CN101280098B - Halogen-free flame-proof strengthened polyethylene glycol terephthalate engineering plastics and preparation thereof - Google Patents
Halogen-free flame-proof strengthened polyethylene glycol terephthalate engineering plastics and preparation thereof Download PDFInfo
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- CN101280098B CN101280098B CN2008100377426A CN200810037742A CN101280098B CN 101280098 B CN101280098 B CN 101280098B CN 2008100377426 A CN2008100377426 A CN 2008100377426A CN 200810037742 A CN200810037742 A CN 200810037742A CN 101280098 B CN101280098 B CN 101280098B
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- halogen
- engineering plastics
- polyethylene terephthalate
- retardant
- flame
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- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 title 1
- 229920001223 polyethylene glycol Polymers 0.000 title 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 title 1
- 239000003063 flame retardant Substances 0.000 claims abstract description 48
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003365 glass fiber Substances 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000012745 toughening agent Substances 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 46
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 46
- -1 polyethylene terephthalate Polymers 0.000 claims description 29
- 230000002708 enhancing effect Effects 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- 238000005453 pelletization Methods 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 239000003094 microcapsule Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000454 talc Substances 0.000 claims description 8
- 229910052623 talc Inorganic materials 0.000 claims description 8
- 235000012222 talc Nutrition 0.000 claims description 8
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 4
- 241001112258 Moca Species 0.000 claims description 4
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 229910052901 montmorillonite Inorganic materials 0.000 abstract 1
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 25
- 238000001291 vacuum drying Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 150000001282 organosilanes Chemical class 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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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
- B29C48/395—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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- B29C2948/92704—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
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a halogen-free high-flame-retardant reinforced PET engineering plastic, which is composed of PET, composite flame retardant, toughener, nucleating agent, lubricant, composite antioxidant, toughening agent, compatibilizer and chain extender, wherein, the composite flame-retardant is the mixture of red phosphorus and modified nano-montmorillonite. The preparation method is that dried PET master batches and various promoters are fully mixed in a high-speed mixer and then added into a twin-screw extruder; at the time when the master batches are melted and extruded out of the extruder, glass fibers are added to a second feeding port of the twin-screws and then melted and extruded for granulation. The product of the invention has excellent flame retardant properties, low warpage, high modulus, high heat-resistant and impact-resistant performances and can be widely used in electronic, electrical, automotive and other fields.
Description
Technical field
The present invention relates to enhancing polyethylene terephthalate engineering plastics of a kind of halogen-free high flame-retardant performance and preparation method thereof, belong to the modified engineered plastic technical field.
Background technology
Polyethylene terephthalate (PET) is one of topmost kind in the thermoplastic polyester.Have advantages such as good mechanical performance, electrical insulation capability, chemical proofing, and a low price, therefore widespread usage in life not only also begins a large amount of uses in industry.Along with the fast development of China's engineering plastics, the PET plastics have become the fifth-largest engineering plastics after nylon, polycarbonate, polyoxymethylene, polyphenylene oxide, and its demand increases year by year in recent years.PET can be used for industries such as electric appliance and electronic, automobile, machinery, home appliances, electrical equipment as engineering plastics, and these industries have strict requirement to material combustion and safety performance, and the flame retardant properties that therefore improves PET is one of basic demand of PET engineering plastics application.Improving effective, the most economic means of PET flame retardant properties is to add fire retardant.The halogen-free flame retardants that is used for matrix material should possess following performance: the flame retarding efficiency height, and can give matrix material good flame retardancy; Has good intermiscibility, can be in the PET matrix uniform and stable dispersion; Decomposition temperature is higher; Nontoxic pollution-free; Good endurance etc.
In halogen-free flame retardants, red phosphorus is a kind of fire retardant preferably, has advantages such as addition is few, purposes is wide.But red phosphorus combustion inhibitor is darker reddish-brown or red-purple under normal conditions, and this has limited the scope of its use greatly.Development along with red phosphorus combustion inhibitor, the exploitation of whiteness microcapsule red phosphorus fire retardant, overcome the limits of color that red phosphorus combustion inhibitor is used in material, have, in use not general red, advantage such as addition few, flame retarding efficiency high, toxicity little good, be suitable for the production of begin-color flame-proof PET engineering plastics with resin compatible.The exploitation of nano inorganic powder receives much concern nanocomposite applications recently in flame-retarded technology, and polynite is as a class natural clay mineral of China high yield receiving publicity gradually.Its nano composite material is the most potential class nano composite material in current numerous inorganic nano particle modified matrix materials, has excellent flame-retardant, mechanical property, thermal characteristics and other physicalies.In view of the premium properties of red phosphorus and polynite, the present invention adopts whiteness microcapsule red phosphorus and modified Nano polynite to prepare the PET engineering plastics with high flame resistance as composite flame-retardant agent.
