CN103951957A - Polycarbonate (PC) composition used for in-mold decoration (IMD) and preparation method thereof - Google Patents
Polycarbonate (PC) composition used for in-mold decoration (IMD) and preparation method thereof Download PDFInfo
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- CN103951957A CN103951957A CN201410198480.7A CN201410198480A CN103951957A CN 103951957 A CN103951957 A CN 103951957A CN 201410198480 A CN201410198480 A CN 201410198480A CN 103951957 A CN103951957 A CN 103951957A
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- Engineering & Computer Science (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention discloses a polycarbonate (PC) composition used for in-mold decoration (IMD) and a preparation method thereof. The PC composition is prepared from the following raw materials in parts by weight: 65-95 parts of PC, 5-35 parts of polyethylene glycol terephthalate-1,4-cyclohexanedimethanol ester, 0.1-3 parts of toluene diisocyanate, 0.1-3 parts of 2,2'-(1,3-phenylene)-dioxazoline, 0.1-1 part of main antioxidant, 0.1-1 part of auxiliary antioxidant and 0.1-1 part of lubricating agent, wherein the sum of parts by weight of the PC and the polyethylene glycol terephthalate-1,4-cyclohexanedimethanol ester is 100 parts. The PC composition which has low forming temperature, good processing fluidity, high impact strength and high transparency and is used for IMD injection molding materials is prepared by a method of in-situ reactive compatibilization.
Description
Technical field
The present invention relates to Material Field, particularly relate to a kind of polycarbonate compositions for decoration technique inside mold and preparation method thereof.
Background technology
The develop rapidly of China in Recent Years industry, constantly expands the application surface of polycarbonate (PC), and its demand also constantly increases.But along with science and technology progress with rapid changepl. never-ending changes and improvements, the continuous renewal of Industrial products is regenerated, requirement to material property is more and more harsh, the polycarbonate of conventional model can not meet all types of requirements of product in product performance, and PC exists that melt viscosity is large, poor fluidity, high temperature facile hydrolysis, poor solvent resistance, susceptibility to breach is high, easily there is swelling and stress cracking, and the shortcomings such as frictional coefficient is large, higher, the special trade mark price of melt temperature height, thereby directly affect its further deeply application and popularization.
At present, in prior art, the modification of PC has been done to some researchs, for example patent CN201210571434.8 discloses by add copolyesters in PC, improve the mobility of PC resin, reduce machine-shaping temperature, but this PC blend adds after compatilizer modification POE, larger on its transparency impact; Patent CN201010208937.X discloses by the method for rolling press calendering formation and has prepared Makrolon/modified polyester blending thing, this blend is applied to smart card base material, but this PC blend adds after titanium dioxide, calcium carbonate, larger on its transparency impact; Patent CN201310298832.1 discloses a kind of polycarbonate compositions that can low temperature moulding and preparation method thereof, first it is to prepare compatilizer copolyester composition with copolyester, polyesteramide, transesterify promotor, then copolyester composition, polycarbonate, ester exchange inhibitor, functional additive blending extrusion is obtained to polycarbonate compositions.
Decoration technique inside mold (IMD) is the new technology of plastics molding growing up in order to solve traditional decoration technical deficiency.IMD technique (process flow sheet as shown in Figure 1) is first desired product pattern, color to be printed on transparent plastic film (PC, PET, transparent ABS), film thickness is 0.1～0.2mm approximately, then by thin-film sheet premolding, be die-cut into definite shape and size, again sheet material is embedded in the die cavity of mould and fixing, injection moulding in the most backward mould, plastic melt is in the moulding of the inner side of sheet material and contact and fuse together with sheet material.Thin-film sheet is just attached to the surface of product securely like this, produces the high-grade plastics with surface decoration.
In IMD technique because the carrier for pattern (thin film layer material) and ink logo itself can not stand high temperature, select the thermoplastics of lower injection temperature as its injectable plastic material so general, and this injectable plastic material must possess the feature that mold temperature is low, processing fluidity good, shock strength is high and transparency is high.But the temporary material without possessing such performance in prior art.
Summary of the invention
The deficiency existing for prior art, the object of the invention is to utilize the method for in situ reactive compatibilization to prepare and there is the polycarbonate compositions that mold temperature is low, processing fluidity good, shock strength is high and transparency is high, can be applicable to decoration technique inside mold injectable plastic material.
The following scheme of the concrete employing of the present invention:
For a polycarbonate compositions for decoration technique inside mold, be prepared from by the raw material of following weight part:
65～95 parts of polycarbonate (PC),
5～35 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
Described Hinered phenols antioxidant is the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid;
Described phosphite ester kind antioxidant is tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester;
Described lubricant is pentaerythritol stearate.
In some embodiment, for the polycarbonate compositions of decoration technique inside mold, be prepared from by the raw material of following weight part therein:
75～85 parts of polycarbonate (PC),
15～25 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
In an embodiment, for the polycarbonate compositions of decoration technique inside mold, be prepared from by the raw material of following weight part therein:
80 parts of polycarbonate (PC),
20 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
In some embodiment, described polycarbonate is dihydroxyphenyl propane aromatic copolycarbonate therein, and number-average molecular weight is 15000～30000; The content of the 1,4 cyclohexane dimethanol ester in described polyethylene terephthalate-1,4 cyclohexane dimethanol ester is 12%～47%.
In some embodiment, the content of the 1,4 cyclohexane dimethanol ester in described polyethylene terephthalate-1,4 cyclohexane dimethanol ester is 25%～35% therein.
Another object of the present invention is to provide the preparation method for the polycarbonate compositions of decoration technique inside mold.
The preparation method of above-mentioned polycarbonate compositions, concrete technical scheme, comprises the following steps:
(1) described polycarbonate (PC) is placed in to 100～120 DEG C, dry 4～12 hours, by described polyethylene terephthalate-1,4-cyclohexanedimethanoester ester (PETG) is placed in 70～90 DEG C, dry 4～12 hours, after cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 220～240 DEG C, two district's temperature: 230～250 DEG C, three district's temperature are 240～270 DEG C, four district's temperature: 240～270 DEG C, five district's temperature are 240～270 DEG C, six district's temperature: 240～270 DEG C, die head temperature: 230～260 DEG C, driving screw rotating speed is: 100～400rpm.
In some embodiment, in described step (1), polycarbonate is placed in 110 DEG C therein, and dry 4～6 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester was placed in 80 DEG C, dry 4～6 hours; Processing parameter in described step (3) is: district's temperature is 220～230 DEG C, two district's temperature: 240～250 DEG C, three district's temperature are 250～260 DEG C, four district's temperature: 250～260 DEG C, five district's temperature are 250～260 DEG C, six district's temperature: 250～260 DEG C, die head temperature: 240～250 DEG C, driving screw rotating speed is: 150～250rpm.
In some embodiment, the screw rod of described parallel double-screw extruder is shaped as single thread therein; The ratio L/D of spiro rod length L and diameter D is 30～60; Described screw rod is provided with more than one gear block district and more than one left-hand thread district.
In some embodiment, the ratio L/D of described spiro rod length L and diameter D is 40～55 therein; Described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Principle of the present invention is as follows:
Polyethylene terephthalate-1,4-cyclohexanedimethanoester ester (PETG) transparency is high, glossiness good, a kind of novel transparent engineering plastics, PETG has that shock strength is high, good heat resistance, bending do not whiten, mar-proof, ageing-resistant, anti-electrostatic, chemical resistant properties excellence, hydrolysis, good fluidity, strong coloring force, be easy to the advantage such as forming process, wholesomeness good (meeting FDA), belongs to environmentally-friendly plastic of new generation.
PC and PETG melt blending are prepared to PC/PETG alloy, keep to a certain extent the mechanical property such as tensile strength, flexural strength of PC, while is due to the introducing of PETG, increased product toughness, improved notched Izod impact strength and elongation at break, also improved the stress cracking of Drawing abillity, anti-chemical and goods etc. simultaneously, reach the object of learning from other's strong points to offset one's weaknesses, further expanded the Application Areas of PC and PETG, meet Industrial products performance requriements widely.
In situ reactive compatibilization refers to two kinds of superpolymer, puts in the lump in parallel double-screw extruder containing the monomer of double reactive functional group, in extrusion, produce on the spot compatilizer, should react with these two kinds of superpolymer respectively containing the monomer of double reactive functional group, form the compatilizer of superpolymer-co-containing monomer-co-superpolymer of double reactive functional group.
The present invention adopts the method for in situ reactive compatibilization, in parallel double-screw extruder, the terminal hydroxy group of polycarbonate can be respectively and the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, polyethylene terephthalate-1, the terminal hydroxy group of 4-cyclohexanedimethanoester ester, end carboxyl can be respectively and the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, form compatilizer PC-co-TDI-co-PETG, compatilizer PC-co-PBO-co-PETG, thereby improve the consistency of PC/PETG system, obtain thering is mold temperature low, processing fluidity is good, shock strength height and the high polycarbonate compositions of transparency.
In the building-up process of PETG, 1,4 cyclohexane dimethanol ester (CHDM) replaces the ethylene glycol (EG) of some amount, along with the increase of CHDM in polymkeric substance, Tg rises, melting point depression, degree of crystallinity declines, and finally forms transparent amorphous copolyester.The present invention draws in experimentation, and the CHDM content in PETG is 12%～47% comparatively suitable, and just can reach technique effect of the present invention.The ratio that replaces EG as CHDM is lower than 10% time, and its fusing point is higher, processibility is poor, can not reach the effect of the performance of improving PC; When replacing the ratio of EG, CHDM reaches 50% or when higher, copolyester is transformed into PCTG or PCTA, and PCTG and PCTA have with respect to PETG and have slightly high thermotolerance and chemical resistant properties, mechanical property also has the lifting of certain amplitude, but the cost of material also significantly goes up, and due to the increasing of CHDM content, the crystallizing power grow of PCTG and PCTA, easily there is the crystallization phenomenon such as turn white in forming process goods, thereby makes it can not be applied to decoration technique inside mold injectable plastic material.
In situ reactive compatibilization provided by the present invention has the following advantages for the preparation of the method for the polycarbonate compositions of decoration technique inside mold:
1, polycarbonate compositions of the present invention, in the situation that keeping original degradation few, can at not higher than the temperature of 260 DEG C, process again, and have that mold temperature is low, processing fluidity good, shock strength is high and the advantage such as transparency high (refractive index of PC, PETG is respectively 1.58,1.57), be especially suitable for use as the injectable plastic material of IMD technique.
2, adopt the polycarbonate compositions of method of the present invention for the preparation of decoration technique inside mold, its technique is simple, is easy to control, and not high to equipment requirements, the equipment using is general polymer processing equipment, invests not high.
Brief description of the drawings
Figure 1 shows that IMD process flow sheet;
Figure 2 shows that preparation technology's schema of polycarbonate compositions of the present invention;
Figure 3 shows that the scanning electron microscope (SEM) photograph of the polycarbonate compositions of the embodiment of the present invention 4 gained.
Embodiment
For further understanding feature of the present invention, technique means and the specific purposes that reach, function, resolve the advantages and spirit of the present invention, by following examples, the present invention is further elaborated.
In situ reactive compatibilization of the present invention is prepared the reaction mechanism following (preparation technology's schema is asked for an interview Fig. 2) of polycarbonate compositions:
Reaction mechanism
From upper reaction formula, the terminal hydroxy group of polycarbonate can be respectively and the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, polyethylene terephthalate-1, the terminal hydroxy group of 4-cyclohexanedimethanoester ester, end carboxyl can be respectively and the isocyanate groups of tolylene diisocyanate, 2, 2'-(1, 3-phenylene) the oxazoline group of-bisoxazoline reacts, form compatilizer PC-co-TDI-co-PETG, compatilizer PC-co-PBO-co-PETG, thereby improve the consistency of PC/PETG system, obtain thering is mold temperature low, processing fluidity is good, shock strength height and the high polycarbonate compositions of transparency.
The raw material that the embodiment of the present invention is used is as follows:
Polycarbonate, is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Dow Chemical company, and number-average molecular weight is 15000;
Polycarbonate, is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Japanese Supreme Being people and changes into company, and number-average molecular weight is 23000;
Polycarbonate, is dihydroxyphenyl propane aromatic copolycarbonate 0, is selected from Korea S three and supports company, and number-average molecular weight is 3000;
Polycarbonate, is dihydroxyphenyl propane aromatic copolycarbonate, is selected from Korea S three and supports company, and number-average molecular weight is 50000;
Polyethylene terephthalate-1,4 cyclohexane dimethanol ester, viscosity is 1.2dL/g, and transmittance is 90%, and wherein the content of 1,4 cyclohexane dimethanol ester, 25%, is selected from Yisiman Chemical Company of the U.S.;
Polyethylene terephthalate-1,4 cyclohexane dimethanol ester, viscosity is 1.2dL/g, and transmittance is 90%, and wherein the content of 1,4 cyclohexane dimethanol ester, 30%, is selected from Yisiman Chemical Company of the U.S.;
Polyethylene terephthalate-1,4 cyclohexane dimethanol ester, wherein the content of 1,4 cyclohexane dimethanol ester, 35%, is selected from SK company of Korea S;
Polyethylene terephthalate-1,4 cyclohexane dimethanol ester, wherein the content of 1,4 cyclohexane dimethanol ester, 55%, is selected from SK company of Korea S;
Tolylene diisocyanate, is selected from Shanghai Sheng Yu Chemical Co., Ltd.;
2,2'-(1,3-phenylene)-bisoxazoline, is selected from colon, Nanjing medication chemistry company limited;
β-(4-hydroxy phenyl-3,5-di-t-butyl) positive octadecanol ester of propionic acid (antioxidant 1076), as primary antioxidant, is selected from Switzerland's vapour Bagong department;
Tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (irgasfos 168), as auxiliary antioxidant, is selected from Switzerland's vapour Bagong department;
Pentaerythritol stearate, is selected from Clariant company of the U.S..
Comparative example 1:
A kind of polycarbonate compositions of this comparative example, is prepared from by following raw material:
80 parts of polycarbonate (PC, number-average molecular weight is 23000),
20 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 30%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, by polyethylene terephthalate-1 of above-mentioned weight part, 4-cyclohexanedimethanoester ester (PETG) is placed in 80 DEG C, dry 4 hours, after cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as double thread, and the ratio L/D of spiro rod length L and diameter D is 20, and described screw rod is provided with 1 gear block district, without left-hand thread district.
Comparative example 2:
A kind of polycarbonate compositions of this comparative example, is prepared from by following raw material:
85 parts of polycarbonate (PC, number-average molecular weight is 23000),
15 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 30%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
0.2 part of primary antioxidant,
0.2 part of auxiliary antioxidant,
0.1 part of lubricant.
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) primary antioxidant, auxiliary antioxidant and lubricant are joined in another homogenizer and mixed, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Comparative example 3:
A kind of polycarbonate compositions of this comparative example, is prepared from by following raw material:
80 parts of polycarbonate (PC, number-average molecular weight is 50000),
20 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 30%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Comparative example 4
A kind of polycarbonate compositions of this comparative example, is prepared from by following raw material:
80 parts of polycarbonate (PC, number-average molecular weight is 23000),
20 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 55%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 1:
A kind of polycarbonate compositions of the present embodiment, is prepared from by following raw material:
95 parts of polycarbonate (PC, number-average molecular weight is 30000),
5 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 35%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 400rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 40, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 2:
A kind of polycarbonate compositions of the present embodiment, is prepared from by following raw material:
90 parts of polycarbonate (PC, number-average molecular weight is 15000),
10 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 25%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 100rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 3:
A kind of polycarbonate compositions of the present embodiment, is prepared from by following raw material:
85 parts of polycarbonate (PC, number-average molecular weight is 23000),
15 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 30%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 4:
A kind of polycarbonate compositions of the present embodiment, is prepared from by following raw material:
80 parts of polycarbonate (PC, number-average molecular weight is 23000),
20 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 30%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
The scanning electron microscope (SEM) photograph of the polycarbonate compositions of the present embodiment gained as shown in Figure 3, has shown the dispersing morphology of PETG in PC in figure.As can be seen from Figure 3, section has obvious crazing-shear zone to produce, and phase interface becomes very fuzzy, and PETG particle is scattered in the matrix of PC well, shows as ductile rupture.
Embodiment 5:
A kind of polycarbonate compositions of the present embodiment, is prepared from by following raw material:
75 parts of polycarbonate (PC, number-average molecular weight is 23000),
25 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 30%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 55, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 6:
A kind of polycarbonate compositions of the present embodiment, is prepared from by following raw material:
70 parts of polycarbonate (PC, number-average molecular weight is 23000),
30 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 30%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 60, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Embodiment 7:
A kind of polycarbonate compositions of the present embodiment, is prepared from by following raw material:
65 parts of polycarbonate (PC, number-average molecular weight is 23000),
35 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters (PETG, wherein the content of 1,4 cyclohexane dimethanol ester is 30%),
Polycarbonate (PC) is 100 parts with the weight part summation of polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG),
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) polycarbonate of above-mentioned weight part (PC) is placed in to 110 DEG C, dry 4 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) of above-mentioned weight part is placed in to 80 DEG C, dry 4 hours.After cooling, polycarbonate, polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliary antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture mixing being placed in to parallel double-screw extruder melt extrudes, granulation, processing parameter is as follows: district's temperature is 230 DEG C, two district's temperature: 240 DEG C, three district's temperature are 250 DEG C, four district's temperature: 260 DEG C, five district's temperature are 260 DEG C, six district's temperature: 260 DEG C, die head temperature: 250 DEG C, driving screw rotating speed is: 200rpm.
The screw rod of described parallel double-screw extruder is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Be below comparative example and embodiment table look-up:
Table 1 comparative example and embodiment raw material composition weight part table look-up
Above-mentioned comparative example and the made sample of embodiment are carried out to following performance test:
Tensile property: press GB/T1042-1992 standard testing, rate of extension 50mm/min;
Impact property: press GB/T1843-1996 standard testing, batten thickness is 3.2mm;
Transmittance: press ASTMD1003 standard testing, thickness of test piece 1.0mm;
Melting index: press ASTMD1238 test, 260 DEG C of probe temperatures, load 2.16kg.
Table 2 comparative example and embodiment performance table look-up
Comparative example 1 is for screw rod is shaped as double thread, and the ratio L/D of spiro rod length L and diameter D is 20, and screw rod is provided with 1 gear block district, the polycarbonate compositions preparing without the twin screw extruder in left-hand thread district; Embodiment 4 is for screw rod is shaped as single thread, and the ratio L/D of spiro rod length L and diameter D is 50, and screw rod is provided with the polycarbonate compositions that the twin screw extruder in 2 gear block districts and 2 left-hand thread districts prepares.Can find out by contrast, adopt screw rod of the present invention to be shaped as single thread, the ratio L/D of spiro rod length L and diameter D is 50, when screw rod is provided with 2 gear block districts and 2 left-hand thread districts, tensile strength, notched Izod impact strength, transmittance and the melting index of polycarbonate compositions are greatly improved, and obtain the beneficial effect of the polycarbonate compositions that mold temperature is low, processing fluidity good, shock strength is high and transparency is high.
Comparative example 2 is not for adding the polycarbonate compositions containing the monomer of double reactive functional group; Embodiment 3 is for adding tolylene diisocyanate (TDI), 2, the polycarbonate compositions of 2'-(1,3-phenylene)-bisoxazoline (PBO).Can find out by contrast, add containing tensile strength, notched Izod impact strength, transmittance and the melting index of the polycarbonate compositions of the monomer of double reactive functional group and be better than and do not add containing the polycarbonate compositions of the monomer of double reactive functional group.
The polycarbonate compositions that the number-average molecular weight that comparative example 3 is polycarbonate is 50000; The polycarbonate compositions that the number-average molecular weight that embodiment 4 is polycarbonate is 23000.Can find out by contrast, the number-average molecular weight of polycarbonate is that the tensile strength of 50000 polycarbonate compositions and notched Izod impact strength are larger than polycarbonate compositions that the number-average molecular weight of polycarbonate is 23000, both transmittances change little, and the melting index of the polycarbonate compositions that the number-average molecular weight of polycarbonate is 50000 only has 5g/10min, its processing characteristics is poor, is not suitable for being applied to decoration technique inside mold injectable plastic material.
The polycarbonate compositions that comparative example 4 is 55% for the content of 1,4 cyclohexane dimethanol ester in PETG; The polycarbonate compositions that embodiment 4 is 30% for the content of 1,4 cyclohexane dimethanol ester in PETG.Can find out by contrast, the two tensile strength, notched Izod impact strength and melting index changes little, but the transmittance of the polycarbonate compositions that in PETG, the content of 1,4 cyclohexane dimethanol ester is 55% only has 62%, be not suitable for being applied to decoration technique inside mold injectable plastic material.
Embodiment 1～7 is for adjusting the weight part of PC and PETG, and as can be seen from Table 2, along with the addition of PETG increases, the tensile strength of polycarbonate compositions and notched Izod impact strength present and first reduce the variation tendency of reduction again that raises afterwards; The transmittance of polycarbonate compositions changes little; The melting index of polycarbonate compositions presents the variation tendency of increase.Wherein, over-all properties the best of embodiment 4.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (8)
1. for a polycarbonate compositions for decoration technique inside mold, it is characterized in that, be prepared from by the raw material of following weight part:
65～95 parts of polycarbonate,
5～35 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters,
The weight part summation of polycarbonate and polyethylene terephthalate-1,4 cyclohexane dimethanol ester is 100 parts,
Described Hinered phenols antioxidant is the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid;
Described phosphite ester kind antioxidant is tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester;
Described lubricant is pentaerythritol stearate.
2. the polycarbonate compositions for decoration technique inside mold according to claim 1, is characterized in that, is prepared from by the raw material of following weight part:
75～85 parts of polycarbonate,
15～25 parts of polyethylene terephthalate-1,4 cyclohexane dimethanol esters,
The weight part summation of polycarbonate and polyethylene terephthalate-1,4 cyclohexane dimethanol ester is 100 parts,
3. the polycarbonate compositions for decoration technique inside mold according to claim 1 and 2, is characterized in that, described polycarbonate is dihydroxyphenyl propane aromatic copolycarbonate, and number-average molecular weight is 15000～30000; The content of the 1,4 cyclohexane dimethanol ester in described polyethylene terephthalate-1,4 cyclohexane dimethanol ester is 12%～47%.
4. the polycarbonate compositions for decoration technique inside mold according to claim 3, is characterized in that, the content of the 1,4 cyclohexane dimethanol ester in described polyethylene terephthalate-1,4 cyclohexane dimethanol ester is 25%～35%.
5. a preparation method for the polycarbonate compositions for decoration technique inside mold described in claim 1～4 any one, is characterized in that, comprises the following steps:
(1) described polycarbonate is placed in to 100～120 DEG C, dry 4～12 hours, by described polyethylene terephthalate-1,4-cyclohexanedimethanoester ester is placed in 70～90 DEG C, dry 4～12 hours, after cooling, polycarbonate and polyethylene terephthalate-1,4 cyclohexane dimethanol ester are joined and in homogenizer, carry out pre-mixing;
(2) by tolylene diisocyanate, 2,2'-(1,3-phenylene)-bisoxazoline, Hinered phenols antioxidant, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then the mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premixture step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, processing parameter is as follows: district's temperature is 220～240 DEG C, two district's temperature: 230～250 DEG C, three district's temperature are 240～270 DEG C, four district's temperature: 240～270 DEG C, five district's temperature are 240～270 DEG C, six district's temperature: 240～270 DEG C, die head temperature: 230～260 DEG C, driving screw rotating speed is: 100～400rpm.
6. preparation method according to claim 5, is characterized in that, in described step (1), polycarbonate is placed in 110 DEG C, and dry 4～6 hours, polyethylene terephthalate-1,4 cyclohexane dimethanol ester was placed in 80 DEG C, dry 4～6 hours; Processing parameter in described step (3) is: district's temperature is 220～230 DEG C, two district's temperature: 240～250 DEG C, three district's temperature are 250～260 DEG C, four district's temperature: 250～260 DEG C, five district's temperature are 250～260 DEG C, six district's temperature: 250～260 DEG C, die head temperature: 240～250 DEG C, driving screw rotating speed is: 150～250rpm.
7. preparation method according to claim 5, is characterized in that, the screw rod of described parallel double-screw extruder is shaped as single thread; The ratio L/D of spiro rod length L and diameter D is 30～60; Described screw rod is provided with more than one gear block district and more than one left-hand thread district.
8. preparation method according to claim 5, is characterized in that, the ratio L/D of described spiro rod length L and diameter D is 40～55; Described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
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| 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 |
| CN104672880A (en) * | 2015-02-17 | 2015-06-03 | 深圳市光华伟业实业有限公司 | PC/PETG alloy material and preparation method thereof |
| CN106751406A (en) * | 2016-12-26 | 2017-05-31 | 上海锦湖日丽塑料有限公司 | It is adapted to polymer blend of ultrasonic bonding and preparation method thereof |
| CN108727797A (en) * | 2017-04-13 | 2018-11-02 | 江苏华信新材料股份有限公司 | A kind of in-mold decoration polycarbonate substrate and preparation method thereof |
| CN114103364A (en) * | 2021-12-07 | 2022-03-01 | 合肥乐凯科技产业有限公司 | Optical polyester film and preparation method thereof |
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| CN103073865A (en) * | 2012-12-25 | 2013-05-01 | 安徽科聚新材料有限公司 | PC and copolyester blend and preparation method thereof |
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| CN101798457A (en) * | 2010-01-20 | 2010-08-11 | 华东理工大学 | Production method of super-toughness engineering plastic of nylon 6/ polycarbonate/ elastomer/ HDI |
| CN103073865A (en) * | 2012-12-25 | 2013-05-01 | 安徽科聚新材料有限公司 | PC and copolyester blend and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104672880A (en) * | 2015-02-17 | 2015-06-03 | 深圳市光华伟业实业有限公司 | PC/PETG alloy material and preparation method thereof |
| CN106751406A (en) * | 2016-12-26 | 2017-05-31 | 上海锦湖日丽塑料有限公司 | It is adapted to polymer blend of ultrasonic bonding and preparation method thereof |
| CN108727797A (en) * | 2017-04-13 | 2018-11-02 | 江苏华信新材料股份有限公司 | A kind of in-mold decoration polycarbonate substrate and preparation method thereof |
| CN108727797B (en) * | 2017-04-13 | 2020-06-09 | 江苏华信新材料股份有限公司 | Polycarbonate substrate for in-mold decoration and preparation method thereof |
| CN114103364A (en) * | 2021-12-07 | 2022-03-01 | 合肥乐凯科技产业有限公司 | Optical polyester film and preparation method thereof |
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