CN101423659B - Flame retardant polyphenylene oxide composition and preparation method thereof - Google Patents
Flame retardant polyphenylene oxide composition and preparation method thereof Download PDFInfo
- Publication number
- CN101423659B CN101423659B CN2008102275003A CN200810227500A CN101423659B CN 101423659 B CN101423659 B CN 101423659B CN 2008102275003 A CN2008102275003 A CN 2008102275003A CN 200810227500 A CN200810227500 A CN 200810227500A CN 101423659 B CN101423659 B CN 101423659B
- Authority
- CN
- China
- Prior art keywords
- polyphenylene oxide
- flame
- oxide composition
- retardant
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
-
- 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
- B29C2948/92866—Inlet shaft or slot, e.g. passive hopper; Injector, e.g. injector nozzle on barrel
-
- 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
Abstract
The invention discloses a fire retardant polyphenylene oxide composition, which comprises the following components in weight percentage: 50 to 60 percent of polyphenylene oxide resin, 20 to 30 percent of high impact polystyrene resin, 8 to 10 percent of elastomer, 1 to 13 percent of fire retarding agent, 0 to 3.3 percent of compatilizer and 0.2 to 1 percent of antioxidant. The fire retardant polyphenylene oxide composition has the advantages of fire resistance, weather resistance, good mechanical performance, good fluidity, easy machine shaping and the like, and is applied to office automatization and a magnetic tape transfer piece, particularly the fields of vehicle external decoration such as vehicle front plates, seat bottom plates and bumpers and vehicle internal decoration such as ventilators, seat back rests and brackets. The method for preparing the fire retardant polyphenylene oxide composition adopts double screw extrusion processing equipment and has the advantages of simple and continuous flow, high production efficiency and stable quality of the prepared product.
Description
Technical field
The present invention relates to a kind of polyphenylene ether composition, particularly relate to a kind of flame-retardant polyphenylene oxide composition, the invention still further relates to the preparation method of this polyphenylene ether composition.
Background technology
Polyphenylene oxide resin (PPE) has excellent comprehensive performances, and is wide as the use temperature scope, water-absorbent is little, mechanical property and electrical property excellence etc.; But its melt viscosity height, processing forming are poor, are difficult for adopting the injecting method moulding, and restriction is received in practical application.Therefore normal the employing and its polystyrene compatible in wide compositing range (PS), improve its processing fluidity, the PPE/PS polymer alloy that forms has excellent low rate of moisture absorption, processing and good dimensional stability energy easily, can be used for the part preparation of Special Pump, water gaging equipment, military equipment part, various household electrical appliance element, automobile, boats and ships and the military vehicles.But the adding of PS tends to cause the flame retardant properties of PPE to descend, so need to add the flame retardant resistance material to increase its flame retardant resistance.
The flame-retardant modified polyphenylene oxide system of current report mostly is the employing phosphoric acid ester.As, at " plastics " 2007, (36) 5, report among the p49, Xin Fei etc. carry out flame-retardant modified with two (phenylbenzene) phosphoric acid ester of dihydroxyphenyl propane and two (phenylbenzene) phosphoric acid ester of Resorcinol to the PPE/HIPS alloy, at the total consumption of fire retardant is to obtain flame retardant properties preferably at 28% o'clock, but tensile strength has descended about 20%.
Patent CN1116359C discloses a kind of flame-retardant polyphenyl ether composition, and it comprises: a) at least a polyphenylene oxide resin; B) at least a polystyrene resin; C) about 5wt% to 20wt% organophosphate resin; D) about 5wt% is to about 40wt% glass fibre; E) mica.At the organophosphate consumption is to obtain flame retardant properties preferably at 20% o'clock, but this patent is not reported the mechanical property and the resistance toheat of composition.
