CN108467560A - Aobvious shell of high-strength V R and preparation method thereof - Google Patents
Aobvious shell of high-strength V R and preparation method thereof Download PDFInfo
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- CN108467560A CN108467560A CN201810355392.1A CN201810355392A CN108467560A CN 108467560 A CN108467560 A CN 108467560A CN 201810355392 A CN201810355392 A CN 201810355392A CN 108467560 A CN108467560 A CN 108467560A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of aobvious shells of high-strength V R and preparation method thereof, and the preparation method includes：Silicon powder and ammonium polyphosphate solution are mixed, reacted 12 hours at 70 80 DEG C, modified silicon powder is obtained after filtering；Modified silicon powder, acrylic resin, haloflex, diatomite, phenolic resin, zinc stearate, filler, lubricant and plasticizer are mixed, mixture M is obtained；Mixture M is added twin-screw extrude, the aobvious shell of high-strength V R is obtained after extruded, molding；Solve the problems, such as that the aobvious shell of existing high-strength V R is difficult to ensure superior mechanical property and flame retardant property simultaneously.
Description
Technical field
The present invention relates to VR manufacturing field of equipment, and in particular, to a kind of aobvious shell of high-strength V R and preparation method thereof.
Background technology
Since the harmfulness of fire is very big, therefore fire-retardant problem is paid attention to by people already, and the application of plastic products has been popularized
Arrived the every field of national economy, such as appliance cord, construction material, aerospace parts be required to it is fire-retardant.Universal raising modeling
Expect that the method for anti-flammability is that fire retardant is added in plastic raw materials, contain halogen in the fire retardant of plurality, when burning releases
Hydrogen halide is toxic to human body and has strong smothering action, moreover, most fire retardants is often accompanied by dense smoke in burning,
Hinder visibility when rescue.Later people, which notice, develops less toxic side effect, the fire retardant new varieties of low cigarette, but these
The shortcomings of addition of fire retardant, which is also difficult to overcome, makes plastics heat resistance and mechanical properties decrease, and craftsmanship is deteriorated.
Therefore it provides it is a kind of under the premise of guarantee plastics excellent mechanical property, effectively improve the high-strength of plastic material flame retardant
Spend the problem of VR aobvious shell and preparation method thereof is urgent need to resolve of the present invention.
Invention content
The object of the present invention is to provide a kind of aobvious shells of high-strength V R and preparation method thereof, solve existing VR and show
Shell is difficult the problem of ensureing superior mechanical property and flame retardant property simultaneously.
To achieve the goals above, the present invention provides a kind of preparation method of the aobvious shell of high-strength V R, the preparations
Method includes：
(1) silicon powder and ammonium polyphosphate solution are mixed, is reacted 1-2 hours at 70-80 DEG C, modified silicon is obtained after filtering
Micro mist；
It (2) will modified silicon powder, acrylic resin, haloflex, diatomite, phenolic resin, zinc stearate, filling
Agent, lubricant and plasticizer mixing, obtain mixture M；
(3) mixture M is added twin-screw extrude, the aobvious shell of high-strength V R is obtained after extruded, molding；Its
In, the condition of extrusion includes：The rotating speed of screw rod is 200-300 revs/min, and the temperature of feeding section is 200-210 DEG C, fusion plastification
The temperature of section is 240-250 DEG C, and the temperature for mixing homogenizing zone is 210-220 DEG C, and the temperature of melt conveying metering section is 180-200
℃。
The present invention also provides a kind of aobvious shells of high-strength V R, and the aobvious shell of high-strength V R is by above-mentioned preparation side
Method is made.
