CN106700487B - One kind can injection molding, high wave-penetrating composite material and preparation method thereof - Google Patents
One kind can injection molding, high wave-penetrating composite material and preparation method thereof Download PDFInfo
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- CN106700487B CN106700487B CN201611236556.6A CN201611236556A CN106700487B CN 106700487 B CN106700487 B CN 106700487B CN 201611236556 A CN201611236556 A CN 201611236556A CN 106700487 B CN106700487 B CN 106700487B
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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
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- 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 present invention relates to engineering plastics technical field, it is specifically a kind of can injection molding, high wave-penetrating composite material and preparation method thereof, it is described can injection molding, high wave-penetrating composite material be prepared according to parts by weight by following components：20~40 parts of 50~80 parts of POK, PFA, 0.8~2 part of LLDPE, 10~15 parts of compounded mix, 0.1~0.3 part of coupling agent, 0.5~1 part of antioxidant, 0~1 part of lubricant.The present invention can injection molding, high wave-penetrating composite material injection moldable, while there is high wave transmission rate, in terms of can be applied to radar or antenna house.
Description
Technical field
The present invention relates to engineering plastics technical field, especially one kind can injection molding, high wave-penetrating composite material and its system
Preparation Method.
Background technology
In terms of electromagnetic wave transparent material is mainly used in radar or antenna house, high wave transmission rate can be largely anti-to avoid incident electromagnetic wave
It penetrates, to avoid enemy radar electromagnetic wave detection, is required in links such as the reception of microwave signal, transmission, amplification, mixing high saturating
Wave material；In antenna house application aspect, at present the main production method of resin base antenna house be epoxy resin coating glass cloth or
Using fiberglass or the machining of PTFE bars, epoxy resin coating glass cloth or using fiberglass dielectric constant and dielectric loss angle
It is bigger, signal transmission is influenced greatly, complicated component cannot to be made, PTFE bar mechanical strengths are low, are easily deformed,
Inefficiency is machined, spillage of material is big, causes expensive.
Invention content
Present invention seek to address that the above problem, providing one kind can injection molding, high wave-penetrating composite material and its preparation side
Method with injection moldable, while having high wave transmission rate, and the technical solution of use is as follows：
One kind can injection molding, high wave-penetrating composite material, be prepared according to parts by weight by following components：
50~80 parts of aliphatic polyketone, 20~40 parts of perfluoroalkoxy resin, 0.8~2 part of linear low density polyethylene are multiple
Close 10~15 parts of filler, 0.1~0.3 part of coupling agent, 0.5~1 part of antioxidant, 0~1 part of lubricant.
On the basis of said program, under ten thousand~120,000,0.45MPa of the aliphatic polyketone number-average molecular weight Mn=8.6
HDT=215 DEG C.
On the basis of said program, the MI=20g/10min of the perfluoroalkoxy resin, the mesh of 8000 mesh~10000.
On the basis of said program, the linear low density polyethylene number-average molecular weight Mn=8 ten thousand~200,000, copolymerization
Monomer is ethylene and 1- butylene, and the 1- butylene accounts for the 5%~8% of comonomer total weight.
On the basis of said program, the composition by weight ratio of the compounded mix is perlite：Poly- terephthaldehyde
Amide p-phenylenediamine=30~70:70~30, the perlite mesh number is 5000~8000 mesh；The poly- paraphenylene terephthalamide is to benzene
Diamines is the fiber of 10 μm of diameter, the length of 0.2~0.5mm.
On the basis of said program, the coupling agent is zirconium ester coupling agent, purity > 99.5%.
On the basis of said program, the antioxidant is by 1010,168 and HP-136 according to weight ratio 1:1.2:1 composition.
On the basis of said program, the lubricant is aliphatic silicone oil, and molecular weight is Mn=60 ten thousand~1,200,000.
Aliphatic silicone oil is a kind of silicone oil containing phenyl ring in organic group.
