CN104910592B - A kind of preparation method of Novel PET strap masterbatch - Google Patents
A kind of preparation method of Novel PET strap masterbatch Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of Novel PET strap masterbatch, comprises the following steps：(1) fly ash float is cleaned, add hydrofluoric acid solution stirring, wash with water after sucking filtration, be placed in baking oven and dry, obtain being acidified fly ash float；(2) acidifying fly ash float is added in the aqueous solution of hexadecyltrimethylammonium chloride, stand after ultrasonic agitation, pour in drainage screen and filter, filtering residue washes with water, be placed in baking oven and be dried, obtain modified coal ash floating bead；(3) bismuth oxychloride is added to the water stirring and suspension is obtained, add PAMAM half in the aqueous solution of tree shaped polymer, magnetic agitation, filters after discharging, filtering residue absolute ethanol washing, is placed in baking oven and is dried, obtain modified bismuth oxychloride；(4) add blender stirring after PET pellet being dried, add modified coal ash floating bead, modified bismuth oxychloride to continue stirring, obtain PET strap masterbatch.The strap masterbatch that the present invention prepares has preferable ageing-resistant performance, can be suitably used for rugged environment.
Description
Technical field：
The present invention relates to a kind of packaging material, more particularly to a kind of preparation method of PET strap masterbatch.
Background technology：
PET strap is a kind of polyester packing belt with PET for primary raw material extruded simple tension molding, is current state
On border, most popular replacement steel band, steel wire, the novel environment friendly packaging material of heavy PP strap, have many advantages, such as：(1) tension
Power is strong, the stretching resistance as existing steel band, has the shock proof ductility of energy again, more can ensure that the transportation safety of product；(2) elongation percentage
Little, percentage elongation is only 1/6th of polypropylene tape, can keep tightening force for a long time；(3) safety is good, does not have steel band to get rusty dirt
The drawbacks of dye is by bundle object, color light can reflect；(4) economic benefit is good, and the length of 1 ton of PET strap is equivalent to 6 tons of same specifications
Steel band length, every meter of unit price is lower by more than 40% than steel band, and packing cost can be greatly reduced.But, PET there is also resistance to ag(e)ing
Defect that can not be good, thermal degradation and photooxidative degradation are the major concern that PET is subject to, and lead to PET strap in rugged environment
Easily aging down.
Publication No. CN101348601B, publication date are 2011.02.09, apply for that the Chinese patent of artificial Southeast China University is public
Open " plastic-steel baling belt Nano-meter SiO_22The preparation method of activeness and quietness PET composite material ", is received using melt-blending process preparation
Rice SiO2Reinforced PET Composite masterbatch, gas phase SiO2Weight/mass percentage composition be 25-40%, molten system remains at a high speed
Shearing dispersion, and mixed in the ultrasound environments of 20KHz, it is also added into coupling agent KH550 or Al120 in molten system,
Its consumption is SiO2The 2.5-4% of consumption, masterbatch is fed intake with PET blending by a certain percentage, obtains Nano-meter SiO_22Activeness and quietness
PET composite material, its Nano-meter SiO_22Content be 1-3.5%, Nano-meter SiO_22Particle is uniformly dispersed in PET, crystal property is good,
Substantially, good with PET compatibility, simultaneously again simple to operate, cost is relatively low for reinforced effects.This invention PET master batch is produced with PET blending
Plastic-steel baling belt, can preferably improve intensity, toughness of PET etc..But, this PET composite material equally exists ageing-resistant performance
Not good problem is easily aging under rugged environment.
Content of the invention：
The technical problem to be solved in the present invention is to provide a kind of preparation method of PET strap masterbatch, the packing prepared
Band masterbatch has preferable ageing-resistant performance, can be suitably used for rugged environment.
