CN103965516A - Fully biodegradable masterbatch and preparation method thereof - Google Patents
Fully biodegradable masterbatch and preparation method thereof Download PDFInfo
- Publication number
- CN103965516A CN103965516A CN201310042024.9A CN201310042024A CN103965516A CN 103965516 A CN103965516 A CN 103965516A CN 201310042024 A CN201310042024 A CN 201310042024A CN 103965516 A CN103965516 A CN 103965516A
- Authority
- CN
- China
- Prior art keywords
- parts
- starch
- master batch
- district
- complete biodegradable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Belonging to the technical field of high polymer materials, the invention relates to a fully biodegradable masterbatch and a preparation method thereof. The fully biodegradable masterbatch is prepared from the following components by weight: 70-95 parts of starch, 5-30 parts of PBAT, 30-50 parts of a plasticizer, 0.5-3 parts of a compatilizer, 0.05-2 parts of an initiator, 0.5-5 parts of a hydrophobic modifier, 0.1-0.6 part of a lubricant, 0.1-0.5 part of an antioxidant, and 0-20 parts of a packing. The fully biodegradable masterbatch provided by the invention not only has good thermoplasticity, good processability, and good dispersion effect in a polymer matrix, but also has low water absorption capacity, can ensure the mechanical properties of materials during long-term storage, and can greatly reduce the preparation cost of blends after being added into biodegradable polyester.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of complete biodegradable master batch and preparation method thereof.
Background technology
The use of plastics film has been penetrated into the every field of people's life, is widely used as food product pack, electric equipment products packaging and market shopping bag, refuse bag etc.Traditional plastic film material, if the starting material of polypropylene (PP) film, polyethylene (PE) film etc. are oil, uses and is discarded into hard degradation in nature, has caused huge harm to environment.Be accompanied by the day by day exhausted and continuous enhancing of people to environmental consciousness of petroleum resources, the environmentally friendly macromolecular material of exploitation degradable is applied to thin-film material field has become following Developing mainstream.
Poly(lactic acid) (PLA), poly butylene succinate (PBS), poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester (PBAT), PHA (PHA) etc. can both complete biodegradables, after using, be discarded in the Nature, can degradable be water and carbonic acid gas under the effect of microorganism.Therefore, can be widely used in plastics film field, the pollution that the use of minimizing conventional films brings environment.But above these biodegradable material prices are higher, the film being prepared into compared with traditional in price competitive power very weak.
Starch is extensively present in the middle of natural plant, and aboundresources and cheap is simultaneously biodegradable.So, starch is added in above-mentioned Biodegradable polyester, the blend of preparation not only can be realized complete biodegradable, but also can reduce the preparation cost of blend, increases its market competitiveness.
Starch add a kind of method in high molecular weight polyesters be by starch and softening agent, various processing aid directly with polyester after high-speed mixer and mixing is even, add extruding pelletization in screw machine to obtain blend, as described in patent CN1315927.Because undressed starch thermoplastic is poor, be difficult to processing, when therefore starch adds, all need to add softening agent to carry out plasticising processing to it, to improve the processing characteristics of starch.But above-mentioned working method, because the polyester that has a large amount of high molecular exists, easily makes starch plasticizing uneven, causes its dispersed variation in polyester.For improving the workability of starch and the dispersiveness in polyester, starch can be prepared into thermoplastic starch master batch, and then extrude with the polyester blend of high molecular the blend that obtains complete biodegradable.Therefore, the quality of thermoplastic starch master batch performance is very large to the blend performance impact of final preparation.The water-absorbent that topmost problem is exactly starch is large, and in order to improve the plasticity of starch, the polyalcohols softening agent adding makes the thermoplastic starch water-absorbent of preparation larger, and this can make the mechanical property of amyloid Biodegradable polyester blend can decline along with the prolongation in storage time obviously.Patent CN101328285 and patent CN101225117 have adopted two kinds of monomers with reactive terminal group and hydrophobic alkyl chain and starch storage crop to carry out hydrophobization processing, can reduce significantly the water-intake rate of treated starch, but the starch plasticity obtaining is poor.
