CN103013065B - Composite material for poly(butylene succinate) degradable film and preparation method thereof - Google Patents
Composite material for poly(butylene succinate) degradable film and preparation method thereof Download PDFInfo
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- CN103013065B CN103013065B CN201210540118.4A CN201210540118A CN103013065B CN 103013065 B CN103013065 B CN 103013065B CN 201210540118 A CN201210540118 A CN 201210540118A CN 103013065 B CN103013065 B CN 103013065B
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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
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/92885—Screw or gear
-
- 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)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of composite materials for a film, and provides a composite material for a poly(butylene succinate) degradable film and a preparation method thereof. The composite material for a poly(butylene succinate) degradable film comprises the following components in parts by weight: 50-90 parts of poly(butylene succinate), 10-50 parts of poly(butylene adipate-terephthalate), 10-50 parts of filler and 5-25 parts of lubricant. The preparation method comprises the following steps: mixing dried poly(butylene succinate), dried poly(butylene adipate-terephthalate), filler and lubricant; performing melt blending through a double screw extruder; and granulating. The prepared composite material for a poly(butylene succinate) degradable film has the characteristics of simple preparation process, low raw material cost, excellent mechanical property and biodegradability; the production cost is lowered; and the environmental requirements are met.
Description
Technical field
The present invention relates to film technical field of composite materials, is a kind of poly butylene succinate degradable films matrix material and preparation method thereof.
Background technology
As the widely used product of one, polymeric film is commonly used for semiconductor material, electrical material, isolated material etc., is particularly used in a large number in agricultural and packaging industry.Conventional polymer thin-film material has PVC, LDPE, HDPE, metallocene PE, PP, PS, EVA, PET, PA, PC, EVOH, F4 and PI etc.A shortcoming of these materials is not have complete biodegradability, so in use can produce environmental pollution problem, i.e. " white pollution "; The production cost of these materials is high simultaneously, large to the dependency of oil.
Summary of the invention
The invention provides a kind of poly butylene succinate degradable films matrix material and preparation method thereof, overcome the deficiency of above-mentioned prior art, it can effectively solve existing polymer thin-film material in use can produce white pollution, problem that production cost is high and large to the dependency of oil.
One of technical scheme of the present invention realizes by following measures: a kind of poly butylene succinate degradable films matrix material, contains 50 parts to 90 parts of poly butylene succinates, 10 parts to 50 parts of poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol esters, 10 parts to 50 parts of fillers, 5 parts to 25 parts of lubricants by weight; This poly butylene succinate degradable films obtains in the steps below with matrix material: the first step is dry 8 h to 20h at 60 DEG C to 100 DEG C by the poly butylene succinate of aequum and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester in temperature; Second step, filler and the lubricant of dried poly butylene succinate, dried poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, aequum are mixed, mixed poly butylene succinate, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, filler and lubricant are added in twin screw extruder, carry out blending extrusion, cooling, pelletizing obtains poly butylene succinate degradable films matrix material.
The further optimization and/or improvements to one of foregoing invention technical scheme below:
Above-mentioned filler is micron order calcium carbonate or W-Gum.
The particle diameter of above-mentioned calcium carbonate is 2000 order to 10000 orders; Or/and the particle diameter of W-Gum is 800 order to 1000 orders.
Above-mentioned lubricant is that fatty acid amide series lubricant agent is or/and hydro carbons lubricant.
Above-mentioned poly butylene succinate is that 150 DEG C, the pressure melt flow rate (MFR) while being 2.16kg is 8g/10min to 12g/10min in temperature.
Above-mentioned poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester is that 190 DEG C, the pressure melt flow rate (MFR) while being 2.16kg is 3g/10min to 8g/10min in temperature.
The rotating speed of above-mentioned twin screw extruder is 50r/min to 150r/min.
The barrel of above-mentioned twin screw extruder and the temperature of extrusion neck ring mold are 105 DEG C to 155 DEG C.
The rotating speed of above-mentioned dicing machine is 150 r/min to 300 r/min.
Two of technical scheme of the present invention realizes by following measures: the preparation method of matrix material for a kind of poly butylene succinate degradable films, carry out in the steps below: the first step is dry 8 h to 20h at 60 DEG C to 100 DEG C by the poly butylene succinate of aequum and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester in temperature; Second step, filler and the lubricant of dried poly butylene succinate, dried poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, aequum are mixed, mixed poly butylene succinate, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, filler and lubricant are added in twin screw extruder, carry out blending extrusion, cooling, pelletizing obtains poly butylene succinate degradable films matrix material.
Two the further optimization and/or improvements to foregoing invention technical scheme below:
The rotating speed of above-mentioned twin screw extruder is 50r/min to 150r/min.
The barrel of above-mentioned twin screw extruder and the temperature of extrusion neck ring mold are 105 DEG C to 155 DEG C.
