CN110499007A - A kind of halogen-free antiflaming polyester composite material and preparation method of high-temp resisting high-humidity resisting - Google Patents
A kind of halogen-free antiflaming polyester composite material and preparation method of high-temp resisting high-humidity resisting Download PDFInfo
- Publication number
- CN110499007A CN110499007A CN201910877738.9A CN201910877738A CN110499007A CN 110499007 A CN110499007 A CN 110499007A CN 201910877738 A CN201910877738 A CN 201910877738A CN 110499007 A CN110499007 A CN 110499007A
- Authority
- CN
- China
- Prior art keywords
- halogen
- polyester composite
- composite material
- resisting
- parts
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to charging pile polyester material technical fields, more particularly to a kind of halogen-free antiflaming polyester composite material and preparation method of high-temp resisting high-humidity resisting, the halogen-free antiflaming polyester composite material includes the raw material of following parts by weight: 40-60 parts of polyester resin, 2-6 parts of compatilizer, 0.1-0.2 parts of antioxidant, 0.5-1.0 parts of hydrolysis agent, 10-20 parts of phosphinate flame retardant, 0.5-1.0 parts of fire retarding synergist, 0.5-1.5 parts of ester exchange inhibitor, 0.5-1 parts of chain extender, 10-30 parts and other auxiliary agent 0.5-1.0 parts of glass fibre, the polyester composite is in 1000 hours under the conditions of double 85, with high CTI characteristic, material mechanical performance is relatively stable, flame retardant property remains unchanged, the surface of polyester composite is without precipitate.
Description
Technical field
The present invention relates to charging pile polyester material technical fields, and in particular to a kind of halogen-free flameproof of high-temp resisting high-humidity resisting is poly-
Ester composite material and preparation method.
Background technique
Relative discharge tracking index (Comparative Tracking Index, abbreviation CTI) is insulating materials surface energy
Withstand maximum voltage value of the 50 drop electrolyte (0.1wt% aqueous ammonium chloride solution) without forming tracking, unit V.
That is, CTI is ambroin in energization, 50 drop conducting liquids are added dropwise without generating carbonixed matirials in surface
Maximum voltage value.In general, the CTI value of ambroin is higher, then its resistance to leakage property is better.
As the increasingly raising and the continuous pursuit to convenient traffic, auto industry of people's living standard are rapidly sent out
Exhibition；Future is the inexorable trend of automobile industry development using electric car as the energy-saving and environment-friendly automobile of new generation of representative.Charging pile is made
For the indispensable energy recharge device of electric car, higher requirement is proposed to charging pile cable, such as in 85% humidity, 85
More demanding CTI value (600V or more) under the conditions of DEG C temperature, higher force stability and compared with high fire-retardance stability, and it is existing poly-
Ester composite material is difficult to reach the requirement.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of high-temp resisting high-humidity resistings
Halogen-free antiflaming polyester composite material, which has high CTI characteristic in 1000 hours under the conditions of double 85,
Material mechanical performance is relatively stable, and flame retardant property remains unchanged, the surface of polyester composite without precipitate, particularly suitable as
Charging pile materials'use.
Another object of the present invention is to provide a kind of preparation sides of the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting
Method, the preparation method is easy to operate, easy to control, and high production efficiency, production cost is low, can be used for being mass produced.
The purpose of the invention is achieved by the following technical solution: a kind of halogen-free antiflaming polyester composite wood of high-temp resisting high-humidity resisting
Material, the raw material including following parts by weight:
Phase is added in the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting of the invention, the material based on polyester resin
Hold agent, antioxidant, hydrolysis agent, phosphinate flame retardant, fire retarding synergist, ester exchange inhibitor, chain extender, glass fibre and
Other auxiliary agents are composite modified to material of main part progress, improve relative discharge tracking index, the anti-flammability, power of the polyester composite
Performance and stability are learned, its heat-resisting quantity is improved and Nai Gao is moist；The polyester composite meets 1000 under the conditions of double 85
There is high CTI characteristic, material mechanical performance is relatively stable, and flame retardant property remains unchanged, the surface of polyester composite in hour
Without precipitate.Wherein, compatilizer is added and chain extender acts synergistically, improves the compatibility of material, increases melt strength, promote material
The mechanical property of material, promotes the processing stability and mechanical property of feed back, while also can be further improved polymer resistant to hydrolysis
Stability；Phosphinate flame retardant, fire retarding synergist and glass fibre, which are distributed in polyester resin, to act synergistically, and prevents polyester
Resin forms the probability in carbon channel, to improve the CTI value of polyester composite；Hydrolysis agent and antioxidant are in polyester resin
Hydrolysis, anti-aging effect under the conditions of middle performance high temperature and humidity, polyester composite is avoided to hydrolyze under hot and humid environment,
Aging and reduce mechanical stability and fire-retardant stability.If the dosage of phosphinate flame retardant is greater than 20 parts by weight, in polyester
Compatibility poor in composite material makes phosphinate flame retardant assemble and lead to polyester composite under the condition of high temperature and high humidity
Surface be more likely formed carbon channel cause CTI value reduction；If the dosage of phosphinate flame retardant is less than 10 parts by weight, in high temperature height
The flame retardant effect of polyester composite is deteriorated under the conditions of wet, is unfavorable for preventing carbon channel from being formed and leading to the reduction of CTI value.Further
, other auxiliary agents include toner.
