CN106589769A - Low-temperature-resistant and high-flame-retardant ABS composite material and preparation method thereof - Google Patents
Low-temperature-resistant and high-flame-retardant ABS composite material and preparation method thereof Download PDFInfo
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- CN106589769A CN106589769A CN201611113729.5A CN201611113729A CN106589769A CN 106589769 A CN106589769 A CN 106589769A CN 201611113729 A CN201611113729 A CN 201611113729A CN 106589769 A CN106589769 A CN 106589769A
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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
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Fireproofing Substances (AREA)
Abstract
The invention relates to a low-temperature-resistant and high-flame-retardant ABS composite material and a preparation method thereof. The low-temperature-resistant and high-flame-retardant ABS composite material is prepared from the following raw materials in parts by weight: 60 to 80 parts of ABS resin, 40 to 60 parts of PC resin, 5 to 10 parts of EPDM resin, 6 to 10 parts of an anti-oxidant, 5 to 8 parts of nanometer silver, 8 to 12 parts of a composite flame retardant and 5 to 8 parts of a low-temperature-resistant plasticizer. According to the invention, the composite flame retardant is used in the composite material; with phosphoric acid and urea as main raw materials, and diatomite and magnetic ordered mesoporous nickel ferrite as carriers, an ammonium polyphosphate-diatomite/magnetic ordered mesoporous nickel ferrite composite flame retardant is prepared through in-situ polymerization, so synergistic and flame-retardant effects among ammonium polyphosphate, silicon element, iron element and nickel element can be fully exerted; thus, good flame retardance of the ABS composite material is obtained.
Description
Technical field
The present invention relates to a kind of low temperature resistant high fire-retardance ABS composite material its preparation method.
Background technology
ABS resin（Acrylonitrile-butadiene-styrene copolymer）It is a kind of intensity height, good toughness, easily processed into type
Thermoplastics type's Polymer Materials ' Structure.
ABS is the general thermoplastic engineering plastic for growing up 1940's, be a comprehensive mechanical property very
Outstanding plastics variety, not only with good rigid, hardness and processing fluidity, and with high tenacity feature, can note
Modeling, extrusion or thermoforming.
Most of automobile component is processed with injection molding forming method, the advantage of ABS resin be impact resilience, sound-proofing,
Scratch-resistant, heat resistance is more preferably, more attractive than PP, is particularly well-suited to horizontal impact resilience and using the more strict part of temperature.
ABS resin is that polyurethane and polyacrylic the third-largest resin are only second to used in automobile.ABS resin can be used for outside in-car and car
Shell, the widget such as steering wheel, oil guide pipe and handle and button, car outside includes front radiator grille and lampshade etc., current
ABS resin fire resistance and resistance to low temperature be not good, present invention seek to address that this technical problem.
The content of the invention
It is an object of the invention to solve the deficiencies in the prior art, there is provided a kind of low temperature resistant high fire-retardance ABS composite material its
Preparation method.
The technical solution adopted for the present invention to solve the technical problems is：
Low temperature resistant high fire-retardance ABS composite material, the low temperature resistant high fire-retardance ABS composite material by following weight portion Raw material processing
Form：ABS resin 60-80 parts, PC resin 40-60 part, EPDM resin 5-10 parts, antioxidant 6-10 parts, Nano Silver 5-8 parts,
Composite flame-retardant agent 8-12 parts, low temperature resistant plasticizer 5-8 parts, the composite flame-retardant agent is APP-silicon prepared by in-situ polymerization
The order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of diatomaceous earth/magnetic, the preparation method of composite flame-retardant agent is specific as follows：85% SPA is fallen
In entering reactor, heating stirring, temperature is raised to 60-80 DEG C and adds appropriate urea, when temperature is raised to 120-125 DEG C, adds suitable
Amount diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, the min of stirring reaction 10 ~ 20 is then solid at 280-320 DEG C by product
Change 1-2h, Jing after nano grinder is crushed composite flame-retardant agent is obtained.
Preferably, the low temperature resistant high fire-retardance ABS composite material is formed by the Raw material processing of following weight portion：ABS resin
70 parts, 50 parts of PC resin, 6 parts of EPDM resins, 8 parts of antioxidant, 6 parts of Nano Silver, 8 parts of composite flame-retardant agent, low temperature resistant plasticizer 6
Part, the preparation method of composite flame-retardant agent is specific as follows：The SPA of 85% concentration is poured in reactor, heating stirring, temperature liter
Appropriate urea is added to 70 DEG C, when temperature is raised to 122 DEG C, appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic is added,
Stirring reaction 15min, then solidifies 1.5h by product at 300 DEG C, and Jing after nano grinder is crushed composite flame-retardant agent is obtained.