Through the above technical solutions, the present invention provides a kind of aobvious shell of high-strength V R and preparation method thereof, the system
Preparation Method includes：Silicon powder and ammonium polyphosphate solution are mixed, is reacted 1-2 hours at 70-80 DEG C, modified silicon is obtained after filtering
Micro mist；It will modified silicon powder, acrylic resin, haloflex, diatomite, phenolic resin, zinc stearate, filler, lubrication
Agent and plasticizer mixing, obtain mixture M；Mixture M is added twin-screw extrude, is obtained after extruded, molding high-strength
Spend VR aobvious shell；Pass through the synergistic effect between each raw material so that flame retardant plastics obtained is provided simultaneously with excellent mechanicalness
Can and flame retardant property, meanwhile, the method that is used to prepare the flame retardant plastics is simple, raw material is easy to get.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of the aobvious shell of high-strength V R, the preparation method includes：
(1) silicon powder and ammonium polyphosphate solution are mixed, is reacted 1-2 hours at 70-80 DEG C, modified silicon is obtained after filtering
Micro mist；
It (2) will modified silicon powder, acrylic resin, haloflex, diatomite, phenolic resin, zinc stearate, filling
Agent, lubricant and plasticizer mixing, obtain mixture M；
(3) mixture M is added twin-screw extrude, the aobvious shell of high-strength V R is obtained after extruded, molding；Its
In, the condition of extrusion includes：The rotating speed of screw rod is 200-300 revs/min, and the temperature of feeding section is 200-210 DEG C, fusion plastification
The temperature of section is 240-250 DEG C, and the temperature for mixing homogenizing zone is 210-220 DEG C, and the temperature of melt conveying metering section is 180-200
℃。
In a kind of preferred embodiment of the present invention, in order to further increase mechanical property and the resistance of plastics obtained
Performance is fired, relative to the acrylic resin of 100 parts by weight, the dosage of modified silicon powder is 2-8 parts by weight, the use of haloflex
Amount is 20-30 parts by weight, and diatomaceous dosage is 25-45 parts by weight, and the dosage of phenolic resin is 40-80 parts by weight, stearic acid
The dosage of zinc is 2-10 parts by weight, and the dosage of filler is 2-7 parts by weight, and the dosage of lubricant is 2-7 parts by weight, plasticizer
Dosage is 2-8 parts by weight.
In a kind of preferred embodiment of the present invention, in order to further increase mechanical property and the resistance of plastics obtained
Performance is fired, relative to the acrylic resin of 100 parts by weight, the dosage of modified silicon powder is 4-6 parts by weight, the use of haloflex
Amount is 24-26 parts by weight, and diatomaceous dosage is 30-40 parts by weight, and the dosage of phenolic resin is 50-70 parts by weight, stearic acid
The dosage of zinc is 4-6 parts by weight, and the dosage of filler is 4-5 parts by weight, and the dosage of lubricant is 4-5 parts by weight, plasticizer
Dosage is 4-6 parts by weight.
In a kind of preferred embodiment of the present invention, in order to further increase mechanical property and the resistance of plastics obtained
Performance is fired, in step (1), silicon powder and ammonium polyphosphate solution are 1 according to mass ratio：20-30 ratios are mixed.
In a kind of preferred embodiment of the present invention, in order to further increase mechanical property and the resistance of plastics obtained
Performance is fired, the mass concentration of ammonium polyphosphate solution is 40-60%.
In a kind of preferred embodiment of the present invention, in order to further increase mechanical property and the resistance of plastics obtained
Performance is fired, filler is one or more in calcium carbonate, clay, silicate and silicon powder.
In a kind of preferred embodiment of the present invention, in order to further increase mechanical property and the resistance of plastics obtained
Performance is fired, lubricant is one or more in stearic acid, stearate, polyethylene wax, paraffin and oleamide.
In a kind of preferred embodiment of the present invention, in order to further increase mechanical property and the resistance of plastics obtained
Performance is fired, plasticizer is selected from phthalate compound, terephthalic acid ester compound and trimellitic acid esters chemical combination
It is one or more in object.
In a kind of preferred embodiment of the present invention, in order to further increase mechanical property and the resistance of plastics obtained
Fire performance, the weight average molecular weight of haloflex is 5000-8000, and the weight average molecular weight of phenolic resin is 9000-12000, third
The weight average molecular weight of olefin(e) acid resin is 5000-6000.
The present invention also provides a kind of aobvious shells of high-strength V R, and the aobvious shell of high-strength V R is by above-mentioned preparation side
Method is made.
The present invention will be described in detail by way of examples below.In following embodiment, haloflex is divided equally again
Son amount is 5000-8000, and the weight average molecular weight of phenolic resin is 9000-12000, and the weight average molecular weight of acrylic resin is
5000-6000；The commercially available product that organic silicon fibre retardant is KR-2710 by the trade mark that Shanghai Guang Bin trade Co., Ltds provide.Below
Tensile strength parameter is measured by the method for GB1040-2006, and elongation at break parameter is the method by GB1040-2006
It measures, flame retardant property passes through GB/T2406.2-2009《Plastics measure burning behavior with oxygen index method》Method measure.
