CN104231525A - Long-glass-fiber-reinforced environment-friendly flame-retardant ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof - Google Patents
Long-glass-fiber-reinforced environment-friendly flame-retardant ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a long-glass-fiber-reinforced environment-friendly flame-retardant ABS (acrylonitrile-butadiene-styrene) composite material. The composite material is prepared from the following raw materials in parts by weight: 40-80 parts of ABS (acrylonitrile-butadiene-styrene), 5-50 parts of continuous glass fiber, 5-25 parts of flame retardant, 1-5 parts of compatilizer, 0.1-0.5 part of processing assistant and 0.1-0.5 part of antioxidant. The preparation method comprises the following steps: preparing a long-glass-fiber-reinforced ABS master batch and a flame-retardant ABS master batch, and proportionally mixing the master batches. The method changes the complex technique of preimpregnation and extrusion in the existing long-glass-fiber-reinforced flame-retardant ABS preparation process, and can perform melt processing directly by using twin screw equipment, thereby simplifying the production technique and enhancing the production efficiency; the prepared composite material completely satisfies the European Union RoHS standard, and has higher mechanical properties and favorable flame retardancy; and compared with the prior art, the composite material has the advantages of simple production technique and higher cost performance.
Description
Technical field
The present invention relates to polymeric material field, specifically, a kind ofly can be used for injection moulding, long glass fiber reinforced environment-friendly flame-resistant ABS matrix material of simultaneously have environmental protection flame retardant requirement or electronic electric equipment for export and household appliances a kind of high strength good flame-retardance and preparation method thereof.
Background technology
ABS is a kind of novel macromolecular material occurred the forties in 20th century, and have good thermotolerance, impact and excellent processibility, be widely used in automobile component, household electrical appliance and electronic devices and components.
Due to the butadiene structure in ABS backbone molecule structure and lack aromatic group, therefore itself flame retardant properties is poor, often does fire-retardant finish for the ABS product be applied on electric and household electrical appliance.European Union is defined in the electric/electronic device product of newly putting on market, forbids or limits six kinds of objectionable impuritiess such as using lead, mercury, cadmium, sexavalent chrome, Poly Brominated Diphenyl Ethers (PBDE) and Polybrominated biphenyl (PBB).Therefore, environment-friendly flame-resistant ABS will replace the flame-proof ABS product containing ether and heavy metal one class gradually.
As everyone knows, glass gives the characteristics such as resin high strength, high rigidity, high impact, low density, low warpage creep properties as strongthener, and glass fiber reinforced materials is high because of its cost performance, is widely used in the structural elements such as automobile, household electrical appliances.In glass fibre reinforced composite material, the length of glass is longer, and namely the length-to-diameter ratio of glass is larger, and its reinforced effects as strongthener is more obvious.What provide as patent CN201210369026.4 high-strengthly has halogen fire-retardant long glass fiber reinforced AS matrix material and preparation method thereof, and a CN201110425445.0 halogen-free flameproof long glass fiber-reinforced polypropylene materials and preparation method thereof, be all prepare with special die head the short fiber commonly used before long glass fiber reinforced material replaces, thus obtain the material with high-strength mechanical property.And prepared by long glass fiber reinforced flame-proof ABS for extrusion by melting, not relevant patent report.Chinese patent CN200510111533.8, a kind of preparation method of long fiber reinforced ABS composite material provides a kind of method of soaking damp butadiene graft emulsion and SAN resin powder in advance, post-drying, melting, extrusion molding pelletizing.Operation is more loaded down with trivial details and complicated, is not suitable for suitability for industrialized production, and does not relate to the preparation of flame-proof ABS.
Summary of the invention
The object of the invention is for deficiency of the prior art, a kind of long glass fiber reinforced environment-friendly flame-resistant ABS matrix material is provided, short and cause the technical problem of its reinforced effects difference to solve glass length-to-diameter ratio in the matrix material of existing fiberglass reinforced fire retardant ABS, select the fire retardant of environment-friendly type simultaneously, make it meet the Rohs standard of European Union completely.
Second object of the present invention is, provides a kind of preparation method of long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.