Patent CN1711317A discloses a kind of resin combination that is used for the electric wire and cable covering material, and it comprises polyarylene ether resin, polystyrene, olefin type elastomer, hydrogenated styrene-Ding ethylene block copolymer and phosphoric acid ester fire retardant.Although said composition has good weathering resistance, thermotolerance, compression deformability and favorable environment protection energy, the phosphate flame retardant large usage quantity that it adopts makes fire retardant very easily separate out from product surface, causes product surface to be clamminess, easily binding dust.Although this explanation phosphoric acid ester fire retardant can make system obtain flame retardant properties preferably, it is big that but the phosphoric acid ester fire retardant often has plastification and fire-retardant effectiveness to hang down consumption to system, rigidity, the thermotolerance of polyphenylene ether itself cause greater loss easily, so the flame-retardant modified polyphenylene oxide mechanical property that adopts this based flame retardant to produce is lower, temperature classification is not high.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of flame-retardant polyphenylene oxide composition, have fire-retardant, weather-proof, thermally-stabilised, mechanical property is good, good fluidity, be easy to advantages such as machine-shaping, the constant product quality that preparation method's flow process of said composition is simple, production efficiency is high, make.
For solving the problems of the technologies described above, the invention provides a kind of flame-retardant polyphenylene oxide composition, it comprises following component:
Polyphenylene oxide resin (PPE) 50～60 weight %;
High-impact polystyrene resin (HIPS) 20～30 weight %;
Elastomerics 8～10 weight %;
Fire retardant 1～13 weight %;
Compatilizer 0～3.3 weight %;
Oxidation inhibitor 0.2～1 weight %;
Said components weight percentage sum is 10 0%.
Above-mentioned flame-retardant polyphenylene oxide composition, wherein, the intrinsic viscosity of described polyphenylene oxide resin is 0.2～0.6dL/g, be preferably 0.2～0.45dL/g, can use a kind of polyphenylene oxide resin of independent limiting viscosity, also can select the polyphenyl ether resin composition of the polyphenylene oxide composition of several different qualities viscosity for use, the product that can select for use Ruicheng branch office of Lanxing Chemical New Material Co., Ltd. to produce.
Above-mentioned flame-retardant polyphenylene oxide composition, wherein, described polyphenylene oxide resin is poly-(2, the 6-dimethyl benzene) ether, 2,6-xylenol and 2,3, the copolymer resins of 6-pseudocuminol.
Above-mentioned flame-retardant polyphenylene oxide composition, wherein, described high-impact polystyrene resin (HIPS) trade mark that can adopt Beijing Yanshan Petrochemical Company to produce is that the trade mark of HIPS632EP, HIPS514P or Shanghai Secco Petrochemical Co., Ltd. is one or more among the HIPS632EP.The adding of HIPS can improve the processing fluidity of polyphenylene ether composition.
Above-mentioned flame-retardant polyphenylene oxide composition, wherein, described elastomerics is styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymers or vulcanizes in the butylbenzene powdered rubber (being also referred to as ultrafine powder SBS) one or more entirely.Preferably, the particle diameter that vulcanizes the butylbenzene powdered rubber entirely is 50～120 nanometers.It is that the SBS of SBS4452 or the trade mark of Beijing Chemical Research Institute's production are the ultrafine powder SBS of VP101 that elastomerics can adopt the trade mark of SINOPEC Beijing Yanshan Company.Elastomeric adding can make material obtain good impact property.
Above-mentioned flame-retardant polyphenylene oxide composition, wherein, described fire retardant is the brominated epoxy resin based flame retardant, and can adopt Chinese Suzhou Industrial Park day bromine content of producing of novel material company limited is among CR-210K or the CR-225K one or more at the trade mark more than 50%.
Above-mentioned flame-retardant polyphenylene oxide composition, wherein, described compatilizer is the polyethylene-octene elastomerics (POE-g-MAH) of maleic anhydride graft, maleic anhydride grafting ratio is 0.1-1%, is preferably between the 0.3-0.6%.The adding of compatilizer can improve the consistency between each component of composition.
