CN101817972A - Flame-retardant enhanced PBT material and preparation method thereof - Google Patents
Flame-retardant enhanced PBT material and preparation method thereof Download PDFInfo
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- CN101817972A CN101817972A CN201010163834A CN201010163834A CN101817972A CN 101817972 A CN101817972 A CN 101817972A CN 201010163834 A CN201010163834 A CN 201010163834A CN 201010163834 A CN201010163834 A CN 201010163834A CN 101817972 A CN101817972 A CN 101817972A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
Abstract
The invention discloses a flame-retardant enhanced PBT material and a preparation method thereof. The flame-retardant enhanced PBT material comprises the following components in percentage by weight: 45 to 60 percent of PBT resin, 3 to 10 percent of brominated flame retardant, 1 to 10 percent of phosphorus-nitrogen flame retardant, 1 to 5 percent of inorganic flame retardant, 2 to 5 percent of toughening agent, 20 to 35 percent of glass fiber, 0.3 to 1 percent of lubricating agent, and 0.1 to 0.6 percent of antioxidant. The flame-retardant enhanced PBT material has high ignition temperature of glowing filament, high comparative tracking index, and better mechanical property, and can be widely applied to the field of unattended electronic and electric products.
Description
[technical field]
The present invention relates to technical field of polymer materials, relate in particular to a kind of flame-retardant enhanced PBT material and preparation method thereof.
[background technology]
Polybutylene terephthalate (PBT) is by a class newer thermoplast engineering plastics of U.S. Celanese company in the seventies in 20th century exploitation and suitability for industrialized production, be one of five big general engineering plastic, it is heat-resisting, weather-proof good, and dimensional stability is good, and electrical property is good, arc resistance is good, chemical proof is extremely excellent, still keeps various rerum naturas (for electrical property) in wet environment, and crystallization velocity is fast, good forming ability is widely used in fields such as automobile, electronic apparatus, industrial machinery.
Element in the electronic apparatus can cause local superheating and may cause burning under situations such as overload, short circuit, therefore, the ignition hazard of the parts in the electric equipment products must be reduced to a certain degree.(Glow～wireIgnitability Test GWIT) must reach more than 750 ℃ IEC 60335～1 standard-required non-metallic material glowing filament ignition temperatures.And unattended electronic apparatus also has quite high requirement to phase ratio creepage tracking index (CTI) simultaneously, and looking household electricity voltage is that 220V, commercial power voltage are 380V, and the CTI value of material is high more good more in a word.At present, still with being most widely used of brominated flame retardant, the fire retardant PBT with no halogen material is subjected to the restriction of technology and cost big to the flame-retardant PBT material.It is very difficult will reaching 750 ℃ of GWIT nonflammable with brominated flame retardant, and addition is also bigger usually, and because the existence of free bromine has a strong impact on CTI value, more than difficulty arrival 250V; Be easy to satisfy simultaneously the requirement of GWIT and CTI with halogen-free flame retardants, but more a lot of in mechanical properties than bromine class flame-retardant PBT material difference, and cost is higher.These effects limit the application of PBT engineering plastics in unattended field of electronics.。
[summary of the invention]
The technical problem to be solved in the present invention provides a kind of a kind of flame-retardant enhanced PBT material that has high GWIT, high CTI and better mechanical property simultaneously and preparation method thereof.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is, a kind of flame-retardant enhanced PBT material is made up of following component by weight percentage:
PBT resin 45～60%;
Bromide fire retardant 3～10%;
Phosphor nitrogen combustion inhibitor 1～10%;
Inorganic combustion inhibitor 1～5%.
Toughner 2～5%;
Glass fibre 20～35%;
Lubricant 0.3～1%;
Oxidation inhibitor 0.1～0.6%.
Described PBT resin is a polybutylene terephthalate, and its relative density is 1.35～1.38, and fusing point is 220～230 ℃, and viscosity is 0.6～1.1PS.
Described bromide fire retardant is two (hydroxy ethoxy) ethers of brominated Polystyrene, TDE, 1,2～two (tetrabromo phthalimide) ethane, tetrabromo-bisphenol, a kind of in the brominated triazine.
