CN105038083A - Method for preparing PLA/PBAT/PPC composite modified material through reactive extrusion - Google Patents
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Abstract
The invention relates to a method for preparing a PLA/PBAT/PPC composite modified material through reactive extrusion. The composite modified material is characterized by comprising the following components in parts by weight: 5 to 35 parts of PLA, 30 to 55 parts of PBAT, and 5 to 15 parts of PPC; wherein by taking 100 parts by weight of PPC as the benchmark, the composite modified material comprises 0.5 to 2 parts of plasticizer; and by taking 100 parts by weight of PBAT, the composite modified material comprises 0.01 to 0.08 part of initiator, 0.01 to 0.05 part of catalyst, 1 to 3 parts of grafting monomer, and 0.5 to 1.5 parts of anti-aging aid. The provided composite modified material has a good obstructing performance and a complete biodegradation property, the price is low, and the composite material, which is prepared by mixing three materials, has excellent comprehensive performances. The composite material has the advantages of high PLA content, good biodegradable property, and excellent mechanical performance and comprehensive performance.
Description
Technical field
The present invention relates to a kind of method that Reaction extrusion prepares PLA/PBAT/PPC composite modification material, belong to a kind of polymer blend of modification.
Background technology
Current China most area meets with haze weather and wreaks havoc, and brings have a strong impact on to the health of people, traffic safety etc.Along with petroleum based material consumption increases increasingly, the amount of carbon dioxide of conventional plastic discharge is also in sustainable growth.Therefore, there is environmental protection, trend that bio-based materials that is renewable and low-carbon (LC) feature becomes future development, an environmental protection will be caused to change.
In recent years, have poly(lactic acid) (PLA) Materials that is renewable, low-carbon (LC) rapid, output increases year by year.But PLA material hardness is comparatively large, easily embrittlement, thermo-labile, price is higher, thus in use range, is subject to a definite limitation; And poly-hexanodioic acid/butylene terephthalate (PBAT) material type is like polyethylene character, material is softer, good film-forming property, but expensive; Poly (propylene carbonate) (PPC) is carbonic acid gas sill, by collecting exhaust carbon dioxide through purifying, be prepared from Polymerization of Propylene Oxide again, there is good film-forming properties and excellent resistance oxygen, block-water performance and biological degradability, but second-order transition temperature is lower, store transport inconvenience.Therefore, after blended for ternary bio-based materials, fill up respective Biopolvester and be used alone and there is more or less defect, can rational allocation ternary material component according to product requirement.But at present in patent all to ternary material physical blending, or prepared by the mode such as adding portion compatilizer, and all materials performance is not high, limits materials application and development.
Summary of the invention
A kind of Reaction extrusion is the object of the present invention is to provide to prepare the method for PLA/PBAT/PPC composite modification material, its blending and modifying is a kind of very economical effective polymer composite modified method, PBAT has long methene chain concurrently, the tertiary blending material prepared by Reaction extrusion is for biological base material material products, overcome above-mentioned materials existing defects, composite materials property, consistency is made to be changed the toughness of kindliness and aromatic ring greatly, existing good ductility and elongation at break, also have good thermotolerance impact property; PPC by exhaust carbon dioxide after purifying with propylene oxide copolymer, there is excellent barrier properties and completely biodegradable energy, and price is lower, prepares matrix material by tertiary blending and there is excellent over-all properties; It is high that matrix material has PLA content, and biodegradability is good, mechanical property and excellent combination property.
Technical scheme of the present invention is achieved in that a kind of Reaction extrusion prepares PLA/PBAT/PPC composite modification material, by PLA, PBAT, PPC, softening agent, initiator, help reagent, grafted monomer, anti-aging promoter material prepared by reactive Screw Extrusion; It is characterized in that composite modification material by weight ratio respectively PLA5 ~ 35, PBAT30 ~ 55, PPC5 ~ 15, with PPC100 weight part for benchmark, plasticizer loading is 0.5 ~ 2 weight part; With PBAT100 weight part for benchmark, initiator content is 0.01 ~ 0.08 weight part, helps that reagent content is 0.01 ~ 0.05 weight part, graft monomer contents is 1 ~ 3 weight part, anti-aging auxiliary agent content is 0.5 ~ 1.5 weight part.
Described softening agent is: one or both combinations in paraffin oil, n-Butyl lactate, dibutyl phosphate, blending ratio paraffin oil: n-Butyl lactate=1:1 or n-Butyl lactate: dibutyl phosphate=1:1 or paraffin oil: dibutyl phosphate=1:1; Relative molecular mass is at 500-2000.
Described initiator is: one or both mixtures in cyclohexanone peroxide, ammonium persulphate, isopropyl benzene hydroperoxide, blending ratio cyclohexanone peroxide: ammonium persulphate=2:1 or isopropyl benzene hydroperoxide: ammonium persulphate=1:1 or cyclohexanone peroxide: isopropyl benzene hydroperoxide=1:1.
Described helps reagent: one or both mixtures in benzoyl peroxide, 2,5-dimethyl-2,5 di-t-butyl hexane peroxides; Mixture ratio benzoyl peroxide: 2,5-dimethyl-2,5 di-t-butyl hexane peroxides=2:1.
Described grafted monomer is: one or both mixtures in lactic acid, vinylbenzene, vinyl cyanide, lactic acid: vinylbenzene=5:1 or vinyl cyanide: vinylbenzene=5:1.
Described anti-aging auxiliary agent is: one or more combinations in the two lauryl of thio-2 acid, Salicylate Isomyl, phenylformic acid resorcinol; The two lauryl of mixture ratio thio-2 acid: Salicylate Isomyl=1:1 or the two lauryl of thio-2 acid: phenylformic acid resorcinol=1:1 or phenylformic acid resorcinol: Salicylate Isomyl=2:1 or three kind of blend 1:1:1.
The concrete preparation method that described a kind of Reaction extrusion prepares PLA/PBAT/PPC composite modification material is as follows: PPC, PLA and softening agent are added design temperature pre-mixing 5 minutes in 100 DEG C of cold height mixing machines of heat according to predetermined proportion by (1), proceed in cold mixed pot and mix 5 minutes, for subsequent use; Setting each heating interval temperature of reactive twin screw extruder is: the firstth district: 155-160 DEG C, secondth district: 160-165 DEG C, 3rd district: 170-175 DEG C, 4th district: 170-175 DEG C, the 5th district: 175-180 DEG C, the 6th district: 180-185 DEG C, SECTOR-SEVEN: 185-190 DEG C, tenth district: 175-180 DEG C, the 11 district: 170-175 DEG C, extrusion die: 180-185 DEG C; Arrive after design temperature until temperature and stablize 30 minutes again, slowly open engine speed, restart the first feeding zone screw speed, PBAT is added from reactive twin-screw extrusion owner charging opening, by reactive twin screw extruder heating also high-speed revolution shearing, PBAT resin is molten state;
2); Liquid quantitative drawing-in device is set at the first charging opening, adds initiator in proportion in accurate measurement, help reagent, the mixture of anti-aging auxiliary agent and grafted monomer;
3) initiator and help reagent effect under, PBAT melt is reacted monomer-grafted on PBAT molecular chain by situ-formed graft and prepolymer, by the second charging opening, PPC, PLA of having mixed and plasticiser mixture are added again, under reactive screw rod high speed shearing action, PBAT grafts and PPC, PLA blend is mixing, composite modification material is prepared in frit reaction;
4) unreacted monomer and small-molecule substance are extracted out by continuous vacuum orifice, finally extrude at reactive twin screw extruder die head, can according to the injection moulding of component addition difference preparation bio-based, plastic uptake and blowing matrix material and goods; 5) in extrusion, because blend is at screw rod melt zone generation chemical reaction, barrel internal pressure is comparatively large, therefore selects length-to-diameter ratio 48-52:1, preferred length-to-diameter ratio 52:1 twin screw extruder, and moment of torsion selects 1680-1720N ﹒ m, preferred 1720N ﹒ m.
