CN106566179A - Aluminum powder filling and modifying flame-retardant insulation type automobile plastic uptake material and preparation method thereof - Google Patents
Aluminum powder filling and modifying flame-retardant insulation type automobile plastic uptake material and preparation method thereof Download PDFInfo
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- CN106566179A CN106566179A CN201610934266.2A CN201610934266A CN106566179A CN 106566179 A CN106566179 A CN 106566179A CN 201610934266 A CN201610934266 A CN 201610934266A CN 106566179 A CN106566179 A CN 106566179A
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- resin
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- plastic uptake
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- automobile plastic
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an aluminum powder filling and modifying flame-retardant insulation type automobile plastic uptake material and a preparation process thereof. The aluminum powder filling and modifying flame-retardant insulation type automobile plastic uptake material is characterized in that ABS (Acrylonitrile Butadiene Styrene) copolymers, linear phenolic resin, microencapsulated red phosphorus, magnesium salt whiskers, nitrile rubber, mesoporous molecular sieves SBA-15, ammonium polyphosphate, melamine resin, kaolin, Sb2O3, simethicone, graphene, aluminum powder, Intropin, trihydroxymethyl aminomethane, epoxide resin, m-Xylylenediamine and the like are used as raw materials. The mesoporous molecular sieves and linear phenolic resin generate a key joint effect, so that the thermal stability of matrix resin is improved; microencapsulated ammonium polyphosphate and antimony oxide/kaolin composite flame-retardant micro powder generate a synergistic effect; the flame-retardant effect is better; the grapheme is added into an ABS resin matrix, so that the flame-retardant performance and the thermal stability of the resin are obviously improved; the mechanical property is higher; and the aluminum powder filling and modifying flame-retardant insulation type automobile plastic uptake material is obtained.
Description
Technical field
The present invention relates to the field of fire-proof technology of composite, and in particular to a kind of filling-modified fire retardant insulating type of aluminium powder
Automobile plastic uptake material, and its preparation technology.
Background technology
The terpolymer that ABS is made up of acrylonitrile, butadiene and styrene, as a kind of thermoplastic engineering plastic,
With its excellent mechanical property, chemical inertness and workability, auto industry, electronics, electrical equipment, weaving, device are widely used in
The field such as tool and building materials.But the fire resistance of ABS resins is poor, a kind of additive how is found, ABS resin can be made
While fire resistance is improved, and reduce the premium properties of itself, become the focus of research.
Yang Bing is in Master's thesis《Research based on linear phenol-aldehyde resin and microcapsule red phosphorus halogen-free flame retardant ABS》Profit in one text
With the low cigarette of low toxicity, high temperature resistant, high fixing carbon, economical and efficient linear phenol-aldehyde resin as carbon forming agent, with microencapsulated powder oil association
With fire-retardant, with alkali magnesium sulfate crystal whisker as inorganic combustion inhibitor, select and increased with the preferable nitrile rubber of the ABS matrix compatibilitys
It is tough modified, sequentially add antioxidant and mixed uniformly line style after during experiment ABS is plastified in 180 DEG C of two-roll mill
Phenolic resin, microcapsule red phosphorus, inorganic combustion inhibitor alkali magnesium sulfate crystal whisker, nitrile rubber blends, discharge simultaneously after mixing is uniform
In being positioned over mould, then hot pressing 10 minutes on 180 DEG C of vulcanizing press cold pressing at room temperature 10 minutes, and depanning is obtained
Modified ABS plastic sheet material, but it is not enough to there is flame retardant effect.
The present invention on this basis, by mesopore molecular sieve and linear phenolic resin bonded effect is produced, and strand runs through
Inside and outside the duct of mesopore molecular sieve, organic-inorganic hybrid material is formed, improve matrix resin heat stability；With in-situ polymerization
Method is prepared for micro encapsulation APP, and with ball-milling method Ultrafine Antimony-Oxide/Kaolin Composite Powder is prepared for, and Graphene is added to
In ABS resin matrix, hence it is evident that improve the anti-flammability and heat stability of resin, mechanical property is also higher；Finally obtain a kind of aluminum
Powder filled modified fire retardant insulating type automobile plastic uptake material.
The content of the invention
The invention mainly solves the technical problem of providing a kind of aluminium powder filling-modified fire retardant insulating type automobile plastic uptake material
Material and its preparation technology, the automobile plastic uptake material that makes according to the technique has light weight, heat-resisting, fire protection flame retarding, heat conductive insulating
Premium properties.
The technical problem to be solved is realized using following technical scheme：
Acrylonitrile-butadiene-styrene copolymer (ABS) 38-46, linear phenol-aldehyde resin 3-7, microcapsule red phosphorus 4-8, alkali formula
Magnesium sulfate crystal whisker 2-5, nitrile rubber 3-4, mesoporous molecular sieve SBA-15 4-10, APP 4-9, melamine resin
3-5, Kaolin 1-3, Sb2O35-9, dimethicone 1-2, Graphene 4-8, aluminium powder 2-4, Dopamine Hydrochloride 1-3, trihydroxy methyl
Aminomethane 1-2, epoxy resin 1-2, the methanediamine 0.5-1 of isophthalic two, ethanol, distilled water, appropriate acetic acid.
The preparation method of the filling-modified fire retardant insulating type automobile plastic uptake material of a kind of aluminium powder, it is characterised in that by following
Step is carried out：
A. mesoporous molecular sieve SBA-15 is mixed with linear phenol-aldehyde resin, after reacting 1-3h at 180-190 DEG C,
Microcapsule red phosphorus are added, continues to react 1-2h, product is placed in dehydrated alcohol, 25-40 DEG C of stirring 10-12h, second
Alcohol dissolves unreacted resin, filters, alcohol is washed, dry hybrid material；
B. in APP 1:2-3 adds ethanol and distilled water, after dispersed with stirring 10-30min, adds melamino-formaldehyde
Resin, it is 4-5 to adjust pH with acetic acid, is warming up to 80-90 DEG C of stirring reaction 2-3h, sucking filtration, washing, it is dry not exclusively coat it is micro-
Encapsulated APP；
C. 1-2h, and Sb are calcined in Kaolin grinding washing after 600-900 DEG C2O3Mixing, is placed in water ultrasonic disperse and makes
Serosity, after ball milling 4-6h baking oven is put into, and in 110-130 DEG C of drying 5-8h, obtains composite micro-powder, and it is mixed with resulting material in b
Uniformly, dimethicone is added at 60-120 DEG C, whip modified 15-60min, sucking filtration, washing, dry composite flame-retardant agent；
D. Dopamine Hydrochloride, trishydroxymethylaminomethane and ethanol are added in aluminium powder, 1-2h is stirred under room temperature to be carried out to aluminium powder
Cladding, filters after standing, and washing, alcohol are washed 3-5 time, are mixed with epoxy resin after drying, then adds the methanediamine of isophthalic two, ultrasonic magnetic force
Stirring 1-3h, drying obtains heat conductive insulating composite；
E. ABS resin is added in 180-190 DEG C of two-roll mill and is plastified, after ABS resin into after molten condition, then added
Enter resulting material in Graphene and a, d, after mixing 10-40min material must be kneaded；
F. the composite flame-retardant agent in c, the mixing material in e and other residual componentss are blended at 185-195 DEG C, mixing is equal
Discharge after even and be positioned in mould, the hot pressing 10-30min on 180-190 DEG C of vulcanizing press, then cold pressing at room temperature
10-30min, depanning is obtained modified ABS plastic sheet material, that is, obtain a kind of filling-modified fire retardant insulating type automobile plastic uptake of aluminium powder
Material.
The present invention reaction mechanism and have the beneficial effect that：
（1）Mesopore molecular sieve/linear phenol-aldehyde resin organic-inorganic hybrid material, linear phenol are prepared for by the method for in-situ polymerization
Urea formaldehyde is distributed in inside and outside mesopore molecular sieve duct, and there is bonded effect with SBA-15, forms organic-inorganic interpenetrating networks knot
Structure, improves matrix resin heat stability.
（2）Micro encapsulation APP is prepared with situ aggregation method（MCAPP）, APP can be significantly reduced after cladding
（APP）Water solubility and hygroscopicity, improve the resistance to leaching and limited oxygen index of material, melamine resin（MF）
There is good synergism with APP, in the case of APP claddings are incomplete, can more effectively play both interactions,
Improve the anti-flammability of composite.
（3）Sb is prepared for ball-milling method2O3/ Kaolin composite flame-proof micropowder, Sb2O3Belong to additive flame retardant, with stibium trioxide
Based on powder, Kaolin is attached to stibium trioxide powder surface, fully physics, chemical action occurs with stibium trioxide powder；
It is used in combination with APP, produces cooperative effect, flame retardant effect is more preferably.
（4）One layer of organic poly-dopamine is coated on aluminium powder using the method for chemistry cladding, based on epoxy resin, bag
It is heat filling to cover modified aluminium powder, with the methanediamine of isophthalic two as firming agent, using casting method high heat conductive insulating ring is prepared for
Epoxide composite.
（5）Graphene as the new lover in material with carbon element family, with incomparable excellent performance, can as the additive of ABS,
Graphene is added in ABS resin matrix, hence it is evident that improve the anti-flammability and heat stability of resin, mechanical property is also higher.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below
Specific embodiment is closed, the present invention is expanded on further.
Embodiment
A kind of filling-modified fire retardant insulating type automobile plastic uptake material of aluminium powder, is obtained by the raw material of following weight parts (g)：
Acrylonitrile-butadiene-styrene copolymer (ABS) 46, linear phenol-aldehyde resin 7, microcapsule red phosphorus 4, alkali magnesium sulfate is brilliant
Palpus 2, nitrile rubber 3, mesoporous molecular sieve SBA-15 4, APP 4, melamine resin 3, Kaolin 1, Sb2O35, two
Methyl-silicone oil 1, Graphene 4, aluminium powder 2, Dopamine Hydrochloride 1, trishydroxymethylaminomethane 2, epoxy resin 1, the methanediamine of isophthalic two
0.5, ethanol, distilled water, appropriate acetic acid.
The preparation method of the filling-modified fire retardant insulating type automobile plastic uptake material of a kind of aluminium powder, it is characterised in that by following
Step is carried out：
A. mesoporous molecular sieve SBA-15 is mixed with linear phenol-aldehyde resin, after reacting 1h at 180 DEG C, adds microcapsule red phosphorus,
Continue to react 2h, product is placed in dehydrated alcohol, 40 DEG C of stirring 10h, ethanol dissolves unreacted resin, filtration, alcohol
Wash three times, dry hybrid material；
B. in APP 1:2 add ethanol and distilled water, after dispersed with stirring 10min, add melamine resin,
Adjust pH to 5 with acetic acid, be warming up to 80 DEG C of stirring reactions 3h, sucking filtration, washing, dry the micro encapsulation polyphosphoric acid for not exclusively coating
Ammonium；
C. 1h, and Sb are calcined in Kaolin grinding washing after 750 DEG C2O3Mixing, is placed in water ultrasonic disperse and makes serosity,
Baking oven is put into after ball milling 4h, in 130 DEG C of dryings 5h, composite micro-powder is obtained, it is mixed homogeneously with resulting material in b, at 80 DEG C
Add dimethicone, whip modified 30min, sucking filtration, washing, dry composite flame-retardant agent；
D. Dopamine Hydrochloride, trishydroxymethylaminomethane and ethanol are added in aluminium powder, 1h is stirred under room temperature aluminium powder is wrapped
Cover, filter after standing, washing, alcohol are washed 3 times, are mixed with epoxy resin after drying, then add the methanediamine of isophthalic two, ultrasonic magnetic agitation
2h, drying, obtains heat conductive insulating composite；
E. ABS resin is added in 180-190 DEG C of two-roll mill and is plastified, after ABS resin into after molten condition, then added
Enter resulting material in Graphene and a, d, after mixing 40min material must be kneaded；
F. the composite flame-retardant agent in c, the mixing material in e and other residual componentss are blended at 185-195 DEG C, mixing is equal
Discharge after even and be positioned in mould, the hot pressing 30min on 180-190 DEG C of vulcanizing press, then cold pressing at room temperature
30min, depanning is obtained modified ABS plastic sheet material, that is, obtain a kind of filling-modified fire retardant insulating type automobile plastic uptake material of aluminium powder
Material.
A kind of performance detection knot of the filling-modified fire retardant insulating type automobile plastic uptake material of aluminium powder prepared by above-described embodiment
It is really as follows：
Up to UL-94 V-0 levels, LOI values 32%, carbon yield (600 DEG C) 17%, tensile strength reaches the vertical combustion performance of flame-proof ABS
46MPa, notch impact strength is 31KJ/m2, elongation at break 38%.
Claims (2)
1. the filling-modified fire retardant insulating type automobile plastic uptake material of a kind of aluminium powder, it is characterised in that by the raw material of following weight parts
It is obtained：
Acrylonitrile-butadiene-styrene copolymer (ABS) 38-46, linear phenol-aldehyde resin 3-7, microcapsule red phosphorus 4-8, alkali formula
Magnesium sulfate crystal whisker 2-5, nitrile rubber 3-4, mesoporous molecular sieve SBA-15 4-10, APP 4-9, melamine resin
3-5, Kaolin 1-3, Sb2O35-9, dimethicone 1-2, Graphene 4-8, aluminium powder 2-4, Dopamine Hydrochloride 1-3, trihydroxy methyl
Aminomethane 1-2, epoxy resin 1-2, the methanediamine 0.5-1 of isophthalic two, ethanol, distilled water, appropriate acetic acid.
2. the preparation method of the filling-modified fire retardant insulating type automobile plastic uptake material of a kind of aluminium powder according to claim 1,
Characterized in that, carrying out according to the following steps：
Mesoporous molecular sieve SBA-15 is mixed with linear phenol-aldehyde resin, after reacting 1-3h at 180-190 DEG C, adds microcapsule red
Phosphorus, continues to react 1-2h, and product is placed in dehydrated alcohol, and 25-40 DEG C of stirring 10-12h, ethanol dissolves unreacted tree
Fat, filters, alcohol is washed, dry hybrid material；
B. in APP 1:2-3 adds ethanol and distilled water, after dispersed with stirring 10-30min, adds melamino-formaldehyde
Resin, it is 4-5 to adjust pH with acetic acid, is warming up to 80-90 DEG C of stirring reaction 2-3h, sucking filtration, washing, it is dry not exclusively coat it is micro-
Encapsulated APP；
C. 1-2h, and Sb are calcined in Kaolin grinding washing after 600-900 DEG C2O3Mixing, is placed in water ultrasonic disperse and makes
Serosity, after ball milling 4-6h baking oven is put into, and in 110-130 DEG C of drying 5-8h, obtains composite micro-powder, and it is mixed with resulting material in b
Uniformly, dimethicone is added at 60-120 DEG C, whip modified 15-60min, sucking filtration, washing, dry composite flame-retardant agent；
D. Dopamine Hydrochloride, trishydroxymethylaminomethane and ethanol are added in aluminium powder, 1-2h is stirred under room temperature to be carried out to aluminium powder
Cladding, filters after standing, and washing, alcohol are washed 3-5 time, are mixed with epoxy resin after drying, then adds the methanediamine of isophthalic two, ultrasonic magnetic force
Stirring 1-3h, drying obtains heat conductive insulating composite；
E. ABS resin is added in 180-190 DEG C of two-roll mill and is plastified, after ABS resin into after molten condition, then added
Enter resulting material in Graphene and a, d, after mixing 10-40min material must be kneaded；
F. the composite flame-retardant agent in c, the mixing material in e and other residual componentss are blended at 185-195 DEG C, mixing is equal
Discharge after even and be positioned in mould, the hot pressing 10-30min on 180-190 DEG C of vulcanizing press, then cold pressing at room temperature
10-30min, depanning is obtained modified ABS plastic sheet material, that is, obtain a kind of filling-modified fire retardant insulating type automobile plastic uptake of aluminium powder
Material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610934266.2A CN106566179A (en) | 2016-10-25 | 2016-10-25 | Aluminum powder filling and modifying flame-retardant insulation type automobile plastic uptake material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116426069A (en) * | 2023-03-09 | 2023-07-14 | 湖南中楚新材料科技有限公司 | Polydopamine modified kaolinite reinforced flame-retardant waste resin composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694370A (en) * | 2016-04-08 | 2016-06-22 | 西南石油大学 | Toughened-flame-retardant epoxy resin material and preparation method thereof |
| CN105968491A (en) * | 2016-05-20 | 2016-09-28 | 温州泓呈祥科技有限公司 | Cable insulation material containing flame retardant compound agent LDHS/SBA-15 and application of cable insulation material |
-
2016
- 2016-10-25 CN CN201610934266.2A patent/CN106566179A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694370A (en) * | 2016-04-08 | 2016-06-22 | 西南石油大学 | Toughened-flame-retardant epoxy resin material and preparation method thereof |
| CN105968491A (en) * | 2016-05-20 | 2016-09-28 | 温州泓呈祥科技有限公司 | Cable insulation material containing flame retardant compound agent LDHS/SBA-15 and application of cable insulation material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116426069A (en) * | 2023-03-09 | 2023-07-14 | 湖南中楚新材料科技有限公司 | Polydopamine modified kaolinite reinforced flame-retardant waste resin composite material and preparation method thereof |
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Application publication date: 20170419 |