CN106893284A - The preparation method of polylactic acid/nano-cellulose composite material - Google Patents
The preparation method of polylactic acid/nano-cellulose composite material Download PDFInfo
- Publication number
- CN106893284A CN106893284A CN201710212358.4A CN201710212358A CN106893284A CN 106893284 A CN106893284 A CN 106893284A CN 201710212358 A CN201710212358 A CN 201710212358A CN 106893284 A CN106893284 A CN 106893284A
- Authority
- CN
- China
- Prior art keywords
- nano
- cellulose
- polylactic acid
- composite material
- preparation
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a kind of preparation method of polylactic acid/nano-cellulose composite material, including step in detail below：1）Prepare nano-cellulose organogel；2）By step 1）The nano-cellulose organogel block of middle preparation is immersed in 24 48 hours in the chloroform soln of PLA, after taking-up gel piece is dried 25 hours at normal temperatures from solution, it is put into vacuum drying chamber and is vacuum dried 10 15 hours under the conditions of 50 60 DEG C, polylactic acid/nano-cellulose composite material is obtained with hot press hot pressing, reaction condition of the present invention is gentle, method applicability is strong, other additives need not be added to be reacted, be effectively increased nano-cellulose in the composite accounting while, also ensure nano-cellulose in PLA matrix dispersiveness.
Description
Technical field
The present invention relates to technical field of polymer processing, and in particular to a kind of polylactic acid/nano-cellulose composite material
Preparation method.
Background technology
With macromolecular material extensive use, largely consumption causes plastic garbage constantly to increase to petroleum resources, global environment
Pollution problem aggravates.A large amount of consumption of non-renewable energy resources cause that poly-lactic acid material is more and more paid attention to.PLA can
It is that fermenting raw materials polymerization is obtained by corn and other natural plants, water and titanium dioxide can be completely resolved under microbial action
Carbon, it is completely environment-friendly.But PLA matter is hard and crisp, impact strength and hydrophily are poor, limit its range of application.
It is a kind of method for designing for being applied to the fields such as material science during nano-cellulose is mixed into polymer.The method should
It is very attractive with having a extensive future.It can be prepared with new capability or property by mixing various other polymeric materials
Can enhanced material.Polylactic acid/nano-cellulose composite material compared to pure poly-lactic acid material, its hydrophily, biological degradability
Etc. aspect be all significantly improved, biology can be widely used in, the field such as medical science and packaging.And the high-ratio surface of nano-cellulose
Generally there is product and energy, nano-particle strong aggregation to be inclined to, and this causes that they are difficult to be dispersed in PLA.
At present, the preparation of polylactic acid/nano-cellulose composite material is typically modified by nano-cellulose surface
Or addition bulking agent solves dispersion problem of the nano-cellulose in PLA matrix.But the above method is only preparing low accounting for
PLA can effectively be strengthened during the nano-cellulose composite of ratio, the further increase of nano-cellulose filler can the group of being formed
It is poly-, cause to strengthen the declines of PLA.
The content of the invention
The technical problems to be solved by the invention are the shortcomings for overcoming above prior art：A kind of reaction condition temperature is provided
With method applicability is strong, is reacted without adding other additives, is effectively increased nano-cellulose accounting in the composite
While, also ensure the preparation of nano-cellulose polylactic acid/nano-cellulose composite material of dispersiveness in PLA matrix
Method.
Technical solution of the invention is as follows：A kind of preparation method of polylactic acid/nano-cellulose composite material, it is special
Levy and be：Including step in detail below：
1）Prepare nano-cellulose organogel：During nano-cellulose powder added into 0-20 DEG C of deionized water, ultrasonically treated
To nano-cellulose suspension, to 70-80 DEG C, ultrasonic froth breaking is added oil bath heating after being cooled to room temperature after standing 24-48 hours
Organic solvent, stands, until forming supernatant liquor and lower floor's gel layer, removes supernatant liquor, adds organic solvent to replace upper strata
Clear liquid, upper strata organic solvent layer was changed every 12-24 hours, after changing 5-8 times altogether, removed upper strata organic solvent layer；Under taking-up
Layer gel layer organic solvent rinses 2-3 acquisition nano-cellulose organogel, nano-cellulose organogel is cut into small
Block is placed in standby in 4 DEG C of environment；
2）By step 1）24-48 is small during the nano-cellulose organogel block of middle preparation is immersed in the chloroform soln of PLA
When, taken out from solution after gel piece dries 2-5 hour at normal temperatures, it is put into vacuum drying chamber under the conditions of 50-60 DEG C very
Sky dries 10-15 hours, and gel piece that drying is finished then is paved with into hot pressing die, with hot press in 155-160 DEG C of upper and lower plates,
Hot pressing under the conditions of pressure 2000-2200psi, obtains polylactic acid/nano-cellulose composite material.
