CN109608863A - Polyether ketone ketone composite material and preparation method for nanometer injection molding - Google Patents
Polyether ketone ketone composite material and preparation method for nanometer injection molding Download PDFInfo
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- CN109608863A CN109608863A CN201811444367.7A CN201811444367A CN109608863A CN 109608863 A CN109608863 A CN 109608863A CN 201811444367 A CN201811444367 A CN 201811444367A CN 109608863 A CN109608863 A CN 109608863A
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- Prior art keywords
- ketone
- injection molding
- composite material
- nanometer injection
- polyether ketone
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The invention belongs to thermoplas tic resin composite's technical fields, and in particular to a kind of polyether ketone ketone composite material and preparation method for nanometer injection molding.The polyether ketone ketone composite material for nanometer injection molding, is made: polyether ketone ketone 44~84.85% of the raw material of following weight percent；Inorganic filler 15~50%；Organic filler 0.1~5%；Pigment 0.05~1%；The preparation method comprises the following steps: being granulated after polyether ketone ketone, inorganic filler, organic filler and pigment are mixed through extruder, the polyether ketone ketone composite material for nanometer injection molding is obtained.Polyether ketone ketone composite material prepared by the present invention for nanometer injection molding can greatly promote the adhesive strength of resin and metal under nanometer Shooting Technique, and during secondary anode, color does not change；Also, temperature tolerance is good, solvent resistance is good.The preparation method, it is scientific and reasonable, simple and easy.
Description
Technical field
The invention belongs to thermoplas tic resin composite's technical fields, and in particular to a kind of polyether-ketone for nanometer injection molding
Ketone composite material and preparation method.
Background technique
Since nanometer Shooting Technique (NMT) has invented in Japanese great achievement (Taisei) company, and apply a series of
Patented technology (WO2007040245 etc.), nanometer injection molding technology using more and more extensive, be mainly used in electronics industry,
It is popularized in mobile phone industry at present.In general, the resin of use is modified polyphenyl thioether (PPS) and poly- terephthaldehyde
Sour butanediol ester (PBT), but PPS and PBT material at present on the market has the obvious disadvantage that: PPS processing difficulties, resistance to purple
Outer ability is poor, it is difficult to provide colorful solution；PBT cohesive force is insufficient.Although mentioning polyolefinic in the patent of Taisei
Matter can be improved the binding force of plastic cement and metal, but for PBT, binding force is still inadequate, and temperature tolerance is not also high,
The solvent resistance of PBT is poor simultaneously, often generates color difference during two-step anodization.
Polyether ketone ketone (PEKK) resin is a kind of special engineering plastics with excellent properties, belongs to the one of poly(aryl ether ketone)
Kind, phenyl ring in molecular structure, ehter bond, the mutual proper alignment of ketone group chemical structure, impart the stable chemistry of numberator height
Key characteristic makes it have excellent mechanical performance, radiation resistance, high temperature resistant, chemical corrosion resistance and good electrical isolation
Property and flame retardant property, can by the processing methods such as extrusion, injection molding, molding carry out machine-shaping, if being applied to nanometer
Phenomena such as above-mentioned binding force is inadequate, solvent resistance is poor will be solved in injection industry field.
Through retrieving, there is presently no the records that polyethylene-ketone-ketone resin is used for nanometer injection molding.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of polyether ketone ketone composite woods for nanometer injection molding
Material, solves in the prior art that cohesive force is insufficient, temperature tolerance is poor, solvent resistance difference defect.
Another object of the present invention is to provide a kind of preparation method of polyether ketone ketone composite material for nanometer injection molding, science
Rationally, simple and easy.
Polyether ketone ketone composite material of the present invention for nanometer injection molding, by the raw material system of following weight percent
At:
Wherein:
The polyether ketone ketone has a structure that
A is representedStructure；
B is representedStructure；
D is representedStructure；
Wherein, (a), (b) structure proportional presence in the polymer backbone, the amount of (a) structure in the polymer backbone are
60~90%, (b) amount of structure in the polymer backbone is 10~40%.
Preferably, the amount of (a) structure in the polymer backbone is 60~75%, (b) amount of structure in the polymer backbone
It is 25~40%.
The inorganic filler is one or more of solid glass pearl, cylindrical glass fiber or mica mineral.
The D of the solid glass pearl50Partial size≤35 μm；Diameter≤15 μm of the cylindrical glass fiber, preferably
≤10μm；The mica mineral is mica powder, and partial size is 600 mesh.
The organic filler is one or both of LCP polymer or PPS polymer.
The pigment is one or both of carbon black or titanium dioxide.
The preparation method of polyether ketone ketone composite material of the present invention for nanometer injection molding, comprising the following steps: will
After polyether ketone ketone, inorganic filler, organic filler and pigment mixing, it is granulated through extruder, obtains the polyether ketone ketone for nanometer injection molding
Composite material.
Using double screw extruder extruding pelletization, wherein prilling temperature is 300~380 DEG C.
Preferably, 330~370 DEG C of the prilling temperature.
Compared with prior art, beneficial effects of the present invention are as follows:
1, the present invention provides a kind of polyether ketone ketone composite materials for nanometer injection molding, under nanometer Shooting Technique, energy
Enough adhesive strengths for greatly promoting resin and metal, and during secondary anode, color does not change.
2, due to polyether ketone ketone melting temperature with higher and glass transition temperature, 220 DEG C are up to using temperature,
Therefore its heat resistance has more apparent raising for the materials such as PPS, PBT that compare.
3, preparation method of the present invention, it is scientific and reasonable, simple and easy.
Detailed description of the invention
Fig. 1 is that metal plastic tests unitarily formed structure chart in the embodiment of the present invention.
Specific embodiment
Below in conjunction with attached drawing 1, technical solution of the present invention is clearly and completely described, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without making creative work belongs to what the present invention protected
Range.
Metal cohesive force testing standard used in the present invention is as follows:
It is as shown in Figure 1 metal plastic test single piece, the faying surface area of metal and plastic cement is 50 square millimeters.
In all comparative experimentss, all injecting conditions are listed in Table 1 below.Binding force test is that biaxial tension is tested.
Embodiment 1-2 and comparative example 1-3
After each component in table 1 is mixed in mixing machine by weight ratio shown in table 1, it is granulated, is made with double screw extruder
Grain temperature is 330 DEG C to 370 DEG C.Gained particle is formed using horizontal injection press injection molding, and machined parameters are as follows: front-end temperature
For 320 DEG C, middle section temperature be 375 DEG C, back segment temperature is 380 DEG C, nozzle temperature is 385 DEG C, mold temperature is 180 DEG C.It is adopted
Aluminium flake is 6061 type aluminium alloys, is handled using anode oxidative treatment method, its surface hole defect size is 50~200 after processing
μm, test result is listed in Table 1 below.
By the comparison of sample in table 1 it is found that for the polyether-ether-ketone that compares, polyether ketone ketone since tool is there are two carbonyl, because
This its molecule chain rigidity is bigger, causes its glass transition temperature higher, at the same its crystallization rate than for polyether-ether-ketone substantially
Degree reduces, and the reduction of crystallinity has been given in the easier nano aperture for penetrating into metal surface of plastic cement, to enhance it
Binding force, in addition the addition of LCP helps to improve the mobility of polyether ketone ketone, and plastic cement is more greatly improved after being added
With the binding force of metal, the addition of bead and mica declines plastic cement with the binding force of metal, but its shrinking percentage is big
Big reduction.
The test of solvent resistance:
After each component double-screw extruding pelletizing in table 1, gained particle is used as in embodiment 1-2 and comparative example 1-3
The machined parameters processing, prepares colour atla, first uses precise colorimeter to test its Lab value obtained colour atla, then set
2min (80 DEG C), are subsequently placed in the sulfuric acid of 200g/L in 40% phosphoric acid, at 25 DEG C, 60min under the conditions of anode.Cleaning
Completely, after dry, then using precise colorimeter test, the results are shown in table 2.As can be seen from the table, before and after anodic oxidation,
Nanometer is molded the chromatic aberration very little of dedicated polyether ketone ketone composite material, and the variation of △ E value is respectively less than 1.
The formulation parameter of 1 nanometer of the table dedicated polyether ketone ketone of injection molding
The trade mark referred to above is conventional commercial product.Wherein, T443 is that Taishan glass fiber Ltd is commercially available
Product.
Testing result before and after 2 anodic oxidation of table
Claims (10)
1. a kind of polyether ketone ketone composite material for nanometer injection molding, it is characterised in that: by the raw material system of following weight percent
At:
2. the polyether ketone ketone composite material according to claim 1 for nanometer injection molding, it is characterised in that: the polyethers
Ketone ketone has a structure that
A is representedStructure；
B is representedStructure；
D is representedStructure；
Wherein, (a), (b) structure proportional presence in the polymer backbone, the amount of (a) structure in the polymer backbone be 60~
90%, (b) amount of structure in the polymer backbone is 10~40%.
3. the polyether ketone ketone composite material according to claim 2 for nanometer injection molding, it is characterised in that: (a) structure exists
Amount in main polymer chain is 60~75%, and (b) amount of structure in the polymer backbone is 25~40%.
4. the polyether ketone ketone composite material according to claim 1 for nanometer injection molding, it is characterised in that: described is inorganic
Filler is one or more of solid glass pearl, cylindrical glass fiber or mica mineral.
5. the polyether ketone ketone composite material according to claim 4 for nanometer injection molding, it is characterised in that: described is solid
The D of bead50Partial size≤35 μm；Diameter≤15 μm of the cylindrical glass fiber；The mica mineral is mica
Powder, partial size are 600 mesh.
6. the polyether ketone ketone composite material according to claim 1 for nanometer injection molding, it is characterised in that: described is organic
Filler is one or both of LCP polymer or PPS polymer.
7. the polyether ketone ketone composite material according to claim 1 for nanometer injection molding, it is characterised in that: the pigment
For one or both of carbon black or titanium dioxide.
8. a kind of preparation method of the polyether ketone ketone composite material as claimed in claim 1 to 7 for nanometer injection molding, special
Sign is: the following steps are included:
It after polyether ketone ketone, inorganic filler, organic filler and pigment are mixed, is granulated, is obtained for the poly- of nanometer injection molding through extruder
Ether ketone ketone composite material.
9. preparation method according to claim 8, it is characterised in that: double screw extruder extruding pelletization is used, wherein making
Grain temperature is 300~380 DEG C.
10. preparation method according to claim 9, it is characterised in that: 330~370 DEG C of the prilling temperature.
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| CN201811444367.7A CN109608863A (en) | 2018-11-29 | 2018-11-29 | Polyether ketone ketone composite material and preparation method for nanometer injection molding |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114616286A (en) * | 2019-10-31 | 2022-06-10 | 韩华思路信株式会社 | Polymer composition with improved crystallization rate and preparation method thereof |
| CN118599259A (en) * | 2024-08-07 | 2024-09-06 | 长春吉大特塑工程研究有限公司 | High-insulation polyether-ether-ketone composite material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198453A (en) * | 1997-05-05 | 1998-11-11 | 中国科学院化学研究所 | Polyether ether ketone compound material modified by thermotropic liquid crystal polymer |
| CN1871277A (en) * | 2003-09-26 | 2006-11-29 | 维克特雷斯制造有限公司 | Polymeric ketone |
| CN101151322A (en) * | 2005-04-06 | 2008-03-26 | 威格斯制造有限公司 | Polymeric material |
| CN101812170A (en) * | 2010-03-12 | 2010-08-25 | 重庆澳瑞玛高性能聚合物有限公司 | Method for preparing high glass-transition temperature crystal type polyethylene-ketone-ketone resin material |
| CN106574185A (en) * | 2014-08-21 | 2017-04-19 | 提克纳有限责任公司 | Polyaryletherketone composition |
| CN108779244A (en) * | 2016-03-18 | 2018-11-09 | 提克纳有限责任公司 | Poly(aryl ether ketone) composition |
| CN110878146A (en) * | 2018-09-05 | 2020-03-13 | 张家港祥成医用材料科技有限公司 | Preparation method of yellow polyether ketone powder |
-
2018
- 2018-11-29 CN CN201811444367.7A patent/CN109608863A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198453A (en) * | 1997-05-05 | 1998-11-11 | 中国科学院化学研究所 | Polyether ether ketone compound material modified by thermotropic liquid crystal polymer |
| CN1871277A (en) * | 2003-09-26 | 2006-11-29 | 维克特雷斯制造有限公司 | Polymeric ketone |
| CN101151322A (en) * | 2005-04-06 | 2008-03-26 | 威格斯制造有限公司 | Polymeric material |
| CN101812170A (en) * | 2010-03-12 | 2010-08-25 | 重庆澳瑞玛高性能聚合物有限公司 | Method for preparing high glass-transition temperature crystal type polyethylene-ketone-ketone resin material |
| CN106574185A (en) * | 2014-08-21 | 2017-04-19 | 提克纳有限责任公司 | Polyaryletherketone composition |
| CN108779244A (en) * | 2016-03-18 | 2018-11-09 | 提克纳有限责任公司 | Poly(aryl ether ketone) composition |
| CN110878146A (en) * | 2018-09-05 | 2020-03-13 | 张家港祥成医用材料科技有限公司 | Preparation method of yellow polyether ketone powder |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114616286A (en) * | 2019-10-31 | 2022-06-10 | 韩华思路信株式会社 | Polymer composition with improved crystallization rate and preparation method thereof |
| CN118599259A (en) * | 2024-08-07 | 2024-09-06 | 长春吉大特塑工程研究有限公司 | High-insulation polyether-ether-ketone composite material and preparation method thereof |
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Application publication date: 20190412 |