Preferably, phosphoric acid：Urea：Diatomite：The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of magnetic is：1:（0.6~0.7）:（0.2
~0.3）:（0.1-0.2）.
Preferably, the antioxidant is pentaerythrite four (3- lauryl thiopropionates) and/or four [β-(3,5- bis-
Tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Preferably, the antioxidant is pentaerythrite four (3- lauryl thiopropionates) and four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) propionic acid] pentaerythritol ester in mass ratio 2:3 mixture.
The preparation method of low temperature resistant high fire-retardance ABS composite material of the present invention is specific as follows：
（1）The order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic prepared by in-situ polymerization：By 85% SPA
In pouring reactor into, heating stirring, temperature is raised to 60-80 DEG C and adds appropriate urea, when temperature is raised to 120-125 DEG C, adds
Appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, the min of stirring reaction 10 ~ 20, then by product at 280-320 DEG C
Solidification 1-2h, Jing after nano grinder is crushed composite flame-retardant agent is obtained；
（2）By the mixing of ABS resin, PC resin, EPDM resins, antioxidant, Nano Silver, low temperature resistant plasticizer and composite flame-retardant agent
Uniformly, Jing melting mixings, extruding pelletization is obtained.
The preparation method of the order mesoporous nickel ferrite based magnetic loaded of magnetic that the present invention is used is as follows：
1）By Ni (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in methyl alcohol, appropriate porous silicon KIT-6 is put into and is filled
In the polytetrafluoroethylcontainer container of n-hexane, it is sufficiently stirred for；
2）By solution 1）Raw material be added dropwise over step 2）In, the mixed solution for being formed is sufficiently stirred for, in 70-80 DEG C of heating
5-8h；
3）Step 2) gained solid calcination 1-2 h at 300-320 DEG C；
4）By step 3）Gained solid is cooled to room temperature, polished to be transferred in the round-bottomed flask for filling NaOH solution, in 30-
It is refluxed centrifugation after 8-12h under 40 DEG C of water bath conditions to reclaim；
5）By step 4）Gained solid is cleaned to neutrality respectively repeatedly with ethanol and deionized water, vacuum dried.
The order mesoporous nickel ferrite based magnetic loaded of magnetic of the present invention possesses huge specific surface area and abundant three-dimensional pore space knot
Structure, high-specific surface area is conducive to adsorbing flue gas, reduces the smoke-producing amount of ABS composite material burning；Regular orderly open duct,
The aperture of size adjustable is APP, Nano Silver, antioxidant and low temperature resistant plasticizer provide storage and release way, is carried
The using effect of high ABS composite material, extends its service life.
The invention has the beneficial effects as follows：
（1）Improve the anti-flammability of ABS composite material
With phosphoric acid and urea as primary raw material, with diatomite and the order mesoporous nickel ferrite based magnetic loaded of magnetic as carrier, by in-situ polymerization system
The standby order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic, can give full play to APP and element silicon and
Cooperative flame retardant effect between iron, nickel element, makes ABS composite material have good fire resistance, it is possible to additionally incorporate appropriate antioxygen
Agent and Nano Silver, loaded body adsorption storage can continue slowly to discharge active ingredient, extend the use of ABS composite material
Life-span.
（2）Improve the smoke-suppressing of ABS composite material
On the one hand using diatomaceous porous and adsorptivity, and the absorption of the order mesoporous nickel ferrite based magnetic loaded of high-specific surface area magnetic
Property, reduce the smoke-producing amount of ABS composite material burning；On the other hand utilize between APP and element silicon and iron, nickel element
High cooperative flame retardant effect, the good heat point for acting on into charcoal covering, reducing ABS composite material composition is played to ABS composite material
The generation of solution and imflammable gas.
（3）Reduces cost, reduces the impact to ABS composite material performance
Due to the high fire-retardance smoke-suppressing of the order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic, in resin
Addition is appropriate, so affecting little to the physical strength of ABS composite material, is conducive to keeping preferable ABS resin physical strength
Performance, while also can reduces cost.
