CN102304238A - Renewable cellulose composite film and preparation method thereof - Google Patents
Renewable cellulose composite film and preparation method thereof Download PDFInfo
- Publication number
- CN102304238A CN102304238A CN201110215330A CN201110215330A CN102304238A CN 102304238 A CN102304238 A CN 102304238A CN 201110215330 A CN201110215330 A CN 201110215330A CN 201110215330 A CN201110215330 A CN 201110215330A CN 102304238 A CN102304238 A CN 102304238A
- Authority
- CN
- China
- Prior art keywords
- composite film
- regenerated cellulose
- cellulose composite
- preparation
- organic solvent
- 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
Images
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a renewable cellulose composite film, which comprises 60 to 97.5 mass percent of cellulose and 2.5 to 40 mass percent of halogenated polymer, and has the characteristics of high flexibility, high biodegrability, high compatability, and the like. The invention also discloses a method for preparing the renewable cellulose composite film, which comprises: 1) adding cellulose into a pretreated organic solvent, treating for 0.5 to 1 hour at 155 to 165 DEG C and squeezing; 2) adding the squeezed pretreated cellulose into a cosolvent organic solvent system, stirring till gel is produced, standing for 12 to 30 hours and obtaining transparent solution; 3) adding the halogenated polymer into the transparent solution, stirring, blending for 20 to 40 minutes and obtaining mixed solution; and 4) subjecting the mixed solution to film forming and film forming post treatment to obtain a renewable cellulose composite film. The method has the characteristics of simple preparation process, high controllability, high suitability for industrial production and the like.
Description
Technical field
The present invention relates to regenerated cellulose composite film and preparation field thereof, be specifically related to a kind of regenerated cellulose composite film and preparation method thereof.
Background technology
China is one of ten big plastics production and consumption states in the world.About 1,100 ten thousand tons of nineteen ninety-five whole nation plastics total quantity consumed, wherein, the packaging plastics reach 2,110,000 tons.The major part of packaging plastics is abandoned arbitrarily with the form of waste and old film, plastics bag and porous plastics tableware.According to investigations, 3% of Beijing's domestic refuse is the waste or used plastics packing material, and annual generation is about 140,000 tons; 7% of Shanghai City domestic refuse is the waste or used plastics packing material, and annual generation is about 190,000 tons.Be discarded in the waste and old packing plastics in the environment, not only influence the appearance of the city and natural landscape, produce " visual pollution ", and, also can cause potential hazard ecotope because of it is difficult to degraded.China is used for the improvement funds about about 1,850 ten thousand of white pollution every year.Therefore, to such problem, the development of Biodegradable material has obtained fervent concern both domestic and external in recent years with use, and the scientific worker of countries in the world is in the research of carrying out biodegradable polymer energetically.
Mierocrystalline cellulose is a kind of renewable resources of cheapness, estimates according to scientist, and the annual Mierocrystalline cellulose that obtains through photosynthesis surpasses 1,000 hundred million tons, surpasses present oil reserves.Viscose process and cuprammonium process are mainly adopted in the production of regenerated cellulose film, and its product has been compared following characteristics with synthetic polymeric membrane: one, mechanical strength is high, makes very thin film easily; Two, have good gamma ray resistant ability and good thermotolerance; Three, have security and stability, nontoxic; Four, film can decompose under action of microorganisms after discarding, and can not reproduce into environmental pollution.
The use of regenerated cellulose provides a kind of effective technical means for solving white pollution problems, has bright application prospect.Yet traditional viscose process and cuprammonium process production process are seriously polluted, and film plasticity ratio under dry state is relatively poor simultaneously, and the elongation at break under dry state is no more than 10%.Therefore, the plasticity of developing a kind of green production process of cellulose membrane and improving cellulose membrane is necessary.
Publication number is that the one Chinese patent application of 101733002A discloses a kind of pH sensitive type cation regenerated cellulose composite film and Preparation method and use, and this regenerated cellulose composite film comprises the Mierocrystalline cellulose of mass percent 80%～99.9% and 0.1%～20% chitosan; 1), with after the cellulose solution deaeration preparation method that it discloses the pH sensitive type cation regenerated cellulose composite film may further comprise the steps:, hydrostomia becomes solution layer on substrate, solidifies then, obtains the cellulose solution layer; 2), chitosan is dissolved in the solvent, make chitosan solution; 3), the cellulose solution layer after step 1) solidified immerses in the chitosan solution, Mierocrystalline cellulose is separated out film forming with regeneration, dries after the cleaning, promptly makes the pH sensitive type cation regenerated cellulose composite film.Though this pH sensitive type cation regenerated cellulose composite film has excellent biological compatibility, biocidal property and degradability; It is outstanding focuses on having outstanding bacteriostasis property; But its mechanical property, particularly toughness intensity is obviously on the low side, exists technical problem.
