CN103013065A - 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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- CN103013065A CN103013065A CN2012105401184A CN201210540118A CN103013065A CN 103013065 A CN103013065 A CN 103013065A CN 2012105401184 A CN2012105401184 A CN 2012105401184A CN 201210540118 A CN201210540118 A CN 201210540118A CN 103013065 A CN103013065 A CN 103013065A
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- butylene succinate
- poly butylene
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- phenenyl
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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
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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
- B29C2948/92885—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
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 the film technical field of composite materials, is a kind of poly butylene succinate degradable films matrix material and preparation method thereof.
Background technology
As a kind of widely used product, 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.Polymer thin-film material commonly used has PVC, LDPE, HDPE, metallocene PE, PP, PS, EVA, PET, PA, PC, EVOH, F4, reaches 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, and is 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, and existing polymer thin-film material in use can produce white pollution, production cost is high and the problem 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, contain 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, with poly butylene succinate and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester dry 8 h to 20h under temperature is 60 ℃ to 100 ℃ of aequum; 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 carry out blending extrusion, cooling, pelletizing in the twin screw extruder and obtain poly butylene succinate degradable films matrix material.
The below is the further optimization and/or improvements to one of foregoing invention technical scheme:
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 the fatty acid amide series lubricant agent is or/and the hydro carbons lubricant.
Above-mentioned poly butylene succinate is 150 ℃ in temperature, the melt flow rate (MFR) when pressure is 2.16kg is 8g/10min to 12g/10min.
Above-mentioned poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester is 190 ℃ in temperature, the melt flow rate (MFR) when pressure is 2.16kg is 3g/10min to 8g/10min.
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 ℃ to 155 ℃.
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: a kind of poly butylene succinate degradable films composite manufacture method, carry out in the steps below: the first step, with poly butylene succinate and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester dry 8 h to 20h under temperature is 60 ℃ to 100 ℃ of aequum; 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 carry out blending extrusion, cooling, pelletizing in the twin screw extruder and obtain poly butylene succinate degradable films matrix material.
The below is two further optimization and/or improvements to the foregoing invention technical scheme:
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 ℃ to 155 ℃.
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 the fatty acid amide series lubricant agent is or/and the hydro carbons lubricant.
Above-mentioned poly butylene succinate is 150 ℃ in temperature, the melt flow rate (MFR) when pressure is 2.16kg is 8g/10min to 12g/10min.
Above-mentioned poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester is 190 ℃ in temperature, the melt flow rate (MFR) when pressure is 2.16kg is 3g/10min to 8g/10min.
The present invention obtains after by the granulation of twin screw extruder melt blending by dried poly butylene succinate, dried poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester, filler and mix lubricant; 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 characteristics, has reduced production cost, has reached environmental requirement.
Embodiment
The present invention is not subjected to the restriction of following embodiment, can determine concrete embodiment according to technical scheme of the present invention and practical situation.
The invention will be further described below in conjunction with embodiment:
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, are micron order calcium carbonate or W-Gum as the filler of the optimization of above-described embodiment: embodiment 3.Calcium carbonate is the inorganic mineral powder material that a kind of use is the most extensive, consumption is maximum, and it is abundant, cheap that it has the 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, are 2000 order to 10000 orders as the particle diameter of the calcium carbonate of the optimization of above-described embodiment: embodiment 4; Or/and the particle diameter of W-Gum is 800 order to 1000 orders.
Embodiment 5, are that the fatty acid amide series lubricant agent is or/and the hydro carbons lubricant as the lubricant of the optimization of above-described embodiment: embodiment 5.
Embodiment 6, as the poly butylene succinate of the optimization of above-described embodiment: embodiment 6 be 150 ℃ in temperature, melt flow rate (MFR) when pressure is 2.16kg is 8g/10min to 12g/10min.
Embodiment 7, as poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester of the optimization of above-described embodiment: embodiment 7 be 190 ℃ in temperature, melt flow rate (MFR) when pressure is 2.16kg is 3 g/10min to 8g/10min.
Embodiment 8, the poly butylene succinate degradable films composite manufacture method of above-described embodiment 1 to embodiment 7, carry out in the steps below: the first step, with poly butylene succinate and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester dry 8 h to 20h under temperature is 40 ℃ to 100 ℃ of aequum; 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 carry out blending extrusion, cooling, pelletizing in the twin screw extruder and obtain poly butylene succinate degradable films matrix material.Poly butylene succinate (PBS), its fusing point are about 108 ° of C, but the toughness of poly butylene succinate (PBS) is bad, the 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 about 115 ° of C, easily processing, stronger toughness, entanglement, biodegradation rate are faster arranged, have 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 the change ratio degradation time of matrix material.
Embodiment 9, the poly butylene succinate degradable films composite manufacture method of above-described embodiment 1 to embodiment 7, carry out in the steps below: the first step is 40 ℃ or 100 ℃ of lower dry 8 h or 20h with 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 carry out blending extrusion, cooling, pelletizing in the twin screw extruder and obtain poly butylene succinate degradable films matrix material.
Embodiment 10, are 50 r/min to 150r/min as the rotating speed of the twin screw extruder of the optimization of above-described embodiment: embodiment 10.
Embodiment 11, are 105 ℃ to 155 ℃ as the barrel of the twin screw extruder of the optimization of above-described embodiment: embodiment 11 and the temperature of extrusion neck ring mold.
Embodiment 12, are 150 r/min to 300 r/min as the rotating speed of the dicing machine of the optimization of above-described embodiment: embodiment 12.
Above-described embodiment gained poly butylene succinate degradable films carries out extrusion-blown modling after being put in the convection oven oven dry with matrix material in inflation film manufacturing machine, obtain the thick sample film of the present invention of 20 μ m; 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) | Vertically | 13.02 to 14.93 | 12.5 |
| Tear strength (N/mm) | Laterally | 82.0 to 95.5 | 70 |
| Tear strength (N/mm) | Vertically | 83.7 to 96.7 | 70 |
| Elongation at break (%) | Laterally | 230.8 to 297.4 | 230 |
| Elongation at break (%) | Vertically | 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 all are better than the data among the GB GBT13735-1992; By table 1 experimental data as can be known, the laminated film that adopts the present invention to obtain, when 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 satisfy GB fully to the requirement of thin-film material, 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, such 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, compare 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, compare with biodegradable materials such as PBS, PCL, PBAT, when the parts by weight of the filler that adds among the present invention reach 10 to 50 parts, can effectively reduce material cost 20% to 50%, cost is low; Adopt the extruding pelletization method, technique is simple, is fit to suitability for industrialized production.
Above technical characterictic has consisted of embodiments of the invention, and it has stronger adaptability and implementation result, can increase and decrease according to actual needs non-essential technical characterictic, satisfies 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, with poly butylene succinate and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester dry 8 h to 20h under temperature is 60 ℃ to 100 ℃ of aequum; 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 carry out blending extrusion, cooling, pelletizing in the twin screw extruder and obtain poly butylene succinate degradable films matrix material.
2. poly butylene succinate degradable films matrix material according to claim 1 is characterized in that filler is micron order calcium carbonate or W-Gum.
3. poly butylene succinate degradable films matrix material according to claim 2, the particle diameter that it is characterized in that calcium carbonate is 2000 order to 10000 orders; Or/and the particle diameter of W-Gum is 800 order to 1000 orders.
4. according to claim 1 and 2 or 3 described poly butylene succinate degradable films matrix materials, it is characterized in that lubricant is that the fatty acid amide series lubricant agent is or/and the hydro carbons lubricant.
5. according to claim 1 and 2 or 3 or 4 described poly butylene succinate degradable films matrix materials, it is characterized in that poly butylene succinate is 150 ℃ in temperature, the melt flow rate (MFR) when pressure is 2.16kg is 8g/10min to 12g/10min.
6. according to claim 1 and 2 or 3 or 4 or 5 described poly butylene succinate degradable films matrix materials, it is characterized in that poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester is 190 ℃ in temperature, the melt flow rate (MFR) when pressure is 2.16kg is 3g/10min to 8g/10min.
7. it is characterized in that carrying out in the steps below: the first step, with poly butylene succinate and poly-hexanodioic acid-mutual-phenenyl two acid bromide two alcohol ester dry 8 h to 20h under temperature is 40 ℃ to 100 ℃ of aequum; 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 carry out blending extrusion, cooling, pelletizing in the twin screw extruder and obtain poly butylene succinate degradable films matrix material.
8. poly butylene succinate degradable films composite manufacture method according to claim 7, the rotating speed that it is characterized in that twin screw extruder is 50r/min to 150r/min.
9. according to claim 7 or 8 described poly butylene succinate degradable films composite manufacture methods, it is characterized in that the barrel of twin screw extruder and the temperature of extrusion neck ring mold are 105 ℃ to 155 ℃.
10. according to claim 7 or 8 or 9 described poly butylene succinate degradable films composite manufacture methods, the rotating speed that it is characterized in that dicing machine is 150 r/min to 300 r/min.
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Cited By (10)
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| CN104109360A (en) * | 2014-06-24 | 2014-10-22 | 安徽精良美瑞塑膜科技股份有限公司 | Rapidly and completely degraded mulch film and preparation method thereof |
| CN111117173A (en) * | 2019-12-30 | 2020-05-08 | 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 |
| CN113025008A (en) * | 2021-03-19 | 2021-06-25 | 厦门峰百塑胶有限公司 | Wear-resistant plastic bag 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 |
| CN115197542A (en) * | 2021-04-12 | 2022-10-18 | 陆平林 | Preparation method of high-melt-index degradable material |
| WO2023272569A1 (en) * | 2021-06-29 | 2023-01-05 | 浙江中邦塑胶股份有限公司 | Bioplastic for manufacturing degradable film, and preparation method therefor |
| 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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| 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 |
| CN104109360A (en) * | 2014-06-24 | 2014-10-22 | 安徽精良美瑞塑膜科技股份有限公司 | Rapidly and completely degraded mulch 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 |
| CN111117173A (en) * | 2019-12-30 | 2020-05-08 | 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 |
| CN113025008A (en) * | 2021-03-19 | 2021-06-25 | 厦门峰百塑胶有限公司 | Wear-resistant plastic bag and preparation method thereof |
| 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 |
| WO2023272569A1 (en) * | 2021-06-29 | 2023-01-05 | 浙江中邦塑胶股份有限公司 | Bioplastic for manufacturing degradable film, and preparation method therefor |
| CN114456551A (en) * | 2021-12-21 | 2022-05-10 | 吴国辉 | Composite NIO and poly (butylene succinate) degradable film and manufacturing 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. |