Preferably, the polyester resin is polybutylene terephthalate (PBT), polyethylene terephthalate and poly- pair
At least two combinations in phthalic acid -1,4 cyclohexane dimethanol ester；The inherent viscosity of the polyester resin is 0.7-
1.2dL/g。
By adopting the above technical scheme, polyester resin selects polybutylene terephthalate (PBT), polyethylene terephthalate
At least two combinations in ester and poly terephthalic acid -1,4-CHDM ester are blended, and interaction compensates for single group
Divide the defect in performance, improves the impact strength, tensile strength and bending strength of polyester composite；In addition, above-mentioned polyester
Resin is higher compared to the dimensional stability of nylon, less hygroscopic.The inherent viscosity of the polyester resin is controlled in 0.7-
1.2dL/g, the i.e. inherent viscosity of polybutylene terephthalate (PBT) are 0.7-1.2dL/g, polyethylene terephthalate
Inherent viscosity is 0.7-1.2dL/g, and the inherent viscosity of poly terephthalic acid 1,4-CHDM ester is 0.7-1.2dL/g,
The processing fluidity and toughness that composite material can be improved, are more advantageous to processing, avoid in damp and hot lower use since hydrolysis causes
The molecular weight of polyester resin reduces and mechanical property is caused to reduce.It is furthermore preferred that the polyester resin is poly terephthalic acid fourth
Diol ester and polyethylene terephthalate are mixed with weight ratio 1-3:1.
Preferably, the compatilizer is glycidyl methacrylate graft polyolefin elastomer, methacrylic acid contracting
Water glyceride grafted propylene nitrile-butadiene-styrene terpolymer, methyl methacrylate-methyl propenoic acid glycidyl
Copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, the ethylene-methyl acrylate-metering system of ester
At least one of acid glycidyl ester copolymer and Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer；Institute
Stating chain extender is the acrylic-styrene copolymer containing epoxy group.
By adopting the above technical scheme, the compatilizer is not only only capable of improving compatibility, while also taking into account hydrolysis function, phase
The epoxy group held in agent can react with hydroxyl and carboxyl, can effectively limit the number of active carboxyl end group in polyester resin
Amount, play the role of sealing end, it is furthermore preferred that the compatilizer be glycidyl methacrylate graft polyolefin elastomer and
Styrene-acrylonitrile-glycidyl methacrylate copolymer is mixed by weight 3:1-2, the phase of the compatilizer
To molecular weight 5 × 104-1×105, because having lower molecular weight to make it have excellent processing flowability, and because having
Epoxy group makes it have excellent compatibility.The weight average molecular weight of polyester composite can be improved in the chain extender, increases molten
Body intensity and viscosity promote the mechanical property of material, promote the processing stability and mechanical property of feed back, improve solid-phase tack producing effect
Rate improves the stability of polymer resistant to hydrolysis, improves the compatibility between two kinds of different polyester resin.Further, described to contain
The acrylic-styrene copolymer of epoxy group be acrylicstyrene-glycidyl methacrylate copolymer and/or
Methacrylic acid-styrene-t glycidyl ester copolymer.The compatilizer and chain extender act synergistically, with control
The molecular weight of polyester resin processed increases to OK range, to improve its rheological performance, avoids the molecular weight mistake of polyester resin
Cause melt viscosity excessive greatly and influences processing.
Preferably, the antioxidant is that Hinered phenols primary antioxidant and thioether class auxiliary antioxidant are mixed by weight 1:2-5
It closes.
By adopting the above technical scheme, Hinered phenols primary antioxidant and thioether class auxiliary antioxidant synergistic effect, it is multiple in polyester
In condensation material ageing process, peroxylradicals are captured effectively to terminate oxidation process, thus reach antioxidant effect,
Antioxidant effect under high temperature is good, and is not easy to be hydrolyzed under high humidity state；Compared with amine type antioxidant, antioxidant of the invention exists
It is not easy to be precipitated under the conditions of high temperature and humidity, to keep lasting antiageing effect；With Hinered phenols primary antioxidant and phosphorous acid
The collaboration of esters auxiliary antioxidant is compared, and Hinered phenols primary antioxidant of the invention and thioether class auxiliary antioxidant are by weight 1:2-
5 mixing, although the antioxidant effect cooperateed in the short time unlike Hinered phenols primary antioxidant and phosphorous acid esters auxiliary antioxidant
It is good, but phosphorous acid esters auxiliary antioxidant has been hydrolyzed, and antioxidant of the invention is not easy to be hydrolyzed, so that of the invention is anti-
Oxidant can keep antiageing effect for a long time, be more advantageous to and play antioxidation under the condition of high temperature and high humidity.
Preferably, the Hinered phenols primary antioxidant was four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta
Four alcohol esters, 2,2' methylene bis (4- methyl-6-tert-butylphenol), β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid positive ten
Eight carbon alcohol esters, 2,6 di-tert-butyl p-cresol, 1,1,3- tri- (5- tertiary butyl-4-hydroxy -2- aminomethyl phenyl) butane, 1,3,5- tri-
In (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene of methyl -2,4,6- three and 2,2- methylene bis-(4- ethyl -6- tert-butyl phenol)
At least one；The thioether class auxiliary antioxidant is dilauryl thiodipropionate, 2,4- bis- (n-octylthiomethylene) -6-
At least one of methylphenol and thio-2 acid octadecanol ester.
By adopting the above technical scheme, the effect for capturing free radical can be preferably played, it is made to be no longer participate in oxidation cycle,
Prevent the progress of the polyester composite Auto-oxidation reaction.The Hinered phenols primary antioxidant is four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyl) propionic acid] pentaerythritol ester and 2,2' methylene bis (4- methyl-6-tert-butylphenol) be by weight 5:1-
3 mix；The thioether class auxiliary antioxidant is dilauryl thiodipropionate and 2,4- bis- (n-octylthiomethylene) -6-
Methylphenol is mixed by weight 1-3:1.
Preferably, the hydrolysis agent is at least one of Carbodiimides hydrolysis agent and polyester polyol.
By adopting the above technical scheme, capturing living radical prevents the polyester composite self-catalysis from degrading, and avoids polyester
The carbochain of resin is broken, and improves the service life of polyester composite, the especially hydrolysis under high temperature and humidity use condition
Stability.It is furthermore preferred that the hydrolysis agent is Carbodiimides hydrolysis agent and polyester polyol by weight 5-8:
0.5-2 is mixed.
