CN104592731B - A kind of silicon system fire retardation PC/ABS - Google Patents
A kind of silicon system fire retardation PC/ABS Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
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Abstract
The present invention relates to a kind of silicon system fire retardation PC/ABS, it is characterized in that including by weight following components: PC resin 50～60 parts, ABS resin 40～50 parts, amino polydimethyl siloxane 2.0～6.0 parts, eight (aminophenyl)-T8-silsesquioxane 3.0～8.0 parts, glytidyl methacrylate 1.0～5.0 parts, benzoyl peroxide 0.5～2.0 part, silane coupler 0.5～2.0 part, attapulgite 2.0～6.0 parts, 0.1～0.5 part of antioxidant. The preparation method that the invention still further relates to silicon system fire retardation PC/ABS. Glytidyl methacrylate in the present invention and eight (aminophenyl)-T8-silsesquioxane construct the star structure of linear structure and the assorted arm of multi-arm respectively in PC/ABS matrix, and pass through a large amount of attapulgites of different group grafting, silane coupler has promoted that each material is uniformly dispersed in PC/ABS, improve the crosslinking degree between silicon-containing material and material matrix molecule, be effectively increased the fire resistance of PC/ABS alloy.
Description
Technical field
The present invention relates to the PC/ABS technical field of alloy with fire resistance, refer specifically to a kind of silicon system fire retardation PC/ABS.
Background technology
Merlon (PC) is the thermoplastic engineering plastic of a kind of high comprehensive performance, not only shock resistance degree is strong, light transmittance is high for it, good stability of the dimension, easy coloring, ageing-resistant, and there is excellent electrical insulating property, apply all extremely wide in all trades and professions. But, Merlon (PC) exist wear no resistance, the shortcoming of processing fluidity difference, this severely limits it and develop application further in corresponding industry. Acrylonitrile-butadiene-styrene copolymer (ABS) is a kind of intensity height, good toughness, thermoplastic engineering plastic easily processed into type, but, acrylonitrile-butadiene-styrene copolymer (ABS) non-refractory and weatherability are poor. In order to make up the performance deficiency of Merlon (PC) and acrylonitrile-butadiene-styrene copolymer (ABS) self, researcher has prepared PC/ABS composite by blended for PC and ABS, the advantage that this material can give full play to PC and ABS, make them obtain complementation in overall performance, improve the combination property of material.
At present, PC/ABS composite is widely used in construction material, electronic apparatus, automobile shipbuilding industry, but its inflammability limits their use scope, therefore, it is necessary to PC/ABS composite is optimized further, improves its fire resistance. Silicone flame retardant have cigarette efficient, low, drippage nontoxic, anti-, to advantages such as matrix material performance impact are little, but, traditional organic silicon fibre retardant linear polysiloxanes such as polydimethylsiloxane, owing to its heat stability when high temperature is poor, and easily produce transport phenomena in the polymer, cause that its flame retardant effect is not ideal enough.
Therefore, for current silicon system fire retardation PC/ABS, await doing further improvement.
Summary of the invention
The technical problem to be solved is the present situation for prior art, it is provided that a kind of Heat stability is good, flame retardant effect desirable silicon system fire retardation PC/ABS.
To be solved by this invention another technical problem is that the present situation for prior art, it is provided that the preparation method of a kind of above-mentioned silicon system fire retardation PC/ABS.
This invention address that the technical scheme that above-mentioned technical problem adopts is: a kind of silicon system fire retardation PC/ABS, it is characterised in that include following components by weight:
As improvement, described amino polydimethyl siloxane is amino-terminated polydimethylsiloxane, and the number-average molecular weight of this amino polydimethyl siloxane is 2000～5000.
Improving further, described silane coupler is that end is with any one silane coupler in epoxy radicals, amino, (methyl) acryloxy, NCO.
In above-mentioned each scheme, the structural formula of described eight (aminophenyl)-T8-silsesquioxane is
As preferably, described antioxidant is AX-303, ADK, one or both compound in 1010.
The preparation method of a kind of above-mentioned silicon system fire retardation PC/ABS, it is characterised in that comprise the following steps:
(1) granulation material is prepared
50～60gPC resin, 40～50gABS resin, 0.5～2.0g silane coupler, 2.0～6.0g attapulgite, 2.0～6.0g amino polydimethyl siloxane, 3.0～8.0g eight (aminophenyl)-T8-silsesquioxane and 1.0～5.0g glytidyl methacrylate is put into successively in the mixer that rotating speed is 800～1200r/min, mixing 7～8min is continued after input, 0.1～0.5g antioxidant and 0.5～2.0g benzoyl peroxide is put into again successively in mixer, mixing 2～3min, namely obtains described granulation material;
(2) extruding pelletization
Step (1) gained granulation material is put in double screw extruder and melt extrudes, cooling granulation.
As preferably, screw rod each heating region temperature of double screw extruder described in step (2) is respectively set to: district's temperature 230～235 DEG C, two district's temperature 235～240 DEG C, three district's temperature 235～240 DEG C, four district's temperature 235～240 DEG C, five district's temperature 235～240 DEG C, six district's temperature 240～245 DEG C, seven district's temperature 240～245 DEG C, eight district's temperature 245～250 DEG C, nine district's temperature 245～250 DEG C, ten district's temperature 240～245 DEG C.
Compared with prior art, it is an advantage of the current invention that:
(1) in the present invention, under the catalytic action of benzoyl peroxide, double bond in glytidyl methacrylate is opened and is grafted on PC/ABS main chain by radical reaction, eight (aminophenyl)-T8-silsesquioxane is then bonded, with the epoxy radicals in glytidyl methacrylate, the side-chain radical becoming PC/ABS by amino, owing to eight (aminophenyl)-T8-silsesquioxane has cage structure, and the active group of its end, it is easy to be combined with other compound, so that on the side chain of PC/ABS alloy centered by eight (aminophenyl)-T8-silsesquioxane, construct the star structure of the assorted arm of multi-arm, such structure is compared with linear structure of the prior art, it is easier to reduce interfacial tension, improve PC/ABS stability at high temperature, and the active group of eight (aminophenyl)-T8-silsesquioxane end easily and other material carry out graft reaction, improve the crosslinking degree between silicon-containing material and material matrix molecule, strengthen the anti-flammability of PC/ABS,
(2) attapulgite has good heat stability and catalysis activity, can keep the stability of skeleton in combustion, play the effect of stable layer of charcoal, thus significantly improving the thermo oxidative stability of PC/ABS;Silane coupler in the present invention is in order to attapulgite modified, attapulgite surface after modified is with the active group that can react, so that being grafted on glytidyl methacrylate or eight (aminophenyl)-T8-silsesquioxane of PC/ABS side chain, amino polydimethyl siloxane in the present invention can also pass through amino and be bonded, with the epoxy radicals in glytidyl methacrylate, the side-chain radical becoming PC/ABS, thus substantially increasing the percent grafting of attapulgite, increase the compatibility of attapulgite and PC/ABS matrix, be effectively improved the heat stability of PC/ABS;
(3) glytidyl methacrylate used in the present invention and eight (aminophenyl)-T8-silsesquioxane construct the star structure of linear structure and the assorted arm of multi-arm respectively in PC/ABS matrix, and pass through a large amount of attapulgites of different group grafting, and the use of silane coupler has promoted that each material is uniformly dispersed in PC/ABS, improve the crosslinking degree between silicon-containing material and material matrix molecule, PC/ABS material is made to be more prone in combustion form ceramic-like protective layer, this protective layer oxygen barrier is adiabatic, both the material that burning produces had been prevented outwards to overflow, inhibit again the thermal decomposition of base material, thus being effectively increased the fire resistance of PC/ABS alloy, and reach low cigarette, the effect of low toxicity,
(4) preparation method of the present invention, makes chemical reaction directly occur in double screw extruder in the course of processing, has saved preparation cost, convenient, quick.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
The silicon system fire retardation PC/ABS of the present embodiment includes following components by weight:
The preparation method of above-mentioned silicon system fire retardation PC/ABS, comprises the following steps:
(1) granulation material is prepared
PC resin, ABS resin, Silane coupling agent KH550, attapulgite, amino polydimethyl siloxane KF-8012, eight (aminophenyl)-T8-silsesquioxane and glytidyl methacrylate is put into successively in the mixer that rotating speed is 900r/min, mixing 7min is continued after input, antioxidant AX-303 and benzoyl peroxide is put into again successively in mixer, mixing 2min, namely obtains granulation material;
(2) extruding pelletization
Step (1) gained granulation material is put in double screw extruder and melt extrudes, cooling granulation; Concrete, screw rod each heating region temperature of double screw extruder is respectively set to: district's temperature 230 DEG C, two district's temperature 235 DEG C, three district's temperature 235 DEG C, four district's temperature 235 DEG C, five district's temperature 235 DEG C, six district's temperature 240 DEG C, seven district's temperature 240 DEG C, eight district's temperature 245 DEG C, nine district's temperature 245 DEG C, ten district's temperature 240 DEG C.
Embodiment 2:
The silicon system fire retardation PC/ABS of the present embodiment includes following components by weight:
The preparation method of above-mentioned silicon system fire retardation PC/ABS, comprises the following steps:
(1) granulation material is prepared
PC resin, ABS resin, silane coupler KH560, attapulgite, amino polydimethyl siloxane KF-8012, eight (aminophenyl)-T8-silsesquioxane and glytidyl methacrylate is put into successively in the mixer that rotating speed is 1000r/min, mixing 7.5min is continued after input, antioxidant ADK and benzoyl peroxide is put into again successively in mixer, mixing 2.5min, namely obtains granulation material;
(2) extruding pelletization
Step (1) gained granulation material is put in double screw extruder and melt extrudes, cooling granulation;Concrete, screw rod each heating region temperature of double screw extruder is respectively set to: district's temperature 232 DEG C, two district's temperature 237 DEG C, three district's temperature 237 DEG C, four district's temperature 237 DEG C, five district's temperature 237 DEG C, six district's temperature 242 DEG C, seven district's temperature 242 DEG C, eight district's temperature 247 DEG C, nine district's temperature 247 DEG C, ten district's temperature 242 DEG C.
Embodiment 3:
The silicon system fire retardation PC/ABS of the present embodiment includes following components by weight:
The preparation method of above-mentioned silicon system fire retardation PC/ABS, comprises the following steps:
(1) granulation material is prepared
PC resin, ABS resin, silane coupler DMT25, attapulgite, amino polydimethyl siloxane KF-8008, eight (aminophenyl)-T8-silsesquioxane and glytidyl methacrylate is put into successively in the mixer that rotating speed is 800r/min, mixing 8min is continued after input, antioxidant 1010 and benzoyl peroxide is put into again successively in mixer, mixing 2min, namely obtains granulation material;
(2) extruding pelletization
Step (1) gained granulation material is put in double screw extruder and melt extrudes, cooling granulation; Concrete, screw rod each heating region temperature of double screw extruder is respectively set to: district's temperature 233 DEG C, two district's temperature 238 DEG C, three district's temperature 239 DEG C, four district's temperature 238 DEG C, five district's temperature 238 DEG C, six district's temperature 243 DEG C, seven district's temperature 244 DEG C, eight district's temperature 248 DEG C, nine district's temperature 249 DEG C, ten district's temperature 243 DEG C.
Embodiment 4:
The silicon system fire retardation PC/ABS of the present embodiment includes following components by weight:
The preparation method of above-mentioned silicon system fire retardation PC/ABS, comprises the following steps:
(1) granulation material is prepared
PC resin, ABS resin, silane coupler KH560, attapulgite, amino polydimethyl siloxane KF-8012, eight (aminophenyl)-T8-silsesquioxane and glytidyl methacrylate is put into successively in the mixer that rotating speed is 1100r/min, mixing 7min is continued after input, antioxidant 1010 and benzoyl peroxide is put into again successively in mixer, mixing 3min, namely obtains granulation material;
(2) extruding pelletization
Step (1) gained granulation material is put in double screw extruder and melt extrudes, cooling granulation. Concrete, screw rod each heating region temperature of double screw extruder is respectively set to: district's temperature 234 DEG C, two district's temperature 234 DEG C, three district's temperature 236 DEG C, four district's temperature 236 DEG C, five district's temperature 237 DEG C, six district's temperature 243 DEG C, seven district's temperature 243 DEG C, eight district's temperature 249 DEG C, nine district's temperature 249 DEG C, ten district's temperature 244 DEG C.
The silicon system fire retardation PC/ABS of preparation in the various embodiments described above is carried out performance test, and wherein, limited oxygen index (LOI) measures according to GB/T2406-1993, and vertical combustion presses UL94 test, and concrete test result is as shown in table 1.
Table 1
It can be seen that the silicon system fire retardation PC/ABS in the present invention has good fire resistance.
Attapulgite specification in the present invention is 200 orders, purchased from Anhui Bo Shuo Science and Technology Ltd.; Glytidyl methacrylate is purchased from Aladdin; Eight (aminophenyl)-T8-silsesquioxane is purchased from BOCScience; Amino polydimethyl siloxane (KF-8012, KF-8008) is purchased from Guangzhou Yue Cheng Fine Chemical Co., Ltd; Silane coupler (KH550, KH560, KH570, DMT25) is purchased from Nanjing Lian Gui Chemical Co., Ltd.; Antioxidant (AX-303, ADK, 1010) is purchased from Dongguan Heng Li plastic material company limited.
Claims (6)
1. silicon system fire retardation PC/ABS, it is characterised in that include following components by weight:
2. silicon system according to claim 1 fire retardation PC/ABS, it is characterised in that: described amino polydimethyl siloxane is amino-terminated polydimethylsiloxane, and the number-average molecular weight of this amino polydimethyl siloxane is 2000～5000.
3. silicon system according to claim 1 fire retardation PC/ABS, it is characterised in that: described silane coupler is that end is with any one silane coupler in epoxy radicals, amino, (methyl) acryloxy, NCO.
4. silicon system according to claim 1 fire retardation PC/ABS, it is characterised in that: the structural formula of described eight (aminophenyl)-T8-silsesquioxane is
5. the preparation method of silicon system fire retardation PC/ABS described in any claim in a Claims 1 to 4, it is characterised in that comprise the following steps:
(1) granulation material is prepared
50～60gPC resin, 40～50gABS resin, 0.5～2.0g silane coupler, 2.0～6.0g attapulgite, 2.0～6.0g amino polydimethyl siloxane, 3.0～8.0g eight (aminophenyl)-T8-silsesquioxane and 1.0～5.0g glytidyl methacrylate is put into successively in the mixer that rotating speed is 800～1200r/min, mixing 7～8min is continued after input, 0.1～0.5g antioxidant and 0.5～2.0g benzoyl peroxide is put into again successively in mixer, mixing 2～3min, namely obtains described granulation material;
(2) extruding pelletization
Step (1) gained granulation material is put in double screw extruder and melt extrudes, cooling granulation.
6. preparation method according to claim 5, it is characterized in that: screw rod each heating region temperature of double screw extruder described in step (2) is respectively set to: district's temperature 230～235 DEG C, two district's temperature 235～240 DEG C, three district's temperature 235～240 DEG C, four district's temperature 235～240 DEG C, five district's temperature 235～240 DEG C, six district's temperature 240～245 DEG C, seven district's temperature 240～245 DEG C, eight district's temperature 245～250 DEG C, nine district's temperature 245～250 DEG C, ten district's temperature 240～245 DEG C.
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| CN106832581A (en) * | 2017-01-20 | 2017-06-13 | 广东优科艾迪高分子材料有限公司 | A kind of flame-retardant polypropelene resin combination |
| CN106867221B (en) * | 2017-01-20 | 2019-04-23 | 广东优科艾迪高分子材料有限公司 | A kind of flame retardant type polycarbonate compositions |
| CN106832813B (en) * | 2017-01-20 | 2019-04-23 | 广东优科艾迪高分子材料有限公司 | Flame-retardant polyethylene terephthalate resin composition |
| CN107057346B (en) * | 2017-01-20 | 2019-08-16 | 广东优科艾迪高分子材料有限公司 | Flame-retardant nylon composition |
| CN106867033B (en) * | 2017-04-10 | 2019-01-25 | 广东优科艾迪高分子材料有限公司 | A kind of inorganic matter cladding organic silicon fibre retardant of alternative antimony oxide and the preparation method and application thereof |
| CN107236511B (en) * | 2017-06-19 | 2020-06-19 | 上海都昱新材料科技有限公司 | Polyurethane adhesive composition for shoes and preparation method thereof |
| CN107090263B (en) * | 2017-06-19 | 2020-11-13 | 上海都昱新材料科技有限公司 | Epoxy resin adhesive for photovoltaic cutting and preparation method thereof |
| CN108285536A (en) * | 2018-02-27 | 2018-07-17 | 同济大学 | A kind of super-hydrophobic fire proofing of organosilicon and preparation method thereof |
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| AU5869500A (en) * | 1999-06-11 | 2001-01-02 | Gas Separation Technology, Inc. | Porous gas permeable material for gas separation |
| CN101113231A (en) * | 2006-07-28 | 2008-01-30 | 佛山市顺德区汉达精密电子科技有限公司 | Modified PC/ABS alloy |
| CN101875771B (en) * | 2010-07-14 | 2012-06-13 | 深圳市科聚新材料有限公司 | Environmentally-friendly halogen-free PC/ABS alloy and preparation method thereof |
| CN102344658A (en) * | 2011-06-24 | 2012-02-08 | 深圳市科聚新材料有限公司 | PC/ABS alloy possessing metal luster and its preparation method |
| CN102516732A (en) * | 2011-12-02 | 2012-06-27 | 四川长虹电器股份有限公司 | Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof |
| CN103232699A (en) * | 2013-03-31 | 2013-08-07 | 青岛永卓真塑料制品有限公司 | High flame resistant PC/ABS alloy material |
| CN103360739B (en) * | 2013-07-08 | 2016-06-22 | 青岛科技大学 | A kind of phosphorus system synergistic fire retardation PC/ABS alloy material and preparation method thereof |
| CN103602024A (en) * | 2013-11-12 | 2014-02-26 | 青岛广联达精密机械有限公司 | Environment-friendly flame retardant alloy |
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