CN103333479A - Polycarbonate composition capable of being formed at low temperature and preparation method of polycarbonate composition - Google Patents
Polycarbonate composition capable of being formed at low temperature and preparation method of polycarbonate composition Download PDFInfo
- Publication number
- CN103333479A CN103333479A CN2013102988321A CN201310298832A CN103333479A CN 103333479 A CN103333479 A CN 103333479A CN 2013102988321 A CN2013102988321 A CN 2013102988321A CN 201310298832 A CN201310298832 A CN 201310298832A CN 103333479 A CN103333479 A CN 103333479A
- Authority
- CN
- China
- Prior art keywords
- temperature
- controlled region
- temperature controlled
- polycarbonate
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
Abstract
The invention relates to a polycarbonate composition capable of being formed at the low temperature and a preparation method of the polycarbonate composition. The polycarbonate composition comprises raw materials in parts by weight as follows: 70-85 parts of polycarbonate, 5-20 parts of copolyester, 5-10 parts of polyesteramide, 0.01-0.1 parts of an ester exchange accelerant, 0.2-1 part of an ester exchange inhibitor and 0.2-1 part of a functional additive. The preparation method of the polycarbonate composition adopts a two-step method. The polycarbonate composition is used for injection molding of inserts in a die, can be used for manufacturing casings of electronic appliance products such as a mobile phone, a computer, a household appliance and the like, and has the advantages of low forming temperature, good processing fluidity, high impact strength and transparency, good heat resistance and the like.
Description
Technical field
The present invention relates to the material field, but particularly relate to polycarbonate compositions of a kind of low temperature moulding and preparation method thereof.
Background technology
All there are product processing fraction defective height in traditional common silk screen printing of decorative plastic technology, hot transfer printing, bat printing, vacuum plating, secondary processing such as spray paint, these technologies, the wear-resisting deficiency of printing-ink, and the production cycle is long, the deficiency bigger to the pollution level of environment.
In-mode inserts injection moulding (In-mold labelling, IML), be a kind of in the decoration technique inside mold, the characteristics of its technology highly significant are: the surface is the layer of transparent film, and the centre is printing pattern layer, and the back side is the plastic rubber substrate layer, because because printing ink is clipped in the middle, be difficult for being scratched and wearing and tearing, and ink colors can keep bright-coloured stable for a long time, fugitive color not.This technology has been eliminated the secondary processing operation, has improved productive rate.This technology is mainly used in making shells of electronics parts such as mobile phone, computer, household electrical appliances.
The shell that IML technology is produced, its " information display area " are the zones that is used for printing opacity in the product and shows back side content, for example: mobile phone, information display area such as MP3/MP4 player, lamp hole and shooting hole.Require substrate layer to have high-clarity to this.After its " decorative pattern district " is the product assembling, under normal service condition, all decorative pattern districts that can see, for example: decorate color lump, lines, literal and corporate logo etc.The ink logo in this district and the carrier of pattern---sclerosis polyethylene terephthalate (PET) film all can not stand the temperature greater than 265 ℃.And the bonding strength of printing ink and PET is limited, and the melt of mobile difference needs big injection pressure moulding, and this can cause, and printing ink and PET film break away from, skew.Therefore, require substrate layer being lower than 265 ℃, preferably be less than or equal to and have high fluidity of molten and easily injection moulding under 260 ℃ of conditions.Comprehensive these requirements adopt polycarbonate alloy, transparent ABS, these transparent materials of polymethacrylate as substrate layer usually.
In addition; use except making decorative appearance with the outer casing member that IML technology is produced; also play the effect of protection product; this just requires sheating material must have good mechanical property and resistance toheat; could well protect product; transparent polyester, transparent ABS, these transparent material mechanical properties of polymethacrylate are all poor, can not well satisfy the shell product of performance requriements, the especially thin-walled (thickness is less than 1.00mm) of outer casing member.
Polycarbonate (PC) has high impact-resistant, high-clarity, high heat-resisting advantage, is suitable for as transparent outer casing member.But PC exists the shortcoming of processing fluidity difference and mold temperature height (290 ℃ of-310 ℃ of good moulding of ability), can not satisfy the service requirements of IML technology.
In the prior art, normally improve PC composition processing characteristics by interpolation transparent polystyrene (GPPS), acrylonitrile-butadiene-styrene copolymer polymkeric substance such as (ABS), but but cause the mechanical property of PC composition or transparency to descend.
Existing usual preparation method about this polycarbonate compositions generally adopts single stage method, but is to use transparency and the shock resistance of the polycarbonate compositions that this preparation method obtains poor, so can not satisfy IML technology to the performance requriements of substrate layer resin.
Therefore, this area needs polycarbonate compositions that a kind of mold temperature is low, processing fluidity good, shock strength is high and transparency is high and preparation method thereof.
Summary of the invention
Based on this, be necessary at the problems referred to above, polycarbonate compositions that a kind of mold temperature is low, processing fluidity good, shock strength is high and transparency is high and preparation method thereof is provided.