Embodiment 1
It (is 1 according to mass ratio that 10g silicon powders and ammonium polyphosphate solution, which are mixed,：20 ratios are mixed, wherein poly- phosphorus
The mass concentration of acid ammonium solution is 40%), to be reacted 1 hour at 70 DEG C, and modified silicon powder is obtained after filtering；4g modified silicons is micro-
Powder, 100g acrylic resins, 24g haloflexes, 30g diatomite, 50g phenolic resin, 4g zinc stearates, 4g calcium carbonate, 4g
Stearic acid and the mixing of 4g phthalate compounds, obtain mixture M；Mixture M is added twin-screw extrude, is passed through
It squeezes out, obtained after molding (being molded by the way of hot-forming, and the temperature of hot pressing is 40 DEG C, the pressure of hot pressing is 30MPa)
The aobvious shell A1 of high-strength V R；Wherein, the condition of extrusion includes：The rotating speed of screw rod is 200 revs/min, and the temperature of feeding section is
200 DEG C, the temperature of fusion plastification section is 240 DEG C, and the temperature for mixing homogenizing zone is 210 DEG C, and the temperature of melt conveying metering section is
180℃.The tensile strength of the aobvious shell A1 of high-strength V R is 16.2Mpa, elongation at break 249%, oxygen index (OI) 56.
Embodiment 2
It (is 1 according to mass ratio that 10g silicon powders and ammonium polyphosphate solution, which are mixed,：30 ratios are mixed, wherein poly- phosphorus
The mass concentration of acid ammonium solution is 60%), to be reacted 2 hours at 80 DEG C, and modified silicon powder is obtained after filtering；6g modified silicons is micro-
Powder, 100g acrylic resins, 26g haloflexes, 40g diatomite, 70g phenolic resin, 6g zinc stearates, 5g silicate (silicon
Sour sodium), 5g polyethylene waxes and 6g terephthalic acid ester compounds mixing, obtain mixture M；Twin-screw is added in mixture M
In extruder, extruded, molding (is molded by the way of hot-forming, and the temperature of hot pressing is 40 DEG C, the pressure of hot pressing is
The aobvious shell A2 of high-strength V R is obtained after 30MPa)；Wherein, the condition of extrusion includes：The rotating speed of screw rod is 300 revs/min, is added
Expect that the temperature of section is 210 DEG C, the temperature of fusion plastification section is 250 DEG C, and the temperature for mixing homogenizing zone is 220 DEG C, melt conveying meter
The temperature for measuring section is 200 DEG C.The tensile strength of the aobvious shell A2 of high-strength V R is 16.1Mpa, elongation at break 241%, oxygen
Index is 57.