In the prior art; Developed the plain green solvent system of some fibre; Like LiCl/DMAC, LiCl/DMF and LiCl/DMSO; The LiCl/DMAC solvent system is one of them; Use the preprocessing process of LiCl/DMAC solvent system may further comprise the steps: Mierocrystalline cellulose is added in the LiCl/DMAC solvent system; Heated and stirred 30min～60min in 160 ℃ of oil baths, squeezing then, oven drying at low temperature is subsequent use.Particularly oven drying at low temperature needs freeze drier, and cost is high, and length consuming time generally surpasses 6 hours, is confined to the experimental phase always, can't suitability for industrialized production, exist technological deficiency.
Summary of the invention
The invention provides a kind of regenerated cellulose composite film, have high tenacity, biodegradable, characteristics such as consistency is good.
The present invention also provides a kind of preparation method of regenerated cellulose composite film, has that preparation technology is simple, controllability good, be easy to characteristics such as suitability for industrialized production.
A kind of regenerated cellulose composite film, form by following component by mass percent:
Mierocrystalline cellulose 60%～97.5%;
Halo polymer 2.5%～40%.
Described Mierocrystalline cellulose is natural lignocellulose, specifically can select a kind of or two or more in seaweed fiber element, bacteria cellulose, short velveteen, flax, hemp, wood pulp, Microcrystalline Cellulose, cotton, timber, bamboo powder, the bagasse for use.
Described halo polymer is that polyvinylidene difluoride (PVDF) (PVDF), polyvinylidene dichloride (PVDC) etc. contain a kind of or two or more in the polymer of a large amount of fluorine and chlorine atom, and these polymers generally all have high tenacity and/or high-ductility.The present invention changes the strong hydrogen bond action of cellulosic molecule interchain through adding some polymers (micromolecular softening agent is prone to run off) with cellulose blending; Improve cellulose chain motor capacity at normal temperatures to reach, thereby improve the toughness of regenerated cellulose composite film.Because the reactive force of halogen atom such as the fluorine that the electronegativity on the halo macromolecular chain is very strong, chlorine and hydrogen atom is strong, so halo polymer and cellulosic consistency are good, can improve the mechanical strength of regenerated cellulose composite film.
The preparation method of described regenerated cellulose composite film may further comprise the steps:
1) Mierocrystalline cellulose is joined in the pre-treatment organic solvent, handle 0.5h～1h, through squeezing, obtain pretreated Mierocrystalline cellulose again at 155 ℃～165 ℃;
2) the pretreated Mierocrystalline cellulose that obtains in the step 1) is joined be dissolved with altogether in the machine solvent system, until producing gel, leave standstill 12h～30h again, obtain clear solution 70 ℃～100 ℃ stirrings;
3) to step 2) in add the halo polymer in the clear solution that obtains, at 70 ℃～100 ℃ blended under agitation 15min～40min, obtain mixing solutions;
4) mixing solutions that step 3) is obtained obtains regenerated cellulose composite film through film forming and film forming aftertreatment.
Better invent effect in order to obtain the present invention, below as of the present invention further preferred:
In the step 1), described pre-treatment organic solvent is a kind of in N,N-DIMETHYLACETAMIDE (DMAC), dimethyl formamide (DMF), the dimethyl sulfoxide (DMSO) (DMSO), can avoid introducing multiple organic solvent and the preparation that influences regenerated cellulose composite film.
Step 2) in; The described machine solvent system that is dissolved with altogether is a kind of in lithium chloride and N,N-DIMETHYLACETAMIDE (LiCl/DMAC) organic solvent system, lithium chloride and dimethyl formamide (LiCl/DMF) organic solvent system, lithium chloride and dimethyl sulfoxide (DMSO) (LiCl/DMSO) organic solvent system; Wherein, the mass ratio of lithium chloride and organic solvent (being DMAC, DMF, DMSO) is preferably 1/9.
Because in step 1); Though added the pre-treatment organic solvent; But the removal step that does not comprise the pre-treatment organic solvent; For fear of in the preparation process, introducing multiple organic solvent; Thereby influence the preparation of regenerated cellulose composite film; The organic solvent that described pre-treatment organic solvent is dissolved with in the machine solvent system together preferably is consistent, and is specially: when being dissolved with the machine solvent system altogether is LiCl/DMAC, and at this moment the pre-treatment organic solvent is just selected DMAC; When being dissolved with the machine solvent system altogether is LiCl/DMF, and at this moment the pre-treatment organic solvent is just selected DMF; When being dissolved with the machine solvent system altogether is LiCl/DMSO, and at this moment the pre-treatment organic solvent is just selected DMSO.
