CN107033575B - Laser direct organization polycarbonate Alloys composition, preparation and application - Google Patents
Laser direct organization polycarbonate Alloys composition, preparation and application Download PDFInfo
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- CN107033575B CN107033575B CN201710350526.6A CN201710350526A CN107033575B CN 107033575 B CN107033575 B CN 107033575B CN 201710350526 A CN201710350526 A CN 201710350526A CN 107033575 B CN107033575 B CN 107033575B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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Abstract
The invention discloses a kind of laser direct organization polycarbonate Alloys composition, preparation and applications, wherein specifically including that the polycarbonate Alloys of 70%-90% and the organosilicon modifier of 0.3%-5% in percentage by weight for composition;The polycarbonate Alloys include the polycarbonate of initial polycarbonate and recycling, wherein the weight percent of the polycarbonate Zhan recycled total blend composition is 20%-60%.The present invention solves the problems, such as that recycling PC, which is added, causes toughness of material to be remarkably decreased, reach the notch impact strength of polycarbonate Alloys and the pure comparable level of PC system by innovative modified method, material moulding processability is excellent simultaneously, laser carving, change plating work well, the technical requirements of laser direct organization can sufficiently be met, there is considerable economic benefit and great social value.
Description
Technical field
The invention belongs to laser direct organization field shaping techniques, are specifically related to a kind of poly- carbon of laser direct organizationization
Acid esters blend composition, preparation and application.
Background technique
Polycarbonate (PC) is a kind of engineering plastics with superior comprehensive performance, has excellent impact flexibility, ruler
The advantages that very little stability, electric insulating quality, creep resistant, weatherability, the transparency and nontoxicity, is widely used in mechanical equipment, builds
Build the numerous areas such as engineering, communications and transportation, instrument, electric and illumination.Meanwhile there are also apparent defects as processed by PC
Poor fluidity, easy stress cracking, to notch sensitive, be prone to wear, chemical resistance difference etc..Most as growth rate in recent years
The consumption of fast general engineering plastic, PC is larger, while defective material, regrinding-material and the reclaimed materials generated in article manufacturing process
Amount is also more, therefore PC reclaimed materials is modified and can be reused, and has great importance.But since regenerated PC expects
By using and removal process, material can be inevitably generated a degree of degradation, make its performance compared with virgin material compared with
More decline, it is difficult to be directly used in engineering plastics.Therefore, it is necessary to carry out modification again to them, it is multiple to obtain high-performance
It is recycled after condensation material.Further, for the demand of plastics industry sustainable development, if it is possible to change PC reclaimed materials
Property enable the functional material field for being applied to high added value, realize the perfect combination of environmental protection with science and technology, will generate
Considerable economic benefit and great social value.
Laser direct structuring technique (LDS (LaserDirect Structuring)) is using laser technology in special modeling
The technology of Direct Three-dimensional printed circuit board on materials and parts.The characteristics of this technology, is the flexibility of laser, precision and engineering
The plasticity of plastics and functional combination, considerably simplify production procedure, provide flexible and changeable design
Space, simultaneous processing high resolution (laser beam spot sizes < 80 μm).Therefore, LDS technology is in exigent field, such as
Communication, automotive electronics, electromechanical equipment, medical instrument etc. are got a lot of applications.
Common laser direct forming material mainly includes matrix resin at present, (or laser is straight for laser-sensitive additive
Connect structuring additive, LDS auxiliary agent) and the other components such as toughener, inorganic filler.Wherein matrix resin generallys use poly- carbon
Acid esters.When attempting for the polycarbonate material of recycling to be directly used in laser direct forming material, the toughness meeting of obtained material
It is remarkably decreased, is unable to satisfy material requirements.
Summary of the invention
Impact modified containing recycling component and has the polycarbonate Alloys group of LDS function the present invention provides a kind of
Object is closed, solves the problems, such as that recycling PC material is added directly in laser direct forming material causes toughness of material to be remarkably decreased.
The present invention also provides a kind of methods for preparing above-mentioned polycarbonate Alloys composition.
Invention also provides a kind of products being prepared by above-mentioned polycarbonate Alloys composition.
The invention adopts the following technical scheme:
A kind of laser direct organization polycarbonate Alloys composition specifically includes that in percentage by weight
The polycarbonate Alloys of 70%-90% and the organosilicon modifier of 0.3%-5%;The polycarbonate Alloys include initial
The polycarbonate of polycarbonate and recycling, wherein the weight percent of the polycarbonate Zhan recycled total blend composition is
20%-60%;As further preferred, the weight percent of the polycarbonate Zhan of the recycling total blend composition is
50%-60%;The weight percent of the organosilicon modifier Zhan total blend composition is 0.5~2%, further excellent
It is selected as 0.8~1.5%.
In the present invention, the polycarbonate (polycarbonate including initial polycarbonate and recycling, wherein initially
Polycarbonate refers to the polycarbonate starting material for not being processed to product) include the homopolymerization carbonic acid with repetitive structure carbonate unit
Ester and Copolycarbonate can be fatty poly-ester carbonate, one kind or two in alicyclic polycarbonate or aromatic copolycarbonate
The mixture of kind.In the present invention, suitable polycarbonate can be prepared for example, by the methods of interfacial polymerization and melt polymerization.?
In a kind of specific embodiment, polycarbonate is derived from the linear homopolymer of bisphenol-A, i.e., containing the aromatic series of structure of bisphenol A
Polycarbonate is shown below:
The polycarbonate of heretofore described recycling is that the PC material of recycling squeezes out after separating, being crushed, clean, dry
It is granulated regeneration PC resin obtained, production process can be derived from, it can also be from the packaging material of recycling, electronic apparatus
Outer casing member, building board, CD, bucket and other polycarbonate products etc..
The polycarbonate that the present invention actually uses can use existing various polycarbonate commercial product, for example can select
From the bisphenol A polycarbonate purchased from Bayer A.G, Japanese Supreme Being people or domestic some companies.
Organosilicon modifier can be polymer or oligomer.Preferably, the organosilicon modifier includes hydroxyl-functional
Group.Preferably, the organosilicon modifier includes one or more benzene ring structures.Preferably, the organosilicon modifier is
Siloxane polymer containing one or more hydroxy functional groups and one or more benzene ring structures.
Preferably, the organosilicon modifier structure is as follows:
Wherein, R1Selected from hydroxyl, hydroxyalkyl vinyl or hydroxyalkyl group.R2And R3Independently selected from alkyl, vinyl,
Sealing end or uncapped polysiloxane group;Preferably, the R2And R3It independently is methyl, ethyl or hydroxy-end capped poly- silicon
Oxyalkyl;R4And R5Independently selected from unsubstituted or substituted phenyl, preferably, R4And R5Independently selected from phenyl, tolyl
(including o-, m-, to replace).Wherein, the integer that x is 1 to 10000;The integer that y is 1 to 1000, and x:y is with 1:1 to 200:
1 ratio exists.
Preferably, the organosilicon modifier includes hydroxyl;As further preferred, the organosilicon modifier includes
Hydroxyl and phenyl.Preferably, the organosilicon modifier structure is as follows:
Preferably, in percentage by weight, the laser direct organization polycarbonate Alloys composition includes:
Preferably, the toughener is selected from rubber toughener and thermoplastic elastomehc with core-shell structure in the present invention
Property body.Such as Styrene-Butadiene-Styrene Block Copolymer (SBS), styrene ethylene butadiene-styrene block are total
Polymers (SEBS), ABS (acrylonitrile butadiene styrene copolymer), acrylonitrile-ethylene-propylene-diene-styrene
(AES), Methyl Methacrylate-Butadiene-Styrene Copolymer (MBS), polyolefin elastomer (POE) and organosilicon nucleocapsid are poly-
Close object etc..In one aspect, toughener is preferably acrylonitrile-butadiene-styrene copolymer (ABS) and methyl methacrylate
Ester-butadiene-styrene (MBS).
In the present invention, the laser direct organization additive is the metallization with spinelle or octahedral crystal structure
Close object and/or metal complex.The metallic compound can for the oxide of zinc, the organic compound of zinc, copper oxide,
The organic compound of copper, the oxide of cobalt, the organic compound of cobalt, the oxide of magnesium, magnesium organic compound, tin oxidation
Object, the organic compound of tin, titanyl compound, the organic compound of titanium, the oxide of iron, the organic compound of iron, aluminium oxygen
Compound, the organic compound of aluminium, the oxide of nickel, the organic compound of nickel, the oxide of manganese, the organic compound of manganese, chromium
One of organic compound of oxide or chromium or at least two mixture, the preferred organic compound of the oxide of copper, copper
One of organic compound of object, the oxide of tin and tin or at least two mixture;The metal complex is zinc
Complex, the complex of copper, the complex of cobalt, the complex of magnesium, the complex of tin, the complex of titanium, the complex of iron, aluminium
Complex, the complex of nickel, one of the complex of the complex of manganese or chromium or at least two mixture, preferably copper matches
Close the mixture of one of complex of object, tin or at least two.The example of laser direct forming additive includes but unlimited
In, metal oxide, the filler of metal oxide-coated and heavy metallic mixture oxide spinel, such as cupric and chromic oxide
Spinelle;Mantoquita, such as alkali formula cupric phosphate, cupric phosphate, copper sulphate, cuprous sulfocyanide;Organometallic compounds, such as palladium/contain
Palladium heavy metal complex or copper complex;Or the combination including at least one aforementioned LDS additive.
In one aspect, polycarbonate compositions of the invention can further include filler, such as mineral filler.Filler
It may include silicate and SiO 2 powder, such as talcum, mica, wollastonite, silicate ball, alumina silicate, kaolin, and
Mono-crystlling fibre or " whisker " etc..Preferably, the inorganic filler is selected from silicates.
In the present invention, disclosed polycarbonate compositions can optionally include flame retardant additives.The fire retardant
Additive include oligomer organophosphorous fire retardant for example low polyphosphate, polyphosphate, oligomeric phosphonate, mixing phosphate/phosphine
Ester flame-proof agent composition or phosphazene flame retardant.
Other additives: in addition to above-mentioned component, disclosed polycarbonate compositions can optionally comprising a kind of or
Multiple additives material, including such as heat stabilizer (such as antioxidant 1010 and/or irgasfos 168), hydrolysis stabilizer, chain extension
Agent or light stabilizer, UV absorbing additives, plasticizer, lubricant, release agent, antistatic agent, colorant (such as pigment or dye
Material) or any combination of them, it can add according to actual needs.
Preferably, the notch impact strength of the laser direct organization polycarbonate Alloys composition at room temperature
Greater than 450J/m.Wherein the laser direct organization polycarbonate Alloys composition is using can be into after laser activation
Row plating.
A kind of preparation method of above-mentioned laser direct organization polycarbonate Alloys composition, comprising: by each component
After premixing, by double screw extruder blending extrusion obtain.The extrusion item of premixed conditions and double screw extruder
The prior art can be used in part etc..Preferably, extruder temperature control is between 240-270 DEG C in double screw extruder.Later
The pellet of extrusion is subjected to injection molding after forced air drying 3~8 hours under the conditions of 90~120 DEG C.The premixing can be in height
It completes, does time in advance generally 3~5 minutes in fast mixing machine.
In the present invention, for the polycarbonate of recycling before use, selectable dried, drying condition is general are as follows: 90~
Forced air drying 4-6 hours under the conditions of 110 DEG C.
A kind of product being made by above-mentioned laser direct organization polycarbonate Alloys composition.It is wherein described
Product is selected from mobile phone, PC, medical instrument, automobile related application or RFID related application.Of the invention can be with laser
The polycarbonate Alloys composition of direct organization can be made of the existing technical approach of the technical field it is various forms of at
Type product are for utilization.
The present invention is by the control to recycling PC additive amount, and is used cooperatively specific organosilicon modifier, perfectly
It solves the technical issues of addition recycling PC causes toughness of material to be remarkably decreased, polycarbonate is made by innovative modified method
The notch impact strength of blend reaches > level of 450J/m, and the pure comparable level of PC system, while material molding processibility
Can be excellent, laser carving, change plating work well, and can sufficiently meet the technical requirements of laser direct organization, with considerable economic effect
Beneficial and great social value.
Specific embodiment
For more detailed description summary of the invention of the invention, further illustrate combined with specific embodiments below.
PC reclaimed materials used in the examples is usually to expect to squeeze out after separating, being crushed, clean, dry by the PC of recycling
It is granulated regeneration PC resin obtained.PC bucket material of the PC reclaimed materials from recycling.
Polycarbonate used in the examples is the aromatic copolycarbonate containing structure of bisphenol A, is shown below:
The commercially available bisphenol-A product of Japanese Di Ren company specifically can be used.
Embodiment 1-5
PC-1 used is polycarbonate virgin material in embodiment, is 18g/min in the MFR of 300 DEG C, 1.2Kg;PC-2 used is
The polycarbonate bucket material of recycling is 6g/min in the MFR of 300 DEG C, 1.2Kg.
First by PC reclaimed materials (PC-2) forced air drying 5 hours under the conditions of 100 DEG C.Pure PC material (PC- is weighed in proportion
1), the components such as MBS, cupric and chromic oxide (LDS), wollastonite (WOLL), organosiloxane (Siloxane) and heat stabilizer, then
Dried PC reclaimed materials (PC-2) is put into high-speed mixer high speed together with the above various raw materials to be pre-mixed 5 minutes.It will
Pre- mixed raw mixture, which is added in double screw extruder hopper, in a high speed mixer is melted, is kneaded, being squeezed out, is cold
But, the extruder temperature of dry, pelletizing, double screw extruder controls between 240-250 DEG C.Later by the pellet of extrusion 110
Injection molding is carried out under the conditions of DEG C after forced air drying 4 hours, and observation comparison is carried out to moulding appearance, while carrying out every power
It learns performance test and changes plating assessment.
Wherein, silicone-modified dose of Si-1 structure used is as follows:
Its trade name steps figure SF-1023, it is known that contains alkyl, hydroxyl and phenyl group in its structure simultaneously.Wherein, respectively
Item Mechanics Performance Testing uses following standard:
Impact property test: ASTM D256;
Tensile property test: ASTM D 638;
Bending property test: ASTM D 790;
Thermal deformation test: ASTM D 648.
Table 1
Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
PC-1 (wt%) | 90 | 50 | 40 | 30 | 39 |
PC-2 (wt%) | 40 | 50 | 60 | 50 | |
MBS (wt%) | 2 | 2 | 2 | 2 | 2 |
LDS (wt%) | 4 | 4 | 4 | 4 | 4 |
WOLL (wt%) | 3 | 3 | 3 | 3 | 3 |
Si-1 (wt%) | 1 | ||||
Notch impact strength (J/m) | 640 | 210 | 132 | 114 | 593 |
Tensile strength (MPa) | 57 | 58 | 58 | 59 | 56 |
Bending strength (MPa) | 88 | 90 | 90 | 90 | 86 |
Heat distortion temperature (C) | 113 | 112 | 112 | 112 | 108 |
Moulding surface | Well | Well | Well | Well | It is excellent |
Change plating performance | It is excellent | It is excellent | It is excellent | It is excellent | It is excellent |
It can be seen that by the test result of table 1, with the addition (embodiment 2-4) of the recycling PC material of 40-60wt%, poly- carbonic acid
The impact flexibility of ester blend composition significantly reduces, and other performance is maintained at similar level., it is surprising that with
The addition (embodiment 5) of the Si-1 of 1wt%, the notch impact strength of polycarbonate Alloys composition can rise to close
600J/m, while the intensity of material and heat distortion temperature only have slight decline.At the same time, in embodiment 5 moulding it is outer
It is more excellent to see performance, it is often more important that, change plating performance and is also maintained at good level.
Embodiment 6-11
Similarly, by PC reclaimed materials (PC-2) forced air drying 5 hours under the conditions of 100 DEG C.Pure PC material is weighed in proportion
(PC-1), the components such as MBS, cupric and chromic oxide (LDS), talcum (talc), organosiloxane (Siloxane) and heat stabilizer, so
Afterwards by various raw material high speed pre-mixings, it is added to double screw extruder and carries out blending processing.
Wherein, the trade name of organic siloxane modified dose of Si-2 used steps figure TSF437, it is known that contains alkane in its structure
Base, phenyl are without hydroxyl;The trade name of organic siloxane modified dose of Si-3 used steps figure SFR-100, it is known that in its structure
Contain hydroxyl group in addition to alkyl.
