CN105237997A - Halogen-free flame-retardant PC/ABS alloy and preparation method thereof - Google Patents
Halogen-free flame-retardant PC/ABS alloy and preparation method thereof Download PDFInfo
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- CN105237997A CN105237997A CN201510767980.2A CN201510767980A CN105237997A CN 105237997 A CN105237997 A CN 105237997A CN 201510767980 A CN201510767980 A CN 201510767980A CN 105237997 A CN105237997 A CN 105237997A
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Abstract
The invention relates to the technical field of chemical materials, in particular to halogen-free flame-retardant PC/ABS alloy and a preparation method thereof. The halogen-free flame-retardant PC/ABS alloy is prepared from polycarbonate, acrylonitrile/butadiene/styrene copolymer, halogen-free flame-retardant bisphenol A diphosphonate diplenyl ester, oligomerization aryl phosphate, anti-dripping agent and machining auxiliaries according to a certain ratio and formula. The halogen-free flame-retardant PC/ABS alloy has good flame retardance and halogen-free performance, can meet the requirements for the current biological environment and human health, has good mechanical performance, thermal property and other comprehensive physical performance basically equivalent to physical performance of traditional non-flame-retardant PC/ABS alloy, and has the advantage of being good in cost; the halogen-free flame-retardant PC/ABS alloy can be widely applied to the aspects of automobiles, machinery, household appliances, computers, communication devices, office devices and the like.
Description
Technical field
The present invention relates to chemical material technical field, refer in particular to a kind of halogen-free flame retardant PC/ABS and preparation method thereof.
Background technology
PC (polycarbonate) a kind ofly applies increasingly extensive engineering plastics, and it has the mechanical property of comprehensive stability, thermal property and electrical property, simultaneously, there is shock resistance, dimensional stabilizing, heat-resisting, the transparent performance waiting excellence, its output is only only second to nylon (PA).But his some shortcoming is as processing difficulties, goods unrelieved stress is large, is easy to stress cracking, to notch sensitive, poor solvent resistance and the shortcoming such as to wear no resistance, constrain it in a lot of fields in application.Co-blended aurification is a kind of important means of PC modification, and it makes PC performance more excellent, thus has widened the Application Areas of PC.
PC/ABS copolymer alloy is industrialization the earliest and current most important PC alloy product.Add relative to PC, ABS the processing flowability that improve PC, reduce the susceptibility of goods counter stress and reduce costs, and PC improves temperature capability and the shock strength of ABS, and product surface depression and warpage defect can be improved.
Fire retardation PC/ABS is well positioned to meet the requirement of the fields such as electronic apparatus to Flame Retardancy energy; But along with people's improving constantly environmental requirement, halogen is that the fire retardation PC/AB of fire retardant can produce gas and the violent poisonous dense smokes such as the virose hydrogenchloride of tool, hydrogen bromide when burning, these smog are enough to make people because being choked to death, people are hindered to withdraw from fire and fire-fighting work, critical facility (as computer etc.) is paralysed, the serious harm security of the lives and property because of corrosion.Based on to preserve the ecological environment and human health is set out, fire retardant non-halogen cry day is high.
Halogen-free flame retardant PC/ABS material also obtains significant progress, but the problem of the mechanical property problem generally on the low side existed, comprehensive physical poor-performing.
Summary of the invention
The invention reside in the deficiency existed for current halogen-free flame retardant PC/ABS, and a kind of halogen-free flame retardant PC/ABS overcome the above problems is provided.
For achieving the above object, the present invention adopts following technical scheme:
A kind of halogen-free flame retardant PC/ABS, it is characterized in that, composition and the mass parts content of described polycarbonate material are:
Preferably, described polycarbonate is the bisphenol A-type aromatic copolycarbonate of weight-average molecular weight between 20000 ~ 40000g/mol; Can select and can adopt Korea S's Samsung 1100, strange U.S. 110 etc.
Preferably, the optional Taiwan 15A1 of acrylonitrile/butadiene/styrene multipolymer, strange U.S. 757.
Preferably, dihydroxyphenyl propane bis phosphoric acid diphenyl ester (BDP) is for containing WSFR-BDP in Zhejiang ten thousand.
Preferably, oligomeric aryl phosphate ester is that WSFR-PX-220 is contained in Zhejiang ten thousand.
Preferably, described anti-dripping agent selects Guangzhou entropy energy tetrafluoroethylene SN3300B7.
Preferably, described processing aid is one or more in primary antioxidant, auxiliary antioxidant, internal lubricant, external lubricant.
Preferably, described primary antioxidant is β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, two (2,4-di-tert-butyl-phenyl) one or more in tetramethylolmethane or 2,6-di-t-butyl-4-4 cresols.
Preferably, described auxiliary antioxidant is one or more in the two stearic alcohol ester of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, sulfo-three propionic acid two lauryl or thio-2 acid.
Preferably, described internal lubricant is E wax, one or more in calcium stearate or polyethylene wax (PE wax).
Preferably, described external lubricant is silicone master batch or tetramethylolmethane stearate.
As the preparation method of the halogen-free flame retardant PC/ABS of above-mentioned any one, comprise following processing step:
A, stirring raw material: PC resin, acrylonitrile/butadiene/styrene multipolymer, oligomeric aryl phosphate ester, anti-dripping agent and processing aid are put into homogenizer and stirs 0.5-5 minute;
B, then add dihydroxyphenyl propane bis phosphoric acid diphenyl ester to high mixer high-speed stirring 1-6 minute;
C, feeding are extruded: will join the main feeder of forcing machine by the raw material after step B stirs, material extrude after through water-cooled, pelletizing, packaging.
Preferably, described step 3 extruder temperature is set to: be respectively to head by feed zone: 190-210 DEG C, 220-230 DEG C, 230-240 DEG C, 235-245 DEG C, 235-245 DEG C, 235-245 DEG C, 243-255 DEG C, 245-260 DEG C, die head temperature: 235-245 DEG C.
Beneficial effect of the present invention is, a kind of halogen-free flame retardant PC/ABS of the present invention and preparation method thereof, halogen-free flame retardant PC wherein/ABS adopts polycarbonate, acrylonitrile/butadiene/styrene multipolymer, the dihydroxyphenyl propane bis phosphoric acid diphenyl ester of halogen-free flameproof, oligomeric aryl phosphate ester, anti-dripping agent, the processing aid of certain proportion formula, PC/ABS alloy of the present invention has the performance of good fire-retardant and halogen, can meet the demand of current ecotope and human health; There is good mechanical property and thermal property and other comprehensive physical performances, basic suitable with the PC/ABS alloy physics performance containing traditional non-flame resistant, there is good cost advantage; The aspects such as automobile, machinery, household electrical appliances, computer, Communication Equipment, office equipment can be widely used in.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated:
Halogen-free flame retardant PC/ABS of the present invention, embodiment as 1-6 by each composition and mass parts as shown in Table 1:
Table one
Above embodiment as in, its concrete select materials is as follows:
Polycarbonate is the bisphenol A-type aromatic copolycarbonate of molecular-weight average between 20000 ~ 40000g/mol, selects Korea S's Samsung 1100 in embodiment 1-3, uses strange U.S. 110 in embodiment 4-6.
Select Taiwan 15A1 in acrylonitrile/butadiene/styrene multipolymer embodiment 1,3,4, in embodiment 2,5,6, select strange U.S. 757.
In embodiment, dihydroxyphenyl propane bis phosphoric acid diphenyl ester (BDP) is for containing WSFR-BDP in Zhejiang ten thousand, and oligomeric aryl phosphate ester is that WSFR-PX-220 is contained in Zhejiang ten thousand, and anti-dripping agent selects Guangzhou entropy energy tetrafluoroethylene SN3300B7.
The primary antioxidant of processing aid is β-(3 in embodiment 1,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, be four [β-(3 in embodiment 2,3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, be two (2 in embodiment 6,4-di-tert-butyl-phenyl) tetramethylolmethane or 2, the mixture of the weight ratios such as 6-di-t-butyl-4-4 cresols and four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
The auxiliary antioxidant of processing aid is in embodiment 1 for auxiliary antioxidant is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, be sulfo-three propionic acid two lauryl in example 2, it is the two stearic alcohol ester of thio-2 acid in embodiment 5, it is three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and the sulfo-three propionic acid two lauryl mixing match by weight 1:2 in embodiment 6.
When the internal lubricant of processing aid is selected, embodiment 1 is E wax, and embodiment 3 is the weight proportion such as calcium stearate and polyethylene wax (PE wax).
The external lubricant of processing aid select into, embodiment 1 is silicone master batch, embodiment 2 is tetramethylolmethane stearate, embodiment 3 is the weight proportion such as silicone master batch and tetramethylolmethane stearate.
Applicant carries out Performance Detection to 6 above embodiments, shown in the performance table two of each material composition:
Table two the performance test results
By above-described embodiment, we can find out, PC/ABS alloy of the present invention has the performance of good fire-retardant and halogen, can meet the demand of current ecotope and human health; There is good mechanical property and thermal property and other comprehensive physical performances, basic suitable with the PC/ABS alloy physics performance containing traditional non-flame resistant, there is good cost advantage; The aspects such as automobile, machinery, household electrical appliances, computer, Communication Equipment, office equipment can be widely used in.
The present invention also protects the preparation method producing above-mentioned halogen-free flame retardant PC/ABS in addition, comprises following processing step:
A, stirring raw material: PC resin, acrylonitrile/butadiene/styrene multipolymer, oligomeric aryl phosphate ester, anti-dripping agent and processing aid are put into homogenizer and stirs 0.5-5 minute;
B, then add dihydroxyphenyl propane bis phosphoric acid diphenyl ester to high mixer high-speed stirring 1-6 minute;
C, feeding are extruded: will join the main feeder of forcing machine by the raw material after step B stirs, material extrude after through water-cooled, pelletizing, packaging.
Be set in step 3 extruder temperature: be respectively to head by feed zone: 190-210 DEG C, 220-230 DEG C, 230-240 DEG C, 235-245 DEG C, 235-245 DEG C, 235-245 DEG C, 243-255 DEG C, 245-260 DEG C, die head temperature: 235-245 DEG C.
As better embodiment, churning time preferably 1 minute in steps A, preferred 2 minutes time in step B; In step C, preferably segmented temperature is: 200 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 240 DEG C, 245 DEG C, 245 DEG C, die head temperature: 240 DEG C; Test bars is by the pellet of preparation at air dry oven, and 90 DEG C of dryings 4 hours, then prepare test bars by injection moulding machine.
The above embodiment, just preferred embodiments of the present invention, be not limit the scope of the present invention, therefore all equivalences done according to structure, feature and the principle described in the present patent application the scope of the claims change or modify, and all should be included in patent claim of the present invention.
Claims (10)
1. halogen-free flame retardant PC/ABS, is characterized in that, composition and the mass parts content of described polycarbonate material are:
2. a kind of halogen-free flame retardant PC/ABS according to claim 1, is characterized in that: described polycarbonate is the bisphenol A-type aromatic copolycarbonate of weight-average molecular weight between 20000 ~ 40000g/mol.
3. a kind of halogen-free flame retardant PC/ABS according to claim 1, is characterized in that: described anti-dripping agent is tetrafluoroethylene.
4. a kind of halogen-free flame retardant PC/ABS according to claim 1, is characterized in that: described processing aid is one or more in primary antioxidant, auxiliary antioxidant, internal lubricant, external lubricant.
5. a kind of halogen-free flame retardant PC/ABS according to claim 4, it is characterized in that: described primary antioxidant is β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, two (2,4-di-tert-butyl-phenyl) one or more in tetramethylolmethane or 2,6-di-t-butyl-4-4 cresols.
6. a kind of halogen-free flame retardant PC/ABS according to claim 4, it is characterized in that: described auxiliary antioxidant is one or more in the two stearic alcohol ester of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, sulfo-three propionic acid two lauryl or thio-2 acid.
7. a kind of halogen-free flame retardant PC/ABS according to claim 4, is characterized in that: described internal lubricant is E wax, one or more in calcium stearate or polyethylene wax.
8. a kind of halogen-free flame retardant PC/ABS according to claim 4, is characterized in that: described external lubricant is silicone master batch or tetramethylolmethane stearate.
9., as the preparation method of the halogen-free flame retardant PC/ABS of claim 1-8 any one, comprise following processing step:
A, stirring raw material: PC resin, acrylonitrile/butadiene/styrene multipolymer, oligomeric aryl phosphate ester, anti-dripping agent and processing aid are put into homogenizer and stirs 0.5-5 minute;
B, then add dihydroxyphenyl propane bis phosphoric acid diphenyl ester to high mixer high-speed stirring 1-6 minute;
C, feeding are extruded: will join the main feeder of forcing machine by the raw material after step B stirs, material extrude after through water-cooled, pelletizing, packaging.
10. the preparation method of halogen-free flame retardant PC/ABS according to claim 9, it is characterized in that: described step 3 extruder temperature is set to: be respectively to head by feed zone: 190-210 DEG C, 220-230 DEG C, 230-240 DEG C, 235-245 DEG C, 235-245 DEG C, 235-245 DEG C, 243-255 DEG C, 245-260 DEG C, die head temperature: 235-245 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353575A (en) * | 2017-09-02 | 2017-11-17 | 苏建 | A kind of high tenacity fire retardation PC/ABS |
| GB2597898A (en) * | 2019-12-05 | 2022-02-16 | Polymer Compounders Ltd | Fire retardant composition |
| CN114539755A (en) * | 2022-02-25 | 2022-05-27 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759976A (en) * | 2008-11-21 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Special polycarbonate/acrylonitrile-butadiene-styrene(PC/ABS) alloy material for notebook computer shell |
| CN102453263A (en) * | 2010-10-22 | 2012-05-16 | 富士施乐株式会社 | Resin composition and resin molded article |
| CN103897374A (en) * | 2012-12-27 | 2014-07-02 | 第一毛织株式会社 | Flame retardant thermoplastic resin composition and molded article including the same |
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2015
- 2015-11-11 CN CN201510767980.2A patent/CN105237997A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759976A (en) * | 2008-11-21 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Special polycarbonate/acrylonitrile-butadiene-styrene(PC/ABS) alloy material for notebook computer shell |
| CN102453263A (en) * | 2010-10-22 | 2012-05-16 | 富士施乐株式会社 | Resin composition and resin molded article |
| CN103897374A (en) * | 2012-12-27 | 2014-07-02 | 第一毛织株式会社 | Flame retardant thermoplastic resin composition and molded article including the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353575A (en) * | 2017-09-02 | 2017-11-17 | 苏建 | A kind of high tenacity fire retardation PC/ABS |
| GB2597898A (en) * | 2019-12-05 | 2022-02-16 | Polymer Compounders Ltd | Fire retardant composition |
| CN114539755A (en) * | 2022-02-25 | 2022-05-27 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
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Application publication date: 20160113 |