The rotating speed of above-mentioned dicing machine is 150 r/min to 300 r/min.
Above-mentioned filler is micron order calcium carbonate or W-Gum.
The particle diameter of above-mentioned calcium carbonate is 2000 order to 10000 orders; The particle diameter of W-Gum is 800 order to 1000 orders.
Above-mentioned lubricant is that fatty acid amide series lubricant agent is or/and hydro carbons lubricant.
Above-mentioned poly butylene succinate is that 150 DEG C, the pressure melt flow rate (MFR) while being 2.16kg is 8g/10min to 12g/10min in temperature.
Above-mentioned poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester is that 190 DEG C, the pressure melt flow rate (MFR) while being 2.16kg is 3g/10min to 8g/10min in temperature.
The present invention obtains after by dried poly butylene succinate, dried poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, filler and mix lubricant after the granulation of twin screw extruder melt blending; The poly butylene succinate degradable films of gained of the present invention has with matrix material that preparation technology is simple, raw materials cost is low, mechanical property is excellent and biodegradable feature, has reduced production cost, has reached environmental requirement.
Embodiment
The present invention is not subject to the restriction of following embodiment, can determine concrete embodiment according to technical scheme of the present invention and practical situation.
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1, this poly butylene succinate degradable films matrix material, contains 50 parts to 90 parts of poly butylene succinates, 10 parts to 50 parts of poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol esters, 10 parts to 50 parts of fillers, 5 parts to 25 parts of lubricants by weight.
Embodiment 2, this poly butylene succinate degradable films matrix material, contains 10 parts of 10 parts of 50 parts of poly butylene succinates or 90 parts, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol esters or 50 parts, fillers or 50 parts, 5 parts or 25 parts of lubricants by weight.
Embodiment 3, the filler of the optimization as above-described embodiment: embodiment 3 is micron order calcium carbonate or W-Gum.Calcium carbonate be a kind of use the most extensively, the maximum inorganic mineral powder material of consumption, it is abundant, cheap that it has source, easily processing, the plurality of advantages such as nontoxic.Starch is the natural macromolecular material of a kind of renewable, cheap, wide material sources, readily biodegradable, adds starch in biodegradable polymer, has both reduced cost, meets again the requirement of environmental protection.
Embodiment 4, the particle diameter of the calcium carbonate of the optimization as above-described embodiment: embodiment 4 is 2000 order to 10000 orders; Or/and the particle diameter of W-Gum is 800 order to 1000 orders.
Embodiment 5, the lubricant of the optimization as above-described embodiment: embodiment 5 is that fatty acid amide series lubricant agent is or/and hydro carbons lubricant.
Embodiment 6, the poly butylene succinate of the optimization as above-described embodiment: embodiment 6 is that 150 DEG C, the pressure melt flow rate (MFR) while being 2.16kg is 8g/10min to 12g/10min in temperature.
Embodiment 7, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester of the optimization as above-described embodiment: embodiment 7 is that 190 DEG C, the pressure melt flow rate (MFR) while being 2.16kg is 3 g/10min to 8g/10min in temperature.
Embodiment 8, the preparation method of matrix material for the poly butylene succinate degradable films of above-described embodiment 1 to embodiment 7, carry out in the steps below: the first step is dry 8 h to 20h at 40 DEG C to 100 DEG C by the poly butylene succinate of aequum and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester in temperature; Second step, filler and the lubricant of dried poly butylene succinate, dried poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, aequum are mixed, mixed poly butylene succinate, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, filler and lubricant are added in twin screw extruder, carry out blending extrusion, cooling, pelletizing obtains poly butylene succinate degradable films matrix material.Poly butylene succinate (PBS), its fusing point is 108 ° of C left and right, but the toughness of poly butylene succinate (PBS) is bad, blown film poor performance; And poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester (PBAT) is the terpolymer of hexanodioic acid, terephthalic acid and butyleneglycol, its fusing point is 115 ° of C left and right, easily processing, there are stronger toughness, entanglement, biodegradation rate faster, there is good biocompatibility with poly butylene succinate (PBS) simultaneously.Because the degradation cycle of poly butylene succinate (PBS) and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester (PBAT) bi-material is different, therefore can regulate by change ratio the degradation time of matrix material.
Embodiment 9, the preparation method of matrix material for the poly butylene succinate degradable films of above-described embodiment 1 to embodiment 7, carry out in the steps below: the first step is dry 8 h or 20h at 40 DEG C or 100 DEG C by the poly butylene succinate of aequum and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester in temperature; Second step, filler and the lubricant of dried poly butylene succinate, dried poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, aequum are mixed, mixed poly butylene succinate, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, filler and lubricant are added in twin screw extruder, carry out blending extrusion, cooling, pelletizing obtains poly butylene succinate degradable films matrix material.
