CN106917157A - Degradable antibacterial polylactic acid elastomer and preparation method thereof - Google Patents
Degradable antibacterial polylactic acid elastomer and preparation method thereof Download PDFInfo
- Publication number
- CN106917157A CN106917157A CN201710160492.4A CN201710160492A CN106917157A CN 106917157 A CN106917157 A CN 106917157A CN 201710160492 A CN201710160492 A CN 201710160492A CN 106917157 A CN106917157 A CN 106917157A
- Authority
- CN
- China
- Prior art keywords
- parts
- polylactic acid
- activated carbon
- degradable antibacterial
- antibacterial polylactic
- 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.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Biological Depolymerization Polymers (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of degradable antibacterial polylactic acid elastomer, 100 parts of PLA, 5 10 parts of compatilizer of maleic anhydride grafting, 12 parts of peroxidized t-butyl perbenzoate, 8 12 parts of antiseptic, 58 parts of citric acid, 10 16 parts of the tert-butyl alcohol, 25 parts of vinylpolydimethyl silane, 0.2 0.5 parts of phosphite are included by mass fraction；The antiseptic presses mass fraction includes 20 parts of nano-cerium oxide, 75 parts of nano zine oxide, 5 parts of modified activated carbon, wherein it is 10 parts of the citric acid solution of 3mol/L that the modified activated carbon presses mass fraction including 80 parts of activated carbon, 5 parts of cerous nitrate, 5 parts of starch, concentration.It is nontoxic or almost nontoxic, composite green chemistry principle that the present invention is raw materials used, and the fiber for obtaining is a kind of degradable, elastic big and degradable antibacterial polylactic acid elastomer with anti-microbial property, and overall preparation method is simple, feasible.
Description
Technical field
The present invention relates to a kind of fiber, particularly degradable antibacterial polylactic acid elastomer.
Background technology
PLA is bound up in units of microbial fermentation product lactic acid.Can be thorough after polylactic acid article is discarded
Resolve into carbon dioxide and who, do not pollute the environment, thus be a kind of degradation material of complete natural circulation type all.But PLA
The defect that fragility is big, hardness is high limits its further application, especially also needs to be carried in fiber art, elastic performance
It is high.As people are to environment and the pay attention to day by day of own health, the functional form requirement to acid fiber by polylactic is also gradually stepped up.
The content of the invention
A kind of degradable, elastic big and tool is provided the invention aims to solve above-mentioned the deficiencies in the prior art
There is the degradable antibacterial polylactic acid elastomer of anti-microbial property.
To achieve these goals, the degradable antibacterial polylactic acid elastomer designed by the present invention, by mass fraction bag
Include 100 parts of PLA, maleic anhydride grafting 5-10 parts of compatilizer, peroxidized t-butyl perbenzoate 1-2 parts, antiseptic 8-12 parts,
Citric acid 5-8 parts, tert-butyl alcohol 10-16 parts, 2-5 parts, phosphite 0.2-0.5 parts of vinylpolydimethyl silane；The antibacterial
Mass fraction is pressed in agent includes 20 parts of nano-cerium oxide, 75 parts of nano zine oxide, 5 parts of modified activated carbon, wherein the modified active
It is 10 parts of the citric acid solution of 3mol/L that charcoal presses mass fraction including 80 parts of activated carbon, 5 parts of cerous nitrate, 5 parts of starch, concentration.
The preparation method of degradable antibacterial polylactic acid elastomer is as follows：
The first step：Modified activated carbon is prepared, activated carbon is first passed through into ethanol soaks and stir suction filtration after 10min, takes 80 parts and is put into
In reactor, 5 parts of citric acid solution, 5 parts of cerous nitrates and starch that 10 parts of concentration are 3mol/L are added, be 75 DEG C in bath temperature
Lower stirring reaction 3h, is put into Muffle furnace after cooling, is taken out after calcining 2h at being 600 DEG C in temperature and is cooled to room temperature, is ground to
Particle diameter is 80-100nm, stand-by；
Second step：Antiseptic is prepared, 20 parts of nano-cerium oxides, 75 parts of nano zine oxides and 5 parts of modified activated carbons is sufficiently mixed,
It is stand-by；
3rd step：Degradable antibacterial polylactic acid elastomer is prepared, 100 parts of PLAs, 5-10 parts of maleic anhydride grafting is compatible
Agent and 1-2 parts of peroxidized t-butyl perbenzoate are put into reactor, uniform mixing, and continue stirring, are reacted at 200-220 DEG C
2h, under slow stirring, then to added in reactor 8-12 parts of antiseptic, 5-8 parts of citric acid, 10-16 parts of tert-butyl alcohol, 2-5 parts
Vinylpolydimethyl silane and 0.2-0.5 parts of phosphite, the frit reaction 2h at 220-240 DEG C, reaction are passed through after terminating
Extruded in screw extruder and granulated, obtain PLA master batch；By PLA master batch send into melt spinning machine hopper in, by spinneret
Head sprays, and is wound in tube filler by coiler device by after crosswind cooling, finally gives degradable antibacterial polylactic acid elastomer.