Summary of the invention
The object of the present invention is to provide a kind of enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance.
Another object of the present invention is to provide a kind of preparation method of enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance.
For achieving the above object, the present invention adopts following technical proposals:
A kind of enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance is characterized in that its composition counts by weight:
(1) polyethylene terephthalate is 50～80 parts
(2) compound flame retardant is 1～20 part
(3) toughener is 20～40 parts
(4) nucleator is 1～5 part
(5) lubricant is 0.1～0.5 part
(6) compound antioxidant is 0.1～0.5 part
(7) toughner is 1～5 part
(8) expanding material is 5～15 parts
(9) chainextender is 0.1～2 part
In the above-mentioned prescription, compound flame retardant is the mixture of red phosphorus and polynite, and red phosphorus is whiteness microcapsule red phosphorus, and polynite is the polynite of modified Nano level, and the weight ratio of red phosphorus and polynite is 1～4: 1.Toughener is a kind of in unmodified alkali-free long glass fibres, unmodified alkali-free short glass fiber, organically-modified long glass fibres and the organically-modified short glass fiber.Nucleator is one or more in talcum, mica, lime carbonate, the nano-sized magnesium hydroxide, and wherein lime carbonate, nano-sized magnesium hydroxide are through surface modification treatment.Lubricant is pentaerythritol stearate (PETS).
The enhancing polyethylene terephthalate engineering plastics of described halogen-free high flame-retardant performance, it is characterized in that described compound antioxidant be Irganox 245 and Irganox 1010 weight ratios be 1: 1 mixture; Described toughner is one or more among MBS, EVA, the ABS; Described expanding material is one or more among POE-g-MAH, PPO-g-MAH, the PP-g-MAH.Described chainextender is equal benzene dianhydride (PMDA), Pyrogentisinic Acid's dihydroxyl ether (HQEE), 1, and the 4-butyleneglycol (1,4-BD), 3,3 '-two chloro-4, one or more in 4 '-diamino-ditan (MOCA).
The preparation method who is used for the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance, its technological process is as follows: the polyethylene terephthalate master batch that drying is good, fire retardant, nucleator, lubricant, oxidation inhibitor, toughner and chainextender auxiliary agent are in high-speed mixer behind the thorough mixing, add in the twin screw extruder, when melt extruding, second charging opening adding glass at twin screw melt extrudes, the temperature of forcing machine is set at 240～275 ℃ of scopes, head temperature is 250～260 ℃, vacuum tightness is-0.08Pa extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Fire retardant mechanism relevant among the present invention is as follows:
1. red phosphorus: red phosphorus flame-retardant is effective, and usage quantity is less.When burning took place, frosting took fire, and red phosphorus generates phosphoric acid, condensed into solid phosphoric acid and the hydrogen of incendiary frosting and oxygen was removed and plastics are transformed into carbon-coating.
2. polynite: polynite not only can with the compound nano composite material of producing high physicals of polymer, and give product good flame performance.Its fire retardant mechanism is to have good promotion material and becomes carbon, and heat insulation fire insulation stops burning.It is a kind of fire-retardant collaborative auxiliary agent of very potential and superior performance.Almost can have good synergism, flame retardant properties is significantly improved with all organic and inorganic fire retardants.
These PET engineering plastics have excellent flame-retardant, low warpage, high-modulus, high heat-resisting and high impact property.And have low cigarette, nontoxic, flame propagation velocity is slow, flame retardant properties reaches characteristics such as UL 94 V-0 levels.In addition, this project plastics are owing to adopted whiteness microcapsule red phosphorus, and its color is more shallow, can add the desired toner of product arbitrarily in the middle of the process of using, thereby have wide development and application prospect.Can be used for fields such as electronics, electric, automobile.
Embodiment
In conjunction with following specific embodiment, the present invention is described in further detail.
Embodiment 1
PET master batch dry 10h in 100 ℃ of vacuum drying ovens with 2kg; Take by weighing the alkali-free short glass fiber of 600g with the modification of KH550 organo silane coupling agent; Take by weighing 100g whiteness microcapsule red phosphorus and the polynite of 60g nano modification; Take by weighing the 10g talcum; Take by weighing 6g PETS; Take by weighing 3g Irganox 245 and 3g Irganox1010; 60gABS; 200gPOE-g-MAH; The equal benzene dianhydride of 10g; With various auxiliary agents dry 3h in 60 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, be added in first charging opening adding that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 240; Two districts 245; Three districts 250; Four districts 255; Five districts 260; Six districts 260; Seven districts 260; Eight districts 260; Nine districts 260; The head Heating temperature (℃): 250, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Embodiment 2
PET master batch dry 4h in 120 ℃ of vacuum drying ovens with 3kg; Take by weighing the alkali-free roving glass fiber of 880gKH570 organo silane coupling agent modification; Take by weighing 120g whiteness microcapsule red phosphorus and the polynite of 40g nano modification; Take by weighing the 12g talcum; Take by weighing 9gPETS; Take by weighing 4.5g Irganox 245 and 4.5g Irganox1010; 150gABS; 220gPOE-g-MAH; 20g 3,3 '-two chloro-4,4 '-diamino-ditan (MOCA); With various auxiliary agents dry 12h in 60 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, be added in first charging opening adding that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 245; Two districts 250; Three districts 255; Four districts 260; Five districts 265; Six districts 270; Seven districts 265; Eight districts 260; Nine districts 255; The head Heating temperature (℃): 255, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Embodiment 3
PET master batch dry 5h in 100 ℃ of vacuum drying ovens with 2Kg; Take by weighing the roving glass fiber of 700g with the modification of KH550 organo silane coupling agent; Take by weighing 150g whiteness microcapsule red phosphorus and the polynite of 40g nano modification; Take by weighing the 10g talcum; Take by weighing 6gPETS; Take by weighing 3g Irganox 245 and 3g Irganox1010; 100gEVA; 200gPPO-g-MAH; 6g Pyrogentisinic Acid dihydroxyl ether (HQEE); With whiteness microcapsule red phosphorus, nano modification polynite, talcum dry 3h in 80 ℃ vacuum drying oven, all the other auxiliary agents are dry 2h in 60 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, and feed intake at first charging opening that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 240; Two districts 245; Three districts 250; Four districts 255; Five districts 260; Six districts 260; Seven districts 260; Eight districts 260; Nine districts 260; The head Heating temperature (℃): 250, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Embodiment 4
PET master batch dry 10h in 120 ℃ of vacuum drying ovens with 3kg; Take by weighing the alkali-free short glass fiber of 880gKH570 organo silane coupling agent modification; Take by weighing 180g whiteness microcapsule red phosphorus and the polynite of 60g nano modification; Take by weighing the 12g talcum; Take by weighing 9gPETS; Take by weighing 4.5g Irganox 245 and 4.5g Irganox1010; 90gABS; 20geEVA; 300gPP-g-MAH; 30g1, and the 4-butyleneglycol (1,4-BD); Alkali-free short glass fiber, whiteness microcapsule red phosphorus, nano modification polynite dry 5h in 80 ℃ vacuum drying oven with the organo silane coupling agent modification; All the other auxiliary agents are dry 2h in 50 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, be added in first charging opening adding that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 245; Two districts 250; Three districts 255; Four districts 260; Five districts 265; Six districts 270; Seven districts 265; Eight districts 260; Nine districts 255; The head Heating temperature (℃): 255, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
Embodiment 5
PET master batch dry 6h in 120 ℃ of vacuum drying ovens with 2Kg; Take by weighing the short fiber of 400g with the modification of KH550 organo silane coupling agent; Take by weighing 80g whiteness microcapsule red phosphorus and the polynite of 60g nano modification; Take by weighing the 10g talcum; Take by weighing 6gPETS; Take by weighing 3g Irganox 245 and 3g Irganox1010; 100gABS; 100gPOE-g-MAH; 100gPP-g-MAH; The equal benzene dianhydride of 10g; 10g 3,3 '-two chloro-4,4 '-diamino-ditan (MOCA).Alkali-free short glass fiber, whiteness microcapsule red phosphorus, nano modification polynite dry 4h in 80 ℃ vacuum drying oven with the organo silane coupling agent modification; All the other auxiliary agents are dry 2h in 50 ℃ vacuum drying oven.Various auxiliary agents and PET master batch except glass are mixed in high-speed mixer, be added in first charging opening adding that twin screw is extruded, glass adds at second charging opening of twin screw extruder, melt extrudes.The temperature of twin screw extruder heating zone (℃) be set at: a district 240; Two districts 245; Three districts 250; Four districts 255; Five districts 260; Six districts 260; Seven districts 260; Eight districts 260; Nine districts 260; The head Heating temperature (℃): 250, vacuum tightness-0.08Pa.Extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
The product of preparing according to the method described above, through carrying out performance test after the injection moulding:
| Test event | Testing method | Unit | Embodiment 1 | Embodiment 2 |
| Tensile strength | ASTM?D?638 | MPa | 115 | 135 |
| Modulus in flexure | ASTM?D?790 | MPa | 9800 | 10300 |
| Flexural strength | ASTM?D?790 | MPa | 180 | 190 |
| The cantilever notched Izod impact strength | ASTM?D?256 | J/m | 80 | 90 |
| Flame retardant rating | UL-94 | - | V-0 | V-0 |
| Oxygen index | ASTM?D?2863 | ％ | 29 | 31 |
The foregoing description for explanation technical conceive of the present invention and characteristics, is not in order to limit claim of the present invention only.All equivalences that spirit is done according to the present invention change or improve, and all should be included within protection scope of the present invention.
Claims (7)
1. the enhancing polyethylene terephthalate engineering plastics of a halogen-free high flame-retardant performance is characterized in that its composition counts by weight:
(1) polyethylene terephthalate is 50～80 parts
(2) compound flame retardant is 1～20 part
(3) toughener is 20～40 parts
(4) nucleator is 1～5 part
(5) lubricant is 0.1～0.5 part
(6) compound antioxidant is 0.1～0.5 part
(7) toughner is 1～5 part
(8) expanding material is 5～15 parts
(9) chainextender is 0.1～2 part
Described compound flame retardant is the mixture of red phosphorus and polynite, and red phosphorus is whiteness microcapsule red phosphorus, and polynite is the polynite of modified Nano level, and the weight ratio of red phosphorus and polynite is 1～4: 1.
2. the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance according to claim 1 is characterized in that described toughener is a kind of in unmodified alkali-free long glass fibres, unmodified alkali-free short glass fiber, organically-modified long glass fibres and the organically-modified short glass fiber.
3. the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance according to claim 1, it is characterized in that described nucleator is one or more in talcum, mica, lime carbonate, the nano-sized magnesium hydroxide, wherein lime carbonate, nano-sized magnesium hydroxide are through surface modification treatment.
4. the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance according to claim 1 is characterized in that described lubricant is a pentaerythritol stearate.
5. the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance according to claim 1, it is characterized in that described compound antioxidant be Irganox 245 and Irganox 1010 weight ratios be 1: 1 mixture; Described toughner is one or more among MBS, EVA, the ABS; Described expanding material is one or more among POE-g-MAH, PPO-g-MAH, the PP-g-MAH.
6. the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance according to claim 1, it is characterized in that described chainextender is equal benzene dianhydride (PMDA), Pyrogentisinic Acid's dihydroxyl ether (HQEE), 1,4-butyleneglycol (1,4-BD), 3,3 '-two chloro-4, one or more in 4 '-diamino-ditan (MOCA).
7. preparation method who is used for the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance according to claim 1, it is characterized in that this method has following technological process: the polyethylene terephthalate master batch that drying is good, fire retardant, nucleator, lubricant, oxidation inhibitor, toughner and chainextender auxiliary agent are in high-speed mixer behind the thorough mixing, add in the twin screw extruder, when melt extruding, second charging opening adding glass at twin screw melt extrudes, the temperature of forcing machine is set at 240～275 ℃ of scopes, head temperature is 250～260 ℃, vacuum tightness is-0.08Pa extruding pelletization; Extruded material after the drying, promptly gets the enhancing polyethylene terephthalate engineering plastics of halogen-free high flame-retardant performance through cooling, air-dry, pelletizing.
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| CN102234414A (en) * | 2010-05-07 | 2011-11-09 | 财团法人塑胶工业技术发展中心 | Toughened poly(ethylene terephthalate)/polycarbonate composition |
| CN103146154B (en) * | 2011-12-07 | 2016-12-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of PET composite material, preparation method and applications |
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