The squeezing condition: pressure is that 3MPa～10MPa, pressing temperature are that 165 ℃～210 ℃, dwell time are 1min～5min.The release drying can realize the dissolving of Mierocrystalline cellulose in organic solvent after the pressurize.
In the step 3), described halo polymer adds with form of powder.This adding mode is easy, and the halo polymer can be dispersed in the transparent mixing solutions uniformly.Perhaps; The high molecular powder of described halo stirs at 70 ℃～100 ℃ and adds in the mixing solutions again after 10min～30min is dissolved in the machine that is dissolved with the altogether solvent system of getting in addition; This adding mode can make the halo polymer be dispersed in transparent mixing solutions better, and the add-on of halo polymeric powder ratio is easier to control.
In the step 4), described film forming and film forming aftertreatment comprise: 20 ℃～40 ℃ following film forming, place 0.5h～3h after the film forming, in water, soak 10h～20h again, change water 2～8 times.
Film forming step and film forming aftertreatment through concrete obtain the stable regenerated cellulose composite film of over-all properties, and its mechanical strength is higher, better under action of microorganisms, decompose after film is discarded, can not cause environmental pollution.Therefore, the use of regenerated cellulose film has brought bright prospect for solving white pollution problems.
Compared with prior art, the present invention has following advantage:
Regenerated cellulose composite film of the present invention, its main raw material adopts Mierocrystalline cellulose, is renewable resources, has biodegradable preferably; Through adding the halo polymer of high tenacity or plasticity; Make itself and Mierocrystalline cellulose polymer have consistency preferably; The regenerated cellulose composite film of preparation has high tenacity, and its elongation at break all has raising largely, its superior than pure regenerated cellulose composite film.
The preparation method of regenerated cellulose composite film of the present invention; Simplified the preprocessing process of traditional LiCl/DMAC solvent system; Remove this step consuming time, power consumption of cryodrying; Make that the inventive method preparation technology is simple, easy and simple to handle, controllability is good; Owing to simplified preprocessing process; Make the preparation method of regenerated cellulose composite film of the present invention can more easily realize suitability for industrialized production, and help reducing the cost of suitability for industrialized production.
Description of drawings
Fig. 1 is the electron-microscope scanning figure of the regenerated cellulose composite film of embodiment 1 preparation;
Fig. 2 is the electron-microscope scanning figure of the regenerated cellulose composite film of embodiment 3 preparations;
Fig. 3 is the electron-microscope scanning figure of the regenerated cellulose composite film of embodiment 4 preparations.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but be not limited to embodiment.
Comparative Examples 1
1) cellulosic pre-treatment
With 1 gram Mierocrystalline cellulose (Dezhou heavenly steed Mierocrystalline cellulose company limited; Purified cotton; The polymerization degree (DP)=800) joins among the 100 gram DMAC; 160 ℃ of activation treatment 0.5 hour; Again through squeezing; The squeezing condition: pressure is that 4MPa, pressing temperature are that 175 ℃, dwell time are 3min, obtains pretreated Mierocrystalline cellulose, and this process does not almost have cellulosic loss;
2) cellulosic dissolving
The pretreated 0.9 gram Mierocrystalline cellulose that obtains in the step 1) is joined in the 29.1 gram LiCl/DMAC organic solvent systems (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system); Under 100 ℃ of conditions, stir until producing gel (approximately stirring 3h); Leave standstill 24h under the room temperature again; Obtain clear solution 30 grams, containing cellulosic mass percent in the clear solution is 3%;
3) cellulose film forming
With step 2) the 30 gram clear solutions that obtain take out, 25 ℃ down can the striking film forming, in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is for being about 30 microns.
Adopt universal testing machine that the regenerated cellulose composite film of Comparative Examples 1 preparation is carried out Mechanics Performance Testing.The batten standard is that 10mm is wide, and anchor clamps length is 50mm.Draw speed is 5mm/min.Its test result sees table 1 for details.
Embodiment 1
1) cellulosic pre-treatment
With 0.9 gram Mierocrystalline cellulose (Dezhou heavenly steed Mierocrystalline cellulose company limited; Purified cotton; DP=800) join among the 100 gram DMAC; Handled 0.5 hour at 160 ℃; Again through squeezing; The squeezing condition: pressure is that 4MPa, pressing temperature are that 175 ℃, dwell time are 3min, obtains pretreated Mierocrystalline cellulose, and this process does not almost have cellulosic loss;
2) cellulosic dissolving
The pretreated 0.9 gram Mierocrystalline cellulose that obtains in the step 1) is joined in the 29.1 gram LiCl/DMAC organic solvent systems (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system); