CN109535641A - One kind is exempted to spray ABS composite material and preparation method thereof - Google Patents
One kind is exempted to spray ABS composite material and preparation method thereof Download PDFInfo
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- CN109535641A CN109535641A CN201811514176.3A CN201811514176A CN109535641A CN 109535641 A CN109535641 A CN 109535641A CN 201811514176 A CN201811514176 A CN 201811514176A CN 109535641 A CN109535641 A CN 109535641A
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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 present invention relates to ABS technical fields, and in particular to one kind is exempted to spray ABS composite material and preparation method thereof, and ABS composite material includes ABS, PMMA, toughener, compatilizer, antioxidant and lubricant.In the present invention, PMMA and compatilizer appropriate are added in ABS, it can effectively improve the glossiness of composite material, while in order to improve the toughness of composite material, special toughener is added in the present invention, the toughener is the polyurethane elastomer for coating nano silica, based on the elastic body toughening mechanism of polyurethane elastomer, supplemented by the Rigid Particles Toughened mechanism of nano silica, greatly improve the toughness of composite material, and polyurethane and nano silica itself have certain whiteness, can be further improved the glossiness of composite material.
Description
Technical field
The present invention relates to ABS technical fields, and in particular to one kind is exempted to spray ABS composite material and preparation method thereof.
Background technique
ABS is widely used in the industries such as automobile and household electrical appliances as one of general synthetic resin.As market produces ABS
The continuous improvement that moral character energy diversification requires, especially in field of household appliances, it is desirable that plastic product surface has high glaze, high abrasion
And impact resistance, and traditional high finish surface, it needs to carry out plastic product secondary operation, passes through the processes such as spraying polishing
It realizes, not only generates the waste of manpower and resource, but also pollute the environment.ABS/PMMA co-mixing system (or co-blended
Gold) in household electric appliances, excellent comprehensive performance especially is embodied in shell product application, to develop bloom green resin material
Provide a new approach.But with the increase of PMMA content, property declines at the beginning of while blend alloy glossiness improves, limitation
Application of the blend alloy in certain fields.For polymer as structural material, intensity and first property are two important mechanical properties,
Increase the important topic of just modified always polymer material science research to polymer.At present both at home and abroad to ABS/PMMA co-blended
The research of gold is fewer, especially also undesirable in terms of increasing just modification.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of light extensively pool degree,
Toughness it is strong exempt from spray ABS composite material and preparation method thereof.
The purpose of the invention is achieved by the following technical solution:
One kind is exempted to spray ABS composite material, the raw material including following parts by weight:
30-50 parts of ABS
20-30 parts of PMMA
5-10 parts of toughener
1-3 parts of compatilizer
0.5-1 parts of antioxidant
1-2 parts of lubricant；
Wherein, the preparation method of toughener described in every parts by weight includes the following steps:
A, 4, the 4- methyl diphenylene diisocyanate of 60-80 parts by weight and the polytetrahydrofuran ether two of 100-120 parts by weight are taken
Alcohol is dissolved in the n,N-dimethylacetamide of 100 parts by weight, in 50-60 DEG C of reaction 120-150min, obtains performed polymer after cooling
Solution；
B, the nano silica of 6-18 parts by weight and the chain extender of 3-6 parts by weight are added into the prepolymer solution, then
35-45 DEG C at a temperature of be stirred to react 30-60min, obtain polymer solution；
C, the polymer solution is subjected to electrostatic spray to get the toughener is arrived.
In the present invention, PMMA and compatilizer appropriate are added in ABS, can effectively improve the glossiness of composite material,
While in order to improve the toughness of composite material, special toughener is added in the present invention, which is cladding nano silica
Polyurethane elastomer, based on the elastic body toughening mechanism of polyurethane elastomer, the Rigid Particles Toughened of nano silica
Supplemented by mechanism, the toughness of composite material is greatly improved, and polyurethane and nano silica itself have certain whiteness, it can
To further increase the glossiness of composite material.
Wherein, the molecular weight of the polytetrahydrofuran ether glycol is 2000-2500.By controlling polytetrahydrofuran ether glycol
The property that toughener obtained can be regulated and controled, improves its toughening effect.
Wherein, the partial size of the nano silica is 100-200nm.The nano silica of the partial size is molten in polymer
There is preferable dispersibility, polyurethane is good to the covering property of nano silica after electrostatic spray, and toughener obtained is simultaneous in liquid
Has the effect of elastic body toughening and rigid body toughening.
