CN102993621A - Glass fiber reinforced flame-retardant ABS composite material having high impact resistance and high heat resistance, and its preparation technology - Google Patents
Glass fiber reinforced flame-retardant ABS composite material having high impact resistance and high heat resistance, and its preparation technology Download PDFInfo
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- CN102993621A CN102993621A CN2011102686252A CN201110268625A CN102993621A CN 102993621 A CN102993621 A CN 102993621A CN 2011102686252 A CN2011102686252 A CN 2011102686252A CN 201110268625 A CN201110268625 A CN 201110268625A CN 102993621 A CN102993621 A CN 102993621A
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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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
-
- 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
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
-
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
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Abstract
The invention relates to a glass fiber reinforced flame-retardant ABS composite material having a high impact resistance and a high heat resistance, and its preparation technology. The composite material is prepared through adding proper amounts of a compatilizer, a dispersant, a coupling agent and an antioxidant to main raw materials comprising 20-85 parts of ABS, 10-30 parts of GF (glass fiber), 0-15 parts of a flexibilizer and 5-35 parts of a flame retardant. The above raw materials are weight according proportions, and undergo blending extrusion on a double screw extruder. The flexibilizer introduced to the glass fiber reinforced flame-retardant ABS composite material having a high impact resistance and a high heat resistance is novel, has a good compatibility with the ABS, and can promote the dispersion of the flame retardant, improve the interface combination of the flame retardant and the resin, greatly improve the impact strength of the plastic, reduce the application amount of the flame retardant, reduce the cost, and improve the market competitiveness. The flame retardant introduced in the invention is novel, has the advantages of high heat stability, ideal ultraviolet resistance, ideal migration resistance, and ideal notch impact strength, and is suitable for glass fiber reinforced systems.
Description
Technical field
The invention discloses a kind of HI high impact, high-heat-resisting glass-fiber enhancing flame-retardant ABS compound material and preparation technology thereof.Be specifically related to a kind of high fire protection requirement that is applied to, such as the HI high impact in the industries such as automobile, household electrical appliances, building, high heat-resisting, high flame retardant ABS matrix material.
Technical background
ABS resin is preferably engineering plastics of a kind of over-all properties, has the characteristics such as good cold tolerance, oil resistance, electrical property, dimensional stability and processing fluidity.Being widely used in the fields such as automobile component, household electrical appliance, building, instrument, office equipment, household utensils, is most widely used kind in the present general engineering plastic.Raising along with the whole society awareness of safety, most products all require to have flame retardant resistance, possesses simultaneously higher thermotolerance, fire burns easily and heat-drawn wire is not high yet ABS meets, the adding of fire retardant also can cause the reduction of heat-drawn wire, so, for make its meet the difficult combustion of fire or from fire from putting out and improve thermotolerance, must carry out flame-retardant modified and glass enhancing modified to ABS.
At present, the fire retardant that ABS is commonly used has tetrabromo-bisphenol (TBBPA), octa-BDE (OBDPO), decabromodiphenyl oxide (DBDPO), the two tetrabromo phthalimides (BT-93w) of ethylene, two (tribromophenoxy) ethane (ff-680) and antimonous oxide (Sb with matching
2O
3) etc., yet though above flame-retardant system can keep original mechanical property, ultra-violet resistance is poor.In addition, among the ABS owing to add fire retardant and toughener, notched Izod impact strength can decrease, therefore need to add a certain amount of toughner, toughner commonly used has styrene-butadiene-styrene (SBS), chlorinatedpolyethylene (CPE) etc., though yet SBS can significantly improve the shock strength of matrix material, but addition is larger, not only to not having favourable influence the flame retardant properties of material volume, and so that the tensile strength of material, flexural strength, Rockwell hardness, heat-drawn wire and oxygen index have reduction in various degree; Though the toughening effect of CPE in flame-retardant system is better than SBS, heat resisting temperature own is low, occurs easily the yellowing phenomenon in the course of processing.Matrix material of the present invention adds novel toughner and novel fire retardant and prepares fiberglass reinforced fire retardant ABS, not only the addition of toughner and fire retardant all reduces, and over-all properties also is improved, so matrix material of the present invention has the excellent characteristics such as HI high impact, high heat-resisting, high flame retardant, low cost, a kind of ideal, the matrix material that has very much market outlook.
Summary of the invention
The present invention is not high in order to solve the mechanical property that exists at present traditional flame-proof ABS product, thermotolerance is low, resistance to migration is poor, UV resistant is poor and the high in cost of production problem, has proposed a kind of HI high impact, high-heat-resisting glass-fiber enhancing flame-retardant ABS compound material and preparation technology thereof.Technical scheme of the present invention is ABS, 20～85 parts; GF, 10～30 parts; Toughner, 0～15 part; Fire retardant, 5～35 parts; Compatilizer, 3～8 parts; Dispersion agent, 1～2 part; Coupling agent, 0.5～1 part and oxidation inhibitor, 0～0.5 part.
Described ABS resin is acrylonitrile-styrene-acrylic ester copolymer, rubber content 〉=30%, heat-drawn wire 〉=90 ℃.Described toughner is halogen-containing elastomerics, and processes good processing stability through special thermo-stabilizer.Described long glass fibres is the alkali-free roving, and intensity is 2 * 10
3～6 * 10
3MPa.Described fire retardant is novel halogen containing flame-retardant three (tribromo phenyl) triazine (FR-245), and thermostability is high, uvioresistant, anti-migration, notched Izod impact strength ideal.
Described compatilizer is one or more the mixture among SMA (styrene-maleic anhydride copolymer), the ABS-g-MAH (maleic anhydride grafted ABS).Described dispersion agent is one or more the mixture in EBS (vinyl bis-stearamides), dibutyl maleinate, the toxilic acid dibutyl tin.Coupling agent is one or more the mixture in KH-550, Y-aminopropyl triethoxysilane or the γ-glycidyl ether oxygen propyl trimethoxy silicane.Described oxidation inhibitor is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) mixture of one or more in the positive octadecanol ester of propionic acid or three [2,4-di-tert-butyl-phenyl] phosphorous acid ester.
A kind of HI high impact of the present invention, high-heat-resisting glass-fiber enhancing flame-retardant ABS compound material and preparation technology thereof are as follows: (1) selective enhancement decentralized screw combinations, make glass and fire retardant reach the optimum dispersion effect, and select suitable processing temperature and screw speed, barrel temperature is: 170～200 ℃ of back segments, 180～210 ℃ in stage casing, 190～220 ℃ of leading portions, screw slenderness ratio 35～40, screw speed 300～500r/min.(2) at first ABS, fire retardant, toughner and processing aid join in the twin screw extruder after high-speed mixer mixes, then the CF after surface treatment being added entrance from specialty adds, carry out mixing, extrude, cooling, pelletizing, get the cylindrical pellet product.
Matrix material of the present invention is to adopt fiberglass reinforced fire retardant ABS.The easy burning of ABS chance fire and heat-drawn wire are not high, the adding of fire retardant can improve the flame retardant resistance of ABS, uvioresistant and anti-transport property are strong simultaneously, the adding of glass can improve the thermotolerance of ABS, yet the affiliation that adds of fire retardant and glass reduces the shock strength of material, the adding of new type of toughening agent can increase substantially the shock strength of matrix material, and less on other mechanical property impact, and addition is few, flame retardant resistance to material has positive effect, can reduce the consumption of fire retardant, reduce production costs.So prepared fiberglass reinforced fire retardant ABS excellent combination property, especially thermotolerance, flame retardant resistance, the toughness of the present invention is given prominence to, and good weatherability, cost is low.
Embodiment:
The present invention is described in more detail below in conjunction with specific embodiment, but the present invention is not limited to each example of following enforcement:
Present embodiment is doubly grand twin screw extruder and sea day injection moulding machine of use section all; Main raw material is mainly the import material, and ABS originates in BASF Aktiengesellschaft, and glass originates in Zhejiang megalith group, and fire retardant originates in U.S.'s big lake chemical industry, and compatilizer SMA originates in Japan, and other processing aids are domestic.
A kind of HI high impact of the present invention, high-heat-resisting glass-fiber enhancing flame-retardant ABS compound material and preparation technology thereof are as follows: (1) selective enhancement decentralized screw combinations, make glass and fire retardant reach the optimum dispersion effect, and select suitable processing temperature and screw speed, barrel temperature is: 170～200 ℃ of back segments, 180～210 ℃ in stage casing, 190～220 ℃ of leading portions, screw slenderness ratio 35～40, screw speed 300～500r/min.(2) at first ABS, fire retardant, toughner and processing aid join in the twin screw extruder after high-speed mixer mixes, then the CF after surface treatment being added entrance from specialty adds, carry out mixing, extrude, cooling, pelletizing, get the cylindrical pellet product.
The ABS matrix material of gained in the various embodiments of the present invention is injection molded into test bars by following injecting condition, injecting condition: injection temperature 180-220 ℃, and injection pressure 30-50MPa, injection speed: 30-60mm/s.
Each embodiment physicals is all tested by DIN and China's national standard, and concrete examination criteria is as follows:
The prescription that each embodiment of table 1 is corresponding
The physicals that each embodiment sample of table 2 is corresponding
As can be seen from Table 2, when reaching certain toughening effect, the consumption of new type of toughening agent is few than the consumption of SBS, simultaneously, when reaching UL 94V-0 level, the consumption of fire-retardant FR-2 45 is few than the consumption of TBBPA, and this mainly is because new type of toughening agent is halogen-containing elastomerics, not only can increase substantially the shock strength of material, can also reduce the consumption of fire retardant.The present invention selects suitable toughner and fire retardant, can not only obtain HI high impact, high flame retardant ABS matrix material, can also reduce production costs, and improves the market competitiveness.In sum, material of the present invention has the excellent properties such as height is heat-resisting, HI high impact, high flame retardant, low cost, is a kind of matrix material that has very much market potential.
Claims (10)
1. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that HI high impact, high heat-resisting, and its component and content are as follows: ABS, 20～85 parts; GF, 10～30 parts; Toughner, 0～15 part; Fire retardant, 5～35 parts; Compatilizer, 3～8 parts; Dispersion agent, 1～2 part; Coupling agent, 0.5～1 part and oxidation inhibitor, 0～0.5 part.
2. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that described ABS resin is acrylonitrile-styrene-acrylic ester copolymer, rubber content 〉=30%, heat-drawn wire 〉=90 ℃.
3. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that described toughner is halogen-containing elastomerics, and process good processing stability through special thermo-stabilizer.
4. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that described long glass fibres is the alkali-free roving, and intensity is 2 * 10
3～6 * 10
3MPa.
5. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that described fire retardant is novel halogen containing flame-retardant three (tribromo phenyl) triazine (FR-245), thermostability is high, uvioresistant, anti-migration, notched Izod impact strength ideal.
6. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that described compatilizer is one or more the mixture among SMA (styrene-maleic anhydride copolymer), the ABS-g-MAH (maleic anhydride grafted ABS).
7. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that described dispersion agent is one or more the mixture in EBS (vinyl bis-stearamides), dibutyl maleinate, the toxilic acid dibutyl tin.
8. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that described coupling agent is one or more the mixture in KH-550, Y-aminopropyl triethoxysilane or the γ-glycidyl ether oxygen propyl trimethoxy silicane.
9. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that described oxidation inhibitor is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) mixture of one or more in the positive octadecanol ester of propionic acid or three [2,4-di-tert-butyl-phenyl] phosphorous acid ester.
10. a kind of HI high impact according to claim 1, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof, it is characterized in that: (1) selective enhancement decentralized screw combinations, make glass and fire retardant reach the optimum dispersion effect, and select suitable processing temperature and screw speed, barrel temperature is: 170～200 ℃ of back segments, 180～210 ℃ in stage casing, 190～220 ℃ of leading portions, screw slenderness ratio 35～40, screw speed 300～500r/min.(2) at first ABS, fire retardant, toughner and processing aid join in the twin screw extruder after high-speed mixer mixes, then the CF after surface treatment being added entrance from specialty adds, carry out mixing, extrude, cooling, pelletizing, get the cylindrical pellet product.
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|---|---|---|---|
| CN201110268625.2A CN102993621B (en) | 2011-09-13 | 2011-09-13 | A kind of HI high impact, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof |
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| CN201110268625.2A CN102993621B (en) | 2011-09-13 | 2011-09-13 | A kind of HI high impact, high-heat-resisting glass-fiber strengthen flame-retardant ABS compound material and preparation technology thereof |
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| CN102993621A true CN102993621A (en) | 2013-03-27 |
| CN102993621B CN102993621B (en) | 2015-09-30 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242617A (en) * | 2013-05-10 | 2013-08-14 | 苏州工业园区方圆金属制品有限公司 | ABS (Acrylonitrile Butadiene Styrene) plastic plate |
| CN103304911A (en) * | 2013-06-28 | 2013-09-18 | 青岛国恩科技股份有限公司 | Flame-retardant reinforced ABS (Acrylonitrile Butadiene Styrene) material and preparation method thereof |
| CN103409107A (en) * | 2013-07-26 | 2013-11-27 | 安徽昕宏通用设备制造有限公司 | Friction material for brake pad and preparation technology of friction material |
| CN104419105A (en) * | 2013-08-22 | 2015-03-18 | 黑龙江鑫达企业集团有限公司 | Preparation method for enhanced flame-retardant ABS material |
| CN109096684A (en) * | 2018-07-11 | 2018-12-28 | 合肥铭佑高温技术有限公司 | A kind of heat-resistant engineering plastic of high tenacity |
| CN109735046A (en) * | 2018-11-29 | 2019-05-10 | 苏州斯英铂聚合材料有限公司 | Fire-retardant heat-staple ABS composite material of enhancing of one kind and preparation method thereof |
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| CN101311222A (en) * | 2007-05-25 | 2008-11-26 | 佛山市顺德区汉达精密电子科技有限公司 | High impact resistance fiberglass reinforced engineering plastics and preparation method |
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| CN101130617A (en) * | 2006-08-25 | 2008-02-27 | 佛山市顺德区汉达精密电子科技有限公司 | ABS composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242617A (en) * | 2013-05-10 | 2013-08-14 | 苏州工业园区方圆金属制品有限公司 | ABS (Acrylonitrile Butadiene Styrene) plastic plate |
| CN103304911A (en) * | 2013-06-28 | 2013-09-18 | 青岛国恩科技股份有限公司 | Flame-retardant reinforced ABS (Acrylonitrile Butadiene Styrene) material and preparation method thereof |
| CN103409107A (en) * | 2013-07-26 | 2013-11-27 | 安徽昕宏通用设备制造有限公司 | Friction material for brake pad and preparation technology of friction material |
| CN103409107B (en) * | 2013-07-26 | 2016-04-27 | 安徽昕宏通用设备制造有限公司 | A kind of Brake pad friction material and preparation technology thereof |
| CN104419105A (en) * | 2013-08-22 | 2015-03-18 | 黑龙江鑫达企业集团有限公司 | Preparation method for enhanced flame-retardant ABS material |
| CN109096684A (en) * | 2018-07-11 | 2018-12-28 | 合肥铭佑高温技术有限公司 | A kind of heat-resistant engineering plastic of high tenacity |
| CN109735046A (en) * | 2018-11-29 | 2019-05-10 | 苏州斯英铂聚合材料有限公司 | Fire-retardant heat-staple ABS composite material of enhancing of one kind and preparation method thereof |
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| CN102993621B (en) | 2015-09-30 |
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