For achieving the above object, the technical scheme that the present invention takes is: a kind of long glass fiber reinforced environment-friendly flame-resistant ABS matrix material, and described matrix material is made up of the raw material of following weight part:
ABS:40-80 part,
Continuous long glass fiber: 5-50 part,
Fire retardant: 5-25 part,
Compatilizer: 1-5 part,
Processing aid: 0.1-0.5 part,
Oxidation inhibitor: 0.1-0.5 part,
The preparation method of described matrix material comprises the following steps:
(1) long fiber reinforced ABS master batch: by ABS, compatilizer, processing aid, oxidation inhibitor is blended in proportion, by twin-screw extrusion in immersion equipment, continuous long glass fiber, by infiltrating die head, fully infiltrates, then cool, pelletizing, obtain long fiber reinforced ABS master batch;
(2) prepare flame retardant ABS master batch: by fire retardant, ABS is blended in proportion, by twin-screw extrusion, and cooling, pelletizing obtains flame retardant ABS master batch;
(3) blended long fiber reinforced ABS master batch and flame retardant ABS master batch in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.
Described step (3) is blended long fiber reinforced ABS master batch, flame retardant ABS master batch and ABS raw material in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.
The described ABS preparing roving glass fiber ABS masterbatch is high workability material, and when test condition is 220 DEG C/10Kg, it melts to refer to be 20g-500g/min.
Described continuous long glass fiber is high strength alkali-free long glass fibres.
Described fire retardant is TDE, brominated Polystyrene, three (tribromophenoxy) triazine and SB
2o
3the cooperative flame retardant mixture of one or more.
Described compatilizer is take ABS, SBS, AS, PS polymer as the high-molecular copolymer of matrix grafted maleic anhydride or GMA and derivative thereof.
Described oxidation inhibitor is the compound system of Hinered phenols antioxidant 1076 and phosphite ester kind antioxidant 168, and wherein the compound proportion of 1076 and 168 is 1:1.
Described processing aid is one or more in ethylene bis stearamide, polyether silicone oil, hydroxy silicon oil, polyethylene wax or tetramethylolmethane stearate.
For realizing above-mentioned second object, the technical scheme that the present invention takes is: a kind of preparation method of long glass fiber reinforced environment-friendly flame-resistant ABS matrix material, and the preparation method of described matrix material comprises the following steps:
(1) long fiber reinforced ABS master batch: by ABS, compatilizer, processing aid, oxidation inhibitor is blended in proportion, by twin-screw extrusion in immersion equipment, continuous long glass fiber, by infiltrating die head, fully infiltrates, then cool, pelletizing, obtain long fiber reinforced ABS master batch;
(2) prepare flame retardant ABS master batch: by fire retardant, ABS is blended in proportion, by twin-screw extrusion, and cooling, pelletizing obtains flame retardant ABS master batch;
(3) blended long fiber reinforced ABS master batch and flame retardant ABS master batch in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material;
Described matrix material is made up of the raw material of following weight part:
ABS:40-80 part,
Continuous long glass fiber: 5-50 part,
Fire retardant: 5-25 part,
Compatilizer: 1-5 part,
Processing aid: 0.1-0.5 part,
Oxidation inhibitor: 0.1-0.5 part.
Described step (3) is blended long fiber reinforced ABS master batch, flame retardant ABS master batch and ABS raw material in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.
The invention has the advantages that:
1, the present invention changes current long glass fiber reinforced flame-proof ABS of preparing needs preimpregnation, the loaded down with trivial details technique of extruding, directly can pass through twin screw device melt-processed, simplify corresponding production technique, more fast efficient, improves production efficiency;
2, the long glass fiber reinforced environment-friendly flame-resistant ABS matrix material of preparation meets the Rohs standard of European Union completely, has higher mechanical property, and has good flame retardant resistance, has high-strength and high-modulus, the characteristic of HI high impact relative to the general anti-flaming ABS material that strengthens;
3, the present invention is compared with current techniques, and production technique is simple, has higher cost performance.
Embodiment
Below in conjunction with embodiment, embodiment provided by the invention is elaborated.
The invention provides a kind of long glass fiber reinforced environment-friendly flame-resistant ABS matrix material, described matrix material is made up of the raw material of following weight part:
ABS:40-80 part,
Continuous long glass fiber: 5-50 part,
Fire retardant: 5-25 part,
Compatilizer: 1-5 part,
Processing aid: 0.1-0.5 part,
Oxidation inhibitor: 0.1-0.5 part,
The preparation method of described matrix material comprises the following steps:
(1) long fiber reinforced ABS master batch: by ABS, compatilizer, processing aid, oxidation inhibitor is blended in proportion, by twin-screw extrusion in immersion equipment, continuous long glass fiber, by infiltrating die head, fully infiltrates, then cool, pelletizing, obtain long fiber reinforced ABS master batch;
(2) prepare flame retardant ABS master batch: by fire retardant, ABS is blended in proportion, by twin-screw extrusion, and cooling, pelletizing obtains flame retardant ABS master batch;
(3) blended long fiber reinforced ABS master batch and flame retardant ABS master batch in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.
Described step (3) is blended long fiber reinforced ABS master batch, flame retardant ABS master batch and ABS raw material in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.
The described ABS preparing roving glass fiber ABS masterbatch is high workability material, and when test condition is 220 DEG C/10Kg, it melts to refer to be 20g-500g/min.Described continuous long glass fiber is high strength alkali-free long glass fibres.Described fire retardant is TDE, brominated Polystyrene, three (tribromophenoxy) triazine and SB
2o
3the cooperative flame retardant mixture of one or more.Described compatilizer is take ABS, SBS, AS, PS polymer as the high-molecular copolymer of matrix grafted maleic anhydride or GMA and derivative thereof.Described oxidation inhibitor is the compound system of Hinered phenols antioxidant 1076 and phosphite ester kind antioxidant 168, and wherein the compound proportion of 1076 and 168 is 1:1.Described processing aid is one or more in ethylene bis stearamide, polyether silicone oil, hydroxy silicon oil, polyethylene wax or tetramethylolmethane stearate.
It should be noted that, following examples and the ABS preparing roving glass fiber ABS masterbatch described in comparative example are high workability material, and when test condition is 220 DEG C/10Kg, it melts to refer to be 20g-500g/min.Described alkali-free long glass fibres is the high strength alkali-free long glass fibres being applicable to doing long glass fiber reinforced material.Described irgasfos 168/1076, for irgasfos 168 and 1076 compound system, wherein the compound proportion of 1076 and 168 is 1:1.
embodiment 1
(1) long fiber reinforced ABS master batch is prepared: according to above-mentioned technique and proportioning, by blended to ABS, compatilizer, processing aid and oxidation inhibitor by twin-screw extrusion to infiltration die head (extrusion temperature 220-250 DEG C), alkali free glass fibre is by infiltrating die head, cooling, pelletizing obtains long glass fiber reinforced master batch;
(2) prepare flame retardant ABS master batch: by the blended three kinds of raw materials of above-mentioned formula, by twin-screw extrusion (extrusion temperature 210-230 DEG C), cooling, pelletizing obtains fire-retardant master granule;
(3) long glass fiber reinforced environment-friendly flame-resistant ABS matrix material is prepared:
By blended according to 60:40 weight ratio for above-mentioned two kinds of master batches, obtain described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.Fire-retardant and the ASTM standard batten of injection moulding, test material performance.
embodiment 2
Long fiber reinforced ABS master batch and flame retardant ABS master batch is prepared according to the ratio in embodiment 1 and step, according to long fiber reinforced ABS master batch: flame retardant ABS master batch: ABS raw material three weight ratio is that 20:40:50 takes each component, blended, obtain described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.Fire-retardant and the ASTM standard batten of injection moulding, test material performance.
embodiment 3
(1) long fiber reinforced ABS master batch is prepared: according to above-mentioned technique and proportioning, by blended to ABS, compatilizer, processing aid and oxidation inhibitor by twin-screw extrusion to infiltration die head (extrusion temperature 220-250 DEG C), alkali free glass fibre is by infiltrating die head, cooling, pelletizing obtains long glass fiber reinforced master batch;
(2) prepare flame retardant ABS master batch: by the blended three kinds of raw materials of above-mentioned formula, by twin-screw extrusion (extrusion temperature 210-230 DEG C), cooling, pelletizing obtains fire-retardant master granule;
(3) long glass fiber reinforced environment-friendly flame-resistant ABS matrix material is prepared:
By blended according to 60:40 weight ratio for above-mentioned two kinds of master batches, obtain described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.Fire-retardant and the ASTM standard batten of injection moulding, test material performance.
embodiment 4
Long fiber reinforced ABS master batch and flame retardant ABS master batch is prepared according to the ratio in embodiment 3 and step, according to long fiber reinforced ABS master batch: flame retardant ABS master batch: ABS raw material three weight ratio is that 60:30:10 takes each component, blended, obtain described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.Fire-retardant and the ASTM standard batten of injection moulding, test material performance.
embodiment 5
(1) long fiber reinforced ABS master batch is prepared: according to above-mentioned technique and proportioning, by blended to ABS, compatilizer, processing aid and oxidation inhibitor by twin-screw extrusion to infiltration die head (extrusion temperature 220-250 DEG C), alkali free glass fibre is by infiltrating die head, cooling, pelletizing obtains long glass fiber reinforced master batch;
(2) prepare flame retardant ABS master batch: by the blended three kinds of raw materials of above-mentioned formula, by twin-screw extrusion (extrusion temperature 210-230 DEG C), cooling, pelletizing obtains fire-retardant master granule;
(3) long glass fiber reinforced environment-friendly flame-resistant ABS matrix material is prepared:
By blended according to 60:40 weight ratio for above-mentioned two kinds of master batches, obtain described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.Fire-retardant and the ASTM standard batten of injection moulding, test material performance.
comparative example 1
Take material according to above-mentioned formula, blended, by twin-screw extrusion (extrusion temperature 200-225 DEG C), cooling, pelletizing obtains short glass fiber and strengthens flame-proof ABS, then injection moulding ASTM batten and fire-retardant batten, test performance.
comparative example 2
Take material according to above-mentioned formula, blended, by twin-screw extrusion (extrusion temperature 200-225 DEG C), cooling, pelletizing obtains short glass fiber and strengthens flame-proof ABS, then injection moulding ASTM batten and fire-retardant batten, test performance.
embodiment 6 performance data
The performance data of embodiment 1-5 and comparative example 1-2 sees the following form 1:
The performance data of table 1 embodiment 1-5 and comparative example 1-2
As can be seen from physical property contrast, roving glass fiber environment friendly flame-proof ABS material provided by the invention has good mechanical property relative to short fiber strengthens flame-proof ABS, has high-strength and high-modulus, the characteristic of HI high impact.The preparation method of matrix material of the present invention, directly can pass through twin screw device melt-processed, not need preimpregnation, the techniques such as extruding, simplify corresponding production technique, more fast efficient, and the product produced meets the Rohs standard of European Union completely, and there is good flame retardant resistance.Compared with current techniques, production technique is simple, has higher cost performance.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the inventive method; can also make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.
Claims (10)
1. a long glass fiber reinforced environment-friendly flame-resistant ABS matrix material, is characterized in that, described matrix material is made up of the raw material of following weight part:
ABS:40-80 part,
Continuous long glass fiber: 5-50 part,
Fire retardant: 5-25 part,
Compatilizer: 1-5 part,
Processing aid: 0.1-0.5 part,
Oxidation inhibitor: 0.1-0.5 part,
The preparation method of described matrix material comprises the following steps:
(1) long fiber reinforced ABS master batch: by ABS, compatilizer, processing aid, oxidation inhibitor is blended in proportion, by twin-screw extrusion in immersion equipment, continuous long glass fiber, by infiltrating die head, fully infiltrates, then cool, pelletizing, obtain long fiber reinforced ABS master batch;
(2) prepare flame retardant ABS master batch: by fire retardant, ABS is blended in proportion, by twin-screw extrusion, and cooling, pelletizing obtains flame retardant ABS master batch;
(3) blended long fiber reinforced ABS master batch and flame retardant ABS master batch in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.
2. matrix material according to claim 1, is characterized in that, described step (3) is blended long fiber reinforced ABS master batch, flame retardant ABS master batch and ABS raw material in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.