Above-mentioned flame-retardant polyphenylene oxide composition, wherein, described oxidation inhibitor is phenolic antioxidant, phosphite ester kind antioxidant, contain in thioesters kind antioxidant or the metal passivator oxidation inhibitor one or more.Used phenolic antioxidant is β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester (antioxidant 1076) or 2,2 methylene-biss (4-methyl-6-tert butyl phenol) (antioxidant 2246); Phosphite ester kind antioxidant is tricresyl phosphite (nonyl phenyl) (oxidation inhibitor TNPP) or tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) esters (oxidation inhibitor 168); Containing the thioesters kind antioxidant is Tyox B (anti-oxidant DLTP); Metal passivator oxidation inhibitor is N, N-diacetyl adipyl two hydrazides (passivator GI-09-367).IRGANOX1076 and IRGAFOS168 that oxidation inhibitor can adopt GIBA company to produce.
The present invention also provides the preparation method of above-mentioned flame-retardant polyphenylene oxide composition, and it comprises the steps:
A stirs polyphenylene oxide, high-impact polystyrene, elastomerics, fire retardant, compatilizer and oxidation inhibitor in high-speed mixer;
B puts into twin screw extruder with mixed raw material then and melt extrudes.
Above-mentioned preparation method, wherein, churning time is 3～5 minutes among the described step a.
Above-mentioned preparation method, wherein, the length-to-diameter ratio of twin screw extruder is 32～40 among the described step b.
Above-mentioned preparation method, wherein, rate of feeding is 5～10rpm/min among the described step b, and screw speed is 200～400rpm/min, and each subregion temperature of barrel is 200～280 ℃.
Flame-retardant polyphenylene oxide composition of the present invention owing to added efficient flame-retarding agent in composite body system, when obtaining flame retardant properties, has kept the over-all propertieies such as resistance toheat, mechanical property of product again.That the gained polyphenylene ether composition has is fire-retardant, weather-proof, thermally-stabilised, mechanical property is good, good fluidity, be easy to a series of outstanding advantages such as machine-shaping, is very suitable for office automation, magnetic tape transport part and especially is widely used in interior trim fields such as automobile exteriors such as automobile header board, seat bottom plate, collision bumper and ventilator, backrest, carriage.The preparation method of this flame-retardant polyphenylene oxide composition adopts the twin screw extrusion technique device, has the advantages such as constant product quality that flow process is simple, continuous, production efficiency is high, make.
Embodiment
Describe the present invention in detail below in conjunction with embodiment.
Comparative Examples
With the polyphenylene oxide resin (intrinsic viscosity is 0.35dL/g) of 60 weight %, the high-impact polystyrene resin (HIPS) of 30 weight %, the elastomerics SBS of 9 weight % and the oxidation inhibitor β-(3 of 1 weight %, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester stirred in high-speed mixer 5 minutes, after mixing, drop into the twin screw extruder extruding pelletization.The length-to-diameter ratio of twin screw extrusion equipment is 35, the control rate of feeding is that 8rpm/min, screw speed are that 200rpm/min, each subregion temperature of barrel are first section 200 ℃, second section 245 ℃, the 3rd section 245 ℃, the 4th section 245 ℃, the 5th section 245 ℃, the 6th section 245 ℃, the 7th section 245 ℃, the 8th section 245 ℃, the 9th section 245 ℃, 245 ℃ of die head temperatures, tie rod is crossed the water pelletizing.
Embodiment 1
With the brominated epoxy resin based flame retardant of elastomerics SBS, the 5 weight % of the high-impact polystyrene resin (HIPS) of the polyphenylene oxide resin (intrinsic viscosity is 0.35dL/g) of 55 weight %, 30 weight %, 9 weight % and the oxidation inhibitor β-(3 of 1 weight %, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester stirred in high-speed mixer 5 minutes, after mixing, drop into the twin screw extruder extruding pelletization.The length-to-diameter ratio of twin screw extrusion equipment is 35, the control rate of feeding is that 8rpm/min, screw speed are that 200rpm/min, each subregion temperature of barrel are first section 200 ℃, second section 245 ℃, the 3rd section 245 ℃, the 4th section 245 ℃, the 5th section 245 ℃, the 6th section 245 ℃, the 7th section 245 ℃, the 8th section 245 ℃, the 9th section 245 ℃, 245 ℃ of die head temperatures, tie rod is crossed the water pelletizing.
Embodiment 2
With the polyethylene-octene elastomerics POE-g-MAH (maleic anhydride grafting ratio is 0.5%) of the compatilizer maleic anhydride graft of the brominated epoxy resin based flame retardant of elastomerics SBS, the 5 weight % of the high-impact polystyrene resin (HIPS) of the polyphenylene oxide resin (intrinsic viscosity is 0.35dL/g) of 55 weight %, 27 weight %, 9 weight %, 3.3 weight % and the oxidation inhibitor β-(3 of 0.7 weight %, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester stirred in high-speed mixer 5 minutes, after mixing, drop into the twin screw extruder extruding pelletization.The length-to-diameter ratio of twin screw extrusion equipment is 35, the control rate of feeding is that 8rpm/min, screw speed are that 200rpm/min, each subregion temperature of barrel are first section 200 ℃, second section 245 ℃, the 3rd section 245 ℃, the 4th section 245 ℃, the 5th section 245 ℃, the 6th section 245 ℃, the 7th section 245 ℃, the 8th section 245 ℃, the 9th section 245 ℃, 245 ℃ of die head temperatures, tie rod is crossed the water pelletizing.
Embodiment 3
With the polyethylene-octene elastomerics POE-g-MAH (maleic anhydride grafting ratio is 0.3%) of the compatilizer maleic anhydride graft of the brominated epoxy resin based flame retardant of ultrafine powder SBS, the 7 weight % of elastomerics 100 nanometers of the high-impact polystyrene resin of the polyphenylene oxide resin (intrinsic viscosity is 0.45dL/g) of 60 weight %, 20 weight %, 10 weight %, 2.8 weight % and the oxidation inhibitor tricresyl phosphite (2 of 0.2 weight %, the 4-di-tert-butyl-phenyl) ester stirred in high-speed mixer 3 minutes, after mixing, drop into the twin screw extruder extruding pelletization.The length-to-diameter ratio of twin screw extrusion equipment is 32, the control rate of feeding is that 5rpm/min, screw speed are that 300rpm/min, each subregion temperature of barrel are first section 220 ℃, second section 240 ℃, the 3rd section 240 ℃, the 4th section 245 ℃, the 5th section 245 ℃, the 6th section 245 ℃, the 7th section 260 ℃, the 8th section 260 ℃, the 9th section 260 ℃, 250 ℃ of die head temperatures, tie rod is crossed the water pelletizing.
Embodiment 4
Polyethylene-octene elastomerics the POE-g-MAH (maleic anhydride grafting ratio is 1%) of the compatilizer maleic anhydride graft of the brominated epoxy resin based flame retardant of ultrafine powder SBS, the 1 weight % of elastomerics 120 nanometers of the high-impact polystyrene resin of the polyphenylene oxide resin (intrinsic viscosity is 0.2dL/g) of 59 weight %, 30 weight %, 8 weight %, 1.5 weight % and the oxidation inhibitor Tyox B of 0.5 weight % were stirred in high-speed mixer 4 minutes, after mixing, drop into the twin screw extruder extruding pelletization.The length-to-diameter ratio of twin screw extrusion equipment is 40, the control rate of feeding is that 10rpm/min, screw speed are that 200rpm/min, each subregion temperature of barrel are first section 220 ℃, second section 240 ℃, the 3rd section 240 ℃, the 4th section 245 ℃, the 5th section 245 ℃, the 6th section 260 ℃, the 7th section 260 ℃, the 8th section 260 ℃, the 9th section 280 ℃, 260 ℃ of die head temperatures, tie rod is crossed the water pelletizing.
Embodiment 5
With the polyethylene-octene elastomerics POE-g-MAH (maleic anhydride grafting ratio is 0.6%) of the compatilizer maleic anhydride graft of the brominated epoxy resin based flame retardant of ultrafine powder SBS, the 13 weight % of elastomerics 50 nanometers of the high-impact polystyrene resin of the polyphenylene oxide resin (intrinsic viscosity is 0.6dL/g) of 50 weight %, 24 weight %, 8.7 weight %, 3.3 weight % and the oxidation inhibitor N of 1 weight %; N-diacetyl adipyl two hydrazides stirred in high-speed mixer 5 minutes; after mixing, drop into the twin screw extruder extruding pelletization.The length-to-diameter ratio of twin screw extrusion equipment is 37, the control rate of feeding is that 8rpm/min, screw speed are that 200rpm/min, each subregion temperature of barrel are first section 220 ℃, second section 240 ℃, the 3rd section 240 ℃, the 4th section 245 ℃, the 5th section 245 ℃, the 6th section 260 ℃, the 7th section 260 ℃, the 8th section 260 ℃, the 9th section 280 ℃, 260 ℃ of die head temperatures, tie rod is crossed the water pelletizing.
Embodiment 6
Polyphenylene oxide resin (intrinsic viscosity is 0.45dL/g) with 60 weight %, the high-impact polystyrene resin of 24 weight %, the elastomerics SEBS of 10 weight %, 4.2 the brominated epoxy resin based flame retardant of weight %, 0.8 the oxidation inhibitor β-(3 of polyethylene of the compatilizer maleic anhydride graft of weight %-octene elastomerics POE-g-MAH (maleic anhydride grafting ratio is 0.6%) and 1 weight %, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester stirred in high-speed mixer 5 minutes, after mixing, drop into the twin screw extruder extruding pelletization.The length-to-diameter ratio of twin screw extrusion equipment is 37, the control rate of feeding is that 8rpm/min, screw speed are that 400rpm/min, each subregion temperature of barrel are first section 220 ℃, second section 240 ℃, the 3rd section 240 ℃, the 4th section 245 ℃, the 5th section 245 ℃, the 6th section 260 ℃, the 7th section 260 ℃, the 8th section 260 ℃, the 9th section 260 ℃, 260 ℃ of die head temperatures, tie rod is crossed the water pelletizing.
Embodiment 7
Polyphenylene oxide resin (intrinsic viscosity is 0.45dL/g) with 51 weight %, the high-impact polystyrene resin of 24 weight %, the ultrafine powder SBS of elastomerics 80 nanometers of 10 weight %, 11.7 the brominated epoxy resin based flame retardant of weight %, 3.3 the oxidation inhibitor β-(3 of polyethylene of the compatilizer maleic anhydride graft of weight %-octene elastomerics POE-g-MAH (maleic anhydride grafting ratio is 0.1%) and 1 weight %, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester and tricresyl phosphite (2,4-two its phenyl of uncle's fourth) ester stirred in high-speed mixer 5 minutes, after mixing, drop into the twin screw extruder extruding pelletization.The length-to-diameter ratio of twin screw extrusion equipment is 37, the control rate of feeding is that 5rpm/min, screw speed are that 300rpm/min, each subregion temperature of barrel are first section 240 ℃, second section 240 ℃, the 3rd section 240 ℃, the 4th section 245 ℃, the 5th section 245 ℃, the 6th section 260 ℃, the 7th section 260 ℃, the 8th section 260 ℃, the 9th section 260 ℃, 260 ℃ of die head temperatures, tie rod is crossed the water pelletizing.
The composition of above-mentioned Comparative Examples and each embodiment preparation is injection molded into the standard batten of test usefulness by standard size, physicals sees Table 1, physicals is tested by China's national standard, and concrete testing method sees Table 2, and second-order transition temperature utilizes the Hakke rheometer to adopt the method for rocking to test.
Among embodiment 1～4 and the embodiment 6, the flame retardant properties of polyphenylene ether composition reaches the V1 level and all is better than V2 level in the Comparative Examples, and the flame retardant resistance of polyphenylene ether composition reaches the V0 level in embodiment 5 and 7, and has good thermotolerance, impact resistance and tensile property.
