CN102020814A - Recycled polypropylene modified polrvinyl chloride sectional material and preparation method thereof - Google Patents
Recycled polypropylene modified polrvinyl chloride sectional material and preparation method thereof Download PDFInfo
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- CN102020814A CN102020814A CN2009100443140A CN200910044314A CN102020814A CN 102020814 A CN102020814 A CN 102020814A CN 2009100443140 A CN2009100443140 A CN 2009100443140A CN 200910044314 A CN200910044314 A CN 200910044314A CN 102020814 A CN102020814 A CN 102020814A
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- section bar
- recovery
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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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- 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
-
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a recycled polypropylene modified polrvinyl chloride sectional material and a preparation method thereof. The sectional material is mainly prepared by blending 100 parts of polrvinyl chloride, 8 to 20 parts of crosslinking recycled polypropylene, 3 to 6 parts of stabilizer, 3 to 6 parts of titanium white powder, 3 to 10 parts of chlorinated polyethylene, 1 to 4 parts of acrylic impact modifier, 0.2 to 1.0 part of lubricant and 0 to 30 parts of active calcium carbonate. The sectional material has excellent performance, can effectively improve recycling utilization rate, saves resources and cost and is environmentally-friendly and safe.
Description
Technical field
The present invention relates to a kind of polychloroethylene section bar and preparation method thereof, relate in particular to a kind of rejected material and carry out polychloroethylene section bar of modification and preparation method thereof with recovery.
Background technology
In the time of the plastic industry fast development, waste or used plastics is also increasing year by year, and wherein polypropylene (being called for short PP) is because purposes is wide, consumption is big, and it accounts for 25% of waste or used plastics total amount through processing and the waste material that uses the back to be produced.The waste or used plastics pollution on the environment also more and more is subject to people's attention, and this makes the reclaiming and utilizing waste plastics technology become the focus of domestic and international colleague's research.
Polyvinyl chloride (being called for short PVC) section bar is more corrosion-resistant than timber and steel, have than aluminium section bar and the better stopping property of shaped steel, sound insulation, heat-insulation and heat-preservation, and outward appearance exquisiteness, various shapes, but the characteristics that PVC easily degrades, melt viscosity is big cause its processing inconvenient, and PP has good thermostability and processing characteristics, in view of PP and PVC this two kinds of polymkeric substance characteristics separately and vital role in actual applications, how just to become the important research direction in this area by blending and modifying acquisition high strength and the good blend PVC material of processing characteristics.
At present, the PP that utilization is reclaimed carries out modification to PVC rare the mentioning of relevant report, prior art is mainly paid close attention to the blend of virgin material PP and PVC, and improve the consistency between PP and the PVC, and then improve the performance of intermingling material by adding solubilizing agent (for example chlorinatedpolyethylene, Chlorinated Polypropylene III, the many monomer graft polymers of PP, PP grafting hyperbranched poly (amide-ester), chlorinatedpolyethylene and dioctyl phthalate (DOP) are worked in coordination with, PP grafted maleic anhydride, PP grafting methylpropanoic acid methyl esters etc.).Result of study shows that the matrix material consistency that obtains under this mode is improved to some extent, but mechanical property is relatively poor, does not reach the physicals requirement of PVC section bar.Though the method for utilizing discarded PP and other multiple material blend to prepare section bar of mentioning is arranged in indivedual documents, but it fills a prescription complicated, preparation technology is loaded down with trivial details, and the section bar finished product for preparing is excellent not enough on mechanical property, and the performance of product and quality are still waiting further raising.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide a kind of and can improve the technics of reclaim of plastic waste utilization ratio, economize on resources and production cost, Environmental Safety, excellent performance with the PVC section bar that reclaims the PP modification, the preparation method of this PVC section bar that a kind of cost is little, technology is simple, resource utilization is high also is provided at the PVC section bar that reclaims the PP modification.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of with the PVC section bar that reclaims the PP modification, it is characterized in that described PVC section bar is mainly prepared by the raw material blend of following mass fraction:
The characteristics of technique scheme are to have adopted crosslinked recovery PP that the PVC section bar is carried out modification, thereby have obtained performance index and higher PP and the PVC blend section bar of quality, have made full use of waste resource, have saved cost, help the protection to environment simultaneously.
The present invention also provides a kind of above-mentioned preparation method with the PVC section bar that reclaims the PP modification, may further comprise the steps:
(1) batch mixing: raw material PVC, stablizer, titanium dioxide, CPE, ACR and lubricant are carried out high-speed mixing by said ratio, the heating of mixing raw material self friction, when temperature rises to 80 ℃～95 ℃, add crosslinked recovery PP or add crosslinked recovery PP and treated carbonates, heat is mixed blowing when temperature reaches 115 ℃～125 ℃, begin cold mixing then, obtain dry blend to room temperature;
(2) moulding:, prepare with the PVC section bar that reclaims the PP modification with the extrusion moulding under 140 ℃～205 ℃ temperature of described dry blend.
In the above-mentioned technical scheme, to carry out crosslinked pretreated method a lot of to reclaiming PP, general linking agent and crosslinking reaction technology all can realize reclaiming the crosslinked of PP, described crosslinked recovery PP carries out preparing after the crosslinking reaction to reclaiming PP with general linking agent, but the raw material of the following mass fraction of preferred main employing prepares after mixing crosslinking reaction:
The melting index of described recovery PP is less than 12.0g/10min, and solid content is lower than 15%.
The concrete steps of above-mentioned mixing crosslinking reaction can be: elder generation is dissolved in 0.05～1 part DCP in 0.5～2.0 part of additional crosslinker, again with spray solution on the CPE of 100 parts recovery PP and 5～30 parts, recovery PP and the CPE high-speed mixing that to spray solution then stir, churning time is no less than 4min, stirred materials is carried out extruder grain under 120 ℃～180 ℃ temperature, make crosslinked recovery PP.
In above-mentioned each technical scheme, described additional crosslinker preferably adopts vinylbenzene and/or Vinylstyrene, because through our test to product, these two kinds of linking agents can be realized also preventing high molecular degraded better to reclaiming the crosslinked and high molecular formation of PP better.Certainly, the present invention does not get rid of and selects other general or known additional crosslinkers (for example diallyl maleate, vinyltrimethoxy silane etc.) for use.In the technique scheme, the model of described raw material PVC generally is to adopt general PVC-SG-4, PVC-SG-5 or PVC-SG-6, preferably adopts PVC-SG-5, because with the section bar of the present invention of these model preparations more excellent performance is arranged on performance.In the technique scheme, described lubricant can be selected known in this field or general lubricant (for example whiteruss, oxidic polyethylene etc.) for use, can not only reduce the energy consumption of explained hereafter by adding lubricant, and can make product surface Paint Gloss, outward appearance is better.The lubricant that the present invention preferably adopts is stearic acid and/or polyethylene wax, if mixing, the two uses, and better effects if, because the two lubricant effect separately has complementarity, the mass ratio of stearic acid and polyethylene wax is preferably 3 when mixing use: (0.5～2).In the technique scheme, described stablizer can be selected known in this field or general stablizer (for example complex lead salt stabilizer, metallic soap class etc.) for use, but the present invention preferably adopts rare earth composite stabilizer.The present invention also can add a certain amount of treated carbonates, because we find by experiment, add a certain amount of treated carbonates and can improve the flexural strength and the modulus in flexure of product, but suitable last interpolation of treated carbonates can hinder the absorption of raw material PVC to other auxiliary agents because add treated carbonates too early.