Table 2
Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | |
PC-1 (wt%) | 87.5 | 37 | 36.5 | 26.5 | 26.5 | 26.5 |
PC-2 (wt%) | 50 | 50 | 60 | 60 | 60 | |
MBS (wt%) | 4 | 4 | 4 | 4 | 4 | 4 |
LDS (wt%) | 5 | 5 | 5 | 5 | 5 | 5 |
Talc (wt%) | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
Si-1 (wt%) | 0.5 | 1 | 1 | |||
Si-2 (wt%) | 1 | |||||
Si-3 (wt%) | 1 | |||||
Notch impact strength (J/m) | 562 | 365 | 527 | 513 | 123 | 495 |
Tensile strength (MPa) | 57 | 56 | 56 | 56 | 55 | 54 |
Bending strength (MPa) | 90 | 90 | 88 | 88 | 87 | 85 |
Heat distortion temperature (C) | 112 | 109 | 107 | 107 | 107 | 106 |
Moulding surface | Well | Well | It is excellent | It is excellent | It is excellent | It is excellent |
Change plating performance | It is excellent | It is excellent | It is excellent | It is excellent | It is excellent | It is excellent |
Test result in table 2 further illustrates there is specified chemical structure (hydroxyl or hydroxyl and phenyl) by selecting
Silicone-modified dose, the impact modified polycarbonate Alloys containing a large amount of recycling PC obtained of the present invention have and PC virgin material
The comparable mechanical property of system and hot property, while there is excellent apparent and change plating performance, it can be used as high functionality completely
Material recycles to form new product again, so that PC reclaimed materials is obtained the recycling of high added value, eliminates it to nature
The pollution of environment has considerable economic benefit and social benefit.
Certainly, the above is only presently preferred embodiments of the present invention, therefore all according to structure described in present patent application range
It makes, the equivalent change or modification that feature and principle are done, is included in the scope of the patent application of the present invention.
Claims (8)
1. a kind of laser direct organization polycarbonate Alloys composition, which is characterized in that in percentage by weight, master
It include: the polycarbonate Alloys of 70%-90% and the organosilicon modifier of 0.3%-5%;The polycarbonate Alloys
Polycarbonate including initial polycarbonate and recycling, wherein the weight hundred of the polycarbonate Zhan recycled total blend composition
Divide than being 20%-60%;The organosilicon modifier is the siloxane polymer containing one or more hydroxy functional groups, this has
Machine silica modifier also contains one or more benzene ring structures.
2. laser direct organization polycarbonate Alloys composition according to claim 1, which is characterized in that described to have
Machine silica modifier is the one or more siloxane polymers having the following structure:
Wherein, R1Selected from hydroxyl, hydroxyalkyl vinyl or hydroxyalkyl group;
R2And R3Independently selected from alkyl, vinyl, sealing end or uncapped polysiloxane group;
R4And R5Independently selected from unsubstituted or substituted phenyl;
Wherein, the integer that x is 1 to 10000;The integer that y is 1 to 1000, and x:y exists with the ratio of 1:1 to 200:1.
3. laser direct organization polycarbonate Alloys composition according to claim 2, which is characterized in that described to have
Machine silica modifier has the following structure:
Wherein, the integer that x is 1 to 10000;The integer that y is 1 to 1000, and x:y exists with the ratio of 1:1 to 200:1.
4. laser direct organization polycarbonate Alloys composition according to claim 1, which is characterized in that according to weight
Percentages are measured, the laser direct organization polycarbonate Alloys composition includes:
5. laser direct organization polycarbonate Alloys composition according to claim 4, which is characterized in that described to swash
Light direct organization additive is selected from metallic compound and/or metal complex with spinelle or octahedral crystal structure.
6. laser direct organization polycarbonate Alloys composition according to claim 1, which is characterized in that described poly-
Carbonic ester is the aromatic copolycarbonate containing structure of bisphenol A.
7. a kind of preparation side of laser direct organization polycarbonate Alloys composition described in any one of claims 1-6
Method characterized by comprising after each component is pre-mixed, by double screw extruder blending extrusion obtain.
8. one kind is made by laser direct organization polycarbonate Alloys composition described in any one of claims 1-6
Product.
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