Table 1
| Physicals | Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Tensile strength (MPa) | 51.4 | 51.6 | 51 | 52.7 | 54.5 | 53.1 | 49.5 | 50.8 |
| Elongation (%) | 38.5 | 38.4 | 45.2 | 52.5 | 53.1 | 47.3 | 38.9 | 57.5 |
| Flexural strength (MPa) | 85.9 | 87.4 | 86.6 | 83.9 | 84.3 | 87.4 | 88.9 | 84.4 |
| Modulus in flexure (MPa) | 2108 | 2138 | 2052 | 2029 | 2045 | 2080 | 2117 | 2060 |
| Unnotched impact strength (KJ.m-2) | 122.4 | 120.15 | 144.9 | 151.91 | 163.5 | 147.2 | 133.7 | 145.3 |
| Flame retardant properties | V2 | V1 | V1 | V1 | V1 | V0 | V1 | V0 |
| Tg℃ | 150 | 149 | 150 | 154 | 154 | 155 | 151 | 151 |
Table 2
| Physicals | Unit | Testing method |
| Tensile strength | MPa | GB/T?1040.1 |
| Elongation | ％ | GB/T?1040.1 |
| Flexural strength | MPa | GB/T?9341 |
| Modulus in flexure | MPa | GB/T?9341 |
| The Izod unnotched impact strength | KJ.m-2 | GB?1843 |
| Flame retardant properties | / | UL94 |
Claims (19)
1. flame-retardant polyphenylene oxide composition, it comprises following component:
Polyphenylene oxide resin 50～60 weight %;
High-impact polystyrene resin 24～30 weight %;
Elastomerics 8～9 weight %;
Fire retardant 1～11.7 weight %;
Compatilizer 1.5～3.3 weight %;
Oxidation inhibitor 0.2～0.7 weight %;
Said components weight percentage sum is 100%.
2. flame-retardant polyphenylene oxide composition as claimed in claim 1, wherein, the intrinsic viscosity of described polyphenylene oxide resin is 0.2～0.6dL/g.
3. flame-retardant polyphenylene oxide composition as claimed in claim 2, wherein, the intrinsic viscosity of described polyphenylene oxide resin is 0.2～0.45dL/g.
4. flame-retardant polyphenylene oxide composition as claimed in claim 1, wherein, described polyphenylene oxide resin is poly-(2, the 6-dimethyl benzene) ether, 2,6-xylenol and 2,3, the copolymer resins of 6-pseudocuminol.
5. flame-retardant polyphenylene oxide composition as claimed in claim 1, wherein, described elastomerics is styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymers or vulcanizes in the butylbenzene powdered rubber one or more entirely.
6. flame-retardant polyphenylene oxide composition as claimed in claim 5, wherein, the particle diameter of described full sulfuration butylbenzene powdered rubber is 50～120 nanometers.
7. flame-retardant polyphenylene oxide composition as claimed in claim 1, wherein, described fire retardant is the brominated epoxy resin based flame retardant.
8. flame-retardant polyphenylene oxide composition as claimed in claim 1, wherein, described compatilizer is the polyethylene-octene elastomerics of maleic anhydride graft.
9. flame-retardant polyphenylene oxide composition as claimed in claim 8, wherein, described maleic anhydride grafting ratio is 0.1-1%.
10. flame-retardant polyphenylene oxide composition as claimed in claim 9, wherein, described maleic anhydride grafting ratio is between the 0.3-0.6%.
11. flame-retardant polyphenylene oxide composition as claimed in claim 1, wherein, described oxidation inhibitor is phenolic antioxidant, phosphite ester kind antioxidant, contain in thioesters kind antioxidant or the metal passivator oxidation inhibitor one or more.
12. flame-retardant polyphenylene oxide composition as claimed in claim 11, wherein, described phenolic antioxidant is β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester or 2,2-methylene-bis (4-methyl-6-tert butyl phenol).
