CN109135017A - A kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics - Google Patents
A kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics Download PDFInfo
- Publication number
- CN109135017A CN109135017A CN201810994664.2A CN201810994664A CN109135017A CN 109135017 A CN109135017 A CN 109135017A CN 201810994664 A CN201810994664 A CN 201810994664A CN 109135017 A CN109135017 A CN 109135017A
- Authority
- CN
- China
- Prior art keywords
- parts
- oxidative aging
- preparation
- thermo oxidative
- thermoplastic plastics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000032683 aging Effects 0.000 title claims abstract description 32
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 32
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000003851 corona treatment Methods 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 230000010355 oscillation Effects 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 208000002173 dizziness Diseases 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 22
- 239000004033 plastic Substances 0.000 abstract description 22
- 229910021389 graphene Inorganic materials 0.000 abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 239000004408 titanium dioxide Substances 0.000 abstract description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 238000010892 electric spark Methods 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002990 reinforced plastic Substances 0.000 abstract description 2
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000007551 Shore hardness test Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920001887 crystalline plastic Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000003709 heart valve Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
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)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The present invention relates to a kind of preparation methods of thermo oxidative aging high-strength thermoplastic plastics, belong to plastics preparation technical field.The present invention is aoxidized graphite powder in the concentrated sulfuric acid by potassium ferrate, nano graphene oxide material is made, sulfonic acid group is introduced in graphene oxide, the organo-functional groups such as hydroxyl, to which graphene oxide and nano-titanium dioxide generate hydrogen bond and intermolecular force absorption, the present invention is using citric acid to titanium dioxide, graphene oxide is surface modified and is modified, make to introduce carboxylic group abundant in composite material, citric acid and the hydroxyl group of surface of graphene oxide react simultaneously, form covalent bond absorption, and titanium dioxide is reacted, utilize HIGH PRESSURE TREATMENT, electric spark impact is generated in frosting, the oxygen of frosting is set to form ozone molecule, ozone molecule makes frosting form hydroxyl, carboxyl isopolarity group, the reducing power of reinforced plastics, improve the thermo oxidative aging performance of plastics, before wide application Scape.
Description
Technical field
The present invention relates to a kind of preparation methods of thermo oxidative aging high-strength thermoplastic plastics, belong to plastics technology of preparing neck
Domain.
Background technique
Thermoplastic refers to the plastics with heating and softening, hardening by cooling characteristic.Our big portions used in daily life
Plastics are divided to belong to this scope.Soften when heating so that flowing, cooling are hardened, this process is reversible, and can be repeated.
Including polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyformaldehyde, polycarbonate is polyamide, acrylics, other
Polyolefin and its copolymer, polysulfones, polyphenylene oxide.
Thermoplastic can be divided into general-purpose plastics, work according to performance characteristics, widely used property and forming technique versatility etc.
Engineering plastics, special plastics etc..The main feature of general-purpose plastics: widely used, easy to process, good combination property.Such as polyethylene
(PE), polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene (ABS) (ABS) are generally called again
For " five big general-purpose plastics ".The characteristics of engineering plastics and special plastics is: the certain structures and performance of high polymer are particularly pertinent, or
Person's forming processing technology difficulty is larger etc., is often applied to specialized engineering or special field, occasion.Main engineering plastics have:
Nylon (Nylon), polycarbonate (PC), polyurethane (PU), polytetrafluoroethylene (PTFE) (Teflon PTFE), polyethylene terephthalate
Ester (PET) etc., " the synthesis heart valve ", " joint prosthesis " of special plastics such as " medical high polymer " class.According to total high polymer
Aggregated structure and performance characteristics can be divided into again: crystalline plastic and amorphism plastics two major classes.Amorphism plastics are again
Referred to as unformed plastics.
One important development direction of plastic processing is to existing modifying plastics to improve service performance.It is such as fine using enhancing
Dimension prepares enhanced modified plastics, can effectively improve the mechanical performance and heat resistance of plastics, and reach in some aspects
Or the performance more than metal material.Such material is referred to as fiber reinforced thermoplastics FRTP.
There are two ways to traditional mode of production FRTP, one is mouth is added by the fiber in the middle part of double screw extruder bunchy is added
Long fibre.Another kind is that chopped strand and raw material are added together in feed opening by single screw extrusion machine.
