CN103951953A - PC/PBT composition and preparation method thereof - Google Patents
PC/PBT composition and preparation method thereof Download PDFInfo
- Publication number
- CN103951953A CN103951953A CN201410198204.0A CN201410198204A CN103951953A CN 103951953 A CN103951953 A CN 103951953A CN 201410198204 A CN201410198204 A CN 201410198204A CN 103951953 A CN103951953 A CN 103951953A
- Authority
- CN
- China
- Prior art keywords
- district
- temperature
- pbt
- pbt composition
- polycarbonate
- 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
- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a PC/PBT composition and a preparation method thereof. The PC/PBT composition is prepared from the following raw materials in parts by weight: 60-90 parts of PC, 10-40 parts of PBT, 0.1-3 parts of toluene diisocynate, 0.1-3 parts of 2,2'-(1,3-phenylene)-bisoxazoline, 0.1-3 parts of an ester exchange inhibitor, 0.1-2 parts of an anti-dripping agent, 0.1-1 part of a hindered phenol antioxidant, 0.1-1 part of a phosphite ester antioxidant and 0.1-1 part of a lubricating agent. By adopting an in situ reaction capacity increasing method, the PC/PBT composition with good mechanical properties, high fire resistance and good chemical resistance and processability is obtained, and the obtained PC/PBT composition can be applied to a vehicle bumper, a vehicle body plate, plates of other appliances and the like.
Description
Technical field
The present invention relates to Material Field, particularly relate to a kind of PC/PBT composition and method of making the same.
Background technology
The develop rapidly of China in Recent Years industry, constantly expands the application surface of polycarbonate (PC), and its demand also constantly increases.But along with science and technology progress with rapid changepl. never-ending changes and improvements, the continuous renewal of Industrial products is regenerated, requirement to material property is more and more harsh, the polycarbonate of conventional model can not meet all types of requirements of product in product performance, and PC exists that melt viscosity is large, poor fluidity, high temperature facile hydrolysis, poor solvent resistance, susceptibility to breach is high, easily there is swelling and stress cracking, and the shortcomings such as frictional coefficient is large, higher, the special trade mark price of melt temperature height, thereby directly affect its further deeply application and popularization.
Polybutylene terephthalate (PBT) is crystal type thermoplastic resin, and crystallization rate is fast, can be at lower temperature crystallization rapidly, be conducive to forming process.The creep resistance excellence of PBT, mechanical property is subject to the impact of temperature less, and excellent size stability under high temperature can be used for the stressed structure product of high temperature.PBT belongs to esters polymer, and oil-proofness is good, stable to alcohols, ethers, high-molecular weight ester class, aliphatic hydrocarbon etc., and organic solvent is had to very strong stress cracking resistance, and processability is good, can processing thin-walled accurate product, and product surface also has good gloss.
By PC and PBT blend, can obviously improve PC mobility, improve its processing characteristics, stress crack resistance performance and chemical resistance, and reduce costs,, easily there is man-hour such as buckling deformation etc. as added in the deficiency also can improve PBT and use separately time simultaneously.PC/PBT blend has good solvent resistance, wear resistance, dimensional stability and stress cracking resistance, and processing characteristics is better, heat-drawn wire is high, can be used for the plate of bumper, car body panel and other various apparatuses etc.
