CN103342880A - High-surface-gloss environment-friendly halogen-free flame-retardant PBT (polybutylene terephthalate) composite material and preparation method thereof - Google Patents
High-surface-gloss environment-friendly halogen-free flame-retardant PBT (polybutylene terephthalate) composite material and preparation method thereof Download PDFInfo
- Publication number
- CN103342880A CN103342880A CN2013103230706A CN201310323070A CN103342880A CN 103342880 A CN103342880 A CN 103342880A CN 2013103230706 A CN2013103230706 A CN 2013103230706A CN 201310323070 A CN201310323070 A CN 201310323070A CN 103342880 A CN103342880 A CN 103342880A
- Authority
- CN
- China
- Prior art keywords
- pbt
- halogen
- free
- matrix material
- district
- 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
- 239000003063 flame retardant Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 polybutylene terephthalate Polymers 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 title abstract description 13
- 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 title abstract description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 title abstract description 6
- 239000003365 glass fiber Substances 0.000 claims abstract description 25
- 239000000314 lubricant Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 229920001897 terpolymer Polymers 0.000 claims description 8
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- 238000001994 activation Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002341 toxic gas Substances 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000012745 toughening agent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920013683 Celanese Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and discloses a high-surface-gloss environment-friendly halogen-free flame-retardant PBT (polybutylene terephthalate) composite material and a preparation method thereof. The preparation method comprises the following steps: blending PBT used as the main raw material with PET (polyethylene terephthalate), toughener, halogen-free flame retardant, high-gloss black seed, antioxidant, lubricant, glass fiber and coupling agent, carrying out melt extrusion, and granulating. The invention has the advantages of wide raw material sources, favorable technical adaptability and low production cost; the obtained engineering plastic product has the advantages of high surface gloss and excellent material properties, and the impact strength reaches 8.2 KJ/m<2> above; the sample thickness is 1.6mm, and the flame retardancy can reach UL94V-0; and less black smoke and toxic gas are generated in the combustion process, and thus, the composite material achieves the environment-friendly level.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of high finish surface environment friendly halogen-free fireproof PBT matrix material and preparation method thereof.
Background technology
Polybutyl terapthalate (PBT) is called terylene again, is studied successfully by U.S. Celanese company in phase early 1970s, and with Celanex trade(brand)name listing, subsequently a lot of producers ranks of PBT that all put into production.Advantages such as PBT has thermotolerance, weathering resistance, chemical-resistant, electric property excellence, water-absorbent is little, the surface is good, be widely used in electric, automobile, machinery, household electrical appliance etc., especially electronics/electric utility, and the sector has fire-retardant requirement mostly to material.
For a long time, the PBT flame-retardant system is mainly halogenated flame retardant, and it is fire-retardant particularly adopting bromine.But Halogen class PBT matrix material potential sizable potential safety hazard, influence the healthy of field worker and surrounding resident.Can generate a large amount of cigarettes and poisonous and corrosive gas during its burning, endanger very big.In case presence of fire because thermolysis and burning, can produce a large amount of smog and poisonous corrosive gases, thereby hinder fire fighting and evacuating personnel, corrosion instrument and equipment.It is found that particularly it is that dense smoke and the toxic gas of material production causes that fatalities in the fire has more than 80%.
Along with the drawback all unfavorable to environment, that have potential safety hazard of halogenated flame retardant is identified, European Union announced two instructions of WEEE and ROHS in 2003.The instruction of various environmental protection is subsequently put into effect successively, and electric on European Union, North America market, information, that office man electric light industry begins the requirement material is non-halogen.The research and development of halogen-free anti-flaming PBT composite technology and product become the focus of domestic and international research.
New halogen-free anti-flaming PBT composite system, the amount of being fuming is little during burning, does not produce poisonous, corrosive gases.Fire retardant additive without halogen is mainly phosphorus series compound and metallic hydrogen oxygen compound.This two compounds, non-volatile during burning, do not produce corrosive gases, be called as nuisanceless fire retardant, also have the novel halogen-free flame retardantss of several classes such as silicon-series five-retardant and nitrogen flame retardant in addition.These novel halogen-free flame retardantss become the product innovation that meets the international standard development trend.
