010 and irgasfos 168
, 0.5 part of KH550 system, mass ratio 2: 1), by its mixture with SEBS in step (1) in high-speed mixer and mixing 5min；
(3) extruding pelletization is carried out to the mixture in step (2) with double screw extruder and just obtains halogen-free flameproof TPO elasticity
Body.
Embodiment 2
(1) 15 parts of SEBS and 30 part of naphthenic base white oil is weighed, the white oil weighed is then divided into trisection and is gradually added
Enter in SEBS, add the mixture of SEBS and white oil every time after white oil in high-speed mixer and mixing 5min, after finally mixing
Mixture stand for 24 hours；
(2) weigh homopolymerization PP that LLDPE, 15 parts of melt index that 35 parts of melt index are 2g/10min are 5g/10min,
10 parts of MCA, 2 portions of triphenyl phosphates, 2 parts of hypo-aluminum orthophosphates, 0.1 part of antioxidant (compound ligand of antioxidant 1010 and irgasfos 168
, 0.2 part of KH560 system, mass ratio 2: 1), by its mixture with SEBS in step (1) in high-speed mixer and mixing 5min；
(3) extruding pelletization is carried out to the mixture in step (2) with double screw extruder and just obtains halogen-free flameproof TPO elasticity
Body.
Embodiment 3
(1) 30 parts of SEBS and 40 part of naphthenic base white oil is weighed, the white oil weighed is then divided into trisection and is gradually added
Enter in SEBS, add the mixture of SEBS and white oil every time after white oil in high-speed mixer and mixing 5min, after finally mixing
Mixture stand for 24 hours；
(2) homopolymerization that LLDPE, 15 parts of melt index that 35 parts of melt index are 20g/10min are 20g/10min is weighed
PP, 20 parts of MCA, 5 portions of triphenyl phosphates, 5 parts of hypo-aluminum orthophosphates, 0.5 part of antioxidant (compounding of antioxidant 1010 and irgasfos 168
, 1 part of KH570 system, mass ratio 2: 1), by its mixture with SEBS in step (1) in high-speed mixer and mixing 5min；
(3) extruding pelletization is carried out to the mixture in step (2) with double screw extruder and just obtains halogen-free flameproof TPO elasticity
Body.
Embodiment 4
(1) 25 parts of SEBS and 40 part of paraffinic base white oil is weighed, the white oil weighed is then divided into trisection and is gradually added
Enter in SEBS, add the mixture of SEBS and white oil every time after white oil in high-speed mixer and mixing 5min, after finally mixing
Mixture stand for 24 hours；
(2) homopolymerization that LLDPE, 10 parts of melt index that 25 parts of melt index are 15g/10min are 10g/10min is weighed
PP, 15 parts of MCA, 4 portions of triphenyl phosphates, 3 parts of hypo-aluminum orthophosphates, 0.4 part of antioxidant (compounding of antioxidant 1010 and irgasfos 168
, 0.8 part of KH550 system, mass ratio 2: 1), by its mixture with SEBS in step (1) in high-speed mixer and mixing 5min；
(3) extruding pelletization is carried out to the mixture in step (2) with double screw extruder and just obtains halogen-free flameproof TPO elasticity
Body.
Embodiment 5
(1) 18 parts of SEBS and 42 part of paraffinic base white oil is weighed, the white oil weighed is then divided into trisection and is gradually added
Enter in SEBS, add the mixture of SEBS and white oil every time after white oil in high-speed mixer and mixing 5min, after finally mixing
Mixture stand for 24 hours；
(2) homopolymerization that LLDPE, 15 parts of melt index that 25 parts of melt index are 18g/10min are 12g/10min is weighed
PP, 18 parts of MCA, 4 portions of triphenyl phosphates, 5 parts of hypo-aluminum orthophosphates, 0.3 part of antioxidant (compounding of antioxidant 1010 and irgasfos 168
, 0.6 part of KH550 system, mass ratio 2: 1), by its mixture with SEBS in step (1) in high-speed mixer and mixing 5min；
(3) extruding pelletization is carried out to the mixture in step (2) with double screw extruder and just obtains halogen-free flameproof TPO elasticity
Body.