Wherein, each regional temperature control of the screw extruder is at 200-240 DEG C；The temperature used of spinning-drawing machine is in 240-
290 DEG C, spinning head aperture is 0.15mm, and the temperature of the crosswind is 23 DEG C, and wind speed is 0.4m/s, and humidity is 75%.
It with lactic acid is polymer that main polymerizable raw material is obtained that PLA is, raw material sources fully and can regenerate.It is poly-
The production process of lactic acid is pollution-free, and product can realize the circulation in nature, therefore be preferably green with biodegradation
Color macromolecular material.It is applied in production fiber, the presence of PLA causes that the fiber has more degradable performance.Maleic acid
Acid anhydride is grafted compatilizer by introducing highly polar reactive group, material is had polarity and reactivity high, is a kind of macromolecule circle
Face coupling agent, compatilizer, dispersion enhancing agents, also, it also has certain toughness reinforcing, enhancing performance, can improve to a certain extent
The more fragile shortcoming of pure acid fiber by polylactic, lifts toughness.Wherein, peroxidized t-butyl perbenzoate is used as a kind of initiator, energy
Enough carrying out for promoting to react so that reaction is more abundant.In order that the acid fiber by polylactic that must be prepared has certain anti-microbial property,
We add antiseptic in system, and the antiseptic is the mixture of nano-cerium oxide, nano zine oxide and modified activated carbon.
On the antibacterial functions that nano zine oxide originally has, add modified activated carbon, can promote to a certain extent to germ,
The harmful microbe suction-operated such as bacterium, and adding for nano-cerium oxide can strengthen the suction-operated of modified activated carbon,
It is interspersed in the structural system of activated carbon, nano-cerium oxide has absorption to ultraviolet, the antibacterial of nano zine oxide can be strengthened
Performance.Additionally, the cerium ion in the cerous nitrate that includes of modified activated carbon is grafted under the solutions of weak acidity of citric acid solution
On activated carbon structure, increase the adsorption capacity of activated carbon, the starch of the addition degradable environment for modified activated carbon is provided.Except this it
Outward, citric acid can carry out the regulation of acid-base value to reaction system, promote the good of reaction to carry out；Vinylpolydimethyl silane is
A kind of organic silicon rubber, can improve the elasticity of fiber in addition system, the addition of phosphite has facilitation to it, can
The elasticity that fiber is obtained is lifted to a certain extent.The tert-butyl alcohol can make solvent and use, and promote being uniformly distributed for each component.
The degradable antibacterial polylactic acid elastomer that the present invention is obtained, it has the technical effect that raw materials used for nontoxic or intimate
It is nontoxic, composite green chemistry principle, and the fiber for obtaining is a kind of degradable, elastic big and dropping with anti-microbial property
Solution antibacterial polylactic acid elastomer, overall preparation method is simple, feasible.
Specific embodiment
With reference to embodiment, the present invention is further described.
Embodiment 1：
The degradable antibacterial polylactic acid elastomer that the present embodiment is provided, 100 parts of PLA, maleic acid are included by mass fraction
8 parts of compatilizer of acid anhydride grafting, 2 parts of peroxidized t-butyl perbenzoate, 8 parts of antiseptic, 6 parts of citric acid, 12 parts of the tert-butyl alcohol, vinyl gather
3 parts of dimethylsilane, 0.3 part of phosphite；The antiseptic presses mass fraction includes 20 parts of nano-cerium oxide, nano zine oxide
75 parts, 5 parts of modified activated carbon, wherein the modified activated carbon presses mass fraction includes 80 parts of activated carbon, 5 parts of cerous nitrate, starch 5
Part, concentration are 10 parts of the citric acid solution of 3mol/L.
The preparation method of degradable antibacterial polylactic acid elastomer is as follows：
The first step：Modified activated carbon is prepared, activated carbon is first passed through into ethanol soaks and stir suction filtration after 10min, takes 80 parts and is put into
In reactor, 5 parts of citric acid solution, 5 parts of cerous nitrates and starch that 10 parts of concentration are 3mol/L are added, be 75 DEG C in bath temperature
Lower stirring reaction 3h, is put into Muffle furnace after cooling, is taken out after calcining 2h at being 600 DEG C in temperature and is cooled to room temperature, is ground to
Particle diameter is 90nm, stand-by；
Second step：Antiseptic is prepared, 20 parts of nano-cerium oxides, 75 parts of nano zine oxides and 5 parts of modified activated carbons is sufficiently mixed,
It is stand-by；
3rd step：Prepare degradable antibacterial polylactic acid elastomer, by 100 parts of PLAs, 8 parts of maleic anhydrides grafting compatilizers and
2 parts of peroxidized t-butyl perbenzoates are put into reactor, uniform mixing, and continue stirring, 2h are reacted at 200 DEG C, slow
Under stirring, then in reactor add 8 parts of antiseptics, 6 parts of citric acids, 12 parts of tert-butyl alcohols, 3 parts of vinylpolydimethyl silane and
0.3 part of phosphite, the frit reaction 2h at 240 DEG C, reaction is passed through in screw extruder after terminating and extrudes and granulate, and is gathered
Lactic acid master batch；By in PLA master batch feeding melt spinning machine hopper, sprayed by spinning head, filled by winding by after crosswind cooling
Put and be wound in tube filler, finally give degradable antibacterial polylactic acid elastomer.
Wherein, each regional temperature control of the screw extruder is at 210 DEG C；The temperature used of spinning-drawing machine is in 270 DEG C, spinneret
Head bore footpath is 0.15mm, and the temperature of the crosswind is 23 DEG C, and wind speed is 0.4m/s, and humidity is 75%.
Obtained degradable antibacterial polylactic acid elastomer is carried out into performance detection, the lower recovery rate of 100% elongation is
94.8%；Inhibition zone test result shows that the degradable antibacterial polylactic acid elastomer that the present embodiment is provided is to E
The inhibiting rate of bacterium and staphylococcus aureus is up to 99.97%.
Embodiment 2：
The degradable antibacterial polylactic acid elastomer that the present embodiment is provided, raw material and preparation method embodiment 1 of making peace greatly are identical,
It is differred primarily in that, in the present embodiment, mass fraction used by antiseptic is 10 parts, and vinylpolydimethyl silane is 4 parts.
Obtained degradable antibacterial polylactic acid elastomer is carried out into performance detection, the lower recovery rate of 100% elongation is
95.6%；Inhibition zone test result shows that the degradable antibacterial polylactic acid elastomer that the present embodiment is provided is to ETEC
With the inhibiting rate of staphylococcus aureus up to 99.98%.
Embodiment 3：
The degradable antibacterial polylactic acid elastomer that the present embodiment is provided, raw material and preparation method embodiment 1 of making peace greatly are identical,
It is differred primarily in that, in the present embodiment, mass fraction used by antiseptic is 12 parts, and vinylpolydimethyl silane is 5 parts.
Obtained degradable antibacterial polylactic acid elastomer is carried out into performance detection, the lower recovery rate of 100% elongation is
96.9%；Inhibition zone test result shows that the degradable antibacterial polylactic acid elastomer that the present embodiment is provided is to ETEC
With the inhibiting rate of staphylococcus aureus up to 99.99%.
Claims (3)
1. a kind of degradable antibacterial polylactic acid elastomer, it is characterised in that：Include 100 parts of PLA, Malaysia by mass fraction
5-10 parts of compatilizer of acid anhydrides grafting, peroxidized t-butyl perbenzoate 1-2 parts, antiseptic 8-12 parts, citric acid 5-8 parts, the tert-butyl alcohol
10-16 parts, 2-5 parts, phosphite 0.2-0.5 parts of vinylpolydimethyl silane；The antiseptic is included receiving by mass fraction
20 parts of cerium oxide of rice, 75 parts of nano zine oxide, 5 parts of modified activated carbon, wherein the modified activated carbon presses mass fraction to include living
Property 80 parts of charcoal, 5 parts of cerous nitrate, 5 parts of starch, concentration for 3mol/L 10 parts of citric acid solution.
2. a kind of preparation method of degradable antibacterial polylactic acid elastomer as claimed in claim 1, it is characterised in that：
The first step：Modified activated carbon is prepared, activated carbon is first passed through into ethanol soaks and stir suction filtration after 10min, takes 80 parts and is put into
In reactor, 5 parts of citric acid solution, 5 parts of cerous nitrates and starch that 10 parts of concentration are 3mol/L are added, be 75 DEG C in bath temperature
Lower stirring reaction 3h, is put into Muffle furnace after cooling, is taken out after calcining 2h at being 600 DEG C in temperature and is cooled to room temperature, is ground to
Particle diameter is 80-100nm, stand-by；
Second step：Antiseptic is prepared, 20 parts of nano-cerium oxides, 75 parts of nano zine oxides and 5 parts of modified activated carbons is sufficiently mixed,
It is stand-by；
3rd step：Degradable antibacterial polylactic acid elastomer is prepared, 100 parts of PLAs, 5-10 parts of maleic anhydride grafting is compatible
Agent and 1-2 parts of peroxidized t-butyl perbenzoate are put into reactor, uniform mixing, and continue stirring, are reacted at 200-220 DEG C
2h, under slow stirring, then to added in reactor 8-12 parts of antiseptic, 5-8 parts of citric acid, 10-16 parts of tert-butyl alcohol, 2-5 parts
Vinylpolydimethyl silane and 0.2-0.5 parts of phosphite, the frit reaction 2h at 220-240 DEG C, reaction are passed through after terminating
Extruded in screw extruder and granulated, obtain PLA master batch；By PLA master batch send into melt spinning machine hopper in, by spinneret
Head sprays, and is wound in tube filler by coiler device by after crosswind cooling, finally gives degradable antibacterial polylactic acid elastomer.
3. the preparation method of degradable antibacterial polylactic acid elastomer according to claim 2, it is characterised in that：The spiral shell
Each regional temperature control of bar extruder is at 200-240 DEG C；At 240-290 DEG C, spinning head aperture is the temperature used of spinning-drawing machine
0.15mm, the temperature of the crosswind is 23 DEG C, and wind speed is 0.4m/s, and humidity is 75%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710160492.4A CN106917157B (en) | 2017-03-17 | 2017-03-17 | Degradable antibacterial polylactic acid elastomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710160492.4A CN106917157B (en) | 2017-03-17 | 2017-03-17 | Degradable antibacterial polylactic acid elastomer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106917157A true CN106917157A (en) | 2017-07-04 |
| CN106917157B CN106917157B (en) | 2019-06-21 |
Family
ID=59461255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710160492.4A Active CN106917157B (en) | 2017-03-17 | 2017-03-17 | Degradable antibacterial polylactic acid elastomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106917157B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107699981A (en) * | 2017-09-20 | 2018-02-16 | 安徽锦翔纺织服饰有限公司 | A kind of environment-friendly degradable fiber and preparation method thereof |
| CN111549392A (en) * | 2020-04-24 | 2020-08-18 | 北京化工大学 | Preparation method of antibacterial polyphenylene sulfide fiber |
| CN111728293A (en) * | 2020-05-28 | 2020-10-02 | 南京微米电子产业研究院有限公司 | Novel degradable nanofiber mask |
| CN113529206A (en) * | 2020-04-22 | 2021-10-22 | 中国石油化工股份有限公司 | Antibacterial and deodorant ES fiber and preparation method thereof |
| CN113754916A (en) * | 2021-10-19 | 2021-12-07 | 江苏金世缘乳胶制品股份有限公司 | Preparation process of rare earth antibacterial natural latex product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358382A (en) * | 2008-08-26 | 2009-02-04 | 东华大学 | Antibacterial nano fiber material and preparation method thereof |
| CN102086565A (en) * | 2010-12-08 | 2011-06-08 | 江南大学 | Polylactic acid antibacterial nanofiber membrane and preparation method thereof |
| CN102212896A (en) * | 2011-05-27 | 2011-10-12 | 东华大学 | High-efficiency antibacterial mildew-proof PLA (poly lactic acid) fiber with skin-core structure and preparation method thereof |
| CN105239194A (en) * | 2015-11-20 | 2016-01-13 | 王庆 | Method of preparing flame-retarding anti-microbial polylactic acid fibers, spinning fibers into yarn and making fabric |
-
2017
- 2017-03-17 CN CN201710160492.4A patent/CN106917157B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358382A (en) * | 2008-08-26 | 2009-02-04 | 东华大学 | Antibacterial nano fiber material and preparation method thereof |