For solving above-mentioned technical problem, the technical scheme is that：
A kind of preparation method of Novel PET strap masterbatch, comprises the following steps：
(1) fly ash float is washed, adds hydrofluoric acid solution and stir 8 minutes, wash with water after sucking filtration 5 times,
It is placed in baking oven and dries 3 hours, obtain being acidified fly ash float；
(2) the acidifying fly ash float that step (1) obtains is added in the aqueous solution of hexadecyltrimethylammonium chloride, surpass
Sound stands 2 hours after stirring 2 hours, and the acidifying fly ash float being suspended in upper strata and the acidifying flyash being deposited in bottom are floated
Pearl is poured into together in drainage screen and filters, and filtering residue washes with water 5 times, is placed in baking oven and is dried 10 hours, obtains modified coal ash drift
Pearl；
(3) bismuth oxychloride is added to the water 30 minutes prepared suspensions of stirring, suspension is added PAMAM half for tree-like poly-
In the aqueous solution of compound, magnetic agitation 24 hours, filters after discharging, filtering residue absolute ethanol washing 5 times, is placed in baking oven and is dried
8 hours, obtain modified bismuth oxychloride；
(4) add blender to stir after PET pellet being dried 40 minutes, add the modified coal ash drift that step (2) obtains
The modified bismuth oxychloride that pearl, step (3) obtain continues stirring 2 hours, obtains PET strap masterbatch, counts by weight, PET
Pellet 84-88 part, modified coal ash floating bead 8-10 part, modified bismuth oxychloride 4-6 part.
Preferably, in step (1) of the present invention, fly ash float, the weight of hydrofluoric acid solution are than for 1:25.
Preferably, in step (1) of the present invention, the concentration of hydrofluoric acid solution is 0.5mol/L.
Preferably, in step (1) of the present invention, the temperature of baking oven is 140 DEG C.
Preferably, in step (2) of the present invention, the mass fraction of the aqueous solution of hexadecyltrimethylammonium chloride is
5%, the weight of acidifying fly ash float and the aqueous solution of hexadecyltrimethylammonium chloride ratio is for 1:36.
Preferably, in step (2) of the present invention, the temperature of baking oven is 90 DEG C.
Preferably, in step (3) of the present invention, bismuth oxychloride and PAMAM half are 1 for the mol ratio of tree shaped polymer:
1.
Preferably, in step (3) of the present invention, the temperature of baking oven is 80 DEG C.
Preferably, in step (4) of the present invention, the mixing speed of blender is 800r/min.
Compared with prior art, the invention has the advantages that：
(1) fly ash float is a kind of fly ash hollow ball that can bubble through the water column, and has the structure of hollow and thin-walled, in cavity
For partial vacuum, therefore conduction of heat is extremely atomic slowly, has good heat insulating function, can effectively improve its heat-proof quality, greatly after adding PET
The big weakening harmful effect to strap masterbatch for the thermal degradation, but there is substantial amounts of hydroxyl on fly ash float surface, shows substantially
Hydrophilic and polarity, lead to that itself compatibility and PET matrix between is poor, the dispersibility after addition is not also good, thus this
The bright Fluohydric acid. that first passes through carries out acidification to it, and the hydroxyl on Fluohydric acid. and its surface reacts and reduces surface polarity, from
And improve dispersibility, and then surface modification is carried out by cationic surfactant hexadecyltrimethylammonium chloride, 16
The cation that alkyl trimethyl ammonium chloride ionizes out is adsorbed in fly ash float surface by electrostatic interaction and defines organic
Cladding, the hydrophilic on its surface is become hydrophobicity, improves itself compatibility and PET matrix between, so as to fully send out
Wave its heat-proof quality, substantially reduce the harmful effect to it for the thermal degradation, effectively improve the ageing-resistant performance of strap masterbatch；
(2) bismuth oxychloride has very high optical index, and most of anaclasis can be gone out, but it is inorganic matters, table
Face also assumes hydrophilic, not good with the compatibility of PET matrix, and therefore the present invention passes through PAMAM half for tree shaped polymer to carrying out
Modification, the two has carried out abundant complexation, introduces organic group on bismuth oxychloride surface, the hydrophilic on its surface is become
Hydrophobicity, improves itself compatibility and PET matrix between, can effectively improve the anaclasis ability of strap masterbatch, significantly drop
The harmful effect to it for the low light degradation, improves ageing-resistant performance further so as to can be suitably used for rugged environment.
Specific embodiment
To describe the present invention, the illustrative examples of the here present invention and explanation below in conjunction with specific embodiment in detail
It is used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1
A kind of preparation method of Novel PET strap masterbatch, comprises the following steps：
(1) fly ash float is washed, add the hydrofluoric acid solution that concentration is 0.5mol/L and stir 8 minutes, powder
Coal ash floating bead, the weight of hydrofluoric acid solution are than for 1:25, wash with water after sucking filtration 5 times, be placed in the baking oven that temperature is 140 DEG C and dry
Dry 3 hours, obtain being acidified fly ash float；
(2) the acidifying fly ash float that step (1) obtains is added the cetyl trimethyl chlorination that mass fraction is 5%
In the aqueous solution of ammonium, the weight of acidifying fly ash float and the aqueous solution of hexadecyltrimethylammonium chloride ratio is for 1:36, ultrasonic
Stirring stood 2 hours after 2 hours, by the acidifying fly ash float being suspended in upper strata and the acidifying fly ash float being deposited in bottom
Pour into together in drainage screen and filter, filtering residue washes with water 5 times, be placed in the baking oven that temperature is 90 DEG C and be dried 10 hours, changed
Property fly ash float；
(3) bismuth oxychloride is added to the water 30 minutes prepared suspensions of stirring, suspension is added PAMAM half for tree-like poly-
In the aqueous solution of compound, bismuth oxychloride and PAMAM half are 1 for the mol ratio of tree shaped polymer:1, magnetic agitation 24 hours, discharging
After filter, filtering residue absolute ethanol washing 5 times, be placed in the baking oven that temperature is 80 DEG C and be dried 8 hours, obtain modified oxychloride
Bismuth；
(4) count by weight, add blender to stir after 86 parts of PET pellets are dried 40 minutes, the stirring of blender
Speed is 800r/min, adds the modified oxychloride that the modified coal ash floating bead that 10 parts of steps (2) obtain, 4 parts of steps (3) obtain
Bismuth continues stirring 2 hours, obtains PET strap masterbatch.
Embodiment 2
A kind of preparation method of Novel PET strap masterbatch, comprises the following steps：
(1) fly ash float is washed, add the hydrofluoric acid solution that concentration is 0.5mol/L and stir 8 minutes, powder
Coal ash floating bead, the weight of hydrofluoric acid solution are than for 1:25, wash with water after sucking filtration 5 times, be placed in the baking oven that temperature is 140 DEG C and dry
Dry 3 hours, obtain being acidified fly ash float；
(2) the acidifying fly ash float that step (1) obtains is added the cetyl trimethyl chlorination that mass fraction is 5%
In the aqueous solution of ammonium, the weight of acidifying fly ash float and the aqueous solution of hexadecyltrimethylammonium chloride ratio is for 1:36, ultrasonic
Stirring stood 2 hours after 2 hours, by the acidifying fly ash float being suspended in upper strata and the acidifying fly ash float being deposited in bottom
Pour into together in drainage screen and filter, filtering residue washes with water 5 times, be placed in the baking oven that temperature is 90 DEG C and be dried 10 hours, changed
Property fly ash float；
(3) bismuth oxychloride is added to the water 30 minutes prepared suspensions of stirring, suspension is added PAMAM half for tree-like poly-
In the aqueous solution of compound, bismuth oxychloride and PAMAM half are 1 for the mol ratio of tree shaped polymer:1, magnetic agitation 24 hours, discharging
After filter, filtering residue absolute ethanol washing 5 times, be placed in the baking oven that temperature is 80 DEG C and be dried 8 hours, obtain modified oxychloride
Bismuth；
(4) count by weight, add blender to stir after 85 parts of PET pellets are dried 40 minutes, the stirring of blender
Speed is 800r/min, adds the modified oxychloride that the modified coal ash floating bead that 9 parts of steps (2) obtain, 6 parts of steps (3) obtain
Bismuth continues stirring 2 hours, obtains PET strap masterbatch.
Embodiment 3
A kind of preparation method of Novel PET strap masterbatch, comprises the following steps：
(1) fly ash float is washed, add the hydrofluoric acid solution that concentration is 0.5mol/L and stir 8 minutes, powder
Coal ash floating bead, the weight of hydrofluoric acid solution are than for 1:25, wash with water after sucking filtration 5 times, be placed in the baking oven that temperature is 140 DEG C and dry
Dry 3 hours, obtain being acidified fly ash float；
(2) the acidifying fly ash float that step (1) obtains is added the cetyl trimethyl chlorination that mass fraction is 5%
In the aqueous solution of ammonium, the weight of acidifying fly ash float and the aqueous solution of hexadecyltrimethylammonium chloride ratio is for 1:36, ultrasonic
Stirring stood 2 hours after 2 hours, by the acidifying fly ash float being suspended in upper strata and the acidifying fly ash float being deposited in bottom
Pour into together in drainage screen and filter, filtering residue washes with water 5 times, be placed in the baking oven that temperature is 90 DEG C and be dried 10 hours, changed
Property fly ash float；
(3) bismuth oxychloride is added to the water 30 minutes prepared suspensions of stirring, suspension is added PAMAM half for tree-like poly-
In the aqueous solution of compound, bismuth oxychloride and PAMAM half are 1 for the mol ratio of tree shaped polymer:1, magnetic agitation 24 hours, discharging
After filter, filtering residue absolute ethanol washing 5 times, be placed in the baking oven that temperature is 80 DEG C and be dried 8 hours, obtain modified oxychloride
Bismuth；
(4) count by weight, add blender to stir after 87 parts of PET pellets are dried 40 minutes, the stirring of blender
Speed is 800r/min, adds the modified oxychloride that the modified coal ash floating bead that 8 parts of steps (2) obtain, 5 parts of steps (3) obtain
Bismuth continues stirring 2 hours, obtains PET strap masterbatch.
Embodiment 4
A kind of preparation method of Novel PET strap masterbatch, comprises the following steps：
(1) fly ash float is washed, add the hydrofluoric acid solution that concentration is 0.5mol/L and stir 8 minutes, powder
Coal ash floating bead, the weight of hydrofluoric acid solution are than for 1:25, wash with water after sucking filtration 5 times, be placed in the baking oven that temperature is 140 DEG C and dry
Dry 3 hours, obtain being acidified fly ash float；
(2) the acidifying fly ash float that step (1) obtains is added the cetyl trimethyl chlorination that mass fraction is 5%
In the aqueous solution of ammonium, the weight of acidifying fly ash float and the aqueous solution of hexadecyltrimethylammonium chloride ratio is for 1:36, ultrasonic
Stirring stood 2 hours after 2 hours, by the acidifying fly ash float being suspended in upper strata and the acidifying fly ash float being deposited in bottom
Pour into together in drainage screen and filter, filtering residue washes with water 5 times, be placed in the baking oven that temperature is 90 DEG C and be dried 10 hours, changed
Property fly ash float；
(3) bismuth oxychloride is added to the water 30 minutes prepared suspensions of stirring, suspension is added PAMAM half for tree-like poly-
In the aqueous solution of compound, bismuth oxychloride and PAMAM half are 1 for the mol ratio of tree shaped polymer:1, magnetic agitation 24 hours, discharging
After filter, filtering residue absolute ethanol washing 5 times, be placed in the baking oven that temperature is 80 DEG C and be dried 8 hours, obtain modified oxychloride
Bismuth；
(4) count by weight, add blender to stir after 84 parts of PET pellets are dried 40 minutes, the stirring of blender
Speed is 800r/min, adds the modified oxychloride that the modified coal ash floating bead that 10 parts of steps (2) obtain, 6 parts of steps (3) obtain
Bismuth continues stirring 2 hours, obtains PET strap masterbatch.
Embodiment 5
A kind of preparation method of Novel PET strap masterbatch, comprises the following steps：
(1) fly ash float is washed, add the hydrofluoric acid solution that concentration is 0.5mol/L and stir 8 minutes, powder
Coal ash floating bead, the weight of hydrofluoric acid solution are than for 1:25, wash with water after sucking filtration 5 times, be placed in the baking oven that temperature is 140 DEG C and dry
Dry 3 hours, obtain being acidified fly ash float；
(2) the acidifying fly ash float that step (1) obtains is added the cetyl trimethyl chlorination that mass fraction is 5%
In the aqueous solution of ammonium, the weight of acidifying fly ash float and the aqueous solution of hexadecyltrimethylammonium chloride ratio is for 1:36, ultrasonic
Stirring stood 2 hours after 2 hours, by the acidifying fly ash float being suspended in upper strata and the acidifying fly ash float being deposited in bottom
Pour into together in drainage screen and filter, filtering residue washes with water 5 times, be placed in the baking oven that temperature is 90 DEG C and be dried 10 hours, changed
Property fly ash float；
(3) bismuth oxychloride is added to the water 30 minutes prepared suspensions of stirring, suspension is added PAMAM half for tree-like poly-
In the aqueous solution of compound, bismuth oxychloride and PAMAM half are 1 for the mol ratio of tree shaped polymer:1, magnetic agitation 24 hours, discharging
After filter, filtering residue absolute ethanol washing 5 times, be placed in the baking oven that temperature is 80 DEG C and be dried 8 hours, obtain modified oxychloride
Bismuth；
(4) count by weight, add blender to stir after 88 parts of PET pellets are dried 40 minutes, the stirring of blender
Speed is 800r/min, adds the modified oxychloride that the modified coal ash floating bead that 8 parts of steps (2) obtain, 4 parts of steps (3) obtain
Bismuth continues stirring 2 hours, obtains PET strap masterbatch.
Embodiment 6
A kind of preparation method of Novel PET strap masterbatch, comprises the following steps：
(1) fly ash float is washed, add the hydrofluoric acid solution that concentration is 0.5mol/L and stir 8 minutes, powder
Coal ash floating bead, the weight of hydrofluoric acid solution are than for 1:25, wash with water after sucking filtration 5 times, be placed in the baking oven that temperature is 140 DEG C and dry
Dry 3 hours, obtain being acidified fly ash float；
(2) the acidifying fly ash float that step (1) obtains is added the cetyl trimethyl chlorination that mass fraction is 5%
In the aqueous solution of ammonium, the weight of acidifying fly ash float and the aqueous solution of hexadecyltrimethylammonium chloride ratio is for 1:36, ultrasonic
Stirring stood 2 hours after 2 hours, by the acidifying fly ash float being suspended in upper strata and the acidifying fly ash float being deposited in bottom
Pour into together in drainage screen and filter, filtering residue washes with water 5 times, be placed in the baking oven that temperature is 90 DEG C and be dried 10 hours, changed
Property fly ash float；
(3) bismuth oxychloride is added to the water 30 minutes prepared suspensions of stirring, suspension is added PAMAM half for tree-like poly-
In the aqueous solution of compound, bismuth oxychloride and PAMAM half are 1 for the mol ratio of tree shaped polymer:1, magnetic agitation 24 hours, discharging
After filter, filtering residue absolute ethanol washing 5 times, be placed in the baking oven that temperature is 80 DEG C and be dried 8 hours, obtain modified oxychloride
Bismuth；
(4) count by weight, add blender to stir after 86 parts of PET pellets are dried 40 minutes, the stirring of blender
Speed is 800r/min, adds the modified chlorine that the modified coal ash floating bead that 9.5 parts of steps (2) obtain, 4.5 parts of steps (3) obtain
Bismuth oxide continues stirring 2 hours, obtains PET strap masterbatch.
After tested, the strap masterbatch that embodiment 1-6 is obtained and the ageing-resistant performance of comparative example are as shown in the table, wherein
Comparative example is the Chinese patent of Publication No. 101348601B, and ageing-resistant performance test process is：Determinand is placed in outdoor certainly
So aging, test its every mechanical property conservation rate after 1 year：
As seen from the above table, the present invention is obtained the stretching strength retentivity of strap masterbatch, bending strength conservation rate, breach
Impact strength conservation rate, all significantly better than comparative example, shows good ageing-resistant performance.
Above-described embodiment only principle of the illustrative present invention and its effect, not for the restriction present invention.Any ripe
The personage knowing this technology all can carry out modifications and changes without prejudice under the spirit and the scope of the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
All equivalent modifications becoming or change, must be covered by the claim of the present invention.
Claims (9)
1. a kind of preparation method of Novel PET strap masterbatch it is characterised in that：Comprise the following steps：
(1) fly ash float is washed, add hydrofluoric acid solution and stir 8 minutes, wash with water after sucking filtration 5 times, be placed in
Dry 3 hours in baking oven, obtain being acidified fly ash float；
(2) the acidifying fly ash float that step (1) obtains is added in the aqueous solution of hexadecyltrimethylammonium chloride, ultrasonic stir
2 hours are stood, by the acidifying fly ash float being suspended in upper strata and the acidifying fly ash float one being deposited in bottom after mixing 2 hours
Rise to pour in drainage screen and filter, filtering residue washes with water 5 times, is placed in baking oven and is dried 10 hours, obtains modified coal ash floating bead；
(3) bismuth oxychloride is added to the water 30 minutes prepared suspensions of stirring, suspension is added PAMAM half for tree shaped polymer
Aqueous solution in, magnetic agitation 24 hours, filter after discharging, filtering residue absolute ethanol washing 5 times, be placed in baking oven that to be dried 8 little
When, obtain modified bismuth oxychloride；
(4) will PET pellet be dried after add blender stir 40 minutes, add step (2) obtain modified coal ash floating bead, step
Suddenly the modified bismuth oxychloride that (3) obtain continues stirring 2 hours, obtains PET strap masterbatch, counts by weight, PET pellet
84-88 part, modified coal ash floating bead 8-10 part, modified bismuth oxychloride 4-6 part.
2. a kind of Novel PET strap masterbatch according to claim 1 preparation method it is characterised in that：Described step
(1), in, fly ash float, the weight of hydrofluoric acid solution are than for 1:25.
3. a kind of Novel PET strap masterbatch according to claim 1 preparation method it is characterised in that：Described step
(1), in, the concentration of hydrofluoric acid solution is 0.5mol/L.
4. a kind of Novel PET strap masterbatch according to claim 1 preparation method it is characterised in that：Described step
(1), in, the temperature of baking oven is 140 DEG C.
5. a kind of Novel PET strap masterbatch according to claim 1 preparation method it is characterised in that：Described step
(2), in, the mass fraction of the aqueous solution of hexadecyltrimethylammonium chloride is 5%, is acidified fly ash float and cetyl three
The weight of the aqueous solution of ammonio methacrylate is than for 1:36.
6. a kind of Novel PET strap masterbatch according to claim 1 preparation method it is characterised in that：Described step
(2), in, the temperature of baking oven is 90 DEG C.
7. a kind of Novel PET strap masterbatch according to claim 1 preparation method it is characterised in that：Described step
(3), in, bismuth oxychloride and PAMAM half are 1 for the mol ratio of tree shaped polymer:1.
8. a kind of Novel PET strap masterbatch according to claim 1 preparation method it is characterised in that：Described step
(3), in, the temperature of baking oven is 80 DEG C.
9. a kind of Novel PET strap masterbatch according to claim 1 preparation method it is characterised in that：Described step
(4), in, the mixing speed of blender is 800r/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109181246A (en) * | 2018-08-25 | 2019-01-11 | 马鞍山卓凡新材料科技有限公司 | A kind of high wearable Combined baling belt masterbatch |
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| CN1114571C (en) * | 2000-11-27 | 2003-07-16 | 中国科学院长春应用化学研究所 | Extruding-out and injection method for producing composite products of used plastics and powdered coal ash |
| CN104231555A (en) * | 2013-06-18 | 2014-12-24 | 无锡市方正金属捆带有限公司 | Preparation technique of high-strength high-toughness polyester packaging tape |
| CN104231559A (en) * | 2013-06-18 | 2014-12-24 | 无锡市方正金属捆带有限公司 | High-strength high-toughness polyester packing belt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109181246A (en) * | 2018-08-25 | 2019-01-11 | 马鞍山卓凡新材料科技有限公司 | A kind of high wearable Combined baling belt masterbatch |
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Effective date of registration: 20161229 Address after: 523125 Guangdong city of Dongguan province Dongcheng District Xiakou Liuhua Street No. 230 Applicant after: Dongguan packaging materials Co., Ltd. Address before: 313000 Zhejiang city of Huzhou Province Economic and Technological Development Zone of Huzhou Tianmen Yang Town three village thatched No. 82 Applicant before: Wang Hongcheng |
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| GR01 | Patent grant |