Positively effect of the present invention can prepare bio-based injection moulding, plastic uptake and blow-molded article, as disposable food or beverage container, knife-fork-spoon, hotel article, shopping bag, refuse bag, mulch film etc. according to component addition difference; It is high that matrix material has PLA content, and biodegradability is good, mechanical property and excellent combination property.
The reactive twin screw extruder of table 1 and typical twin screw extruder prepare all kinds of master batch mechanical performance data contrast table
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described: a kind of Reaction extrusion prepares PLA/PBAT/PPC composite modification material, by PLA, PBAT, PPC, softening agent, initiator, help reagent, grafted monomer, anti-aging promoter material prepared by reactive Screw Extrusion; It is characterized in that composite modification material is that (per-cent understands some problem when calculating by weight ratio respectively, preferably be expressed as good with parts by weight) PLA5 ~ 35, PBAT30 ~ 55, PPC5 ~ 15, with PPC100 weight part for benchmark, plasticizer loading is 0.5 ~ 2 weight part; With PBAT100 weight part for benchmark, initiator content is 0.01 ~ 0.08 weight part, helps that reagent content is 0.01 ~ 0.05 weight part, graft monomer contents is 1 ~ 3 weight part, anti-aging auxiliary agent content is 0.5 ~ 1.5 weight part.
Described softening agent is: one or both combinations in paraffin oil, n-Butyl lactate, dibutyl phosphate, blending ratio paraffin oil: n-Butyl lactate=1:1 or n-Butyl lactate: dibutyl phosphate=1:1 or paraffin oil: dibutyl phosphate=1:1; Relative molecular mass is at 500-2000;
Described initiator is: one or both mixtures in cyclohexanone peroxide, ammonium persulphate, isopropyl benzene hydroperoxide, blending ratio cyclohexanone peroxide: ammonium persulphate=2:1 or isopropyl benzene hydroperoxide: ammonium persulphate=1:1 or cyclohexanone peroxide: isopropyl benzene hydroperoxide=1:1;
Described helps reagent: one or both mixtures in benzoyl peroxide, 2,5-dimethyl-2,5 di-t-butyl hexane peroxides; Mixture ratio benzoyl peroxide: 2,5-dimethyl-2,5 di-t-butyl hexane peroxides=2:1;
Described grafted monomer is: one or both mixtures in lactic acid, vinylbenzene, vinyl cyanide, lactic acid: vinylbenzene=5:1 or vinyl cyanide: vinylbenzene=5:1;
Described anti-aging auxiliary agent is: one or more combinations in the two lauryl of thio-2 acid, Salicylate Isomyl, phenylformic acid resorcinol; The two lauryl of mixture ratio thio-2 acid: Salicylate Isomyl=1:1 or the two lauryl of thio-2 acid: phenylformic acid resorcinol=1:1 or phenylformic acid resorcinol: Salicylate Isomyl=2:1 or three kind of blend 1:1:1;
The concrete preparation method that described a kind of Reaction extrusion prepares PLA/PBAT/PPC composite modification material is as follows: PPC, PLA and softening agent are added design temperature pre-mixing 5 minutes in 100 DEG C of cold height mixing machines of heat according to predetermined proportion by (1), proceed in cold mixed pot and mix 5 minutes, for subsequent use; Setting each heating interval temperature of reactive twin screw extruder is: the firstth district: 155-160 DEG C, secondth district: 160-165 DEG C, 3rd district: 170-175 DEG C, 4th district: 170-175 DEG C, the 5th district: 175-180 DEG C, the 6th district: 180-185 DEG C, SECTOR-SEVEN: 185-190 DEG C, tenth district: 175-180 DEG C, the 11 district: 170-175 DEG C, extrusion die: 180-185 DEG C; Arrive after design temperature until temperature and stablize 30 minutes again, slowly open engine speed, restart the first feeding zone screw speed, PBAT is added from reactive twin-screw extrusion owner charging opening 3, by reactive twin screw extruder heating also high-speed revolution shearing, PBAT resin is molten state;
2); Liquid quantitative drawing-in device is set at the first charging opening 1, adds initiator in proportion in accurate measurement, help reagent, the mixture of anti-aging auxiliary agent and grafted monomer;
3) initiator and help reagent effect under, PBAT melt is reacted monomer-grafted on PBAT molecular chain by situ-formed graft and prepolymer, by the second charging opening 2, PPC, PLA of having mixed and plasticiser mixture are added again, under reactive screw rod high speed shearing action, PBAT grafts and PPC, PLA blend is mixing, composite modification material is prepared in frit reaction;
4) unreacted monomer and small-molecule substance are extracted out by continuous vacuum orifice 4, finally extrude at reactive twin screw extruder die head, can according to the injection moulding of component addition difference preparation bio-based, plastic uptake and blowing matrix material and goods; 5) in extrusion, because blend is at screw rod melt zone generation chemical reaction, barrel internal pressure is comparatively large, therefore selects length-to-diameter ratio 48-52:1, preferred length-to-diameter ratio 52:1 twin screw extruder, and moment of torsion selects 1680-1720N ﹒ m, preferred 1720N ﹒ m.
embodiment 1
Take PLA70kg, PPC10kg, paraffin oil 0.5kg, n-Butyl lactate 0.5kg add design temperature pre-mixing 5 minutes in 100 DEG C of cold height mixing machines of heat, proceed in cold mixed pot and mix 5 minutes, for subsequent use, setting each heating interval temperature of reactive twin screw extruder is: the firstth district: 155 DEG C, secondth district: 160 DEG C, 3rd district: 170 DEG C, 4th district: 175 DEG C, the 5th district: 180 DEG C, the 6th 185 DEG C, district, SECTOR-SEVEN: 190 DEG C, tenth district: 180 DEG C, the 11st district: 175 DEG C, extrusion die: 185 DEG C, arrive after design temperature until temperature and stablize 30 minutes again, slowly open engine speed, restart the first feeding zone screw speed, PBAT resin 100kg is added from reactive twin-screw extrusion owner charging opening 3, by the effect of reactive extruder screw rod shearing, PBAT is molten state, isopropyl benzene hydroperoxide 0.06kg is added from the first charging opening 1 weigh feeder, 2, 5-dimethyl-2, 5 di-t-butyl hexane peroxide 0.02kg, acrylonitrile monemer 2.5kg, styrene monomer 0.5kg, phenylformic acid resorcinol 1.2kg, Salicylate Isomyl 0.6kg mixture, under the effect of initiator and aided initiating, grafted monomer is increased by original position and Acrylic Acid Monomer is grafted to (PBAT-g-AA-St) on PBAT molecular chain by prepolymer grafting, again by PPC that the second charging opening 2 will mix, PLA and plasticiser mixture add, under reactive screw rod high speed shearing action, PBAT grafts and PPC, PLA blend is mixing, composite modification material is prepared in frit reaction, unreacted monomer and small-molecule substance are extracted out by continuous vacuum orifice 4, finally extrude about 200kg modified composite material at reactive twin screw extruder die head, can according to the injection moulding of component addition difference preparation bio-based, plastic uptake and blowing matrix material and goods.
embodiment 2
Take PLA60kg, PPC20kg, paraffin oil 1.0kg, dibutyl phosphate 1.0kg add design temperature pre-mixing 5 minutes in 100 DEG C of cold height mixing machines of heat, proceed in cold mixed pot and mix 5 minutes, for subsequent use, setting each heating interval temperature of reactive twin screw extruder is: the firstth district: 155 DEG C, secondth district: 160 DEG C, 3rd district: 170 DEG C, 4th district: 175 DEG C, the 5th district: 180 DEG C, the 6th 185 DEG C, district, SECTOR-SEVEN: 190 DEG C, tenth district: 180 DEG C, the 11st district: 175 DEG C, extrusion die: 180 DEG C, arrive after design temperature until temperature and stablize 30 minutes again, slowly open engine speed, restart the first feeding zone screw speed, PBAT resin 120kg is added from reactive twin-screw extrusion owner charging opening 3, by the effect of reactive extruder screw rod shearing, PBAT is molten state, cyclohexanone peroxide 0.06kg is added from the first charging opening 1 weigh feeder, ammonium persulphate 0.03kg, lactic acid monomer 3.6kg, styrene monomer 0.72kg, the two lauryl 1.5kg of thio-2 acid, Salicylate Isomyl 1.5kg mixture, under the effect of initiator and aided initiating, grafted monomer is increased by original position and lactic acid monomer is grafted to (PBAT-g-lactic acid-St) on PBAT molecular chain by prepolymer grafting, again by PPC that the second charging opening 2 will mix, PLA and plasticiser mixture add, under reactive screw rod high speed shearing action, PBAT grafts and PPC, PLA blend is mixing, composite modification material is prepared in frit reaction, unreacted monomer and small-molecule substance are extracted out by continuous vacuum orifice 4, finally extrude about 200kg modified composite material at reactive twin screw extruder die head, can according to the injection moulding of component addition difference preparation bio-based, plastic uptake and blowing matrix material and goods.
embodiment 3
Take PLA60kg, PPC30kg, paraffin oil 0.5kg, dibutyl phosphate 0.5kg, n-Butyl lactate 0.5kg add design temperature pre-mixing 5 minutes in 100 DEG C of cold height mixing machines of heat, proceed in cold mixed pot and mix 5 minutes, for subsequent use, setting each heating interval temperature of reactive twin screw extruder is: the firstth district: 150 DEG C, secondth district: 160 DEG C, 3rd district: 165 DEG C, 4th district: 170 DEG C, the 5th district: 175 DEG C, the 6th 180 DEG C, district, SECTOR-SEVEN: 185 DEG C, tenth district: 180 DEG C, the 11st district: 175 DEG C, extrusion die: 175 DEG C, arrive after design temperature until temperature and stablize 30 minutes again, slowly open engine speed, restart the first feeding zone screw speed, PBAT resin 110kg is added from reactive twin-screw extrusion owner charging opening 3, by the effect of reactive extruder screw rod shearing, PBAT is molten state, isopropyl benzene hydroperoxide 0.035kg is added from the first charging opening 1 weigh feeder, 2, 5-dimethyl-2, 5 di-t-butyl hexane peroxide 0.015kg, Acrylic Acid Monomer 4.2kg, styrene monomer 0.82kg, the two lauryl 1.1kg mixture of thio-2 acid, under the effect of initiator and aided initiating, grafted monomer is increased by original position and lactic acid monomer is grafted to (PBAT-g-AA-St) on PBAT molecular chain by prepolymer grafting, again by PPC that the second charging opening 2 will mix, PLA and plasticiser mixture add, under reactive screw rod high speed shearing action, PBAT grafts and PPC, PLA blend is mixing, composite modification material is prepared in frit reaction, unreacted monomer and small-molecule substance are extracted out by continuous vacuum orifice 4, finally extrude about 200kg modified composite material at reactive twin screw extruder die head, can according to the injection moulding of component addition difference preparation bio-based, plastic uptake and blowing matrix material and goods.
Claims (7)
1. Reaction extrusion prepares a PLA/PBAT/PPC composite modification material, by PLA, PBAT, PPC, softening agent, initiator, help reagent, grafted monomer, anti-aging promoter material prepared by reactive Screw Extrusion; It is characterized in that composite modification material be respectively by weight ratio PLA5 ~ 35, PBAT30 ~ 55, PPC5 ~ 15, with PPC100 weight part for benchmark, plasticizer loading is 0.5 ~ 2 weight part; With PBAT100 weight part for benchmark, initiator content is 0.01 ~ 0.08 weight part, helps that reagent content is 0.01 ~ 0.05 weight part, graft monomer contents is 1 ~ 3 weight part, anti-aging auxiliary agent content is 0.5 ~ 1.5 weight part.
2. prepare PLA/PBAT/PPC composite modification material according to a kind of Reaction extrusion described in claim 1, it is characterized in that described softening agent is: one or both combinations in paraffin oil, n-Butyl lactate, dibutyl phosphate, blending ratio paraffin oil: n-Butyl lactate=1:1 or n-Butyl lactate: dibutyl phosphate=1:1 or paraffin oil: dibutyl phosphate=1:1; Relative molecular mass is at 500-2000.
3. prepare PLA/PBAT/PPC composite modification material according to a kind of Reaction extrusion described in claim 1, it is characterized in that described initiator is: one or both mixtures in cyclohexanone peroxide, ammonium persulphate, isopropyl benzene hydroperoxide, blending ratio cyclohexanone peroxide: ammonium persulphate=2:1 or isopropyl benzene hydroperoxide: ammonium persulphate=1:1 or cyclohexanone peroxide: isopropyl benzene hydroperoxide=1:1.
4. prepare PLA/PBAT/PPC composite modification material according to a kind of Reaction extrusion described in claim 1, it is characterized in that described helping reagent: benzoyl peroxide, 2, one or both mixtures in 5-dimethyl-2,5 di-t-butyl hexane peroxide; Mixture ratio benzoyl peroxide: 2,5-dimethyl-2,5 di-t-butyl hexane peroxides=2:1.
5. prepare PLA/PBAT/PPC composite modification material according to a kind of Reaction extrusion described in claim 1, it is characterized in that described grafted monomer is: one or both mixtures in lactic acid, vinylbenzene, vinyl cyanide, lactic acid: vinylbenzene=5:1 or vinyl cyanide: vinylbenzene=5:1.
6. prepare PLA/PBAT/PPC composite modification material according to a kind of Reaction extrusion described in claim 1, it is characterized in that described anti-aging auxiliary agent is: one or more combinations in the two lauryl of thio-2 acid, Salicylate Isomyl, phenylformic acid resorcinol; The two lauryl of mixture ratio thio-2 acid: Salicylate Isomyl=1:1 or the two lauryl of thio-2 acid: phenylformic acid resorcinol=1:1 or phenylformic acid resorcinol: Salicylate Isomyl=2:1 or three kind of blend 1:1:1.
7. prepare PLA/PBAT/PPC composite modification material according to a kind of Reaction extrusion described in claim 1, it is characterized in that described a kind of Reaction extrusion prepares the concrete preparation method of PLA/PBAT/PPC composite modification material as follows: PPC, PLA and softening agent are added design temperature pre-mixing 5 minutes in 100 DEG C of cold height mixing machines of heat according to predetermined proportion by (1), proceed in cold mixed pot and mix 5 minutes, for subsequent use; Setting each heating interval temperature of reactive twin screw extruder is: the firstth district: 155-160 DEG C, secondth district: 160-165 DEG C, 3rd district: 170-175 DEG C, 4th district: 170-175 DEG C, the 5th district: 175-180 DEG C, the 6th district: 180-185 DEG C, SECTOR-SEVEN: 185-190 DEG C, tenth district: 175-180 DEG C, the 11 district: 170-175 DEG C, extrusion die: 180-185 DEG C; Arrive after design temperature until temperature and stablize 30 minutes again, slowly open engine speed, restart the first feeding zone screw speed, PBAT is added from reactive twin-screw extrusion owner charging opening 3, by reactive twin screw extruder heating also high-speed revolution shearing, PBAT resin is molten state;
2); Liquid quantitative drawing-in device is set at the first charging opening 1, adds initiator in proportion in accurate measurement, help reagent, the mixture of anti-aging auxiliary agent and grafted monomer;
3) initiator and help reagent effect under, PBAT melt is reacted monomer-grafted on PBAT molecular chain by situ-formed graft and prepolymer, by the second charging opening 2, PPC, PLA of having mixed and plasticiser mixture are added again, under reactive screw rod high speed shearing action, PBAT grafts and PPC, PLA blend is mixing, composite modification material is prepared in frit reaction;
4) unreacted monomer and small-molecule substance are extracted out by continuous vacuum orifice 4, finally extrude at reactive twin screw extruder die head, can according to the injection moulding of component addition difference preparation bio-based, plastic uptake and blowing matrix material and goods; 5) in extrusion, because blend is at screw rod melt zone generation chemical reaction, barrel internal pressure is comparatively large, therefore selects length-to-diameter ratio 48-52:1, preferred length-to-diameter ratio 52:1 twin screw extruder, and moment of torsion selects 1680-1720N ﹒ m, preferred 1720N ﹒ m.
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Cited By (7)
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| CN106046723A (en) * | 2016-06-28 | 2016-10-26 | 郭庆平 | Degradable composite polylactic acid granules for shopping bags and application thereof |
| CN106418750A (en) * | 2016-11-11 | 2017-02-22 | 深圳市六月玫瑰内衣科技有限公司 | Integrated vertical cotton shaping bra and making method thereof |
| CN106957514A (en) * | 2016-07-21 | 2017-07-18 | 上海弘睿化工产品有限公司 | PBAT base biodegradation composites with high water vapor barrier |
| CN111372744A (en) * | 2017-11-21 | 2020-07-03 | 西门子股份公司 | Method for producing a spacer for a winding unit and voltage-proof spacer for a resin-cast transformer |
| CN113025009A (en) * | 2021-03-24 | 2021-06-25 | 山东道恩高分子材料股份有限公司 | Ultraviolet aging resistant PBAT material and preparation method thereof |
| WO2023045889A1 (en) * | 2021-09-23 | 2023-03-30 | 山东联欣环保科技有限公司 | Degradable barrier composition, preparation method therefor and use thereof |
| WO2023045850A1 (en) * | 2021-09-24 | 2023-03-30 | 山东联欣环保科技有限公司 | High-toughness composition of semi-aromatic carbon dioxide-based copolymer and preparation method therefor |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046723A (en) * | 2016-06-28 | 2016-10-26 | 郭庆平 | Degradable composite polylactic acid granules for shopping bags and application thereof |
| CN106957514A (en) * | 2016-07-21 | 2017-07-18 | 上海弘睿化工产品有限公司 | PBAT base biodegradation composites with high water vapor barrier |
| CN106957514B (en) * | 2016-07-21 | 2019-03-22 | 上海弘睿化工产品有限公司 | PBAT base biodegradation composite material with high water vapor barrier property |
| CN106418750A (en) * | 2016-11-11 | 2017-02-22 | 深圳市六月玫瑰内衣科技有限公司 | Integrated vertical cotton shaping bra and making method thereof |
| CN111372744A (en) * | 2017-11-21 | 2020-07-03 | 西门子股份公司 | Method for producing a spacer for a winding unit and voltage-proof spacer for a resin-cast transformer |
| CN111372744B (en) * | 2017-11-21 | 2022-06-03 | 西门子能源全球有限公司 | Method for producing a spacer for a winding unit and voltage-proof spacer for a resin-cast transformer |
| CN113025009A (en) * | 2021-03-24 | 2021-06-25 | 山东道恩高分子材料股份有限公司 | Ultraviolet aging resistant PBAT material and preparation method thereof |
| WO2023045889A1 (en) * | 2021-09-23 | 2023-03-30 | 山东联欣环保科技有限公司 | Degradable barrier composition, preparation method therefor and use thereof |
| WO2023045850A1 (en) * | 2021-09-24 | 2023-03-30 | 山东联欣环保科技有限公司 | High-toughness composition of semi-aromatic carbon dioxide-based copolymer and preparation method therefor |
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