| CN102086565A (en) * | 2010-12-08 | 2011-06-08 | 江南大学 | Polylactic acid antibacterial nanofiber membrane and preparation method thereof |
| CN102212896A (en) * | 2011-05-27 | 2011-10-12 | 东华大学 | High-efficiency antibacterial mildew-proof PLA (poly lactic acid) fiber with skin-core structure and preparation method thereof |
| CN105239194A (en) * | 2015-11-20 | 2016-01-13 | 王庆 | Method of preparing flame-retarding anti-microbial polylactic acid fibers, spinning fibers into yarn and making fabric |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107699981A (en) * | 2017-09-20 | 2018-02-16 | 安徽锦翔纺织服饰有限公司 | A kind of environment-friendly degradable fiber and preparation method thereof |
| CN113529206A (en) * | 2020-04-22 | 2021-10-22 | 中国石油化工股份有限公司 | Antibacterial and deodorant ES fiber and preparation method thereof |
| CN111549392A (en) * | 2020-04-24 | 2020-08-18 | 北京化工大学 | Preparation method of antibacterial polyphenylene sulfide fiber |
| CN111549392B (en) * | 2020-04-24 | 2021-04-23 | 北京化工大学 | Preparation method of antibacterial polyphenylene sulfide fiber |
| CN111728293A (en) * | 2020-05-28 | 2020-10-02 | 南京微米电子产业研究院有限公司 | Novel degradable nanofiber mask |
| CN113754916A (en) * | 2021-10-19 | 2021-12-07 | 江苏金世缘乳胶制品股份有限公司 | Preparation process of rare earth antibacterial natural latex product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106917157B (en) | 2019-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106917157A (en) | Degradable antibacterial polylactic acid elastomer and preparation method thereof | |
| CN107022804B (en) | Fire-retardant degradable antibacterial polylactic acid elastomer and preparation method thereof | |
| CN106884226B (en) | Coloured degradable antibacterial polylactic acid elastomer and preparation method thereof | |
| CN107099869A (en) | A kind of modified polypropylene fiber and preparation method thereof and modified polypropylene fiber reinforced mortar concrete | |
| CN105038284A (en) | Method for preparing wood-plastic composite material by using wood fibers | |
| CN106917161B (en) | Polylactic acid nylon superfine composite fibre and preparation method thereof | |
| CN106280218B (en) | A kind of preparation method of the composition for being used to prepare antimicrobial composite material and antimicrobial composite material | |
| CN103360679B (en) | Non-woven fabrics strengthens anti-agglomeration antibacterial filler masterbatch and preparation technology thereof with efficient | |
| CN107141595A (en) | A kind of High-strength wood plastic floor and preparation method thereof | |
| CN107955244A (en) | A kind of functionalized polyethy-lene resin with anti-microbial property and preparation method thereof | |
| CN103265669B (en) | Method for preparing special compatibilizer for straw fiber/ poly(butylene succinate) (PBS) composite material and application | |
| CN107286463A (en) | A kind of TRPP pellet | |
| CN106928670A (en) | Oxidation modification lignin-base lactic acid composite material and preparation method thereof and oxidation unit | |
| CN106917159A (en) | Coloured PLA nylon superfine composite fibre and preparation method thereof | |
| CN103773042A (en) | Plastic-wood section material prepared from bamboo powder and preparation method thereof | |
| CN112175361B (en) | High-barrier stretch-resistant antibacterial film type degradable material and preparation method thereof | |
| CN110408127A (en) | A kind of fiber reinforcement polypropylene random copolymer composite tube and preparation method thereof | |
| CN107841037A (en) | High adsorption polylactic acid composite biological membrane carrier materials and preparation method thereof | |
| CN107162481A (en) | A kind of preparation method of diatom ooze building and ornament materials | |
| CN108727792A (en) | A kind of antibacterial PCL plant fiber composite wires and preparation method thereof for 3D printing | |
| CN208667571U (en) | A kind of fiber reinforcement polypropylene random copolymer composite tube | |
| CN115679474B (en) | Hydrolysis-resistant polylactic acid fiber composite material and preparation method thereof | |
| CN114854215B (en) | Biodegradable agricultural mulching film modified material and preparation method thereof | |
| CN107383814B (en) | Wheat stalk lactic acid composite material and preparation method thereof | |
| CN108547425A (en) | A kind of environment-friendlyweather-proof weather-proof wood moulding floor tile and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |