CN108912643A - A kind of weather-proof chemical resistance PC composite material and preparation method - Google Patents
A kind of weather-proof chemical resistance PC composite material and preparation method Download PDFInfo
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- CN108912643A CN108912643A CN201810663950.0A CN201810663950A CN108912643A CN 108912643 A CN108912643 A CN 108912643A CN 201810663950 A CN201810663950 A CN 201810663950A CN 108912643 A CN108912643 A CN 108912643A
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- 239000002131 composite material Substances 0.000 title claims abstract description 106
- 239000000126 substance Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 74
- 239000011256 inorganic filler Substances 0.000 claims abstract description 57
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 57
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 46
- 239000004917 carbon fiber Substances 0.000 claims abstract description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000835 fiber Substances 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006096 absorbing agent Substances 0.000 claims abstract description 19
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004417 polycarbonate Substances 0.000 claims description 79
- 238000009987 spinning Methods 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 16
- -1 tert-butyl -5- aminomethyl phenyl Chemical group 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000010041 electrostatic spinning Methods 0.000 claims description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 8
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 7
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- NFVZIERLAZUYBQ-UHFFFAOYSA-N [K].[Zn] Chemical compound [K].[Zn] NFVZIERLAZUYBQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000006084 composite stabilizer Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012994 photoredox catalyst Substances 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 33
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 5
- 229920000515 polycarbonate Polymers 0.000 description 78
- 230000000052 comparative effect Effects 0.000 description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 150000002825 nitriles Chemical class 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- WMJBVALTYVXGHW-UHFFFAOYSA-N 3,3-diphenylprop-2-enoic acid Chemical compound C=1C=CC=CC=1C(=CC(=O)O)C1=CC=CC=C1 WMJBVALTYVXGHW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
Landscapes
- 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)
- Artificial Filaments (AREA)
Abstract
The present invention relates to PC technical field of composite materials, and in particular to a kind of weather-proof chemical resistance PC composite material and preparation method, PC composite material include：PC, PET, PPO, composite fibre, heat stabilizer, antioxidant and ultraviolet absorbing agent, the composite fibre is mixed by inorganic filler and polyacrylonitrile carbon fiber, and the inorganic filler is at least one of nano aluminium oxide, nano silica and nano-titanium dioxide.The present invention carries out blending and modifying by the way that suitable PET and PPO is added in PC, effectively improves the tensile strength, impact strength and corrosion resistance of PC composite material；Polyacrylonitrile carbon fiber is also added into be mixed with inorganic filler, solve the problems, such as that inorganic filler is easy to reunite, and the mechanical properties such as the tensile strength of PC composite material can be improved in polyacrylonitrile carbon fiber, and inorganic filler can improve the corrosion resistance of PC composite material.
Description
Technical field
The present invention relates to PC technical field of composite materials, and in particular to a kind of weather-proof chemical resistance PC composite material and its system
Preparation Method.
Background technique
Polycarbonate (PC) refers to the quasi polymer that macromolecular chain is made of carbonate constitutional repeating unit, is that collection is rigid
The Typical Representative for the plastic material that property, hardness, toughness are integrated, is widely used in national defence and all sectors of the national economy,
The fields such as automobile, electric, building, office equipment, packaging, sports equipment, health care are now widely used for, with changing
Property technical research deepens continuously, and is just being extended to the high-tech areas such as aerospace, computer, CD rapidly, but it there is also
Some disadvantages, such as processing fluidity is poor, to be easy to stress cracking, and fatigue durability more sensitive to notch poor.
Thus while PC has excellent mechanical property, but it is poor in tensile strength, impact resistance performance, and PC
In processing, storage use process, due to the influence of various factors, aging gradually can occur and cause under PC machine tool performance
Drop.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of weather-proof chemically-resistants
Property, and the PC composite material with high tensile and impact strength, it is multiple that another object of the present invention is to provide the PC
The preparation method of condensation material, preparation method are simple and efficient, conducive to being uniformly mixed for each raw material, to produce uniform product.