Described phosphor nitrogen combustion inhibitor is phosphotriester class, phosphinates (ester), and a kind of or combination in the derivative of trimeric cyanamide and trimeric cyanamide is as the criterion to have phosphoric and nitrogen element in the flame-retardant system simultaneously.
Described inorganic combustion inhibitor is that in aluminium hydroxide, magnesium hydroxide, antimonous oxide and the antimony peroxide one or both are composite.
Described bromide fire retardant, phosphor nitrogen combustion inhibitor and inorganic combustion inhibitor composite so that the fire retardant mechanism of fire retardant systems have heat-absorbing action, covering effect, suppress in chain reaction and four kinds of fire retardant mechanisms of non-flammable gas smothering action at least two kinds and concur and be as the criterion.
Described glass fibre is an alkali-free reinforcing glass fiber; Described toughner is a kind of in ethene～butyl methacrylate～glycidyl acrylate multipolymer, ethene～methyl acrylate copolymer and the polyethylene octene～glycidyl acrylate multipolymer; Described lubricant is the one or more combination thing in OP wax, ethylene bis stearamide and modifier thereof, polysiloxane, the Zinc Stearate; Described antioxidant is four [3～(3,5～di-t-butyl～4～hydroxy phenyl) propionic acid] pentaerythritol ester and tricresyl phosphite (2,4～di-t-butyl phenyl ester) composite mixture or triglycol be two～a kind of in 3～(3～tertiary butyl～4～hydroxyl～5～aminomethyl phenyl) vinyl cyanide, three (2, the 4～di-tert-butylphenol) phosphorous acid ester.
A kind of above-mentioned flame-retardant enhanced PBT material preparation method's technical scheme is, take by weighing raw material by above-mentioned proportioning, other raw materials except that glass fibre stirred in agitation vat 4 to 8 minutes, melt extruded granulation through twin screw extruder again, added glass fibre simultaneously from the forcing machine stage casing; Its complete processing is as follows: 180～220 ℃ in twin screw extruder one district, 200～240 ℃ in two districts, 200～240 ℃ in three districts, 200～240 ℃ in four districts, 180～210 ℃ in five districts, 180～210 ℃ in six districts, 190～220 ℃ in seven districts, 220～240 ℃ in eight districts; 350～500 rev/mins of screw speeds.
Flame-retardant enhanced PBT material of the present invention is the glowing filament ignition temperature height not only, and the phase ratio creepage tracking index height has better mechanical property simultaneously, can be widely used in unattended field of electronics.
[embodiment]
Flame-retardant enhanced PBT material of the present invention is made by weight ratio by following material:
PBT resin 45～60%;
Bromide fire retardant 3～10%;
Phosphor nitrogen combustion inhibitor 1～10%;
Inorganic combustion inhibitor 1～5%.
Toughner 2～5%;
Glass fibre 20～35%;
Lubricant 0.3～1%;
Oxidation inhibitor 0.1～0.6%.
Wherein, the PBT resin is a polybutylene terephthalate, and its relative density is 1.35～1.38, and fusing point is 220～230 ℃, and viscosity is 0.6～1.1PS, and the manufacturer is Changchun, Taiwan (1100-211M); Bromide fire retardant is a kind of in brominated Polystyrene (refined precious 7010), TDE (refined precious 8010), 1,2～two (tetrabromo phthalimide) ethane (refined precious BT-93W), phenoxy group tetrabromobisphenol a polycarbonate oligopolymer (big lake BC58), the brominated triazine (Dead Sea bromine FR 245); Phosphor nitrogen combustion inhibitor is phosphotriester class, phospho acid salt, a kind of or combination in the derivative of trimeric cyanamide and trimeric cyanamide (commercially available MCA, TPP, MPP, OP1240 etc.); Inorganic combustion inhibitor is aluminium hydroxide (refined precious OL-104/LE), magnesium hydroxide (refined precious H-5IV), antimonous oxide (Hunan Chen Zhou), one or both in the antimony peroxide (east, Hunan); Glass fibre is alkali-free reinforcing glass fiber (long fine 988A of megalith or short fiber 534D); Toughner is a kind of (commercially available PTW, AX～8900, the E516 etc.) in ethene～butyl methacrylate～glycidyl acrylate multipolymer, ethene～methyl acrylate copolymer and the polyethylene octene～glycidyl acrylate multipolymer; Lubricant is the one or more combination thing (commercially available OP wax, EBS, TAF, P728 etc.) in OP wax, ethylene bis stearamide and modifier thereof, polysiloxane, the Zinc Stearate; Antioxidant is four [3～(3,5～di-t-butyl～4～hydroxy phenyl) propionic acid] pentaerythritol ester and tricresyl phosphite (2,4～di-t-butyl phenyl ester) composite mixture or triglycol be two～3～(3～tertiary butyl～4～hydroxyl～5～aminomethyl phenyl) vinyl cyanide, three (2,4～di-tert-butylphenol) a kind of (the commercially available model 1010 in the phosphorous acid ester, 168, PW～225 etc.).