Compared with prior art, the invention has the advantages that: than the blend of nonpolar virgin material PP and PVC, the present invention is by utilizing crosslinked recovery PP and PVC blend, and the modified PVC section bar of preparation has the excellent properties of existing PVC section bar, and the quality of product is greatly improved.Simultaneously, the present invention has realized reclaiming the recycle of PP, both improved China's reclaiming and utilizing waste plastics rate, alleviated the pressure that waste or used plastics causes environment, realize the saving of the energy and resource, reduced the production cost and the energy consumption of PVC goods again, promoted the market competitiveness of enterprise product, have the double meaning of alleviating domestic plastic raw materials imbalance between supply and demand and improving the business economic benefit, help the realization of domestic PVC section bar industry target of sustainable development.
Embodiment
Below in conjunction with embodiment the present invention is described in more detail.
Embodiment 1:
A kind of of the present invention with the PVC section bar that reclaims the PP modification, this section bar is that the raw material blend by following mass fraction prepares:
The preparation method with the PVC section bar that reclaims the PP modification of the invention described above specifically may further comprise the steps:
(1) batch mixing: raw material PVC, stablizer, titanium dioxide, CPE, ACR and lubricant are carried out high-speed mixing by said ratio, when temperature rises to 80 ℃～95 ℃, add crosslinked recovery PP or add crosslinked recovery PP and treated carbonates, heat is mixed blowing when temperature reaches 115 ℃～125 ℃, begin cold mixing then, obtain dry blend to room temperature;
(2) moulding:, prepare of the present invention with the PVC section bar that reclaims the PP modification with dry blend extrusion moulding under 140 ℃～205 ℃ temperature.
Present embodiment is by utilizing crosslinked recovery PP and PVC blend, and the modified PVC section bar of preparation has the excellent properties of existing PVC section bar, and the quality and the performance of product all are greatly improved; Simultaneously, also realize reclaiming the recycle of PP, improved China's reclaiming and utilizing waste plastics rate.
Below to the present invention more specifically or more preferred embodiment be further described.
Embodiment 2:
Pressing component list ready raw material in the table 1 reclaims PP (melting index that reclaims PP is less than 12.0g/10min, solid content is lower than 15%), CPE, DCP and additional crosslinker (vinylbenzene or Vinylstyrene), DCP is dissolved in the additional crosslinker, again with spray solution to reclaiming on PP and the CPE, put into blowing (rotating speed of high-speed mixer reaches 700rpm) behind the high-speed mixer mixing 5min then; The material that mixes is utilized the twin screw extruder extruding pelletization under 120 ℃～180 ℃ temperature, the crosslinked recovery PP that makes three kinds of different proportionings is standby.
Table 1: the different ingredients of crosslinked recovery PP
With raw material PVC (PVC-SG-5), rare earth composite stabilizer, titanium dioxide, CPE, ACR and lubricant (present embodiment select for use lubricant be stearic acid and polyethylene wax) according to the form below 2 listed proportionings join the high-speed mixer high speed and mix, when the temperature of mixture rises to 90 ℃ again in the according to the form below 2 listed component add the crosslinked recovery PP of above-mentioned preparation and the treated carbonates of preparation, continue the mixed blowing that when temperature reaches 120 ℃, begins of heat, cold then mixed 3min makes the temperature of mixture reduce to room temperature and obtains dry blend, with dry blend extrusion moulding under 140 ℃～205 ℃ temperature, make the polychloroethylene section bar of four kinds of different recovery PP modifications.
The PVC section bar formula table of the present invention that makes among table 2: the embodiment 2
To obtain by above-mentioned prescription and prepared four kinds reclaim the polychloroethylene section bar of PP modification and do not carry out polychloroethylene section bar, PP/PVC blend section bar of the prior art that crosslinked pre-treatment prepares and carry out the contrast of mechanical property, and its test data is as shown in table 3 below:
Table 3: the PVC section bar mechanical property synopsis of different treatment
Table is annotated: going up table 3 medium section A is PP/PVC blend section bar of the prior art; Section bar B does not carry out the prescription 1 PP/PVC blend section bar for preparing in crosslinked pretreated recovery PP and the table 2 for adopting; Section bar C, section bar D and section bar E are respectively crosslinked recovery PP-1 in the table 1
#, crosslinked recovery PP-2
#With crosslinked recovery PP-3
#PVC section bar by the prescription 1 recovery PP modification for preparing in the table 2; Section bar F is crosslinked recovery PP-1 in the table 1
#PVC section bar by the prescription 2 recovery PP modifications that prepare in the table 2.