3. matrix material according to claim 1, is characterized in that, the described ABS preparing roving glass fiber ABS masterbatch is high workability material, and when test condition is 220 DEG C/10Kg, it melts to refer to be 20g-500g/min.
4. matrix material according to claim 1, is characterized in that, described continuous long glass fiber is high strength alkali-free long glass fibres.
5. matrix material according to claim 1, is characterized in that, described fire retardant is TDE, brominated Polystyrene, three (tribromophenoxy) triazine and SB
2o
3the cooperative flame retardant mixture of one or more.
6. matrix material according to claim 1, is characterized in that, described compatilizer is take ABS, SBS, AS, PS polymer as the high-molecular copolymer of matrix grafted maleic anhydride or GMA and derivative thereof.
7. matrix material according to claim 1, is characterized in that, described oxidation inhibitor is the compound system of Hinered phenols antioxidant 1076 and phosphite ester kind antioxidant 168, and wherein the compound proportion of 1076 and 168 is 1:1.
8. matrix material according to claim 1, is characterized in that, described processing aid is one or more in ethylene bis stearic acid amide, polyether silicone oil, hydroxy silicon oil, polyethylene wax or tetramethylolmethane stearate.
9. a preparation method for long glass fiber reinforced environment-friendly flame-resistant ABS matrix material, is characterized in that, the preparation method of described matrix material comprises the following steps:
(1) long fiber reinforced ABS master batch: by ABS, compatilizer, processing aid, oxidation inhibitor is blended in proportion, by twin-screw extrusion in immersion equipment, continuous long glass fiber, by infiltrating die head, fully infiltrates, then cool, pelletizing, obtain long fiber reinforced ABS master batch;
(2) prepare flame retardant ABS master batch: by fire retardant, ABS is blended in proportion, by twin-screw extrusion, and cooling, pelletizing obtains flame retardant ABS master batch;
(3) blended long fiber reinforced ABS master batch and flame retardant ABS master batch in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material;
Described matrix material is made up of the raw material of following weight part:
ABS:40-80 part,
Continuous long glass fiber: 5-50 part,
Fire retardant: 5-25 part,
Compatilizer: 1-5 part,
Processing aid: 0.1-0.5 part,
Oxidation inhibitor: 0.1-0.5 part.
10. preparation method according to claim 9, is characterized in that, described step (3) is blended long fiber reinforced ABS master batch, flame retardant ABS master batch and ABS raw material in proportion, namely prepares described long glass fiber reinforced environment-friendly flame-resistant ABS matrix material.
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| CN201410427726.3A CN104231525A (en) | 2014-08-27 | 2014-08-27 | Long-glass-fiber-reinforced environment-friendly flame-retardant ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof |
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| CN201410427726.3A CN104231525A (en) | 2014-08-27 | 2014-08-27 | Long-glass-fiber-reinforced environment-friendly flame-retardant ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383758A (en) * | 2017-09-04 | 2017-11-24 | 广州湘融新材料科技有限公司 | A kind of ABS composites and preparation method thereof |
| CN111484702A (en) * | 2019-12-20 | 2020-08-04 | 四川鑫达企业集团有限公司 | Low-shrinkage precipitation-resistant halogen-free flame-retardant ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN114957853A (en) * | 2022-05-27 | 2022-08-30 | 句容市百事特复合材料有限公司 | Heat-conducting long glass fiber PP and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044843A (en) * | 2011-10-17 | 2013-04-17 | 合肥杰事杰新材料股份有限公司 | Continuous long-fiber reinforced ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof |
-
2014
- 2014-08-27 CN CN201410427726.3A patent/CN104231525A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044843A (en) * | 2011-10-17 | 2013-04-17 | 合肥杰事杰新材料股份有限公司 | Continuous long-fiber reinforced ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383758A (en) * | 2017-09-04 | 2017-11-24 | 广州湘融新材料科技有限公司 | A kind of ABS composites and preparation method thereof |
| CN111484702A (en) * | 2019-12-20 | 2020-08-04 | 四川鑫达企业集团有限公司 | Low-shrinkage precipitation-resistant halogen-free flame-retardant ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN114957853A (en) * | 2022-05-27 | 2022-08-30 | 句容市百事特复合材料有限公司 | Heat-conducting long glass fiber PP and preparation method thereof |
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