Embodiment 10, the rotating speed of the twin screw extruder of the optimization as above-described embodiment: embodiment 10 is 50 r/min to 150r/min.
Embodiment 11, the barrel of the twin screw extruder of the optimization as above-described embodiment: embodiment 11 and the temperature of extrusion neck ring mold are 105 DEG C to 155 DEG C.
Embodiment 12, the rotating speed of the dicing machine of the optimization as above-described embodiment: embodiment 12 is 150 r/min to 300 r/min.
Above-described embodiment gained poly butylene succinate degradable films carries out extrusion-blown modling after being put in convection oven and drying with matrix material in inflation film manufacturing machine, obtains the sample film of the present invention that 20 μ m are thick; Sample film of the present invention and country are as shown in table 1 to the mechanical property parameters of respective films product standard.
Table 1
| ? | ? | Sample film of the present invention | GB GBT13735-1992 |
| Tensile strength (MPa) | Laterally | 12.71 to 15.85 | 12.5 |
| Tensile strength (MPa) | Longitudinally | 13.02 to 14.93 | 12.5 |
| Tear strength (N/mm) | Laterally | 82.0 to 95.5 | 70 |
| Tear strength (N/mm) | Longitudinally | 83.7 to 96.7 | 70 |
| Elongation at break (%) | Laterally | 230.8 to 297.4 | 230 |
| Elongation at break (%) | Longitudinally | 243.6 to 326.8 | 230 |
The transverse tensile strength of sample film of the present invention, longitudinal tensile strength, cross direction tear strength, machine direction tear, transverse breakage elongation, longitudinal fracture elongation are respectively 12.71 MPa to 15.85 MPa, 13.02 MPa to 14.93 MPa, 82.0 N/mm to 95.5 N/mm, 83.7N/mm to 96.7N/mm, 230.8% to 297.4%, 243.6% to 326.8% as can be seen from Table 1, and these data are all better than the data in GB GBT13735-1992; Known by table 1 experimental data, the laminated film that adopts the present invention to obtain, in the time that the parts by weight of filler reach 10 to 50 parts, its tensile strength is still greater than 13MPa, tear strength is greater than 80N/mm, elongation at break is higher than 230%, can meet the requirement of GB to thin-film material completely, gained poly butylene succinate degradable films of the present invention can be for the preparation of the film article that meets service requirements with matrix material, as mulch film, shopping bag for supermarket etc., substitute traditional PE, PP bag film, reduce white pollution; Compare, the main technique effect of the present invention is: the one, compared with traditional plastics, the degradable poly butylene succinate of employing of the present invention itself, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, filler and lubricant are raw material, the product of making is nontoxic to nature, environmental friendliness, can solve white pollution problems; The 2nd, compared with the biodegradable materials such as PBS, PCL, PBAT, when the parts by weight of the filler adding in the present invention reach 10 to 50 parts, can effectively reduce material cost 20% to 50%, cost is low; Adopt extruding pelletization method, technique is simple, is applicable to suitability for industrialized production.
Above technical characterictic has formed embodiments of the invention, and it has stronger adaptability and implementation result, can increase and decrease according to actual needs non-essential technical characterictic, meets the demand of different situations.
Claims (10)
1. a poly butylene succinate degradable films matrix material, is characterized in that containing by weight 50 parts to 90 parts of poly butylene succinates, 10 parts to 50 parts of poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol esters, 10 parts to 50 parts of fillers, 5 parts to 25 parts of lubricants; This poly butylene succinate degradable films obtains in the steps below with matrix material: the first step is dry 8 h to 20h at 60 DEG C to 100 DEG C by the poly butylene succinate of aequum and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester in temperature; Second step, filler and the lubricant of dried poly butylene succinate, dried poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, aequum are mixed, mixed poly butylene succinate, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, filler and lubricant are added in twin screw extruder, carry out blending extrusion, cooling, pelletizing obtains poly butylene succinate degradable films matrix material; Wherein: filler is micron order calcium carbonate or W-Gum, the particle diameter of calcium carbonate is 2000 order to 10000 orders, and the particle diameter of W-Gum is 800 order to 1000 orders.
2. poly butylene succinate degradable films matrix material according to claim 1, is characterized in that lubricant is that fatty acid amide series lubricant agent is or/and hydro carbons lubricant.
3. poly butylene succinate degradable films matrix material according to claim 1 and 2, is characterized in that poly butylene succinate is that 150 DEG C, the pressure melt flow rate (MFR) while being 2.16kg is 8g/10min to 12g/10min in temperature.
4. poly butylene succinate degradable films matrix material according to claim 1 and 2, is characterized in that poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester is that 190 DEG C, the pressure melt flow rate (MFR) while being 2.16kg is 3g/10min to 8g/10min in temperature.
5. poly butylene succinate degradable films matrix material according to claim 3, is characterized in that poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester is that 190 DEG C, the pressure melt flow rate (MFR) while being 2.16kg is 3g/10min to 8g/10min in temperature.
6.
a kind ofpreparation method according to the poly butylene succinate degradable films described in claim 1 or 2 or 3 or 4 or 5 with matrix material, it is characterized in that carrying out in the steps below: the first step is dry 8 h to 20h at 60 DEG C to 100 DEG C by the poly butylene succinate of aequum and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester in temperature; Second step, filler and the lubricant of dried poly butylene succinate, dried poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, aequum are mixed, mixed poly butylene succinate, poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, filler and lubricant are added in twin screw extruder, carry out blending extrusion, cooling, pelletizing obtains poly butylene succinate degradable films matrix material.
7. the preparation method of matrix material for poly butylene succinate degradable films according to claim 6, the rotating speed that it is characterized in that twin screw extruder is 50r/min to 150r/min.
8. the preparation method with matrix material according to the poly butylene succinate degradable films described in claim 6 or 7, is characterized in that the barrel of twin screw extruder and the temperature of extrusion neck ring mold are 105 DEG C to 155 DEG C.
9. the preparation method with matrix material according to the poly butylene succinate degradable films described in claim 6 or 7, the rotating speed that it is characterized in that dicing machine is 150 r/min to 300 r/min.
10. the preparation method of matrix material for poly butylene succinate degradable films according to claim 8, the rotating speed that it is characterized in that dicing machine is 150 r/min to 300 r/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104109360B (en) * | 2014-06-24 | 2016-01-27 | 安徽精良美瑞塑膜科技股份有限公司 | A kind of quick and complete degradative plastic film and preparation method thereof |
| CN111117173B (en) * | 2019-12-30 | 2022-03-15 | 广东丹青印务有限公司 | Environment-friendly beverage packaging bag and processing technology thereof |
| CN111732820A (en) * | 2020-07-13 | 2020-10-02 | 滁州睿兴高分子材料有限公司 | Degradable thermoplastic elastomer composite material and preparation method thereof |
| CN112251002A (en) * | 2020-09-11 | 2021-01-22 | 新疆蓝山屯河降解材料有限公司 | PBS (Poly Butylene succinate) degradable packaging material with excellent toughness and temperature resistance and preparation method thereof |
| CN112708248A (en) * | 2020-12-30 | 2021-04-27 | 大连大富塑料彩印有限公司 | Paper-based degradable packaging film |
| CN113025008B (en) * | 2021-03-19 | 2023-05-16 | 厦门峰百塑胶有限公司 | Wear-resistant plastic bag and preparation method thereof |
| CN115197542A (en) * | 2021-04-12 | 2022-10-18 | 陆平林 | Preparation method of high-melt-index degradable material |
| CN113354928B (en) * | 2021-06-29 | 2022-02-15 | 浙江中邦塑胶股份有限公司 | Biological plastic for manufacturing degradable film and preparation method thereof |
| CN114456551A (en) * | 2021-12-21 | 2022-05-10 | 吴国辉 | Composite NIO and poly (butylene succinate) degradable film and manufacturing method thereof |
| CN115819880A (en) * | 2022-09-15 | 2023-03-21 | 上海普利特复合材料股份有限公司 | PP/PBS (polypropylene/polybutylene succinate) degradable film for poultry breeding and preparation method thereof |
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| CN102516723A (en) * | 2011-12-12 | 2012-06-27 | 金发科技股份有限公司 | Filling masterbatch used in biodegradable plastic, and preparation method thereof |
| CN102675839A (en) * | 2011-03-14 | 2012-09-19 | 美亚无纺布工业有限公司 | Biological degradable film and laminated material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102675839A (en) * | 2011-03-14 | 2012-09-19 | 美亚无纺布工业有限公司 | Biological degradable film and laminated material |
| CN102516723A (en) * | 2011-12-12 | 2012-06-27 | 金发科技股份有限公司 | Filling masterbatch used in biodegradable plastic, and preparation method thereof |
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Effective date of registration: 20170922 Address after: 831800 the Xinjiang Uygur Autonomous Region Hui Autonomous Prefecture of Qitai County Changji Lama Lake Industrial Park Lanshan Tun River Energy Co., Ltd. Patentee after: XINJIANG LANSHAN TUNHE ENERGY CO., LTD. Address before: 831100 No. 316 South Beijing Road, Changji Hui Autonomous Prefecture, the Xinjiang Uygur Autonomous Region, Changji Co-patentee before: Xinjiang general plastics High Performance Engineering Technology Research Center (Co., Ltd.) Patentee before: Xinjiang Blue Ridge Tunhe Chemical Industry Co., Ltd. |