Embodiment 1
Weight percent PBT 59.0%, PBT 60%, bromide fire retardant 10%, phosphor nitrogen combustion inhibitor 5%, inorganic combustion inhibitor 3%, toughner 5%, lubricant 0.3%, oxidation inhibitor 0.3% were stirred 5 minutes in agitation vat, melt extrude granulation through twin screw extruder again, add long by fine 20% simultaneously from the forcing machine stage casing.Its complete processing is as follows: 200 ℃ in twin screw extruder one district, 220 ℃ in two districts, 220 ℃ in three districts, 220 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts, 210 ℃ in seven districts, 230 ℃ in eight districts; The screw rod revolution is controlled at 420～480 rev/mins.
Embodiment 2
Weight percent PBT 50%, bromide fire retardant 7%, phosphor nitrogen combustion inhibitor 4%, inorganic combustion inhibitor 3%, toughner 4%, lubricant 0.5%, oxidation inhibitor 0.3% were stirred 5 minutes in agitation vat, melt extrude granulation through twin screw extruder again, add long by fine 30.0% simultaneously from the forcing machine stage casing.Its complete processing is as follows: 200 ℃ in twin screw extruder one district, 230 ℃ in two districts, 230 ℃ in three districts, 230 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts, 210 ℃ in seven districts, 230 ℃ in eight districts; The screw rod revolution is controlled at 420～480 rev/mins.
Embodiment 3
Weight percent PBT 50%, bromide fire retardant 3%, phosphor nitrogen combustion inhibitor 10%, inorganic combustion inhibitor 1%, toughner 4%, lubricant 0.5%, oxidation inhibitor 0.3% were stirred 5 minutes in agitation vat, melt extrude granulation through twin screw extruder again, add long by fine 30.0% simultaneously from the forcing machine stage casing.Its complete processing is as follows: 190 ℃ in twin screw extruder one district, 210 ℃ in two districts, 210 ℃ in three districts, 210 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts, 210 ℃ in seven districts, 230 ℃ in eight districts; The screw rod revolution is controlled at 420～480 rev/mins.
Embodiment 4
Weight percent PBT 45%, bromide fire retardant 8%, phosphor nitrogen combustion inhibitor 2%, inorganic combustion inhibitor 5%, toughner 2%, lubricant 0.6%, oxidation inhibitor 0.3% were stirred 5 minutes in agitation vat, melt extrude granulation through twin screw extruder again, add long by fine 35.0% simultaneously from the forcing machine stage casing.Its complete processing is as follows: 200 ℃ in twin screw extruder one district, 230 ℃ in two districts, 230 ℃ in three districts, 230 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts, 210 ℃ in seven districts, 230 ℃ in eight districts; The screw rod revolution is controlled at 420～480 rev/mins.
Comparative Examples 1
Weight percent PBT 60%, brominated Polystyrene 12%, antimonous oxide 4%, toughner 5%, lubricant 0.3%, oxidation inhibitor 0.3% were stirred 5 minutes in agitation vat, melt extrude granulation through twin screw extruder again, add long by fine 20% simultaneously from the forcing machine stage casing.Its complete processing is as follows: 200 ℃ in twin screw extruder one district, 220 ℃ in two districts, 220 ℃ in three districts, 220 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts, 210 ℃ in seven districts, 230 ℃ in eight districts; The screw rod revolution is controlled at 420～480 rev/mins.
