CN107090127A - A kind of RPP material with good microwave absorbing property - Google Patents
A kind of RPP material with good microwave absorbing property Download PDFInfo
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- CN107090127A CN107090127A CN201710429693.XA CN201710429693A CN107090127A CN 107090127 A CN107090127 A CN 107090127A CN 201710429693 A CN201710429693 A CN 201710429693A CN 107090127 A CN107090127 A CN 107090127A
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- Prior art keywords
- glass fibre
- microwave absorbing
- absorbing property
- glass
- polypropylene
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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
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
-
- 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
Abstract
The invention provides a kind of RPP material with good microwave absorbing property and preparation method thereof, comprising 60~87 parts of polypropylene；10~30 parts of the glass fibre of special surface processing；2~6 parts of polypropylene grafted maleic anhydride；1~3 part of nano ferriferrous oxide；0.1~0.5 part of heat stabilizer；0.1~0.5 part of lubricant；A kind of RPP material with good microwave absorbing property is prepared for using double screw extruder extrusion, the material shows more preferable microwave absorbing property, and intensity is high, pollution-free, and the preparation method of the present invention is simple, available for the military and anti-electromagnetic pollution field of building.
Description
Technical field
The present invention relates to polypropylene technology field, and in particular to a kind of RPP with good microwave absorbing property
Material and preparation method thereof.
Background technology
As electromagnetic wave is in the extensive use in telecommunications field, the electromagnetism that mobile phone, wireless network, radar etc. are brought
The problem of radiation, interference, is increasingly taken seriously；Meanwhile, electromagnetic wave technology is also widely used in present military field, such as
Radar Technology.Based on requirements above, the research and development of microwave absorbing material are particularly important.Glass fibre is the conventional enhancing of engineering plastics
Material, prepare electroconductive glass fibre turns into the important method for solving the problems, such as electromagnetic shielding as the conductive filler of composite,
It can reach the effect of Material reinforcement and electromagnetic shielding simultaneously.Traditional chemical plating be prepare electroconductive glass fibre common technology it
One, but its complex process, and heavy metal is expensive and causes severe contamination to environment, while effectiveness and paying no attention to
Think.
The content of the invention
It is an object of the invention to provide a kind of RPP material with good microwave absorbing property and its preparation side
Method.
A kind of RPP material with good microwave absorbing property, prepared by weight by following components and
Into：
60~87 parts of polypropylene；
10~30 parts of the glass fibre of special surface processing；
2~6 parts of polypropylene grafted maleic anhydride；
1~3 part of nano ferriferrous oxide；
0.1~0.5 part of heat stabilizer；
0.1~0.5 part of lubricant；
Described glass fibre is the chopped E glasses of alkali-free, and 6~9 μm of glass fiber single filament diameter, length are 3~6mm, compared with
Thin glass fiber single filament diameter is conducive to improving capability of electromagnetic shielding to being more beneficial for surface treatment；The special surface
The glass fibre of processing is mixture surface treatment obtained glass fibers of the fiber surface by SrBiTiO and rare earth compound
Dimension, SrBiTiO: rare earth compound mixture weight ratio is 5: 1~10: 1, and the rare earth compound is in lanthanum chloride, ytterbium chloride
One kind, SrBiTiO and rare earth compound, which are jointly processed by glass surface, has cooperative effect；At least contain 10 in the polypropylene
~30 parts of physical aspect is the polypropylene of powdery, and powdered granule helps to improve nano ferriferrous oxide due to magnetic
Caused aggregation, is conducive to it to disperse and add the ratio that concentration reaches formula design in RPP；The nanometer
The size of ferroso-ferric oxide powder is that the addition of ferroso-ferric oxide further improves capability of electromagnetic shielding no more than 300 nanometers.
The preparation method of the glass fibre special surface processing is as follows：
(1) soaking and washing in acetone soln is put into after first glass fibre is calcined 60~100 minutes at 200~300 DEG C
30~60 minutes；By the glass fibre after cleaning be put into 2mol/L~4mol/L hydrochloric acid solution carry out hydroxylating processing 30~
80 minutes, dried after then being washed through deionized water under the conditions of 40~70 DEG C.
(2) dimethylformamide, acetic acid and polyvinylpyrrolidone are passed through at room temperature according to the ratio of weight ratio 4: 1: 1
Mechanical agitation has configured mixed solution, and the mixture of SrBiTiO and rare earth compound is added to by 60~120rpm of mixing speed
The weight ratio of mixed solution, mixture and mixed solution is 1: 10, and aaerosol solution is configured to through mechanical agitation, mixing speed 60~
120rpm。
(3) glass fibre after being handled through (1) is added in the aaerosol solution handled through (2), glass fibre is with suspending
The mass ratio of both solution is 4: 1, adds glass fibre and 3~5 times of distilled water of aaerosol solution weight, mechanical agitation 10~15
Minute, 80~100rpm of mixing speed；Glass is filtered out, is then dried at 50~60 DEG C, you can special surface processing is made
Glass fibre.
The polyacrylic melt flow rate (MFR) is in pressure 2.16kg, 0.1~100g/min of condition of 230 DEG C of temperature.
The heat stabilizer be phenolic thermostabilizers, amine heat stabilizer, one kind in phosphite ester type thermal stabilizing agent or
It is a variety of.
The lubricant is one kind in metal soap lubricant, stearic acid compound ester lubricant and acid amides series lubricant agent
Or it is a variety of.
The maleic anhydride content 1%~50% of described polypropylene grafted maleic anhydride.
A kind of preparation method of the RPP material with good microwave absorbing property, comprises the following steps：
(1), by proportioning, by polypropylene, polypropylene grafted maleic anhydride, heat stabilizer, lubricant, nano ferriferrous oxide
Put into height and stir pot stirring 3~5 minutes, mixing speed 500rpm.
(2), the mixed material that will be stirred through (1) is fed by the main feeding of double screw extruder, special surface processing
Glass fibre by lateral feeding add double screw extruder in, in double screw extruder carry out melt blending, extrusion make
The obtained RPP material of grain；The draw ratio of the screw extruder is 40: 1~48: 1, and processing temperature is 170~250 DEG C,
400~600rpm of screw speed, negative-pressure vacuum 0.04~0.06MPa of degree, enhancing poly- third is prepared by water cooling bracing pelletizing
Alkene.
Although being due to that nano ferriferrous oxide is easily rolled into a ball in extrusion present invention employs powdered polypropylene
It is poly-, and because ferroso-ferric oxide has ferromagnetism in itself, easily absorption is in equipment in process, and is not easy to disperse, root
The RPP mechanical property of materials prepared according to such scheme is low, especially poor toughness, and the RPP material prepared
The content of middle ferroso-ferric oxide is less than formula setting value, invention further provides prioritization scheme, by following components by weight
Number is prepared from：
60~87 parts of polypropylene；
10~30 parts of the glass fibre of special surface processing；
2~6 parts of polypropylene grafted maleic anhydride；
It is dissolved in 1.5~4.5 parts of iron chloride mixture in organic acid；
0.1~0.5 part of heat stabilizer；
0.1~0.5 part of lubricant；
The preparation method of the RPP material of further prioritization scheme, comprises the following steps：
(1), first by iron chloride FeCL3Mixed with organic acid according to 1.5: 1 ratios in agitated kettle, organic acid is lemon
One kind in acid, tartaric acid, citric acid, tartaric acid, glutamic acid, stearic acid, palmitic acid, mixing speed is 120~200rpm, stirring
5~8 minutes time, the iron chloride mixture being dissolved in organic acid is made.
(2), by proportioning, by polypropylene, polypropylene grafted maleic anhydride, heat stabilizer, lubricant, through (1) handle it is molten
Iron chloride mixture of the solution in organic acid is put into stir in pot and stirred 2~3 minutes, and 250~300rpm of mixing speed takes more
Low mixing speed be for prevent high-speed stirred easily cause overheat cause organic acid melting volatilization, cause material to lump.
(3) mixed material that will be stirred through (2) is fed by the main feeding of double screw extruder, special surface processing
Glass fibre is added in double screw extruder by lateral feeding, carries out melt blending, extruding pelletization and RPP material is made
Material；The draw ratio of the screw extruder is 48: 1~60: 1,160~230 DEG C of processing temperature, 300~500rpm of screw speed, more
Low screw speed helps to elongate residence time of the material in twin-screw, negative-pressure vacuum degree 0.06~0.1MPa, higher
Vacuum, contributes to the abundant devolatilization of organic acid low molecule in material, favorably improves the final mechanical property of materials, and extrusion passes through water
Cold drawn bar pelletizing prepares RPP.
Prioritization scheme is FeCL3For presoma, organic acid is dispersant, is directly scattered in polypropylene, then by squeezing
Go out machine original position thermal decomposition FeCL3, nanoscale Fe 3 O 4 magnetic particle is formed under dispersant effect, while prepared by control
The technological parameters such as mixing time, mixing speed, extrusion temperature, screw speed, the vacuum of journey, so that the increasing finally prepared
Strong polypropylene mechanical performance is improved, and especially toughness is greatly improved.
Embodiment
The formula of comparative example 1~2 and embodiment 1~4 is shown in Table 1
The formula of the comparative example 1~2 of table 1 and embodiment 1~4
Heat stabilizer selects 1010 and 168, and the two ratio is 1: 1 (weight ratio), and lubricant selects ethylene bis stearamide.
A diameter of 13 μm of the glass fiber single filament that comparative example 1 is used, remaining formula filament diameter is 8 μm.Embodiment 3 is to glass fibers dimension table
Face processing is ytterbium chloride using rare earth compound, and remaining uses lanthanum chloride.The screw rod for the double screw extruder that embodiment 4 is used is long
Footpath is than 52: 1, the screw slenderness ratio 44: 1 for the double screw extruder that remaining embodiment and comparative example are used.The screw rod of embodiment 4 turns
Speed is 500rpm, the screw speed 300rpm of embodiment 2.
Fiberglass surfacing process step in comparative example 1~2 and embodiment 1~4 is as follows：
(1) 50 points of soaking and washing in acetone soln are put into after first glass fibre is calcined 90 minutes at 200~300 DEG C
Clock；Glass fibre after cleaning is put into 3mol/L hydrochloric acid solution and carries out hydroxylating processing 50 minutes, then through deionization
Dried after water washing under the conditions of 50 DEG C；
(2) dimethylformamide, acetic acid and polyvinylpyrrolidone are passed through at room temperature according to the ratio of weight ratio 4: 1: 1
Mechanical agitation has configured mixed solution, and SrBiTiO and rare earth compound mixture are added to mixing by mixing speed 100rpm
The weight ratio of solution, mixture and mixed solution is 1: 10, and aaerosol solution, mixing speed 100rpm are configured to through mechanical agitation；
(3) glass fibre after being handled through (1) is added in the aaerosol solution handled through (2), glass fibre is with suspending
The mass ratio of both solution is 4: 1, adds glass fibre and 3 times of distilled water of aaerosol solution weight, and mechanical agitation 12 minutes is stirred
Mix speed 90rpm；Glass is filtered out, is then dried at 55 DEG C, you can the glass fibre of special surface processing is made.
The preparation method of the RPP material of comparative example 1~2 and implementation 1 and embodiment 3, comprises the following steps：
(1), by proportioning, by polypropylene, polypropylene grafted maleic anhydride, heat stabilizer, lubricant, nano ferriferrous oxide
(the no added nano ferriferrous oxide of comparative example 2) puts into height and stirs pot stirring 4 minutes, mixing speed 500rpm.
(2), the mixed material that will be stirred through (1) is fed by the main feeding of double screw extruder, special surface processing
Glass fibre by lateral feeding add double screw extruder in, in double screw extruder carry out melt blending, extrusion make
The obtained RPP material of grain；The draw ratio of the screw extruder is 44: 1, and processing temperature is 170~250 DEG C, and screw rod turns
Fast 500rpm, negative-pressure vacuum 0.04~0.06MPa of degree, RPP is prepared by water cooling bracing pelletizing.
The preparation method for implementing the RPP material of 2 and embodiment 4 comprises the following steps：
(1), first by iron chloride FeCL3Mixed with stearic acid according to 1.5: 1 ratios in agitated kettle, mixing speed is
The iron chloride mixture being dissolved in organic acid is made in 180rpm, mixing time 6 minutes.
(2), by proportioning, by polypropylene, polypropylene grafted maleic anhydride, heat stabilizer, lubricant, through (1) handle it is molten
Iron chloride mixture of the solution in organic acid is put into stir in pot and stirred 3 minutes, mixing speed 280rpm.
(3), the mixed material that will be stirred through (2) is fed by the main feeding of double screw extruder, special surface processing
Glass fibre by lateral feeding add double screw extruder in, carry out melt blending, extruding pelletization be made RPP
Material；The draw ratio of the double screw extruder of embodiment 2 is 44: 1, and the draw ratio of the double screw extruder of embodiment 4 is 52: 1,
160~230 DEG C of processing temperature, the screw speed 300rpm of embodiment 2, the screw speed 500rpm of embodiment 4, negative-pressure vacuum degree 0.06
~0.1MPa, extrusion prepares RPP by water cooling bracing pelletizing.
By the polypropylene material prepared by above-described embodiment 1~4 and comparative example 1~2 according to use coaxial line transmission/reflection
The electromagnetic parameter of method measurement gained fibrous material, is made external diameter 7.00mm, internal diameter 3.04mm, thickness about 2mm ring-shaped sample, in U.S.
Their complex dielectric permittivities in 2~18GHz frequency ranges are measured on state's Agilent E5071C type vector network analyzers and multiple
Magnetic conductivity, the microwave absorbing property for calculating and analyzing corresponding individual layer and double-decker microwave absorbing coating is simulated according to transmission line theory.
The mechanical performance of material is tested according to national standard.
The performance test results of comparative example 1~2 and embodiment 1~4 are shown in Table 2
The performance of the comparative example 1~2 of table 2 and embodiment 1~4
Comparative example 1 and embodiment 1, which compare, to be shown, the electro-magnetic wave absorption performance of thinner filament diameter is more preferable.Comparative example 2 and reality
Apply example 1 and compare the addition for showing nano ferriferrous oxide, can further improve the electro-magnetic wave absorption performance of RPP.Implement
Example 3 and the contrast of embodiment 1 show that ytterbium chloride is more beneficial for improving the electro-magnetic wave absorption performance of material than lanthanum chloride.The He of embodiment 4
The contrast of embodiment 2 shows that lower screw speed, shorter screw slenderness ratio are more beneficial for improving the electromagnetic wave absorbability of material
Energy.
The mechanical performance testing result of embodiment 1~2 is shown in Table 3
The mechanical performance of the embodiment 1~2 of table 3
Embodiment 1 and the contrast of embodiment 2 show, direct addition is substituted using the iron chloride mixture being dissolved in organic acid
Nano ferriferrous oxide prepares RPP, and its mechanical performance is greatly improved, and especially toughness is obviously improved, simultaneously
The electro-magnetic wave absorption performance of material slightly improves.
It can be seen that from table 2 and table 3, the wave-sucking performance of polypropylene material produced by the present invention and to microwave absorption frequency range
Width, makes modified polypropylene material show more preferable microwave absorbing property, and intensity is high, pollution-free, available for military and
Anti- electromagnetic pollution field is built, and the preparation method of the present invention is simple.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to implementation here
Example, those skilled in the art do not depart from improvement that scope made and change all should be according to the announcement of the present invention
Within protection scope of the present invention.
Claims (7)
1. a kind of RPP material with good microwave absorbing property, it is characterised in that：By following components by weight
Number is prepared from：
60~87 parts of polypropylene；
10~30 parts of the glass fibre of special surface processing；
2~6 parts of polypropylene grafted maleic anhydride；
1~3 part of nano ferriferrous oxide；
0.1~0.5 part of heat stabilizer；
0.1~0.5 part of lubricant；
Described glass fibre is the chopped E glasses of alkali-free, and 6~9 μm of glass fiber single filament diameter, length are 3~6mm；The spy
The glass fibre being very surface-treated is mixture surface treatment obtained glass of the fiber surface by SrBiTiO and rare earth compound
Glass fiber, SrBiTiO: rare earth compound mixture weight ratio is 5: 1~10: 1, the rare earth compound is lanthanum chloride, chlorination
One kind in ytterbium；At least containing the polypropylene that 10~30 parts of physical aspect is powdery in the polypropylene；The oxygen of nanometer four
The size for changing three iron powder bodies is no more than 300 nanometers.
2. a kind of RPP material with good microwave absorbing property according to claim 1, the glass fibers
The preparation method for tieing up special surface processing is as follows：
(1) be put into after first glass fibre is calcined 60~100 minutes at 200~300 DEG C soaking and washing 30 in acetone soln~
60 minutes；Glass fibre after cleaning is put into 2mol/L~4mol/L hydrochloric acid solution and carries out 30~80 points of hydroxylating processing
Clock, is dried after then being washed through deionized water under the conditions of 40~70 DEG C；
(2) by dimethylformamide, acetic acid and polyvinylpyrrolidone according to the ratio of weight ratio 4: 1: 1 at room temperature through machinery
Mixed solution is configured to be stirred, SrBiTiO and rare earth compound mixture are added to mixing by 60~120rpm of mixing speed
The weight ratio of solution, mixture and mixed solution is 1: 10, and aaerosol solution is configured to through mechanical agitation, mixing speed 60~
120rpm；
(3) glass fibre after being handled through (1) is added in the aaerosol solution handled through (2), glass fibre and aaerosol solution
Both mass ratioes are 4: 1, add glass fibre and 3~5 times of distilled water of aaerosol solution weight, 10~15 points of mechanical agitation
Clock, 80~100rpm of mixing speed；Glass is filtered out, is then dried at 50~60 DEG C, you can the glass of special surface processing is made
Glass fiber.
3. a kind of RPP material with good microwave absorbing property according to claim 1, it is characterised in that：
The polyacrylic melt flow rate (MFR) is 0.1~100g/min under conditions of pressure 2.16kg, 230 DEG C of temperature.
4. a kind of RPP material with good microwave absorbing property according to claim 1, it is characterised in that：
The heat stabilizer is the one or more in phenolic thermostabilizers, amine heat stabilizer, phosphite ester type thermal stabilizing agent.
5. a kind of RPP material with good microwave absorbing property according to claim 1, it is characterised in that：
The lubricant is the one or more in metal soap lubricant, stearic acid compound ester lubricant and acid amides series lubricant agent.
6. a kind of RPP material with good microwave absorbing property according to claim 1, it is characterised in that：
The maleic anhydride content 1%~50% of described polypropylene grafted maleic anhydride.
7. a kind of RPP material with good microwave absorbing property according to claim 1, it is characterised in that：
Described nano ferriferrous oxide is replaced using the iron chloride mixture being dissolved in organic acid.
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| CN201710429693.XA CN107090127B (en) | 2017-05-11 | 2017-05-11 | A kind of reinforced polypropylene material with good microwave absorbing property |
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| CN201710429693.XA CN107090127B (en) | 2017-05-11 | 2017-05-11 | A kind of reinforced polypropylene material with good microwave absorbing property |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446234A (en) * | 2017-05-11 | 2017-12-08 | 温州市赢创新材料技术有限公司 | A kind of preparation method of RPP material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004059832A (en) * | 2002-07-31 | 2004-02-26 | Hitachi Cable Ltd | Electromagnetic wave absorbing material composition and electromagnetic wave absorber |
| CN101378854A (en) * | 2006-02-10 | 2009-03-04 | 萨斯堤那普尔科技股份有限公司 | Method for protecting base |
| CN106479038A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of RPP material of high electro-magnetic wave absorption performance and preparation method thereof |
-
2017
- 2017-05-11 CN CN201710429693.XA patent/CN107090127B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004059832A (en) * | 2002-07-31 | 2004-02-26 | Hitachi Cable Ltd | Electromagnetic wave absorbing material composition and electromagnetic wave absorber |
| CN101378854A (en) * | 2006-02-10 | 2009-03-04 | 萨斯堤那普尔科技股份有限公司 | Method for protecting base |
| CN106479038A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of RPP material of high electro-magnetic wave absorption performance and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446234A (en) * | 2017-05-11 | 2017-12-08 | 温州市赢创新材料技术有限公司 | A kind of preparation method of RPP material |
| CN107446234B (en) * | 2017-05-11 | 2019-07-16 | 上海田强环保科技股份有限公司 | A kind of preparation method of reinforced polypropylene material |
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Effective date of registration: 20210119 Address after: No.7, Xiwu Road, Jingbei village committee, Zhangxi she autonomous Township, Dongyuan County, Heyuan City, Guangdong Province 517551 Patentee after: Wu Shanshan Address before: 325011 No. 21 Yueqing Road, Zhuang Yuan Street, Longwan District, Wenzhou, Zhejiang. Patentee before: WENZHOU YINGCHUANG NEW MATERIAL TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20210816 Address after: 201202 No. 32 Lubin Road, Luyuan Industrial Park, Chuansha new town, Pudong New Area, Shanghai Patentee after: PULIXIN PACKAGING MATERIALS (SHANGHAI) Co.,Ltd. Address before: No.7, Xiwu Road, Jingbei village committee, Zhangxi she autonomous Township, Dongyuan County, Heyuan City, Guangdong Province 517551 Patentee before: Wu Shanshan |