CN104592731A - Silicon-based flame-retardant PC/ABS alloy - Google Patents
Silicon-based flame-retardant PC/ABS alloy Download PDFInfo
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- CN104592731A CN104592731A CN201510038992.1A CN201510038992A CN104592731A CN 104592731 A CN104592731 A CN 104592731A CN 201510038992 A CN201510038992 A CN 201510038992A CN 104592731 A CN104592731 A CN 104592731A
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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
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- 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
Abstract
The invention relates to a silicon-based flame-retardant PC/ABS alloy. The silicon-based flame-retardant PC/ABS alloy is characterized by comprising the following components in parts by weight: 50-60 parts of PC resin, 40-50 parts of ABS resin, 2.0-6.0 parts of amidogen polydimethylsiloxane, 3.0-8.0 parts of 8(aminophenyl)-T8-silsesquioxane, 1.0-5.0 parts of epoxypropyl methacrylate, 0.5-2.0 parts of benzoyl peroxide, 0.5-2.0 parts of a silane coupling agent, 2.0-6.0 parts of attapulgite and 0.1-0.5 part of an antioxidant. The invention further relates to a preparation method of the silicon-based flame-retardant PC/ABS alloy. A linear structure and a dobby miktoarm star structure are respectively constructed by the epoxypropyl methacrylate and the 8(aminophenyl)-T8-silsesquioxane; a large amount of attapulgite is grafted through different groups; even dispersion of various substances in PC/ABS is promoted by the silane coupling agent; the crosslinking degree between silicon-containing substances and material matrix molecules is improved; and the flame retardant property of the PC/ABS alloy is effectively improved.
Description
Technical field
The present invention relates to the PC/ABS technical field of alloy with flame retardant properties, specifically refer to a kind of silicon system fire retardation PC/ABS.
Background technology
Polycarbonate (PC) is a kind of thermoplastic engineering plastic of high comprehensive performance, not only shock resistance degree is strong, transmittance is high for it, good stability of the dimension, easy coloring, ageing-resistant, and there is excellent electrical insulating property, apply all very extensive in all trades and professions.But, polycarbonate (PC) exist wear no resistance, the shortcoming of processing fluidity difference, this severely limits its further Application and Development in corresponding industry.Acrylonitrile-butadiene-styrene copolymer (ABS) is that a kind of intensity is high, good toughness, be easy to the thermoplastic engineering plastic of machine-shaping, but, acrylonitrile-butadiene-styrene copolymer (ABS) non-refractory and weathering resistance is poor.In order to make up the performance deficiency of polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS) self, investigator has prepared PC/ABS matrix material by blended for PC and ABS, this material can give full play to the advantage of PC and ABS, make them in overall performance, obtain complementation, improve the over-all properties of material.
At present, PC/ABS matrix material is widely used in material of construction, electronic apparatus, automobile shipbuilding industry, but its inflammableness limits their use range, therefore, is necessary to optimize further PC/ABS matrix material, improves its flame retardant properties.Silicone flame retardant have efficient, low cigarette, nontoxic, anti-drippage, to advantages such as body material performance impact are little, but, traditional organic silicon fibre retardant linear polysiloxanes is as polydimethylsiloxane, because its thermostability when high temperature is poor, and easily produce transport phenomena in the polymer, cause its flame retardant effect not ideal enough.
Therefore, for current silicon system fire retardation PC/ABS, await doing further improvement.
Summary of the invention
Technical problem to be solved by this invention is the present situation for prior art, the silicon system fire retardation PC/ABS providing a kind of Heat stability is good, flame retardant effect desirable.
Another technical problem to be solved by this invention is the present situation for prior art, provides the preparation method of a kind of above-mentioned silicon system fire retardation PC/ABS.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of silicon system fire retardation PC/ABS, is characterized in that comprising following component 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.
Further improvement, described silane coupling agent is end with any one silane coupling agent in epoxy group(ing), amino, (methyl) acryloxy, isocyanate group.
In above-mentioned each scheme, the structural formula of described eight (aminophenyl)-T8-silsesquioxane is
As preferably, described oxidation inhibitor is one or both the compound in AX-303, ADK, SAG-001,1010.
The preparation method of a kind of above-mentioned silicon system fire retardation PC/ABS, is characterized in that comprising the following steps:
(1) granulation material is prepared
Be in the mixing machine of 800 ~ 1200r/min, drop into 50 ~ 60g PC resin, 40 ~ 50gABS resin, 0.5 ~ 2.0g silane coupling agent, 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 successively to rotating speed, mixing 7 ~ 8min is continued after input, 0.1 ~ 0.5g oxidation inhibitor and 0.5 ~ 2.0g benzoyl peroxide is dropped into successively again in mixing machine, mixing 2 ~ 3min, namely obtains described granulation material;
(2) extruding pelletization
Step (1) gained granulation material is dropped in twin screw extruder and melt extrudes, cooling granulation.
As preferably, screw rod each heating region temperature of twin screw extruder described in step (2) is set to respectively: 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, the invention has the advantages that:
(1) in the present invention, under the katalysis of benzoyl peroxide, double bond in glytidyl methacrylate is opened and is grafted on PC/ABS main chain by free radical reaction, eight (aminophenyl)-T8-silsesquioxane then becomes the side-chain radical of PC/ABS by the epoxy group(ing) bonding in amino and glytidyl methacrylate, because eight (aminophenyl)-T8-silsesquioxane has cage structure, and its end has active group, be convenient to be combined with other compound, thus on the side chain making PC/ABS alloy centered by eight (aminophenyl)-T8-silsesquioxane, construct multi-arm to mix the star structure of arm, such structure is compared with linear structure of the prior art, more easily reduce interfacial tension, improve PC/ABS stability at high temperature, and the active group of eight (aminophenyl)-T8-silsesquioxane end is easy and other material carries out graft reaction, improve the crosslinking degree between silicon-containing material and material matrix molecule, strengthen the flame retardant resistance of PC/ABS,
(2) attapulgite has good thermostability and catalytic activity, can keep the stability of skeleton in combustion, plays the effect of stable layer of charcoal, thus significantly improves the thermo-oxidative stability of PC/ABS; Silane coupling agent in the present invention is in order to attapulgite modified, attapulgite through modified surface with the active group that can react, so that on the glytidyl methacrylate being grafted to PC/ABS side chain or eight (aminophenyl)-T8-silsesquioxane, amino polydimethyl siloxane in the present invention also can become the side-chain radical of PC/ABS by the epoxy group(ing) bonding in amino and glytidyl methacrylate, thus substantially increase the percentage of grafting of attapulgite, increase the consistency of attapulgite and PC/ABS matrix, effectively improve the thermostability of PC/ABS;
(3) glytidyl methacrylate used in the present invention and eight (aminophenyl)-T8-silsesquioxane construct linear structure and multi-arm respectively and to mix the star structure of arm in PC/ABS matrix, and by different group grafting a large amount of attapulgite, and the use of silane coupling agent facilitates 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 having prevented burning to produce outwards overflows, inhibit again the thermolysis of base material, thus effectively improve the flame retardant properties 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 twin screw extruder in the course of processing, has saved preparation cost, convenient, quick.
Embodiment
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 comprises following component by weight:
The preparation method of above-mentioned silicon system fire retardation PC/ABS, comprises the following steps:
(1) granulation material is prepared
Be in the mixing machine of 900r/min, drop into PC resin, ABS resin, Silane coupling agent KH550, attapulgite, amino polydimethyl siloxane KF-8012, eight (aminophenyl)-T8-silsesquioxane and glytidyl methacrylate successively to rotating speed, mixing 7min is continued after input, oxidation inhibitor AX-303 and benzoyl peroxide is dropped into successively again in mixing machine, mixing 2min, namely obtains granulation material;
(2) extruding pelletization
Step (1) gained granulation material is dropped in twin screw extruder and melt extrudes, cooling granulation; Concrete, screw rod each heating region temperature of twin screw extruder is set to respectively: 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 comprises following component by weight:
The preparation method of above-mentioned silicon system fire retardation PC/ABS, comprises the following steps:
(1) granulation material is prepared
Be in the mixing machine of 1000r/min, drop into PC resin, ABS resin, silane coupling agent KH560, attapulgite, amino polydimethyl siloxane KF-8012, eight (aminophenyl)-T8-silsesquioxane and glytidyl methacrylate successively to rotating speed, mixing 7.5min is continued after input, oxidation inhibitor ADK and benzoyl peroxide is dropped into successively again in mixing machine, mixing 2.5min, namely obtains granulation material;
(2) extruding pelletization
Step (1) gained granulation material is dropped in twin screw extruder and melt extrudes, cooling granulation; Concrete, screw rod each heating region temperature of twin screw extruder is set to respectively: 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 comprises following component by weight:
The preparation method of above-mentioned silicon system fire retardation PC/ABS, comprises the following steps:
(1) granulation material is prepared
Be in the mixing machine of 1200r/min, drop into PC resin, ABS resin, silane coupling agent KH570, attapulgite, amino polydimethyl siloxane KF-8008, eight (aminophenyl)-T8-silsesquioxane and glytidyl methacrylate successively to rotating speed, mixing 8min is continued after input, oxidation inhibitor SAG-001 and benzoyl peroxide is dropped into successively again in mixing machine, mixing 3min, namely obtains granulation material;
(2) extruding pelletization
Step (1) gained granulation material is dropped in twin screw extruder and melt extrudes, cooling granulation; Concrete, screw rod each heating region temperature of twin screw extruder is set to respectively: district's temperature 235 DEG C, two district's temperature 240 DEG C, three district's temperature 240 DEG C, four district's temperature 240 DEG C, five district's temperature 240 DEG C, six district's temperature 245 DEG C, seven district's temperature 245 DEG C, eight district's temperature 250 DEG C, nine district's temperature 250 DEG C, ten district's temperature 245 DEG C.
Embodiment 4:
The silicon system fire retardation PC/ABS of the present embodiment comprises following component by weight:
The preparation method of above-mentioned silicon system fire retardation PC/ABS, comprises the following steps:
(1) granulation material is prepared
Be in the mixing machine of 800r/min, drop into PC resin, ABS resin, silane coupling agent DMT25, attapulgite, amino polydimethyl siloxane KF-8008, eight (aminophenyl)-T8-silsesquioxane and glytidyl methacrylate successively to rotating speed, mixing 8min is continued after input, antioxidant 1010 and benzoyl peroxide is dropped into successively again in mixing machine, mixing 2min, namely obtains granulation material;
(2) extruding pelletization
Step (1) gained granulation material is dropped in twin screw extruder and melt extrudes, cooling granulation; Concrete, screw rod each heating region temperature of twin screw extruder is set to respectively: 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 5:
The silicon system fire retardation PC/ABS of the present embodiment comprises following component by weight:
The preparation method of above-mentioned silicon system fire retardation PC/ABS, comprises the following steps:
(1) granulation material is prepared
Be in the mixing machine of 1100r/min, drop into PC resin, ABS resin, silane coupling agent KH560, attapulgite, amino polydimethyl siloxane KF-8012, eight (aminophenyl)-T8-silsesquioxane and glytidyl methacrylate successively to rotating speed, mixing 7min is continued after input, antioxidant 1010 and benzoyl peroxide is dropped into successively again in mixing machine, mixing 3min, namely obtains granulation material;
(2) extruding pelletization
Step (1) gained granulation material is dropped in twin screw extruder and melt extrudes, cooling granulation.Concrete, screw rod each heating region temperature of twin screw extruder is set to respectively: 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.
Carry out performance test to the silicon system fire retardation PC/ABS prepared in the various embodiments described above, wherein, limiting oxygen index(LOI) (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
Can find out, the silicon system fire retardation PC/ABS in the present invention has good flame retardant properties.
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 BOC Science; Amino polydimethyl siloxane (KF-8012, KF-8008) is purchased from Guangzhou Yue Cheng Fine Chemical Co., Ltd; Silane coupling agent (KH550, KH560, KH570, DMT25) is purchased from Nanjing Lian Gui Chemical Co., Ltd.; Oxidation inhibitor (AX-303, ADK, SAG-001,1010) is purchased from Dongguan Heng Li plastic material company limited.
Claims (7)
1. silicon system fire retardation PC/ABS, is characterized in that comprising following component by weight:
2. silicon system according to claim 1 fire retardation PC/ABS, is characterized in that: described amino polydimethyl siloxane is amino-terminated polydimethylsiloxane, the number-average molecular weight of this amino polydimethyl siloxane is 2000 ~ 5000.
3. silicon system according to claim 1 fire retardation PC/ABS, is characterized in that: described silane coupling agent is end with any one silane coupling agent in epoxy group(ing), amino, (methyl) acryloxy, isocyanate group.
4. silicon system according to claim 1 fire retardation PC/ABS, is characterized in that: the structural formula of described eight (aminophenyl)-T8-silsesquioxane is
5. silicon system according to claim 1 fire retardation PC/ABS, is characterized in that: described oxidation inhibitor is one or both the compound in AX-303, ADK, SAG-001,1010.
6. a preparation method for the silicon system fire retardation PC/ABS in Claims 1 to 5 described in arbitrary claim, is characterized in that comprising the following steps:
(1) granulation material is prepared
Be in the mixing machine of 800 ~ 1200r/min, drop into 50 ~ 60g PC resin, 40 ~ 50gABS resin, 0.5 ~ 2.0g silane coupling agent, 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 successively to rotating speed, mixing 7 ~ 8min is continued after input, 0.1 ~ 0.5g oxidation inhibitor and 0.5 ~ 2.0g benzoyl peroxide is dropped into successively again in mixing machine, mixing 2 ~ 3min, namely obtains described granulation material;
(2) extruding pelletization
Step (1) gained granulation material is dropped in twin screw extruder and melt extrudes, cooling granulation.
7. preparation method according to claim 6, it is characterized in that: screw rod each heating region temperature of twin screw extruder described in step (2) is set to respectively: 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 |
| CN106832813A (en) * | 2017-01-20 | 2017-06-13 | 广东优科艾迪高分子材料有限公司 | Flame-retardant polyethylene terephthalate resin composition |
| CN106867221A (en) * | 2017-01-20 | 2017-06-20 | 广东优科艾迪高分子材料有限公司 | A kind of flame retardant type polycarbonate compositions |
| CN106867033A (en) * | 2017-04-10 | 2017-06-20 | 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 preparation method and application |
| CN107057346A (en) * | 2017-01-20 | 2017-08-18 | 广东优科艾迪高分子材料有限公司 | Flame-retardant nylon composition |
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