It is a kind of can injection molding, high wave-penetrating composite material preparation method, comprise the steps of：
1. perfluoroalkoxy resin is worn into 8000~10000 mesh powder；
2. coupling agent obtains material 1 with compounded mix in high-speed mixer mixing 20min, 300~1000rpm of rotating speed；
3. aliphatic polyketone, linear low density polyethylene, antioxidant and lubricant are uniformly mixed in high-speed mixer,
Rotating speed is 300rpm, and time 5min obtains material 2；
4. by step 3. in material 2 from main spout, step 1. perfluoroalkoxy resin powder and step 2. material 1 from side
Spout is added in parallel double-screw extruder and is granulated, and prilling temperature is 240~260 DEG C, and screw speed is 400~600rpm,
Using water cooling pelletizing, by gained pellet after 80 DEG C, 4h dryings, obtaining can injection molding, high wave-penetrating composite material.
PFA is the copolymer of a small amount of perfluoro propyl perfluoroalkyl vinyl ether and polytetrafluoroethylene (PTFE), also referred to as perfluoroalkoxy resin.
POK is the novel green polymer material synthesized by carbon monoxide, alkene (ethylene, propylene), also referred to as polyketone or
Aliphatic polyketone.
LLDPE is linear low density polyethylene.
Aliphatic polyketone (POK) selected in the present invention, perfluoroalkoxy resin (PFA) resin all have very low Jie
Electric constant and dielectric loss；Compounded mix has reinforcement work while with lower dielectric constant, to material stiffness and intensity
With zirconium ester coupling agent can improve the compatibility of compounded mix and matrix resin；Linear low density polyethylene (LLDPE) and lubrication
Agent makes material flowability improve and plays demoulding when being molded in the later stage；Conventional 1010 in antioxidant:It is compounded on the basis of 168
HP-136 is that prevention free radical is formed, and prevents matrix resin from degrading in process.
Specific implementation mode
It is that the present invention will be further described for specific implementation mode, but following implementation is only to this hair with lower part
Bright is explained further, and does not represent the scope of the present invention and is only limitted to this, the equivalence replacement that every thinking with the present invention is done,
It in protection scope of the present invention, is only used for explaining the present invention, and is not considered as limiting the invention.
Embodiment 1
1. 30 parts of perfluoroalkoxy resins (PFA) are worn into 8000-10000 mesh powder, it is spare；
2. high speed batch mixing pot is added in 5 parts of crushed crude pearlites and 5 parts of poly(p-phenylene terephthalamide), it is then added 0.15 part
Zirconium ester coupling agent mixes 20min under 500rpm speed conditions, obtains material 1, spare；
3. by 60 parts of aliphatic polyketones (POK), 1.5 parts of linear low density polyethylene (LLDPE), 0.6 part of antioxidant, 0.4
Part lubricant, which is added in high speed batch mixing pot, to be mixed, and is mixed rotating speed 300rpm, incorporation time 5min, is obtained material 2, spare；
4. the material 2 of step 3. is added from main spout, the material 1 of the PFA powder and step of step 1. 2. is fed from side
Material mouth is added in parallel double-screw extruder and is granulated, 240 DEG C, screw speed 500rpm of prilling temperature, water cooling pelletizing, by gained grain
Material passes through 80 DEG C, and after 4h dryings, packaging obtains can injection molding, high wave-penetrating composite material.
Embodiment 2
1. 25 parts of perfluoroalkoxy resins (PFA) are worn into 8000-10000 mesh powder, it is spare；
2. high speed batch mixing pot is added in 6 parts of crushed crude pearlites and 7 parts of poly(p-phenylene terephthalamide), it is then added 0.18 part
Zirconium ester coupling agent mixes 20min under 500rpm speed conditions, obtains material 1, spare；
3. by 65 parts of aliphatic polyketones (POK), 2 parts of linear low density polyethylene (LLDPE), 0.5 part of antioxidant, 0.5 part
Lubricant is added in high speed batch mixing pot and mixes, and mixes rotating speed 300rpm, incorporation time 5min, obtains material 2, spare；
4. the material 2 of step 3. is added from main spout, the material 1 of the PFA powder and step of step 1. 2. is fed from side
Material mouth is added in parallel double-screw extruder and is granulated, 245 DEG C, screw speed 450rpm of prilling temperature, water cooling pelletizing, by gained grain
Material passes through 80 DEG C, and after 4h dryings, being packaged to be can injection molding, high wave-penetrating composite material.
Embodiment 3
1. 35 parts of perfluoroalkoxy resins (PFA) are worn into 8000-10000 mesh powder, it is spare；
2. high speed batch mixing pot is added in 4 parts of crushed crude pearlites and 6 parts of poly(p-phenylene terephthalamide), it is then added 0.15 part
Zirconium ester coupling agent mixes 20min under 500rpm speed conditions, obtains material 1, spare；
3. by 55 parts of aliphatic polyketones (POK), 1.5 parts of linear low density polyethylene (LLDPE), 0.7 part of antioxidant, 0.3
Part lubricant, which is added in high speed batch mixing pot, to be mixed, and is mixed rotating speed 300rpm, incorporation time 5min, is obtained material 2, spare；
4. the material 2 of step 3. is added from main spout, the material 1 of the PFA powder and step of step 1. 2. is fed from side
Material mouth is added in parallel double-screw extruder and is granulated, 260 DEG C, screw speed 500rpm of prilling temperature, water cooling pelletizing, by gained grain
Material passes through 80 DEG C, and after 4h dryings, being packaged to be can injection molding, high wave-penetrating composite material.
Embodiment 4
1. 20 parts of perfluoroalkoxy resins (PFA) are worn into 8000-10000 mesh powder, it is spare；
2. high speed batch mixing pot is added in 7 parts of crushed crude pearlites and 8 parts of poly(p-phenylene terephthalamide), it is then added 0.25 part
Zirconium ester coupling agent mixes 20min under 500rpm speed conditions, obtains material 1, spare；
3. by 60 parts of aliphatic polyketones (POK), 1 part of linear low density polyethylene (LLDPE), 1 part of antioxidant, 0.6 part of profit
Lubrication prescription is added in high speed batch mixing pot and mixes, and mixes rotating speed 300rpm, incorporation time 5min, obtains material 2, spare；
4. by the material 2 of step 3. from main spout, the material 1 of the PFA powder and step of step 1. 2. is from side spout
It is added in parallel double-screw extruder and is granulated, 240 DEG C, screw speed 450rpm of prilling temperature, water cooling pelletizing passes through gained pellet
80 DEG C are crossed, after 4h dryings, being packaged to be can injection molding, high wave-penetrating composite material.
1~embodiment of embodiment 4 is molded into test bars/plate (by iso standard) under the conditions of 280 DEG C, by 15% glass
Glass cloth coats epoxy resin, 15% glass cloth reinforced plastics, and PTFE cuts into the test of corresponding size with mach method
Batten/plate；
Above-mentioned batten/plate is tested for the property, the results are shown in table below：
From the point of view of 1~embodiment of embodiment, 4 performance, it is satisfied by the mechanical strength and wave transparent performance requirement of material, 15% glass
Cloth coats epoxy resin, and 15% glass cloth reinforced plastics are below 1~embodiment of embodiment in terms of mechanical performance and wave transparent
4, and be difficult to make the more complex product of structure, in terms of wave transparent very well, but intensity is low by PTFE, using mach method,
Not only inefficiency is limited to the size of bar, cannot make the product of large-size；Therefore the present invention has practical well
Use meaning.
The present invention is described by way of example above, but the present invention is not limited to above-mentioned specific embodiment, all to be based on
Any changes or modifications that the present invention is done belong to the scope of protection of present invention.
Claims (7)
1. one kind can injection molding, high wave-penetrating composite material, which is characterized in that prepared according to parts by weight by following components and
At：
50~80 parts of aliphatic polyketone, 20~40 parts of perfluoroalkoxy resin, 0.8~2 part of linear low density polyethylene are compound to fill out
10~15 parts of material, 0.1~0.3 part of coupling agent, 0.5~1 part of antioxidant, 0~1 part of lubricant；
HDT=215 DEG C under ten thousand~120,000,0.45MPa of the aliphatic polyketone number-average molecular weight Mn=8.6；The perfluoroalkoxy
The MI=20g/10min of base resin, the mesh of 8000 mesh~10000；The linear low density polyethylene number-average molecular weight Mn=8 ten thousand~
200000, comonomer is ethylene and 1- butylene, and the 1- butylene accounts for the 5%~8% of comonomer total weight.
2. according to claim 1 can injection molding, high wave-penetrating composite material, which is characterized in that the compounded mix
Composition by weight ratio is perlite：Polyterephthalamide p-phenylenediamine=30~70:70~30, the perlite mesh number
For 5000~8000 mesh；The poly(p-phenylene terephthalamide) is the fiber of 10 μm of diameter, the length of 0.2-0.5mm.
3. according to claim 1 can injection molding, high wave-penetrating composite material, which is characterized in that the coupling agent is zirconium
Acid esters coupling agent, purity > 99.5%.
4. according to claim 1 can injection molding, high wave-penetrating composite material, which is characterized in that the antioxidant by
1010,168 and HP-136 is according to weight ratio 1:1.2:1 composition.
5. according to claim 1 can injection molding, high wave-penetrating composite material, which is characterized in that the lubricant is fat
Fat race silicone oil, molecular weight are Mn=60 ten thousand~1,200,000.
6. it is a kind of according to any one of Claims 1 to 5 can injection molding, high wave-penetrating composite material preparation side
Method, which is characterized in that comprise the steps of：
1. perfluoroalkoxy resin is worn into 8000~10000 mesh powder；
2. coupling agent obtains material 1 with compounded mix in high-speed mixer mixing 20min, 300~1000rpm of rotating speed；
3. aliphatic polyketone, linear low density polyethylene, antioxidant and lubricant are uniformly mixed in high-speed mixer, rotating speed
Material 2 is obtained for 300rpm, time 5min；
4. by step 3. in material 2 from main spout, step 1. perfluoroalkoxy resin powder and step 2. material 1 from side feeding
Mouth is added in parallel double-screw extruder and is granulated, and prilling temperature is 240~260 DEG C, and screw speed is 400~600rpm, is used
Water cooling pelletizing, by gained pellet after 80 DEG C, 4h dryings, obtaining can injection molding, high wave-penetrating composite material.
7. it is a kind of it is according to claim 6 can injection molding, high wave-penetrating composite material preparation method prepare be molded
Molding, high wave-penetrating composite material.
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| CN201611236556.6A CN106700487B (en) | 2016-12-28 | 2016-12-28 | One kind can injection molding, high wave-penetrating composite material and preparation method thereof |
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| CN201611236556.6A CN106700487B (en) | 2016-12-28 | 2016-12-28 | One kind can injection molding, high wave-penetrating composite material and preparation method thereof |
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| CN106700487B true CN106700487B (en) | 2018-10-30 |
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| CN109762321B (en) * | 2018-12-19 | 2021-09-07 | 青岛科凯达橡塑有限公司 | Preparation method of nuclear radiation prevention composite material |
| CN109852033A (en) * | 2019-01-23 | 2019-06-07 | 上海延锋金桥汽车饰件系统有限公司 | A kind of preparation method of moulding and thus obtained moulding |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101107397A (en) * | 2005-01-18 | 2008-01-16 | 旭化成化学株式会社 | Polyketone fiber paper, polyketone fiber paper core material for printed wiring board and printed wiring board |
| CN101439605A (en) * | 2008-12-19 | 2009-05-27 | 南京工业大学 | Microwave millimeter-wave composite medium substrate and preparation method thereof |
| CN101914255A (en) * | 2010-09-02 | 2010-12-15 | 中国工程物理研究院化工材料研究所 | High-temperature resistant polyphenylene sulfide composite material with low dielectric constant and preparation method thereof |
| CN102558863A (en) * | 2012-01-04 | 2012-07-11 | 四川华通特种工程塑料研究中心有限公司 | Low-dielectric-property polyphenylene sulphide composite material and preparation method thereof |
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- 2016-12-28 CN CN201611236556.6A patent/CN106700487B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101107397A (en) * | 2005-01-18 | 2008-01-16 | 旭化成化学株式会社 | Polyketone fiber paper, polyketone fiber paper core material for printed wiring board and printed wiring board |
| CN101439605A (en) * | 2008-12-19 | 2009-05-27 | 南京工业大学 | Microwave millimeter-wave composite medium substrate and preparation method thereof |
| CN101914255A (en) * | 2010-09-02 | 2010-12-15 | 中国工程物理研究院化工材料研究所 | High-temperature resistant polyphenylene sulfide composite material with low dielectric constant and preparation method thereof |
| CN102558863A (en) * | 2012-01-04 | 2012-07-11 | 四川华通特种工程塑料研究中心有限公司 | Low-dielectric-property polyphenylene sulphide composite material and preparation method thereof |
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