Further, the Carbodiimides hydrolysis agent is two (2,6- diisopropyl phenyl) carbodiimides, two
(1- (1- methyl-1-phenylethyl)-2,6- diisopropyl phenyl) carbodiimides, two (4- phenoxy group-2,6- diisopropyl benzenes
Base) carbodiimides, two Asia of two (4- tert-butyl -2,6- diisopropyl phenyl) carbodiimides, carbodiimides and poly- carbonization
At least one of amine；The polyester polyol be by dibasic acid component and diol component under the conditions of 140-200 DEG C of temperature
The number-average molecular weight that polycondensation reaction obtains is the polyester polyol of 500-2500；Wherein, the dibasic acid component be succinic acid, oneself
At least one of diacid, azelaic acid, fumaric acid, maleic acid and suberic acid；The diol component is 1,4- butanediol, 1,3-
Butanediol, ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 2- methyl-1,3-propanediol, 1,6-HD, caprolactone glycol,
At least one of polycarbonate glycol, diethylene glycol (DEG), 1,6-HD, 1,5 pentanediols and dodecyl hexylene glycol.More preferably
, the Carbodiimides hydrolysis agent be two (2,6- diisopropyl phenyl) carbodiimides and carbodiimides by weight
It is mixed than 1:2-4, especially suitable for removing acid and water in polyester composite under the condition of high temperature and high humidity, prevents polyester
Self-catalysis degradation occurs for resin.
Preferably, the phosphinate flame retardant is aluminum diethylphosphinate, diethyl phosphinic acids magnesium, dipropyl hypophosphorous acid
Aluminium, dimethylphosphinic acid aluminium, Methylethyl phosphinic acids aluminium, ethyl propyl phosphinic acids aluminium, ethyl-butyl phosphinic acids aluminium, butyl
Phosphinic acids aluminium, dibutyl phosphinic acids aluminium, aluminum phenylphosphinate, diphenyl phosphonic acid aluminium, methylphenylphosphinic acid aluminium and ethane -1,
At least one of 2- diphosphinic acid aluminium；The fire retarding synergist is that organic silicon-type of the relative molecular weight in 20000-38000 hinders
Fire agent.
By adopting the above technical scheme, phosphinate flame retardant and silicone flame retardant form flame-retardant system, the two collaboration
Effect prevents polyester resin to form the probability in carbon channel, to improve the CTI value of polyester composite.The organosilicon
Flame retardant be dimethyl silicone polymer, polydiethylsiloxane, polymethyl siloxane and polymethylphenylsiloxane in extremely
Few one kind, the flame-retardant system synergist that Nitrogen element series easily high temperature and humidity is not precipitated, can effectively improve polyester composite
Charring rate in burning, improves flame retardant effect.The relative molecular weight control of machine silicon-series five-retardant has in 20000-38000,
In the graded polymer materials of the formation silicone flame retardant enriched layer on polyester composite surface, polyester composite is firing
It generates that polysiloxanes is distinctive, inorganic oxygen barrier heat-insulating protective layer containing Si-O key and (or) Si-C key when burning, had both prevented combustion
It burns decomposition product to escape, guarantees that the surface of polyester composite without precipitate, and inhibits the thermal decomposition of polyester resin, reach resistance
Combustion, low cigarette, less toxic effect.
Preferably, the ester exchange inhibitor is disodium hydrogen phosphate, ethyl orthosilicate, zinc sulfate, triphenyl phosphate, phosphoric acid
At least one of triethyl, trimethyl phosphate, sodium dihydrogen phosphate and Sodium Acid Pyrophosphate.
By adopting the above technical scheme, it is suppressed that ester exchange reaction occurs in recombination process for two different polyester resin,
The generation of statistic copolymer is prevented, system impact strength, elongation at break and thermal stability are improved.
Preferably, the glass fibre is via the coupling agent modified processed glass fibre of hydrolysis；The hydrolysis
Coupling agent is the organo-silicon coupling agent containing isopropoxy.
By adopting the above technical scheme, the hydrolytic resistance for keeping glass fibre, the organo-silicon coupling agent containing isopropoxy it is only
Special structure makes glass fibre have extraordinary stability in aqueous based systems, keeps permanent stability and validity.Further,
The organo-silicon coupling agent containing isopropoxy is vinyl silane triisopropoxide and/or the modified γ-metering system of isopropanol
Acryloxypropylethoxysilane trimethoxy silane；Isopropyl alcohol part replaces γ-methacryloxypropyl trimethoxy silane methoxy
Base makes γ-methacryloxypropyl trimethoxy silane introduce the biggish isopropoxy of steric hindrance, makes modified to have
Machine silicone couplet hydrolysis rate is slack-off, to play hydrolysis effect.Compared with γ aminopropyltriethoxy silane, this hair
The hydrolytic resistance of the bright organo-silicon coupling agent containing isopropoxy is stronger, is more advantageous to and plays a role under hot and humid environment.
Another object of the present invention is achieved through the following technical solutions: the preparation of above-mentioned halogen-free antiflaming polyester composite material
Method includes the following steps:
(S1), raw material is weighed by weight, it is spare；
(S2), polyester resin is first premixed into 1-3min with diffusing oil in a high speed mixer, then 1- is blended with other raw materials
It discharges after 3min, through double screw extruder extruding pelletization, the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting is made.
Preparation method of the invention is easy to operate, easy to control, and high production efficiency, production cost is low, can be used for extensive
Production.Wherein, in step (S2), polyester resin is first premixed in a high speed mixer with diffusing oil and is blended again with other raw materials, is had
Conducive to uniformity and stability of the material in extrusion process.The diffusing oil can the indissolubles such as evenly dispersed glass fibre, toner
The solids of the inorganic/organic pigment of property, while can also prevent the sedimentation and cohesion of solids.
