CN106009565B - A kind of nylon enhancing lactic acid composite material and preparation method thereof - Google Patents
A kind of nylon enhancing lactic acid composite material and preparation method thereof Download PDFInfo
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- CN106009565B CN106009565B CN201610458233.5A CN201610458233A CN106009565B CN 106009565 B CN106009565 B CN 106009565B CN 201610458233 A CN201610458233 A CN 201610458233A CN 106009565 B CN106009565 B CN 106009565B
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000004677 Nylon Substances 0.000 title claims abstract description 44
- 229920001778 nylon Polymers 0.000 title claims abstract description 44
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 30
- 239000004310 lactic acid Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004626 polylactic acid Substances 0.000 claims abstract description 25
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 22
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- -1 poly butylene succinate Polymers 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 7
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 229920000571 Nylon 11 Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 claims 1
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005461 lubrication Methods 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- 239000008117 stearic acid Substances 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract 2
- 238000010146 3D printing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical group O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- CZMRCDWAGMRECN-UHFFFAOYSA-N Rohrzucker Natural products OCC1OC(CO)(OC2OC(CO)C(O)C(O)C2O)C(O)C1O CZMRCDWAGMRECN-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of nylon to enhance lactic acid composite material and preparation method thereof, and nylon enhances lactic acid composite material according to the mass fraction：60~90 parts of polylactic acid, 5~30 parts of nylon, 1~5 part of maleic anhydride of styrene, 1~5 part of toughener, 0.1~3 part of lubricant.Nylon enhancing lactic acid composite material good biocompatibility obtained by the present invention, mechanical performance are excellent and easy to process, can be applied to the multiple fields such as 3D printing, health care, Household ornament, industry, have good development prospect.
Description
Technical field
The present invention relates to field of polymer composite material more particularly to a kind of nylon enhancing lactic acid composite material and its systems
Preparation Method.
Background technology
Thermoplastic polymer is widely used in packaging material and other consumer products, has excellent performance, such as quality
Gently, processing temperature low (being compared with metal and glass), changeable barrier property, impressionability, elevated-temperature seal, hot formability etc..
Most of plastic products derive from non-renewable oil and natural gas resource now, although some plastics can recycle,
But landfill disposal is needed after most of plastic product uses, environmental pollution can be caused.It makes a general survey of in the past few decades, from renewable
The degradable polymer of resource has caused extensive concern.
It is the effective way for solving above-mentioned problem of environmental pollution to substitute conventional petroleum based polyalcohol with biodegradable polymers
Diameter, polylactic acid are considered as the biodegradable polymers of most development and application values, it is by lactic acid direct polycondensation or lactic acid
Lactide dimer ring-opening polymerisation and the macromolecule formed, and lactic acid is mainly derived from the renewable plant of nature very abundant
The fermentation of resource such as cornstarch, beet sugar etc., can be hydrolyzed in the natural environment or microbial degradation is non-harmful final
Product CO2And H2O, compost or burning disposal are carried out to it will not bring new environmental pollution.
Polylactic acid is at normal temperatures glassy state, and rigidity is maximum in Biodegradable high molecular, but its poor toughness, thermal deformation temperature
The disadvantages such as low, melt strength is low are spent to limit its scope of application.Twin-screw extrusion is generally used for the modified device of polylactic acid
Machine, under the action of high shear force, polylactic acid is easy to decompose, and reduces the mechanical performance of material.Therefore, how to overcome
Disadvantage mentioned above improves one of the research emphasis that its performance is polylactic acid modified.
Invention content
Present invention aims to overcome that above-mentioned deficiency, a kind of nylon enhancing lactic acid composite material and its preparation side are provided
Method.
The purpose of the present invention is achieved through the following technical solutions：
A kind of nylon enhancing lactic acid composite material, nylon enhance lactic acid composite material according to the mass fraction：Polylactic acid
60~90 parts, 5~30 parts of nylon, 1~5 part of phenylethylene-maleic anhydride, 1~5 part of toughener, 0.1~3 part of lubricant.
