CN1696195A - Non halogenic, low smoky fire retardant polycarbonate/resin of acrylonitrile butylbenzene and preparation method - Google Patents
Non halogenic, low smoky fire retardant polycarbonate/resin of acrylonitrile butylbenzene and preparation method Download PDFInfo
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- CN1696195A CN1696195A CN 200410018246 CN200410018246A CN1696195A CN 1696195 A CN1696195 A CN 1696195A CN 200410018246 CN200410018246 CN 200410018246 CN 200410018246 A CN200410018246 A CN 200410018246A CN 1696195 A CN1696195 A CN 1696195A
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- acrylonitrile butadiene
- butadiene styrene
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Abstract
A non-halogen low-smoke flame-retarding polycarbonate/acrylonitrile butadiene-styrene resin is proportionally prepared from polycarbonate/acrylonitrile butadiene-styrene resin, non-halogen primary flame retardant, Si-type secondary flame retardant, efficient compatibilier, anti-impact modifier and machining assistant.
Description
Technical field
The present invention relates to a kind of fire-retardant polycarbonate/ABS resin, relate in particular to a kind of LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin and preparation method thereof.
Background technology
PC resin (PC/ABS) alloy is a kind of heterogeneous heterogeneous system, combine the premium properties of ABS and PC, can improve thermotolerance, shock resistance and the tensile property of ABS on the one hand, replace ABS to be used for the high-performance field; Can reduce cost and the melt viscosity of PC on the other hand, improve flowability, improve its processing characteristics, reduce goods internal stress and shock strength susceptibility products thickness, replacing PC to be used for the goods processing of the long flow process of thin-walled, is the comprehensive polymer alloy of a kind of performance.Numerous patent documentations has been reported the system method of halogen-free flame retardant PC, according to patent and document, the fire retardant of halogen-free flame retardant PC adopts phosphoric acid salt (ester) class, sulfonate (ester) class, antimony type oxide, basic metal and fire retardants such as alkaline earth salt, siloxanes more.Reduce because the adding of fire retardant, the shock strength of PC have significantly, patent has also been reported by adding rubber elastomer, ABS, styrenic elastomerics and has been waited the toughness of improving material.Simultaneously, in order to adapt to the requirement of thin-walled, large-scale product, the flowability of the material of PC and the consistency of material also need further raising, and the poly-second wax of the general employing of patent report etc. improves the processing fluidity of material.
US616174944 has reported the PC fire retardant material that is applicable to the IT industry, and material has good flowability, processability, appearance property, has high impulse strength and flame retardant properties.Material is made of PC, fibrous packing, rubber graft copolymer, phosphate cpd and tetrafluoroethylene, and its shock strength is greater than 500J/m, and flame retardant properties reaches the V-0 level, and modulus in flexure is 2500MPa.In the material, rubber graft copolymer is a toughner, and tetrafluoroethylene is a modifier.US6127465 then reported and guaranteed under the prerequisite of flame retardant properties, adds HIPS, core-shell type rubber elastomer, tetrafluoroethylene and wait toughness and the processing characteristics that improves material in PC.The employed fire retardant of fire retardation PC of patent US6348527 report is a phosphoric acid salt, also adds the cinnamic multipolymer of 1-30% in the material, and tetramethylolmethane and saturated aliphatic carboxylic acid esters, improve the flowability of material as softening agent, and consumption is 0.1-5%.
And the technology of above-mentioned patent and bibliographical information, the fire retardation PC/ABS of anti-marquis's level seldom occurs.With the electric equipment products that common fire retardation PC/ABS makes, in use be easy to be subjected to ultraviolet irradiation, color and outward appearance take place can obvious variation, have in addition serious aging takes place and destroy.PC/ABS produces a large amount of smog in combustion processes, especially fire retardation PC/ABS is all the more so, and with its electric equipment products of making, in case the short circuit initiation fire takes place, a large amount of smog is with serious threat people's life security.In addition, low temperature takes place by its component of making and falls quality problems such as cracking, packed and transported cracking, back assembling cracking and application printing cracking in fire retardation PC/ABS sometimes that sell on Chinese market.Therefore, research and develop a kind of weather-proof low-smoke flame-retarded PC/ABS high performance alloys, it is imperative to satisfy the growing requirement in electrical equipment market.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin and preparation method thereof, to overcome the above-mentioned defective that prior art exists, satisfy the needs of appliance field development.
The component and the parts by weight of LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin of the present invention comprise:
50～95 parts of polycarbonate/acrylonitrile butadiene styrene resins
1～25 part of without halide main flame retardant
1～5 part of the auxilliary fire retardant of silicon system
1～5 part of high efficiency bulking agent
1～10 part of impact modifier
Other processing aid 0.5～5.
Said polycarbonate/acrylonitrile butadiene styrene resin is a body material, can adopt conventional method to be prepared, as US 6,500, and 546 document disclosed methods, the present invention repeats no more;
Said without halide main flame retardant comprises that model is one or more among CR-741, FP-700 or the PX-202, can adopt the commercially available prod, and as the product that big eight companies of Japan produce, its general structure is:
Herein, R
1With R
2Can be identical also can be different, be short-chain fat family alkyl, R
3, R
4Be hydrogen atom or short-chain fat family alkane, Y is-CH
2-,-C (CH
3)
2-,-S-, SO
2-,-CO-,-O-or-a kind of among the N=N-, k is 0 or is 1, and m is 0～4 a integer.
The auxilliary fire retardant effect of silicon system is to increase into carbon and improve Drawing abillity; Silicon is that the add-on of auxilliary fire retardant can not be too high, and the too high production cost that will make increases, and influences the outward appearance of product, but can not be too low, crosses to hang down to cause the material at low temperature degradation, and flame retardant properties is descended
The auxilliary fire retardant general structure of said silicon system is:
Wherein, X=CH
3R=P
h, CH
3
Can adopt the commercially available prod.
Said high efficiency bulking agent comprises one or more in poly-(methyl) acrylate (as AS-g-PtBuAc, AS-g-PGMA etc.) of acrylonitrile styrene copolymer grafting; Its effect is by a certain proportion of composite, improves the consistency of material, improves the mechanical property of material.
Said impact modifier comprises one or more in ABS high glue powder or the ultrahigh molecular weight polyethylene(UHMWPE)-g-acrylic elastomer (UHMWPE-g-Poly (Acrylate)), its effect is a mechanical property of improving material, particularly improve the low-temperature performance of material, and improve the flowing property of material and the heat-resisting degradation property of material;
Said other processing aid comprises PTFE, one or more in perfluorinated sulfonate, lubricant or the oxidation inhibitor; Its effect is to improve Drawing abillity and thermostability, and the effect of fire-retardant synergistic do.
The preparation method of LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin of the present invention comprises the steps:
The polycarbonate/acrylonitrile butadiene styrene resin is adopted conventional forcing machine mixing extruding pelletization in proportion with without halide main flame retardant, the auxilliary fire retardant of silicon system, high efficiency bulking agent, impact modifier and other processing aid, mixing temperature is 50～90 ℃, is LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin of the present invention.
LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin of the present invention, fundamentally having overcome bromine is that fire-retardant polycarbonate/vinyl cyanide styrene-butadiene rubber(SBR) (PC/ABS) alloy material produces tetrabromo for carcinogenic substance harm such as dibenzodioxin alkane and tetrabromo two cumarones of generation in burning and thermal cracking processes.Particularly these series product are when having excellent flame-retardant (reaching U.S. UL 94 1.6V-0 grade standards), still have PC/ABS alloy material very excellent mechanical property, thermal characteristics, low-temperature performance and low smoke performance, and improved Drawing abillity significantly.
Embodiment
Embodiment 1
With 80 kilograms of polycarbonate/acrylonitrile butadiene styrene resins, 10 kilograms of without halide main flame retardant CR-741,1 kilogram of auxilliary fire retardant (polymethyl siloxane) of silicon system, 2 kilograms of high efficiency bulking agent (acrylonitrile styrene copolymer grafted maleic anhydride), 7 kilograms of impact modifiers (ABS high glue powder) and 1 kilogram of other processing aid (general antioxidant 1010,168 each 0.3 kilogram, 0.4 kilogram of tetrafluoroethylene), in the 75A twin screw extruder that Rhea company produces, mix extruding pelletization, mixing temperature is 50～90 ℃, is LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin of the present invention.
Adopt the ASTM standard to detect, its result is as follows:
LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin, the performance of embodiment 1:
| Performance | The ASTM standard | Unit | Measured value | |
| Water-intake rate | ??D570 | ??％ | ??0.2 | |
| Tensile strength | ??D638 | ??MPa | ??55 | |
| Elongation at break | ??％ | ??＞50 | ||
| The IZOD notched Izod impact strength | ??23℃ | ??D256 | ??J/m | ??＞400 |
| ??-40℃ | ??J/m | ??＞200 | ||
| Flexural strength | ??D790 | ??MPa | ??90 | |
| Modulus in flexure | ??MPa | ??2500 | ||
| Incendivity | ??UL94 | ??- | ??1.6V-0 | |
| Specific optical density | ??D843 | ??45 | ||
| Heat-drawn wire | ??D648 | ??℃ | ??90(0.45MPa) | |
| ??℃ | ??80(1.8MPa) | |||
Embodiment 2
With 70 kilograms of polycarbonate/acrylonitrile butadiene styrene resins, 14 kilograms of without halide main flame retardant CR-741, the mixture of PX-202,5 kilograms of auxilliary fire retardants (polymethyl siloxane) of silicon system, 2 kilograms of high efficiency bulking agent (acrylonitrile styrene copolymer grafted maleic anhydrides, 1: 1 the mixture by weight of acrylonitrile styrene copolymer grafting methacrylic ester), 8 kilograms of impact modifiers (ABS high glue powder) and 1 kilogram, other processing aid (general antioxidant 1010,168 each 0.3 kilogram, tetrafluoroethylene mixes extruding pelletization for 0.4 kilogram in the 75A twin screw extruder that Rhea company produces, mixing temperature is 50～90 ℃, is LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin of the present invention.
Adopt the ASTM standard to detect, its result is as follows:
LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin, the performance of embodiment 2:
| Performance | The ASTM standard | Unit | Measured value | |
| Water-intake rate | ??D570 | ??％ | ??0.2 | |
| Tensile strength | ??D638 | ??MPa | ??53 | |
| Elongation at break | ??％ | ??＞50 | ||
| The IZOD notched Izod impact strength | ??23℃ | ??D256 | ??J/m | ??＞400 |
| ??-40℃ | ??J/m | ??＞300 | ||
| Flexural strength | ??D790 | ??MPa | ??85 | |
| Modulus in flexure | ??MPa | ??2400 | ||
| Incendivity | ??UL94 | ??- | ??1.6V-0 | |
| Specific optical density | ??D843 | ??65 | ||
| Heat-drawn wire | ??D648 | ??℃ | ??85(0.45MPa) | |
| ??℃ | ??70(1.8MPa) | |||
Embodiment 3
With 85 kilograms of polycarbonate/acrylonitrile butadiene styrene resins, 9 kilograms of without halide main flame retardant PX-202,1 kilogram of auxilliary fire retardant (polymethyl siloxane) of silicon system, 2 kilograms of high efficiency bulking agent, (acrylonitrile styrene copolymer grafting methacrylic ester), 2 kilograms of impact modifiers (ABS high glue powder) and 1 kilogram of other processing aid (general antioxidant 1010,168 each 0.3 kilogram, 0.4 kilogram of tetrafluoroethylene), in the 75A twin screw extruder that Rhea company produces, mix extruding pelletization, mixing temperature is 50～90 ℃, is LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin of the present invention.
LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin, the performance of embodiment 3:
| Performance | The ASTM standard | Unit | Measured value | |
| Water-intake rate | ??D570 | ??％ | ??0.2 | |
| Tensile strength | ??D638 | ??MPa | ??60 | |
| Elongation at break | ??％ | ??＞50 | ||
| The IZOD notched Izod impact strength | ??23℃ | ??D256 | ??J/m | ??＞600 |
| ??-40℃ | ??J/m | ??＞300 | ||
| Flexural strength | ??D790 | ??MPa | ??95 | |
| Modulus in flexure | ??MPa | ??2900 | ||
| Incendivity | ??UL94 | ??- | ??1.6V-0 |
| Specific optical density | ??D843 | ??50 | |
| Heat-drawn wire | ??D648 | ??℃ | ??130(0.45MPa) |
| ??℃ | ??118(1.8MPa) |
Claims (8)
1. LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin is characterized in that component and parts by weight comprise:
50～95 parts of polycarbonate/acrylonitrile butadiene styrene resins
1～25 part of without halide main flame retardant
1～5 part of the auxilliary fire retardant of silicon system
1～5 part of high efficiency bulking agent
1～10 part of impact modifier
0.5～5 part of other processing aid.
2. LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin according to claim 1, it is characterized in that, said without halide main flame retardant comprises one or more among CR-741, FP-700, PX-202 (for the oligomerization phosphate compound) or the TPP (phosplate compound), and chemical structure of general formula is:
Herein, R
1With R
2Can be identical also can be different, be short-chain fat family alkyl, R
3, R
4Be hydrogen atom or short-chain fat family alkane, Y is-CH
2-,-C (CH
3)
2-,-S-, SO
2-,-CO-,-O-or-a kind of among the N=N-, k is 0 or is 1, and m is 0～4 a integer.
3. LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin according to claim 1 is characterized in that, the auxilliary fire retardant general structure of said silicon system is:
Wherein, X=CH
3R=Ph, CH
3
4. LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin according to claim 1 is characterized in that, said high efficiency bulking agent comprises that the acrylonitrile styrene copolymer grafting gathers (methyl) acrylate.
5. LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin according to claim 1 is characterized in that, said impact modifier comprises one or more of ABS high glue powder or ultrahigh molecular weight polyethylene(UHMWPE) graft acrylic acid acid esters rubber.
6. LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin according to claim 1 is characterized in that said other processing aid comprises one or more in perfluorinated sulfonate, lubricant or the oxidation inhibitor.
7. according to the preparation method of each described LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin of claim 1～6, it is characterized in that comprising the steps:
The polycarbonate/acrylonitrile butadiene styrene resin is adopted conventional forcing machine mixing extruding pelletization in proportion with without halide main flame retardant, the auxilliary fire retardant of silicon system, high efficiency bulking agent, impact modifier and other processing aid, be LSOH anti-flaming polycarbonate/acrylonitrile butadiene styrene resin of the present invention.
8. method according to claim 7 is characterized in that, mixing temperature is 50～90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100182468A CN100509954C (en) | 2004-05-11 | 2004-05-11 | Non halogenic, low smoky fire retardant polycarbonate/resin of acrylonitrile butylbenzene and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100182468A CN100509954C (en) | 2004-05-11 | 2004-05-11 | Non halogenic, low smoky fire retardant polycarbonate/resin of acrylonitrile butylbenzene and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1696195A true CN1696195A (en) | 2005-11-16 |
| CN100509954C CN100509954C (en) | 2009-07-08 |
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ID=35349099
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100182468A Expired - Fee Related CN100509954C (en) | 2004-05-11 | 2004-05-11 | Non halogenic, low smoky fire retardant polycarbonate/resin of acrylonitrile butylbenzene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100509954C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101067038B (en) * | 2007-05-30 | 2010-05-26 | 深圳市科聚新材料有限公司 | Environment friendly fire retardant no-halogen PC composite material and its preparation method |
| CN101205359B (en) * | 2007-11-30 | 2010-07-14 | 上海锦湖日丽塑料有限公司 | Polycarbonate resin / styryl resin non-halogen flame-retardant composite material |
| CN103724970A (en) * | 2013-12-31 | 2014-04-16 | 奉化市旭日新材料有限公司 | Flame-retardant polycarbonate/acrylonitrile butadiene styrene resin |
| CN104592617A (en) * | 2015-02-06 | 2015-05-06 | 佛山市汉科塑料功能材料有限公司 | Ultrahigh molecular weight polyethylene pipe with long-acting anti-static property and flame retardant property and preparation method thereof |
| CN105086025A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | Low-smoke and flame retardant powdered styrene butadiene rubber and preparation method thereof |
| CN109825056A (en) * | 2019-01-21 | 2019-05-31 | 金发科技股份有限公司 | A kind of polycarbonate alloy and preparation method thereof |
| CN110564027A (en) * | 2019-09-05 | 2019-12-13 | 徐州工业职业技术学院 | preparation method of halogen-free flame-retardant rubber composite material |
| CN111040307A (en) * | 2019-12-31 | 2020-04-21 | 广州广化塑料管道有限公司 | Polypropylene corrugated pipe composite material and preparation method of composite polypropylene corrugated pipe |
-
2004
- 2004-05-11 CN CNB2004100182468A patent/CN100509954C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101067038B (en) * | 2007-05-30 | 2010-05-26 | 深圳市科聚新材料有限公司 | Environment friendly fire retardant no-halogen PC composite material and its preparation method |
| CN101205359B (en) * | 2007-11-30 | 2010-07-14 | 上海锦湖日丽塑料有限公司 | Polycarbonate resin / styryl resin non-halogen flame-retardant composite material |
| CN103724970A (en) * | 2013-12-31 | 2014-04-16 | 奉化市旭日新材料有限公司 | Flame-retardant polycarbonate/acrylonitrile butadiene styrene resin |
| CN103724970B (en) * | 2013-12-31 | 2016-02-03 | 奉化市旭日新材料有限公司 | A kind of Flame-retardant polycarbonate/acrylobutadiene butadiene styrene resin |
| CN105086025A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | Low-smoke and flame retardant powdered styrene butadiene rubber and preparation method thereof |
| CN104592617A (en) * | 2015-02-06 | 2015-05-06 | 佛山市汉科塑料功能材料有限公司 | Ultrahigh molecular weight polyethylene pipe with long-acting anti-static property and flame retardant property and preparation method thereof |
| CN109825056A (en) * | 2019-01-21 | 2019-05-31 | 金发科技股份有限公司 | A kind of polycarbonate alloy and preparation method thereof |
| CN109825056B (en) * | 2019-01-21 | 2022-07-19 | 金发科技股份有限公司 | Polycarbonate alloy and preparation method thereof |
| CN110564027A (en) * | 2019-09-05 | 2019-12-13 | 徐州工业职业技术学院 | preparation method of halogen-free flame-retardant rubber composite material |
| CN111040307A (en) * | 2019-12-31 | 2020-04-21 | 广州广化塑料管道有限公司 | Polypropylene corrugated pipe composite material and preparation method of composite polypropylene corrugated pipe |
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Assignee: Jiangsu golden hair science and technology new material development Co Ltd Assignor: Shanghai Kingfa Science and Technology Development Co., Ltd. Contract record no.: 2012310000035 Denomination of invention: Non halogenic, low smoky fire retardant polycarbonate/resin of acrylonitrile butylbenzene and preparation method Granted publication date: 20090708 License type: Exclusive License Open date: 20051116 Record date: 20120309 |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
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Granted publication date: 20090708 Termination date: 20200511 |