The mass percent concentration of nano-cellulose is 4%-15% in the nano-cellulose suspension.
The organic solvent is the one kind in ethanol, acetone, isopropanol.
As optimization, step 1）In, lower floor's gel layer is 1 ︰ 4-5 with the volume ratio of supernatant liquor.
Used as optimization, the mass percent concentration of PLA is 2%-15% in the chloroform soln of the PLA.
The beneficial effects of the invention are as follows：The present invention is prepared for the nanometer with three-dimensional net structure using sol-gel method
Cellulose organogel block, then will prepare composite in gel piece immersion PLA enables nano-cellulose in composite wood
Fine dispersion is obtained relative to PLA in material, while the accounting of nano-cellulose in composite is improve, preparation process bar
Part is gentle, simple to operate, the polylactic acid/nano-cellulose composite material and pure poly-lactic acid material phase obtained by the preparation method
Than, its elongation at break obtains larger raising with impact strength, and preparing raw material of the present invention derives from regenerative resource,
Degradable green, without environmental pressure, meets environment-friendly theory, has good development prospect in medical packaging field.
Brief description of the drawings
Fig. 1 is 2K times of SEM figure of composite prepared by the embodiment of the present invention three.
Fig. 2 is 5K times of SEM figure of composite prepared by the embodiment of the present invention three.
Specific embodiment
The present invention is described in further details with specific embodiment below, but the present invention is not only limited in detail below in fact
Apply example.
Embodiment one
A kind of preparation method of polylactic acid/nano-cellulose composite material, including step in detail below：
1）Prepare nano-cellulose organogel：During nano-cellulose powder added into 0-20 DEG C of deionized water, ultrasonically treated
To nano-cellulose suspension, the mass percent concentration of nano-cellulose is 4%-15% in the nano-cellulose suspension,
To 70-80 DEG C, ultrasonic froth breaking adds organic solvent to oil bath heating after being cooled to room temperature after standing 24-48 hours, stands, until
Supernatant liquor and lower floor's gel layer are formed, lower floor's gel layer is 1 ︰ 4-5 with the volume ratio of supernatant liquor, removes supernatant liquor, plus
Enter organic solvent and replace supernatant liquor, upper strata organic solvent layer was changed every 12-24 hours, after changing 5-8 times altogether, remove upper strata
Organic solvent layer；Take out lower floor's gel layer organic solvent and rinse 2-3 acquisition nano-cellulose organogel, by nanofiber
Plain organogel be cut into the fritter of 12mmX12mmX12mm be placed in it is standby in 4 DEG C of environment；
2）By step 1）24-48 is small during the nano-cellulose organogel block of middle preparation is immersed in the chloroform soln of PLA
When, the mass percent concentration of PLA is 2%-15% in the chloroform soln of the PLA, and gel is taken out from solution
After block dries 2-5 hours at normal temperatures, it is put into vacuum drying chamber and is vacuum dried 10-15 hours under the conditions of 50-60 DEG C, then
The gel piece that finishes of drying is paved with hot pressing die, with hot press in 155-160 DEG C of upper and lower plates, pressure 2000-2200psi conditions
Lower hot pressing, obtains polylactic acid/nano-cellulose composite material.The organic solvent is the one kind in ethanol, acetone, isopropanol.