The nylon enhances lactic acid composite material, and the polylactic acid is l-lactic acid and/or dextrorotation polylactic acid.
The nylon enhances lactic acid composite material, and the nylon is nylon 6, nylon 7, nylon 9, nylon 11, nylon
12, nylon 13, nylon 46, nylon66 fiber, nylon 610, nylon 612, one or more of nylon 1010.
The nylon enhances lactic acid composite material, the mass content of maleic anhydride in the phenylethylene-maleic anhydride
8%~42%.
The nylon enhances lactic acid composite material, and the toughener is polycaprolactone and/or poly-succinic acid-butanediol
Ester.
The nylon enhances lactic acid composite material, and the lubricant is in zinc stearate, calcium stearate, polyethylene wax
One or more.
The preparation method of the nylon enhancing lactic acid composite material, (1) score meter by weight：By polylactic acid 60~90
Part, 5~30 parts of nylon, 1~5 part of phenylethylene-maleic anhydride, 1~5 part of toughener, 0.1~3 part of lubricant are put into high mixer
Mixing 5~15 minutes, mixing temperature are 40~60 DEG C, and rotating speed is 2500~5000r/min；
(2) mixing is placed on extruding pelletization in single screw extrusion machine, screw slenderness ratio 20:1, extrusion temperature be 185~
220℃。
Advantages of the present invention：
The present invention, for breach, enhances the mechanical performance of polylactic acid using nylon with polylactic acid modified, and optimization compatilizer increases
Tough dose reduces boundary tension, the alternate mutual compatibility of raising and cohesive force with lubricant in poly-lactic acid material, playing, and reaches increasing
Tough purpose.Composite material preparation process is simple, in process, avoids the effect of high shear force, polylactic acid is made to have
Good moulding processability expands the application range of poly-lactic acid material.
Specific implementation mode
The present invention is described further with reference to specific embodiment：
Embodiment 1
A kind of nylon enhancing lactic acid composite material, it is prepared by the raw material of following mass fraction：It will be described
85 parts of polylactic acid, 8 parts of nylon 1010,2 parts of phenylethylene-maleic anhydride, 4 parts of polycaprolactone, 1 part of calcium stearate are put into high mixer
Middle mixing 10 minutes, mixing temperature are 50 DEG C, rotating speed 3000r/min.
Mixed material is placed in extruding pelletization in single screw extrusion machine, screw slenderness ratio 20:1, extrusion temperature 200
℃。
Embodiment 2
A kind of nylon enhancing lactic acid composite material, it is prepared by the raw material of following mass fraction：It will be described
82 parts of polylactic acid, 6 11 parts of nylon, 3 parts of phenylethylene-maleic anhydride, 2.8 parts of polycaprolactone, 1.2 parts of zinc stearate are put into high mixed
It is mixed 12 minutes in machine, mixing temperature is 55 DEG C, rotating speed 3500r/min.
Mixed material is placed in extruding pelletization in single screw extrusion machine, screw slenderness ratio 20:1, extrusion temperature 210
℃。
Embodiment 3
A kind of nylon enhancing lactic acid composite material, it is prepared by the raw material of following mass fraction：It will be described
71 parts of polylactic acid, 20 parts of nylon 11,4.2 parts of phenylethylene-maleic anhydride, 3.3 parts of poly butylene succinate, polyethylene wax 1.5
Part, it is put into high-speed mixer and mixing 10 minutes, mixing temperature is 50 DEG C, rotating speed 4000r/min.
Mixed material is placed in extruding pelletization in single screw extrusion machine, screw slenderness ratio 20:1, extrusion temperature 205
℃。
Embodiment 4
A kind of nylon enhancing lactic acid composite material, it is prepared by the raw material of following mass fraction：It will be described
77 parts of polylactic acid, 14 parts of nylon66 fiber, 3.4 parts of phenylethylene-maleic anhydride, 3.8 parts of polycaprolactone, 0.8 part of zinc stearate are stearic
1 part of sour calcium, is put into high-speed mixer and mixing 8 minutes, and mixing temperature is 50 DEG C, rotating speed 3500r/min.
Mixed material is placed in extruding pelletization in single screw extrusion machine, screw slenderness ratio 20:1, extrusion temperature 210
℃。
Embodiment 5
A kind of nylon enhancing lactic acid composite material, it is prepared by the raw material of following mass fraction：It will be described
80 parts of polylactic acid, 12 parts of nylon 610,2.8 parts of phenylethylene-maleic anhydride, 2.6 parts of polycaprolactone, poly butylene succinate
1.4 parts, 1.2 parts of polyethylene wax is put into high-speed mixer and mixing 14 minutes, and mixing temperature is 55 DEG C, rotating speed 4000r/min.
Mixed material is placed in extruding pelletization in single screw extrusion machine, screw slenderness ratio 20:1, extrusion temperature 210
℃。
Lactic acid composite material obtained above is detected, obtained result is：
Claims (5)
1. a kind of nylon enhances lactic acid composite material, it is characterised in that：Nylon enhances lactic acid composite material and presses mass fraction
Meter：71~82 parts of polylactic acid, nylon 11~20 part, 2.8~4.2 parts of phenylethylene-maleic anhydride, 2.8-3.8 parts of toughener, lubrication
1.2~1.8 parts of agent；
The nylon is nylon 6, nylon 7, nylon 9, nylon 11, nylon 12, nylon 13, nylon 46, nylon66 fiber, nylon 610, Buddhist nun
Dragon 612, one or more of nylon 1010；
The toughener is polycaprolactone and/or poly butylene succinate.
2. nylon according to claim 1 enhances lactic acid composite material, it is characterised in that：The polylactic acid is left-handed poly-
Lactic acid and/or dextrorotation polylactic acid.
3. nylon according to claim 1 enhances lactic acid composite material, it is characterised in that：The styrene-maleic acid
The mass content 8%~42% of maleic anhydride in acid anhydride.
4. nylon according to claim 1 enhances lactic acid composite material, it is characterised in that：The lubricant is stearic acid
One or more of zinc, calcium stearate, polyethylene wax.
5. a kind of preparation method of nylon enhancing lactic acid composite material described in claim 1, it is characterised in that：
(1) score meter by weight：By 71~82 parts of polylactic acid, nylon 11~20 part, 2.8~4.2 parts of phenylethylene-maleic anhydride,
2.8~3.8 parts of toughener, 1.2~1.8 parts of lubricant, is put into high-speed mixer and mixing 5~15 minutes, and mixing temperature is 40~60
DEG C, rotating speed is 2500~5000r/min；
(2) mixing is placed on extruding pelletization in single screw extrusion machine, screw slenderness ratio 20:1, extrusion temperature is 185~220
℃。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610458233.5A CN106009565B (en) | 2016-06-22 | 2016-06-22 | A kind of nylon enhancing lactic acid composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610458233.5A CN106009565B (en) | 2016-06-22 | 2016-06-22 | A kind of nylon enhancing lactic acid composite material and preparation method thereof |
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| CN106009565A CN106009565A (en) | 2016-10-12 |
| CN106009565B true CN106009565B (en) | 2018-10-02 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107141744B (en) * | 2017-07-06 | 2018-08-28 | 广东云曌医疗科技有限公司 | A kind of polylactic acid/polyamide boiomacromolecule alloy material and preparation method thereof |
| CN110964299A (en) * | 2018-09-28 | 2020-04-07 | 句容市飞达箱包有限公司 | Preparation method and application of biodegradable composite material |
| CN110964300A (en) * | 2018-09-28 | 2020-04-07 | 句容市飞达箱包有限公司 | Biodegradable composite material with antibacterial property and preparation method thereof |
| CN113773625B (en) * | 2021-10-12 | 2023-04-28 | 沈阳浩博实业有限公司 | Antibacterial environment-friendly degradable electronic cigarette shell material and preparation method thereof |
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