CN103951957B - Be used for polycarbonate compositions of decoration technique inside mold and preparation method thereof - Google Patents
Be used for polycarbonate compositions of decoration technique inside mold and preparation method thereof Download PDFInfo
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- CN103951957B CN103951957B CN201410198480.7A CN201410198480A CN103951957B CN 103951957 B CN103951957 B CN 103951957B CN 201410198480 A CN201410198480 A CN 201410198480A CN 103951957 B CN103951957 B CN 103951957B
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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)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of polycarbonate compositions for decoration technique inside mold and preparation method thereof, described polycarbonate compositions is prepared from by the raw material of following weight portion: 65～95 parts of Merlon, PETG-1, 5～35 parts of 4-cyclohexanedimethanoester esters, Merlon and PETG-1, the weight portion summation of 4-cyclohexanedimethanoester ester is 100 parts, 0.1～3 part of toluene di-isocyanate(TDI), 2, 2 ˊ-(1, 3-phenylene) 0.1～3 part of-bisoxazoline, 0.1～1 part of primary antioxidant, 0.1～1 part of auxiliary antioxidant, 0.1～1 part of lubricant. the present invention is prepared and is had the polycarbonate compositions for decoration technique inside mold injected plastics material that forming temperature is low, processing fluidity good, impact strength is high and transparency is high by the method for 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 andPreparation method.
Background technology
The develop rapidly of China in Recent Years industry, constantly expands the application surface of Merlon (PC), its demandAlso constantly increase. But along with science and technology progress with rapid changepl. never-ending changes and improvements, the continuous renewal of industrial products is regenerated, to wanting of material propertyAsk more and more harsh, the Merlon of conventional model can not meet all types of requirements of product in properties of product, and PCHave that melt viscosity is large, poor fluidity, high temperature facile hydrolysis, poor solvent resistance, high to the sensitiveness of breach, easily occur swelling and shouldPower cracking, and the shortcoming such as coefficient of friction is large, higher, the special trade mark price of melt temperature height, thereby directly affect, it is further darkEnter application and promote.
At present, in prior art, the modification of PC has been done to some researchs, for example patent CN201210571434.8 disclosesBy add copolyesters in PC, improve the mobility of PC resin, reduce machine-shaping temperature, but this PC blend adds phaseHold after agent modification POE, larger on its transparency impact; Patent CN201010208937.X discloses by calender calendering formationMethod prepare Makrolon/modified polyester blending thing, this blend is applied to smart card base material, but this PC blendThing adds after titanium dioxide, calcium carbonate, larger on its transparency impact; Patent CN201310298832.1 discloses one can low temperaturePolycarbonate compositions of moulding and preparation method thereof, first it be with copolyester, polyesteramide, the preparation of ester exchange promoterObtain compatilizer copolyester composition, then by copolyester composition, Merlon, ester exchange inhibitor, functional addingAdd agent blending extrusion and obtain polycarbonate compositions.
Decoration technique inside mold (IMD) is the new work of plastic shaping growing up in order to solve traditional decoration technical deficiencySkill. IMD technique (process chart as shown in Figure 1) be first by desired product pattern, that color is printed on transparent plastic is thinFilm (PC, PET, transparent ABS) is upper, and film thickness is 0.1～0.2mm approximately, then by thin-film sheet preformed, be die-cut into definite shapeWith size, then sheet material is embedded in the die cavity of mould and fixing, injection moulding in the most backward mould, plastic melt becomes in the inner side of sheet materialType also contacts and fuses together with sheet material. Thin-film sheet is just attached to the surface of product securely like this, produces and has surfaceThe high-grade plastic products of decorating.
In IMD technique because the carrier for pattern (thin layer material) and ink logo itself can not stand high temperature, instituteGenerally to select the thermoplastic of lower injection temperature as its injected plastics material, and this injected plastics material must possess forming temperatureThe feature low, processing fluidity good, impact strength is high and transparency is high. But the temporary material without possessing such performance in prior artMaterial.
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 hasThe polycarbonate compositions that forming temperature is low, processing fluidity good, impact strength is high and transparency is high, can be applicable to in-mold decorationTechnology injected plastics 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 portion:
65～95 parts of Merlon (PC),
5～35 parts of PETG-1,4-CHDM esters (PETG),
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 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.
Therein in some embodiment, for the polycarbonate compositions of decoration technique inside mold, former by following weight portionMaterial is prepared from:
75～85 parts of Merlon (PC),
15～25 parts of PETG-1,4-CHDM esters (PETG),
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
Therein in an embodiment, for the polycarbonate compositions of decoration technique inside mold, former by following weight portionMaterial is prepared from:
80 parts of Merlon (PC),
20 parts of PETG-1,4-CHDM esters (PETG),
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
In some embodiment, described Merlon is bisphenol-A aromatic copolycarbonate therein, and number-average molecular weight is15000～30000; 1,4-CHDM in described PETG-1,4-CHDM esterThe content of ester is 12%～47%.
Therein in some embodiment, 1 in described PETG-1,4-CHDM ester,The content of 4-cyclohexanedimethanoester ester is 25%～35%.
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 Merlon (PC) is placed in to 100～120 DEG C, dry 4～12 hours, by described poly terephthalic acidGlycol ester-1,4-CHDM ester (PETG) is placed in 70～90 DEG C, dry 4～12 hours, cooling after, will gather carbonic acidEster, PETG-1,4-CHDM ester join and in homogenizer, carry out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), Hinered phenols antioxygenAgent, phosphite ester kind antioxidant and lubricant join in another homogenizer and mix, then by the mixing obtainingThing joins in the homogenizer in step (1) and mixes;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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 temperatureDegree: 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, mainScrew speed is: 100～400rpm.
In some embodiment, in described step (1), Merlon is placed in 110 DEG C therein, dry 4～6 hours, poly-to benzeneDioctyl phthalate glycol ester-1,4-CHDM ester is placed in 80 DEG C, dry 4～6 hours; Technique ginseng in described step (3)Number 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, and die head temperature: 240～250 DEG C, main spiral shellBar rotating speed is: 150～250rpm.
In some embodiment, the screw rod of described parallel double-screw extruder is shaped as single thread therein; Spiro rod length LWith the ratio L/D of diameter D be 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 with2 gear block districts and 2 left-hand thread districts.
Principle of the present invention is as follows:
PETG-1,4-CHDM ester (PETG) transparency is high, glossiness good, is a kind ofNovel transparent engineering plastics, PETG has that impact strength is high, good heat resistance, bending do not whiten, mar-proof, ageing-resistant, antistatic,Chemical resistance excellence, hydrolysis, good fluidity, strong coloring force, be easy to the advantage such as processing and forming, wholesomeness good (meeting FDA), belong toIn environmentally-friendly plastic of new generation.
PC and PETG melt blending are prepared to PC/PETG alloy, keep to a certain extent the hot strength, bending strong of PCThe mechanical properties such as degree, simultaneously due to the introducing of PETG, increased product toughness, improved notched Izod impact strength and extension at breakRate has also been improved the stress cracking of drawing abillity, anti-chemistry and goods etc. simultaneously, reaches the order of learning from other's strong points to offset one's weaknesses, further expand the application of PC and PETG, meet industrial products performance requirement widely.
In situ reactive compatibilization refers to two kinds of high polymers, puts in the lump parallel double spiral shell containing the monomer of double reactive functional groupIn bar extruder, in extrusion, produce on the spot compatilizer, should containing monomer of double reactive functional group respectively with these two kindsHigh polymer reacts, and forms the compatilizer of high polymer-co-containing monomer-co-high polymer of double reactive functional group.
The present invention adopts the method for in situ reactive compatibilization, and in parallel double-screw extruder, the terminal hydroxy group of Merlon canWith respectively with the isocyanate groups, 2 of toluene di-isocyanate(TDI), the oxazoline group of 2'-(1,3-phenylene)-bisoxazoline is sent outRaw reaction, the terminal hydroxy group of PETG-1,4-CHDM ester, end carboxyl can be respectively and toluene twoThe isocyanate groups, 2 of isocyanates, the oxazoline group of 2'-(1,3-phenylene)-bisoxazoline reacts, and forms phaseHold agent PC-co-TDI-co-PETG, compatilizer PC-co-PBO-co-PETG, thereby improve the compatibility of PC/PETG system,To thering is the polycarbonate compositions that forming temperature is low, processing fluidity good, impact strength is high and transparency is high.
In the building-up process of PETG, 1,4-CHDM ester (CHDM) replaces the ethylene glycol (EG) of some,Along with the increase of CHDM in polymer, Tg rises, melting point depression, and degree of crystallinity declines, and finally forms transparent amorphous copolymerization poly-Ester. The present invention draws in experimentation, and the CHDM content in PETG is 12%～47% comparatively suitable, and just can reach thisBright technique effect. The ratio that replaces EG as CHDM is lower than 10% time, and its fusing point is higher, processability is poor, can not reach and changeThe effect of the performance of kind PC; Reach 50% or when higher when CHDM replaces the ratio of EG, copolyester be transformed into PCTG orPCTA, and PCTG and PCTA have with respect to PETG and have slightly high heat resistance and chemical resistance, mechanical performance also has certain amplitudeLifting, but the cost of material also significantly goes up, and due to the increasing of CHDM content, the crystallizing power of PCTG and PCTAGrow, easily there is the crystallization phenomenon such as turn white in processing and forming goods, thereby makes it can not be applied to decoration technique inside mold injection moulding materialMaterial.
In situ reactive compatibilization provided by the present invention is for the preparation of the method for the polycarbonate compositions of decoration technique inside moldHave the following advantages:
1, polycarbonate compositions of the present invention, is keeping original hydraulic performance decline few in the situation that, again can be not higher than 260DEG C temperature under process, and have that forming temperature is low, processing fluidity good, impact strength is high and transparency high (PC, PETGRefraction index be respectively 1.58,1.57) etc. advantage, be especially suitable for use as the injected plastics 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, easilyIn control, not high to equipment requirement, the equipment using is general Polymer Processing equipment, invests not high.
Brief description of the drawings
Figure 1 shows that IMD process chart;
Figure 2 shows that preparation technology's flow chart 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.
Detailed description of the invention
For further understanding feature of the present invention, technological means and the specific purposes that reach, function, resolve thisBright advantage and spirit, by following examples, the present invention is further elaborated.
In situ reactive compatibilization of the present invention is prepared the reaction mechanism of polycarbonate compositions, and following (preparation technology's flow chart is asked for an interviewFig. 2):
Reaction mechanism
From upper reaction equation, the terminal hydroxy group of Merlon can be respectively and the NCO of toluene di-isocyanate(TDI)Group, 2, the oxazoline group of 2'-(1,3-phenylene)-bisoxazoline reacts, PETG-Isosorbide-5-Nitrae-ringThe terminal hydroxy group of hexane diformazan alcohol ester, end carboxyl can be respectively and the isocyanate groups, 2 of toluene di-isocyanate(TDI), 2'-(1,3-Phenylene) the oxazoline group of-bisoxazoline reacts, and forms compatilizer PC-co-TDI-co-PETG, compatilizer PC-co-PBO-co-PETG, thus the compatibility of PC/PETG system improved, obtain having that forming temperature is low, processing fluidity good, impactIntensity height and the high polycarbonate compositions of transparency.
The raw material that the embodiment of the present invention is used is as follows:
Merlon, is bisphenol-A aromatic copolycarbonate, is selected from Dow Chemical company, and number-average molecular weight is15000；
Merlon, is bisphenol-A aromatic copolycarbonate, is selected from Japanese Supreme Being people and changes into company, and number-average molecular weight is23000；
Merlon, is bisphenol-A aromatic copolycarbonate 0, is selected from Korea S three and supports company, and number-average molecular weight is 3000;
Merlon, is bisphenol-A aromatic copolycarbonate, is selected from Korea S three and supports company, and number-average molecular weight is 50000;
PETG-1,4-CHDM ester, viscosity is 1.2dL/g, light transmittance is 90%, itsThe content of middle 1,4-CHDM ester, 25%, is selected from Yisiman Chemical Company of the U.S.;
PETG-1,4-CHDM ester, viscosity is 1.2dL/g, light transmittance is 90%, itsThe content of middle 1,4-CHDM ester, 30%, is selected from Yisiman Chemical Company of the U.S.;
PETG-1,4-CHDM ester, the wherein content of 1,4-CHDM ester35%, be selected from SK company of Korea S;
PETG-1,4-CHDM ester, the wherein content of 1,4-CHDM ester55%, be selected from SK company of Korea S;
Toluene di-isocyanate(TDI), is selected from Shanghai Sheng Yu Chemical Co., Ltd.;
2,2'-(1,3-phenylene)-bisoxazoline, is selected from colon, Nanjing medication chemistry Co., Ltd;
β-(4-hydroxy phenyl-3,5-di-t-butyl) positive octadecanol ester of propionic acid (antioxidant 1076), as primary antioxidant,Be 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 BagongDepartment;
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 Merlon (PC, number-average molecular weight is 23000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 30%) 20 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours, cooling after, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 Merlon (PC, number-average molecular weight is 23000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 30%) 15 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
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) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) primary antioxidant, auxiliary antioxidant and lubricant are joined in another homogenizer and mixed, thenThe mixture obtaining is joined in the homogenizer in step (1) and mixed;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 Merlon (PC, number-average molecular weight is 50000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 30%) 20 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 Merlon (PC, number-average molecular weight is 23000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 55%) 20 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 Merlon (PC, number-average molecular weight is 30000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 35%) 5 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 Merlon (PC, number-average molecular weight is 15000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 25%) 10 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 Merlon (PC, number-average molecular weight is 23000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 30%) 15 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 Merlon (PC, number-average molecular weight is 23000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 30%) 20 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 in figure that PETG is at PCIn dispersing morphology. As can be seen from Figure 3, section has obvious crazing-shear band to produce, and boundary becomes very mouldStick with paste, 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 Merlon (PC, number-average molecular weight is 23000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 30%) 25 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 Merlon (PC, number-average molecular weight is 23000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 30%) 30 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, techniqueParameter 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, and five district's temperatureDegree is 260 DEG C, six district's temperature: 260 DEG C, and 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,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 Merlon (PC, number-average molecular weight is 23000),
PETG-1,4-CHDM ester (PETG, wherein 1,4-CHDM esterContent is 30%) 35 parts,
Merlon (PC) is total with the weight portion of PETG-1,4-CHDM ester (PETG)Be 100 parts,
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps:
(1) Merlon of above-mentioned weight portion (PC) is placed in to 110 DEG C, dry 4 hours, by gathering benzene of above-mentioned weight portionDioctyl phthalate glycol ester-1,4-CHDM ester (PETG) is placed in 80 DEG C, dry 4 hours. After cooling, by Merlon,PETG-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI) (TDI), 2,2'-(1,3-phenylene)-bisoxazoline (PBO), primary antioxidant, auxiliaryAid anti-oxidants and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix mixing is placed in to parallel double-screw extruder and melt extrudes, granulation, technological parameter asUnder: 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 are260 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,Described screw rod is provided with 2 gear block districts and 2 left-hand thread districts.
Be below comparative example and embodiment list:
Table 1 comparative example and embodiment raw material composition weight portion list
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;
Light transmittance: press ASTMD1003 standard testing, thickness of test piece 1.0mm;
Melt index: press ASTMD1238 test, 260 DEG C of probe temperatures, load 2.16kg.
Table 2 comparative example and embodiment performance list
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 1Gear block district, the polycarbonate compositions preparing without the double screw extruder in left-hand thread district; Embodiment 4 is shaped as for screw rodSingle thread, the ratio L/D of spiro rod length L and diameter D is 50, screw rod is provided with two spiral shells in 2 gear block districts and 2 left-hand thread districtsThe polycarbonate compositions that bar extruder prepares. Can find out by contrast, adopt screw rod of the present invention to be shaped as single lineScrew 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, poly-carbonic acidHot strength, notched Izod impact strength, light transmittance and the melt index of ester composition are greatly improved, obtain forming temperature low,The beneficial effect of the polycarbonate compositions that processing fluidity is good, impact 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 tolueneVulcabond (TDI), 2, the polycarbonate compositions of 2'-(1,3-phenylene)-bisoxazoline (PBO). Can by contrastFind out, add hot strength, notched Izod impact strength, light transmittance containing the polycarbonate compositions of the monomer of double reactive functional groupBe better than and do not add containing the polycarbonate compositions of the monomer of double reactive functional group with melt index.
The polycarbonate compositions that the number-average molecular weight that comparative example 3 is Merlon is 50000; Embodiment 4 is poly-carbonic acidThe number-average molecular weight of ester is 23000 polycarbonate compositions. Can find out by contrast, the number-average molecular weight of Merlon isThe number-average molecular weight that the hot strength of 50000 polycarbonate compositions and notched Izod impact strength are larger than Merlon is23000 polycarbonate compositions, both light transmittances change little, and the number-average molecular weight of Merlon is 50000The melt index of polycarbonate compositions only has 5g/10min, and its processing characteristics is poor, is not suitable for being applied to decoration technique inside moldInjected plastics material.
The polycarbonate compositions that comparative example 4 is 55% for the content of 1,4-CHDM ester in PETG; Embodiment 4For the content of 1,4-CHDM ester in the PETG polycarbonate compositions that is 30%. Can find out by contrast, these are two years oldPerson's hot strength, notched Izod impact strength and melt index changes little, but in PETG, 1,4-CHDM ester containsAmount is that the light transmittance of 55% polycarbonate compositions only has 62%, is not suitable for being applied to decoration technique inside mold injected plastics material.
Embodiment 1～7 is the weight portion of adjustment PC and PETG, as can be seen from Table 2, and along with the addition of PETG increasesAdd, the hot strength of polycarbonate compositions and notched Izod impact strength present and first reduce the variation tendency that raises afterwards and to reduce; Poly-The light transmittance of carbonate composition changes little; The melt index of polycarbonate compositions presents the variation tendency of increase. Wherein,Combination property 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 alsoCan not therefore be interpreted as the restriction to the scope of the claims of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to guarantor of the present inventionProtect scope. 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, prepared by the raw material of following weight portionForm:
65～95 parts of Merlon,
5～35 parts of PETG-1,4-CHDM esters, described polyethylene terephthalateThe content of the 1,4-CHDM ester in ester-1,4-CHDM ester is 12%～47%,
The weight portion summation of Merlon and PETG-1,4-CHDM 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;
The preparation method who is used for the polycarbonate compositions of decoration technique inside mold, comprises the following steps:
(1) described Merlon is placed in to 100～120 DEG C, dry 4～12 hours, by described PETG-1,4-CHDM ester is placed in 70～90 DEG C, dry 4～12 hours, cooling after, by Merlon and poly terephthalic acidGlycol ester-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI), 2,2'-(1,3-phenylene)-bisoxazoline, Hinered phenols antioxidant, phosphorous acid estersAntioxidant and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, technological parameterAs 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, and die head temperature: 230～260 DEG C, main spiral shellBar rotating speed is: 100～400rpm.
2. the polycarbonate compositions for decoration technique inside mold according to claim 1, is characterized in that, by weighing belowThe raw material of amount part is prepared from:
75～85 parts of Merlon,
15～25 parts of PETG-1,4-CHDM esters,
The weight portion summation of Merlon and PETG-1,4-CHDM ester is 100 parts,
3. the polycarbonate compositions for decoration technique inside mold according to claim 1 and 2, is characterized in that, described inMerlon is bisphenol-A aromatic copolycarbonate, and number-average molecular weight is 15000～30000.
4. the polycarbonate compositions for decoration technique inside mold according to claim 3, is characterized in that, described poly-rightThe content of the 1,4-CHDM ester in phthalic acid glycol ester-1,4-CHDM ester is 25%～35%.
5. a preparation method for the polycarbonate compositions for decoration technique inside mold described in claim 1～4 any one,It is characterized in that, comprise the following steps:
(1) described Merlon is placed in to 100～120 DEG C, dry 4～12 hours, by described PETG-1,4-CHDM ester is placed in 70～90 DEG C, dry 4～12 hours, cooling after, by Merlon and poly terephthalic acidGlycol ester-1,4-CHDM ester joins and in homogenizer, carries out premixed;
(2) by toluene di-isocyanate(TDI), 2,2'-(1,3-phenylene)-bisoxazoline, Hinered phenols antioxidant, phosphorous acid estersAntioxidant and lubricant join in another homogenizer and mix, and then the mixture obtaining are joined to step(1) in the homogenizer in, mix;
(3) premix step (2) being mixed is placed in parallel double-screw extruder and melt extrudes, granulation, technological parameterAs 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, and die head temperature: 230～260 DEG C, main spiral shellBar rotating speed is: 100～400rpm.
6. preparation method according to claim 5, is characterized in that, in described step (1), Merlon is placed in 110 DEG C,Dry 4～6 hours, PETG-1,4-CHDM ester was placed in 80 DEG C, dry 4～6 hours; InstituteThe technological parameter of stating in step (3) is: district's temperature is 220～230 DEG C, two district's temperature: 240～250 DEG C, three district's temperature are250～260 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 headTemperature: 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 asSingle 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 oneIndividual above 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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| 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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| 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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