Embodiment two
A kind of preparation method of polylactic acid/nano-cellulose composite material, including step in detail below：
1）Prepare nano-cellulose organogel：It is ultrasonically treated to be received during nano-cellulose powder added into 0 DEG C of deionized water
Rice cellulose suspension, the mass percent concentration of nano-cellulose is 10% in the nano-cellulose suspension, stands 24 small
When after oil bath heating to 80 DEG C, ultrasonic froth breaking adds ethanol after being cooled to room temperature, stand, until formed supernatant liquor and lower floor
Gel layer, lower floor's gel layer is 1 ︰ 4-5 with the volume ratio of supernatant liquor, removes supernatant liquor, adds ethanol to replace supernatant liquor,
Upper strata ethanol was changed every 12 hours, after changing 8 times altogether, upper strata ethanol is removed；Take out lower floor's gel layer alcohol flushing 2-3 times
Nano-cellulose organogel is obtained, the fritter that nano-cellulose organogel is cut into 12mmX12mmX12mm is placed in 4 DEG C of rings
It is standby in border；
2）By step 1）The nano-cellulose organogel block of middle preparation is immersed in 48 hours in the chloroform soln of PLA,
The mass percent concentration of PLA is 15% in the chloroform soln of the PLA, and gel piece is taken out from solution normal
Temperature is lower dry 2 hours after, be put into vacuum drying chamber and be vacuum dried 15 hours under the conditions of 60 DEG C, then by drying finish it is solidifying
Blob of viscose is paved with hot pressing die, and with hot press in 160 DEG C of upper and lower plates, hot pressing under the conditions of pressure 2200psi obtains polylactic acid/nano
Cellulose composite material.
Embodiment three
A kind of preparation method of polylactic acid/nano-cellulose composite material, including step in detail below：
1）Prepare nano-cellulose organogel：It is ultrasonically treated to be received during nano-cellulose powder added into 0 DEG C of deionized water
Rice cellulose suspension, the mass percent concentration of nano-cellulose is 8% in the nano-cellulose suspension, stands 24 small
When after oil bath heating to 70 DEG C, ultrasonic froth breaking adds ethanol after being cooled to room temperature, stand, until formed supernatant liquor and lower floor
Gel layer, lower floor's gel layer is 1 ︰ 5 with the volume ratio of supernatant liquor, removes supernatant liquor, adds ethanol to replace supernatant liquor, often
Upper strata ethanol was changed every 48 hours, after changing 5 times altogether, upper strata ethanol is removed；Take out 3 acquisitions of lower floor's gel layer alcohol flushing
Nano-cellulose organogel, is cut into nano-cellulose organogel the fritter of 12mmX12mmX12mm and is placed in 4 DEG C of environment
It is standby；
2）By step 1）The nano-cellulose organogel block of middle preparation is immersed in 48 hours in the chloroform soln of PLA,
The mass percent concentration of PLA is 15% in the chloroform soln of the PLA, and gel piece is taken out from solution normal
Temperature is lower dry 2 hours after, be put into vacuum drying chamber and be vacuum dried 15 hours under the conditions of 60 DEG C, then by drying finish it is solidifying
Blob of viscose is paved with hot pressing die, and with hot press in 160 DEG C of upper and lower plates, hot pressing under the conditions of pressure 2000psi obtains polylactic acid/nano
Cellulose composite material.
Prepared polylactic acid/nano-cellulose composite material passes through sem analysis, as shown in Figure 1-2, can be with bright from figure
Aobvious to find out, NCC is uniformly dispersed in PLA, and composite section is coarse and uneven, in ductile rupture feature.From high magnification numbe
Figure in as can be seen that NCC and PLA nano-celluloses cohere closely with two-phase, the aggregation of nano-cellulose is not observed, receive
Rice cellulose is substantially wrapped by, and both caking property is fine.
The above is only feature implementation example of the invention, the scope of the present invention is not limited in any way.It is all to use same
The technical scheme formed Deng exchange or equivalence replacement, all falls within rights protection scope of the present invention.