But simultaneously, the flame retarding efficiency of the halogen-free flame retardants that present halogen-free anti-flaming PBT composite is used is low, and addition is big, and it is bad to cause it to disperse in the PBT resin, forms coacervate.Add man-hour in injection moulding, macro manifestations is that material flowability is too poor, and glass fibre is exposed to product surface; Microcosmic is characterized by the PBT molecular chain movement and is obstructed, and interior energy is less, to glass fibre constraint power a little less than, thereby cause the glass fibre random motion, the segment glass fiber is exposed to product surface.Finally have a strong impact on the apparent property of product, have apparent flaw, can't form high-end level product.Become the general character difficult problem of industry main force research of technique.
Summary of the invention
The objective of the invention is to disclose a kind of high finish surface environment friendly halogen-free fireproof PBT matrix material.
Another object of the present invention is to disclose the preparation method of above-mentioned high finish surface environment friendly halogen-free fireproof PBT matrix material.
The present invention takes following technical scheme to be achieved for achieving the above object:
A kind of high finish surface environment friendly halogen-free fireproof PBT matrix material is made up of PBT, PET, glass fibre, halogen-free flame retardants, toughner, high light black race, oxidation inhibitor, lubricant, coupling agent, and each components contents of this matrix material is by mass percentage:
Preferably, each components contents of described matrix material is by mass percentage:
Described PBT is polybutylene terephthalate, is that viscosity is respectively two kinds of PBT of 0.84 and 1.0 according to the mixture of the mass ratio of 20～39.5:9～23.5.High sticking low sticking PBT proportioning is used, and plays the purpose that still keeps the high mechanical property of material when improving material flowability (most important condition of surperficial Gao Guang).
Described PET is polyethylene terephthalate, and viscosity is 0.6～0.7.In the blended melting extrusion, transesterification reaction takes place in material in forcing machine, prevents that effectively glass fibre from exposing, and plays the effect of product surface Gao Guang.
Preferably, described glass fibre is the alkali-free long glass fibres, and diameter is 12～13 μ m, and handle through the silane type treating compound on the surface.Alkali free glass fibre has chemical stability, electrical insulation capability, advantage that intensity is good, continuous glass fibre has that intensity is big in addition, flexibility, chemically-resistant and the good characteristics of flame retardant resistance, therefore adds the alkali-free continuous glass fibre and can improve the anti-impact of PBT matrix material, over-all properties such as fire-retardant.
Preferably, described halogen-free flame retardants is one or more the mixture in melamine pyrophosphate, melamine cyanurate, triphenylphosphate and the hypo-aluminum orthophosphate.Fire retardant is heated and decomposes, and the catalysis matrix becomes charcoal, and forms compound, and these compounds and charcoal layer organically combine, and can play good iris action, stop oxidizing reaction, stop proceeding of burning, thereby reach fire-retardant purpose.
Preferably, described toughner is any among ethylene-methyl methacrylate butyl ester-glycidyl acrylate multipolymer, ethylene-methyl methacrylate methyl terpolymer and the POE-g-GMA.Can improve the shock resistance of PBT resin.
Preferably, described high light black race is carrier-free inorganic black race or organic black race.Can improve the glossiness of PBT product surface.
Preferably, described oxidation inhibitor is any in poly-Doutrate, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of four (β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid) and two (2,4-di-tert-butyl-phenyl) poly-Doutrate diphosphites.By adding oxidation inhibitor, can prevent that the PBT resin from oxygenolysis taking place in extrusion process, can slow down PBT engineering plastics deterioration by oxidation speed simultaneously, increase the service life.
Preferably, described lubricant is in the two stearic amides (EBS) of hard acid esters (PETS), second Brace of poly-penta tetrol, silicone powder, the PE wax any.By adding lubricant, can make powder such as halogen-free flame retardants in the PBT resin, disperse more evenly, improve every index of gained PBT material.Simultaneously, lubricant can also improve fluidity of molten, reduces screw torque, reduces the energy consumption of preparation process.