Comparative Examples 2
Weight percent PBT 50%, brominated Polystyrene 9%, antimonous oxide 3%, toughner 4%, lubricant 0.5%, oxidation inhibitor 0.3% were stirred 5 minutes in agitation vat, melt extrude granulation through twin screw extruder again, add long by fine 30.0% simultaneously from the forcing machine stage casing.Its complete processing is as follows: 200 ℃ in twin screw extruder one district, 230 ℃ in two districts, 230 ℃ in three districts, 230 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts, 210 ℃ in seven districts, 230 ℃ in eight districts; The screw rod revolution is controlled at 420～480 rev/mins.
Comparative Examples 3
Weight percent PBT 50%, brominated Polystyrene 12%, antimonous oxide 4%, toughner 4%, lubricant 0.6%, oxidation inhibitor 0.3% were stirred 5 minutes in agitation vat, melt extrude granulation through twin screw extruder again, add long by fine 30.0% simultaneously from the forcing machine stage casing.Its complete processing is as follows: 200 ℃ in twin screw extruder one district, 230 ℃ in two districts, 230 ℃ in three districts, 230 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts, 210 ℃ in seven districts, 230 ℃ in eight districts; The screw rod revolution is controlled at 420～480 rev/mins.
Comparative Examples 4
Weight percent PBT 45%, brominated Polystyrene 9%, antimonous oxide 3%, toughner 2%, lubricant 0.6%, oxidation inhibitor 0.3% were stirred 5 minutes in agitation vat, melt extrude granulation through twin screw extruder again, add long by fine 35.0% simultaneously from the forcing machine stage casing.Its complete processing is as follows: 200 ℃ in twin screw extruder one district, 230 ℃ in two districts, 230 ℃ in three districts, 230 ℃ in four districts, 190 ℃ in five districts, 190 ℃ in six districts, 210 ℃ in seven districts, 230 ℃ in eight districts; The screw rod revolution is controlled at 420～480 rev/mins.
Performance evaluation criterion and performance index
The particle material that aforesaid method is finished granulation in convection oven under 120～130 ℃ the condition dry 4～6 hours earlier uses the particle material that drying is good to make the batten test with injection moulding machine then.
The performance of embodiment and Comparative Examples is respectively as table 1 and table 2:
Table 1
Table 2
As can be seen from Table 1, suitably wherein composite by the fire retardant that will have different fire retardant mechanisms, 7010 play cover and suppress the chain reaction effect, OP 1240 plays covering and cooling effect, MgOH play heat-absorbing action, can obtain the flame-retardant enhanced PBT material of high GWIT, wherein content of glass fiber reaches 30.0% material, the CTI value is all greater than 380V (380V is the commercial power voltage rating), and three thickness (0.75mm of material, 1.5mm, 3.0mm) can both reach 750 ℃ nonflammable, 1.5mm and 3.0mm thickness reach as high as 825 ℃ nonflammable.
Can find out in conjunction with example 2 and example 3, suitably reduce the consumption of bromide fire retardant, improve the consumption of phosphor nitrogen combustion inhibitor or inorganic combustion inhibitor, can make the flame-retardant enhanced PBT material that has higher GWIT and CTI value simultaneously, but physical and mechanical properties can descend to some extent.
Can find out that in conjunction with example 2, Comparative Examples 2 and Comparative Examples 3 Flame Retardancy of example 2 can be 1/16V2, but it is nonflammable to reach 750 ℃ of glowing filaments; Though and the fire-retardant 1/32V0 that reaches of the material of Comparative Examples 3 can't be nonflammable by 750 ℃ of glowing filaments.This illustrates the high glow-wire ignition temperature of the easier realization material of additive effect of multiple effect fire retardant mechanism.
From contrast table 1 and table 2 as can be seen, fire retardant compounded combination of the present invention can not reduce the physical and mechanical properties of material substantially, even indivedual fire retardant compounded combination can further improve the intensity of material.
Claims (8)
1. a flame-retardant enhanced PBT material is characterized in that, is made up of following component by weight percentage:
PBT resin 45～60%;
Bromide fire retardant 3～10%;
Phosphor nitrogen combustion inhibitor 1～10%;
Inorganic combustion inhibitor 1～5%;
Toughner 2～5%;
Glass fibre 20～35%;
Lubricant 0.3～1%;
Oxidation inhibitor 0.1～0.6%.
2. flame-retardant enhanced PBT material according to claim 1 is characterized in that, described PBT resin is a polybutylene terephthalate, and its relative density is 1.35～1.38, and fusing point is 220～230 ℃, and viscosity is 0.6～1.1PS.
3. flame-retardant enhanced PBT material according to claim 1, it is characterized in that, described bromide fire retardant is two (hydroxy ethoxy) ethers of brominated Polystyrene, TDE, 1,2～two (tetrabromo phthalimide) ethane, tetrabromo-bisphenol, a kind of in the brominated triazine.
4. flame-retardant enhanced PBT material according to claim 1, it is characterized in that, described phosphor nitrogen combustion inhibitor is phosphotriester class, phosphinates (ester), and a kind of or combination in the derivative of trimeric cyanamide and trimeric cyanamide is as the criterion to have phosphoric and nitrogen element in the flame-retardant system simultaneously.
5. flame-retardant enhanced PBT material according to claim 1 is characterized in that, described inorganic combustion inhibitor is that in aluminium hydroxide, magnesium hydroxide, antimonous oxide and the antimony peroxide one or both are composite.
6. flame-retardant enhanced PBT material according to claim 1, it is characterized in that, described bromide fire retardant, phosphor nitrogen combustion inhibitor and inorganic combustion inhibitor composite so that the fire retardant mechanism of fire retardant systems have heat-absorbing action, covering effect, suppress in chain reaction and four kinds of fire retardant mechanisms of non-flammable gas smothering action at least two kinds and concur and be as the criterion.
7. flame-retardant enhanced PBT material according to claim 1 is characterized in that, described glass fibre is an alkali-free reinforcing glass fiber; Described toughner is a kind of in ethene～butyl methacrylate～glycidyl acrylate multipolymer, ethene～methyl acrylate copolymer and the polyethylene octene～glycidyl acrylate multipolymer; Described lubricant is the one or more combination thing in OP wax, ethylene bis stearamide and modifier thereof, polysiloxane, the Zinc Stearate; Described antioxidant is four [3～(3,5～di-t-butyl～4～hydroxy phenyl) propionic acid] pentaerythritol ester and tricresyl phosphite (2,4～di-t-butyl phenyl ester) composite mixture or triglycol be two～a kind of in 3～(3～tertiary butyl～4～hydroxyl～5～aminomethyl phenyl) vinyl cyanide, three (2, the 4～di-tert-butylphenol) phosphorous acid ester.
8. the preparation method of the described flame-retardant enhanced PBT material of claim 1, it is characterized in that, take by weighing raw material by the described proportioning of claim 1, other raw materials except that glass fibre stirred in agitation vat 4 to 8 minutes, melt extrude granulation through twin screw extruder again, add glass fibre simultaneously from the forcing machine stage casing; Its complete processing is as follows: 180～220 ℃ in twin screw extruder one district, 200～240 ℃ in two districts, 200～240 ℃ in three districts, 200～240 ℃ in four districts, 180～210 ℃ in five districts, 180～210 ℃ in six districts, 190～220 ℃ in seven districts, 220～240 ℃ in eight districts; 350～500 rev/mins of screw speeds.
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| CN102040810A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Polybutylece terephthalate (PBT) engineering plastics as well as preparation method and application thereof |
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| CN103992624A (en) * | 2014-05-28 | 2014-08-20 | 南通星辰合成材料有限公司 | High-glowing filament initiation temperature halogen-free flame-retardant reinforced PBT (Polybutylene Terephthalate) composition and preparation method thereof |
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| CN104845299A (en) * | 2015-05-27 | 2015-08-19 | 佛山市顺德区美的洗涤电器制造有限公司 | Glass fiber reinforced flame-retardant PBT material for washing pump and washing pump |
| CN105385118A (en) * | 2015-11-18 | 2016-03-09 | 南通开普乐工程塑料有限公司 | High-CTI-value flame-retardant and reinforced PBT (polybutylene terephthalate) composite material |
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