Claims (5)
1. a kind of preparation method of polylactic acid/nano-cellulose composite material, it is characterised in that：Including step in detail below：
1）Prepare nano-cellulose organogel：During nano-cellulose powder added into 0-20 DEG C of deionized water, ultrasonically treated
To nano-cellulose suspension, to 70-80 DEG C, ultrasonic froth breaking is added oil bath heating after being cooled to room temperature after standing 24-48 hours
Organic solvent, stands, until forming supernatant liquor and lower floor's gel layer, removes supernatant liquor, adds organic solvent to replace upper strata
Clear liquid, upper strata organic solvent layer was changed every 12-24 hours, after changing 5-8 times altogether, removed upper strata organic solvent layer；Under taking-up
Layer gel layer organic solvent rinses 2-3 acquisition nano-cellulose organogel, nano-cellulose organogel is cut into small
Block is placed in standby in 4 DEG C of environment；
2）By step 1）24-48 is small during the nano-cellulose organogel block of middle preparation is immersed in the chloroform soln of PLA
When, taken out from solution after gel piece dries 2-5 hour at normal temperatures, it is put into vacuum drying chamber under the conditions of 50-60 DEG C very
Sky dries 10-15 hours, and gel piece that drying is finished then is paved with into hot pressing die, with hot press in 155-160 DEG C of upper and lower plates,
Hot pressing under the conditions of pressure 2000-2200psi, obtains polylactic acid/nano-cellulose composite material.
2. the preparation method of polylactic acid/nano-cellulose composite material according to claim 1, it is characterised in that：It is described
The mass percent concentration of nano-cellulose is 4%-15% in nano-cellulose suspension.
3. the preparation method of polylactic acid/nano-cellulose composite material according to claim 1, it is characterised in that：It is described
Organic solvent is the one kind in ethanol, acetone, isopropanol.
4. the preparation method of polylactic acid/nano-cellulose composite material according to claim 1, it is characterised in that：Step
1）In, lower floor's gel layer is 1 ︰ 4-5 with the volume ratio of supernatant liquor.
5. the preparation method of polylactic acid/nano-cellulose composite material according to claim 1, it is characterised in that：It is described
The mass percent concentration of PLA is 2%-15% in the chloroform soln of PLA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710212358.4A CN106893284B (en) | 2017-04-01 | 2017-04-01 | The preparation method of polylactic acid/nano-cellulose composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710212358.4A CN106893284B (en) | 2017-04-01 | 2017-04-01 | The preparation method of polylactic acid/nano-cellulose composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106893284A true CN106893284A (en) | 2017-06-27 |
| CN106893284B CN106893284B (en) | 2019-04-05 |
Family
ID=59194443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710212358.4A Active CN106893284B (en) | 2017-04-01 | 2017-04-01 | The preparation method of polylactic acid/nano-cellulose composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106893284B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880180A (en) * | 2019-03-13 | 2019-06-14 | 广州谱睿汀新材料科技有限公司 | Nano-cellulose/cellulose composite, enhancing polylactic acid 3D printing material and preparation method thereof |
| CN112092419A (en) * | 2019-06-18 | 2020-12-18 | 中国科学技术大学 | Preparation method of bacterial cellulose composite board with tubular structure |
| CN113311025A (en) * | 2021-07-13 | 2021-08-27 | 浙江农林大学 | Preparation method of novel intelligent gas sensing material suitable for indoor ammonia gas detection |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666669A (en) * | 2009-09-14 | 2012-09-12 | 诺丁汉大学 | Cellulose nanoparticle aerogels, hydrogels and organogels |
| CN103044871A (en) * | 2012-11-26 | 2013-04-17 | 浙江大学宁波理工学院 | Preparation method of polylactic acid/nano-cellulose composite material |
| US20150231069A1 (en) * | 2014-02-20 | 2015-08-20 | Pankaj Modi | Oral formulations of chemotherapeutic agents |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
-
2017
- 2017-04-01 CN CN201710212358.4A patent/CN106893284B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666669A (en) * | 2009-09-14 | 2012-09-12 | 诺丁汉大学 | Cellulose nanoparticle aerogels, hydrogels and organogels |
