CN109054309A - A kind of preparation method of PLA high-barrier mulch - Google Patents
A kind of preparation method of PLA high-barrier mulch Download PDFInfo
- Publication number
- CN109054309A CN109054309A CN201810776537.5A CN201810776537A CN109054309A CN 109054309 A CN109054309 A CN 109054309A CN 201810776537 A CN201810776537 A CN 201810776537A CN 109054309 A CN109054309 A CN 109054309A
- Authority
- CN
- China
- Prior art keywords
- pla
- mulch
- barrier
- added
- pbat
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention discloses a kind of preparation methods of PLA high-barrier mulch, PLA 30~33%, PBAT 63~65%, PGA 3~5%, UV-531 0.2~0.4%, UV-326 0.2~0.4, EBS 0.3~0.5%, PLA is first mixed into 2min under the revolving speed of 200r/min with PBAT with high speed mixer, then it releases, it is added in double screw extruder, again by PGA, UV-531, UV-326, EBS is added in double screw extruder from side spout, it squeezes out, tie rod, it is cooling, it is resin dedicated that modified PLA high-barrier mulch is obtained after pelletizing, 170 DEG C of barrel temperature, 175 DEG C of die head temperature, extruder screw draw ratio is 52:1；Extrusion in the resin dedicated addition inflation film manufacturing machine unit of the PLA high-barrier mulch of obtained modification, inflation, cooling, winding are obtained into PLA high-barrier mulch, barrel temperature is 170 DEG C, 175 DEG C of die head temperature, blow-up ratio 3；The present invention has expanded PLA application field, can replace traditional PE mulch, it is possible to reduce white pollution, and there is high barrier, there is good water-retaining effect, very big help can be provided to the growth of farming.
Description
Technical field
The present invention relates to technical field of macromolecules, in particular to a kind of preparation method of PLA high-barrier mulch.
Background technique
Previous mulch is all that non-biodegradable PE class inhales mulch, and white pollution is generated after discarded, destroys ecological ring
Border, mulch dosage increases in recent years, and white pollution increasingly sharpens, and plastics pollution is very urgent.PLA is to be with cornstarch
Primary raw material, biodegradated polymer materal obtained from reacting by series of physicochemical have good biological degradability.Mesh
Before, PLA has been widely used for film class product, injection molding class product, plastic uptake class product.But polylactic acid has both good breathe freely again
Property, so, while doing mulch with polylactic acid, how to guarantee that mulch has good barrier property at a great problem.This hair
A kind of bright preparation method for being intended to provide transparent polylactic acid high-barrier mulch.
Summary of the invention
It is existing to solve technical problem to be solved by the invention is to provide a kind of preparation method of PLA high-barrier mulch
Caused above-mentioned defects in technology.
To achieve the above object, the present invention provides a kind of technical solution below: preparation method of PLA high-barrier mulch,
Each component and ratio are as follows: PLA 30~33%, PBAT 63~65%, PGA 3~5%, UV-531 0.2~0.4%, UV-326
0.2~0.4, EBS 0.3~0.5%, specific production stage are as follows:
PLA and PBAT are first added in high speed mixer, high speed mixer by the first step according to the ratio prepared in advance
2min is mixed under the revolving speed of 200r/min, is then released and is obtained mixture；
Mixture is added in double screw extruder by second step from main spout, then by PGA, UV-531, UV-326,
EBS is added in double screw extruder from side spout, is squeezed out, tie rod, cooling, modified PLA high-barrier is obtained after pelletizing
Film is resin dedicated, and 170 DEG C of barrel temperature, 175 DEG C of die head temperature, extruder screw draw ratio is 52:1；
Third step, will be from the resin dedicated addition inflation film manufacturing machine unit of PLA high-barrier mulch modified obtained in second step
Extrusion, inflation, cooling, winding obtain PLA high-barrier mulch, and barrel temperature is 170 DEG C, and 175 DEG C of die head temperature, blow-up ratio 3.
It is using the beneficial effect of above technical scheme: a kind of preparation method of PLA high-barrier mulch of the invention, preferably
The polyglycolic acid PGA and PBAT of a small amount of particular molecule amount, increase the toughness and barrier property of PLA resin, make PLA mulch obtained
With good toughness, preferably EBS, UV-531 and UV-326 dosage and special PLA mulch film-blowing process, improves PLA mulch and blow
Membrane stability and weatherability, film thickness, obtains PLA mulch in homogeneous thickness, thickness deviation is in 0.005mm with stabilizing PLA
Within, a kind of preparation method of the PLA mulch of high-barrier is provided, PLA application field has been expanded, with can replace traditional PE
Film, it is possible to reduce white pollution, and there is high barrier, there is good water-retaining effect, the growth of farming can be mentioned
For very big help.
Specific embodiment
The preferred embodiment of the present invention.
Embodiment 1
High speed mixer is added in the PLA of 30 parts by weight, the PBAT of 65 parts by weight, 2min is mixed with 200r/min high, it will be mixed
Material be added in the double screw extruder that draw ratio is 52:1, then by the PGA of 4 parts by weight, the UV-531 of 0.3 parts by weight, 0.3
Parts by weight UV-326, the EBS of 0.4 parts by weight are added in side feed material, and extrusion, tie rod, cooling, pelletizing are with obtaining PLA high-barrier
The dedicated modified resin of film, twin-screw extruder barrel temperature are 170 DEG C, 175 DEG C of die head temperature；PLA high-barrier mulch is dedicated
Modified resin investment is added extrusion, inflation, cooling, winding in inflation film manufacturing machine unit and obtains PLA high-barrier mulch, and barrel temperature is
170 DEG C, 175 DEG C of threeway, die head temperature, blow-up ratio 3；The thickness deviation of mulch is within 0.005mm；OTR oxygen transmission rate is
214cm3/(m2), datm moisture-vapor transmission is 86gmm/ (m2·d·atm)；Lateral Z angle tear strength
129.88N/mm, longitudinal Z angle tear strength 139.09N/mm, transverse breakage elongation 212.3%, longitudinal elongation at break rate
151.0%.After irradiating 48 hours in the UV lamp, lateral Z angle tear strength 100.08N/mm, longitudinal Z angle tear strength
112.65N/mm, transverse breakage elongation 170.6%, longitudinal elongation at break rate 103.4%.
Embodiment 2
High speed mixer is added in the PLA of 31.5 parts by weight, the PBAT of 63.5 parts by weight, 2min is mixed with 200r/min high, it will
Mixed material is added in the double screw extruder that draw ratio is 52:1, then by the PGA of 3.5 parts by weight, the UV- of 0.5 parts by weight
531,0.5 parts by weight UV-326, the EBS of 0.5 parts by weight are added in side feed material, and extrusion, tie rod, cooling, pelletizing obtain PLA high
The dedicated modified resin of mulch is obstructed, twin-screw extruder barrel temperature is 170 DEG C, 175 DEG C of die head temperature；By PLA high-barrier
The dedicated modified resin investment of film is added extrusion, inflation, cooling, winding in inflation film manufacturing machine unit and obtains PLA high-barrier mulch, barrel temperature
Degree is 170 DEG C, 175 DEG C of threeway, die head temperature, blow-up ratio 3；The thickness deviation of mulch is within 0.005mm；OTR oxygen transmission rate
For 263cm3/(m2), datm moisture-vapor transmission is 104gmm/ (m2·d·atm)；Lateral Z angle tear strength
122.73N/mm, longitudinal Z angle tear strength 134.26N/mm, transverse breakage elongation 197.6%, longitudinal elongation at break rate
144.5%.After irradiating 48 hours in the UV lamp, lateral Z angle tear strength 102.23N/mm, longitudinal Z angle tear strength
115.41N/mm, transverse breakage elongation 169.6%, longitudinal elongation at break rate 125.3%.
Embodiment 3
High speed mixer is added in the PLA of 33 parts by weight, the PBAT of 62 parts by weight, 2min is mixed with 200r/min high, it will be mixed
Material be added in the double screw extruder that draw ratio is 52:1, then by the PGA of 4.5 parts by weight, the UV-531 of 0.2 parts by weight,
0.2 parts by weight UV-326, the EBS of 0.1 parts by weight are added in side feed material, and extrusion, tie rod, cooling, pelletizing obtain PLA high-barrier
The dedicated modified resin of mulch, twin-screw extruder barrel temperature are 170 DEG C, 175 DEG C of die head temperature；PLA high-barrier mulch is special
Extrusion, inflation, cooling, winding in addition inflation film manufacturing machine unit are put into modified resin and obtains PLA high-barrier mulch, and barrel temperature is
170 DEG C, 175 DEG C of threeway, die head temperature, blow-up ratio 3；The thickness deviation of mulch is within 0.005mm；OTR oxygen transmission rate is
174cm3/(m2), datm moisture-vapor transmission is 65gmm/ (m2·d·atm)；Lateral Z angle tear strength
118.73N/mm, longitudinal Z angle tear strength 130.29N/mm, transverse breakage elongation 189.7%, longitudinal elongation at break rate
135.0%.After irradiating 48 hours in the UV lamp, lateral Z angle tear strength 89.36N/mm, longitudinal Z angle tear strength
92.33N/mm, transverse breakage elongation 146.6%, longitudinal elongation at break rate 99.6%.
Comparative example 1
High speed mixer is added in the PLA of 34 parts by weight, the PBAT of 65 parts by weight, 2min is mixed with 200r/min high, it will be mixed
Material be added in the double screw extruder that draw ratio is 52:1, the UV-531 of 0.3 parts by weight, 0.3 parts by weight UV-326,0.4
The EBS of parts by weight is added in side feed material, and extrusion, tie rod, cooling, pelletizing obtain the dedicated modified resin of PLA high-barrier mulch, double
Screw extruder barrel temperature is 170 DEG C, 175 DEG C of die head temperature；The dedicated modified resin investment of PLA high-barrier mulch is added and is blown
Extrusion, inflation, cooling, winding obtain PLA high-barrier mulch in film machine unit, and barrel temperature is 170 DEG C, threeway, die head temperature
175 DEG C, blow-up ratio 3；The thickness deviation of mulch is within 0.005mm；OTR oxygen transmission rate is 944cm3/(m2), datm water
Vapor transmission rates are 587gmm/ (m2·d·atm)；Lateral Z angle tear strength 123.21N/mm, longitudinal Z right-angle tearing are strong
Spend 134.44N/mm, transverse breakage elongation 206.6%, longitudinal elongation at break rate 142.3%.It irradiates 48 hours in the UV lamp
Afterwards, lateral Z angle tear strength 109.32N/mm, longitudinal Z angle tear strength 125.47N/mm, transverse breakage elongation
188.3%, longitudinal elongation at break rate 123.9%., pass through comparative example 1 and example 1, it can be deduced that PGA is mainly improved in system
The barrier property of mulch.
Comparative example 2
High speed mixer is added in the PLA of 30.6 parts by weight, the PBAT of 65 parts by weight, 2min is mixed with 200r/min high, will mixed
Good material is added in the double screw extruder that draw ratio is 52:1, then the PGA of 4 parts by weight, the EBS of 0.4 parts by weight are added
Into side feed material, extrusion, tie rod, cooling, pelletizing obtain the dedicated modified resin of PLA high-barrier mulch, twin-screw extruder barrel
Temperature is 170 DEG C, 175 DEG C of die head temperature；The dedicated modified resin investment of PLA high-barrier mulch is added in inflation film manufacturing machine unit and is squeezed
Out, inflation, cooling, winding obtain PLA high-barrier mulch, and barrel temperature is 170 DEG C, 175 DEG C of threeway, die head temperature, blow-up ratio
It is 3；The thickness deviation of mulch is within 0.005mm；OTR oxygen transmission rate is 212cm3/(m2), datm moisture-vapor transmission is
85g·mm/(m2·d·atm)；Lateral Z angle tear strength 130.35N/mm, longitudinal Z angle tear strength 139.98N/mm,
Transverse breakage elongation 221.6%, longitudinal elongation at break rate 155.3%.After irradiating 48 hours in the UV lamp, the lateral right angle Z
Tearing strength 98.37N/mm, longitudinal Z angle tear strength 106.79N/mm, transverse breakage elongation 168.3%, longitudinal fracture
Elongation 92.6%.Pass through comparative example 2 and example 1, it can be deduced that UV-531, UV-326 play ageing-resistant work in system
With improving the weatherability of resin.
Based on a kind of above-mentioned, the preparation method of PLA high-barrier mulch of structure of the invention, preferably a small amount of particular molecule amount
Polyglycolic acid PGA and PBAT increase the toughness and barrier property of PLA resin, and PLA mulch obtained is made to have good toughness,
It is preferred that EBS, UV-531 and UV-326 dosage and special PLA mulch film-blowing process, improve PLA mulch blown film stability with it is weather-proof
Property, film thickness, obtains PLA mulch in homogeneous thickness with stabilizing PLA, and thickness deviation is within 0.005mm, OTR oxygen transmission rate
In 263cm3/(m2Datm within), moisture-vapor transmission is 104gmm/ (m2Datm within).The present invention provides
A kind of preparation method of the PLA mulch of high-barrier, has expanded PLA application field, can replace traditional PE mulch, it is possible to reduce
White pollution, and there is high barrier, there is good water-retaining effect, very big help can be provided to the growth of farming.
By the PBAT of the addition high molecular weight in PLA resin to improve the toughness of PLA film, while Japanese Wu Yu is added in the present invention
PGA increase the barrier property of PLA film, add ultraviolet absorber UV-531 and light stabilizer UV-326 and improve PLA film
Weatherability finally obtains the very high PLA mulch of a barrier property.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention
Protection scope.
Claims (1)
1. a kind of preparation method of PLA high-barrier mulch, each component and parts by weight are as follows: PLA 30~33%, PBAT 63~
65%, PGA 3~5%, UV-5310.2~0.4%, UV-3260.2~0.4, EBS 0.3~0.5%, specific production stage is such as
Under:
PLA and PBAT are first added in high speed mixer, high speed mixer exists by the first step according to the ratio prepared in advance
2min is mixed under the revolving speed of 200r/min, is then released and is obtained mixture；
Mixture is added in double screw extruder by second step from main spout, then by PGA, UV-531, UV-326, EBS from
Side spout is added in double screw extruder, is squeezed out, tie rod, cooling, and it is dedicated that modified PLA high-barrier mulch is obtained after pelletizing
Resin, 170 DEG C of barrel temperature, 175 DEG C of die head temperature, extruder screw draw ratio is 52:1；
Third step, will be squeezed out from the resin dedicated addition inflation film manufacturing machine unit of PLA high-barrier mulch modified obtained in second step,
Inflation, cooling, winding obtain PLA high-barrier mulch, and barrel temperature is 170 DEG C, and 175 DEG C of die head temperature, blow-up ratio 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810776537.5A CN109054309A (en) | 2018-07-12 | 2018-07-12 | A kind of preparation method of PLA high-barrier mulch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810776537.5A CN109054309A (en) | 2018-07-12 | 2018-07-12 | A kind of preparation method of PLA high-barrier mulch |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109054309A true CN109054309A (en) | 2018-12-21 |
Family
ID=64816538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810776537.5A Pending CN109054309A (en) | 2018-07-12 | 2018-07-12 | A kind of preparation method of PLA high-barrier mulch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109054309A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113442401A (en) * | 2021-06-22 | 2021-09-28 | 广东工业大学 | High-strength high-barrier PGA/PBAT food packaging film and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010138081A1 (en) * | 2009-05-26 | 2010-12-02 | Hyflux Ltd | A biodegradable starch film |
| CN102171289A (en) * | 2008-09-30 | 2011-08-31 | 株式会社吴羽 | Polyglycol acid resin composition and molded body thereof |
| CN103059529A (en) * | 2013-01-17 | 2013-04-24 | 山东省意可曼科技有限公司 | Biodegradable preservative film material and preservative film |
| DE102014223786A1 (en) * | 2013-12-10 | 2015-06-11 | Basf Se | Polymer mixture for barrier film |
| CN106046725A (en) * | 2016-07-01 | 2016-10-26 | 吉林中粮生化有限公司 | High-barrier-property biodegradable mulching film and preparation method thereof |
| CN106881929A (en) * | 2017-01-20 | 2017-06-23 | 山东农业大学 | A kind of polyadipate butylene terephthalate/starch high-barrier composite membrane and preparation method thereof |
| CN107488343A (en) * | 2017-09-12 | 2017-12-19 | 江苏金聚合金材料有限公司 | High-barrier whole life cycle design and preparation method thereof |
| CN108192302A (en) * | 2018-02-05 | 2018-06-22 | 东莞市鑫海环保材料有限公司 | A kind of biodegradation material and preparation method thereof |
| CN109575536A (en) * | 2018-12-25 | 2019-04-05 | 淄博成达塑化有限公司 | Modified polyglycolic acid Biodegradable mulch and preparation method thereof |
-
2018
- 2018-07-12 CN CN201810776537.5A patent/CN109054309A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102171289A (en) * | 2008-09-30 | 2011-08-31 | 株式会社吴羽 | Polyglycol acid resin composition and molded body thereof |
| WO2010138081A1 (en) * | 2009-05-26 | 2010-12-02 | Hyflux Ltd | A biodegradable starch film |
| CN103059529A (en) * | 2013-01-17 | 2013-04-24 | 山东省意可曼科技有限公司 | Biodegradable preservative film material and preservative film |
| DE102014223786A1 (en) * | 2013-12-10 | 2015-06-11 | Basf Se | Polymer mixture for barrier film |
| CN106046725A (en) * | 2016-07-01 | 2016-10-26 | 吉林中粮生化有限公司 | High-barrier-property biodegradable mulching film and preparation method thereof |
| CN106881929A (en) * | 2017-01-20 | 2017-06-23 | 山东农业大学 | A kind of polyadipate butylene terephthalate/starch high-barrier composite membrane and preparation method thereof |
| CN107488343A (en) * | 2017-09-12 | 2017-12-19 | 江苏金聚合金材料有限公司 | High-barrier whole life cycle design and preparation method thereof |
| CN108192302A (en) * | 2018-02-05 | 2018-06-22 | 东莞市鑫海环保材料有限公司 | A kind of biodegradation material and preparation method thereof |
| CN109575536A (en) * | 2018-12-25 | 2019-04-05 | 淄博成达塑化有限公司 | Modified polyglycolic acid Biodegradable mulch and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BIN XU,等: "Preparation of poly(lactic-co-glycolic acid) and chitosan composite nanocarriers via electrostatic self assembly for oral delivery of insulin", 《MATERIALS SCIENCE AND ENGINEERING》 * |
| 崔爱军，等: "生物降解材料聚羟基乙酸及其结晶性能研究", 《化工新型材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113442401A (en) * | 2021-06-22 | 2021-09-28 | 广东工业大学 | High-strength high-barrier PGA/PBAT food packaging film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107304285B (en) | Polyester modified material and preparation method of film product thereof | |
| CN109082086A (en) | A kind of preparation method of the high ventilated membrane of polylactic acid | |
| CN108929527B (en) | PBAT/modified starch full-biodegradable film with high ductility and high barrier property as well as preparation method and application thereof | |
| CN105504363A (en) | Starch and plant fiber composite biodegradable polyester film-blowing grade resin and preparation method | |
| RU2011106751A (en) | POLYMER COMPOSITION AND METHOD FOR PRODUCING PLASTIC BOTTLES IN A TWO-STAGE INJECTION-BLASTING PROCESS | |
| CN103789869A (en) | Method for producing flat filaments by using PET (Polyethylene Terephthalate) | |
| CN105368013A (en) | Method for improving PLA and PBAT compatibility | |
| CN108976731A (en) | A kind of preparation method of polylactic acid opaque straw | |
| CN109504042A (en) | PHA modified TPS/PBAT biodegradable resin and preparation method thereof | |
| CN109054309A (en) | A kind of preparation method of PLA high-barrier mulch | |
| KR101210301B1 (en) | Method of preparing naturally degradable food container using plant fiber powders | |
| CN109181284A (en) | A kind of complete biodegradable high-barrier polyamide-based composite film material and preparation method thereof | |
| CN109553934A (en) | Using the PBS/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation | |
| CN111531741B (en) | Device and method for preparing modified polylactic acid material on line by polylactic acid melt | |
| CN104844908A (en) | Medical air-permeable and antibacterial microporous material and preparation method for same | |
| CN114605798A (en) | Production process of degradable high polymer material film | |
| EP3189095A1 (en) | Thermoplastic polymer composition | |
| US20140206790A1 (en) | Bio-derived polymers having improved processability and method for the production thereof | |
| CN103601970A (en) | High-strength transparent plastic barrel and preparation process thereof | |
| CN104177740B (en) | A kind of high fluidity polyvinyl alcohol/lignin wood plastic composite | |
| CN107418161A (en) | It is a kind of can mechanical film ultra-thin superpower super transparent whole life cycle design and preparation method thereof | |
| CN110317392B (en) | Degradable composite reinforced polypropylene composition and preparation method thereof | |
| CN102942730A (en) | Method for modifying high density polyethylene to prepare chemical container | |
| CN112375354A (en) | Carbon fiber polylactic acid filling master batch and preparation method thereof | |
| CN106589863A (en) | Toughened PLA material for 3D printing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181221 |
|
| RJ01 | Rejection of invention patent application after publication |