The low temperature resistant high fire-retardance ABS plastic of the present invention has preferable anti-flammability, can be processed into Shooting Technique various
The part of shape, can be used to make in automobile and the widget such as car outer enclosure, steering wheel and handle and button.
Specific embodiment
Below by specific embodiment, technical scheme is described in further detail.
Raw materials used in the embodiment of the present invention is commercial convenient source.
Embodiment 1：
Low temperature resistant high fire-retardance ABS composite material, the low temperature resistant high fire-retardance ABS composite material by following weight portion Raw material processing
Form：60 parts of ABS resin, 40 parts of PC resin, 5 parts of EPDM resins, 6 parts of antioxidant, 5 parts of Nano Silver, 8 parts of composite flame-retardant agent,
5 parts of low temperature resistant plasticizer, the composite flame-retardant agent is APP-order mesoporous iron of diatomite/magnetic prepared by in-situ polymerization
Sour nickel composite flame-retardant agent, the preparation method of composite flame-retardant agent is specific as follows：85% SPA is poured in reactor, heating stirring,
Temperature is raised to 60 DEG C and adds appropriate urea, when temperature is raised to 125 DEG C, adds appropriate diatomite and the order mesoporous ferrous acid of magnetic
Nickel by powder, the min of stirring reaction 10, then solidifies 2h by product at 280 DEG C, and Jing after nano grinder is crushed composite flame-proof is obtained
Agent, phosphoric acid：Urea：Diatomite：The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of magnetic is：1:0.6:0.2:0.1, the antioxidant is
Pentaerythrite four (3- lauryl thiopropionates)；
The preparation method of low temperature resistant high fire-retardance ABS composite material of the present invention is specific as follows：By ABS resin, PC resin,
EPDM resins, antioxidant, Nano Silver, low temperature resistant plasticizer and composite flame-retardant agent are well mixed, Jing melting mixings, extruding pelletization
Obtain.
Embodiment 2：
Low temperature resistant high fire-retardance ABS composite material, the low temperature resistant high fire-retardance ABS composite material by following weight portion Raw material processing
Form：80 parts of ABS resin, 60 parts of PC resin, 10 parts of EPDM resins, 10 parts of antioxidant, 8 parts of Nano Silver, composite flame-retardant agent 12
Part, 8 parts of low temperature resistant plasticizer, the composite flame-retardant agent is that APP-diatomite/magnetic prepared by in-situ polymerization is order mesoporous
Nickel ferrite based magnetic loaded composite flame-retardant agent, the preparation method of composite flame-retardant agent is specific as follows：85% SPA is poured in reactor, heating is stirred
Mix, temperature is raised to 80 DEG C and adds appropriate urea, when temperature is raised to 120 DEG C, add appropriate diatomite and the order mesoporous iron of magnetic
Sour nickel by powder, the min of stirring reaction 20, then solidifies 1h by product at 320 DEG C, and Jing after nano grinder is crushed resistance must be combined
Combustion agent, phosphoric acid：Urea：Diatomite：The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of magnetic is：1:0.7:0.3:0.2, the antioxidant
For four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters；
The preparation method of low temperature resistant high fire-retardance ABS composite material of the present invention is specific as follows：By ABS resin, PC resin,
EPDM resins, antioxidant, Nano Silver, low temperature resistant plasticizer and composite flame-retardant agent are well mixed, Jing melting mixings, extruding pelletization
Obtain.
Embodiment 3：
Low temperature resistant high fire-retardance ABS composite material, the low temperature resistant high fire-retardance ABS composite material by following weight portion Raw material processing
Form：70 parts of ABS resin, 50 parts of PC resin, 6 parts of EPDM resins, 8 parts of antioxidant, 6 parts of Nano Silver, 10 parts of composite flame-retardant agent,
6 parts of low temperature resistant plasticizer, the composite flame-retardant agent is APP-order mesoporous iron of diatomite/magnetic prepared by in-situ polymerization
Sour nickel composite flame-retardant agent, the preparation method of composite flame-retardant agent is specific as follows：85% SPA is poured in reactor, heating stirring,
Temperature is raised to 70 DEG C and adds appropriate urea, when temperature is raised to 122 DEG C, adds appropriate diatomite and the order mesoporous ferrous acid of magnetic
Nickel by powder, the min of stirring reaction 15, then solidifies 1.5h by product at 300 DEG C, and Jing after nano grinder is crushed resistance must be combined
Combustion agent, phosphoric acid：Urea：Diatomite：The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of magnetic is：1:0.65:0.25:0.15, the antioxygen
Agent is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and four [β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid] pentaerythritol ester mass ratio 2:3 mixture；
The preparation method of low temperature resistant high fire-retardance ABS composite material of the present invention is specific as follows：By ABS resin, PC resin,
EPDM resins, antioxidant, Nano Silver, low temperature resistant plasticizer and composite flame-retardant agent are well mixed, Jing melting mixings, extruding pelletization
Obtain.