By the test data of last table 3 as can be seen, (B～F) than blend section bar of the prior art (A), its performance index, quality product all are significantly improved to adopt the PVC section bar of the recovery PP modification that present embodiment prescription and prepared obtain; And be the PVC section bar of recovery PP of the present invention modification equally, adopted the crosslinked pretreatment technology of the present invention to carry out crosslinked pretreated PVC section bar (the crosslinked pretreated PVC section bar (B) than not passing through of C～F), its every performance index have had further to be improved to reclaiming PP.
Embodiment 3:
Present embodiment 3 is selected the crosslinked recovery PP-1 of embodiment 2 preparations for use
#Feed composition as preparation modified PVC section bar of the present invention, the mass fraction prescription of all the other components and each component sees the following form 4, the mass fraction of treated carbonates component wherein is divided into four different additions and adjusts one by one, the mass fraction of other each components remains unchanged, and prepares (containing crosslinked pre-treatment) the PVC section bar of the recovery PP modification of four kinds of different activities calcium carbonate contents by embodiment 2 described methods and technology.
The PVC section bar formula table of the present invention that makes among table 4: the embodiment 3
The section bar C that makes among the PVC section bar of the recovery PP modification of four kinds of different activities calcium carbonate contents that present embodiment 3 is prepared and the embodiment 2 carries out the contrast of mechanical property, and its test data is as shown in table 5 below.
Table 5: the PVC section bar mechanical property synopsis of different activities calcium carbonate content
By last table 5 as seen, examined or check CaCO in the present embodiment 3
3The difference of content is to the influence of the PVC section bar product performance of recovery PP modification, and the result shows along with CaCO
3The increase of content, the shock strength and the tensile strength of section bar product of the present invention are on a declining curve, and flexural strength and modulus in flexure show the situation that non-severity ground increases gradually.
Embodiment 4:
Present embodiment 4 is selected the crosslinked recovery PP-2 of embodiment 2 preparations for use
#As the feed composition of preparation PVC section bar of the present invention, the mass fraction of all the other components and each component sees the following form shown in 6, prepares the PVC section bar of recovery PP of the present invention modification by embodiment 2 described methods and technology (containing crosslinked pre-treatment).
The PVC section bar formula table of the present invention that makes among table 6: the embodiment 4
The section bar D that makes among PVC section bar that present embodiment 4 is prepared and the embodiment 2 carries out the contrast of mechanical property, and its test data is as shown in table 7 below.
Table 7: the PVC section bar mechanical property synopsis of different CPE content
By last table 7 as seen, examined or check the influence of the difference of CPE content to the PVC section bar product performance of recovery PP modification in the present embodiment 4, the result shows that the shock resistance of material when increasing the consumption of CPE obviously improves, and stretching and flexural strength descend to some extent.
Claims (9)
1. one kind with the polychloroethylene section bar that reclaims polypropylene modification, it is characterized in that described polychloroethylene section bar is mainly prepared by the raw material blend of following mass fraction:
2. polychloroethylene section bar according to claim 1 is characterized in that: described crosslinked recovery polypropylene prepares after mainly utilizing the raw material of following mass fraction to mix crosslinking reaction:
The polyacrylic melting index of described recovery is less than 12.0g/10min, and solid content is lower than 15%.
3. polychloroethylene section bar according to claim 2 is characterized in that: described additional crosslinker is vinylbenzene and/or Vinylstyrene.
4. polychloroethylene section bar according to claim 1 is characterized in that: described lubricant is meant stearic acid and/or polyethylene wax.
5. polychloroethylene section bar according to claim 4 is characterized in that: described lubricant is meant the compounded lubricant that stearic acid and polyethylene wax are formed, and the mass ratio of described stearic acid and polyethylene wax is 3: (0.5～2).
6. polychloroethylene section bar according to claim 1 is characterized in that: described stablizer is meant rare earth composite stabilizer.
7. the preparation method of a polychloroethylene section bar as claimed in claim 1 may further comprise the steps:
(1) batch mixing: polyvinyl chloride, stablizer, titanium dioxide, chlorinatedpolyethylene, acrylic ester impact-resisting modifier and lubricant are carried out high-speed mixing by proportioning, when temperature rises to 80 ℃～95 ℃, add crosslinked recovery polypropylene or add crosslinked recovery polypropylene and treated carbonates, heat is mixed blowing when temperature reaches 110 ℃～125 ℃, begin cold mixing then, obtain dry blend to room temperature;
(2) moulding:, prepare with the polychloroethylene section bar that reclaims polypropylene modification with the extrusion moulding under 140 ℃～205 ℃ temperature of described dry blend.
8. preparation method according to claim 7, it is characterized in that described crosslinked recovery polypropylene is to prepare by the following method: 0.05～1 part dicumyl peroxide is dissolved in 0.5～2.0 part of additional crosslinker, again with spray solution on 100 parts recovery polypropylene and 5～30 parts of chlorinatedpolyethylenees, recovery polypropylene and the chlorinatedpolyethylene high-speed mixing that to spray solution then stir, churning time is no less than 4min, stirred materials is carried out extruder grain under 120 ℃～180 ℃ temperature, make crosslinked recovery polypropylene.
9. preparation method according to claim 8 is characterized in that: described additional crosslinker is vinylbenzene and/or Vinylstyrene; The model of described polyvinyl chloride is PVC-SG-4, PVC-SG-5 or PVC-SG-6; Described lubricant is meant stearic acid and/or polyethylene wax; Described stablizer is meant rare earth composite stabilizer; The polyacrylic melting index of described recovery is less than 12.0g/10min, and solid content is lower than 15%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100443140A CN102020814B (en) | 2009-09-10 | 2009-09-10 | Recycled polypropylene modified polrvinyl chloride sectional material and preparation method thereof |
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| CN2009100443140A CN102020814B (en) | 2009-09-10 | 2009-09-10 | Recycled polypropylene modified polrvinyl chloride sectional material and preparation method thereof |
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| CN102020814B CN102020814B (en) | 2012-12-05 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167871A (en) * | 2011-05-05 | 2011-08-31 | 湖北众联塑业有限公司 | Modifier for processing polyvinyl chloride profile |
| CN102336979A (en) * | 2011-05-27 | 2012-02-01 | 邓忠权 | Processing modifier for polyvinyl chloride water supply pipeline |
| CN102532668A (en) * | 2012-01-03 | 2012-07-04 | 江苏南亚电缆集团有限公司 | Flame-retarding polyethylene prepared by grafting low-polymerization-degree polyvinyl chloride and preparation method thereof |
| CN102604229A (en) * | 2012-03-21 | 2012-07-25 | 深圳市科聚新材料有限公司 | PP/PVC/CPE (propene polymer/polyvinyl chloride/chlorinated polyethylene) ternary alloy and preparation method thereof |
| CN103509240A (en) * | 2012-06-27 | 2014-01-15 | 合肥杰事杰新材料股份有限公司 | CPVC-PP (Chlorinated Polyvinyl Chloride-Propene Polymer) alloy material and preparation method thereof |
| CN104476694A (en) * | 2014-10-11 | 2015-04-01 | 泰兴市耐热机泵制造厂 | A forming process for fluoridation modification of a polypropylene plastic part |
| CN104672708A (en) * | 2015-02-13 | 2015-06-03 | 北京科技大学 | Recyclable waste plastic polyvinyl chloride composite material and preparation method thereof |
| CN105086143A (en) * | 2015-08-21 | 2015-11-25 | 广州市聚赛龙工程塑料有限公司 | Recovered polypropylene/polyvinylidene chloride (PP/PVDC) composite material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1618864A (en) * | 2004-10-11 | 2005-05-25 | 华东理工大学 | High calcium carbonate filled herd polyvinyl chloride material |
| AP2410A (en) * | 2006-05-01 | 2012-05-30 | Bnt Force Biodegradable Polymers Pvt Ltd | Novel biodegradable polymer composition useful forthe preparation of biodegradable plastic and a pr ocess for the preparation of said composition. |
| CN101168610B (en) * | 2007-10-12 | 2010-10-20 | 唐山金三顺装饰材料有限公司 | Producing method of special-purpose board for building |
| CN101143954B (en) * | 2007-10-24 | 2010-07-14 | 华东理工大学 | Polyvinyl chloride modified resin |
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- 2009-09-10 CN CN2009100443140A patent/CN102020814B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167871A (en) * | 2011-05-05 | 2011-08-31 | 湖北众联塑业有限公司 | Modifier for processing polyvinyl chloride profile |
| CN102167871B (en) * | 2011-05-05 | 2013-03-06 | 武汉新巨创化工有限公司 | Modifier for processing polyvinyl chloride profile |
| CN102336979A (en) * | 2011-05-27 | 2012-02-01 | 邓忠权 | Processing modifier for polyvinyl chloride water supply pipeline |
| CN102532668A (en) * | 2012-01-03 | 2012-07-04 | 江苏南亚电缆集团有限公司 | Flame-retarding polyethylene prepared by grafting low-polymerization-degree polyvinyl chloride and preparation method thereof |
| CN102532668B (en) * | 2012-01-03 | 2014-01-01 | 江苏南亚电缆集团有限公司 | Flame-retarding polyethylene prepared by grafting low-polymerization-degree polyvinyl chloride and preparation method thereof |
| CN102604229A (en) * | 2012-03-21 | 2012-07-25 | 深圳市科聚新材料有限公司 | PP/PVC/CPE (propene polymer/polyvinyl chloride/chlorinated polyethylene) ternary alloy and preparation method thereof |
| CN103509240A (en) * | 2012-06-27 | 2014-01-15 | 合肥杰事杰新材料股份有限公司 | CPVC-PP (Chlorinated Polyvinyl Chloride-Propene Polymer) alloy material and preparation method thereof |
| CN104476694A (en) * | 2014-10-11 | 2015-04-01 | 泰兴市耐热机泵制造厂 | A forming process for fluoridation modification of a polypropylene plastic part |
| CN104672708A (en) * | 2015-02-13 | 2015-06-03 | 北京科技大学 | Recyclable waste plastic polyvinyl chloride composite material and preparation method thereof |
| CN104672708B (en) * | 2015-02-13 | 2018-09-25 | 北京科技大学 | A kind of polyvinyl chloride composite materials and preparation method thereof recycling waste plastics |
| CN105086143A (en) * | 2015-08-21 | 2015-11-25 | 广州市聚赛龙工程塑料有限公司 | Recovered polypropylene/polyvinylidene chloride (PP/PVDC) composite material and preparation method thereof |
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| CN102020814B (en) | 2012-12-05 |
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Address after: Taoyuan County in Hunan province Changde city 415700 disk town Chuangyuan Industrial Park Patentee after: Hunan Wuqiang Property (Group) Co., Ltd. Address before: 410205 Hunan province Changsha city high tech Development Zone Lu Tin Road No. 2 Patentee before: Hunan Wuqiang Property (Group) Co., Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121205 Termination date: 20170910 |