Preferably, described coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-An Bingjisanyiyangjiguiwan.Add the interface binding power that coupling agent can improve resin and strongtheners such as weighting agent, glass fibre, improve product performance.
Another technical scheme of the present invention is as follows: the preparation method of above-mentioned high finish surface environment friendly halogen-free fireproof PBT matrix material may further comprise the steps:
(1) pre-treatment:
Halogen-free flame retardants is carried out surface activation process in stirrer, poling processing technique: 110 ℃ of temperature, 200 rev/mins of rotating speeds, time 10min;
(2) mix:
PBT, PET, toughner, high light black race are put in the stirrer and stir, add coupling agent and mix 1～2min, and then add oxidation inhibitor and lubricant, mix and stir 0.5min;
(3) melt extrude:
Place twin screw extruder to melt extrude the material that mixes, add glass fibre simultaneously in the forcing machine stage casing, in the side feeding equipment, add halogen-free flame retardants;
(4) granulation and aftertreatment:
Material tie rod after will melt extruding, air-dry through tank cooling, blower fan behind the tie rod, dicing machine pelletizing, vibratory screening apparatus filters and homogenizing jar homogenizing after pack, obtain high finish surface environment friendly halogen-free fireproof PBT matrix material.
Preferably, the described processing parameter that melt extrudes is as follows: 210～220 ℃ of twin screw extruder one district's temperature, 220～230 ℃ of two district's temperature, 230～240 ℃ of three district's temperature, 230～240 ℃ of four district's temperature, 215～225 ℃ of five district's temperature, 215～225 ℃ of six district's temperature, 220～230 ℃ of seven district's temperature, 230～240 ℃ of eight district's temperature, 240～250 ℃ of head temperatures, 880～920 rev/mins of main-machine screw rotating speeds, 180～190 rev/mins of main feed system rotating speeds, side feed system rotating speed 4～4.5Hz.
Preferably, the screw slenderness ratio of described twin screw extruder is 36:1.
The described cooling of step (4), air-dry, pelletizing, filtration and homogenizing adopt the conventional steps of this area to get final product, and do not do at this and give unnecessary details.
Beneficial effect of the present invention is as follows: the PBT matrix material of the present invention's preparation has excellent processibility, and burning does not simultaneously produce a large amount of black smokes and toxic gas, has the feature of environmental protection; And PBT composite material surface high-luster is good, and alternative traditional bromine is the flame-retardant PBT material, is conducive to energy-saving and emission-reduction, protection environment, economizes on resources, and the market requirement is stronger, produces better economic benefit.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of high finish surface environment friendly halogen-free fireproof PBT matrix material, its prescription is formed as shown in table 1:
Table 1 composite-material formula
| Raw material | Mass fraction |
| PBT (Nantong PBT1100, viscosity is 1.0) | 9 |
| PBT (Nantong PBT1084, viscosity is 0.84) | 34.5 |
| PET (Yizheng PETSB500, viscosity is 0.6～0.7) | 8 |
| Alkali-free long glass fibres long filament (Mount Taishan glass) | 26 |
| Hypo-aluminum orthophosphate | 14 |
| Triphenylphosphate | 2 |
| The ethylene-methyl methacrylate methyl terpolymer | 3 |
| Carrier-free inorganic black race | 2 |
| Oxidation inhibitor 1100 | 0.6 |
| Lubricant PETS | 0.6 |
| γ-glycidyl ether oxygen propyl trimethoxy silicane | 0.3 |
Embodiment 2:
A kind of high finish surface environment friendly halogen-free fireproof PBT matrix material, its prescription is formed as shown in table 2:
Table 2 composite-material formula
| Raw material | Mass fraction |
| PBT (Nantong PBT1100, viscosity is 1.0) | 23.5 |
| PBT (Nantong PBT1084, viscosity is 0.84) | 20 |
| PET (Yizheng PETSB500, viscosity is 0.6～0.7) | 8 |
| Alkali-free long glass fibres long filament (Mount Taishan glass) | 26 |
| Hypo-aluminum orthophosphate | 14 |
| Triphenylphosphate | 2 |
| The ethylene-methyl methacrylate methyl terpolymer | 3 |
| Carrier-free inorganic black race | 2 |
| Oxidation inhibitor 1100 | 0.6 |
| Lubricant PETS | 0.6 |
| γ-glycidyl ether oxygen propyl trimethoxy silicane | 0.3 |
[0046]Embodiment 3:
A kind of high finish surface environment friendly halogen-free fireproof PBT matrix material, its prescription is formed as shown in table 3:
Table 3 composite-material formula
| Raw material | Mass fraction |
| PBT (Nantong PBT1100, viscosity is 1.0) | 9 |
| PBT (Nantong PBT1084, viscosity is 0.84) | 39.5 |
| PET (Yizheng PETSB500, viscosity is 0.6～0.7) | 3 |
| Alkali-free long glass fibres long filament (Mount Taishan glass) | 26 |
| Hypo-aluminum orthophosphate | 14 |
| Triphenylphosphate | 2 |
| The ethylene-methyl methacrylate methyl terpolymer | 3 |
| Carrier-free inorganic black race | 2 |
| Oxidation inhibitor 1100 | 0.6 |
| Lubricant PETS | 0.6 |
| γ-glycidyl ether oxygen propyl trimethoxy silicane | 0.3 |
Embodiment 4:
A kind of high finish surface environment friendly halogen-free fireproof PBT matrix material, its prescription is formed as shown in table 4:
Table 4 composite-material formula
| Raw material | Mass fraction |
| PBT (Nantong PBT1100, viscosity is 1.0) | 9 |
| PBT (Nantong PBT1084, viscosity is 0.84) | 27.5 |
| PET (Yizheng PETSB500, viscosity is 0.6～0.7) | 15 |
| Alkali-free long glass fibres long filament (Mount Taishan glass) | 26 |
| Hypo-aluminum orthophosphate | 14 |
| Triphenylphosphate | 2 |
| The ethylene-methyl methacrylate methyl terpolymer | 3 |
| Carrier-free inorganic black race | 2 |
| Oxidation inhibitor 1100 | 0.6 |
[0054]?
| Lubricant PETS | 0.6 |
| γ-glycidyl ether oxygen propyl trimethoxy silicane | 0.3 |
Embodiment 5:
A kind of high finish surface environment friendly halogen-free fireproof PBT matrix material, its prescription is formed as shown in table 5:
Table 5 composite-material formula
| Raw material | Mass fraction |
| PBT (Nantong PBT1100, viscosity is 1.0) | 11 |
| PBT (Nantong PBT1084, viscosity is 0.84) | 34.5 |
| PET (Yizheng PETSB500, viscosity is 0.6～0.7) | 8 |
| Alkali-free long glass fibres long filament (Mount Taishan glass) | 26 |
| Hypo-aluminum orthophosphate | 14 |
| The ethylene-methyl methacrylate methyl terpolymer | 3 |
| Carrier-free inorganic black race | 2 |
| Oxidation inhibitor 1100 | 0.6 |
| Lubricant PETS | 0.6 |
| γ-glycidyl ether oxygen propyl trimethoxy silicane | 0.3 |
Embodiment 6:
A kind of high finish surface environment friendly halogen-free fireproof PBT matrix material, its prescription is formed as shown in table 5:
Table 6 composite-material formula
| Raw material | Mass fraction |
| PBT (Nantong PBT1100, viscosity is 1.0) | 11 |
| PBT (Nantong PBT1084, viscosity is 0.84) | 34.5 |
| PET (Yizheng PETSB500, viscosity is 0.6～0.7) | 8 |
| Alkali-free long glass fibres long filament (Mount Taishan glass) | 26 |
| Hypo-aluminum orthophosphate | 12 |
| Triphenylphosphate | 2 |
| The ethylene-methyl methacrylate methyl terpolymer | 3 |
| Carrier-free inorganic black race | 2 |
| Oxidation inhibitor 1100 | 0.6 |
[0063]?
| Lubricant PETS | 0.6 |
| γ-glycidyl ether oxygen propyl trimethoxy silicane | 0.3 |
Embodiment 7
The preparation method of high finish surface environment friendly halogen-free fireproof PBT matrix material may further comprise the steps:
(1) pre-treatment:
At first respectively the halogen-free flame retardants in embodiment 1～6 prescription is put into stirrer and carry out surface activation process, stand-by; Wherein, poling processing technique is as follows: 110 ℃ of temperature, 200 rev/mins of rotating speeds, time 10min;
(2) mix
Respectively PBT, PET in embodiment 1～6 prescription, toughner, high light black race are put in the stirrer and stir, add coupling agent and mix 1～2min, and then add oxidation inhibitor and lubricant, mix and stir 0.5min;
(3) melt extrude:
The material that step (2) is mixed places twin screw extruder to melt extrude, and adds glass fibre simultaneously in the forcing machine stage casing, adds the pretreated halogen-free flame retardants of step (1) in the side feeding equipment;
(4) granulation and aftertreatment:
Material tie rod after will melt extruding, air-dry through tank cooling, blower fan behind the tie rod, dicing machine pelletizing, vibratory screening apparatus filters and homogenizing jar homogenizing after pack, make high finish surface environment friendly halogen-free fireproof PBT matrix material pellet 1,2,3,4,5,6 respectively.
The processing parameter that melt extrudes in the step (3) is as follows: 210～220 ℃ of twin screw extruder one district's temperature, 220～230 ℃ of two district's temperature, 230～240 ℃ of three district's temperature, 230～240 ℃ of four district's temperature, 215～225 ℃ of five district's temperature, 215～225 ℃ of six district's temperature, 220～230 ℃ of seven district's temperature, 230～240 ℃ of eight district's temperature, 240～250 ℃ of head temperatures, 880～920 rev/mins of main-machine screw rotating speeds, 180～190 rev/mins of main feed system rotating speeds, side feed system rotating speed 4～4.5Hz.The screw slenderness ratio of described twin screw extruder is 36:1.
Above-mentioned 6 embodiment goods were placed in the bellows under 120 ℃ of temperature dry 4 hours, by the GB standard goods are injection molded into sample test then, the performance perameter of test is referring to table 7:
Table 7 performance test table
The performance perameter of table in the contrast, preferably adopt the weight percent content among the embodiment 1 as can be seen, black smoke and the toxic gas content of product reach best effect in the time of can making the over-all properties of high finish surface environment friendly halogen-free fireproof PBT matrix material and flame retardant properties, surface gloss, burning.
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. high finish surface environment friendly halogen-free fireproof PBT matrix material is made up of PBT, PET, glass fibre, halogen-free flame retardants, toughner, high light black race, oxidation inhibitor, lubricant, coupling agent, it is characterized in that each components contents is by mass percentage:
2. a kind of high finish surface environment friendly halogen-free fireproof PBT matrix material according to claim 1 is characterized in that each components contents of described matrix material is by mass percentage:
3. a kind of high finish surface environment friendly halogen-free fireproof PBT matrix material according to claim 1 is characterized in that, described PBT is that viscosity is respectively two kinds of PBT of 0.84 and 1.0 according to the mixture of the mass ratio of 20～39.5:9～23.5; Described PET viscosity is 0.6～0.7.
4. a kind of high finish surface environment friendly halogen-free fireproof PBT matrix material according to claim 1 is characterized in that described glass fibre is the alkali-free long glass fibres, and diameter is 12～13 μ m, and handle through the silane type treating compound on the surface; Described halogen-free flame retardants is one or more the mixture in melamine pyrophosphate, melamine cyanurate, triphenylphosphate and the hypo-aluminum orthophosphate; Described toughner is any among ethylene-methyl methacrylate butyl ester-glycidyl acrylate multipolymer, ethylene-methyl methacrylate methyl terpolymer and the POE-g-GMA.
5. a kind of high finish surface environment friendly halogen-free fireproof PBT matrix material according to claim 1 is characterized in that, described high light black race is carrier-free inorganic black race or organic black race; Described oxidation inhibitor is any in poly-Doutrate, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of four (β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid) and two (2,4-di-tert-butyl-phenyl) poly-Doutrate diphosphites.
6. a kind of high finish surface environment friendly halogen-free fireproof PBT matrix material according to claim 1 is characterized in that, described lubricant is in the two stearic amides (EBS) of hard acid esters (PETS), second Brace of poly-penta tetrol, silicone powder, the PE wax any.
7. a kind of high finish surface environment friendly halogen-free fireproof PBT matrix material according to claim 1 is characterized in that described coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-An Bingjisanyiyangjiguiwan.
8. the preparation method of each described a kind of high finish surface environment friendly halogen-free fireproof PBT matrix material of claim 1～7 is characterized in that, may further comprise the steps:
(1) pre-treatment:
Halogen-free flame retardants is carried out surface activation process in stirrer, poling processing technique: 110 ℃ of temperature, 200 rev/mins of rotating speeds, time 10min;
(2) mix:
PBT, PET, toughner, high light black race are put in the stirrer and stir, add coupling agent and mix 1～2min, and then add oxidation inhibitor and lubricant, mix and stir 0.5min;
(3) melt extrude:
Place twin screw extruder to melt extrude the material that mixes, add glass fibre simultaneously in the forcing machine stage casing, in the side feeding equipment, add halogen-free flame retardants;
(4) granulation and aftertreatment:
Material tie rod after will melt extruding, air-dry through tank cooling, blower fan behind the tie rod, dicing machine pelletizing, vibratory screening apparatus filters and homogenizing jar homogenizing after pack, obtain high finish surface environment friendly halogen-free fireproof PBT matrix material.
9. preparation method according to claim 8, it is characterized in that, the described processing parameter that melt extrudes is as follows: 210～220 ℃ of twin screw extruder one district's temperature, 220～230 ℃ of two district's temperature, 230～240 ℃ of three district's temperature, 230～240 ℃ of four district's temperature, 215～225 ℃ of five district's temperature, 215～225 ℃ of six district's temperature, 220～230 ℃ of seven district's temperature, 230～240 ℃ of eight district's temperature, 240～250 ℃ of head temperatures, 880～920 rev/mins of main-machine screw rotating speeds, 180～190 rev/mins of main feed system rotating speeds, side feed system rotating speed 4～4.5Hz.
10. preparation method according to claim 8 is characterized in that, the screw slenderness ratio of described twin screw extruder is 36:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310323070.6A CN103342880B (en) | 2013-07-29 | 2013-07-29 | A kind of high finish surface environment friendly halogen-free fireproof PBT composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310323070.6A CN103342880B (en) | 2013-07-29 | 2013-07-29 | A kind of high finish surface environment friendly halogen-free fireproof PBT composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103342880A true CN103342880A (en) | 2013-10-09 |
| CN103342880B CN103342880B (en) | 2016-02-03 |
Family
ID=49277711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310323070.6A Active CN103342880B (en) | 2013-07-29 | 2013-07-29 | A kind of high finish surface environment friendly halogen-free fireproof PBT composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103342880B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312108A (en) * | 2014-09-28 | 2015-01-28 | 滁州华胜新材料科技有限公司 | Preparation method of high-performance weather-resistant halogen-free flame-retardant reinforced PBT of high glow-wire |
| CN104804384A (en) * | 2015-05-14 | 2015-07-29 | 广东顺德顺炎新材料有限公司 | Halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) material having low wrappage and high mechanical performance and preparation method thereof |
| CN104861595A (en) * | 2015-06-08 | 2015-08-26 | 江苏理工学院 | Halogen-free flame-retardant PBT (polybutylene terephthalate) material and preparation method thereof |
| WO2016179770A1 (en) * | 2015-05-11 | 2016-11-17 | 深圳华力兴新材料股份有限公司 | Pbt engineering plastic composition used for nmt |
| CN107163517A (en) * | 2017-06-20 | 2017-09-15 | 中山市大亮彩塑胶新材料有限公司 | A kind of weather-proof glass fiber reinforcement PBT composite and preparation method thereof |
| CN108659264A (en) * | 2018-04-19 | 2018-10-16 | 深圳市飞荣达科技股份有限公司 | Mixed type fire retardant for modified plastics and preparation method thereof, modified plastics |
| CN113736221A (en) * | 2020-05-28 | 2021-12-03 | 中蓝晨光化工研究设计院有限公司 | Halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) modified material and preparation method thereof |
| CN116814050A (en) * | 2023-07-10 | 2023-09-29 | 广东合诚实业有限公司 | High IPT halogen-free flame retardant reinforced PBT composite material and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070885A (en) * | 2010-12-15 | 2011-05-25 | 深圳市富恒塑胶新材料有限公司 | Halogen-free flame-retardant glass fiber reinforced polyester terephthalate (PET)/poly butylenes terephthalate (PBT) alloy and preparation method thereof |
| CN103073857A (en) * | 2012-12-27 | 2013-05-01 | 宝天高科（广东）有限公司 | Halogen-free heat-proof low-smoke and flame-retardant polyester compound and preparation method thereof |
-
2013
- 2013-07-29 CN CN201310323070.6A patent/CN103342880B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070885A (en) * | 2010-12-15 | 2011-05-25 | 深圳市富恒塑胶新材料有限公司 | Halogen-free flame-retardant glass fiber reinforced polyester terephthalate (PET)/poly butylenes terephthalate (PBT) alloy and preparation method thereof |
| CN103073857A (en) * | 2012-12-27 | 2013-05-01 | 宝天高科（广东）有限公司 | Halogen-free heat-proof low-smoke and flame-retardant polyester compound and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312108A (en) * | 2014-09-28 | 2015-01-28 | 滁州华胜新材料科技有限公司 | Preparation method of high-performance weather-resistant halogen-free flame-retardant reinforced PBT of high glow-wire |
| WO2016179770A1 (en) * | 2015-05-11 | 2016-11-17 | 深圳华力兴新材料股份有限公司 | Pbt engineering plastic composition used for nmt |
| CN104804384A (en) * | 2015-05-14 | 2015-07-29 | 广东顺德顺炎新材料有限公司 | Halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) material having low wrappage and high mechanical performance and preparation method thereof |
| CN104861595A (en) * | 2015-06-08 | 2015-08-26 | 江苏理工学院 | Halogen-free flame-retardant PBT (polybutylene terephthalate) material and preparation method thereof |
| CN107163517A (en) * | 2017-06-20 | 2017-09-15 | 中山市大亮彩塑胶新材料有限公司 | A kind of weather-proof glass fiber reinforcement PBT composite and preparation method thereof |
| CN108659264A (en) * | 2018-04-19 | 2018-10-16 | 深圳市飞荣达科技股份有限公司 | Mixed type fire retardant for modified plastics and preparation method thereof, modified plastics |
| CN113736221A (en) * | 2020-05-28 | 2021-12-03 | 中蓝晨光化工研究设计院有限公司 | Halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) modified material and preparation method thereof |
| CN116814050A (en) * | 2023-07-10 | 2023-09-29 | 广东合诚实业有限公司 | High IPT halogen-free flame retardant reinforced PBT composite material and its preparation method and application |
| CN116814050B (en) * | 2023-07-10 | 2025-01-17 | 广东合诚实业有限公司 | High-IPT halogen-free flame-retardant reinforced PBT composite material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103342880B (en) | 2016-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103342880B (en) | A kind of high finish surface environment friendly halogen-free fireproof PBT composite and preparation method thereof | |
| CN102250450B (en) | Flame-retardant polyester material with high glow wire ignition temperature and preparation method thereof | |
| CN102850661B (en) | Halogen-free flame-retardant PP/polyester alloy and preparation method thereof | |
| CN101717560B (en) | Halogen-free antiflaming polyester molding composition and preparation method thereof | |
| CN103435887B (en) | A kind of high workability halide-free fireproof composite polyolefine material and preparation method thereof | |
| CN101659779B (en) | Halogen-free flame-retardant ABS resin and preparation method thereof | |
| CN101343392B (en) | Halogen-free flame-proof reinforced polypropylene composite material and preparation thereof | |
| CN104231575B (en) | Halogen-free and phosphorus-free PBT enhanced composite material and preparation method thereof | |
| CN104177791B (en) | A kind of halogen-free intumescent flame-retardant PBT and preparation method thereof | |
| CN103087518B (en) | Glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material and preparation method thereof | |
| CN103951959A (en) | Intumescent flame-retardant reinforced PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy and preparation method thereof | |
| CN101747616A (en) | Modified polyphenyl ether material and preparation method thereof | |
| CN102775744B (en) | Environment-friendly polybutylece terephthalate (PBT) engineering plastic and preparation method thereof | |
| CN102532826A (en) | Low-cost flame-retardant fiberglass-reinforced PBT (Polybutylene Terephthalate) engineering plastic and preparation method thereof | |
| CN102492272A (en) | Halogen-free flame retardant polybutylece terephthalate (PBT) material and preparation method | |
| CN104479353A (en) | Novel halogen-free flame-retardant composition, halogen-free flame-retardant PBT engineering plastic composite material and preparation method thereof | |
| CN103333469A (en) | Halogen-free flame-retardant PET (polyethylene terephthalate) composite material and preparation method thereof | |
| CN102504412B (en) | Low-smoke halogen-free flame-retarding polypropylene cable material and preparation method thereof | |
| CN109535666A (en) | Inexpensive, high CTI, high GWIT fire-retardant reinforced PBT composite material and preparation method thereof | |
| CN103160080A (en) | A halogen free flame retardant long glass fiber reinforced PBT composite material and a preparation method thereof | |
| CN105061896A (en) | Halogen-free flame-retardant LGFPP (long glass fiber reinforced polypropylene) material and preparation method thereof | |
| CN102040810A (en) | Polybutylece terephthalate (PBT) engineering plastics as well as preparation method and application thereof | |
| CN114806110B (en) | Low-smoke, high-GWIT and high-CTI flame-retardant reinforced material and preparation method thereof | |
| CN104403293B (en) | A kind of transparent halogen-free flameproof polycarbonate resin and preparation method thereof | |
| CN101768341A (en) | Polybutylene terephthalate halogen-free flame-retardant composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Zhaopeng Inventor after: Xiao Xiongwei Inventor after: Yao Daai Inventor after: Yang Zijiang Inventor after: Lei Jian Inventor after: Lin Sixin Inventor before: Zhang Zhaopeng Inventor before: Lin Sixin Inventor before: Yao Daai Inventor before: Yang Zijiang Inventor before: Liao Qianming Inventor before: Zheng Chongshen Inventor before: Zhang Haiyong Inventor before: Chen Jiwu Inventor before: Chen Yue Inventor before: Huang Qiang |
|
| COR | Change of bibliographic data | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 5 road 528325 Guangdong city Foshan province wheat village Shunde District Xingtan town seven Kau Industrial Zone No. 2 Patentee after: GUANGDONG SHUNDE SHUNYAN NEW MATERIAL CO., LTD. Address before: 5 road 528325 Guangdong city Foshan province wheat village Shunde District Xingtan town seven Kau Industrial Zone No. 2 Patentee before: Guangdong Shunde New Materials Co., Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Environment friendly halogen free flame retardant PBT composite with high gloss surface and its preparation method Effective date of registration: 20201222 Granted publication date: 20160203 Pledgee: Shunde Guangdong rural commercial bank Limited by Share Ltd. Daliang branch Pledgor: GUANGDONG SHUNDE SHUNYAN NEW MATERIAL Co.,Ltd. Registration number: Y2020980009785 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20211215 Granted publication date: 20160203 Pledgee: Shunde Guangdong rural commercial bank Limited by Share Ltd. Daliang branch Pledgor: GUANGDONG SHUNDE SHUNYAN NEW MATERIAL Co.,Ltd. Registration number: Y2020980009785 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The invention relates to a high gloss surface environment-friendly halogen-free flame retardant PBT composite and a preparation method thereof Effective date of registration: 20211217 Granted publication date: 20160203 Pledgee: Guangdong Shunde Rural Commercial Bank Co.,Ltd. science and technology innovation sub branch Pledgor: GUANGDONG SHUNDE SHUNYAN NEW MATERIAL Co.,Ltd. Registration number: Y2021980015381 |