Comparative example
90 parts of ABS resin, 50 parts of PC resin, 8 parts of EPDM resins, ABS resin, PC resin, EPDM mixed with resin is uniform, and Jing melts
Melt mixing, extruding pelletization is obtained.
Test case
Embodiment 1-3 is tested, the concrete data of fire resistance are shown in Table 1.
In sum, the present invention can significantly improve the anti-flammability of ABS composite material：With phosphoric acid and urea as main former
Material, with diatomite and the order mesoporous nickel ferrite based magnetic loaded of magnetic as carrier, the APP-diatomite/magnetic prepared by in-situ polymerization
Order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent, can give full play to the cooperative flame retardant between APP and element silicon and iron, nickel element
Effect, makes ABS composite material have good fire resistance.
Embodiment 1-3 is tested, the concrete data of smoke suppressing are shown in Table 2.
In sum, the present invention can significantly improve the smoke-suppressing of ABS composite material, on the one hand using diatomaceous porous
Property and adsorptivity, and the adsorptivity of the order mesoporous nickel ferrite based magnetic loaded of high-specific surface area magnetic, reduce the product cigarette of ABS composite material burning
Amount；On the other hand using the high cooperative flame retardant effect between APP and element silicon and iron, nickel element, to ABS composite material
Play good into charcoal covering effect, reduce the thermal decomposition of ABS composite material composition and the generation of imflammable gas.
Embodiment 1-3 is tested, anti-microbial property test：Anti-microbial property detection is with reference to state of People's Republic of China (PRC) light industry
Professional standard QB/T2591-2003, using film applicator coating, investigates the antibiotic rate of sample 24h, and total plate count is determined with reference to GB/
T4789.2-2003 is counted.50mm × 50mm antibacterial models are made by pellet is hot-forming.The calculating formula of antibiotic rate is as follows： R
(%)=(B-C)/B × 100, wherein R is antibiotic rate (%)；B be the average bacterial count recovered of blank control sample, cfu/ pieces；C is anti-
The average bacterial count recovered of bacterium plastic sample, cfu/ pieces.
In sum, low temperature resistant high fire-retardance ABS material of the invention has good anti-microbial property.
Embodiment 1-3 is tested, by ISO179, -30 DEG C of punching press intensity is tested, it is as a result as follows：
In sum, low temperature resistant high fire-retardance ABS material of the invention has good resistance to low temperature.Embodiment described above
Simply one kind preferably scheme of the invention, also other on the premise of without departing from the technical scheme described in claim
Variant and remodeling.
Claims (6)
1. low temperature resistant high fire-retardance ABS composite material, it is characterised in that：The low temperature resistant high fire-retardance ABS composite material is by following heavy
The Raw material processing of amount part is formed：ABS resin 60-80 parts, PC resin 40-60 part, EPDM resin 5-10 parts, antioxidant 6-10
Part, Nano Silver 5-8 parts, composite flame-retardant agent 8-12 parts, low temperature resistant plasticizer 5-8 parts, the composite flame-retardant agent is in-situ polymerization system
The standby order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic, the preparation method of composite flame-retardant agent is concrete such as
Under：85% SPA is poured in reactor, heating stirring, temperature is raised to 60-80 DEG C and adds appropriate urea, when temperature is raised to
When 120-125 DEG C, add appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, the min of stirring reaction 10 ~ 20 then will produce
Thing solidifies 1-2h at 280-320 DEG C, and Jing after nano grinder is crushed composite flame-retardant agent is obtained.
2. low temperature resistant high fire-retardance ABS composite material according to claim 1, it is characterised in that：The low temperature resistant high fire-retardance
ABS composite material is formed by the Raw material processing of following weight portion：70 parts of ABS resin, 50 parts of PC resin, 6 parts of EPDM resins, antioxygen
8 parts of agent, 6 parts of Nano Silver, 8 parts of composite flame-retardant agent, 6 parts of low temperature resistant plasticizer, the preparation method of composite flame-retardant agent is specific as follows：
The SPA of 85% concentration is poured in reactor, heating stirring, temperature is raised to 70 DEG C and adds appropriate urea, when temperature is raised to
When 122 DEG C, appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, stirring reaction 15min, then by product 300 are added
Solidify 1.5h at DEG C, Jing after nano grinder is crushed composite flame-retardant agent is obtained.
3. low temperature resistant high fire-retardance ABS composite material according to claim 1 and 2, it is characterised in that：Phosphoric acid：Urea：Diatom
Soil：The mass ratio of the order mesoporous nickel ferrite based magnetic loaded of magnetic is：1:（0.6~0.7）:（0.2~0.3）:（0.1-0.2）.
4. low temperature resistant high fire-retardance ABS composite material according to claim 1 and 2, it is characterised in that：The antioxidant is
Pentaerythrite four (3- lauryl thiopropionates) and/or four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi
Alcohol ester.
5. low temperature resistant high fire-retardance ABS composite material according to claim 4, it is characterised in that：The antioxidant is season
Penta tetrol four (3- lauryl thiopropionates) and four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters are pressed
Mass ratio 2:3 mixture.
6. a kind of preparation method of the low temperature resistant high fire-retardance ABS composite material described in claim 1-5 any one, its feature exists
In：The preparation method is specific as follows：
（1）The order mesoporous nickel ferrite based magnetic loaded composite flame-retardant agent of APP-diatomite/magnetic prepared by in-situ polymerization：By 85% SPA
In pouring reactor into, heating stirring, temperature is raised to 60-80 DEG C and adds appropriate urea, when temperature is raised to 120-125 DEG C, adds
Appropriate diatomite and the order mesoporous ferrous acid nickel by powder of magnetic, the min of stirring reaction 10 ~ 20, then by product at 280-320 DEG C
Solidification 1-2h, Jing after nano grinder is crushed composite flame-retardant agent is obtained；
（2）By the mixing of ABS resin, PC resin, EPDM resins, antioxidant, Nano Silver, low temperature resistant plasticizer and composite flame-retardant agent
Uniformly, Jing melting mixings, extruding pelletization is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201611113729.5A CN106589769A (en) | 2016-12-07 | 2016-12-07 | Low-temperature-resistant and high-flame-retardant ABS composite material and preparation method thereof |
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| CN201611113729.5A CN106589769A (en) | 2016-12-07 | 2016-12-07 | Low-temperature-resistant and high-flame-retardant ABS composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312288A (en) * | 2017-06-26 | 2017-11-03 | 俞惠英 | A kind of low temperature resistant flame retardant material |
| CN107746561A (en) * | 2017-09-28 | 2018-03-02 | 雷晓琴 | A kind of household electrical appliances composite plastic and preparation method thereof |
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| CN103073862A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof |
| CN103937144A (en) * | 2014-04-30 | 2014-07-23 | 山东瀚氏汽车零部件有限公司 | ABS (acrylonitrile-butadiene-styrene) plastic for automobile inner ornaments and preparation method thereof |
| CN105754436A (en) * | 2016-04-24 | 2016-07-13 | 龙泉市嘉文木业有限公司 | Water and mildew resistant paint for wooden wireless loudspeaker tea set box and preparing method thereof |
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| CN102389837A (en) * | 2011-09-23 | 2012-03-28 | 常州大学 | Magnetic polypyrrole/titanium dioxide/clay nano-composite photocatalyst and preparation method thereof |
| CN103073862A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof |
| CN103937144A (en) * | 2014-04-30 | 2014-07-23 | 山东瀚氏汽车零部件有限公司 | ABS (acrylonitrile-butadiene-styrene) plastic for automobile inner ornaments and preparation method thereof |
| CN105754436A (en) * | 2016-04-24 | 2016-07-13 | 龙泉市嘉文木业有限公司 | Water and mildew resistant paint for wooden wireless loudspeaker tea set box and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312288A (en) * | 2017-06-26 | 2017-11-03 | 俞惠英 | A kind of low temperature resistant flame retardant material |
| CN107746561A (en) * | 2017-09-28 | 2018-03-02 | 雷晓琴 | A kind of household electrical appliances composite plastic and preparation method thereof |
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