The performance test results of halogen-free flameproof TPO elastomeric materials that above-described embodiment and comparative example obtain see the table below 2：
Table 2
From table 2 it can be seen that the halogen-free flameproof TPO elastomeric materials of the present invention have preferable elongation at break, pass through
The modification of polyolefin and the addition of white oil, SEBS have preferable processing performance, are particularly added in into the matrix of modified SEBS
After the less amount of halogen-free flame retardants being made of MCA (melamine cyanurate), triphenyl phosphate and hypo-aluminum orthophosphate, realize
The TPO elastomeric materials have higher limit oxygen index, have preferable flame retardant property.Halogen-free flameproof TPO elastomeric rings
It protects, it is at low cost and easy to process, auto industry and civilian field of sealing technology can be widely used in.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.This specification is chosen and specifically describes these embodiments, is in order to preferably explain the present invention
Principle and practical application, so as to which skilled artisan be enable to be best understood by and utilize the present invention.The present invention is only
It is limited by claims and its four corner and equivalent.
Claims (10)
1. a kind of halogen-free flameproof TPO elastomeric materials, which is characterized in that be made of the raw material for including following parts by weight：
Wherein, the total amount of the LLDPE, the homopolymerization PP, the SEBS and the white oil is 100 parts by weight.
2. a kind of halogen-free flameproof TPO elastomeric materials according to claim 1, which is characterized in that the LLDPE is
20-30 parts；Or the homopolymerization PP is 10-12 parts；Or the SEBS is 20-25 parts；Or the white oil is 35-40 parts.
3. a kind of halogen-free flameproof TPO elastomeric materials according to claim 1, which is characterized in that the MCA is 15
Part；Or the triphenyl phosphate is 4 parts；Or the hypo-aluminum orthophosphate is 4 parts；Or the antioxidant is 0.3 part；It is or described
Coupling agent be 0.5 part.
A kind of 4. halogen-free flameproof TPO elastomeric materials according to claim 1, which is characterized in that the LLDPE meltings
Index is 2-20g/10min.
5. a kind of halogen-free flameproof TPO elastomeric materials according to claim 1, which is characterized in that the homopolymerization PP
Melt index is 5-20g/10min.
6. a kind of halogen-free flameproof TPO elastomeric materials according to claim 1, which is characterized in that the white oil is ring
One or both of alkyl white oil or paraffinic base white oil.
7. a kind of halogen-free flameproof TPO elastomeric materials according to claim 1, which is characterized in that the antioxidant is
The compound system of Hinered phenols antioxidant and phosphite ester kind antioxidant.
8. a kind of halogen-free flameproof TPO elastomeric materials according to claim 7, which is characterized in that the antioxidant is
The mass ratio of the compound system of antioxidant 1010 and irgasfos 168, the antioxidant 1010 and irgasfos 168 is 2: 1.
9. a kind of halogen-free flameproof TPO elastomeric materials according to claim 1, which is characterized in that the coupling agent is
One kind in KH550, KH-560 or KH-570.
10. a kind of preparation method of such as claim 1~9 any one of them halogen-free flameproof TPO elastomeric materials, feature exist
In including the following steps：
(1) parts by weight of each raw material described in claim 1 are weighed respectively, for use；The white oil is first separated into several pieces, and
It is added to portionwise in the SEBS, adds mixing after the white oil every time；It is stood after adding, obtains mixture；
(2) into the mixture, the LLDPE, the homopolymerization PP, the MCA, the phosphoric acid triphen are added in
Ester, the hypo-aluminum orthophosphate, the antioxidant and the coupling agent, mixing；Then double screw extruder extruding pelletization is used,
Obtain the halogen-free flameproof TPO elastomeric materials.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978779A (en) * | 2019-05-05 | 2020-11-24 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | Pearlescent powder, pearlescent paint and TPO product coated with pearlescent paint |
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| CN102719049A (en) * | 2012-05-28 | 2012-10-10 | 深圳市盛嘉伦橡塑工业有限公司 | Non-flame-retardant thermoplastic elastomer material and preparation method thereof |
| CN103660306A (en) * | 2012-09-24 | 2014-03-26 | 东丽先端材料研究开发（中国）有限公司 | Method for molding halogen-free flame-retardant thermoplastic polyester composition |
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| CN104861595A (en) * | 2015-06-08 | 2015-08-26 | 江苏理工学院 | Halogen-free flame retardant PBT material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111978779A (en) * | 2019-05-05 | 2020-11-24 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | Pearlescent powder, pearlescent paint and TPO product coated with pearlescent paint |
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Application publication date: 20180626 |