| CN103044871A (en) * | 2012-11-26 | 2013-04-17 | 浙江大学宁波理工学院 | Preparation method of polylactic acid/nano-cellulose composite material |
| US20150231069A1 (en) * | 2014-02-20 | 2015-08-20 | Pankaj Modi | Oral formulations of chemotherapeutic agents |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880180A (en) * | 2019-03-13 | 2019-06-14 | 广州谱睿汀新材料科技有限公司 | Nano-cellulose/cellulose composite, enhancing polylactic acid 3D printing material and preparation method thereof |
| CN109880180B (en) * | 2019-03-13 | 2021-03-02 | 广州谱睿汀新材料科技有限公司 | Nano-cellulose/cellulose compound, reinforced polylactic acid 3D printing material and preparation method thereof |
| CN112092419A (en) * | 2019-06-18 | 2020-12-18 | 中国科学技术大学 | Preparation method of bacterial cellulose composite board with tubular structure |
| CN112092419B (en) * | 2019-06-18 | 2022-04-19 | 中国科学技术大学 | Preparation method of bacterial cellulose composite board with tubular structure |
| CN113311025A (en) * | 2021-07-13 | 2021-08-27 | 浙江农林大学 | Preparation method of novel intelligent gas sensing material suitable for indoor ammonia gas detection |
| CN113311025B (en) * | 2021-07-13 | 2023-06-27 | 浙江农林大学 | Preparation method of novel intelligent gas sensing material suitable for indoor ammonia gas detection |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106893284B (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dai et al. | Green pH/magnetic sensitive hydrogels based on pineapple peel cellulose and polyvinyl alcohol: Synthesis, characterization and naringin prolonged release | |
| Zhang et al. | An eco-friendly slow-release urea fertilizer based on waste mulberry branches for potential agriculture and horticulture applications | |
| Ji et al. | An in-situ fabrication of bamboo bacterial cellulose/sodium alginate nanocomposite hydrogels as carrier materials for controlled protein drug delivery | |
| Deng et al. | Cellulose nanofibril as a crosslinker to reinforce the sodium alginate/chitosan hydrogels | |
| George et al. | Bacterial cellulose nanocrystals exhibiting high thermal stability and their polymer nanocomposites | |
| CN104845301B (en) | A kind of ultraviolet light screener and preparation method thereof and polylactic acid film comprising the ultraviolet light screener and preparation method thereof | |
| CN106893284A (en) | The preparation method of polylactic acid/nano-cellulose composite material | |
| CN108467499B (en) | A kind of regenerated bacteria cellulose microsphere and preparation method and application | |
| CN103866487A (en) | Method for preparing NCC/CS/PVA composite nano-membrane | |
| CN105295063B (en) | A kind of surface modification of microcrystalline cellulose and preparation method thereof | |
| CN102295827A (en) | Method for preparing fully biodegradable nano-composite polyester plastic | |
| CN101240085A (en) | Cellulose solution and preparation thereof thereof | |
| CN110857337A (en) | Method for synchronously preparing multiple biomass materials | |
| CN104558677A (en) | Preparation method of nano cellulose/chitosan composite foam | |
| CN108864667A (en) | A kind of biodegradable laminated film and preparation method thereof of nano-cellulose enhancing | |
| Blaker et al. | Ice-microsphere templating to produce highly porous nanocomposite PLA matrix scaffolds with pores selectively lined by bacterial cellulose nano-whiskers | |
| CN104226268A (en) | Modified cellulose/graphene oxide composite microsphere and preparation method thereof | |
| CN103360679A (en) | High-efficient reinforced anti-agglomeration antibacterial filler masterbatch for non-woven fabric and preparation process thereof | |
| CN108409984A (en) | A kind of method that Fast synchronization prepares lignin nanoparticle and carbon quantum dot | |
| CN107459664A (en) | A kind of method that spherex is prepared based on double-aqueous phase system | |
| CN109134944A (en) | A kind of porous small ball and its application with different chemical functional groups | |
| Zhao et al. | Development and characterisation of multi-form composite materials based on silver nanoclusters and cellulose nanocrystals | |
| CN107522877A (en) | Quaternized cellulose bead, preparation method and purposes | |
| Jin et al. | High strength graphene oxide/chitosan composite screws with a steel-concrete structure | |
| CN102604394B (en) | Preparation method of biodegradable emulsion film material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |