CN106883580A - Laser direct forming PC composites and its preparation technology - Google Patents
Laser direct forming PC composites and its preparation technology Download PDFInfo
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- CN106883580A CN106883580A CN201710225882.5A CN201710225882A CN106883580A CN 106883580 A CN106883580 A CN 106883580A CN 201710225882 A CN201710225882 A CN 201710225882A CN 106883580 A CN106883580 A CN 106883580A
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005516 engineering process Methods 0.000 title claims abstract description 15
- 229920002748 Basalt fiber Polymers 0.000 claims abstract description 56
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 47
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 47
- 239000000654 additive Substances 0.000 claims abstract description 42
- 230000000996 additive effect Effects 0.000 claims abstract description 41
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 30
- 239000007822 coupling agent Substances 0.000 claims abstract description 27
- 239000000314 lubricant Substances 0.000 claims abstract description 25
- 239000012745 toughening agent Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- -1 acrylate modified copper Chemical class 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 239000006096 absorbing agent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 8
- 150000002989 phenols Chemical class 0.000 claims abstract description 8
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 238000009955 starching Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004530 micro-emulsion Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 14
- 238000007747 plating Methods 0.000 abstract description 12
- 239000004033 plastic Substances 0.000 abstract description 4
- 239000004568 cement Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 description 10
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- 238000005452 bending Methods 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- 230000002787 reinforcement Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 238000013329 compounding Methods 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
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- 238000005893 bromination reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- KOBKUSXTVUSJEU-UHFFFAOYSA-N copper;prop-2-enoic acid Chemical compound [Cu].OC(=O)C=C KOBKUSXTVUSJEU-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08K2201/004—Additives being defined by their length
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to plastic cement field of new, specifically related to a kind of laser direct forming PC composites and its preparation technology, laser direct forming PC composites, component including following parts by weight, 50 80 parts of PC, 10 50 parts of basalt fibre, 38 parts of laser additive, 0.5 2 parts of antioxidant, 0.2 2 parts of heat stabilizer, 38 parts of toughener, 12 parts of lubricant, 12 parts of coupling agent, 26 parts of compatilizer；The antioxidant is made up of Hinered phenols antioxidant and phosphite ester kind antioxidant, and the heat stabilizer is made up of metallic compound, layered double hydroxide and UV absorbers；Laser additive is through acrylate modified copper nanoparticle.Laser direct forming of the invention with PC composite induced with laser plating performance it is good, heat resistanceheat resistant oxygen performance is good, ageing-resistant performance is good, good mechanical property.
Description
Technical field
The present invention relates to plastic cement field of new, more particularly to laser direct forming is with PC composites and its prepares work
Skill.
Background technology
Laser direct forming (LASER DIRECT STRUCTRING, abbreviation LDS) is a kind of injection, Laser Processing and electricity
3D-MID (Three-dimensional molded interconnect device) production technology that depositing process is combined, its
Principle is to assign electric interconnection function by common plastic cement element, circuit board, makes plastic casing, structural member except support, protection etc.
Outside function, the function such as shielding, antenna for being combined with conducting channel and being produced.LDS materials, add mainly in matrix resin and swash
Light additive, the particle after blending is molded into product again after chemical plating, can form conducting wire, and advantage is that circuit design is freer
And firmly.
The technique for making molding interconnection element using laser direct forming mainly includes three below step：Resin base material
The metallization of injection moulding, the Laser Processing of LDS elements and circuit pattern.In this technical process can laser direct forming it is poly-
The exploitation of compound base material is one of the most key part.Therefore, design and prepare the polymerization with laser direct forming performance
Thing composite has extremely important industrial value.
The polymer composites of laser direct forming performance, need to have excellent induced with laser plating performance and excellent
Thermo oxidative aging performance, in the prior art, to improve the thermo oxidative aging performance of composite, often adds laser straight in resin
Type additive (LDS additives) is connected into increase the thermo oxidative aging performance of composite, but because this kind of additive can be with tree
Fat directly reacts or is the catalyst of molecular resin chain generation degradation reaction, ultimately results in resin macromolecular chain and is easy to forging
Refining, influences the mechanical property of composite.
The content of the invention
To solve the above problems, a kind of induced with laser plating performance of present invention offer is good, heat resistanceheat resistant oxygen performance is good, resistance to ag(e)ing
Laser direct forming PC composites and its preparation technology of the good, good mechanical property of energy.
The technical solution adopted in the present invention is：Laser direct forming PC composites, including following parts by weight
Component, PC 50-80 parts, basalt fibre 10-50 parts, 3-8 parts of laser additive, antioxidant 0.5-2 parts, heat stabilizer 0.2-2
Part, toughener 3-8 parts, lubricant 1-2 parts, coupling agent 1-2 parts, compatilizer 2-6 parts；The antioxidant is by Hinered phenols antioxidant
With phosphite ester kind antioxidant composition, the heat stabilizer is by the suction of metallic compound, layered double hydroxide and ultraviolet light
Receive agent composition；The laser additive is through acrylate modified copper nanoparticle.
To being further improved to for above-mentioned technical proposal, the basalt fibre is continuous fiber that draw ratio is 1500；
The coupling agent is epoxy resin E51 and alicyclic epoxy compounds the KH-550 that starching is obtained；The lubricant is natural paraffin wax；
The compatilizer is the copolymer of styrene and maleic anhydride.
To being further improved to for above-mentioned technical proposal, metallic compound, layered bi-metal hydrogen-oxygen in the heat stabilizer
The mass ratio of compound and UV absorbers is 2:1:0.5；Hinered phenols antioxidant and phosphorous acid esters are anti-in the antioxidant
The mass ratio of oxygen agent is 1：2.
To being further improved to for above-mentioned technical proposal, including following parts by weight component, 75 parts of PC, basalt are fine
Dimension 10 parts, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, 3 parts of toughener, 1.5 parts of lubricant, 1 part of coupling agent,
2 parts of compatilizer.
To being further improved to for above-mentioned technical proposal, including following parts by weight component, 64 parts of PC, basalt are fine
Dimension 20 parts, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, 2 parts of toughener, 1.5 parts of lubricant, 1 part of coupling agent,
4 parts of compatilizer.
To being further improved to for above-mentioned technical proposal, including following parts by weight component, 53 parts of PC, basalt are fine
Dimension 30 parts, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, 2 parts of toughener, 1.5 parts of lubricant, 1 part of coupling agent,
5 parts of compatilizer.
The laser direct forming preparation technology of PC composites, comprises the following steps, and a. prepares laser additive；B. make
Standby basalt fibre；C. PC, basalt fibre, laser additive, antioxidant, heat stabilizer, toughener, the lubrication of formula ratio are taken
Agent, coupling agent, compatilizer, are well mixed；D. each component in step c is imported extrude being expected in screw extruder
Bar；E. water-cooled is carried out to material strip, treatment is air-dried；F. the material strip for taking cool drying in step e carries out pelletizing.
To being further improved to for above-mentioned technical proposal, in step a, the preparation technology of laser additive is, to acrylic acid
Copper nanoparticle, initiator, silane is added dropwise in the positive microemulsion of ester esters monomer/DTAB/water composition
The alcoholic solution of coupling agent, heating response is filtered, dried, and obtains laser activation particle.
To being further improved to for above-mentioned technical proposal, in step d, screw extruder extrusion temperature is 210 DEG C -230 DEG C,
The main-machine screw rotating speed of screw extruder is 250r/min~330r/min, the rotating speed of hopper feed screw rod for 24r/min~
35r/min。
Beneficial effects of the present invention are：
1st, on the one hand, it is the mechanical performance of raising composite, of the invention to be strengthened PC using basalt fibre, PC
It is thermoplastic, relative to traditional fiber reinforcement thermosetting material, the recyclable recycling of thermoplastic resin, and technological requirement
Low, the product after the shaping that can rest and reorganize, chemical-resistance is good；Basalt fibre is a kind of high-strength, Gao Mo inorganic mineral fiber, and
And high temperature resistant, it is corrosion-resistant to wait excellent performance, it is a kind of ideal material of green non-pollution, also, basalt fibre tensile strength
Prominent, basalt fibre to significantly increase the tensile strength of PC, the composite bending strength of preparation is high, tensile strength is high,
Impact strength is good and stable chemical nature, is easy to recycle.Second aspect, to improve the heat resistanceheat resistant oxygen of composite, resistance to old
The performances such as the property changed, employ what is be made up of metallic compound, layered double hydroxide and UV absorbers in the present invention
Heat stabilizer and the antioxidant being made up of Hinered phenols antioxidant and phosphite ester kind antioxidant, because laser additive is yes
Metal oxide or metal simple-substance with special crystalline structure, dissociate the metal ion or atom for existing in system, is catalysis
The catalyst of PC degradeds so that PC macromolecular chains are easy to fracture, mechanical strength declines, and system viscosity declines, and influences composite
Performance, and when the present invention select heat stabilizer and antioxidant be used in mixed way, concerted reaction can occur between each component to press down
Laser additive processed suppresses the thermal degradation and oxidative degradation of PC to the catalytic degradation of PC, while heat endurance and good in oxidation resistance,
Be conducive to being lifted the performances such as heat resistanceheat resistant oxygen, resistance to ag(e)ing, the mechanical strength of composite.The third aspect, what the present invention was selected swashs
Light additive is that, through acrylate modified copper nanoparticle, laser additive has preferably dispersiveness in the composite, has
Beneficial to the induced with laser plating performance for improving composite so that composite can be used for laser direct forming；Meanwhile, by right
Metallic copper is modified, the directly contact of isolation metal copper atom and PC, so as to avoid metal copper atom catalytic degradation PC, prevents
There is thermo-oxidative ageing reaction in PC, be further conducive to improving the performances such as heat resistanceheat resistant oxygen, the resistance to ag(e)ing of composite.Four directions
Face, after tested, composite induced with laser plating performance of the invention is good, heat endurance is good, good in oxidation resistance, ageing-resistant, resistance to
Sour, alkaline-resisting, stable chemical nature, good mechanical property can be used for laser direct structuring technique.
2nd, basalt fibre is the continuous fiber that draw ratio is 1500, in the composite, is used；Continuous fiber so that
The minimum yardstick that retains of basalt fibre is larger, is uniformly dispersed, and in composite inner, continuous basalt fiber can form fibre
The three-dimensional net structure that dimension winds mutually so that fiber reinforcement effect is more obvious, is further conducive to improving composite
Intensity.In addition, the stress concentration point of fiber end is also crackle initiation point, stress cracking is easily caused, so as under causing toughness
Drop.Because the minimum reservation length of fiber in continuous fiber composite material sample is more long, end quantity can then be substantially reduced, so that
Maintain preferable impact property.
3rd, coupling agent is epoxy resin E51 and alicyclic epoxy compounds the KH-550 that starching is obtained, due to basalt fibre
Modulus is higher, and PC resin bears load, such as basalt fibre and PC as an entirety after basalt fibre is bonded together
Interfacial adhesion strength it is not high, then the intensity enhancing of composite is not obvious, therefore, the present invention in add coupling agent, pass through
Coupling agent improves the adhesive strength between basalt fibre and PC, is conducive to improving the overall tensile strength of composite.This hair
The KH-550 that bright middle coupling agent is obtained from epoxy resin E51 and alicyclic epoxy compounding starching, after KH-550 hydrolysis
Group can also be combined, so as to effectively improve with the hydroxyl stable bond of production after basalt fibre water absorbent surface with PC resin
The interface binding power of basalt fibre and PC, is further conducive to improving bending strength, tensile strength and the impact of composite
Intensity.
4th, lubricant is natural paraffin wax, and the addition of lubricant plays lubrication to whole composite macromolecular, is reduced
Product and extraneous coefficient of friction, natural paraffin wax is good with other components compatibility of the invention, and greasy property is good, is conducive to subtracting
Small friction, increases anti-wear performance of the invention.
5th, compatilizer is the copolymer of styrene and maleic anhydride, and compatilizer can react with the polar group in PC, is improved
The adhesive strength of PC and basalt fibre, is further conducive to improving the bending strength of composite, tensile strength and impact by force
Degree.
6th, PC composites of the invention also contain toughener, and toughener is high glue powder, and high glue powder is styrene, propylene
The core-shell polymers of nitrile-butadiene rubber, glue content is 55-70%, can be effectively improved the impact strength of PC, is further had
Beneficial to the bending strength, tensile strength and the impact strength that improve composite.
7th, the mass ratio of metallic compound, layered double hydroxide and UV absorbers is 2 in heat stabilizer:1:
0.5；The mass ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant is 1 in the antioxidant：2.It is steady to heat in the present invention
The mass ratio for determining each several part in agent and antioxidant optimizes treatment so that its synergy is more notable, so as to further enhance
The thermodynamic property and processing characteristics of composite.
8th, laser direct forming PC composites, it is characterised in that：Component including following parts by weight, 64 parts of PC,
20 parts of basalt fibre, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, 2 parts of toughener, 1.5 parts of lubricant, idol
1 part of agent of connection, 4 parts of compatilizer.Load is born mainly by basalt fibre due to composite, if basalt content is relatively low,
Occur larger overlapping between fiber, enhancing effect is poor, if basalt content is high, each component mixing can be caused uneven, PC without
It is poor that method is completely soaked compatibility between parcel basalt fibre, each component, is only formulated from this, the composite of preparation, respectively
The addition of component is most suitable amount, and basalt fibre can be profound in the presence of coupling agent, compatilizer, toughener, lubricant
Military rock fiber can combine closely with PC, and basalt fibre uniform and stable can be distributed in PC surfaces, so as to carry to greatest extent
The intensity of composite high.
9th, the preparation technology based on the enhanced PC composites of basalt fibre, in step a, the preparation work of laser additive
Skill is that Nanometer Copper is added dropwise in the positive microemulsion to acrylate ester monomer/DTAB/water composition
Powder, initiator, the alcoholic solution of silane coupler, heating response are filtered, dried, and obtain laser activation particle.It is so obtained to swash
Light additive can be uniformly distributed in the composite, with more preferable dispersiveness, improve the induced with laser plating of composite
Performance.The directly contact of copper atom and PC can be isolated simultaneously, catalytic degradation of the copper atom to PC is reduced, the anti-of composite is lifted
Thermal-oxidative aging property and mechanical property.
10th, in step d, the selection of extrusion temperature, when extrusion temperature is too low, macromolecular material shows as rigid solid shape
State, it is impossible to exist with molten condition, it is difficult to extrusion molding is carried out, if temperature is too high, during more than 230 DEG C, more than PC resin
Decomposition temperature, PC resin is aging serious, is unfavorable for improving the overall intensity of composite.When temperature is 220 DEG C, now PC trees
The free movement enhancing of strand in fat, resin viscosity reduces, the package action reduction to basalt fibre, by external force field
After shearing and stretching, basalt fibre can produce certain miniature deformation, and basalt fibre average fiber length is elongated, enhancing effect
Fruit more preferably, is further conducive to improving bending strength, tensile strength and the impact strength of composite.The main frame of screw extruder
Screw speed is 250r/min~330r/min, and the rotating speed of hopper feed screw rod is 24r/min~35r/min, if rotating speed is excessive,
Shearing force suffered by composite can be caused big, basalt fibre is twisted disconnected, and average fiber length reduces, tensile strength reduction, if
Rotating speed is too small, and each component in composite can be caused uniformly to mix, and causes the material strip for obtaining uneven, works as main-machine screw
Rotating speed is 300r/min, when the rotating speed of hopper feed screw rod is 28r/min, the composite tensile strength highest for obtaining.
Specific embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Specific embodiment 1：
Laser direct forming PC composites, including following parts by weight component, 75 parts of PC, basalt fibre 10
It is part, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, 3 parts of toughener, 1.5 parts of lubricant, 1 part of coupling agent, compatible
2 parts of agent.
Specific embodiment 2：
Laser direct forming PC composites, including following parts by weight component, 64 parts of PC, basalt fibre 20
It is part, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, 2 parts of toughener, 1.5 parts of lubricant, 1 part of coupling agent, compatible
4 parts of agent.
Specific embodiment 3：
Laser direct forming PC composites, including following parts by weight component, 53 parts of PC, basalt fibre 30
It is part, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, 2 parts of toughener, 1.5 parts of lubricant, 1 part of coupling agent, compatible
5 parts of agent.
Control group 1：
Laser direct forming PC composites, including following parts by weight component, 83 parts of PC, laser additive 8
Part, 2 parts of antioxidant, 2.5 parts of heat stabilizer, 3 parts of toughener, 1.5 parts of lubricant.
Control group 2：
Laser direct forming PC composites, including following parts by weight component, 64 parts of PC, basalt fibre 20
Part, 5 parts of laser additive, 2 parts of antioxidant, 2 parts of toughener, 1.5 parts of lubricant, 1 part of coupling agent, 4 parts of compatilizer.
Control group 3：
Laser direct forming PC composites, including following parts by weight component, 64 parts of PC, basalt fibre 20
It is part, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, 2 parts of toughener, 1.5 parts of lubricant, 1 part of coupling agent, compatible
4 parts of agent.
In the various embodiments described above and control group 1,2, basalt fibre is continuous fiber that draw ratio is 1500；Coupling agent is
The KH-550 that epoxy resin E51 and alicyclic epoxy compounding starching are obtained；Lubricant is natural paraffin wax；Compatilizer be styrene with
The copolymer of maleic anhydride；Heat stabilizer is made up of metallic compound, layered double hydroxide and UV absorbers, and
The mass ratio of each component is 2:1:0.5；Antioxidant is made up of Hinered phenols antioxidant and phosphite ester kind antioxidant, and each component
Mass ratio be 1：2；Toughener is high glue powder, and high glue powder is the core-shell polymers of styrene, acrylonitrile-butadiene rubber,
Glue content is 63%；Laser additive is through acrylate modified copper nanoparticle.
In the various embodiments described above and control group 1,2, the laser direct forming preparation technology of PC composites, including it is following
Step, a. prepares laser additive；B. basalt fibre is prepared；C. take the PC of formula ratio, basalt fibre, laser additive,
Antioxidant, heat stabilizer, toughener, lubricant, coupling agent, compatilizer, are well mixed；D. each component in step c is imported
In screw extruder extrude obtaining material strip；E. water-cooled is carried out to material strip, treatment is air-dried；F. cool drying in step e is taken
Material strip carries out pelletizing.
In step a, the preparation technology of laser additive is, to acrylate ester monomer/trimethyl bromination
Dropwise addition copper nanoparticle, initiator, the alcoholic solution of silane coupler in the positive microemulsion of ammonium/water composition, heating response, filtering,
Dry, obtain laser activation particle.
In step d, screw extruder extrusion temperature is 220 DEG C, and the main-machine screw rotating speed of screw extruder is 300r/min,
The rotating speed of hopper feed screw rod is 28r/min.
In control group 3, laser additive is without acrylate modified copper nanoparticle.
Using each specific embodiment and the composite of control group, the plate of same thickness, formed objects, same nature is made
Shape product, under identical environmental condition, using identical measuring instrument and measuring method, measures the physical of each group material
Matter, measurement result is shown in Table 1.
As seen from Table 1,
(1) relative to control group 1, control group 2 and control group 3, specific embodiment 1, specific embodiment 2 and specific embodiment
3 induced with laser plating performance is good, heat resistanceheat resistant oxygen performance is good, ageing-resistant performance is good, good mechanical property.
(2) specific embodiment 1, the mechanical performance of specific embodiment 2 and specific embodiment 3 and thermo oxidative aging ability, tool
Preferably, this is because in specific embodiment 2, basalt fibre content is 20% to the properties of body embodiment 2.
(3) being provided without basalt fibre relative to specific embodiment 2, in control group 1 strengthens PC, therefore control group
Induced with laser plating performance, heat resistanceheat resistant oxygen performance, ageing-resistant performance, mechanical performance in 1 is than the difference in specific embodiment 2.
(4) relative to specific embodiment 2, the induced with laser in heat stabilizer, therefore control group 2 is provided without in control group 2
Plating performance, heat resistanceheat resistant oxygen performance, ageing-resistant performance, mechanical performance are than the difference in specific embodiment 2.
(5) relative to specific embodiment 2, laser activation agent in control group 3 is not through acrylate modified, therefore control
Induced with laser plating performance, heat resistanceheat resistant oxygen performance, ageing-resistant performance, mechanical performance in group 3 is than the difference in specific embodiment 2.
Interpretation of result：
(1) PC is strengthened when using basalt fibre, PC is thermoplastic, relative to traditional fiber reinforcement heat
Thermoset material, the recyclable recycling of thermoplastic resin, and technological requirement is low, the product after the shaping that can rest and reorganize, chemical-resistance is good；
Basalt fibre is a kind of high-strength, Gao Mo inorganic mineral fiber, and high temperature resistant, corrosion-resistant to wait excellent performance, is a kind of green
The free of contamination ideal material of color, also, basalt fibre tensile strength protrusion, basalt fibre can significantly increase the tension of PC
Intensity, the composite bending strength of preparation is high, tensile strength is high, impact strength good and stable chemical nature, is easy to reclaim profit
With.
(2) heat stabilizer being made up of metallic compound, layered double hydroxide and UV absorbers is employed
With the antioxidant being made up of Hinered phenols antioxidant and phosphite ester kind antioxidant, it is with special to be due to laser additive
The metal oxide or metal simple-substance of crystalline structure, dissociate the metal ion or atom for existing in system, is catalysis PC degradeds
Catalyst so that PC macromolecular chains are easy to fracture, mechanical strength declines, and system viscosity declines, and influences the performance of composite, and
When the heat stabilizer and antioxidant of present invention selection are used in mixed way, concerted reaction can occur between each component to suppress laser addition
Agent suppresses the thermal degradation and oxidative degradation of PC to the catalytic degradation of PC, while heat endurance and good in oxidation resistance, are conducive to lifting
The performances such as heat resistanceheat resistant oxygen, resistance to ag(e)ing, the mechanical strength of composite.
(3) when laser additive is that, through acrylate modified copper nanoparticle, laser additive has in the composite
Preferably dispersiveness, is conducive to improving the induced with laser plating performance of composite so that it is direct that composite can be used for laser
Shaping；Meanwhile, it is modified by metallic copper, the directly contact of isolation metal copper atom and PC, so as to avoid metallic copper former
Muonic catalysis is degraded PC, is prevented PC from thermo-oxidative ageing occurring and is reacted, and is further conducive to improving the heat resistanceheat resistant oxygen, ageing-resistant of composite
The performances such as property.
(4) load is born mainly by basalt fibre due to composite, if basalt content is relatively low, meeting between fiber
Appearance is larger to be overlapped, and enhancing effect is poor, if basalt content is high, each component can be caused to mix uneven, and PC cannot soak completely
Compatibility is poor between bubble parcel basalt fibre, each component, only when basalt fibre content is 20%, the composite wood of preparation
Material, the addition of each component is most suitable amount, basalt fibre can coupling agent, compatilizer, toughener, lubricant effect
Under, basalt fibre can combine closely with PC, and basalt fibre uniform and stable can be distributed in PC surfaces, so as to greatest extent
Raising composite intensity.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Shield scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
1. laser direct forming PC composites, it is characterised in that：Component including following parts by weight, PC 50-80 parts,
Basalt fibre 10-50 parts, 3-8 parts of laser additive, antioxidant 0.5-2 parts, heat stabilizer 0.2-2 parts, toughener 3-8 parts,
Lubricant 1-2 parts, coupling agent 1-2 parts, compatilizer 2-6 parts；The antioxidant is resisted by Hinered phenols antioxidant and phosphorous acid esters
Oxygen agent is constituted, and the heat stabilizer is made up of metallic compound, layered double hydroxide and UV absorbers；It is described to swash
Light additive is through acrylate modified copper nanoparticle.