13. flame-retardant polyphenylene oxide composition as claimed in claim 11, wherein, described phosphite ester kind antioxidant is tricresyl phosphite (nonyl phenyl) or tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
14. flame-retardant polyphenylene oxide composition as claimed in claim 11, wherein, the described thioesters kind antioxidant that contains is a Tyox B.
15. flame-retardant polyphenylene oxide composition as claimed in claim 11, wherein, described metal passivator oxidation inhibitor has N, N-diacetyl adipyl two hydrazides.
16. the preparation method of a flame-retardant polyphenylene oxide composition as claimed in claim 1, it comprises the steps:
A stirs polyphenylene oxide, high-impact polystyrene, elastomerics, fire retardant, compatilizer and oxidation inhibitor in mixing machine;
B puts into twin screw extruder with mixed raw material then and melt extrudes.
17. preparation method as claimed in claim 16, wherein, churning time is 3～5 minutes among the described step a.
18. method as claimed in claim 16, wherein, the length-to-diameter ratio of twin screw extruder is 32～40 among the described step b.
19. method as claimed in claim 16, wherein, rate of feeding is 5～10rpm/min among the described step b, and screw speed is 200～400rpm/min, and each subregion temperature of barrel is 200～280 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102275003A CN101423659B (en) | 2008-11-27 | 2008-11-27 | Flame retardant polyphenylene oxide composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102275003A CN101423659B (en) | 2008-11-27 | 2008-11-27 | Flame retardant polyphenylene oxide composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101423659A CN101423659A (en) | 2009-05-06 |
| CN101423659B true CN101423659B (en) | 2011-04-27 |
Family
ID=40614553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102275003A Expired - Fee Related CN101423659B (en) | 2008-11-27 | 2008-11-27 | Flame retardant polyphenylene oxide composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101423659B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030978B (en) * | 2010-11-26 | 2012-06-20 | 中国蓝星（集团）股份有限公司 | Halogen-free flame retardant polyphenylene oxide polyphenyl ether (PPE) cable material composition and preparation method thereof |
| CN102558825A (en) * | 2010-12-30 | 2012-07-11 | 合肥杰事杰新材料股份有限公司 | Glass-fiber-reinforced polyphenylene oxide/polystyrene (PPO/PS) alloy composition and preparation method thereof |
| CN102234419B (en) * | 2011-05-06 | 2012-12-05 | 深圳市兴盛迪新材料有限公司 | Halogen-free flameproof polyphenylene ether resin composition and preparation method thereof |
| CN102898809A (en) * | 2011-07-27 | 2013-01-30 | 上海凯波特种电缆料厂有限公司 | Halogen-free flame-retardant polyphenylether cable material, its preparation and application |
| CN102382448B (en) * | 2011-09-07 | 2013-05-29 | 上海日之升新技术发展有限公司 | Halogen free inflaming retardant polyphenylene oxide alloy and preparation method thereof |
| CN103044894B (en) * | 2011-10-14 | 2016-05-11 | 比亚迪股份有限公司 | A kind of Noryl composition and method of making the same |
| CN102516724A (en) * | 2011-11-30 | 2012-06-27 | 中国蓝星（集团）股份有限公司 | Polytrimethylene terephthalate/polyphenylether composite material and preparation method thereof |
| CN102643527A (en) * | 2012-04-20 | 2012-08-22 | 金发科技股份有限公司 | Tracking-resistant polyphenylether resin composition |
| CN103122137A (en) * | 2013-02-05 | 2013-05-29 | 苏州市沃特新材料科技有限公司 | Polyphenylether composite material, and preparation method and application thereof |
| WO2015062054A1 (en) * | 2013-10-31 | 2015-05-07 | Dow Global Technologies Llc | Curable compositions which form interpenetrating polymer networks |
| CN103937222A (en) * | 2014-04-29 | 2014-07-23 | 贵州高塑环保新材料有限公司 | Reinforced polyphenyl ether by using grafted block elastomer (SEBS) modification and preparation method thereof |
| CN105131558B (en) * | 2015-08-18 | 2017-10-20 | 上海瀚氏模具成型有限公司 | A kind of automotive upholstery environment protection modification polyphenyl ether material |
| CN106366616B (en) * | 2016-08-26 | 2018-04-06 | 青岛海尔新材料研发有限公司 | A kind of MPPO composites and preparation method thereof |