Because two kinds of component crystal properties in PC/PBT co-mixing system exist greatest differences, compatibility performance is not good enough, has affected performance and the application of co-mixing system.Although some performance of alloy that adopts simple blend method to prepare improves, but because two-phase interface adhesiveproperties is bad, can cause unstable properties, some performance also can decline, in PC/PBT co-mixing system, add the 3rd component expanding material, can further improve the performance of blend, obtain the alloy material having compared with stability.At present, in prior art, the modification of PC is done to some researchs, for example patent CN200610053336.X discloses low temperature resistant PC/PBT polyblend, and it is to carry out toughness reinforcing increase-volume by least one in acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile ethylene styrene copolymer, acrylic polymer, Methacrylate-butadiene-styrene, ethylene-acrylate copolymer, ethylene-propylene acid glycidyl ester; Patent CN200810241524.4 discloses a kind of PC/PBT Alloy And Preparation Method, and its toughness reinforcing compatilizer is MBS (MBS); Patent CN201210292334.1 discloses a kind of low gloss PC/PBT alloy material and preparation method thereof, its main toughner is ethylene-methyl methacrylate butyl ester-glycidyl acrylate multipolymer, the MBS structure impact modifier that auxiliary toughner is nucleocapsid structure; Patent CN201310039143.9 discloses PC, PBT hybrid alloys and preparation method thereof, and its toughness reinforcing compatilizer comprises one or both of following component: ethylene-propylene acid butyl ester-methyl propenoic acid glycidyl alcohol ester, MBS; Patent CN201310297992.4 discloses anti-aging PC/PBT polyblend, and its compatilizer is EBA-GMA, PP-g-MA, PP-g-AA, EAA, PS-g-PMMA, PS-g-MAH, PP-g-PA6, PS-b-PMMA, PS-b-PBA, PE-g-ST, PP-g-ST, ABS-g-MAH, PP-g-MAH, EVA, SEBS, SEBS-g-MAH or PE-g-MAH; Patent CN201310252577.7 discloses halogen-free flame retardant PC/PBT matrix material, and its toughness reinforcing compatilizer is maleic anhydride graft POE; Patent CN201310674229.9 discloses a kind of PC/PBT alloy material and preparation method thereof, and its toughner A is at least one in MBS, ethylene-methyl acrylate multipolymer, ethylene-acrylate-glycidyl methacrylate copolymer; Toughner B is at least one in Low Density Polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer.
The most two step methods that adopt of preparation method of the PC/PBT blend of prior art, its essence is that first first preparation is containing the compatilizer of polar functional group, as: EBA-GMA, EMA-g-GMA, ethylene-propylene acid glycidyl ester etc.Then, then by PC, PBT, carry out blending extrusion containing compatilizer and the toughner of polar functional group, thereby reach the object of toughness reinforcing increase-volume.
Summary of the invention
The deficiency existing for prior art, the object of the invention is to utilize the method for in situ reactive compatibilization to prepare to have that mechanical property is good, flame retardant resistance is high, the PC/PBT composition of chemical resistant properties and good processability, can be applicable to the plate of bumper, car body panel and other various apparatuses etc.
The following scheme of the concrete employing of the present invention:
A kind of PC/PBT composition, is prepared from by the raw material of following weight part:
The number-average molecular weight of described polycarbonate is 15000～30000;
Described ester exchange inhibitor is at least one in triphenyl phosphite (TPPi), triphenylphosphate (TPP), organophosphorus ester;
Described anti-dripping agent is fluoropolymer;
Described Hinered phenols antioxidant is the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid;
Described phosphite ester kind antioxidant is tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
In some embodiment, PC/PBT composition, is prepared from by the raw material of following weight part therein:
In some embodiment, PC/PBT composition, is prepared from by the raw material of following weight part therein:
In some embodiment, described polycarbonate is dihydroxyphenyl propane aromatic copolycarbonate therein, and number-average molecular weight is 18000～27000; The limiting viscosity of described polybutylene terephthalate is 0.62dL/g～0.92dL/g.
In some embodiment, described anti-dripping agent is tetrafluoroethylene therein; Described lubricant is pentaerythritol stearate.
Another object of the present invention is to provide the preparation method of PC/PBT composition.
The preparation method of above-mentioned PC/PBT composition, concrete technical scheme, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 100～120 DEG C, dry 4～12 hours, polybutylene terephthalate (PBT) is placed in 80～100 DEG C, dry 4～12 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), ester exchange inhibitor, anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230～250 DEG C, two district's temperature: 230～250 DEG C, three district's temperature are 240～260 DEG C, four district's temperature: 240～260 DEG C, five district's temperature are 240～260 DEG C, six district's temperature: 240～260 DEG C, die head temperature: 230～250 DEG C, driving screw rotating speed is: 100～400rpm.
In some embodiment, in described step (1), polycarbonate is placed in 110 DEG C therein, and dry 4～6 hours, polybutylene terephthalate was placed in 90 DEG C, dry 4～6 hours; Processing parameter in described step (3) is: district's temperature is 230～240 DEG C, two district's temperature: 235～245 DEG C, three district's temperature are 245～255 DEG C, four district's temperature: 245～255 DEG C, five district's temperature are 245～255 DEG C, six district's temperature: 245～255 DEG C, die head temperature: 235～245 DEG C, driving screw rotating speed is: 150～250rpm.
In some embodiment, the screw rod of described parallel double-screw extruder is shaped as single thread therein; The ratio L/D of spiro rod length L and diameter D is 35～60; Described screw rod is provided with 1 above gear block district and 1 above left-hand thread district.
In some embodiment, the ratio L/D of described spiro rod length L and diameter D is 40～55 therein; Described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Principle of the present invention is as follows:
In situ reactive compatibilization is a kind of brand-new polymer alloy method of modifying getting up along with the development of increasing reaction and in-situ polymerization technology in recent years, be characterized in: the generation of expanding material and blend are carried out simultaneously, in melt blending process, react at two-phase interface place and generate random, grafting or segmented copolymer, thereby realize " on the spot " increase-volume.
The present invention adds tolylene diisocyanate (TDI) and 2 in PC/PBT composition, 2'-(1,3-phenylene)-bisoxazoline (PBO), make said composition that In Situ Compatibilization reaction occur in parallel double-screw extruder, in extrusion, produce on the spot compatilizer, should react with these two kinds of superpolymer respectively containing the monomer of double reactive functional group, form the compatilizer of superpolymer-co-containing monomer-co-superpolymer of double reactive functional group.Thereby reach the object that improves PC/PBT Miscibility, obtain have that mechanical property is good, flame retardant resistance is high, the PC/PBT composition of chemical resistant properties and good processability, use the method to belong at present contriver at home and abroad pioneering.
The present invention adopts the method for in situ reactive compatibilization, in parallel double-screw extruder, the terminal hydroxy group of polycarbonate can be respectively and the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, the terminal hydroxy group of polybutylene terephthalate, end carboxyl can be respectively and the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, form compatilizer PC-co-TDI-co-PBT, compatilizer PC-co-PBO-co-PBT, thereby improve the consistency of PC/PBT system, obtain having mechanical property good, flame retardant resistance is high, the PC/PBT composition of chemical resistant properties and good processability.
The method of PC/PBT composition provided by the present invention has the following advantages:
1, PC/PBT composition of the present invention, the advantage such as it has, and mechanical property is good, flame retardant resistance is high, chemical resistant properties and good processability, can be applicable to the plate of bumper, car body panel and other various apparatuses etc.
2, the preparation method that the present invention adopts belongs to single stage method (In Situ Compatibilization reaction), its two step method compared to prior art has and has reduced operation, shorten flow process, reduced cost, improved the advantage of productivity, its technique is simple, be easy to control, not high to equipment requirements, the equipment using is general polymer processing equipment, invests not high.
Brief description of the drawings
Figure 1 shows that preparation technology's schema of PC/PBT composition of the present invention.
Embodiment
For further understanding feature of the present invention, technique means and the specific purposes that reach, function, resolve the advantages and spirit of the present invention, by following examples, the present invention is further elaborated.
In situ Reactive Compatibility of the present invention is prepared the reaction mechanism following (preparation technology's schema is asked for an interview Fig. 1) of PC/PBT composition:
Reaction mechanism
From upper reaction formula, the terminal hydroxy group of polycarbonate can be respectively and the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, the terminal hydroxy group of polybutylene terephthalate, end carboxyl can be respectively and the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, form compatilizer PC-co-TDI-co-PBT, compatilizer PC-co-PBO-co-PBT, thereby improve the consistency of PC/PBT system, obtain having mechanical property good, flame retardant resistance is high, the PC/PBT composition of chemical resistant properties and good processability.
The raw material that the embodiment of the present invention is used is as follows:
Polycarbonate, is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Dow Chemical company, and number-average molecular weight is 15000;
Polycarbonate, is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Japanese Supreme Being people and changes into company, and number-average molecular weight is 23000;
Polycarbonate, is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Korea S three and supports company, and number-average molecular weight is 30000;
Polycarbonate, is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Korea S three and supports company, and number-average molecular weight is 50000;
Polybutylene terephthalate, is selected from Yizheng Chemical Fibre Co., Ltd., limiting viscosity 0.62dL/g;
Polybutylene terephthalate, is selected from Yizheng Chemical Fibre Co., Ltd., limiting viscosity 0.76dL/g;
Polybutylene terephthalate, is selected from Xingchen Synthetic Matrials Co., Ltd., Nantong, limiting viscosity 0.85dL/g;
Polybutylene terephthalate, is selected from Xingchen Synthetic Matrials Co., Ltd., Nantong, limiting viscosity 0.92dL/g;
Tolylene diisocyanate, is selected from Shanghai Sheng Yu Chemical Co., Ltd.;
2,2'-(1,3-phenylene)-bisoxazoline, is selected from colon, Nanjing medication chemistry company limited;
Triphenyl phosphite, is selected from the purple chemical reagent work in Shanghai;
Triphenylphosphate, is selected from Zhangjiagang Ya Rui Chemical Co., Ltd.;
Anti-dripping agent (tetrafluoroethylene), trade mark TF-1645, Minnesota ,USA mines and production company (3M);
β-(4-hydroxy phenyl-3,5-di-t-butyl) positive octadecanol ester of propionic acid (antioxidant 1076), as primary antioxidant, is selected from Switzerland's vapour Bagong department;
Tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (irgasfos 168), as auxiliary antioxidant, is selected from Switzerland's vapour Bagong department;
Pentaerythritol stearate, is selected from Clariant company of the U.S..
Comparative example 1:
A kind of In situ Reactive Compatibility of this comparative example is prepared PC/PBT composition, is prepared from by following raw material:
70 parts of polycarbonate (PC, number-average molecular weight is 23000),
30 parts of polybutylene terephthalates (PBT, limiting viscosity 0.85dL/g),
Polycarbonate (PC) is 100 parts with the weight part summation of polybutylene terephthalate (PBT),
The preparation method of above-mentioned PC/PBT composition, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 110 DEG C, dry 4 hours, polybutylene terephthalate (PBT) was placed in 90 DEG C, dry 4 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), ester exchange inhibitor triphenyl phosphite (TPPi) join in another homogenizer and mix with triphenylphosphate (TPP), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 235 DEG C, two district's temperature: 245 DEG C, three district's temperature are 250 DEG C, four district's temperature: 250 DEG C, five district's temperature are 250 DEG C, six district's temperature: 250 DEG C, die head temperature: 245 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as double thread, and the ratio L/D of spiro rod length L and diameter D is 20, and described screw rod is provided with 1 gear block district, without left-hand thread district.
Comparative example 2:
A kind of In situ Reactive Compatibility of this comparative example is prepared PC/PBT composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PBT composition, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 110 DEG C, dry 4 hours, polybutylene terephthalate (PBT) was placed in 90 DEG C, dry 4 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) ester exchange inhibitor triphenyl phosphite (TPPi) is joined in another homogenizer and mixed with triphenylphosphate (TPP), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 235 DEG C, two district's temperature: 245 DEG C, three district's temperature are 250 DEG C, four district's temperature: 250 DEG C, five district's temperature are 250 DEG C, six district's temperature: 250 DEG C, die head temperature: 245 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Comparative example 3:
A kind of In situ Reactive Compatibility of this comparative example is prepared PC/PBT composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PBT composition, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 110 DEG C, dry 4 hours, polybutylene terephthalate (PBT) was placed in 90 DEG C, dry 4 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), ester exchange inhibitor triphenyl phosphite (TPPi) join in another homogenizer and mix with triphenylphosphate (TPP), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 235 DEG C, two district's temperature: 245 DEG C, three district's temperature are 250 DEG C, four district's temperature: 250 DEG C, five district's temperature are 250 DEG C, six district's temperature: 250 DEG C, die head temperature: 245 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 1:
A kind of In situ Reactive Compatibility of the present embodiment is prepared PC/PBT composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PBT composition, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 110 DEG C, dry 4 hours, polybutylene terephthalate (PBT) was placed in 90 DEG C, dry 4 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), ester exchange inhibitor triphenylphosphate (TPP), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 240 DEG C, two district's temperature: 245 DEG C, three district's temperature are 255 DEG C, four district's temperature: 255 DEG C, five district's temperature are 255 DEG C, six district's temperature: 255 DEG C, die head temperature: 245 DEG C, driving screw rotating speed is: 400rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 60, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 2:
A kind of In situ Reactive Compatibility of the present embodiment is prepared PC/PBT composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PBT composition, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 110 DEG C, dry 4 hours, polybutylene terephthalate (PBT) was placed in 90 DEG C, dry 4 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), ester exchange inhibitor triphenylphosphate (TPP), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 235 DEG C, three district's temperature are 245 DEG C, four district's temperature: 245 DEG C, five district's temperature are 245 DEG C, six district's temperature: 245 DEG C, die head temperature: 235 DEG C, driving screw rotating speed is: 100rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 35, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 3:
A kind of In situ Reactive Compatibility of the present embodiment is prepared PC/PBT composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PBT composition, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 110 DEG C, dry 4 hours, polybutylene terephthalate (PBT) was placed in 90 DEG C, dry 4 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), ester exchange inhibitor triphenyl phosphite (TPPi), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 245 DEG C, three district's temperature are 245 DEG C, four district's temperature: 255 DEG C, five district's temperature are 250 DEG C, six district's temperature: 250 DEG C, die head temperature: 245 DEG C, driving screw rotating speed is: 150rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 40, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 4:
A kind of In situ Reactive Compatibility of the present embodiment is prepared PC/PBT composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PBT composition, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 110 DEG C, dry 4 hours, polybutylene terephthalate (PBT) was placed in 90 DEG C, dry 4 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), ester exchange inhibitor triphenyl phosphite (TPPi) join in another homogenizer and mix with triphenylphosphate (TPP), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 235 DEG C, two district's temperature: 245 DEG C, three district's temperature are 250 DEG C, four district's temperature: 250 DEG C, five district's temperature are 250 DEG C, six district's temperature: 250 DEG C, die head temperature: 245 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 5:
A kind of In situ Reactive Compatibility of the present embodiment is prepared PC/PBT composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PBT composition, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 110 DEG C, dry 4 hours, polybutylene terephthalate (PBT) was placed in 90 DEG C, dry 4 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), ester exchange inhibitor triphenylphosphate (TPP), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 240 DEG C, two district's temperature: 245 DEG C, three district's temperature are 255 DEG C, four district's temperature: 255 DEG C, five district's temperature are 250 DEG C, six district's temperature: 250 DEG C, die head temperature: 245 DEG C, driving screw rotating speed is: 250rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 45, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 6:
A kind of In situ Reactive Compatibility of the present embodiment is prepared PC/PBT composition, is prepared from by following raw material:
The preparation method of above-mentioned PC/PBT composition, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 110 DEG C, dry 4 hours, polybutylene terephthalate (PBT) was placed in 90 DEG C, dry 4 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), ester exchange inhibitor triphenyl phosphite (TPPi) join in another homogenizer and mix with triphenylphosphate (TPP), anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 235 DEG C, two district's temperature: 245 DEG C, three district's temperature are 250 DEG C, four district's temperature: 250 DEG C, five district's temperature are 250 DEG C, six district's temperature: 250 DEG C, die head temperature: 245 DEG C, driving screw rotating speed is: 250rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 55, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Be below comparative example and embodiment table look-up:
Table 1 comparative example and embodiment raw material composition weight part table look-up
Anti-dripping agent, primary antioxidant, auxiliary antioxidant and the lubricant of above comparative example and embodiment is respectively 0.3 part, 0.1 part, 0.1 part, 0.1 part.
Above-mentioned comparative example and the made sample of embodiment are carried out to following performance test:
Tensile property: press GB/T1042-1992 standard testing, rate of extension 50mm/min;
Impact property: press GB/T1843-1996 standard testing, batten thickness is 3.2mm;
Flame retardant resistance: the XZT-100A oxygen index measurer test oxygen index that the batten of 130mm × 6.5mm × 3.0mm is produced with Chengde great Hua trier company limited.
Chemical resistant properties: tensile bars is put into after Glacial acetic acid 3min, tested its elongation at break.The elongation at break of Glacial acetic acid tensile bars after treatment is not with larger by the ratio of the elongation at break of the tensile bars of Glacial acetic acid processing, and its chemical resistant properties is better.
Melting index: press ASTM D1238 test, 250 DEG C of probe temperatures, load 5kg.
Table 2 comparative example and embodiment performance table look-up
Comparative example 1 is for screw rod is shaped as double thread, and the ratio L/D of spiro rod length L and diameter D is 20, and screw rod is provided with 1 gear block district, the PC/PBT composition preparing without the twin screw extruder in left-hand thread district; Embodiment 4 is for screw rod is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and screw rod is provided with the PC/PBT composition that the twin screw extruder in 2 gear block districts and 2 left-hand thread districts prepares.Can find out by contrast, adopt screw rod of the present invention to be shaped as single thread, the ratio L/D of spiro rod length L and diameter D is 50, when screw rod is provided with 2 gear block districts and 2 left-hand thread districts, tensile strength, notched Izod impact strength, oxygen index, chemical resistant properties and the melting index of PC/PBT composition are greatly improved, and obtain that mechanical property is good, flame retardant resistance is high, the beneficial effect of the PC/PBT composition of chemical resistant properties and good processability.
Comparative example 2 is not for adding the PC/PBT composition containing the monomer of double reactive functional group; Embodiment 4 is for adding tolylene diisocyanate (TDI), 2, the PC/PBT composition of 2'-(1,3-phenylene)-bisoxazoline (PBO).Can find out by contrast, add containing tensile strength, notched Izod impact strength, oxygen index, chemical resistant properties and the melting index of the PC/PBT composition of the monomer of double reactive functional group and be better than and do not add containing the PC/PBT composition of the monomer of double reactive functional group.
The PC/PBT composition that the number-average molecular weight that comparative example 3 is polycarbonate is 50000; The PC/PBT composition that the number-average molecular weight that embodiment 4 is polycarbonate is 23000.Can find out by contrast, the number-average molecular weight of polycarbonate is that tensile strength, notched Izod impact strength, oxygen index and the chemical resistant properties outline of 50000 PC/PBT composition is better than PC/PBT composition that the number-average molecular weight of polycarbonate is 23000, and the melting index of the PC/PBT composition that the number-average molecular weight of polycarbonate is 50000 only has 5g/10min, its processing characteristics is poor.
Embodiment 1～6 is for adjusting the weight part of PC and PBT, and as can be seen from Table 2, along with the addition of PBT increases, the tensile strength of PC/PBT composition and notched Izod impact strength present the variation tendency of minimizing; The chemical resistant properties of PC/PBT composition and melting index present the variation tendency of increase.Can find out by embodiment 1 and embodiment 2 contrasts, ester exchange inhibitor not only can suppress the transesterification reaction between PC and PBT, but also can improve the oxygen index of PC/PBT composition.Wherein, over-all properties the best of embodiment 4.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a PC/PBT composition, is characterized in that, is prepared from by the raw material of following weight part:
The number-average molecular weight of described polycarbonate is 15000～30000;
Described ester exchange inhibitor is at least one in triphenyl phosphite, triphenylphosphate, organophosphorus ester;
Described anti-dripping agent is fluoropolymer;
Described Hinered phenols antioxidant is the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid;
Described phosphite ester kind antioxidant is tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
2. PC/PBT composition according to claim 1, is characterized in that, is prepared from by the raw material of following weight part:
3. PC/PBT composition according to claim 1, is characterized in that, is prepared from by the raw material of following weight part:
4. according to the PC/PBT composition described in claim 1～3 any one, it is characterized in that, described polycarbonate is dihydroxyphenyl propane aromatic copolycarbonate, and number-average molecular weight is 18000～27000; The limiting viscosity of described polybutylene terephthalate is 0.62dL/g～0.92dL/g.
5. according to the PC/PBT composition described in claim 1～3 any one, it is characterized in that, described anti-dripping agent is tetrafluoroethylene; Described lubricant is pentaerythritol stearate.
6. a preparation method for the PC/PBT composition described in claim 1～5 any one, is characterized in that, comprises the following steps:
(1) described polycarbonate is placed in to 100～120 DEG C, dry 4～12 hours, polybutylene terephthalate was placed in 80～100 DEG C, dry 4～12 hours, after cooling, polycarbonate and polybutylene terephthalate are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate, 2,2'-(1,3-phenylene)-bisoxazoline, ester exchange inhibitor, anti-dripping agent, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230～250 DEG C, two district's temperature: 230～250 DEG C, three district's temperature are 240～260 DEG C, four district's temperature: 240～260 DEG C, five district's temperature are 240～260 DEG C, six district's temperature: 240～260 DEG C, die head temperature: 230～250 DEG C, driving screw rotating speed is: 100～400rpm.
7. preparation method according to claim 6, is characterized in that, in described step (1), polycarbonate is placed in 110 DEG C, and dry 4～6 hours, polybutylene terephthalate was placed in 90 DEG C, dry 4～6 hours; Processing parameter in described step (3) is: district's temperature is 230～240 DEG C, two district's temperature: 235～245 DEG C, three district's temperature are 245～255 DEG C, four district's temperature: 245～255 DEG C, five district's temperature are 245～255 DEG C, six district's temperature: 245～255 DEG C, die head temperature: 235～245 DEG C, driving screw rotating speed is: 150～250rpm.
8. preparation method according to claim 6, is characterized in that, the screw rod of described parallel double-screw extruder is shaped as single thread; The ratio L/D of spiro rod length L and diameter D is 35～60; Described screw rod is provided with 1 above gear block district and 1 above left-hand thread district.
9. preparation method according to claim 6, is characterized in that, the ratio L/D of described spiro rod length L and diameter D is 40～55; Described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198204.0A CN103951953B (en) | 2014-05-12 | 2014-05-12 | PC/PBT composition and method of making the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410198204.0A CN103951953B (en) | 2014-05-12 | 2014-05-12 | PC/PBT composition and method of making the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951953A true CN103951953A (en) | 2014-07-30 |
| CN103951953B CN103951953B (en) | 2016-06-08 |
Family
ID=51329319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410198204.0A Active CN103951953B (en) | 2014-05-12 | 2014-05-12 | PC/PBT composition and method of making the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103951953B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530681A (en) * | 2014-12-26 | 2015-04-22 | 上海普利特复合材料股份有限公司 | High-performance ultraviolet-resistant PC/PBT composite material and preparation method thereof |
| CN104559105A (en) * | 2014-12-09 | 2015-04-29 | 惠州市昌亿科技股份有限公司 | Low-shrinkage high-strength PBT/PC (polybutylene terephthalate/polycarbonate) alloy material for 3D printing, and preparation method and application thereof |
| WO2016106837A1 (en) * | 2014-12-31 | 2016-07-07 | 上海锦湖日丽塑料有限公司 | Reactive thermoplastic resin composition and manufacturing method thereof |
| CN108504068A (en) * | 2018-04-25 | 2018-09-07 | 横店集团得邦工程塑料有限公司 | A kind of high endurance fire retardation PC/PBT alloy material and preparation method thereof |
| CN113088005A (en) * | 2021-04-16 | 2021-07-09 | 贵州凯科特材料有限公司 | High-performance composite material for automobile |
| CN114106547A (en) * | 2021-11-29 | 2022-03-01 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367992A (en) * | 2008-09-25 | 2009-02-18 | 上海交通大学 | Method of manufacturing polycarbonate/polyester alloy |
| CN101798457A (en) * | 2010-01-20 | 2010-08-11 | 华东理工大学 | Production method of super-toughness engineering plastic of nylon 6/ polycarbonate/ elastomer/ HDI |
-
2014
- 2014-05-12 CN CN201410198204.0A patent/CN103951953B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367992A (en) * | 2008-09-25 | 2009-02-18 | 上海交通大学 | Method of manufacturing polycarbonate/polyester alloy |
| CN101798457A (en) * | 2010-01-20 | 2010-08-11 | 华东理工大学 | Production method of super-toughness engineering plastic of nylon 6/ polycarbonate/ elastomer/ HDI |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559105A (en) * | 2014-12-09 | 2015-04-29 | 惠州市昌亿科技股份有限公司 | Low-shrinkage high-strength PBT/PC (polybutylene terephthalate/polycarbonate) alloy material for 3D printing, and preparation method and application thereof |
| CN104530681A (en) * | 2014-12-26 | 2015-04-22 | 上海普利特复合材料股份有限公司 | High-performance ultraviolet-resistant PC/PBT composite material and preparation method thereof |
| WO2016106837A1 (en) * | 2014-12-31 | 2016-07-07 | 上海锦湖日丽塑料有限公司 | Reactive thermoplastic resin composition and manufacturing method thereof |
| CN108504068A (en) * | 2018-04-25 | 2018-09-07 | 横店集团得邦工程塑料有限公司 | A kind of high endurance fire retardation PC/PBT alloy material and preparation method thereof |
| CN108504068B (en) * | 2018-04-25 | 2020-06-23 | 横店集团得邦工程塑料有限公司 | High-fatigue-resistance flame-retardant PC/PBT alloy material and preparation method thereof |
| CN113088005A (en) * | 2021-04-16 | 2021-07-09 | 贵州凯科特材料有限公司 | High-performance composite material for automobile |
| CN114106547A (en) * | 2021-11-29 | 2022-03-01 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
| CN114106547B (en) * | 2021-11-29 | 2024-02-23 | 金发科技股份有限公司 | Polycarbonate composition and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103951953B (en) | 2016-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103951953A (en) | PC/PBT composition and preparation method thereof | |
| CN103013060B (en) | Polyethylene toughening thermoplastic polyester composite material and preparation method thereof | |
| Yang et al. | Polyoxymethylene/ethylene butylacrylate copolymer/ethylene‐methyl acrylate‐glycidyl methacrylate ternary blends | |
| CN101508818A (en) | ABS//PET alloy and method for producing the same | |
| CN101143962A (en) | Biodegradable resin composition for modifying toughness and heat resistance and preparation method thereof | |
| CN107446244B (en) | A kind of rose crystal type nano calcium carbonate various dimensions enhancing MPP cable protection pipe material and preparation method thereof | |
| CN102807746B (en) | High-hardness and high-flowability PC/PMMA/AS (polycarbonate/polymethyl methacrylate/acrylonitrile-styrene copolymer) alloy and preparation method thereof | |
| CN101029168A (en) | PC/ABS alloy and its production | |
| CN1887959A (en) | Process of preparing engineering plastics with recovered polyethylene terephthalate | |
| CN103205104A (en) | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane) hybridized polylactic acid/polycarbonate alloy | |
| CN101875768B (en) | Antiaging glass fiber-reinforced polycarbonate composition and preparation method thereof | |
| CN102898798A (en) | Transparent polylactic acid alloy material | |
| CN103937192B (en) | PC/PA11 composition and method of making the same | |
| CN101440182A (en) | Method for producing high quality dynamic vulcanization thermoplastic elastomer | |
| CN104086896A (en) | Low-shrinkage high-weatherproofness polypropylene composite material for shell of electric tool | |
| CN103183935B (en) | High-ductility PBT/PC (polybutylece terephthalate/polycarbonate) alloy and preparation method thereof | |
| CN113956643B (en) | Chemical-resistant scratch-resistant high-hardness PCPBT (Poly-p-phenylene terephthamide) composite material and preparation method thereof | |
| CN103951954A (en) | PC (Polycarbonate)/PET (Polyethylene Terephthalate) composition and preparation method thereof | |
| CN103951955B (en) | PC/PA6 composition and method of making the same | |
| CN103772952B (en) | A kind of preparation method of multi-inlay section thermal plastic copolyesters modified polycarbonate alloy | |
| CN105802117B (en) | Modified ABS new energy battery cell case proprietary material and preparation method thereof | |
| CN103937194B (en) | PC/PA66 composition and method of making the same | |
| CN102942736A (en) | High-glass fiber content reinforced polypropylene material and preparation method thereof | |
| CN109912943A (en) | A kind of the high-impact copolyester alloy modified material and preparation method of case board | |
| CN1605600A (en) | High efficiency polycarbonate / ABS composition and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhu Huaicai Inventor after: Wang Zhongqiang Inventor after: Xiong Hui Inventor after: Hong Shuobo Inventor after: Zhong Yiwen Inventor after: Xu Huanjie Inventor after: Zhu Zhenghong Inventor before: Zhu Huaicai Inventor before: Wang Zhongqiang Inventor before: Zhong Yiwen Inventor before: Xu Huanjie Inventor before: Zhu Zhenghong |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 355 No. 523850 Guangdong city in Dongguan Province town of Changan Wusha Cun BBK Avenue Patentee after: GUANGDONG SINOPLAST ADVANCED MATERIAL CO.,LTD. Address before: 355 No. 523850 Guangdong city in Dongguan Province town of Changan Wusha Cun BBK Avenue Patentee before: DONGGUAN SINOPLAST INDUSTRIAL Ltd. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee after: Guangdong Sinoplast New Materials Co.,Ltd. Address before: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee before: GUANGDONG SINOPLAST ADVANCED MATERIAL CO.,LTD. |
|
| CP01 | Change in the name or title of a patent holder |