2. laser direct forming according to claim 1 PC composites, it is characterised in that：The basalt fibre is
Draw ratio is 1500 continuous fiber；The coupling agent is epoxy resin E51 and alicyclic epoxy compounds the KH- that starching is obtained
550；The lubricant is natural paraffin wax；The compatilizer is the copolymer of styrene and maleic anhydride.
3. laser direct forming according to claim 2 PC composites, it is characterised in that：Gold in the heat stabilizer
The mass ratio of category compound, layered double hydroxide and UV absorbers is 2:1:0.5；Hindered phenol in the antioxidant
The mass ratio of kind antioxidant and phosphite ester kind antioxidant is 1：2.
4. laser direct forming according to claim 3 PC composites, it is characterised in that：Including following parts by weight
Component, 75 parts of PC, 10 parts of basalt fibre, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, toughener 3
Part, 1.5 parts of lubricant, 1 part of coupling agent, 2 parts of compatilizer.
5. laser direct forming according to claim 3 PC composites, it is characterised in that：Including following parts by weight
Component, 64 parts of PC, 20 parts of basalt fibre, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, toughener 2
Part, 1.5 parts of lubricant, 1 part of coupling agent, 4 parts of compatilizer.
6. laser direct forming according to claim 3 PC composites, it is characterised in that：Including following parts by weight
Component, 53 parts of PC, 30 parts of basalt fibre, 5 parts of laser additive, 1 part of antioxidant, 1.5 parts of heat stabilizer, toughener 2
Part, 1.5 parts of lubricant, 1 part of coupling agent, 5 parts of compatilizer.
7. the laser direct forming preparation technology of PC composites, it is characterised in that：Comprise the following steps, a. prepares laser and adds
Plus agent；B. basalt fibre is prepared；C. PC, basalt fibre, laser additive, antioxidant, heat stabilizer, the increasing of formula ratio are taken
Tough dose, lubricant, coupling agent, compatilizer, be well mixed；D. each component in step c is imported and is squeezed in screw extruder
Go out to obtain material strip；E. water-cooled is carried out to material strip, treatment is air-dried；F. the material strip for taking cool drying in step e carries out pelletizing.
8. the laser direct forming according to claim 7 preparation technology of PC composites, it is characterised in that：Step a
In, the preparation technology of laser additive is to be constituted just to acrylate ester monomer/DTAB/water
To the alcoholic solution that copper nanoparticle, initiator, silane coupler are added dropwise in microemulsion, heating response is filtered, dried, and obtains laser
Activated species.
9. the laser direct forming according to claim 8 preparation technology of PC composites, it is characterised in that：Step d
In, screw extruder extrusion temperature is 210 DEG C -230 DEG C, and the main-machine screw rotating speed of screw extruder is 250r/min~330r/
Min, the rotating speed of hopper feed screw rod is 24r/min~35r/min.
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| CN109836775A (en) * | 2017-11-29 | 2019-06-04 | 中国航空工业集团公司济南特种结构研究所 | Preparation method suitable for Laser Direct Deposition technology epoxy resin-matrix prepreg |
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| WO2022024808A1 (en) * | 2020-07-28 | 2022-02-03 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition, and methods respectively for manufacturing molded article and plated molded article |
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| CN116572493A (en) * | 2023-07-07 | 2023-08-11 | 成都希德光安全科技有限公司 | Composite laser protection plate and processing technology thereof |
| CN116925656A (en) * | 2023-09-15 | 2023-10-24 | 广东格林诺实业有限公司 | Laser edge banding and production process thereof |
| CN116925656B (en) * | 2023-09-15 | 2023-12-19 | 广东格林诺实业有限公司 | Laser edge banding and production process thereof |
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