Further, the double screw extruder each section of processing temperature since feeding section be respectively as follows: 170-190 DEG C,
190-210℃、190-210℃、200-220℃、200-220℃、200-220℃、210-230℃、210-230℃、210-230
DEG C, 220-240 DEG C, head temperature be 230-250 DEG C, screw speed 320-400r/min.The present invention passes through control twin-screw
The area extruder Zhong Ge temperature makes polyester composite obtained have excellent mechanical property, and does not turn yellow, is not blistering, surface
It is smooth, glossiness is high.When each area when the temperature is excessively high, be easily reduced the effect of antioxidant since antioxidant heat resistance is not high, because
The control of this processing temperature is being lower than 250 DEG C.
In 1000 hours that the beneficial effects of the present invention are: polyester composites of the invention under the conditions of double 85, tool
Have high CTI characteristic, material mechanical performance is relatively stable, and flame retardant property remains unchanged, the surface of polyester composite without precipitate,
Particularly suitable as charging pile materials'use.
Preparation method of the invention is easy to operate, easy to control, and high production efficiency, production cost is low, can be used for extensive
Production.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting, the raw material including following parts by weight:
The polyester resin is that polybutylene terephthalate (PBT) and polyethylene terephthalate are mixed with weight ratio 2:1
It closes.The inherent viscosity of polybutylene terephthalate (PBT) is 0.9dL/g, the inherent viscosity of polyethylene terephthalate
For 1.1dL/g.
The compatilizer is glycidyl methacrylate graft polyolefin elastomer and styrene-acrylonitrile-methyl
Glycidyl acrylate copolymer is mixed by weight 3:1.5, and the relative molecular weight of the compatilizer is 8.5 × 104。
The chain extender is the acrylic-styrene copolymer containing epoxy group；The acrylicstyrene copolymerization containing epoxy group
Object is acrylicstyrene-glycidyl methacrylate copolymer.
The antioxidant is that Hinered phenols primary antioxidant and thioether class auxiliary antioxidant are mixed by weight 1:4.
The Hinered phenols primary antioxidant be four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and
2,2' methylene bis (4- methyl-6-tert-butylphenol) is mixed by weight 5:2；The thioether class auxiliary antioxidant is
Dilauryl thiodipropionate and 2,4- bis- (n-octylthiomethylene) -6- methylphenol are mixed by weight 2:1.
The hydrolysis agent is that Carbodiimides hydrolysis agent and polyester polyol are mixed by weight 6:1.
The Carbodiimides hydrolysis agent is two (2,6- diisopropyl phenyl) carbodiimides and carbodiimides
It is mixed by weight 1:3.The polyester polyol be by dibasic acid component and diol component under the conditions of 170 DEG C of temperature
The polyester polyol that the number-average molecular weight that polycondensation reaction obtains is 1500；Wherein, the dibasic acid component is succinic acid；Described two
First alkoxide component is 1,4- butanediol.
The phosphinate flame retardant is aluminum diethylphosphinate；The fire retarding synergist is relative molecular weight 30000
Silicone flame retardant.The silicone flame retardant is dimethyl silicone polymer.
The ester exchange inhibitor is disodium hydrogen phosphate.
The glass fibre is via the coupling agent modified processed glass fibre of hydrolysis；The water-fast uncoupler is
Organo-silicon coupling agent containing isopropoxy；The organo-silicon coupling agent containing isopropoxy is the modified γ-metering system of isopropanol
Acryloxypropylethoxysilane trimethoxy silane.
A kind of preparation method of the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting as described above, including walk as follows
It is rapid:
(S1), raw material is weighed by weight, it is spare；
(S2), polyester resin is first premixed into 2min with diffusing oil in a high speed mixer, then 2min is blended with other raw materials
After discharge, through double screw extruder extruding pelletization, the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting is made.
The double screw extruder each section of processing temperature since feeding section be respectively as follows: 180 DEG C, 200 DEG C, 200 DEG C,
210 DEG C, 210 DEG C, 210 DEG C, 220 DEG C, 220 DEG C, 220 DEG C, 230 DEG C, head temperature are 240 DEG C, screw speed 360r/min.
Embodiment 2
A kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting, the raw material including following parts by weight:
The polyester resin is that polybutylene terephthalate (PBT) and polyethylene terephthalate are mixed with weight ratio 3:1
It closes.The inherent viscosity of polybutylene terephthalate (PBT) is 0.7dL/g, the inherent viscosity of polyethylene terephthalate
For 1.2dL/g.
The compatilizer is glycidyl methacrylate graft polyolefin elastomer and styrene-acrylonitrile-methyl
Glycidyl acrylate copolymer is mixed by weight 3:1, and the relative molecular weight of the compatilizer is 5 × 104.It is described
Chain extender is the acrylic-styrene copolymer containing epoxy group；The acrylic-styrene copolymer containing epoxy group is
Methacrylic acid-styrene-t glycidyl ester copolymer.
The antioxidant is that Hinered phenols primary antioxidant and thioether class auxiliary antioxidant are mixed by weight 1:2.
The Hinered phenols primary antioxidant be four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and
2,2' methylene bis (4- methyl-6-tert-butylphenol) is mixed by weight 5:1；The thioether class auxiliary antioxidant is
Dilauryl thiodipropionate and 2,4- bis- (n-octylthiomethylene) -6- methylphenol are mixed by weight 1:1.
The hydrolysis agent is that Carbodiimides hydrolysis agent and polyester polyol are mixed by weight 5:0.5.
The Carbodiimides hydrolysis agent is two (2,6- diisopropyl phenyl) carbodiimides and carbodiimides
It is mixed by weight 1:2.The polyester polyol be by dibasic acid component and diol component under the conditions of 140 DEG C of temperature
The polyester polyol that the number-average molecular weight that polycondensation reaction obtains is 500；Wherein, the dibasic acid component is adipic acid；Described two
First alkoxide component is 1,2- propylene glycol.
The phosphinate flame retardant is dipropyl hypo-aluminum orthophosphate；The fire retarding synergist is relative molecular weight 20000
Silicone flame retardant.The silicone flame retardant is polydiethylsiloxane.
The ester exchange inhibitor is ethyl orthosilicate.
The glass fibre is via the coupling agent modified processed glass fibre of hydrolysis；The water-fast uncoupler is
Organo-silicon coupling agent containing isopropoxy；The organo-silicon coupling agent containing isopropoxy is vinyl silane triisopropoxide.
A kind of preparation method of the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting as described above, including walk as follows
It is rapid:
(S1), raw material is weighed by weight, it is spare；
(S2), polyester resin is first premixed into 1min with diffusing oil in a high speed mixer, then 3min is blended with other raw materials
After discharge, through double screw extruder extruding pelletization, the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting is made.
The double screw extruder each section of processing temperature since feeding section be respectively as follows: 170 DEG C, 190 DEG C, 190 DEG C,
200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, 220 DEG C, head temperature are 230 DEG C, screw speed 320r/min.
Embodiment 3
A kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting, the raw material including following parts by weight:
The polyester resin is that polybutylene terephthalate (PBT) and polyethylene terephthalate are mixed with weight ratio 1:1
It closes.The inherent viscosity of polybutylene terephthalate (PBT) is 1.2dL/g, the inherent viscosity of polyethylene terephthalate
For 0.7dL/g.
The compatilizer is glycidyl methacrylate graft polyolefin elastomer and styrene-acrylonitrile-methyl
Glycidyl acrylate copolymer is mixed by weight 3:2, and the relative molecular weight of the compatilizer is 1 × 105.It is described
Chain extender is the acrylic-styrene copolymer containing epoxy group；The acrylic-styrene copolymer containing epoxy group is
Acrylicstyrene-glycidyl methacrylate copolymer and methacrylic acid-styrene-t shrink sweet
Grease copolymer is mixed by weight 1:1.
The antioxidant is that Hinered phenols primary antioxidant and thioether class auxiliary antioxidant are mixed by weight 1:5.
The Hinered phenols primary antioxidant be four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and
2,2' methylene bis (4- methyl-6-tert-butylphenol) is mixed by weight 5:3；The thioether class auxiliary antioxidant is
Dilauryl thiodipropionate and 2,4- bis- (n-octylthiomethylene) -6- methylphenol are mixed by weight 3:1.
The hydrolysis agent is that Carbodiimides hydrolysis agent and polyester polyol are mixed by weight 8:2.
The Carbodiimides hydrolysis agent is two (2,6- diisopropyl phenyl) carbodiimides and carbodiimides
It is mixed by weight 1:4.The polyester polyol be by dibasic acid component and diol component under the conditions of 200 DEG C of temperature
The polyester polyol that the number-average molecular weight that polycondensation reaction obtains is 2500；Wherein, the dibasic acid component is azelaic acid and pungent two
Acid is mixed by weight 1:1；The diol component is ethylene glycol and dodecyl hexylene glycol mix by weight 1:1 and
At.
The phosphinate flame retardant is that Methylethyl phosphinic acids aluminium and ethyl-butyl phosphinic acids aluminium are mixed by weight 1:2
It forms；The fire retarding synergist is silicone flame retardant of the relative molecular weight 38000.The silicone flame retardant is poly-
Dimethyl siloxane and polymethylphenylsiloxane are mixed by weight 1:2.
The ester exchange inhibitor is that disodium hydrogen phosphate and sodium dihydrogen phosphate are mixed by weight 1:3.
The glass fibre is via the coupling agent modified processed glass fibre of hydrolysis；The water-fast uncoupler is
Organo-silicon coupling agent containing isopropoxy；The organo-silicon coupling agent containing isopropoxy be vinyl silane triisopropoxide and
Modified γ-the methacryloxypropyl trimethoxy silane of isopropanol is mixed by weight 1:1.
A kind of preparation method of the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting as described above, including walk as follows
It is rapid:
(S1), raw material is weighed by weight, it is spare；
(S2), polyester resin is first premixed into 3min with diffusing oil in a high speed mixer, then 1min is blended with other raw materials
After discharge, through double screw extruder extruding pelletization, the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting is made.
The double screw extruder each section of processing temperature since feeding section be respectively as follows: 190 DEG C, 210 DEG C, 210 DEG C,
220 DEG C, 220 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 240 DEG C, head temperature are 250 DEG C, screw speed 400r/min.
Embodiment 4
A kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting, the raw material including following parts by weight:
The polyester resin is polybutylene terephthalate (PBT), polyethylene terephthalate and poly- terephthaldehyde
Acid -1,4 cyclohexane dimethanol ester is mixed with weight ratio 2:1:1.The inherent viscosity of the polyester resin is controlled in 0.8dL/
g。
The compatilizer is ethylene-methyl acrylate-glyceryl methacrylate copolymer.The chain extender be containing
The acrylic-styrene copolymer of epoxy group；The acrylic-styrene copolymer containing epoxy group is acrylic acid-benzene
Ethylene-methyl methacrylate glycidyl ester copolymer.
The antioxidant is that Hinered phenols primary antioxidant and thioether class auxiliary antioxidant are mixed by weight 1:4.
The Hinered phenols primary antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester；Institute
Stating thioether class auxiliary antioxidant is thio-2 acid octadecanol ester.
The hydrolysis agent is Carbodiimides hydrolysis agent.
The Carbodiimides hydrolysis agent is two (4- phenoxy group -2,6- diisopropyl phenyl) carbodiimides.
The phosphinate flame retardant is Methylethyl phosphinic acids aluminium and ethane -1,2- diphosphinic acid aluminium by weight 3:2
It mixes；The fire retarding synergist is silicone flame retardant of the relative molecular weight 25000.The silicone flame retardant
For polymethylphenylsiloxane.
The ester exchange inhibitor is triphenyl phosphate.
The glass fibre is via the coupling agent modified processed glass fibre of hydrolysis；The water-fast uncoupler is
Organo-silicon coupling agent containing isopropoxy；The organo-silicon coupling agent containing isopropoxy is the modified γ-metering system of isopropanol
Acryloxypropylethoxysilane trimethoxy silane.
A kind of preparation method of the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting as described above, including walk as follows
It is rapid:
(S1), raw material is weighed by weight, it is spare；
(S2), polyester resin is first premixed into 2min with diffusing oil in a high speed mixer, then 2min is blended with other raw materials
After discharge, through double screw extruder extruding pelletization, the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting is made.
The double screw extruder each section of processing temperature since feeding section be respectively as follows: 175 DEG C, 195 DEG C, 200 DEG C,
205 DEG C, 210 DEG C, 220 DEG C, 225 DEG C, 230 DEG C, 230 DEG C, 235 DEG C, head temperature are 240 DEG C, screw speed 380r/min.
Embodiment 5
A kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting, the raw material including following parts by weight:
The polyester resin be polybutylene terephthalate (PBT) and poly terephthalic acid -1,4 cyclohexane dimethanol ester with
Weight ratio 1-3:1 is mixed.The inherent viscosity of polybutylene terephthalate (PBT) is 0.7dL/g, poly terephthalic acid Isosorbide-5-Nitrae-
The inherent viscosity of cyclohexanedimethanoester ester is 1.0dL/g.
The compatilizer is methyl methacrylate-glycidyl methacrylate copolymer, the compatilizer
Relative molecular weight is 6 × 104.The chain extender is the acrylic-styrene copolymer containing epoxy group；It is described to contain epoxy group
Acrylic-styrene copolymer be acrylicstyrene-glycidyl methacrylate copolymer.
The antioxidant is that Hinered phenols primary antioxidant and thioether class auxiliary antioxidant are mixed by weight 1:3.
The Hinered phenols primary antioxidant is 1,1,3- tri- (5- tertiary butyl-4-hydroxy -2- aminomethyl phenyl) butane；The sulphur
Ethers auxiliary antioxidant is dilauryl thiodipropionate.
The hydrolysis agent is polyester polyol.
The polyester polyol is that polycondensation reaction obtains under the conditions of 180 DEG C of temperature by dibasic acid component and diol component
Number-average molecular weight be 2000 polyester polyol；Wherein, the dibasic acid component is maleic acid；The diol component is
Interior esterdiol and polycarbonate glycol are mixed by weight 1:1.
The phosphinate flame retardant is ethyl propyl phosphinic acids aluminium and aluminum phenylphosphinate mix by weight 1:4 and
At；The fire retarding synergist is silicone flame retardant of the relative molecular weight 33000.The silicone flame retardant is poly- two
Methylsiloxane.
The ester exchange inhibitor is Sodium Acid Pyrophosphate.
The glass fibre is via the coupling agent modified processed glass fibre of hydrolysis；The water-fast uncoupler is
Organo-silicon coupling agent containing isopropoxy；The organo-silicon coupling agent containing isopropoxy is vinyl silane triisopropoxide.
A kind of preparation method of the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting as described above, including walk as follows
It is rapid:
(S1), raw material is weighed by weight, it is spare；
(S2), polyester resin is first premixed into 1min with diffusing oil in a high speed mixer, then 3min is blended with other raw materials
After discharge, through double screw extruder extruding pelletization, the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting is made.
The double screw extruder each section of processing temperature since feeding section be respectively as follows: 180 DEG C, 190 DEG C, 190 DEG C,
200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 240 DEG C, head temperature are 240 DEG C, screw speed 330r/min.
Comparative example 1
This comparative example the difference from embodiment 1 is that: the chain extender is double benzol carbonates.
Comparative example 2
This comparative example the difference from embodiment 1 is that: the phosphinate flame retardant be substituted for triphenyl phosphate (TPP) resistance
Agent is fired, the fire retarding synergist is substituted for melamine cyanurate sodium synergist.
Embodiment 6
The polyester composite of Example 1-5 and comparative example 1-2 are located respectively under the conditions of 85% humidity and 85 DEG C of temperature
0h, 168h, 500h, 1000h are managed, tests its cantilever beam impact strength, Izod notched impact strength, tensile strength, curved respectively
Qu Qiangdu, flame retardant rating and CTI value.
Test method is as follows:
Cantilever beam impact strength test: with the regulation of ISO180-2000, using its tensile strength of non-notch sample testing,
Unit K J/m2。
Izod notched impact strength test: with the regulation of ISO180-2000, using its stretching of notch type A sample testing
Intensity, unit K J/m2。
Tensile strength test: with the regulation of ISO527, using its tensile strength of 1B type sample testing, units MPa.
Bending strength test: its bending strength, units MPa are tested using ISO178 testing standard.
Flame retardant rating test: UL-94 standard, sample thickness 1.0mm are used.
CTI value test: according to GB/T 4207-2012 " the resistance to electric trace index of solid insulating material and comparative tracking index
Measuring method " regulation, test its CTI value under the conditions of 85% ± 5% relative humidity and 85 DEG C ± 2 DEG C of temperature, it is single
Position is V.
Test result is as follows shown in table 1.
Table 1
By upper table 1 it is found that polyester composite of the invention is in 1000 hours under the conditions of double 85, have high CTI special
Property, impact strength, tensile strength and bending strength slowly reduce, and flame retardant rating remains unchanged, CTI value can maintain 600V with
On, meet the requirement of charging pile material.
Compared with Example 3, the mechanical properties decrease of the polyester composite of embodiment 2 is slower, and mechanical stability is more
Height, possible reason are: in the polyester composite of embodiment 2, the amount ratio of polyester resin and hydrolysis agent and poly-
The dosage of ester resin and antioxidant is bigger, and hydrolysis effect is good, to improve mechanical stability.
Compared with Example 1, the impact strength of comparative example 1 and bending strength are lower, and handle 1000h under the conditions of double 85
Flame retardant rating afterwards be down to V-1 grades, CTI value lower than 600V, possible reason is: the double phenyl-carbonic acids of the chain extender of comparative example 1
Ester is ineffective for the weight average molecular weight for increasing polyester composite, and weight average molecular weight is low compared with embodiment 1, and resistant to hydrolysis
Stability is lower, results in the impact strength of comparative example 1 and bending strength is lower and flame retardant effect is poor.
Compared with Example 1, comparative example 2 tests flame retardant rating under the conditions of double 85 and only reaches V-1 grades, illustrates that the present invention adopts
Phosphinate flame retardant flame retardant effect is more preferable.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way, In
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting, it is characterised in that: the raw material including following parts by weight:
2. a kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting according to claim 1, it is characterised in that: described
Polyester resin is polybutylene terephthalate (PBT), polyethylene terephthalate and poly terephthalic acid -1,4- hexamethylene
At least two combinations in diformazan alcohol ester；The inherent viscosity of the polyester resin is 0.7-1.2dL/g.
3. a kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting according to claim 1, it is characterised in that: described
Compatilizer is glycidyl methacrylate graft polyolefin elastomer, glycidyl methacrylate graft acrylonitrile-
Butadiene-styrene terpolymer, methyl methacrylate-glycidyl methacrylate copolymer, styrene-the third
Alkene nitrile-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glyceryl methacrylate copolymer and
At least one of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer；The chain extender is containing epoxy group
Acrylic-styrene copolymer.
4. a kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting according to claim 1, it is characterised in that: described
Antioxidant is that Hinered phenols primary antioxidant and thioether class auxiliary antioxidant are mixed by weight 1:2-5.
5. a kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting according to claim 4, it is characterised in that: described
Hinered phenols primary antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 2,2'- di-2-ethylhexylphosphine oxide
(4- methyl-6-tert-butylphenol), β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester, 2,6 di-t-butyls
Paracresol, 1,1,3- tri- (5- tertiary butyl-4-hydroxy -2- aminomethyl phenyl) butane, three (3,5- bis- of 1,3,5- trimethyl -2,4,6-
Tertiary butyl-4-hydroxy benzyl) at least one of benzene and 2,2- methylene bis-(4- ethyl -6- tert-butyl phenol)；The thioether class
Auxiliary antioxidant is dilauryl thiodipropionate, (the n-octylthiomethylene) -6- methylphenol of 2,4- bis- and thio-2 acid
At least one of octadecanol ester.
6. a kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting according to claim 1, it is characterised in that: described
Hydrolysis agent is at least one of Carbodiimides hydrolysis agent and polyester polyol.
7. a kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting according to claim 1, it is characterised in that: described
Phosphinate flame retardant be aluminum diethylphosphinate, diethyl phosphinic acids magnesium, dipropyl hypo-aluminum orthophosphate, dimethylphosphinic acid aluminium,
Methylethyl phosphinic acids aluminium, ethyl propyl phosphinic acids aluminium, ethyl-butyl phosphinic acids aluminium, butyl phosphinic acids aluminium, dibutyl time
In phosphonic acids aluminium, aluminum phenylphosphinate, diphenyl phosphonic acid aluminium, methylphenylphosphinic acid aluminium and ethane -1,2- diphosphinic acid aluminium
It is at least one；The fire retarding synergist is silicone flame retardant of the relative molecular weight in 20000-38000.
8. a kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting according to claim 1, it is characterised in that: described
Ester exchange inhibitor be disodium hydrogen phosphate, ethyl orthosilicate, zinc sulfate, triphenyl phosphate, triethyl phosphate, trimethyl phosphate,
At least one of sodium dihydrogen phosphate and Sodium Acid Pyrophosphate.
9. a kind of halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting according to claim 1, it is characterised in that: described
Glass fibre is via the coupling agent modified processed glass fibre of hydrolysis；The water-fast uncoupler is containing isopropoxy
Organo-silicon coupling agent.