For achieving the above object, the present invention adopts following scheme:
But a kind of polycarbonate compositions of low temperature moulding is formed by the feedstock production of following weight part:
70～85 parts of polycarbonate (PC);
5～20 parts of copolyesters (CPET);
5～10 parts of polyesteramides (PEA);
0.01～0.1 part of transesterify promotor;
0.2～1 part of ester exchange inhibitor;
0.2～1 part of functional additive;
Described polycarbonate is aromatic polycarbonate, and number-average molecular weight is 15000～30000;
Described copolyester is polyethylene terephthalate-1,4-cyclohexanedimethanoester ester (PCTG or PETG), PCTA(poly terephthalic acid-1,4-cyclohexanedimethanoester ester/m-phthalic acid-1, the 4-cyclohexanedimethanoester ester), poly-1,4-cyclohexane cyclohexanedimethanodibasic-1, the mixture of one or more of 4-hexanaphthene dimethyl ester (PCCD); Because the consistency of copolyester and polycarbonate is better, can melt extrudes with arbitrary proportion and obtain the transparent blend of height; Copolyester can improve the processing characteristics of this blend, and little to its shock resistance influence;
Described polyesteramide is the aliphatic poly esteramides, and number-average molecular weight is 20000～40000, and wherein amide structure unit content is 40mol%～80mol%;
Described functional additive is one or more mixture of oxidation inhibitor, lubricant, fire retardant, tinting material; Described oxidation inhibitor is one or more mixture of phosphorous acid esters, Hinered phenols, hindered amines; Described lubricant is one or more mixture of laurate, Magnesium Stearate, Zinic stearas, calcium stearate, ethylene bis stearamide, ethylidine bis-stearamides and tetramethylolmethane stearate, organic silicone oil, silicone powder, montanin wax; Described fire retardant is condensed phosphoric acid esters class, annular phosphate class, poly aryl phosphate ester, ammonium polyphosphate, dihydroxyphenyl propane two (diphenyl phosphoester), two (diphenyl phosphoester), tricresyl phosphate (2-chloropropyl) esters of Resorcinol, aromatic sulphonic acid salt, benzenesulfonyl Phenylsulfonic acid potassium (KSS), perfluoro butyl potassium sulfonate (PPFBS), 2, the mixture of one or more of 4,5-trichlorobenzene sodium sulfonate (STB), silicone based, tetrabromo-bisphenol, zinc borate; Described tinting material is one or more mixture of pigment dyestuff, solvent dye, white dyes.
Therein among some embodiment, but the polycarbonate compositions of described low temperature moulding is formed by the feedstock production of following weight part:
78～82 parts of polycarbonate;
12～14 parts of copolyesters;
6～7 parts of polyesteramides;
0.02～0.03 part of transesterify promotor;
0.4～0.6 part of ester exchange inhibitor;
0.5～0.6 part of functional additive.
Among some embodiment, described polycarbonate number-average molecular weight is 17000～30000 therein.
Among some embodiment, the viscosity of described copolyester is that 0.6dL/g～1.2dL/g, transmittance are greater than 85% therein.
Among some embodiment, described polyesteramide number-average molecular weight is 20000～40000 therein, and wherein amide structure unit content is 50mol%～60mol%.
Among some embodiment, described transesterify promotor is tetrabutyl titanate therein.The effect of transesterify promotor is ester-transesterify, the ester-amide exchange reaction that promotes copolyester and polyesteramide, and this reaction product can improve the consistency of copolyester composition and polycarbonate.
Therein among some embodiment, described ester exchange inhibitor is one or more mixture of triphenyl phosphite, triphenylphosphate, organophosphorus ester.Its effect of ester exchange inhibitor is that side reaction takes place when avoiding copolyester composition and polycarbonate blending, thereby reduces the mechanical property of polycarbonate compositions.
But the present invention also provides the preparation method of the polycarbonate compositions of above-mentioned low temperature moulding, specifically may further comprise the steps (asking for an interview Fig. 1):
(1) copolyester, polyesteramide and the transesterify promotor of described weight part is mixed to be placed on melt extrudes granulation in the parallel double-screw extruder, obtain the copolyester composition.Transesterify promotor has promoted ester-transesterify, the ester-acid amide reaction of copolyester and polyesteramide in this step, and the compatilizer that these reactions form can improve the consistency of copolyester composition and polycarbonate.
(2) the resulting copolyester composition of step (1) and described polycarbonate, ester exchange inhibitor and functional additive are mixed by described weight part after, place parallel double-screw extruder to melt extrude granulation, namely.Its effect of ester exchange inhibitor in this step is to avoid copolyester composition and polycarbonate blending and side reaction takes place, thereby reduces the mechanical property of polycarbonate compositions.
But use above-mentioned preparation method to prepare the polycarbonate compositions of low temperature moulding of the present invention, can realize more excellent technique effect, polycarbonate compositions transparency and the shock resistance of gained are good, satisfy IML technology to the performance requriements of substrate layer resin.
Therein among some embodiment, described parallel double-screw extruder comprises 9 temperature controlled region, in described step (1), the temperature of the 1st to the 2nd temperature controlled region is 260 ℃～265 ℃, the temperature of the 3rd to the 4th temperature controlled region is 265 ℃～270 ℃, and the temperature of the 5th to the 6th temperature controlled region is 270 ℃～280 ℃, and the temperature of the 7th to the 8th temperature controlled region is 265 ℃～270 ℃, the temperature of the 9th temperature controlled region is 260 ℃～265 ℃, and the temperature of die head is 250 ℃～255 ℃.
Therein among some embodiment, described parallel double-screw extruder comprises 9 temperature controlled region, in described step (2), the temperature of the 1st to the 2nd temperature controlled region is 240 ℃～250 ℃, the temperature of the 3rd to the 4th temperature controlled region is 245 ℃～255 ℃, and the temperature of the 5th to the 6th temperature controlled region is 250 ℃～260 ℃, and the temperature of the 7th to the 8th temperature controlled region is 250 ℃～260 ℃, the temperature of the 9th temperature controlled region is 245 ℃～255 ℃, and the temperature of die head is 240 ℃～250 ℃.
The beneficial effect that the present invention is compared with the prior art is:
1. polycarbonate compositions of the present invention, keeping under the few situation of original degradation, can possess high workability not being higher than under 260 ℃ the processing temperature again, have that processing fluidity is good, shock strength is high, transparency is high and advantage such as good heat resistance, be especially suitable for use as the substrate layer material of IML technology.
2, preparation method of the present invention is that resulting polycarbonate compositions has more excellent transparency and comprehensive mechanical property compared to existing preparation method's's (single stage method) advantage.But the preparation method who then uses the present invention to adopt prepares the polycarbonate compositions of low temperature moulding of the present invention, can realize more excellent technique effect.
3, the present invention melt extrudes by copolyester and polyesteramide earlier, utilize the ester group of copolyester and ester group, amide group generation ester-transesterification reaction and the ester-amide exchange reaction of polyesteramide, thereby obtain a kind of copolyester composition that can carry out modification to polycarbonate compositions, this copolyester composition is less to shock resistance and the properties of transparency influence of polycarbonate compositions, and can obviously improve the processing characteristics of polycarbonate compositions.
Description of drawings
But Figure 1 shows that preparation method's the schematic flow sheet of the polycarbonate compositions of the present invention's low temperature moulding.
Embodiment
Below in conjunction with specific embodiment, the present invention is done detailed elaboration; Further specify the present invention by following non-limiting example, but the present invention is not restricted to these embodiment.
The raw material that uses among following examples 1-6 and the comparative example 1-8 is described in detail as follows respectively:
Polycarbonate-1, number-average molecular weight is 15000, is selected from Supreme Being people and changes into company;
Polycarbonate-2, number-average molecular weight is 22500, is selected from Supreme Being people and changes into company;
Polycarbonate-3, number-average molecular weight is 30000, is selected from Supreme Being people and changes into company;
Copolyester PCTG, viscosity is 1.2dL/g, transmittance is 87, is selected from Yi Si Man;
Copolyester PCTA, viscosity is 0.6dL/g, transmittance is 92, is selected from Yi Si Man;
Copolyester PCCD, viscosity is 0.9dL/g, transmittance is 90, is selected from Yi Si Man;
Polyesteramide PEA-1, number-average molecular weight is 40000, amide structure unit content 80% is selected from Beyer Co., Ltd;
Polyesteramide PEA-2, number-average molecular weight is 30000, amide structure unit content 60% is selected from Beyer Co., Ltd;
Polyesteramide PEA-3, number-average molecular weight is 20000, amide structure unit content 40% is selected from Beyer Co., Ltd;
Transesterify promotor is tetrabutyl titanate (TBT), is selected from the purple chemical reagent work in Shanghai;
Ester exchange inhibitor is triphenyl phosphite (TPPi), is selected from the purple chemical reagent work in Shanghai;
Functional additive is oxidation inhibitor B-900, is selected from BASF AG;
Acrylonitrile-butadiene-styrene copolymer ABS is selected from 757 of Taiwan Qi Mei company;
Transparent polystyrene GPPS is selected from the PG-22 of Taiwan Qi Mei company.
Embodiment 1
A kind of polycarbonate compositions, the weight part of its each component is as follows:
| Component | Weight part |
| PC-2 | 82 parts |
| PCTG | 12 parts |
| PEA-2 | 6 parts |
| TBT | 0.02 part |
| TPPi | 0.4 part |
| Oxidation inhibitor | 0.5 part |
The preparation method of above-mentioned polycarbonate compositions may further comprise the steps:
(1) PCTG, the PEA-2 of above-mentioned weight part and TBT are mixed to be placed on melt extrudes granulation in the parallel double-screw extruder, obtain the copolyester composition.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 260 ℃, the temperature of the 3rd to the 4th temperature controlled region is 265 ℃, and the temperature of the 5th to the 6th temperature controlled region is 270 ℃, and the temperature of the 7th to the 8th temperature controlled region is 265 ℃, the temperature of the 9th temperature controlled region is 260 ℃, and the temperature of die head is 250 ℃.
(2) PC-2, the TPPi of (1) gained copolyester composition and above-mentioned weight part and oxidation inhibitor are mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 240 ℃, the temperature of the 3rd to the 4th temperature controlled region is 245 ℃, and the temperature of the 5th to the 6th temperature controlled region is 250 ℃, and the temperature of the 7th to the 8th temperature controlled region is 250 ℃, the temperature of the 9th temperature controlled region is 245 ℃, and the temperature of die head is 240 ℃.
Embodiment 2
A kind of polycarbonate compositions, the weight part of its each component is as follows:
| Component | Weight part |
| PC-2 | 80 parts |
| PCTA | 12 parts |
| PEA-2 | 7 parts |
| TBT | 0.03 part |
| TPPi | 0.6 part |
| Oxidation inhibitor | 0.6 part |
The preparation method of above-mentioned polycarbonate compositions may further comprise the steps:
(1) PCTA, the PEA-2 of above-mentioned weight part and TBT are mixed to be placed on melt extrudes granulation in the parallel double-screw extruder, obtain the copolyester composition.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 265 ℃, the temperature of the 3rd to the 4th temperature controlled region is 270 ℃, and the temperature of the 5th to the 6th temperature controlled region is 280 ℃, and the temperature of the 7th to the 8th temperature controlled region is 270 ℃, the temperature of the 9th temperature controlled region is 265 ℃, and the temperature of die head is 255 ℃.
(2) PC-2, the TPPi of (1) gained copolyester composition and above-mentioned weight part and oxidation inhibitor are mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 250 ℃, the temperature of the 3rd to the 4th temperature controlled region is 255 ℃, and the temperature of the 5th to the 6th temperature controlled region is 260 ℃, and the temperature of the 7th to the 8th temperature controlled region is 260 ℃, the temperature of the 9th temperature controlled region is 255 ℃, and the temperature of die head is 250 ℃.
Embodiment 3
A kind of polycarbonate compositions, the weight part of its each component is as follows:
| Component | Weight part |
| PC-2 | 78 parts |
| PCCD | 14 parts |
| PEA-2 | 7 parts |
| TBT | 0.03 part |
| TPPi | 0.5 part |
| Oxidation inhibitor | 0.5 part |
The preparation method of above-mentioned polycarbonate compositions may further comprise the steps:
(1) PCCD, the PEA-2 of above-mentioned weight part and TBT are mixed to be placed on melt extrudes granulation in the parallel double-screw extruder, obtain the copolyester composition.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 265 ℃, the temperature of the 3rd to the 4th temperature controlled region is 270 ℃, and the temperature of the 5th to the 6th temperature controlled region is 275 ℃, and the temperature of the 7th to the 8th temperature controlled region is 270 ℃, the temperature of the 9th temperature controlled region is 265 ℃, and the temperature of die head is 255 ℃.
(2) PC-2, the TPPi of (1) gained copolyester composition and above-mentioned weight part and oxidation inhibitor are mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 245 ℃, the temperature of the 3rd to the 4th temperature controlled region is 250 ℃, and the temperature of the 5th to the 6th temperature controlled region is 255 ℃, and the temperature of the 7th to the 8th temperature controlled region is 255 ℃, the temperature of the 9th temperature controlled region is 250 ℃, and the temperature of die head is 245 ℃.
Embodiment 4
A kind of polycarbonate compositions, the weight part of its each component is as follows:
| Component | Weight part |
| PC-1 | 85 parts |
| PCTA | 5 parts |
| PCCD | 5 parts |
| PEA-3 | 5 parts |
| TBT | 0.01 part |
| TPPi | 0.2 part |
| Oxidation inhibitor | 0.2 part |
The preparation method of above-mentioned polycarbonate compositions may further comprise the steps:
(1) PCTA, PCCD, PEA-3 and the TBT of above-mentioned weight part mixed to be placed on melt extrudes granulation in the parallel double-screw extruder, obtain the copolyester composition.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 260 ℃, the temperature of the 3rd to the 4th temperature controlled region is 267 ℃, and the temperature of the 5th to the 6th temperature controlled region is 275 ℃, and the temperature of the 7th to the 8th temperature controlled region is 267 ℃, the temperature of the 9th temperature controlled region is 263 ℃, and the temperature of die head is 253 ℃.
(2) PC-1, the TPPi of (1) gained copolyester composition and above-mentioned weight part and oxidation inhibitor are mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 245 ℃, the temperature of the 3rd to the 4th temperature controlled region is 250 ℃, and the temperature of the 5th to the 6th temperature controlled region is 255 ℃, and the temperature of the 7th to the 8th temperature controlled region is 255 ℃, the temperature of the 9th temperature controlled region is 250 ℃, and the temperature of die head is 245 ℃.
Embodiment 5
A kind of polycarbonate compositions, the weight part of its each component is as follows:
| Component | Weight part |
| PC-1 | 85 parts |
| PCCD | 5 parts |
| PEA-3 | 10 parts |
| TBT | 0.01 part |
| TPPi | 0.2 part |
| Oxidation inhibitor | 0.2 part |
The preparation method of above-mentioned polycarbonate compositions may further comprise the steps:
(1) PCCD, the PEA-3 of above-mentioned weight part and TBT are mixed to be placed on melt extrudes granulation in the parallel double-screw extruder, obtain the copolyester composition.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 260 ℃, the temperature of the 3rd to the 4th temperature controlled region is 267 ℃, and the temperature of the 5th to the 6th temperature controlled region is 275 ℃, and the temperature of the 7th to the 8th temperature controlled region is 267 ℃, the temperature of the 9th temperature controlled region is 263 ℃, and the temperature of die head is 253 ℃.
(2) PC-1, the TPPi of (1) gained copolyester composition and above-mentioned weight part and oxidation inhibitor are mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 245 ℃, the temperature of the 3rd to the 4th temperature controlled region is 250 ℃, and the temperature of the 5th to the 6th temperature controlled region is 255 ℃, and the temperature of the 7th to the 8th temperature controlled region is 255 ℃, the temperature of the 9th temperature controlled region is 250 ℃, and the temperature of die head is 245 ℃.
Embodiment 6
A kind of polycarbonate compositions, the weight part of its each component is as follows:
| Component | Weight part |
| PC-3 | 70 parts |
| PCTG | 5 parts |
| PCTA | 5 parts |
| PCCD | 10 parts |
| PEA-1 | 10 parts |
| TBT | 0.1 part |
| TPPi | 1 part |
| Oxidation inhibitor | 1 part |
The preparation method of above-mentioned polycarbonate compositions may further comprise the steps:
(1) PCTG, PCTA, PCCD, PEA-1 and the TBT of above-mentioned weight part mixed to be placed on melt extrudes granulation in the parallel double-screw extruder, obtain the copolyester composition.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 260 ℃, the temperature of the 3rd to the 4th temperature controlled region is 267 ℃, and the temperature of the 5th to the 6th temperature controlled region is 275 ℃, and the temperature of the 7th to the 8th temperature controlled region is 267 ℃, the temperature of the 9th temperature controlled region is 263 ℃, and the temperature of die head is 253 ℃.
(2) PC-3, the TPPi of (1) gained copolyester composition and above-mentioned weight part and oxidation inhibitor are mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 245 ℃, the temperature of the 3rd to the 4th temperature controlled region is 250 ℃, and the temperature of the 5th to the 6th temperature controlled region is 255 ℃, and the temperature of the 7th to the 8th temperature controlled region is 255 ℃, the temperature of the 9th temperature controlled region is 250 ℃, and the temperature of die head is 245 ℃.
Comparative example 1
The weight part of each component of polycarbonate compositions is as follows:
| Component | Weight part |
| PC-2 | 82 parts |
| PCCD | 12 parts |
| PEA-2 | 6 parts |
| TPPi | 0.2 part |
| Oxidation inhibitor | 0.5 part |
Its preparation method is as follows:
(1) PCCD of above-mentioned weight part and PEA-2 are mixed to be placed on melt extrudes granulation in the parallel double-screw extruder, obtain the copolyester composition.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 260 ℃, the temperature of the 3rd to the 4th temperature controlled region is 265 ℃, and the temperature of the 5th to the 6th temperature controlled region is 270 ℃, and the temperature of the 7th to the 8th temperature controlled region is 265 ℃, the temperature of the 9th temperature controlled region is 260 ℃, and the temperature of die head is 250 ℃.
(2) PC-2, the TPPi of (1) gained copolyester composition and above-mentioned weight part and oxidation inhibitor are mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 240 ℃, the temperature of the 3rd to the 4th temperature controlled region is 245 ℃, and the temperature of the 5th to the 6th temperature controlled region is 250 ℃, and the temperature of the 7th to the 8th temperature controlled region is 250 ℃, the temperature of the 9th temperature controlled region is 245 ℃, and the temperature of die head is 240 ℃.
Comparative example 2
The weight part of each component of polycarbonate compositions is as follows:
| Component | Weight part |
| PC-2 | 60 parts |
| PCCD | 40 parts |
| TPPi | 0.2 part |
| Oxidation inhibitor | 0.5 part |
Its preparation method is as follows:
PC-2, PCCD, TPPi and the oxidation inhibitor of above-mentioned weight part mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 240 ℃, the temperature of the 3rd to the 4th temperature controlled region is 245 ℃, and the temperature of the 5th to the 6th temperature controlled region is 250 ℃, and the temperature of the 7th to the 8th temperature controlled region is 250 ℃, the temperature of the 9th temperature controlled region is 245 ℃, and the temperature of die head is 240 ℃.
Comparative example 3
The weight part of each component of polycarbonate compositions is as follows:
| Component | Weight part |
| PC-2 | 94 parts |
| PEA-2 | 6 parts |
| TPPi | 0.2 part |
| Oxidation inhibitor | 0.5 part |
Its preparation method is as follows:
PC-2, PEA-2, TPPi and the oxidation inhibitor of above-mentioned weight part mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 260 ℃, the temperature of the 3rd to the 4th temperature controlled region is 265 ℃, and the temperature of the 5th to the 6th temperature controlled region is 260 ℃, and the temperature of the 7th to the 8th temperature controlled region is 260 ℃, the temperature of the 9th temperature controlled region is 265 ℃, and the temperature of die head is 260 ℃.
Comparative example 4
The weight part of each component of polycarbonate compositions is as follows:
| Component | Weight part |
| PC-2 | 100 parts |
| Oxidation inhibitor | 0.5 part |
The PC of above-mentioned weight part and oxidation inhibitor mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 260 ℃, the temperature of the 3rd to the 4th temperature controlled region is 265 ℃, and the temperature of the 5th to the 6th temperature controlled region is 260 ℃, and the temperature of the 7th to the 8th temperature controlled region is 260 ℃, the temperature of the 9th temperature controlled region is 265 ℃, and the temperature of die head is 260 ℃.
Comparative example 5
The weight part of each component of polycarbonate compositions is as follows:
| Component | Weight part |
| PC-2 | 70 parts |
| ABS | 30 parts |
| Oxidation inhibitor | 0.5 part |
Its preparation method is as follows:
PC-2, the ABS of above-mentioned weight part and oxidation inhibitor mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 260 ℃, the temperature of the 3rd to the 4th temperature controlled region is 265 ℃, and the temperature of the 5th to the 6th temperature controlled region is 260 ℃, and the temperature of the 7th to the 8th temperature controlled region is 260 ℃, the temperature of the 9th temperature controlled region is 265 ℃, and the temperature of die head is 260 ℃.
Comparative example 6
The weight part of each component of polycarbonate compositions is as follows:
| Component | Weight part |
| PC-2 | 80 parts |
| GPPS | 20 parts |
| Oxidation inhibitor | 0.5 part |
Its preparation method is as follows:
PC-2, the GPPS of above-mentioned weight part and oxidation inhibitor mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 260 ℃, the temperature of the 3rd to the 4th temperature controlled region is 265 ℃, and the temperature of the 5th to the 6th temperature controlled region is 260 ℃, and the temperature of the 7th to the 8th temperature controlled region is 260 ℃, the temperature of the 9th temperature controlled region is 265 ℃, and the temperature of die head is 260 ℃.
Comparative example 7
The weight part of each component of polycarbonate compositions is as follows:
| Component | Weight part |
| PC-2 | 82 parts |
| PCTG | 12 parts |
| PEA-2 | 6 parts |
| TBT | 0.02 part |
| TPPi | 0.4 part |
| Oxidation inhibitor | 0.5 part |
Its preparation method is as follows:
PC-2, PCTG, PEA-2, TBT, TPPi and the oxidation inhibitor of above-mentioned weight part mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 240 ℃, the temperature of the 3rd to the 4th temperature controlled region is 245 ℃, and the temperature of the 5th to the 6th temperature controlled region is 250 ℃, and the temperature of the 7th to the 8th temperature controlled region is 250 ℃, the temperature of the 9th temperature controlled region is 245 ℃, and the temperature of die head is 240 ℃.
Comparative example 8
The weight part of each component of polycarbonate compositions is as follows:
| Component | Weight part |
| PC-2 | 82 parts |
| PCTG | 12 parts |
| PEA-2 | 6 parts |
| TBT | 0.02 part |
| Oxidation inhibitor | 0.5 part |
Its preparation method is as follows:
PC-2, PCTG, PEA-2, TBT and the oxidation inhibitor of above-mentioned weight part mixed to be placed on melt extrude granulation in the parallel double-screw extruder.Wherein the temperature of twin screw extruder the 1st to the 2nd temperature controlled region is 240 ℃, the temperature of the 3rd to the 4th temperature controlled region is 245 ℃, and the temperature of the 5th to the 6th temperature controlled region is 250 ℃, and the temperature of the 7th to the 8th temperature controlled region is 250 ℃, the temperature of the 9th temperature controlled region is 245 ℃, and the temperature of die head is 240 ℃.
Above-described embodiment and the made sample of comparative example are carried out following performance test:
Transmittance and mist degree test are pressed the ASTMD1003 standard testing, thickness of test piece 1.0mm;
The test of socle girder (IZOD) notched Izod impact strength is pressed the ASTMD256 test, the J/m of unit, thickness of test piece 3.2mm;
The melt flow rate test is pressed the ASTMD1238 test, 260 ℃ of probe temperatures, load 2.16kg, the g/10min of unit;
The ASTMD648 test press in heat-drawn wire test, tests load 1.8MPa, unit ℃;
The IML process test: during the preparation shell product, polycarbonate and the figuratum transparent hard PET film integrated injection molding of printing are gone out outer casing member, wherein printing pattern layer is in the centre of polycarbonate substrate layer and PET film, and injection temperature is 260 ℃.Judge by following standard that at last printed patterns and PET film must be excellent, skew, distortion and variable color do not occur, then are judged to be well-tended appearance;
The ball falling impact test: product is placed on the hollow base, is the steel ball drop impact product of 9mm at the vertical direction 1.2m place of product with diameter, and slight crack does not appear in product, but the bump place allows to occur pit, then is judged to be by ball falling impact and tests;
High temperature test: product is placed 90 ± 2 ℃ of high-temperature cabinets, after 48 hours, sample taken out at room temperature place 1-2 hour, distortion does not appear in product, then is judged to be and passes through high temperature test.
Each ingredients weight parts of table 1 embodiment 1-6
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| PC-1 | 0 | 0 | 0 | 85 | 85 | 0 |
| PC-2 | 82 | 80 | 78 | 0 | 0 | 0 |
| PC-3 | 0 | 0 | 0 | 0 | 0 | 70 |
| PCTG | 12 | 0 | 0 | 0 | 0 | 5 |
| PCTA | 0 | 12 | 0 | 5 | 0 | 5 |
| PCCD | 0 | 0 | 14 | 5 | 5 | 10 |
| PEA-1 | 0 | 0 | 0 | 0 | 0 | 10 |
| PEA-2 | 6 | 7 | 7 | 0 | 0 | 0 |
| PEA-3 | 0 | 0 | 0 | 5 | 10 | 0 |
| TBT | 0.02 | 0.03 | 0.03 | 0.01 | 0.01 | 0.1 |
| TPPi | 0.4 | 0.6 | 0.5 | 0.2 | 0.2 | 1 |
| Oxidation inhibitor | 0.5 | 0.6 | 0.5 | 0.2 | 0.2 | 1 |
Each ingredients weight parts of table 2 comparative example 1-6
| ? | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| PC-2 | 82 | 60 | 94 | 100 | 70 | 80 |
| PCCD | 12 | 40 | 0 | 0 | 0 | 0 |
| PEA-2 | 6 | 0 | 6 | 0 | 0 | 0 |
| TBT | 0 | 0 | 0 | 0 | 0 | 0 |
| TPPi | 0.2 | 0.2 | 0.2 | 0 | 0 | 0 |
| Oxidation inhibitor | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| ABS | 0 | 0 | 0 | 0 | 30 | 0 |
| GPPS | 0 | 0 | 0 | 0 | 0 | 20 |
Each ingredients weight parts of table 3 comparative example 7-8
| ? | Comparative example 7 | Comparative example 8 |
| PC-2 | 82 | 82 |
| PCTG | 12 | 12 |
| PEA-2 | 6 | 6 |
| TBT | 0.02 | 0.02 |
| TPPi | 0.4 | 0 |
| Oxidation inhibitor | 0.5 | 0.5 |
The test result of table 4 embodiment 1-6
The test result of table 5 comparative example 1-4
The test result of table 5 comparative example 5-8
By the result of above-described embodiment 1-6 as can be seen, gained polycarbonate compositions of the present invention has high workability at low temperatures, has kept intrinsic mechanical property, resistance toheat, the high transparent of polycarbonate simultaneously to a great extent.In the IML process test, printing pattern layer and PET film are excellent, and have passed through ball falling impact test and high temperature test, reach in the IML technology performance requriements to substrate layer.
By the result of comparative example 1 as can be seen, owing to do not use transesterify promotor, gained polycarbonate compositions poor transparency and resistance to impact shock are poor, can not satisfy IML technology to the performance requriements of substrate layer resin.Its reason is, the step 1 in the preparation method is not used transesterify promotor, and a little less than the permutoid reaction, the compatilizer that reaction forms is less, thereby causes the consistency of copolyester composition and polycarbonate not good.
By the result of comparative example 2 as can be seen, owing to do not use polyesteramide, the shock resistance of gained polycarbonate compositions, poor heat resistance can not satisfy IML technology to the performance requriements of substrate layer resin.Its reason is, when not using polyesteramide, need to add copolyester and the polycarbonate blending of more weight part, could make polycarbonate compositions satisfy low mold temperature and the high workability requirement of IML technology, but adding too much copolyester can cause the shock resistance of polycarbonate compositions, resistance toheat to descend significantly.
By the result of comparative example 3 as can be seen, owing to do not use copolyester, transparency, the shock resistance of gained polycarbonate compositions are poor, can not satisfy IML technology to the performance requriements of substrate layer resin.Its reason is, only adopts polyesteramide and polycarbonate blending, though increased substantially the flowability of polycarbonate, because the consistency of polyesteramide and polycarbonate is poor, causes the transparency of polycarbonate, shock resistance to descend significantly.
By the result of comparative example 4 as can be seen, owing to do not use copolyester and polyesteramide, the flowability of gained polycarbonate compositions is poor, so can not satisfy IML technology to the performance requriements of substrate layer resin.
By the result of comparative example 5 as can be seen, opaque by polycarbonate and ABS blend gained polycarbonate compositions, so can not satisfy IML technology to the performance requriements of substrate layer resin.
By the result of comparative example 6 as can be seen, poor by polycarbonate and GPPS blend gained polycarbonate compositions shock resistance, so can not satisfy IML technology to the performance requriements of substrate layer resin.
By the result of comparative example 7 as can be seen, it is poor than embodiment that its employed single stage method makes the polycarbonate compositions shock resistance, so can not satisfy IML technology to the performance requriements of substrate layer resin.
By the result of comparative example 8 as can be seen, owing to do not use TPPi and employed single stage method to make polycarbonate compositions transparency, shock resistance, poor heat resistance, so can not satisfy IML technology to the performance requriements of substrate layer resin.
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 claim of the present invention.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 (10)
1. but the polycarbonate compositions of a low temperature moulding is characterized in that, is formed by the feedstock production of following weight part:
70～85 parts of polycarbonate;
5～20 parts of copolyesters;
5～10 parts of polyesteramides;
0.01～0.1 part of transesterify promotor;
0.2～1 part of ester exchange inhibitor;
0.2～1 part of functional additive;
Described polycarbonate is aromatic polycarbonate, and number-average molecular weight is 15000～30000;
Described copolyester is polyethylene terephthalate-1,4 cyclohexane dimethanol ester, PCTA, poly-1,4 cyclohexanedicarboxylic acid-1, the mixture of one or more of 4-hexanaphthene dimethyl ester;
Described polyesteramide is the aliphatic poly esteramides, and number-average molecular weight is 20000～40000, and wherein amide structure unit content is 40mol%～80mol%;
Described functional additive is one or more mixture of oxidation inhibitor, lubricant, fire retardant, tinting material.
2. but the polycarbonate compositions of a kind of low temperature moulding according to claim 1 is characterized in that, is formed by the feedstock production of following weight part:
78～82 parts of polycarbonate;
12～14 parts of copolyesters;
6～7 parts of polyesteramides;
0.02～0.03 part of transesterify promotor;
0.4～0.6 part of ester exchange inhibitor;
0.5～0.6 part of functional additive.
3. but the polycarbonate compositions of a kind of low temperature moulding according to claim 1 and 2 is characterized in that, described polycarbonate number-average molecular weight is 17000～30000.
4. but the polycarbonate compositions of a kind of low temperature moulding according to claim 1 and 2 is characterized in that, the viscosity of described copolyester is that 0.6dL/g～1.2dL/g, transmittance are greater than 85%.
5. but the polycarbonate compositions of a kind of low temperature moulding according to claim 1 and 2 is characterized in that, described polyesteramide number-average molecular weight is 20000～40000, and wherein amide structure unit content is 50mol%～60mol%.
6. but the polycarbonate compositions of a kind of low temperature moulding according to claim 1 and 2 is characterized in that, described transesterify promotor is tetrabutyl titanate.
7. but the polycarbonate compositions of a kind of low temperature moulding according to claim 1 and 2 is characterized in that, described ester exchange inhibitor is one or more mixture of triphenyl phosphite, triphenylphosphate, organophosphorus ester.
8. but the preparation method of the polycarbonate compositions of each described low temperature moulding of claim 1～7 is characterized in that, may further comprise the steps:
(1) copolyester, polyesteramide and the transesterify promotor of described weight part is mixed to be placed on melt extrudes granulation in the parallel double-screw extruder, obtain the copolyester composition;
(2) the resulting copolyester composition of step (1) and described polycarbonate, ester exchange inhibitor and functional additive are mixed by described weight part after, place parallel double-screw extruder to melt extrude granulation, namely.
9. preparation method according to claim 8, it is characterized in that, described parallel double-screw extruder comprises 9 temperature controlled region, in described step (1), the temperature of the 1st to the 2nd temperature controlled region is 260 ℃～265 ℃, and the temperature of the 3rd to the 4th temperature controlled region is 265 ℃～270 ℃, the temperature of the 5th to the 6th temperature controlled region is 270 ℃～280 ℃, the temperature of the 7th to the 8th temperature controlled region is 265 ℃～270 ℃, and the temperature of the 9th temperature controlled region is 260 ℃～265 ℃, and the temperature of die head is 250 ℃～255 ℃.
10. preparation method according to claim 8, it is characterized in that, described parallel double-screw extruder comprises 9 temperature controlled region, in described step (2), the temperature of the 1st to the 2nd temperature controlled region is 240 ℃～250 ℃, and the temperature of the 3rd to the 4th temperature controlled region is 245 ℃～255 ℃, the temperature of the 5th to the 6th temperature controlled region is 250 ℃～260 ℃, the temperature of the 7th to the 8th temperature controlled region is 250 ℃～260 ℃, and the temperature of the 9th temperature controlled region is 245 ℃～255 ℃, and the temperature of die head is 240 ℃～250 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310298832.1A CN103333479B (en) | 2013-07-16 | 2013-07-16 | Polycarbonate composition capable of being formed at low temperature and preparation method of polycarbonate composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310298832.1A CN103333479B (en) | 2013-07-16 | 2013-07-16 | Polycarbonate composition capable of being formed at low temperature and preparation method of polycarbonate composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103333479A true CN103333479A (en) | 2013-10-02 |
| CN103333479B CN103333479B (en) | 2015-07-08 |
Family
ID=49241689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310298832.1A Active CN103333479B (en) | 2013-07-16 | 2013-07-16 | Polycarbonate composition capable of being formed at low temperature and preparation method of polycarbonate composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103333479B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356612A (en) * | 2014-10-24 | 2015-02-18 | 科沃斯机器人有限公司 | Anti-yellowing and hydrolysis-resistant polyester blend |
| CN105802180A (en) * | 2016-05-09 | 2016-07-27 | 李红玉 | Polycarbonate thin-film material and preparation method thereof |
| CN109572117A (en) * | 2018-12-06 | 2019-04-05 | 嘉兴领科材料技术有限公司 | A kind of flame-retarding high performance light composite board and preparation method thereof for aviation interior trim |
| CN110527269A (en) * | 2019-09-02 | 2019-12-03 | 福建鑫邦新材料科技有限公司 | A kind of modified polycarbonate material and preparation method thereof |
| CN112812517A (en) * | 2020-12-31 | 2021-05-18 | 广东国立科技股份有限公司 | Chemical-resistant transparent PC material for NCL process and preparation method thereof |
| CN115286914A (en) * | 2022-08-30 | 2022-11-04 | 广东锦湖日丽高分子材料有限公司 | High-impact transparent low-temperature-formable PC alloy and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101065433A (en) * | 2004-09-29 | 2007-10-31 | 通用电气公司 | A stabilized polycarbonate polyester composition |
| CN101906244A (en) * | 2010-08-12 | 2010-12-08 | 东莞市信诺橡塑工业有限公司 | Polycarbonate combination and preparation method thereof |
| CN101906243A (en) * | 2010-08-12 | 2010-12-08 | 东莞市信诺橡塑工业有限公司 | Polycarbonate/polyester alloy and preparation method thereof |
| CN102875802A (en) * | 2012-10-11 | 2013-01-16 | 南昌博生复合材料有限公司 | High-impact and heat-resistant copolymer and preparation method thereof |
-
2013
- 2013-07-16 CN CN201310298832.1A patent/CN103333479B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101065433A (en) * | 2004-09-29 | 2007-10-31 | 通用电气公司 | A stabilized polycarbonate polyester composition |
| CN101906244A (en) * | 2010-08-12 | 2010-12-08 | 东莞市信诺橡塑工业有限公司 | Polycarbonate combination and preparation method thereof |
| CN101906243A (en) * | 2010-08-12 | 2010-12-08 | 东莞市信诺橡塑工业有限公司 | Polycarbonate/polyester alloy and preparation method thereof |
| CN102875802A (en) * | 2012-10-11 | 2013-01-16 | 南昌博生复合材料有限公司 | High-impact and heat-resistant copolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 土肥羲治等: "《聚酯Ⅱ—特性和化学合成》", 1 April 2005, 化学工业出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356612A (en) * | 2014-10-24 | 2015-02-18 | 科沃斯机器人有限公司 | Anti-yellowing and hydrolysis-resistant polyester blend |
| CN104356612B (en) * | 2014-10-24 | 2016-07-06 | 科沃斯机器人有限公司 | A kind of anti-xanthochromia resistant to hydrolysis polyester blend |
| CN105802180A (en) * | 2016-05-09 | 2016-07-27 | 李红玉 | Polycarbonate thin-film material and preparation method thereof |
| CN109572117A (en) * | 2018-12-06 | 2019-04-05 | 嘉兴领科材料技术有限公司 | A kind of flame-retarding high performance light composite board and preparation method thereof for aviation interior trim |
| CN110527269A (en) * | 2019-09-02 | 2019-12-03 | 福建鑫邦新材料科技有限公司 | A kind of modified polycarbonate material and preparation method thereof |
| CN110527269B (en) * | 2019-09-02 | 2021-10-01 | 福建鑫邦新材料科技有限公司 | Modified polycarbonate material and preparation method thereof |
| CN112812517A (en) * | 2020-12-31 | 2021-05-18 | 广东国立科技股份有限公司 | Chemical-resistant transparent PC material for NCL process and preparation method thereof |
| CN112812517B (en) * | 2020-12-31 | 2023-04-14 | 广东国立科技股份有限公司 | Chemical-resistant transparent PC material for NCL process and preparation method thereof |
| CN115286914A (en) * | 2022-08-30 | 2022-11-04 | 广东锦湖日丽高分子材料有限公司 | High-impact transparent low-temperature-formable PC alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103333479B (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103333479B (en) | Polycarbonate composition capable of being formed at low temperature and preparation method of polycarbonate composition | |
| CN102311627B (en) | Polycarbonate/ABS alloy, its preparation method and its application | |
| CN104962055A (en) | Environmental protection flame retardation type glass fiber reinforcement polycarbonate alloy material and preparation method thereof | |
| CN104497535B (en) | A kind of LDS polycarbonate compositions with good thermal stability | |
| CN102492278A (en) | Halogen-free flame-retardant high-gloss polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) alloy material and preparation method thereof | |
| CN102311625B (en) | Polycarbonate/glass fiber alloy used for cold resistant housing of intelligent water meter and preparation method thereof | |
| CN103740085B (en) | A kind of antistatic mineral strengthen halogen-free flame retardant PC/ABS material and preparation method thereof | |
| CN102532853A (en) | High-hardness and scratch-resistant modified PC (Poly Carbonate) material and preparation method thereof | |
| CN107033575B (en) | Laser direct organization polycarbonate Alloys composition, preparation and application | |
| CN103772885A (en) | Flat PC/ABS (polycarbonate/acrylonitrile butadiene styrene) automobile dashboard material and preparation method thereof | |
| CN106687528B (en) | Flame retardant blended polycarbonate compositions with improved surface appearance | |
| CN103571127A (en) | Modified PC/ABS (Poly Carbonate)/(Acrylonitrile Butadiene Styrene) with marble strip appearance and preparation method thereof | |
| CN102993669A (en) | High-performance and low-warpage IMD (In-Mold Decoration) injection molding material and preparation method thereof | |
| CN101787199B (en) | PPO/PBT composite material used for industrial large-sized workpiece and preparation method thereof | |
| CN102719062B (en) | Glass fiber reinforced flame retardant polybutylene terephthalate resin composition with laser engraving function and preparation method thereof | |
| CN105440627A (en) | Polycarbonate flame-retardant material with high light transmittance and preparation method thereof | |
| CN102311628A (en) | Cold resistant polycarbonate/ABS alloy for intelligent ammeter shell and preparation method thereof | |
| CN111117197B (en) | High-gloss long-acting solvent-resistant polycarbonate material and preparation method thereof | |
| CN103289347B (en) | ABS/PC composite material and preparation method thereof | |
| CN102311626B (en) | Polycarbonate/glass fiber alloy, preparation method and application thereof | |
| CN103044891A (en) | Halogen-free flame-retardant PC (polycarbonate) material and preparation method thereof | |
| CN101735549A (en) | PMMA/ABS (polymethyl methacrylate/acrylonitrile butadiene styrene) composite material and manufacturing method | |
| CN103351589A (en) | High-performance imitated ceramic polycarbonate composite material and preparation method thereof | |
| CN104974463A (en) | High-glossiness heat-resistant ABS/PET (acrylonitrile-butadiene-styrene/polyethylene terephthalate) bottle chip composite material and preparation method thereof | |
| CN104513467A (en) | Polycarbonate (PC) blended alloy material |
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 | ||
| 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 |