| CN112745653B (en) * | 2019-10-30 | 2022-11-18 | 中国石油化工股份有限公司 | Modified polyphenyl ether, halogen-free flame-retardant TPV, preparation methods and applications of modified polyphenyl ether and halogen-free flame-retardant TPV, and composition for preparing halogen-free flame-retardant TPV |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130616A (en) * | 2007-09-28 | 2008-02-27 | 深圳市科聚新材料有限公司 | Low-smoke halogen-freeflame-proof polyphenylene oxide electric wire and cable material, and method for producing the same |
-
2008
- 2008-11-27 CN CN2008102275003A patent/CN101423659B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130616A (en) * | 2007-09-28 | 2008-02-27 | 深圳市科聚新材料有限公司 | Low-smoke halogen-freeflame-proof polyphenylene oxide electric wire and cable material, and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101423659A (en) | 2009-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101423659B (en) | Flame retardant polyphenylene oxide composition and preparation method thereof | |
| CN101805508B (en) | Halogen-free fire-retardant polyphenyl ether composition capable of improving low-temperature toughness and preparation method thereof | |
| CN102234419B (en) | Halogen-free flameproof polyphenylene ether resin composition and preparation method thereof | |
| CN101311223B (en) | High impact resistance fiberglass reinforced fire retardant engineering plastics and preparation method | |
| CN101130616A (en) | Low-smoke halogen-freeflame-proof polyphenylene oxide electric wire and cable material, and method for producing the same | |
| CN103382296B (en) | A kind of poly butylene succinate resin combination and preparation method thereof | |
| CN103589069A (en) | High-shock resistance polypropylene/polybutylene composite material as well as preparation method and purposes thereof | |
| CN101092501A (en) | PA6 / ABS alloy material, and preparation method | |
| CN102558741A (en) | Flame-retarded Acrylonitrile Butadiene Styrene (ABS) resin with good low-temperature toughness and preparation method of flame-retarded ABS resin | |
| KR20130102561A (en) | Polyphenylene ether resin composition and molded article of same | |
| CN101311221A (en) | Fiberglass reinforced fire retardant engineering plastics and preparation method | |
| CN104629338A (en) | Permanently antistatic PC/ABS modified alloy, and preparation method thereof | |
| CN103819866A (en) | High-performance permanently-antistatic flame-retardant ABS (acrylonitrile butadiene styrene) material and preparation method and application | |
| CN102827422B (en) | Long-term heat and oxidation aging resistant polypropylene compound and preparation method thereof | |
| CN103467966A (en) | Inflaming retarding PPE/PS/ABS alloy plastic as well as preparation method and application thereof | |
| CN104194337A (en) | Composite polyphenyl thioether material | |
| CN101423660B (en) | Creep resistance and impact resistance polyphenylene oxide composition at high temperature and preparation method thereof | |
| CN112322020B (en) | Polyphenyl ether resin composition and preparation method thereof, and wire slot and preparation method thereof | |
| CN104725789A (en) | High-performance low-cost flame-retardant PET/ABS composite material | |
| CN102964688B (en) | A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen PP/PA11 alloy material and preparation method thereof | |
| CN101602886B (en) | Polyphenyl ether/nanometer silica composite and preparation method thereof | |
| CN104072927A (en) | Special reinforced regenerated flame-retardant HIPS (high impact polystyrene) for home appliances and preparation technique thereof | |
| CN102775681A (en) | High-temperature precipitation-resistant halogen-free flame-retardant polypropylene composition and preparation method thereof | |
| CN102643526A (en) | Halogen-free flame-retarding polyphenylene oxide composition with ultrahigh heat resistance | |
| CN103059407A (en) | Polypropylene composite material and preparation method thereof and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110427 Termination date: 20181127 |