Currently, existing thermoplastic it is generally existing wear no resistance, hardness it is low, the insufficient defect of thermal ageing resistant performance.
Therefore, inventing a kind of thermo oxidative aging high-strength thermoplastic plastic on plastic preparation technical field has positive effect.
Summary of the invention
The technical problems to be solved by the invention: current thermoplastic wearability, difference of hardness, thermal ageing resistant performance are directed to
Insufficient defect provides a kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics, it is characterised in that specific preparation step are as follows:
A kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics, it is characterised in that specific preparation step are as follows:
(1) graphite is put into grinder and is ground, crossed 150 meshes and obtain sieving, in mass ratio with sulfuric acid solution by sieving
Obtained mixed dispersion liquid is stirred evenly in 1:20 investment beaker, is placed the beaker in ice-water bath, mixing dispersion is added dropwise into beaker
The potassium ferrate solution of liquid quality 3~5% after constant temperature stands 30~40min, increases bath temperature, and constant temperature stands, is obtained by filtration
Filter cake obtains oxidation product filter cake 3~5 times wash with distilled water, spare；
(2) by butyl titanate and ethylene glycol 1:10 in mass ratio investment full of nitrogen glove box in be stirred reaction 6~
Mixing suspension is made in 8h, under stirring, the acetone of the quality such as mixing suspension is added into glove box, persistently stirs 12
~14h is filtered after stirring, successively with dehydrated alcohol and distillation water washing 3~5 times, is placed in oven and dried, reaction solid is made
Powder；
(3) according to parts by weight, 3~5 parts of spare oxidation products, 2~4 parts of above-mentioned reaction solid powders, 12~15 parts are weighed
Disperse in isopropanol and 8~10 parts of dehydrated alcohol investment high speed dispersion instrument, solidliquid mixture is made；
(4) above-mentioned solidliquid mixture and Citric acid crystal powder 20:1 in mass ratio are put into three-necked flask, by three-necked flask
It is placed in sonic oscillation instrument and vibrates, modified filter residue is obtained by filtration after oscillation, drying in modified filter residue investment baking oven is made and is modified
Mixture；
(5) according to parts by weight, weigh 6~8 parts of above-mentioned modified mixtures, 15~18 parts of polyethylene, 12~14 parts of polypropylene,
In 1.5~1.8 parts of calcium carbonate powders and 1.0~1.5 parts of benzoyl peroxide investment vented single -screw extruders, squeezes out and be made
Pre product is put into sided corona treatment in corona treatment equipment by pre product, and thermo oxidative aging high-strength thermoplastic plastics are made.
The mass fraction of sulfuric acid solution as described in step (1) is 80~90%, and the mass fraction of liquor potassic permanganate is 10
~14%, bath temperature is increased to 35~40 DEG C, and constant temperature time of repose is 5~6h.
Magnetic agitation rotating speed described in step (2) is 300~330r/min, and temperature is 10~15 DEG C, is stirred anti-
It for the temperature in 6~8h baking oven is 130~140 DEG C between seasonable, drying time is 5~6h.
Revolving speed in high speed dispersion instrument described in step (3) is 1500~1700r/min, jitter time is 40~
50min。
Frequency in sonic oscillation instrument described in step (4) is 40~42kHz, and duration of oscillation is 3~5h, in baking oven
Temperature is 110~120 DEG C.
Extrusion temperature in vented single -screw extruder described in step (5) is 320~350 DEG C, and screw speed is
High-frequency ac voltage in 40~50r/min corona treatment equipment is 4000~5000V/m2, sided corona treatment speed is 15~
20m/min, sided corona treatment time are 30~40min.
The method have the benefit that:
(1) present invention first puts into graphite in sulfuric acid solution, carries out oxidation reaction with potassium ferrate, and oxidation product is made, then
Butyl titanate is dispersed with stirring in ethylene glycol solution, is gradually flocculated, reaction solid powder is made in filtering drying, then by oxygen
Change product, reaction solid powder and organic solvent mixing, citric acid is added after mixing, it is modified, modified mixing is made
Modified mixture, polymer and other auxiliary agents are then mixed investment extruder high temperature and squeeze out obtained pre product, finally by object
Pre product is subjected to sided corona treatment, thermo oxidative aging high-strength thermoplastic plastics are made, the present invention is by graphite powder in the concentrated sulfuric acid
It is aoxidized by potassium ferrate, nano graphene oxide material is made, introduces the organic functionals such as sulfonic acid group, hydroxyl in graphene oxide
Group makes graphene and titanium dioxide so that graphene oxide and nano-titanium dioxide generate hydrogen bond and intermolecular force adsorbs
Titanium molecule combination degree is even closer, in conjunction with the mechanical strength that graphene and titanium dioxide itself are excellent, improves thermoplastic
Hardness, intensity and wearability；
(2) present invention is surface modified and is modified to titanium dioxide, graphene oxide using citric acid, makes to draw in composite material
Enter carboxylic group abundant, while citric acid and the hydroxyl group of surface of graphene oxide react, form covalent bond absorption,
And titanium dioxide is reacted, titanium is precipitated in ionic state and chelation absorption is formed by carboxylic group, makes composite material table
Face forms hole, and the present invention also carries out sided corona treatment to plastic molecules, generates electric spark in frosting using high-voltage electricity and impacts,
To the degree of roughness on reinforced plastics surface, and the oxygen of frosting is made to form ozone molecule, ozone molecule makes frosting
Hydroxyl, carboxyl isopolarity group are formed, frosting is made to form polar surfaces, surface tension is improved, is inclined to graphene more
In being dispersed in frosting, to improve the thermo oxidative aging performance of plastics, have broad application prospects.
Specific embodiment
Graphite is put into grinder and be ground, 150 meshes is crossed and obtains sieving, by sieving and mass fraction be 80~
Obtained mixed dispersion liquid is stirred evenly in 90% sulfuric acid solution 1:20 in mass ratio investment beaker, is placed the beaker in ice-water bath,
The potassium ferrate solution that the mass fraction of dropwise addition mixed dispersion liquid quality 3~5% is 10~14% into beaker, constant temperature standing 30~
After 40min, increase bath temperature to 35~40 DEG C, constant temperature stands 5~6h, filter cake is obtained by filtration, wash with distilled water filter cake 3~
Obtain oxidation product 5 times, it is spare；Butyl titanate and ethylene glycol 1:10 in mass ratio investment are full of in the glove box of nitrogen,
Under conditions of magnetic agitation rotating speed is 300~330r/min and temperature is 10~15 DEG C, it is stirred 6~8h of reaction and is made mixed
Suspension is closed, under stirring, the acetone of the quality such as mixing suspension is added into glove box, persistently stirs 12~14h, stirs
It filters after mixing, successively with dehydrated alcohol and distillation water washing 3~5 times, is put into baking oven, the condition for being 130~140 DEG C in temperature
Reaction solid powder is made in 5~6h of lower drying；According to parts by weight, weigh 3~5 parts of spare oxidation products, 2~4 parts it is above-mentioned
It reacts in solid powder, 12~15 parts of isopropanols and 8~10 parts of dehydrated alcohol investment high speed dispersion instrument, with 1500~1700r/
Solidliquid mixture is made in revolving speed 40~50min of high speed dispersion of min；Above-mentioned solidliquid mixture and Citric acid crystal powder are pressed
Mass ratio 20:1 put into three-necked flask in, three-necked flask is placed in sonic oscillation instrument, with the hunting of frequency 3 of 40~42kHz~
Modified filter residue is obtained by filtration in 5h after oscillation, the temperature drying in modified filter residue investment baking oven with 110~120 DEG C is made and is modified
Mixture；According to parts by weight, weigh 6~8 parts of above-mentioned modified mixtures, 15~18 parts of polyethylene, 12~14 parts of polypropylene,
In 1.5~1.8 parts of calcium carbonate powders and 1.0~1.5 parts of benzoyl peroxide investment vented single -screw extruders, temperature is being squeezed out
Degree is 320~350 DEG C, squeezes out under conditions of 40~50r/min of screw speed and pre product is made, pre product is put into corona
It is 4000~5000V/m in high-frequency ac voltage in processing equipment2, electricity under conditions of sided corona treatment speed is 15~20m/min
30~40min of dizzy processing, is made thermo oxidative aging high-strength thermoplastic plastics.
Example 1
Graphite is put into grinder and is ground, 150 meshes is crossed and obtains sieving, the sulfuric acid for being 80% by sieving and mass fraction
Obtained mixed dispersion liquid is stirred evenly in solution 1:20 in mass ratio investment beaker, is placed the beaker in ice-water bath, into beaker
The potassium ferrate solution that the mass fraction of mixed dispersion liquid quality 3% is 10% is added dropwise, after constant temperature stands 30min, increases water-bath temperature
For degree to 35 DEG C, constant temperature stands 5h, and filter cake is obtained by filtration, and obtains oxidation product filter cake 3 times wash with distilled water, spare；By metatitanic acid
Four butyl esters and ethylene glycol 1:10 in mass ratio investment are full of in the glove box of nitrogen, are 300r/min and temperature in magnetic agitation rotating speed
Under conditions of degree is 10 DEG C, it is stirred reaction 6h and mixing suspension is made, under stirring, mixing is added into glove box
The acetone of the quality such as suspension persistently stirs 12h, filters after stirring, successively with dehydrated alcohol and distillation water washing 3 times, is put into
In baking oven, reaction solid powder is made in dry 5h under conditions of temperature is 130 DEG C；According to parts by weight, weigh 3 parts it is spare
Oxidation product, 2 parts of above-mentioned reaction solid powders, in 12 parts of isopropanols and 8 parts of dehydrated alcohols investment high speed dispersion instrument, with
Solidliquid mixture is made in the revolving speed high speed dispersion 40min of 1500r/min；By above-mentioned solidliquid mixture and Citric acid crystal powder
20:1 in mass ratio is put into three-necked flask, and three-necked flask is placed in sonic oscillation instrument, with the hunting of frequency 3h of 40kHz, vibration
Modified filter residue is obtained by filtration after swinging, modified mixture is made by drying in modified filter residue investment baking oven with 110 DEG C of temperature；By weight
Number meter is measured, 6 parts of above-mentioned modified mixtures, 15 parts of polyethylene, 12 parts of polypropylene, 1.5 parts of calcium carbonate powders and 1.0 parts of mistakes are weighed
Benzoyl Oxide is put into vented single -screw extruder, is 320 DEG C in extrusion temperature, under conditions of screw speed 40r/min
It squeezes out and pre product is made, pre product is put into corona treatment equipment, be 4000V/m in high-frequency ac voltage2, at corona
Managing speed is sided corona treatment 30min under conditions of 15m/min, and thermo oxidative aging high-strength thermoplastic plastics are made.
Example 2
Graphite is put into grinder and is ground, 150 meshes is crossed and obtains sieving, the sulfuric acid for being 85% by sieving and mass fraction
Obtained mixed dispersion liquid is stirred evenly in solution 1:20 in mass ratio investment beaker, is placed the beaker in ice-water bath, into beaker
The potassium ferrate solution that the mass fraction of mixed dispersion liquid quality 4% is 12% is added dropwise, after constant temperature stands 35min, increases water-bath temperature
For degree to 37 DEG C, constant temperature stands 5.5h, and filter cake is obtained by filtration, and obtains oxidation product filter cake 4 times wash with distilled water, spare；By titanium
Sour four butyl esters and ethylene glycol 1:10 in mass ratio investment full of in the glove box of nitrogen, magnetic agitation rotating speed be 310r/min and
It under conditions of temperature is 12 DEG C, is stirred reaction 7h and mixing suspension is made, under stirring, be added into glove box mixed
The acetone for closing the quality such as suspension, persistently stirs 13h, filters after stirring, successively with dehydrated alcohol and distillation water washing 4 times, puts
Enter in baking oven, reaction solid powder is made in dry 5.5h under conditions of temperature is 135 DEG C；According to parts by weight, 4 parts are weighed
Spare oxidation product, 3 parts of above-mentioned reaction solid powders, 13 parts of isopropanols and 9 parts of dehydrated alcohols are put into high speed dispersion instrument, with
Solidliquid mixture is made in the revolving speed high speed dispersion 45min of 1600r/min；By above-mentioned solidliquid mixture and Citric acid crystal powder
20:1 in mass ratio is put into three-necked flask, and three-necked flask is placed in sonic oscillation instrument, with the hunting of frequency 4h of 41kHz, vibration
Modified filter residue is obtained by filtration after swinging, modified mixture is made by drying in modified filter residue investment baking oven with 115 DEG C of temperature；By weight
Number meter is measured, 7 parts of above-mentioned modified mixtures, 17 parts of polyethylene, 13 parts of polypropylene, 1.7 parts of calcium carbonate powders and 1.2 parts of mistakes are weighed
Benzoyl Oxide is put into vented single -screw extruder, is 340 DEG C in extrusion temperature, under conditions of screw speed 45r/min
It squeezes out and pre product is made, pre product is put into corona treatment equipment, be 4500V/m in high-frequency ac voltage2, at corona
Managing speed is sided corona treatment 35min under conditions of 17m/min, and thermo oxidative aging high-strength thermoplastic plastics are made.
Example 3
Graphite is put into grinder and is ground, 150 meshes is crossed and obtains sieving, the sulfuric acid for being 90% by sieving and mass fraction
Obtained mixed dispersion liquid is stirred evenly in solution 1:20 in mass ratio investment beaker, is placed the beaker in ice-water bath, into beaker
The potassium ferrate solution that the mass fraction of mixed dispersion liquid quality 5% is 14% is added dropwise, after constant temperature stands 40min, increases water-bath temperature
For degree to 40 DEG C, constant temperature stands 6h, and filter cake is obtained by filtration, and obtains oxidation product filter cake 5 times wash with distilled water, spare；By metatitanic acid
Four butyl esters and ethylene glycol 1:10 in mass ratio investment are full of in the glove box of nitrogen, are 330r/min and temperature in magnetic agitation rotating speed
Under conditions of degree is 15 DEG C, it is stirred reaction 8h and mixing suspension is made, under stirring, mixing is added into glove box
The acetone of the quality such as suspension persistently stirs 14h, filters after stirring, successively with dehydrated alcohol and distillation water washing 5 times, is put into
In baking oven, reaction solid powder is made in dry 6h under conditions of temperature is 140 DEG C；According to parts by weight, weigh 5 parts it is spare
Oxidation product, 4 parts of above-mentioned reaction solid powders, in 15 parts of isopropanols and 10 parts of dehydrated alcohols investment high speed dispersion instrument, with
Solidliquid mixture is made in the revolving speed high speed dispersion 50min of 1700r/min；By above-mentioned solidliquid mixture and Citric acid crystal powder
20:1 in mass ratio is put into three-necked flask, and three-necked flask is placed in sonic oscillation instrument, with the hunting of frequency 5h of 42kHz, vibration
Modified filter residue is obtained by filtration after swinging, modified mixture is made by drying in modified filter residue investment baking oven with 120 DEG C of temperature；By weight
Number meter is measured, 8 parts of above-mentioned modified mixtures, 18 parts of polyethylene, 14 parts of polypropylene, 1.8 parts of calcium carbonate powders and 1.5 parts of mistakes are weighed
Benzoyl Oxide is put into vented single -screw extruder, is 350 DEG C in extrusion temperature, under conditions of screw speed 50r/min
It squeezes out and pre product is made, pre product is put into corona treatment equipment, be 5000V/m in high-frequency ac voltage2, at corona
Managing speed is sided corona treatment 40min under conditions of 20m/min, and thermo oxidative aging high-strength thermoplastic plastics are made.
Comparative example
With the thermo oxidative aging high-strength thermoplastic plastics of Beijing company production as a comparison case to heat resistanceheat resistant produced by the present invention
Thermo oxidative aging high-strength thermoplastic plastics in oxygen aging high-strength thermoplastic plastics and comparative example carry out performance detection, detection
The results are shown in Table 1:
Test method:
Elasticity modulus and tensile strength test carry out on Zwick/Roell Z020 instrument, and test method is carried out by GB16421.
Shore hardness test is detected using Shore durometer.
Surface abrasion resistance test is detected by GB/T24508-2009 standard.
Resistance to ag(e)ing test: the plastics in example 1~3 and comparative example are placed in ozone box after 2000h,
Measure fracture load by bending retention rate.
1 thermoplastic performance measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example |
| Elasticity modulus (MPa) | 3835 | 3840 | 3850 | 2500 |
| Tensile strength (MPa) | 67 | 67 | 68 | 40 |
| Shore hardness (A) | 81 | 82 | 83 | 50 |
| Surface abrasion resistance (g/100r) | 0.08 | 0.08 | 0.07 | 0.15 |
| Fracture load by bending retention rate (%) after aging 2000h | 105 | 105 | 106 | 80 |
Good according to the thermo oxidative aging high-strength thermoplastic plastic wear-resisting produced by the present invention of data among the above, hardness is high,
Shore hardness is high, and resistance to heat aging is good, and fracture load by bending retention rate is high after aging 2000h, has broad application prospects.
Claims (6)
1. a kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics, it is characterised in that specific preparation step are as follows:
(1) graphite is put into grinder and is ground, crossed 150 meshes and obtain sieving, in mass ratio with sulfuric acid solution by sieving
Obtained mixed dispersion liquid is stirred evenly in 1:20 investment beaker, is placed the beaker in ice-water bath, mixing dispersion is added dropwise into beaker
The potassium ferrate solution of liquid quality 3~5% after constant temperature stands 30~40min, increases bath temperature, and constant temperature stands, is obtained by filtration
Filter cake obtains oxidation product filter cake 3~5 times wash with distilled water, spare；
(2) by butyl titanate and ethylene glycol 1:10 in mass ratio investment full of nitrogen glove box in be stirred reaction 6~
Mixing suspension is made in 8h, under stirring, the acetone of the quality such as mixing suspension is added into glove box, persistently stirs 12
~14h is filtered after stirring, successively with dehydrated alcohol and distillation water washing 3~5 times, is placed in oven and dried, reaction solid is made
Powder；
(3) according to parts by weight, 3~5 parts of spare oxidation products, 2~4 parts of above-mentioned reaction solid powders, 12~15 parts are weighed
Disperse in isopropanol and 8~10 parts of dehydrated alcohol investment high speed dispersion instrument, solidliquid mixture is made；
(4) above-mentioned solidliquid mixture and Citric acid crystal powder 20:1 in mass ratio are put into three-necked flask, by three-necked flask
It is placed in sonic oscillation instrument and vibrates, modified filter residue is obtained by filtration after oscillation, drying in modified filter residue investment baking oven is made and is modified
Mixture；
(5) according to parts by weight, weigh 6~8 parts of above-mentioned modified mixtures, 15~18 parts of polyethylene, 12~14 parts of polypropylene,
In 1.5~1.8 parts of calcium carbonate powders and 1.0~1.5 parts of benzoyl peroxide investment vented single -screw extruders, squeezes out and be made
Pre product is put into sided corona treatment in corona treatment equipment by pre product, and thermo oxidative aging high-strength thermoplastic plastics are made.
2. a kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics according to claim 1, it is characterised in that:
The mass fraction of sulfuric acid solution as described in step (1) is 80~90%, and the mass fraction of liquor potassic permanganate is 10~14%, water
Bath temperature is increased to 35~40 DEG C, and constant temperature time of repose is 5~6h.
3. a kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics according to claim 1, it is characterised in that:
Magnetic agitation rotating speed described in step (2) is 300~330r/min, and temperature is 10~15 DEG C, and being stirred the reaction time is 6
Temperature in~8h baking oven is 130~140 DEG C, and drying time is 5~6h.
4. a kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics according to claim 1, it is characterised in that:
Revolving speed in high speed dispersion instrument described in step (3) is 1500~1700r/min, and jitter time is 40~50min.
5. a kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics according to claim 1, it is characterised in that:
Frequency in sonic oscillation instrument described in step (4) is 40~42kHz, and duration of oscillation is 3~5h, and the temperature in baking oven is
110~120 DEG C.
6. a kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics according to claim 1, it is characterised in that:
Extrusion temperature in vented single -screw extruder described in step (5) is 320~350 DEG C, and screw speed is 40~50r/
High-frequency ac voltage in min corona treatment equipment is 4000~5000V/m2, sided corona treatment speed is 15~20m/min, electricity
The dizzy processing time is 30~40min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810994664.2A CN109135017A (en) | 2018-08-29 | 2018-08-29 | A kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810994664.2A CN109135017A (en) | 2018-08-29 | 2018-08-29 | A kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109135017A true CN109135017A (en) | 2019-01-04 |
Family
ID=64828912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810994664.2A Pending CN109135017A (en) | 2018-08-29 | 2018-08-29 | A kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109135017A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016726A (en) * | 2019-04-23 | 2019-07-16 | 杭州墨舞神韵文化艺术集团有限公司 | A kind of preparation method of high-strength corrosion-resisting viscose fiber |
| CN112724513A (en) * | 2020-12-24 | 2021-04-30 | 青岛恒凯橡塑有限公司 | High-strength impact-resistant thermoplastic environment-friendly plastic and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245378A2 (en) * | 2001-03-28 | 2002-10-02 | Sealed Air Corporation (US) | Foam composite structure comprising a blend of polypropylene and homogeneous ethylene/alpha-olefin copolymer |
| CN104817673A (en) * | 2015-05-04 | 2015-08-05 | 芜湖市宝艺游乐科技设备有限公司 | A kind of heat-resistant graphene oxide melamine resin and preparation method thereof |
| CN108264687A (en) * | 2018-02-27 | 2018-07-10 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of tear-proof anti-aging modified master |
-
2018
- 2018-08-29 CN CN201810994664.2A patent/CN109135017A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245378A2 (en) * | 2001-03-28 | 2002-10-02 | Sealed Air Corporation (US) | Foam composite structure comprising a blend of polypropylene and homogeneous ethylene/alpha-olefin copolymer |
| CN104817673A (en) * | 2015-05-04 | 2015-08-05 | 芜湖市宝艺游乐科技设备有限公司 | A kind of heat-resistant graphene oxide melamine resin and preparation method thereof |
| CN108264687A (en) * | 2018-02-27 | 2018-07-10 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of tear-proof anti-aging modified master |
Non-Patent Citations (3)
| Title |
|---|
| PENG LI ET AL.: "An iron-based green approach to 1-h production of single-layer graphene oxide", 《NATURE COMMUNICATIONS》 * |
| 伍秋涛编著: "《软包装实用技术问答》", 30 November 2008, 印刷工业出版社 * |
| 化学工业出版社组织 编写: "《中国化工产品大全 下卷》", 31 January 2005, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016726A (en) * | 2019-04-23 | 2019-07-16 | 杭州墨舞神韵文化艺术集团有限公司 | A kind of preparation method of high-strength corrosion-resisting viscose fiber |
| CN112724513A (en) * | 2020-12-24 | 2021-04-30 | 青岛恒凯橡塑有限公司 | High-strength impact-resistant thermoplastic environment-friendly plastic and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105295106B (en) | A preparation method of cellulose-based 3D printing wire | |
| CN109135017A (en) | A kind of preparation method of thermo oxidative aging high-strength thermoplastic plastics | |
| WO2022246778A1 (en) | Preparation method for special nano-modified polyethylene material for resisting aging | |
| WO2018086159A1 (en) | High strength nano plastic and preparation method therefor | |
| CN110588035B (en) | Preparation method of fiber panel with waste textiles as raw materials | |
| CN117701023B (en) | High-strength wood-plastic composite material and preparation method thereof | |
| CN102838782A (en) | Celluloid substituted material for table tennis and manufacturing method | |
| CN107488891A (en) | A kind of new function graphite alkene composite fibre and preparation method and application | |
| CN110467803A (en) | A kind of extrusion reaction increase-volume bagasse base biodegradation composite material and preparation method | |
| CN103333512B (en) | Cortex Salicis Cheilophilae/Polyethylene wood plastic composite material and preparation method thereof | |
| CN107722452A (en) | A kind of anti-static polyolefin composite and preparation method thereof | |
| CN107200868A (en) | A kind of mica compounded mix, preparation method and applications | |
| CN106751142B (en) | A method of preparing the high filling polyvinyl chloride composite material of electrolytic manganese waste residue using electrolytic manganese waste residue and polyvinyl chloride | |
| CN106433044A (en) | Modified bagasse strengthening PBAT/starch complete biodegradation composite material and preparing method and application thereof | |
| CN101851338B (en) | Thermoplastic vegetable protein and preparation method thereof | |
| CN109401253A (en) | A kind of biodegradable toughening composite material and preparation method | |
| CN109401136A (en) | A kind of PVC sheet produced using waste PVC | |
| CN106745245B (en) | A kind of preparation method of sodium pyroantimonate and sodium metaantimonate | |
| CN106893268A (en) | Modified terephtha-late composite of a kind of ramee and preparation method thereof | |
| CN104942932B (en) | Method for constructing calcium carbonate super-hydrophobic structure on surface of bamboo wood | |
| CN106905635A (en) | A kind of modified plastics | |
| CN105802068A (en) | PVC (polyvinyl chloride) nano-plastics and preparation method thereof | |
| CN112724513A (en) | High-strength impact-resistant thermoplastic environment-friendly plastic and preparation method thereof | |
| CN105133064B (en) | A kind of preparation method of PTFE chopped fibers | |
| CN106977871B (en) | Microwave-treated bamboo charcoal modified polyolefin composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190104 |