Embodiment 3
It (is 1 according to mass ratio that 10g silicon powders and ammonium polyphosphate solution, which are mixed,：25 ratios are mixed, wherein poly- phosphorus
The mass concentration of acid ammonium solution is 50%), to be reacted 1.5 hours at 75 DEG C, and modified silicon powder is obtained after filtering；By 5g modified silicons
Micro mist, 100g acrylic resins, 25g haloflexes, 35g diatomite, 60g phenolic resin, 5g zinc stearates, 4.5g silicon are micro-
Powder, 4.5g oleamides and the mixing of 5g trimellitic acid esters compounds, obtain mixture M；Twin-screw extrusion is added in mixture M
In machine, extruded, molding (is molded by the way of hot-forming, and the temperature of hot pressing is 40 DEG C, the pressure of hot pressing is 30MPa)
After obtain the aobvious shell A3 of high-strength V R；Wherein, the condition of extrusion includes：The rotating speed of screw rod is 250 revs/min, feeding section
Temperature is 205 DEG C, and the temperature of fusion plastification section is 245 DEG C, and the temperature for mixing homogenizing zone is 215 DEG C, melt conveying metering section
Temperature is 190 DEG C.The tensile strength of the aobvious shell A3 of high-strength V R is 16.7Mpa, and elongation at break 244%, oxygen index (OI) is
59。
Embodiment 4
It is prepared according to the method for embodiment 3, unlike, relative to the acrylic resin of 100g, modified silicon powder
Dosage be 2g, the dosage of haloflex is 20g, and diatomaceous dosage is 25g, and the dosage of phenolic resin is 40g, stearic acid
The dosage of zinc is 2g, and the dosage of filler is 2g, and the dosage of lubricant is 2g, and the dosage of plasticizer is 2g, obtains high-strength V R
Aobvious shell A4.The tensile strength of the aobvious shell A4 of high-strength V R is 17.5Mpa, and elongation at break 242%, oxygen index (OI) is
51。
Embodiment 5
It is prepared according to the method for embodiment 3, unlike, relative to the acrylic resin of 100g, modified silicon powder
Dosage be 8g, the dosage of haloflex is 30g, and diatomaceous dosage is 45g, and the dosage of phenolic resin is 80g, stearic acid
The dosage of zinc is 10g, and the dosage of filler is 7g, and the dosage of lubricant is 7g, and the dosage of plasticizer is 8g, obtains high-strength V R
Aobvious shell A5.The tensile strength of the aobvious shell A5 of high-strength V R is 17.5Mpa, and elongation at break 229%, oxygen index (OI) is
54。
Embodiment 6
It is prepared according to the method for embodiment 3, unlike, relative to the acrylic resin of 100g, modified silicon powder
Dosage be 1g, the dosage of haloflex is 15g, and diatomaceous dosage is 20g, and the dosage of phenolic resin is 35g, stearic acid
The dosage of zinc is 1g, and the dosage of filler is 1g, and the dosage of lubricant is 1g, and the dosage of plasticizer is 1g, obtains high-strength V R
Aobvious shell A6.The tensile strength of the aobvious shell A6 of high-strength V R is 17.6Mpa, and elongation at break 242%, oxygen index (OI) is
51。
Embodiment 7
It is prepared according to the method for embodiment 3, unlike, relative to the acrylic resin of 100g, modified silicon powder
Dosage be 10g, the dosage of haloflex is 35g, and diatomaceous dosage is 50g, and the dosage of phenolic resin is 85g, stearic
The dosage of sour zinc is 15g, and the dosage of filler is 10g, and the dosage of lubricant is 10g, and the dosage of plasticizer is 10g, obtains height
The aobvious shell A7 of intensity VR.The tensile strength of the aobvious shell A7 of high-strength V R is 17.5Mpa, and elongation at break 243%, oxygen refers to
Number is 58.
Comparative example 1
It is prepared according to the method for embodiment 3, unlike, the condition of expressing technique includes：The rotating speed of screw rod is 150
Rev/min, the temperature of feeding section is 180 DEG C, and the temperature of fusion plastification section is 220 DEG C, and the temperature for mixing homogenizing zone is 180 DEG C,
The temperature of melt conveying metering section is 150 DEG C, obtains the aobvious shell D1 of high-strength V R.The stretching of the aobvious shell D1 of high-strength V R is strong
Degree is 11.1Mpa, elongation at break 142%, oxygen index (OI) 31.
Comparative example 2
It is prepared according to the method for embodiment 3, unlike, the condition of expressing technique includes：The rotating speed of screw rod is 350
Rev/min, the temperature of feeding section is 240 DEG C, and the temperature of fusion plastification section is 260 DEG C, and the temperature for mixing homogenizing zone is 240 DEG C,
The temperature of melt conveying metering section is 220 DEG C, obtains the aobvious shell D2 of high-strength V R.The stretching of the aobvious shell D2 of high-strength V R is strong
Degree is 12.1Mpa, elongation at break 138%, oxygen index (OI) 29.
Comparative example 3
It is prepared according to the method for embodiment 3, unlike, do not include haloflex in raw material, obtains high intensity
VR aobvious shell D3.The tensile strength of the aobvious shell D3 of high-strength V R is 11.4Mpa, and elongation at break 121%, oxygen index (OI) is
24。
Comparative example 4
It is prepared according to the method for embodiment 3, unlike, do not include diatomite in raw material, obtains high-strength V R heads
Aobvious shell D4.The tensile strength of the aobvious shell D4 of high-strength V R is 13.1Mpa, elongation at break 158%, oxygen index (OI) 32.