Summary of the invention
The object of the invention is that the defect for overcoming prior art provides a kind of complete biodegradable master batch and preparation method thereof.
For achieving the above object, the present invention is by the following technical solutions:
A kind of complete biodegradable master batch, made by the component that comprises following weight part:
Described starch is one or more in potato starch, W-Gum, tapioca (flour) or wheat starch.
The weight-average molecular weight of described poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester (PBAT) is 20000-130000, obtains taking terephthalic acid or dimethyl terephthalate (DMT), butyleneglycol, hexanodioic acid as polymerizable raw material.
Described softening agent is one or more in ethylene glycol, propylene glycol, glycerol, sorbyl alcohol, urea, methane amide or ethanamide.
Described compatilizer is one or more in maleic anhydride, maleic anhydride grafted ethene-octene copolymer (POE-g-MAH).
Described initiator is one or more in dicumyl peroxide (DCP) or benzoyl peroxide (BPO).
Described hydrophobically modified agent is the monomer with long-chain fat hydrocarbon and reactive functionality, more preferably one or more in enetutanedioic acid anhydride and alkyl ketene dimer.
Described lubricant is one or more in stearic acid, calcium stearate, amine hydroxybenzene, erucicamide, paraffin, polyethylene wax.
Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] one or more in pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol acid esters, 2-methylene-bis (4-methyl-6-tert-butylphenol) or three (2.4-di-tert-butyl-phenyl) phosphorous acid ester.
Described filler is one or more in calcium carbonate, kaolin, silicon-dioxide, mica, polynite, clay, titanium dioxide, talcum powder etc., preferably 1250 order-8000 orders of particle diameter, further preferred 2000-3000 order.
A preparation method for above-mentioned complete biodegradable master batch, comprises the steps:
(1) starch, poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester (PBAT), filler are carried out to drying treatment;
(2) take each component raw material of following weight part by said ratio: starch 70-95 part, PBAT5-30 part, softening agent 30-50 part, compatilizer 0.5-3 part, initiator 0.05-2 part, hydrophobically modified agent 0.5-5 part, lubricant 0.1-0.6 part, oxidation inhibitor 0.1-0.5 part, filler 0-20 part; Above-mentioned raw materials is even in high-speed mixer and mixing;
(3) raw material step (2) being mixed joins melt blending in twin screw extruder, extrudes, tie rod, granulation;
In described step (1), starch, PBAT, drying temperature are 60-80 DEG C, and be 6-24h time of drying; The drying temperature of filler is 100-120 DEG C, and the time is 5-10h; Drying plant is vacuum drying oven or convection oven.
In described step (3), twin screw extruder is in the same way or out-phase twin screw extruder, and extrusion temperature is 90-160 DEG C, screw speed 60-300rpm, and screw slenderness ratio L/D is 40-50:1.
The present invention has following beneficial effect:
Complete biodegradable master batch provided by the present invention not only has good thermoplasticity, good processability, and in polymeric matrix, dispersion effect is good, and water absorbing properties is low, can ensure the mechanical property of material in long-time storage process; Can greatly reduce the preparation cost of blend for adding Biodegradable polyester to.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Mechanics Performance Testing: tensile property testing standard is ASTM D638, draw speed 50mm/min.
Water-absorbent testing standard: GB/T1034-2008, batten is placed 2h in 23 DEG C of waters bath with thermostatic control.Wherein, in the following example, the weight-average molecular weight of poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester is 20000-130000.
Embodiment 1
(1) by W-Gum, PBAT(weight-average molecular weight 12.5 ten thousand) drying treatment 6h in 80 DEG C of convection oven, titanium dioxide (2000 order) drying treatment 5h in 105 DEG C of convection oven.
(2) then 90 parts of extracting corn starch, PBAT10 part, 40 parts of softening agent glycerol, 0.5 part of compatilizer maleic anhydride, 0.05 part of initiator DCP, 0.5 part of hydrophobically modified agent enetutanedioic acid anhydride, 0.2 part of lubricant stearic acid calcium, oxidation inhibitor are four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.2 part of pentaerythritol ester, 5 parts of normal temperature mixing 10min in high mixer of filler titanium dioxide.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 200rpm, length-to-diameter ratio 40/1.
Embodiment 2
(1) by W-Gum, PBAT(weight-average molecular weight 2.8 ten thousand) drying treatment 24h in 60 DEG C of convection oven, calcium carbonate (2500 order) drying treatment 8h in 105 DEG C of convection oven.
(2) then 70 parts of extracting corn starch, PBAT30 part, 20 parts of softening agent glycerol, 10 parts of softening agent methane amides, compatilizer POE-g-MAH1.5 part, initiator B PO1 part, 2 parts of alkyl ketene dimers, 0.5 part of erucicamide, 0.4 part of three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, 10 parts of normal temperature mixing 10min in high mixer of calcium carbonate.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 250rpm, length-to-diameter ratio 40/1.
Embodiment 3
(1) by W-Gum, PBAT(weight-average molecular weight 100,000) drying treatment 10h in 80 DEG C of convection oven, talcum powder (3000 order) drying treatment 10h in 105 DEG C of convection oven.
(2) then 80 parts of extracting corn starch, PBAT20 part, 20 parts of softening agent glycerol, 10 parts, softening agent urea, POE-g-MAH3 part, BPO1.5 part, 4 parts of alkyl ketene dimers, 0.6 part of polyethylene wax, 0.5 part of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol acid esters, 2 parts of normal temperature mixing 10min in high mixer of talcum powder.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 250rpm, length-to-diameter ratio 40/1.
Embodiment 4
(1) by W-Gum, PBAT(weight-average molecular weight 12.5 ten thousand) drying treatment 10h in 80 DEG C of convection oven, talcum powder (3000 order) drying treatment 10h in 105 DEG C of convection oven.
(2) then 80 parts of extracting corn starch, PBAT20 part, 40 parts of glycerol, 10 parts of sorbyl alcohols, POE-g-MAH3 part, BPO1.5 part, 5 parts of alkyl ketene dimers, 0.6 part, paraffin, 0.5 part of 2-methylene-bis (4-methyl-6-tert-butylphenol), 2 parts of normal temperature mixing 10min in high mixer of talcum powder.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 250rpm, length-to-diameter ratio 40/1.
Embodiment 5
(1) by W-Gum, PBAT(weight-average molecular weight 12.5 ten thousand) drying treatment 10h in 80 DEG C of convection oven, talcum powder (1250 order) drying treatment 10h in 105 DEG C of convection oven.
(2) then 75 parts of extracting corn starch, PBAT25 part, 25 parts of glycerol, 5 parts of ethanamides, 2 parts of maleic anhydrides, DCP1.5 part, 1 part of enetutanedioic acid anhydride, 0.3 part of stearic acid, 0.5 part of 2-methylene-bis (4-methyl-6-tert-butylphenol), 20 parts of normal temperature mixing 10min in high mixer of talcum powder.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 300rpm, length-to-diameter ratio 40/1.
Comparative example 1
(1) by W-Gum, PBAT(weight-average molecular weight 12.5 ten thousand) drying treatment 10h in 80 DEG C of convection oven.
(2) then 75 parts of extracting corn starch, PBAT25 part, 25 parts of glycerol, 5 parts of ethanamides, 2 parts of maleic anhydrides, DCP1.5 part, 0.3 part of stearic acid, 0.5 part of normal temperature mixing 10min in high mixer of 2-methylene-bis (4-methyl-6-tert-butylphenol).
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 300rpm, length-to-diameter ratio 40/1.Each embodiment material property is as table 1
Embodiment 6
(1) by potato starch, PBAT(weight-average molecular weight 20,000) drying treatment 24h in 60 DEG C of convection oven, kaolin (1250 order) drying treatment 5h in 120 DEG C of convection oven.
(2) then get 95 parts of potato starches, PBAT5 part, 25 parts of glycerol, 10 parts of propylene glycol, 1 part of maleic anhydride, DCP2 part, 3 parts of enetutanedioic acid anhydrides, 0.1 part of amine hydroxybenzene, 0.1 part of three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, 15 parts of normal temperature mixing 10min in high mixer of kaolin.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 300rpm, length-to-diameter ratio 50/1.
Embodiment 7
(1) by wheat starch, PBAT(weight-average molecular weight 60,000) drying treatment 18h in 70 DEG C of convection oven, silicon-dioxide (4000 order) drying treatment 7h in 110 DEG C of convection oven.
(2) then get 85 parts of wheat starches, PBAT15 part, 25 parts of glycerol, 20 parts of ethylene glycol, 2.5 parts of maleic anhydrides, DCP0.5 part, 5 parts of enetutanedioic acid anhydrides, 0.4 part of amine hydroxybenzene, 0.3 part of three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, 8 parts of normal temperature mixing 10min in high mixer of silicon-dioxide.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 300rpm, length-to-diameter ratio 50/1
As can be seen from Table 1, master batch after modification not only has good mechanical property and good kindliness, and water-intake rate declines greatly, can be directly used in and prepare the consumer's goods such as wrapping material and disposable tableware with composition prepared by this master batch and polyester blend, to reduce environmental pollution.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various amendments to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from improvement and the amendment that category of the present invention makes all should be within protection scope of the present invention.
Claims (10)
1. a complete biodegradable master batch, is characterized in that: be made up of the component that comprises following weight part:
2. complete biodegradable master batch according to claim 1, is characterized in that: described starch is one or more in potato starch, W-Gum, tapioca (flour) or wheat starch.
3. complete biodegradable master batch according to claim 1, is characterized in that: the weight-average molecular weight of described poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester is 20000-130000.
4. complete biodegradable master batch according to claim 1, is characterized in that: described softening agent is one or more in ethylene glycol, propylene glycol, glycerol, sorbyl alcohol, urea, methane amide or ethanamide.
5. complete biodegradable master batch according to claim 1, is characterized in that: described compatilizer is one or more in maleic anhydride, maleic anhydride grafted ethene-octene copolymer.
6. complete biodegradable master batch according to claim 1, is characterized in that: described initiator is one or more in dicumyl peroxide or benzoyl peroxide;
Or described hydrophobically modified agent is the monomer with long-chain fat hydrocarbon and reactive functionality, more preferably one or more in enetutanedioic acid anhydride and alkyl ketene dimer.
7. complete biodegradable master batch according to claim 1, is characterized in that: described lubricant is one or more in stearic acid, calcium stearate, amine hydroxybenzene, erucicamide, paraffin or polyethylene wax.
8. complete biodegradable master batch according to claim 1, it is characterized in that: described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] one or more in pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol acid esters, 2-methylene-bis (4-methyl-6-tert-butylphenol) or three (2.4-di-tert-butyl-phenyl) phosphorous acid ester;
Or described filler is one or more in calcium carbonate, kaolin, silicon-dioxide, mica, polynite, clay, titanium dioxide, talcum powder etc., preferably 1250 order-8000 orders of particle diameter, further preferred 2000-3000 order.
9. a preparation method for arbitrary described complete biodegradable master batch in claim 1-8, is characterized in that: comprise the steps:
(1) starch, poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester, filler are carried out to drying treatment;
(2) take each component raw material of following weight part by said ratio: starch 70-95 part, poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester 5-30 part, softening agent 30-50 part, compatilizer 0.5-3 part, initiator 0.05-2 part, hydrophobically modified agent 0.5-5 part, lubricant 0.1-0.6 part, oxidation inhibitor 0.1-0.5 part, filler 0-20 part; Above-mentioned raw materials is even in high-speed mixer and mixing;
(3) raw material step (2) being mixed joins melt blending in twin screw extruder, extrudes, tie rod, granulation.
10. preparation method according to claim 9, is characterized in that: in described step (1), starch, poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester, drying temperature are 60-80 DEG C, and be 6-24h time of drying; The drying temperature of filler is 100-120 DEG C, and the time is 5-10h; Drying plant is vacuum drying oven or convection oven;
Or twin screw extruder is in the same way or out-phase twin screw extruder in described step (3), extrusion temperature is 90-160 DEG C, screw speed 60-300rpm, and screw slenderness ratio L/D is 40-50:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310042024.9A CN103965516A (en) | 2013-02-01 | 2013-02-01 | Fully biodegradable masterbatch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310042024.9A CN103965516A (en) | 2013-02-01 | 2013-02-01 | Fully biodegradable masterbatch and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103965516A true CN103965516A (en) | 2014-08-06 |
Family
ID=51235548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310042024.9A Pending CN103965516A (en) | 2013-02-01 | 2013-02-01 | Fully biodegradable masterbatch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965516A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818954A (en) * | 2018-08-10 | 2020-02-21 | 绿世界环保材料科技股份有限公司 | Hydrophobic thermoplastic starch composite material and manufacturing method thereof |
| CN111808325A (en) * | 2019-04-12 | 2020-10-23 | 北京一撕得物流技术有限公司 | Application of starch master batch composition in preparation of bio-based environment-friendly degradable material |
| CN111808329A (en) * | 2019-04-12 | 2020-10-23 | 北京一撕得物流技术有限公司 | Application of starch master batch composition in preparation of environment-friendly degradable material and/or product |
| CN111808324A (en) * | 2019-04-12 | 2020-10-23 | 北京一撕得物流技术有限公司 | Application of starch masterbatch in preparation of bio-based environment-friendly degradable material |
| CN112358657A (en) * | 2020-11-26 | 2021-02-12 | 重庆和泰润佳股份有限公司 | Non-air-permeable biodegradable film and preparation method thereof |
| CN112745647A (en) * | 2020-12-30 | 2021-05-04 | 重庆和泰润佳股份有限公司 | Non-breathable biodegradable resin and preparation method thereof |
| CN113136054A (en) * | 2021-03-25 | 2021-07-20 | 广东工业大学 | Starch/polylactic acid composite material and preparation method and application thereof |
| CN113174069A (en) * | 2021-05-25 | 2021-07-27 | 广州睿安材料科技有限公司 | Biomass functional master batch and preparation method and application thereof |
| CN113925201A (en) * | 2021-10-26 | 2022-01-14 | 湖北中烟工业有限责任公司 | High-filtration low-suction-resistance degradable cigarette filter tip and preparation method thereof |
| CN114292463A (en) * | 2022-01-21 | 2022-04-08 | 江苏富氧岛新材料有限公司 | Calcium carbonate master batch and production process thereof |
| CN114573958A (en) * | 2022-03-28 | 2022-06-03 | 广东省科学院生物与医学工程研究所 | Elastomer and epoxy micromolecule synergistic toughening-reinforcing modified plant fiber-based biodegradable composite material and preparation method thereof |
| CN114685951A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Natural starch-based fully biodegradable polyester and preparation method thereof |
| CN114687066A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Degradable oil absorption material and preparation method thereof |
| CN116925510A (en) * | 2023-09-12 | 2023-10-24 | 寿光金远东变性淀粉有限公司 | Preparation method of fully-degradable starch-based material for membrane bags |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597752A (en) * | 2004-08-23 | 2005-03-23 | 成都新柯力化工科技有限公司 | Biodegradation starch resin masterbatch |
| CN1778833A (en) * | 2004-11-18 | 2006-05-31 | 成都新柯力化工科技有限公司 | Biological-degradable starch/polyester plastic completely and production thereof |
| WO2007147428A1 (en) * | 2006-06-23 | 2007-12-27 | Swetree Technologies Ab | Copolymer, modified polymer carbohydrate material, modified bulk polymer, composite material, and methods of preparation |
| CN101235164A (en) * | 2008-03-10 | 2008-08-06 | 福建百事达生物材料有限公司 | Special-purpose material for whole biological degradation footwear material and preparation method thereof |
| CN101240086A (en) * | 2008-03-14 | 2008-08-13 | 上海悦仕生物材料有限公司 | Total-biodegradation plastic film and preparation method thereof |
| CN101353400A (en) * | 2008-09-11 | 2009-01-28 | 四川大学 | Preparation of biodegradable thermoplastic starch plastic having high starch content |
| CN101516996A (en) * | 2006-07-28 | 2009-08-26 | 比澳格（香港）有限公司 | Masterbatch and polymer composition |
| CN102321249A (en) * | 2011-06-30 | 2012-01-18 | 无锡碧杰生物材料科技有限公司 | Thermoplastic starch (TPS), biodegradable polyester/starch composite material and preparation thereof |
| CN102702580A (en) * | 2012-07-06 | 2012-10-03 | 西南科技大学 | Full-biodegradable starch-base in-situ fiber reinforced composite material and preparation method thereof |
-
2013
- 2013-02-01 CN CN201310042024.9A patent/CN103965516A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597752A (en) * | 2004-08-23 | 2005-03-23 | 成都新柯力化工科技有限公司 | Biodegradation starch resin masterbatch |
| CN1778833A (en) * | 2004-11-18 | 2006-05-31 | 成都新柯力化工科技有限公司 | Biological-degradable starch/polyester plastic completely and production thereof |
| WO2007147428A1 (en) * | 2006-06-23 | 2007-12-27 | Swetree Technologies Ab | Copolymer, modified polymer carbohydrate material, modified bulk polymer, composite material, and methods of preparation |
| CN101516996A (en) * | 2006-07-28 | 2009-08-26 | 比澳格（香港）有限公司 | Masterbatch and polymer composition |
| CN101235164A (en) * | 2008-03-10 | 2008-08-06 | 福建百事达生物材料有限公司 | Special-purpose material for whole biological degradation footwear material and preparation method thereof |
| CN101240086A (en) * | 2008-03-14 | 2008-08-13 | 上海悦仕生物材料有限公司 | Total-biodegradation plastic film and preparation method thereof |
| CN101353400A (en) * | 2008-09-11 | 2009-01-28 | 四川大学 | Preparation of biodegradable thermoplastic starch plastic having high starch content |
| CN102321249A (en) * | 2011-06-30 | 2012-01-18 | 无锡碧杰生物材料科技有限公司 | Thermoplastic starch (TPS), biodegradable polyester/starch composite material and preparation thereof |
| CN102702580A (en) * | 2012-07-06 | 2012-10-03 | 西南科技大学 | Full-biodegradable starch-base in-situ fiber reinforced composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 何小维等: "《淀粉基生物降解材料》", 31 January 2008, 中国轻工业出版社 * |
| 唐皞等: ""增塑剂在热塑性淀粉中的应用研究进展"", 《塑料工业》 * |
| 蒋平平等: "《环保增塑剂》", 31 October 2009, 国防工业出版社 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818954A (en) * | 2018-08-10 | 2020-02-21 | 绿世界环保材料科技股份有限公司 | Hydrophobic thermoplastic starch composite material and manufacturing method thereof |
| CN111808325A (en) * | 2019-04-12 | 2020-10-23 | 北京一撕得物流技术有限公司 | Application of starch master batch composition in preparation of bio-based environment-friendly degradable material |
| CN111808329A (en) * | 2019-04-12 | 2020-10-23 | 北京一撕得物流技术有限公司 | Application of starch master batch composition in preparation of environment-friendly degradable material and/or product |
| CN111808324A (en) * | 2019-04-12 | 2020-10-23 | 北京一撕得物流技术有限公司 | Application of starch masterbatch in preparation of bio-based environment-friendly degradable material |
| CN112358657A (en) * | 2020-11-26 | 2021-02-12 | 重庆和泰润佳股份有限公司 | Non-air-permeable biodegradable film and preparation method thereof |
| CN112745647A (en) * | 2020-12-30 | 2021-05-04 | 重庆和泰润佳股份有限公司 | Non-breathable biodegradable resin and preparation method thereof |
| CN114687066A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Degradable oil absorption material and preparation method thereof |
| CN114685951A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Natural starch-based fully biodegradable polyester and preparation method thereof |
| CN113136054A (en) * | 2021-03-25 | 2021-07-20 | 广东工业大学 | Starch/polylactic acid composite material and preparation method and application thereof |
| CN113174069A (en) * | 2021-05-25 | 2021-07-27 | 广州睿安材料科技有限公司 | Biomass functional master batch and preparation method and application thereof |
| CN113174069B (en) * | 2021-05-25 | 2022-11-22 | 广州睿安材料科技有限公司 | Biomass functional master batch and preparation method and application thereof |
| CN113925201A (en) * | 2021-10-26 | 2022-01-14 | 湖北中烟工业有限责任公司 | High-filtration low-suction-resistance degradable cigarette filter tip and preparation method thereof |
| CN114292463A (en) * | 2022-01-21 | 2022-04-08 | 江苏富氧岛新材料有限公司 | Calcium carbonate master batch and production process thereof |
| CN114573958A (en) * | 2022-03-28 | 2022-06-03 | 广东省科学院生物与医学工程研究所 | Elastomer and epoxy micromolecule synergistic toughening-reinforcing modified plant fiber-based biodegradable composite material and preparation method thereof |
| CN116925510A (en) * | 2023-09-12 | 2023-10-24 | 寿光金远东变性淀粉有限公司 | Preparation method of fully-degradable starch-based material for membrane bags |
| CN116925510B (en) * | 2023-09-12 | 2023-12-29 | 寿光金远东变性淀粉有限公司 | Preparation method of fully-degradable starch-based material for membrane bags |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103965516A (en) | Fully biodegradable masterbatch and preparation method thereof | |
| CN104119647A (en) | High-starch full biodegradable composition and preparation method thereof | |
| CN103992517B (en) | One can be continuously produced fully-degradable starch base plastic alloy and preparation method thereof | |
| CN103627153A (en) | Entire biodegradation PLA/PBAT composite material and preparing method therefor | |
| CN103265798B (en) | Poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof | |
| CN108822514B (en) | Completely biodegradable polylactic acid based blown film and preparation method thereof | |
| US10759911B2 (en) | Thermoplastic starch composition derivatives from agricultural byproducts | |
| CN103319865B (en) | Polylactic acid alloy film and application | |
| CN102634073B (en) | Starch/polypropylene degradable composite material and preparation method thereof | |
| CN103694646A (en) | Polyester/thermoplastic starch biodegradable composition and preparation method thereof | |
| CN103205021A (en) | Thermoplastic and PBAT blend and preparation method thereof | |
| US5654353A (en) | Biodegradable composition, a process for preparing the same and the use thereof | |
| KR101525658B1 (en) | Composition for biomass film using food byproduct of wheat bran or soybean hull and biomass film using thereof | |
| CN103589124A (en) | Fully-biodegradable PLA/PBAT composite film and making method thereof | |
| CN104312121B (en) | Transparent polylactic acid film of high tenacity and preparation method thereof | |
| CN104059342A (en) | Inorganic-filling material full-biodegradation composite material with high compatibility and preparation method thereof | |
| CN101353400A (en) | Preparation of biodegradable thermoplastic starch plastic having high starch content | |
| CN108929527B (en) | PBAT/modified starch full-biodegradable film with high ductility and high barrier property as well as preparation method and application thereof | |
| WO2014032393A1 (en) | Fully biodegradable material and preparation method thereof | |
| CN102653601A (en) | Preparation method of completely biodegradable plastic resin and film products thereof | |
| CN103589125B (en) | A kind of Polylactic acid/polypropylene blend and preparation method thereof | |
| CN103450648A (en) | Biodegradable polylactic acid/starch compound material and preparation method thereof | |
| CN111978691B (en) | Biodegradable mulching film and preparation method thereof | |
| CN103160012A (en) | Oxygen-separating and degradable thin plastic film | |
| CN103897260A (en) | Blended composition of ethylene-ethylene vinyl-acetate copolymer (EVA) and polylactic acid (PLA) and molding product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140806 |