The purpose of the invention is achieved by the following technical solution：
A kind of weather-proof chemical resistance PC composite material, the raw material including following parts by weight：
The composite fibre is mixed by inorganic filler and polyacrylonitrile carbon fiber, and the inorganic filler is nanometer
At least one of aluminium oxide, nano silica and nano-titanium dioxide.
PET (polyethylene terephthalate) is crystalline polymer, have excellent creep resistance, fatigue durability,
Rub resistance, wear resistance, resistance to chemical reagents, dimensional stability, gas and steam permeability are low, and electrical insulating property is excellent, by
A small amount of PET is added in PC composite material and carries out blending and modifying, can effectively improve the impact resistance and resistance toization of PC composite material
Learn corrosivity etc..
PPO has mechanical property outstanding, hard and tough and tensile, especially with tensile strength and impact strength most preferably by compound in PC
A small amount of PPO is added in material, can effectively improve tensile strength and impact strength of PC composite material etc..
Although the shortcomings that PC can be improved to a certain extent by high molecular polymer blending and modifying not of the same race,
Compatibility between high molecular polymer is poor, if excessive high molecular polymer not of the same race is added, melting is easy to cause to flow
Dynamic property is deteriorated, so as to cause the decline of mechanical property.
For this purpose, strict control PET and PPO are 10-20 parts by weight, and in order to further increase mechanical property and anti-ageing
The property changed joined composite fibre and carry out reinforcement.
Composite fibre is mixed by inorganic filler and polyacrylonitrile carbon fiber, and the inorganic filler of selection has nanometer
Characteristic and corrosion resistance, can improve the corrosion resistance of PC composite material, but nano inorganic filler is directly added into
It is easy to lead to the decline of the mechanical properties such as PC impact strength, tensile strength due to poor compatibility.For this purpose, the present invention is also added into
Polyacrylonitrile carbon fiber is mixed with inorganic filler, and in mixed process, inorganic filler can be scattered in polyacrylonitrile
On the surface of carbon fiber, therefore solve the problems, such as that inorganic filler is easy to reunite, and polyacrylonitrile carbon fiber also have it is excellent
The mechanical properties such as the tensile strength of PC composite material can be improved in different mechanical property.
In addition, heat stabilizer, antioxidant and ultraviolet absorbing agent is added in the present invention also in PC composite material, further
Improve the weatherability of PC material.
Wherein, the partial size of the inorganic filler is 48-79nm.
The present invention is by being distributed in polyacrylonitrile fibre silk for the nano inorganic filler of certain partial size, by network of fibers
Structure improves the dispersibility of inorganic filler, so that mechanical strength and corrosion resistance are improved, the present invention preferably grain of 48-79nm
Diameter range is the particle size range for being suitable for dispersion, and the P composite material of function admirable can be made.
Further, the inorganic filler by nano aluminium oxide, nano silica and nano-titanium dioxide by weight
Compare 1-3:1-2:The ratio of 1-2 forms, and PC composite material has excellent chemical corrosion resistance and mechanical property.
Wherein, the length of the polyacrylonitrile carbon fiber is 12.1-33.3 μm, diameter 147-214nm, BET specific surface
Product is 615-861m2/g。
The present invention preferably has the polyacrylonitrile fibre silk of appropriate draw ratio and length, can be effectively improved inorganic filler
Distributivity and improve polyacrylonitrile carbon fiber to the enhancement of PET material；And use the polyacrylonitrile carbon of high-specific surface area
Fiber can be conducive to inorganic filler and polyacrylonitrile carbon fiber and hydrogen bonding occurs and improves polyacrylonitrile carbon fiber and PC
Compatibility is well-dispersed in inorganic filler in PC, and stress concentration phenomenon will not occur, and the stretching for improving PC composite material is strong
Degree and impact strength etc..
Wherein, the preparation method of the composite fibre includes the following steps：
A, polyacrylonitrile is dissolved in n,N-Dimethylformamide and forms spinning solution, the polypropylene in the spinning solution
Nitrile mass concentration is 20-40wt%, then carries out electrostatic spinning, obtains polyacrylonitrile fibril；
B, the polyacrylonitrile fibril is carbonized in atmosphere of inert gases to get the polyacrylonitrile carbon fiber is arrived
Dimension；
C, inorganic filler and polyacrylonitrile carbon fiber are added into deionized water, carry out ultrasonic disperse 2-4h, centrifugation
Washing is dried to get the composite fibre is arrived, wherein the quality of inorganic filler, polyacrylonitrile carbon fiber and deionized water
Than being 1:3-5:50-70.
The present invention makes property and higher ratio of the polyacrylonitrile fibril with appropriate draw ratio by electrostatic spinning, carbonization
Surface area, conducive to the absorption to inorganic filler, and complex structure of filament is stablized, and avoids fiber during melting mixing disconnected
It splits so as to cause generation the phenomenon that the strength reduction of PC composite material.
Wherein, in step A, the spinning voltage of electrostatic spinning is 20-40kV, and spinning temperature is 30-40 DEG C.By to electrostatic
The condition of spinning carries out suitable control, can effectively improve the structural stability and length homogeneity of polyacrylonitrile fibril.
Wherein, in step B, the treatment conditions of carbonization are：1000-1200 is risen to the heating rate of 8.5-10.5 DEG C/min
DEG C, then keep the temperature 1-3h.A large amount of decomposition products can be generated in carbonisation, pass through the treatment conditions of control carbonization, decomposition product
After evolution, sparse porous surface can be left in nano carbon microsphere, so that the specific surface area of polyacrylonitrile carbon fiber is improved, it can
To effectively improve the mechanical property of PC composite material.
Wherein, the heat stabilizer is in calcium-zinc composite stabilizing agent, barium zinc compound stabilizer and potassium zinc composite stabilizer
It is at least one.Heat stabilizer selected above can prevent or delay influence of the heat to PC performance, improve the heat of PC composite material
Stability prolongs the service life.It is further preferred that the heat stabilizer is calcium-zinc composite stabilizing agent and barium zinc compound stabilizer
By weight 1-3:The ratio of 1-3 forms, and can preferably hinder the thermal degradation of PC composite material.
Wherein, the antioxidant is by antioxidant 1076 and antioxidant 1010 by weight 1-3:The ratio of 1-3 forms.This
Invention can be further improved PC composite wood by being suitably added the antioxidant being made of antioxidant 1076 and antioxidant 1010
The antioxygenic property of material, to improve its weatherability.
Wherein, the ultraviolet absorbing agent is cyano -3 2-, 3 '-diphenylacrylate -2- ethylhexyls and/or 2- (2-
- 3 tert-butyl -5- aminomethyl phenyl of hydroxyl) -5- chlorinated benzotriazole.Preferably, the ultraviolet absorbing agent is by cyano -3 2-, and 3 ' -
- 5- chlorinated benzotriazole is by weight by diphenylacrylate -2- ethylhexyl and 2- (- 3 tert-butyl -5- aminomethyl phenyl of 2- hydroxyl)
1:1 ratio mixes composition.Ultraviolet absorbing agent of the invention.Ultraviolet absorbing agent of the invention can consumingly absorb ultraviolet
Line reduces ultraviolet light and to matrix resin destroys, to improve the weatherability of PC composite material.
Another object of the present invention is achieved through the following technical solutions：
Such as a kind of preparation method of above-mentioned weather-proof chemical resistance PC composite material：Weigh each raw material by weight, by PC,
After PET, PPO, heat stabilizer, antioxidant and ultraviolet absorbing agent are mixed, it is added from main feeding mouth into extruder, it is multiple
Condensating fiber is added from side spout into extruder, and melting extrusion is compound to get the weather-proof chemical resistance PC is arrived after being granulated
Material.
The temperature in extruder one area to 5th area is followed successively by 180-200 DEG C, 200-220 DEG C, 220-240 DEG C, 200-220
℃、190-210℃。
The beneficial effects of the present invention are：
1, the present invention carries out blending and modifying by the way that suitable PET and PPO is added in PC, effectively improves PC composite material
Tensile strength, impact strength and corrosion resistance；
2, the inorganic filler that the present invention selects has nano-meter characteristic and corrosion resistance, can improve PC composite material
Corrosion resistance；
3, the present invention is also added into polyacrylonitrile carbon fiber and mixes with inorganic filler, inorganic in mixed process
Filler can be scattered on the surface of polyacrylonitrile carbon fiber, therefore solve the problems, such as that inorganic filler is easy to reunite, and
And polyacrylonitrile carbon fiber also has excellent mechanical property, and the mechanical properties such as the tensile strength of PC composite material can be improved；
4, heat stabilizer, antioxidant and ultraviolet absorbing agent is added in the present invention also in PC composite material, further mentions
The weatherability of high PC material；
5, preparation method of the invention is simple and efficient, conducive to being uniformly mixed for each raw material, to produce uniform product.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of weather-proof chemical resistance PC composite material, the raw material including following parts by weight：
The composite fibre is mixed by inorganic filler and polyacrylonitrile carbon fiber.
Further, the inorganic filler by nano aluminium oxide, nano silica and nano-titanium dioxide by weight
Compare 1-3:1-2:The ratio of 1-2 forms, and the average grain diameter of the nano aluminium oxide is 50nm, the average grain diameter of nano silica
For 56nm, the average grain diameter of nano-titanium dioxide is 72nm.
Wherein, the preparation method of the composite fibre includes the following steps：
A, polyacrylonitrile is dissolved in n,N-Dimethylformamide and forms spinning solution, the polypropylene in the spinning solution
Nitrile mass concentration is 30wt%, then carries out electrostatic spinning, obtains polyacrylonitrile fibril；
B, the polyacrylonitrile fibril is carbonized in atmosphere of inert gases to get the polyacrylonitrile carbon fiber is arrived
Dimension；
C, inorganic filler and polyacrylonitrile carbon fiber are added into deionized water, carry out ultrasonic disperse 2-4h, centrifugation
Washing is dried to get the composite fibre is arrived, wherein the quality of inorganic filler, polyacrylonitrile carbon fiber and deionized water
Than being 1:4:60.
Wherein, in step A, the spinning voltage of electrostatic spinning is 30kV, and spinning temperature is 35 DEG C.
Wherein, in step B, the treatment conditions of carbonization are：1100 DEG C are risen to the heating rate of 9.5 DEG C/min, is then protected
Warm 2h.
Wherein, the heat stabilizer is calcium-zinc composite stabilizing agent and barium zinc compound stabilizer by weight 1:1 ratio group
At.
Wherein, the antioxidant is by antioxidant 1076 and antioxidant 1010 by weight 1:1 ratio composition.
Wherein, the ultraviolet absorbing agent is by cyano -3 2-, 3 '-diphenylacrylate -2- ethylhexyls and 2- (2- hydroxyl
- 3 tert-butyl -5- aminomethyl phenyl of base) -5- chlorinated benzotriazole by weight 1:1 ratio mixes composition.
Such as a kind of preparation method of above-mentioned weather-proof chemical resistance PC composite material：Weigh each raw material by weight, by PC,
After PET, PPO, heat stabilizer, antioxidant and ultraviolet absorbing agent are mixed, it is added from main feeding mouth into extruder, it is multiple
Condensating fiber is added from side spout into extruder, and melting extrusion is compound to get the weather-proof chemical resistance PC is arrived after being granulated
Material.
The temperature in extruder one area to 5th area is followed successively by 190 DEG C, 210 DEG C, 230 DEG C, 210 DEG C, 200 DEG C.
Embodiment 2
A kind of weather-proof chemical resistance PC composite material, the raw material including following parts by weight：
The composite fibre is mixed by inorganic filler and polyacrylonitrile carbon fiber.
Further, the inorganic filler by nano aluminium oxide, nano silica and nano-titanium dioxide by weight
Than 1:1:1 ratio composition, the average grain diameter of the nano aluminium oxide is 48nm, and the average grain diameter of nano silica is
63nm, the average grain diameter of nano-titanium dioxide are 79nm.
Wherein, the preparation method of the composite fibre includes the following steps：
A, polyacrylonitrile is dissolved in n,N-Dimethylformamide and forms spinning solution, the polypropylene in the spinning solution
Nitrile mass concentration is 20wt%, then carries out electrostatic spinning, obtains polyacrylonitrile fibril；
B, the polyacrylonitrile fibril is carbonized in atmosphere of inert gases to get the polyacrylonitrile carbon fiber is arrived
Dimension；
C, inorganic filler and polyacrylonitrile carbon fiber are added into deionized water, carry out ultrasonic disperse 2h, centrifugation is washed
It washs, dry to get the composite fibre is arrived, wherein the mass ratio of inorganic filler, polyacrylonitrile carbon fiber and deionized water
It is 1:3:50.
Wherein, in step A, the spinning voltage of electrostatic spinning is 40kV, and spinning temperature is 40 DEG C.
Wherein, in step B, the treatment conditions of carbonization are：1000 DEG C are risen to the heating rate of 8.5 DEG C/min, is then protected
Warm 1h.
Wherein, the heat stabilizer is calcium-zinc composite stabilizing agent and barium zinc compound stabilizer by weight 1:3 ratio group
At.
Wherein, the antioxidant is by antioxidant 1076 and antioxidant 1010 by weight 1:3 ratio composition.
Wherein, the ultraviolet absorbing agent is by cyano -3 2-, 3 '-diphenylacrylate -2- ethylhexyls and 2- (2- hydroxyl
- 3 tert-butyl -5- aminomethyl phenyl of base) -5- chlorinated benzotriazole by weight 1:2 ratio mixes composition.
Such as a kind of preparation method of above-mentioned weather-proof chemical resistance PC composite material：Weigh each raw material by weight, by PC,
After PET, PPO, heat stabilizer, antioxidant and ultraviolet absorbing agent are mixed, it is added from main feeding mouth into extruder, it is multiple
Condensating fiber is added from side spout into extruder, and melting extrusion is compound to get the weather-proof chemical resistance PC is arrived after being granulated
Material.
The temperature in extruder one area to 5th area is followed successively by 180 DEG C, 200 DEG C, 220 DEG C, 200 DEG C, 190 DEG C.
Embodiment 3
A kind of weather-proof chemical resistance PC composite material, the raw material including following parts by weight：
The composite fibre is mixed by inorganic filler and polyacrylonitrile carbon fiber.
Further, the inorganic filler by nano aluminium oxide, nano silica and nano-titanium dioxide by weight
Than 3:2:2 ratio composition, the average grain diameter of the nano aluminium oxide is 59nm, and the average grain diameter of nano silica is
64nm, the average grain diameter of nano-titanium dioxide are 70nm.
Wherein, the preparation method of the composite fibre includes the following steps：
A, polyacrylonitrile is dissolved in n,N-Dimethylformamide and forms spinning solution, the polypropylene in the spinning solution
Nitrile mass concentration is 40wt%, then carries out electrostatic spinning, obtains polyacrylonitrile fibril；
B, the polyacrylonitrile fibril is carbonized in atmosphere of inert gases to get the polyacrylonitrile carbon fiber is arrived
Dimension；
C, inorganic filler and polyacrylonitrile carbon fiber are added into deionized water, carry out ultrasonic disperse 4h, centrifugation is washed
It washs, dry to get the composite fibre is arrived, wherein the mass ratio of inorganic filler, polyacrylonitrile carbon fiber and deionized water
It is 1:5:70.
Wherein, in step A, the spinning voltage of electrostatic spinning is 40kV, and spinning temperature is 40 DEG C.
Wherein, in step B, the treatment conditions of carbonization are：1200 DEG C are risen to the heating rate of 10.5 DEG C/min, is then protected
Warm 3h.
Wherein, the heat stabilizer is calcium-zinc composite stabilizing agent and barium zinc compound stabilizer by weight 3:1 ratio group
At.
Wherein, the antioxidant is by antioxidant 1076 and antioxidant 1010 by weight 3:1 ratio composition.
Wherein, the ultraviolet absorbing agent is by cyano -3 2-, 3 '-diphenylacrylate -2- ethylhexyls and 2- (2- hydroxyl
- 3 tert-butyl -5- aminomethyl phenyl of base) -5- chlorinated benzotriazole by weight 2:1 ratio mixes composition.
Such as a kind of preparation method of above-mentioned weather-proof chemical resistance PC composite material：Weigh each raw material by weight, by PC,
After PET, PPO, heat stabilizer, antioxidant and ultraviolet absorbing agent are mixed, it is added from main feeding mouth into extruder, it is multiple
Condensating fiber is added from side spout into extruder, and melting extrusion is compound to get the weather-proof chemical resistance PC is arrived after being granulated
Material.
The temperature in extruder one area to 5th area is followed successively by 200 DEG C, 220 DEG C, 240 DEG C, 220 DEG C, 210 DEG C.
Embodiment 4
A kind of weather-proof chemical resistance PC composite material, the raw material including following parts by weight：
The composite fibre is mixed by inorganic filler and polyacrylonitrile carbon fiber.
Further, the inorganic filler is nano aluminium oxide, and the average grain diameter of the nano aluminium oxide is 58nm.
Wherein, the preparation method of the composite fibre includes the following steps：
A, polyacrylonitrile is dissolved in n,N-Dimethylformamide and forms spinning solution, the polypropylene in the spinning solution
Nitrile mass concentration is 25wt%, then carries out electrostatic spinning, obtains polyacrylonitrile fibril；
B, the polyacrylonitrile fibril is carbonized in atmosphere of inert gases to get the polyacrylonitrile carbon fiber is arrived
Dimension；
C, inorganic filler and polyacrylonitrile carbon fiber are added into deionized water, carry out ultrasonic disperse 2.5h, centrifugation
Washing is dried to get the composite fibre is arrived, wherein the quality of inorganic filler, polyacrylonitrile carbon fiber and deionized water
Than being 1:4:55.
Wherein, in step A, the spinning voltage of electrostatic spinning is 25kV, and spinning temperature is 33 DEG C.
Wherein, in step B, the treatment conditions of carbonization are：1050 DEG C are risen to the heating rate of 9 DEG C/min, is then kept the temperature
1.5h。
Wherein, the heat stabilizer is calcium-zinc composite stabilizing agent.
Wherein, the antioxidant is by antioxidant 1076 and antioxidant 1010 by weight 1:2 ratio composition.
Wherein, the ultraviolet absorbing agent is cyano -3 2-, 3 '-diphenylacrylate -2- ethylhexyls.
Such as a kind of preparation method of above-mentioned weather-proof chemical resistance PC composite material：Weigh each raw material by weight, by PC,
After PET, PPO, heat stabilizer, antioxidant and ultraviolet absorbing agent are mixed, it is added from main feeding mouth into extruder, it is multiple
Condensating fiber is added from side spout into extruder, and melting extrusion is compound to get the weather-proof chemical resistance PC is arrived after being granulated
Material.
The temperature in extruder one area to 5th area is followed successively by 185 DEG C, 205 DEG C, 225 DEG C, 205 DEG C, 195 DEG C.
Embodiment 5
A kind of weather-proof chemical resistance PC composite material, the raw material including following parts by weight：
The composite fibre is mixed by inorganic filler and polyacrylonitrile carbon fiber.
Further, the inorganic filler is nano silica, and the average grain diameter of nano silica is 56nm.
Wherein, the preparation method of the composite fibre includes the following steps：
A, polyacrylonitrile is dissolved in n,N-Dimethylformamide and forms spinning solution, the polypropylene in the spinning solution
Nitrile mass concentration is 35wt%, then carries out electrostatic spinning, obtains polyacrylonitrile fibril；
B, the polyacrylonitrile fibril is carbonized in atmosphere of inert gases to get the polyacrylonitrile carbon fiber is arrived
Dimension；
C, inorganic filler and polyacrylonitrile carbon fiber are added into deionized water, carry out ultrasonic disperse 3.5h, centrifugation
Washing is dried to get the composite fibre is arrived, wherein the quality of inorganic filler, polyacrylonitrile carbon fiber and deionized water
Than being 1:4:65.
Wherein, in step A, the spinning voltage of electrostatic spinning is 35kV, and spinning temperature is 37 DEG C.
Wherein, in step B, the treatment conditions of carbonization are：1150 DEG C are risen to the heating rate of 10 DEG C/min, is then kept the temperature
2.5h。
Wherein, the heat stabilizer is barium zinc compound stabilizer.
Wherein, the antioxidant is by antioxidant 1076 and antioxidant 1010 by weight 2:3 ratio composition.
Wherein, the ultraviolet absorbing agent is or 2- (- 3 tert-butyl -5- aminomethyl phenyl of 2- hydroxyl) -5- chloro benzo three
Azoles.
Such as a kind of preparation method of above-mentioned weather-proof chemical resistance PC composite material：Weigh each raw material by weight, by PC,
After PET, PPO, heat stabilizer, antioxidant and ultraviolet absorbing agent are mixed, it is added from main feeding mouth into extruder, it is multiple
Condensating fiber is added from side spout into extruder, and melting extrusion is compound to get the weather-proof chemical resistance PC is arrived after being granulated
Material.
The temperature in extruder one area to 5th area is followed successively by 195 DEG C, 215 DEG C, 235 DEG C, 215 DEG C, 205 DEG C.
The length of the polyacrylonitrile carbon fiber made from the present embodiment 1-5 is 12.1-33.3 μm, diameter 147-
214nm, BET specific surface area 615-861m2/g。
Comparative example 1
This comparative example 1 the difference from embodiment 1 is that：Composite fibre is not contained in PC composite material.
Comparative example 2
This comparative example 2 the difference from embodiment 1 is that：It is inorganic with the composite fibre of the inorganic filler substitution equivalent of equivalent
The composition ratio and partial size of filler are same as Example 1.
The PC composite material of embodiment 1-5 and comparative example 1-2 are tested for the property, testing standard and test result such as table
Shown in 1：
| Tensile strength (MPa) | Bending strength (MPa) | Notch impact strength (KJ/m2) | |
| ASTM D638 | ASTM D790 | ASTM D256 | |
| Embodiment 1 | 184.6 | 244.7 | 113.5 |
| Embodiment 2 | 163.5 | 225.4 | 104.1 |
| Embodiment 3 | 169.3 | 216.8 | 101.5 |
| Embodiment 4 | 158.4 | 200.6 | 100.8 |
| Embodiment 5 | 156.8 | 208.1 | 100.4 |
| Comparative example 1 | 113.3 | 176.1 | 89.4 |
| Comparative example 2 | 92.7 | 142.4 | 75.9 |
Table 1
By upper table comparative example 1 it is found that being modified by PET and PPO to PC, PC composite material can be made to have preferable
Mechanical property performance；By the comparison of comparative example 1 and comparative example 2 it is found that being directly added into for inorganic filler will lead to PC composite wood
Expect the decline of mechanical property；By the comparison of embodiment 1, comparative example 1 and comparative example 2 it is found that composite fibre of the present invention can with gram
The problem of inorganic filler causes PC composite property to deteriorate is taken, and before composite fibre is not added relatively in mechanical property, significantly
Ground improves.
The PC composite material of embodiment 1-5 and comparative example 1-2 is divided into A, B batch, the PC composite material of A batch according to
《ASTM G155-2005 plastic open xenon lamp aging test method》The degradation for carrying out xenon lamp irradiation 1000h, then to PC
Composite material carries out the test of tensile strength, bending strength and impact strength, test result such as table two；The PC of B batch is compound
Material according to《ISO 4611-2011》Carry out 1000h neutral salt spray test, then to PC composite material carry out tensile strength,
The test of bending strength and impact strength, test result such as table three.
Table two
| Tensile strength (MPa) | Bending strength (MPa) | Notch impact strength (KJ/m2) | |
| ASTM D638 | ASTM D790 | ASTM D256 | |
| Embodiment 1 | 146.4 | 206.4 | 84.1 |
| Embodiment 2 | 120.7 | 182.5 | 76.2 |
| Embodiment 3 | 118.4 | 177.6 | 75.2 |
| Embodiment 4 | 116.2 | 161.8 | 68.5 |
| Embodiment 5 | 114.5 | 160.2 | 67.4 |
| Comparative example 1 | 62.6 | 89.3 | 41.7 |
| Comparative example 2 | 64.3 | 92.3 | 43.6 |
Table three
By in upper two tables comparative example 1 and comparative example 2 compare it is found that although being directly added into for inorganic filler will lead to PC
The deterioration of composite materials property, but the light shine degradability of PC composite material and resistant to chemical etching is also substantially increased simultaneously
Property, to improve the weatherability of PC composite material.
By the comparison of embodiment 1, comparative example 1 and comparative example 2 in upper two tables it is found that the present invention utilizes polyacrylonitrile carbon
After fiber loads inorganic filler, PC composite material not only has preferable mechanical property, and in light shine degradability and resistance toization
Learning corrosivity has very big promotion (it was found from from the conservation rate of Computational Mechanics performance and comparing), this is because passing through polypropylene
Nitrile carbon fiber, inorganic filler reach evenly dispersed in PC composite material, to make weatherability of the PC composite material with height
And chemical resistance, and by the reinforcement of polyacrylonitrile carbon fiber, the PC composite material after aging remains to mechanics with higher
Performance.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of weather-proof chemical resistance PC composite material, it is characterised in that：Raw material including following parts by weight：
The composite fibre is mixed by inorganic filler and polyacrylonitrile carbon fiber, and the inorganic filler is nano oxidized
At least one of aluminium, nano silica and nano-titanium dioxide.
2. a kind of weather-proof chemical resistance PC composite material according to claim 1, it is characterised in that：The inorganic filler
Partial size be 48-79nm.
3. a kind of weather-proof chemical resistance PC composite material according to claim 1, it is characterised in that：The polyacrylonitrile carbon
The length of fiber is 12.1-33.3 μm, diameter 147-214nm, BET specific surface area 615-861m2/g。
4. a kind of weather-proof chemical resistance PC composite material according to claim 1, it is characterised in that：The composite fibre
Preparation method includes the following steps：
A, polyacrylonitrile is dissolved in n,N-Dimethylformamide and forms spinning solution, the polyacrylonitrile matter in the spinning solution
Amount concentration is 20-40wt%, then carries out electrostatic spinning, obtains polyacrylonitrile fibril；
B, the polyacrylonitrile fibril is carbonized in atmosphere of inert gases to get the polyacrylonitrile carbon fiber is arrived；
C, inorganic filler and polyacrylonitrile carbon fiber are added into deionized water, progress ultrasonic disperse 2-4h, centrifuge washing,
It is dry to get arriving the composite fibre, wherein the mass ratio of inorganic filler, polyacrylonitrile carbon fiber and deionized water is
1:3-5:50-70。
5. a kind of weather-proof chemical resistance PC composite material according to claim 4, it is characterised in that：In step A, Static Spinning
The spinning voltage of silk is 20-40kV, and spinning temperature is 30-40 DEG C.
6. a kind of weather-proof chemical resistance PC composite material according to claim 4, it is characterised in that：In step B, carbonization
Treatment conditions are：1000-1200 DEG C is risen to the heating rate of 8.5-10.5 DEG C/min, then keeps the temperature 1-3h.
7. a kind of weather-proof chemical resistance PC composite material according to claim 1, it is characterised in that：The heat stabilizer is
At least one of calcium-zinc composite stabilizing agent, barium zinc compound stabilizer and potassium zinc composite stabilizer.
8. a kind of weather-proof chemical resistance PC composite material according to claim 1, it is characterised in that：The antioxidant by
Antioxidant 1076 and antioxidant 1010 are by weight 1-3:The ratio of 1-3 forms.
9. a kind of weather-proof chemical resistance PC composite material according to claim 1, it is characterised in that：The ultraviolet radiation absorption
Agent is 2- cyano -3,3 '-diphenylacrylate -2- ethylhexyl and/or 2- (- 3 tert-butyl -5- aminomethyl phenyl of 2- hydroxyl) -5-
Chlorinated benzotriazole.
10. a kind of preparation method of weather-proof chemical resistance PC composite material described in any one of claim 1-9, feature exist
In：Each raw material is weighed by weight, after PC, PET, PPO, heat stabilizer, antioxidant and ultraviolet absorbing agent are mixed,
Be added from main feeding mouth into extruder, composite fibre is added from side spout into extruder, melting extrusion be granulated after to get
To the weather-proof chemical resistance PC composite material.
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Application publication date: 20181130 |