Comparative example 5
It is prepared according to the method for embodiment 3, unlike, do not include phenolic resin in raw material, obtains high-strength V R
Aobvious shell D5.The tensile strength of the aobvious shell D5 of high-strength V R is 12.3Mpa, and elongation at break 138%, oxygen index (OI) is
24。
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of the aobvious shell of high-strength V R, which is characterized in that the preparation method includes：
(1) silicon powder and ammonium polyphosphate solution are mixed, is reacted 1-2 hours at 70-80 DEG C, it is micro- that modified silicon is obtained after filtering
Powder；
It (2) will modified silicon powder, acrylic resin, haloflex, diatomite, phenolic resin, zinc stearate, filler, profit
Lubrication prescription and plasticizer mixing, obtain mixture M；
(3) mixture M is added twin-screw extrude, the aobvious shell of high-strength V R is obtained after extruded, molding；Wherein, it squeezes
The condition gone out includes：The rotating speed of screw rod is 200-300 revs/min, and the temperature of feeding section is 200-210 DEG C, fusion plastification section
Temperature is 240-250 DEG C, and the temperature for mixing homogenizing zone is 210-220 DEG C, and the temperature of melt conveying metering section is 180-200 DEG C.
2. preparation method according to claim 1, wherein relative to the acrylic resin of 100 parts by weight, modified silicon powder
Dosage be 2-8 parts by weight, the dosage of haloflex is 20-30 parts by weight, and diatomaceous dosage is 25-45 parts by weight, phenol
The dosage of urea formaldehyde is 40-80 parts by weight, and the dosage of zinc stearate is 2-10 parts by weight, and the dosage of filler is 2-7 parts by weight,
The dosage of lubricant is 2-7 parts by weight, and the dosage of plasticizer is 2-8 parts by weight.
3. preparation method according to claim 2, wherein relative to the acrylic resin of 100 parts by weight, modified silicon powder
Dosage be 4-6 parts by weight, the dosage of haloflex is 24-26 parts by weight, and diatomaceous dosage is 30-40 parts by weight, phenol
The dosage of urea formaldehyde is 50-70 parts by weight, and the dosage of zinc stearate is 4-6 parts by weight, and the dosage of filler is 4-5 parts by weight,
The dosage of lubricant is 4-5 parts by weight, and the dosage of plasticizer is 4-6 parts by weight.
4. preparation method according to claim 2 or 3, wherein in step (1), silicon powder and ammonium polyphosphate solution are pressed
It is 1 according to mass ratio：20-30 ratios are mixed.
5. preparation method according to claim 4, wherein the mass concentration of ammonium polyphosphate solution is 40-60%.
6. preparation method according to claim 2 or 3, wherein it is micro- that filler is selected from calcium carbonate, clay, silicate and silicon
It is one or more in powder.
7. preparation method according to claim 2 or 3, wherein lubricant be selected from stearic acid, stearate, polyethylene wax,
It is one or more in paraffin and oleamide.
8. preparation method according to claim 2 or 3, wherein plasticizer is selected from phthalate compound, to benzene
It is one or more in diformic ester compound and trimellitic acid esters compound.
9. preparation method according to claim 2 or 3, wherein the weight average molecular weight of haloflex is 5000-8000,
The weight average molecular weight of phenolic resin is 9000-12000, and the weight average molecular weight of acrylic resin is 5000-6000.
10. a kind of aobvious shell of high-strength V R, which is characterized in that the aobvious shell of high-strength V R in claim 1-9 by appointing
Preparation method described in meaning one is made.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810355392.1A CN108467560A (en) | 2018-04-19 | 2018-04-19 | Aobvious shell of high-strength V R and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810355392.1A CN108467560A (en) | 2018-04-19 | 2018-04-19 | Aobvious shell of high-strength V R and preparation method thereof |
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| CN108467560A true CN108467560A (en) | 2018-08-31 |
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| CN201810355392.1A Withdrawn CN108467560A (en) | 2018-04-19 | 2018-04-19 | Aobvious shell of high-strength V R and preparation method thereof |
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2018
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Application publication date: 20180831 |