10. a kind of preparation of the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting as described in any one of claims 1-9
Method, characterized by the following steps:
(S1), raw material is weighed by weight, it is spare；
(S2), polyester resin is first premixed into 1-3min with diffusing oil in a high speed mixer, then 1-3min is blended with other raw materials
After discharge, through double screw extruder extruding pelletization, the halogen-free antiflaming polyester composite material of high-temp resisting high-humidity resisting is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910877738.9A CN110499007B (en) | 2019-09-17 | 2019-09-17 | High-temperature and high-humidity resistant halogen-free flame-retardant polyester composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910877738.9A CN110499007B (en) | 2019-09-17 | 2019-09-17 | High-temperature and high-humidity resistant halogen-free flame-retardant polyester composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110499007A true CN110499007A (en) | 2019-11-26 |
| CN110499007B CN110499007B (en) | 2021-10-15 |
Family
ID=68592064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910877738.9A Active CN110499007B (en) | 2019-09-17 | 2019-09-17 | High-temperature and high-humidity resistant halogen-free flame-retardant polyester composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110499007B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105727A (en) * | 2021-04-13 | 2021-07-13 | 东莞市东翔塑胶有限公司 | Weather-resistant high-glow-wire polyester composite material and preparation method thereof |
| CN115612261A (en) * | 2022-10-25 | 2023-01-17 | 汉特工程塑料（浙江）有限公司 | Hydrolysis-resistant flame-retardant polyester composite material capable of being subjected to laser welding and preparation method thereof |
| CN115821418A (en) * | 2022-10-18 | 2023-03-21 | 浙江恒逸石化研究院有限公司 | Method for preparing high-sulfonate-content antibacterial flame-retardant cationic dye dyeable polyester fiber based on autocatalysis |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105531A (en) * | 2008-07-23 | 2011-06-22 | 三菱工程塑料株式会社 | Thermoplastic polyester resin composition |
| CN102702699A (en) * | 2012-07-06 | 2012-10-03 | 上海日之升新技术发展有限公司 | Glass-fiber-reinforced hydrolysis-resistant polyester material and preparation method thereof |
| CN102911485A (en) * | 2012-10-24 | 2013-02-06 | 华南理工大学 | Flame-retardant chain-extended polybutylene terephthalate composition and preparation method thereof |
| CN102942770A (en) * | 2012-12-10 | 2013-02-27 | 中国热带农业科学院湛江实验站 | Completely-biodegradable agricultural mulching film |
| CN109608856A (en) * | 2018-11-23 | 2019-04-12 | 中广核俊尔新材料有限公司 | A kind of charging pile shell antiflaming polycarbonate alloy PP Pipe Compound and preparation method thereof |
-
2019
- 2019-09-17 CN CN201910877738.9A patent/CN110499007B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105531A (en) * | 2008-07-23 | 2011-06-22 | 三菱工程塑料株式会社 | Thermoplastic polyester resin composition |
| CN102702699A (en) * | 2012-07-06 | 2012-10-03 | 上海日之升新技术发展有限公司 | Glass-fiber-reinforced hydrolysis-resistant polyester material and preparation method thereof |
| CN102911485A (en) * | 2012-10-24 | 2013-02-06 | 华南理工大学 | Flame-retardant chain-extended polybutylene terephthalate composition and preparation method thereof |
| CN102942770A (en) * | 2012-12-10 | 2013-02-27 | 中国热带农业科学院湛江实验站 | Completely-biodegradable agricultural mulching film |
| CN109608856A (en) * | 2018-11-23 | 2019-04-12 | 中广核俊尔新材料有限公司 | A kind of charging pile shell antiflaming polycarbonate alloy PP Pipe Compound and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王小君: "扩链剂ADR4370S对聚对苯二甲酸丁二醇酯的动态流变行为及力学性能的影响", 《高分子材料科学与工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105727A (en) * | 2021-04-13 | 2021-07-13 | 东莞市东翔塑胶有限公司 | Weather-resistant high-glow-wire polyester composite material and preparation method thereof |
| CN113105727B (en) * | 2021-04-13 | 2023-01-24 | 东莞市东翔塑胶有限公司 | Weather-resistant high-glowing filament polyester composite material and preparation method thereof |
| CN115821418A (en) * | 2022-10-18 | 2023-03-21 | 浙江恒逸石化研究院有限公司 | Method for preparing high-sulfonate-content antibacterial flame-retardant cationic dye dyeable polyester fiber based on autocatalysis |
| CN115821418B (en) * | 2022-10-18 | 2024-04-05 | 浙江恒逸石化研究院有限公司 | Method for preparing high-sulfonate-content antibacterial flame-retardant cationic dye-dyeable polyester fiber based on autocatalysis |
| CN115612261A (en) * | 2022-10-25 | 2023-01-17 | 汉特工程塑料（浙江）有限公司 | Hydrolysis-resistant flame-retardant polyester composite material capable of being subjected to laser welding and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110499007B (en) | 2021-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110499007A (en) | A kind of halogen-free antiflaming polyester composite material and preparation method of high-temp resisting high-humidity resisting | |
| US8080599B2 (en) | Thermoplastic polyester compositions, methods of manufacture, and articles thereof | |
| JP4242481B2 (en) | Modified weather-resistant thermoplastic resin molding composition and article molded therefrom | |
| US5621029A (en) | Flame retardant thermoplastic polycarbonate moulding compositions | |
| CN103108917B (en) | Polyphenylene ether resin composition and molded article of same | |
| KR102575521B1 (en) | Thermoplastic polyester resin composition and molded article | |
| KR102157130B1 (en) | Thermoplastic polyester resin composition and molded article | |
| CN107383829A (en) | Ageing-resistant hydrolysis halogen-free flame-retardant polycarbonate composition and preparation method thereof | |
| CN1117121C (en) | Fire-retardant polyolefin type resin, its prepn. method and fire-retardant cablt | |
| CN1221441A (en) | Flame retardant thermo plastic resin composition | |
| CN106317821A (en) | Flame-retardant PC/ABS composite material with high hydrolysis resistance and preparation method thereof | |
| CN106380861A (en) | Cable material, and preparation method and application thereof | |
| CN102911485B (en) | Flame-retardant chain-extended polybutylene terephthalate composition and preparation method thereof | |
| KR20120120932A (en) | Thermoplastic polymer blends comprising crosslinked polar olefin polymers in a thermoplastic polyurethane matrix | |
| CN108047629A (en) | A kind of charging pile halogen-free flameproof TPE cable material of resistance to cracking and preparation method thereof | |
| CN107987516B (en) | TPU/terpolymer nylon composite halogen-free flame-retardant cable material and preparation method thereof | |
| JP2019073600A (en) | Thermoplastic resin composition, and connection structure for photovoltaic power generation module | |
| CN106221171A (en) | High-weatherability fire retardation PC/ABS composite material and preparation method thereof | |
| CN114437494A (en) | TPE sheath material for charging cable and preparation method thereof | |
| CN101104730A (en) | Low-fluorine anti-flaming polycarbonate/cinnamenyl resin composition | |
| JP2011137059A (en) | Thermoplastic polyester resin composition, molded article using the same and method for producing the same | |
| WO2011153827A1 (en) | Flame-retardant polyester resin composition and molded article thereof | |
| CN107459798B (en) | Flame-retardant resin composition and molded article using same | |
| KR20130132004A (en) | Halogen-free flame retardant polyester resin composition with good mechanical properties and molded article thereof | |
| CN103874735B (en) | Non-migratory halogen free flame retardant thermoplastic polyurethane composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |