CN103333479B - 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
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- CN103333479B CN103333479B CN201310298832.1A CN201310298832A CN103333479B CN 103333479 B CN103333479 B CN 103333479B CN 201310298832 A CN201310298832 A CN 201310298832A CN 103333479 B CN103333479 B CN 103333479B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—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
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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 Material Field, particularly relate to a kind of can the polycarbonate compositions and preparation method thereof of low temperature moulding.
Background technology
Traditional usual silk screen printing of decorative plastic technology, hot transfer printing, bat printing, vacuum plating, the secondary processing such as to spray paint, it is high all to there is Product processing fraction defective in these techniques, the wear-resisting deficiency of printing-ink, and the production cycle is long, the deficiency larger to the pollution level of environment.
In-mode inserts injection moulding (In-mold labelling, IML), it is the one in decoration technique inside mold, the feature of its technique highly significant is: surface is layer of transparent film, and centre is printing pattern layer, and the back side is plastic rubber substrate layer, owing to being clipped in the middle due to ink, not easily scratched and wear and tear, and can keeping for a long time of ink colors is bright-coloured stable, not fugitive color.This technique eliminates secondary processing operation, improve productive rate.This technique is mainly used in the outer casing member making the electric equipment productss such as mobile phone, computer, household electrical appliances.
The shell that IML technology is produced, its " information display area " is the region for printing opacity and display back side content in product, such as: mobile phone, information display area, lamp hole and the camera hole such as MP3/MP4 player.This is required to substrate layer has high-clarity.Its " decorative pattern district " is after Product Assembly, under normal service condition, and all decorative pattern districts that can see, such as: decoration color lump, lines, word and corporate logo etc.The ink logo in this district and the carrier of pattern---polyethylene terephthalate (PET) film that hardens all can not stand the temperature being greater than 265 DEG C.And the bonding strength of ink and PET is limited, the melt of poor fluidity needs large injection pressure shaping, and this can cause ink and PET film to depart from, offset.Therefore, require that substrate layer is lower than 265 DEG C, preferably has high fluidity of molten and easy injection moulding less than or equal under 260 DEG C of conditions.These requirements comprehensive, adopt these transparent materials of polycarbonate alloy, transparent ABS, polymethacrylate as substrate layer usually.
In addition; the outer casing member produced by IML technology is except being used as decorative appearance; also play the effect of protection product; this just requires that sheating material must have good mechanical property and resistance toheat; well could protect product; these transparent material mechanical properties of transparent polyester, transparent ABS, polymethacrylate are all poor, are not well positioned to meet the performance requriements of outer casing member, especially the shell product of thin-walled (thickness is less than 1.00mm).
Polycarbonate (PC) has high impact-resistant, high-clarity, high heat-resisting advantage, is suitable for being used as transparent outer casing member.But PC also exists processing fluidity difference and the shortcoming of mold temperature high (290 DEG C-310 DEG C ability are well shaping), can not meet IML technology service requirements.
In the prior art, normally improve PC composition processing characteristics by adding the polymkeric substance such as transparent polystyrene (GPPS), acrylonitrile-butadiene-styrene copolymer (ABS), but but cause the mechanical property of PC composition or transparency to decline.
The existing usual preparation method about this polycarbonate compositions generally adopts single stage method, but the transparency of the polycarbonate compositions using this preparation method to obtain and shock resistance poor, therefore the performance requriements of IML technology to substrate layer resin can not be met.
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 for 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:
Can the polycarbonate compositions of low temperature moulding, be prepared from by the raw material of following weight part:
Polycarbonate (PC) 70 ~ 85 parts;
Copolyester (CPET) 5 ~ 20 parts;
Polyesteramide (PEA) 5 ~ 10 parts;
Transesterify promotor 0.01 ~ 0.1 part;
Ester exchange inhibitor 0.2 ~ 1 part;
Functional additive 0.2 ~ 1 part;
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; 4-cyclohexanedimethanoester ester), poly-1; one or more mixture of 4-cyclohexane cyclohexanedimethanodibasic-Isosorbide-5-Nitrae-cyclohexane dicarboxylates (PCCD); Because the consistency of copolyester and polycarbonate is better, can melt extrude with arbitrary proportion the blend obtaining high transparency; Copolyester can improve the processing characteristics of this blend, and little on the impact of its shock resistance;
Described polyesteramide is aliphatic polyester amide, 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), Resorcinol two (diphenyl phosphoester), tricresyl phosphate (2-chloropropyl) ester, aromatic sulphonic acid salt, potassium phenylsulphonyl benzene sulfonate (KSS), perfluorobutyl potassium (PPFBS), 2, one or more mixture 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.
Wherein in some embodiments, described can the polycarbonate compositions of low temperature moulding, be prepared from by the raw material of following weight part:
Polycarbonate 78 ~ 82 parts;
Copolyester 12 ~ 14 parts;
Polyesteramide 6 ~ 7 parts;
Transesterify promotor 0.02 ~ 0.03 part;
Ester exchange inhibitor 0.4 ~ 0.6 part;
Functional additive 0.5 ~ 0.6 part.
Wherein in some embodiments, described polycarbonate number-average molecular weight is 17000 ~ 30000.
Wherein in some embodiments, the viscosity of described copolyester is 0.6dL/g ~ 1.2dL/g, transmittance is greater than 85%.
Wherein in some embodiments, described polyesteramide number-average molecular weight is 20000 ~ 40000, and wherein amide structure unit content is 50mol% ~ 60mol%.
Wherein in some embodiments, described transesterify promotor is tetrabutyl titanate.The effect of transesterify promotor promotes that the ester-ester of copolyester and polyesteramide exchanges, ester-amide exchange reaction, and this reaction product can improve the consistency of copolyester composition and polycarbonate.
Wherein in some embodiments, described ester exchange inhibitor is one or more mixture of triphenyl phosphite, triphenylphosphate, organophosphorus ester.Its effect of ester exchange inhibitor is, when avoiding copolyester composition and polycarbonate blending, side reaction occurs, thus reduces the mechanical property of polycarbonate compositions.
The present invention also provide above-mentioned can the preparation method of polycarbonate compositions of low temperature moulding, specifically comprise the following steps (asking for an interview Fig. 1):
(1) copolyester of described weight part, polyesteramide are mixed to be placed in parallel double-screw extruder with transesterify promotor melt extrude granulation, obtain copolyester composition.The ester-ester that in this step, transesterify promotor facilitates copolyester and polyesteramide exchanges, ester-acid amide reacts, and the compatilizers that these reactions are formed can improve the consistency of copolyester composition and polycarbonate.
(2), after the copolyester composition that step (1) obtains being mixed by described weight part with described polycarbonate, ester exchange inhibitor and functional additive, be placed in parallel double-screw extruder and melt extrude granulation, to obtain final product.Its effect of ester exchange inhibitor in this step avoids copolyester composition and polycarbonate blending and side reaction occurs, thus the mechanical property of reduction polycarbonate compositions.
Use above-mentioned preparation method prepare of the present invention can the polycarbonate compositions of low temperature moulding, more excellent technique effect can be realized, the polycarbonate compositions transparency of gained and shock resistance good, meet the performance requriements of IML technology to substrate layer resin.
Wherein in some embodiments, 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 DEG C ~ 265 DEG C, the temperature of the 3rd to the 4th temperature controlled region is 265 DEG C ~ 270 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 270 DEG C ~ 280 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 265 DEG C ~ 270 DEG C, the temperature of the 9th temperature controlled region is 260 DEG C ~ 265 DEG C, and the temperature of die head is 250 DEG C ~ 255 DEG C.
Wherein in some embodiments, 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 DEG C ~ 250 DEG C, the temperature of the 3rd to the 4th temperature controlled region is 245 DEG C ~ 255 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 250 DEG C ~ 260 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 250 DEG C ~ 260 DEG C, the temperature of the 9th temperature controlled region is 245 DEG C ~ 255 DEG C, and the temperature of die head is 240 DEG C ~ 250 DEG C.
The beneficial effect that the present invention is compared with the prior art is:
1. polycarbonate compositions of the present invention, when keeping original degradation few, high workability can be possessed again under not higher than the processing temperature of 260 DEG C, have that processing fluidity is good, shock strength is high, transparency is high and the 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 the polycarbonate compositions obtained has more excellent transparency and comprehensive mechanical property compared to the advantage of existing preparation method (single stage method).The preparation method then using the present invention to adopt prepare of the present invention can the polycarbonate compositions of low temperature moulding, more excellent technique effect can be realized.
3, the present invention is first melt extruded by copolyester and polyesteramide, utilize the ester group of the ester group of copolyester and polyesteramide, amide group generation ester-ester permutoid reaction and ester-amide exchange reaction, thus obtain a kind of copolyester composition that can carry out modification to polycarbonate compositions, this copolyester composition affects less on the shock resistance of polycarbonate compositions and properties of transparency, and obviously can improve the processing characteristics of polycarbonate compositions.
Accompanying drawing explanation
Figure 1 shows that the present invention can the schematic flow sheet of preparation method of polycarbonate compositions of low temperature moulding.
Embodiment
Below in conjunction with specific embodiment, detailed elaboration is done to the present invention; Further illustrate the present invention by non-limiting example below, but the present invention is not restricted to these embodiments.
The raw material used in following examples 1-6 and 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, and transmittance is 87, is selected from Yi Si Man;
Copolyester PCTA, viscosity is 0.6dL/g, and transmittance is 92, is selected from Yi Si Man;
Copolyester PCCD, viscosity is 0.9dL/g, and transmittance is 90, is selected from Yi Si Man;
Polyesteramide PEA-1, number-average molecular weight is 40000, and amide structure unit content 80%, is selected from Beyer Co., Ltd;
Polyesteramide PEA-2, number-average molecular weight is 30000, and amide structure unit content 60%, is selected from Beyer Co., Ltd;
Polyesteramide PEA-3, number-average molecular weight is 20000, and 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, comprises the following steps:
(1) PCTG, PEA-2 and the TBT of above-mentioned weight part are mixed to be placed in parallel double-screw extruder melt extrude granulation, obtain copolyester composition.Wherein twin screw extruder the 1st is 260 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 265 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 270 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 265 DEG C, the temperature of the 9th temperature controlled region is 260 DEG C, and the temperature of die head is 250 DEG C.
(2) PC-2, TPPi of (1) gained copolyester composition and above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor melt extrude granulation.Wherein twin screw extruder the 1st is 240 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 245 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 250 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 250 DEG C, the temperature of the 9th temperature controlled region is 245 DEG C, and the temperature of die head is 240 DEG C.
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, comprises the following steps:
(1) PCTA, PEA-2 and the TBT of above-mentioned weight part are mixed to be placed in parallel double-screw extruder melt extrude granulation, obtain copolyester composition.Wherein twin screw extruder the 1st is 265 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 270 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 280 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 270 DEG C, the temperature of the 9th temperature controlled region is 265 DEG C, and the temperature of die head is 255 DEG C.
(2) PC-2, TPPi of (1) gained copolyester composition and above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor melt extrude granulation.Wherein twin screw extruder the 1st is 250 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 255 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 260 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 260 DEG C, the temperature of the 9th temperature controlled region is 255 DEG C, and the temperature of die head is 250 DEG C.
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, comprises the following steps:
(1) PCCD, PEA-2 and the TBT of above-mentioned weight part are mixed to be placed in parallel double-screw extruder melt extrude granulation, obtain copolyester composition.Wherein twin screw extruder the 1st is 265 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 270 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 275 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 270 DEG C, the temperature of the 9th temperature controlled region is 265 DEG C, and the temperature of die head is 255 DEG C.
(2) PC-2, TPPi of (1) gained copolyester composition and above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor melt extrude granulation.Wherein twin screw extruder the 1st is 245 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 250 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 255 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 255 DEG C, the temperature of the 9th temperature controlled region is 250 DEG C, and the temperature of die head is 245 DEG C.
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, comprises the following steps:
(1) PCTA of above-mentioned weight part, PCCD, PEA-3 and TBT are mixed to be placed in parallel double-screw extruder and melt extrude granulation, obtain copolyester composition.Wherein twin screw extruder the 1st is 260 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 267 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 275 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 267 DEG C, the temperature of the 9th temperature controlled region is 263 DEG C, and the temperature of die head is 253 DEG C.
(2) PC-1, TPPi of (1) gained copolyester composition and above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor melt extrude granulation.Wherein twin screw extruder the 1st is 245 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 250 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 255 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 255 DEG C, the temperature of the 9th temperature controlled region is 250 DEG C, and the temperature of die head is 245 DEG C.
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, comprises the following steps:
(1) PCCD, PEA-3 and the TBT of above-mentioned weight part are mixed to be placed in parallel double-screw extruder melt extrude granulation, obtain copolyester composition.Wherein twin screw extruder the 1st is 260 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 267 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 275 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 267 DEG C, the temperature of the 9th temperature controlled region is 263 DEG C, and the temperature of die head is 253 DEG C.
(2) PC-1, TPPi of (1) gained copolyester composition and above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor melt extrude granulation.Wherein twin screw extruder the 1st is 245 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 250 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 255 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 255 DEG C, the temperature of the 9th temperature controlled region is 250 DEG C, and the temperature of die head is 245 DEG C.
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, comprises the following steps:
(1) PCTG of above-mentioned weight part, PCTA, PCCD, PEA-1 and TBT are mixed to be placed in parallel double-screw extruder and melt extrude granulation, obtain copolyester composition.Wherein twin screw extruder the 1st is 260 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 267 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 275 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 267 DEG C, the temperature of the 9th temperature controlled region is 263 DEG C, and the temperature of die head is 253 DEG C.
(2) PC-3, TPPi of (1) gained copolyester composition and above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor melt extrude granulation.Wherein twin screw extruder the 1st is 245 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 250 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 255 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 255 DEG C, the temperature of the 9th temperature controlled region is 250 DEG C, and the temperature of die head is 245 DEG C.
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 and the PEA-2 of above-mentioned weight part is mixed to be placed in parallel double-screw extruder melt extrude granulation, obtain copolyester composition.Wherein twin screw extruder the 1st is 260 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 265 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 270 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 265 DEG C, the temperature of the 9th temperature controlled region is 260 DEG C, and the temperature of die head is 250 DEG C.
(2) PC-2, TPPi of (1) gained copolyester composition and above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor melt extrude granulation.Wherein twin screw extruder the 1st is 240 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 245 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 250 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 250 DEG C, the temperature of the 9th temperature controlled region is 245 DEG C, and the temperature of die head is 240 DEG C.
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 of above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor and melt extrudes granulation.Wherein twin screw extruder the 1st is 240 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 245 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 250 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 250 DEG C, the temperature of the 9th temperature controlled region is 245 DEG C, and the temperature of die head is 240 DEG C.
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 of above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor and melt extrudes granulation.Wherein twin screw extruder the 1st is 260 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 265 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 260 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 260 DEG C, the temperature of the 9th temperature controlled region is 265 DEG C, and the temperature of die head is 260 DEG C.
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 is mixed to be placed in parallel double-screw extruder with oxidation inhibitor and melt extrudes granulation.Wherein twin screw extruder the 1st is 260 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 265 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 260 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 260 DEG C, the temperature of the 9th temperature controlled region is 265 DEG C, and the temperature of die head is 260 DEG C.
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, ABS of above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor and melt extrudes granulation.Wherein twin screw extruder the 1st is 260 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 265 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 260 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 260 DEG C, the temperature of the 9th temperature controlled region is 265 DEG C, and the temperature of die head is 260 DEG C.
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, GPPS of above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor and melt extrudes granulation.Wherein twin screw extruder the 1st is 260 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 265 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 260 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 260 DEG C, the temperature of the 9th temperature controlled region is 265 DEG C, and the temperature of die head is 260 DEG C.
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 of above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor and melt extrudes granulation.Wherein twin screw extruder the 1st is 240 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 245 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 250 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 250 DEG C, the temperature of the 9th temperature controlled region is 245 DEG C, and the temperature of die head is 240 DEG C.
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 of above-mentioned weight part are mixed to be placed in parallel double-screw extruder with oxidation inhibitor and melt extrudes granulation.Wherein twin screw extruder the 1st is 240 DEG C to the temperature of the 2nd temperature controlled region, the temperature of the 3rd to the 4th temperature controlled region is 245 DEG C, and the temperature of the 5th to the 6th temperature controlled region is 250 DEG C, and the temperature of the 7th to the 8th temperature controlled region is 250 DEG C, the temperature of the 9th temperature controlled region is 245 DEG C, and the temperature of die head is 240 DEG C.
Above-described embodiment and the made sample of comparative example are carried out following performance test:
Transmittance and mist degree are tested, by ASTMD1003 standard testing, and thickness of test piece 1.0mm;
Socle girder (IZOD) notched Izod impact strength is tested, by ASTMD256 test, and unit J/m, thickness of test piece 3.2mm;
Melt flow rate is tested, by ASTMD1238 test, and probe temperature 260 DEG C, load 2.16kg, unit g/10min;
Heat-drawn wire is tested, by ASTMD648 test, and test load 1.8MPa, unit DEG C;
IML technology is tested: when preparing shell product, and polycarbonate and the figuratum transparent hard PET film integrated injection molding of printing are gone out outer casing member, and wherein printing pattern layer is in the centre of polycarbonate substrate layer and PET film, and injection temperature is 260 DEG C.Finally judge by following standard, printed patterns and PET film must be excellent, do not occur skew, distortion and variable color, are then judged to be well-tended appearance;
Ball falling impact is tested: be placed on by product on hollow base, be the steel ball drop impact product of 9mm at the vertical direction 1.2m place diameter of product, product does not occur slight crack, but shock place allows to occur pit, be then judged to be tested by ball falling impact;
High temperature test: product is placed in high-temperature cabinet 90 ± 2 DEG C, after 48 hours, taken out by sample and at room temperature place 1-2 hour, there is not distortion in product, is then judged to pass 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
As can be seen from the result of above-described embodiment 1-6, gained polycarbonate compositions of the present invention has high workability at low temperatures, maintains intrinsic mechanical property, resistance toheat, the high transparent of polycarbonate to a great extent simultaneously.In IML technology test, printing pattern layer and PET film stand intact, and have passed ball falling impact test and high temperature test, reach the performance requriements to substrate layer in IML technology.
As can be seen from the result of comparative example 1, owing to not using transesterify promotor, gained polycarbonate compositions poor transparency and resistance to impact shock poor, the performance requriements of IML technology to substrate layer resin can not be met.Its reason is, the step 1 in preparation method does not use transesterify promotor, and permutoid reaction is weak, and the compatilizer that reaction is formed is less, thus causes the consistency of copolyester composition and polycarbonate not good.
As can be seen from the result of comparative example 2, owing to not using polyesteramide, the shock resistance of gained polycarbonate compositions, poor heat resistance, can not meet the performance requriements of IML technology to substrate layer resin.Its reason is, when not using polyesteramide, need the copolyester and the polycarbonate blending that add more weight part, polycarbonate compositions just can be made to meet low mold temperature and the high workability requirement of IML technology, but add that too much copolyester can cause the shock resistance of polycarbonate compositions, resistance toheat significantly declines.
As can be seen from the result of comparative example 3, owing to not using copolyester, transparency, the shock resistance of gained polycarbonate compositions are poor, can not meet the performance requriements of IML technology to substrate layer resin.Its reason is, only adopts polyesteramide and polycarbonate blending, although increased substantially the mobility of polycarbonate, due to the poor compatibility of polyesteramide and polycarbonate, causes the transparency of polycarbonate, shock resistance significantly declines.
As can be seen from the result of comparative example 4, owing to not using copolyester and polyesteramide, the poor fluidity of gained polycarbonate compositions, therefore the performance requriements of IML technology to substrate layer resin can not be met.
As can be seen from the result of comparative example 5, by polycarbonate and ABS blended gained polycarbonate compositions opaque, therefore the performance requriements of IML technology to substrate layer resin can not be met.
As can be seen from the result of comparative example 6, by polycarbonate and GPPS blended gained polycarbonate compositions shock resistance poor, therefore the performance requriements of IML technology to substrate layer resin can not be met.
As can be seen from the result of comparative example 7, its single stage method used obtains polycarbonate compositions shock resistance, and comparatively embodiment is poor, therefore can not meet the performance requriements of IML technology to substrate layer resin.
As can be seen from the result of comparative example 8, owing to not using TPPi and the single stage method that uses to obtain polycarbonate compositions transparency, shock resistance, poor heat resistance, therefore the performance requriements of IML technology to substrate layer resin can not be met.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 (8)
1. can the polycarbonate compositions of low temperature moulding, it is characterized in that, be prepared from by the raw material of following weight part:
Described polycarbonate is aromatic polycarbonate, and number-average molecular weight is 15000 ~ 30000;
Described copolyester is one or more mixture of polyethylene terephthalate-1,4 cyclohexane dimethanol ester, PCTA, poly-1,4 cyclohexanedicarboxylic acid-Isosorbide-5-Nitrae-cyclohexane dicarboxylates;
Described polyesteramide is aliphatic polyester amide, 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;
Describedly can the polycarbonate compositions of low temperature moulding to prepare by the following method:
(1) copolyester of described weight part, polyesteramide are mixed to be placed in parallel double-screw extruder with transesterify promotor melt extrude granulation, obtain copolyester composition;
Described parallel double-screw extruder comprises 9 temperature controlled region, the temperature of the 1st to the 2nd temperature controlled region is 260 DEG C ~ 265 DEG C, the temperature of the 3rd to the 4th temperature controlled region is 265 DEG C ~ 270 DEG C, the temperature of the 5th to the 6th temperature controlled region is 270 DEG C ~ 280 DEG C, the temperature of the 7th to the 8th temperature controlled region is 265 DEG C ~ 270 DEG C, the temperature of the 9th temperature controlled region is 260 DEG C ~ 265 DEG C, and the temperature of die head is 250 DEG C ~ 255 DEG C;
(2), after the copolyester composition that step (1) obtains being mixed by described weight part with described polycarbonate, ester exchange inhibitor and functional additive, be placed in parallel double-screw extruder and melt extrude granulation, to obtain final product;
Described parallel double-screw extruder comprises 9 temperature controlled region, the temperature of the 1st to the 2nd temperature controlled region is 240 DEG C ~ 250 DEG C, the temperature of the 3rd to the 4th temperature controlled region is 245 DEG C ~ 255 DEG C, the temperature of the 5th to the 6th temperature controlled region is 250 DEG C ~ 260 DEG C, the temperature of the 7th to the 8th temperature controlled region is 250 DEG C ~ 260 DEG C, the temperature of the 9th temperature controlled region is 245 DEG C ~ 255 DEG C, and the temperature of die head is 240 DEG C ~ 250 DEG C.
2. according to claim 1 a kind of can the polycarbonate compositions of low temperature moulding, it is characterized in that, be prepared from by the raw material of following weight part:
3. according to claim 1 and 2 a kind of can the polycarbonate compositions of low temperature moulding, it is characterized in that, described polycarbonate number-average molecular weight is 17000 ~ 30000.
4. according to claim 1 and 2 a kind of can the polycarbonate compositions of low temperature moulding, it is characterized in that, the viscosity of described copolyester is 0.6dL/g ~ 1.2dL/g, transmittance is greater than 85%.
5. according to claim 1 and 2 a kind of can the polycarbonate compositions of low temperature moulding, it is characterized in that, described polyesteramide number-average molecular weight is 20000 ~ 40000, and wherein amide structure unit content is 50mol% ~ 60mol%.
6. according to claim 1 and 2 a kind of can the polycarbonate compositions of low temperature moulding, it is characterized in that, described transesterify promotor is tetrabutyl titanate.
7. according to claim 1 and 2 a kind of can the polycarbonate compositions of low temperature moulding, it is characterized in that, described ester exchange inhibitor is one or more mixture of triphenyl phosphite, triphenylphosphate, organophosphorus ester.
8. described in any one of claim 1 ~ 7 can the preparation method of polycarbonate compositions of low temperature moulding, it is characterized in that, comprise the following steps:
(1) copolyester of described weight part, polyesteramide are mixed to be placed in parallel double-screw extruder with transesterify promotor melt extrude granulation, obtain copolyester composition;
Described parallel double-screw extruder comprises 9 temperature controlled region, the temperature of the 1st to the 2nd temperature controlled region is 260 DEG C ~ 265 DEG C, the temperature of the 3rd to the 4th temperature controlled region is 265 DEG C ~ 270 DEG C, the temperature of the 5th to the 6th temperature controlled region is 270 DEG C ~ 280 DEG C, the temperature of the 7th to the 8th temperature controlled region is 265 DEG C ~ 270 DEG C, the temperature of the 9th temperature controlled region is 260 DEG C ~ 265 DEG C, and the temperature of die head is 250 DEG C ~ 255 DEG C;
(2), after the copolyester composition that step (1) obtains being mixed by described weight part with described polycarbonate, ester exchange inhibitor and functional additive, be placed in parallel double-screw extruder and melt extrude granulation, to obtain final product;
Described parallel double-screw extruder comprises 9 temperature controlled region, the temperature of the 1st to the 2nd temperature controlled region is 240 DEG C ~ 250 DEG C, the temperature of the 3rd to the 4th temperature controlled region is 245 DEG C ~ 255 DEG C, the temperature of the 5th to the 6th temperature controlled region is 250 DEG C ~ 260 DEG C, the temperature of the 7th to the 8th temperature controlled region is 250 DEG C ~ 260 DEG C, the temperature of the 9th temperature controlled region is 245 DEG C ~ 255 DEG C, and the temperature of die head is 240 DEG C ~ 250 DEG C.
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| CN105802180A (en) * | 2016-05-09 | 2016-07-27 | 李红玉 | Polycarbonate thin-film material and preparation method thereof |
| CN109572117B (en) * | 2018-12-06 | 2020-12-15 | 嘉兴领科材料技术有限公司 | Flame-retardant high-performance light composite board for aviation interior trim 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 |
| CN112812517B (en) * | 2020-12-31 | 2023-04-14 | 广东国立科技股份有限公司 | A 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 |
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