Wherein, the chain extender is triisopropanolamine, bis- to quinhydrones-(β-ethoxy) at least one of ether and glycerol.
The polyurethane molecular amount of the adjustable generation of chain extender improves the toughness of polyurethane, and nano silica and polyurethane are sent out
Raw a degree of crosslinking, conducive to the evenly dispersed of nano silica, toughening effect is more uniform, it is not easy to stress collection occur
In phenomenon.Preferably, the chain extender is by triisopropanolamine and to bis- (β-ethoxy) ethers of quinhydrones-by weight 1:1-2's
Ratio composition, toughening effect is more preferably.
Wherein, in the step C, the spray voltage of electrostatic spray is 20-40kV, and vapo(u)rizing temperature is 20-30 DEG C.Pass through control
The technique of electrostatic spray processed can regulate and control the surface topography and size of toughener obtained, the partial size of final toughener obtained
It is 11.5-22.4 μm, there is preferable dispersibility and toughening effect in the composite.
Wherein, the compatilizer is at least one of ABS-g-MAH, SEBS-g-MAH and PS-g-PMMA.Compatilizer can
To improve the compatibility between ABS, PMMA and toughener, further, the compatilizer is by for ABS-g-MAH, SEBS-g-
MAH and PS-g-PMMA is formed by weight the ratio of 1-3:1-2:1, and toughening effect becomes apparent from, and the glossiness of composite material is more equal
It is even.
Wherein, the antioxidant is made of irgasfos 168 and antioxidant 1010, and the ageing-resistant of composite material can be improved
Property, it is preferable that the antioxidant is made of irgasfos 168 and antioxidant 1010 by weight the ratio of 1:1.
Wherein, the lubricant is at least one of calcium stearate, zinc stearate and talcum powder.Lubricant can be promoted
The processing fluidity and release property of composite material, so that final all kinds of profiles obtained are with no current mark, smooth surface.It is preferred that
Ground, the lubricant are made of calcium stearate and talcum powder by weight the ratio of 1-2:1-3.
A kind of preparation method for exempting to spray ABS composite material as described above: ABS, PMMA, toughening are weighed by formula ratio
Agent, compatilizer, antioxidant and mix lubricant it is uniform after, be added to double screw extruder carry out extruding pelletization to get arrive institute
That states exempts from spraying ABS composite material.
Wherein, the processing temperature of double screw extruder is 180-220 DEG C.
The beneficial effects of the present invention are: in the present invention, PMMA and compatilizer appropriate are added in ABS, it can be effective
The glossiness of composite material is improved, while in order to improve the toughness of composite material, special toughener is added in the present invention, the toughening
Agent is the polyurethane elastomer for coating nano silica, based on the elastic body toughening mechanism of polyurethane elastomer, nanometer two
Supplemented by the Rigid Particles Toughened mechanism of silica, the toughness of composite material, and polyurethane and nano silica are greatly improved
Itself has certain whiteness, can be further improved the glossiness of composite material.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
One kind is exempted to spray ABS composite material, the raw material including following parts by weight:
40 parts of ABS
25 parts of PMMA
7.5 parts of toughener
2 parts of compatilizer
0.7 part of antioxidant
1.5 parts of lubricant；
Wherein, the preparation method of toughener described in every parts by weight includes the following steps:
A, the polytetrahydrofuran ether glycol of 4, the 4- methyl diphenylene diisocyanate and 110 parts by weight that take 70 parts by weight is dissolved in
In the n,N-dimethylacetamide of 100 parts by weight, in 55 DEG C of reaction 135min, prepolymer solution is obtained after cooling；
B, the nano silica of 12 parts by weight and the chain extender of 4.5 parts by weight are added into the prepolymer solution, then exists
It is stirred to react 45min at a temperature of 40 DEG C, obtains polymer solution；
C, the polymer solution is subjected to electrostatic spray to get the toughener is arrived.
Wherein, the molecular weight of the polytetrahydrofuran ether glycol is 2200.
Wherein, the partial size of the nano silica is 150nm.
Wherein, the chain extender is by triisopropanolamine and to bis- (β-ethoxy) ethers of quinhydrones-by weight the ratio of 1:1.5
Example composition
Wherein, in the step C, the spray voltage of electrostatic spray is 30kV, and vapo(u)rizing temperature is 25 DEG C.
Wherein, the compatilizer is by the ratio for ABS-g-MAH, SEBS-g-MAH and PS-g-PMMA by weight 2:1.5:1
Example composition.
Wherein, the antioxidant is made of irgasfos 168 and antioxidant 1010 by weight the ratio of 1:1.
Wherein, the lubricant is made of calcium stearate and talcum powder by weight the ratio of 1.5:2.
A kind of preparation method for exempting to spray ABS composite material as described above: ABS, PMMA, toughening are weighed by formula ratio
Agent, compatilizer, antioxidant and mix lubricant it is uniform after, be added to double screw extruder carry out extruding pelletization to get arrive institute
That states exempts from spraying ABS composite material.
Wherein, the processing temperature of double screw extruder is 200 DEG C.
Embodiment 2
One kind is exempted to spray ABS composite material, the raw material including following parts by weight:
30 parts of ABS
20 parts of PMMA
5 parts of toughener
1 part of compatilizer
0.5 part of antioxidant
1 part of lubricant；
Wherein, the preparation method of toughener described in every parts by weight includes the following steps:
A, the polytetrahydrofuran ether glycol of 4, the 4- methyl diphenylene diisocyanate and 100 parts by weight that take 60 parts by weight is dissolved in
In the n,N-dimethylacetamide of 100 parts by weight, in 50 DEG C of reaction 150min, prepolymer solution is obtained after cooling；
B, the nano silica of 6 parts by weight and the chain extender of 3 parts by weight are added into the prepolymer solution, then at 35 DEG C
At a temperature of be stirred to react 60min, obtain polymer solution；
C, the polymer solution is subjected to electrostatic spray to get the toughener is arrived.
Wherein, the molecular weight of the polytetrahydrofuran ether glycol is 2000.
Wherein, the partial size of the nano silica is 100nm.
Wherein, the chain extender is by triisopropanolamine and to bis- (β-ethoxy) ethers of quinhydrones-by weight the ratio of 1:1
Composition
Wherein, in the step C, the spray voltage of electrostatic spray is 20kV, and vapo(u)rizing temperature is 30 DEG C.
Wherein, the compatilizer is by the ratio for ABS-g-MAH, SEBS-g-MAH and PS-g-PMMA by weight 1:1:1
Composition.
Wherein, the antioxidant is made of irgasfos 168 and antioxidant 1010 by weight the ratio of 1:1.
Wherein, the lubricant is made of calcium stearate and talcum powder by weight the ratio of 1:1.
A kind of preparation method for exempting to spray ABS composite material as described above: ABS, PMMA, toughening are weighed by formula ratio
Agent, compatilizer, antioxidant and mix lubricant it is uniform after, be added to double screw extruder carry out extruding pelletization to get arrive institute
That states exempts from spraying ABS composite material.
Wherein, the processing temperature of double screw extruder is 180 DEG C.
Embodiment 3
One kind is exempted to spray ABS composite material, the raw material including following parts by weight:
50 parts of ABS
30 parts of PMMA
10 parts of toughener
3 parts of compatilizer
1 part of antioxidant
2 parts of lubricant；
Wherein, the preparation method of toughener described in every parts by weight includes the following steps:
A, the polytetrahydrofuran ether glycol of 4, the 4- methyl diphenylene diisocyanate and 120 parts by weight that take 80 parts by weight is dissolved in
In the n,N-dimethylacetamide of 100 parts by weight, in 60 DEG C of reaction 120min, prepolymer solution is obtained after cooling；
B, the nano silica of 18 parts by weight and the chain extender of 6 parts by weight are added into the prepolymer solution, then 45
It is stirred to react 30min at a temperature of DEG C, obtains polymer solution；
C, the polymer solution is subjected to electrostatic spray to get the toughener is arrived.
Wherein, the molecular weight of the polytetrahydrofuran ether glycol is 2500.
Wherein, the partial size of the nano silica is 200nm.
Wherein, the chain extender is by triisopropanolamine and to bis- (β-ethoxy) ethers of quinhydrones-by weight the ratio of 1:2
Composition
Wherein, in the step C, the spray voltage of electrostatic spray is 40kV, and vapo(u)rizing temperature is 20 DEG C.
Wherein, the compatilizer is by the ratio for ABS-g-MAH, SEBS-g-MAH and PS-g-PMMA by weight 3:2:1
Composition.
Wherein, the antioxidant is made of irgasfos 168 and antioxidant 1010 by weight the ratio of 1:1.
Wherein, the lubricant is made of calcium stearate and talcum powder by weight the ratio of 2:3.
A kind of preparation method for exempting to spray ABS composite material as described above: ABS, PMMA, toughening are weighed by formula ratio
Agent, compatilizer, antioxidant and mix lubricant it is uniform after, be added to double screw extruder carry out extruding pelletization to get arrive institute
That states exempts from spraying ABS composite material.
Wherein, the processing temperature of double screw extruder is 220 DEG C.
Embodiment 4
40 parts of ABS
25 parts of PMMA
7.5 parts of toughener
2 parts of compatilizer
0.7 part of antioxidant
1.5 parts of lubricant；
Wherein, the preparation method of toughener described in every parts by weight includes the following steps:
A, the polytetrahydrofuran ether glycol of 4, the 4- methyl diphenylene diisocyanate and 110 parts by weight that take 70 parts by weight is dissolved in
In the n,N-dimethylacetamide of 100 parts by weight, in 55 DEG C of reaction 135min, prepolymer solution is obtained after cooling；
B, the nano silica of 12 parts by weight and the chain extender of 4.5 parts by weight are added into the prepolymer solution, then exists
It is stirred to react 45min at a temperature of 40 DEG C, obtains polymer solution；
C, the polymer solution is subjected to electrostatic spray to get the toughener is arrived.
Wherein, the molecular weight of the polytetrahydrofuran ether glycol is 2200.
Wherein, the partial size of the nano silica is 150nm.
Wherein, the chain extender is glycerol
Wherein, in the step C, the spray voltage of electrostatic spray is 30kV, and vapo(u)rizing temperature is 25 DEG C.
Wherein, the compatilizer is ABS-g-MAH.
Wherein, the antioxidant is made of irgasfos 168 and antioxidant 1010 by weight the ratio of 1:1.
Wherein, the lubricant is zinc stearate.
A kind of preparation method for exempting to spray ABS composite material as described above: ABS, PMMA, toughening are weighed by formula ratio
Agent, compatilizer, antioxidant and mix lubricant it is uniform after, be added to double screw extruder carry out extruding pelletization to get arrive institute
That states exempts from spraying ABS composite material.
Wherein, the processing temperature of double screw extruder is 200 DEG C.
Comparative example 1
This comparative example the difference from embodiment 1 is that:
The toughener is commercially available conventional EMA toughener.
Comparative example 2
This comparative example the difference from embodiment 1 is that:
The toughener is commercially available conventional MBS toughener.
Comparative example 3
This comparative example the difference from embodiment 1 is that:
The preparation method of the toughener includes the following steps:
A, the polytetrahydrofuran ether glycol of 4, the 4- methyl diphenylene diisocyanate and 110 parts by weight that take 70 parts by weight is dissolved in
In the n,N-dimethylacetamide of 100 parts by weight, in 55 DEG C of reaction 135min, prepolymer solution is obtained after cooling；
B, the chain extender of 4.5 parts by weight is added into the prepolymer solution, then 40 DEG C at a temperature of be stirred to react
45min obtains polymer solution；
C, the polymer solution is subjected to electrostatic spray to get the toughener is arrived.
The composite material of embodiment 1-4 and comparative example 1-3 are tested for the property, the result is as follows:
| Testing standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Tensile strength (MPa) | ASTM D638 | 57 | 59 | 59 | 58 |
| Elongation at break (%) | ASTM D638 | 30 | 27 | 28 | 25 |
| Bending strength (MPa) | ASTM D790 | 73 | 76 | 75 | 73 |
| Impact strength (kJ/m2) | ASTM D256 | 11.6 | 10.8 | 10.7 | 10.5 |
| Glossiness (%) | ASTM D523 | 81.6 | 80.7 | 80.2 | 79.5 |
| Testing standard | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tensile strength (MPa) | ASTM D638 | 56 | 59 | 60 |
| Elongation at break (%) | ASTM D638 | 20 | 17 | 16 |
| Bending strength (MPa) | ASTM D790 | 71 | 78 | 80 |
| Impact strength (kJ/m2) | ASTM D256 | 8.3 | 7.8 | 7.5 |
| Glossiness (%) | ASTM D523 | 74.6 | 76.2 | 79.1 |
From the comparison of comparative example 1, comparative example 2 and comparative example 3 it is found that EVA, MBS and TPU three are on toughening effect, EVA is most
Good, MBS takes second place, and TPU is worst；In the performance of glossiness, TPU is best, MBS takes second place, and EVA is best.
From embodiment 1, comparative example 1-3 comparison it is found that special toughener of the invention addition, maintain composite material
It is more it will be evident that having especially in shock resistance excellent in the promotion degree of toughness while with certain rigidity
Performance.
From the comparison of embodiment 1 and comparative example 3 it is found that toughener made of nano silica is added in TPU, although
It is slightly reduced on rigid, but the castering action of toughness is very significant.
From the comparison of embodiment 1 and comparative example 4 it is found that compatilizer and lubricant of the invention not chooses at random, pass through
Specific compatilizer and lubricant combination are selected, composite material has the promotion of higher degree in rigidity and toughness.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. one kind is exempted to spray ABS composite material, it is characterised in that: the raw material including following parts by weight:
30-50 parts of ABS
20-30 parts of PMMA
5-10 parts of toughener
1-3 parts of compatilizer
0.5-1 parts of antioxidant
1-2 parts of lubricant；
Wherein, the preparation method of toughener described in every parts by weight includes the following steps:
A, 4, the 4- methyl diphenylene diisocyanate of 60-80 parts by weight and the polytetrahydrofuran ether two of 100-120 parts by weight are taken
Alcohol is dissolved in the n,N-dimethylacetamide of 100 parts by weight, in 50-60 DEG C of reaction 120-150min, obtains performed polymer after cooling
Solution；
B, the nano silica of 6-18 parts by weight and the chain extender of 3-6 parts by weight are added into the prepolymer solution, then
35-45 DEG C at a temperature of be stirred to react 30-60min, obtain polymer solution；
C, the polymer solution is subjected to electrostatic spray to get the toughener is arrived.
2. one kind according to claim 1 is exempted to spray ABS composite material, it is characterised in that: the polytetrahydrofuran ether two
The molecular weight of alcohol is 2000-2500.
3. one kind according to claim 1 is exempted to spray ABS composite material, it is characterised in that: the nano silica
Partial size is 100-200nm.
4. one kind according to claim 1 is exempted to spray ABS composite material, it is characterised in that: the chain extender is three isopropyls
Hydramine, bis- to quinhydrones-(β-ethoxy) at least one of ether and glycerol.
5. one kind according to claim 1 is exempted to spray ABS composite material, it is characterised in that: in the step C, electrostatic
The spray voltage of mist is 20-40kV, and vapo(u)rizing temperature is 20-30 DEG C.
6. one kind according to claim 1 is exempted to spray ABS composite material, it is characterised in that: the compatilizer is ABS-g-
At least one of MAH, SEBS-g-MAH and PS-g-PMMA.
7. one kind according to claim 1 is exempted to spray ABS composite material, it is characterised in that: the antioxidant is by antioxygen
Agent 168 and antioxidant 1010 composition.
8. one kind according to claim 1 is exempted to spray ABS composite material, it is characterised in that: the lubricant is stearic acid
At least one of calcium, zinc stearate and talcum powder.
9. a kind of preparation method for exempting to spray ABS composite material described in claim 1-8 any one, it is characterised in that: press
Formula ratio weigh ABS, PMMA, toughener, compatilizer, antioxidant and mix lubricant it is uniform after, be added to twin-screw extrusion
Machine carries out extruding pelletization and exempts from spraying ABS composite material to get to described.
10. a kind of preparation method for exempting to spray ABS composite material according to claim 9, it is characterised in that: twin-screw squeezes
The processing temperature of machine is 180-220 DEG C out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811514176.3A CN109535641A (en) | 2018-12-12 | 2018-12-12 | One kind is exempted to spray ABS composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811514176.3A CN109535641A (en) | 2018-12-12 | 2018-12-12 | One kind is exempted to spray ABS composite material and preparation method thereof |
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| CN109535641A true CN109535641A (en) | 2019-03-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457575A (en) * | 2020-10-27 | 2021-03-09 | 东莞市鑫塑源塑胶科技有限公司 | Polypropylene halogen-free flame-retardant material and preparation method thereof |
-
2018
- 2018-12-12 CN CN201811514176.3A patent/CN109535641A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457575A (en) * | 2020-10-27 | 2021-03-09 | 东莞市鑫塑源塑胶科技有限公司 | Polypropylene halogen-free flame-retardant material and preparation method thereof |
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Application publication date: 20190329 |
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| WW01 | Invention patent application withdrawn after publication |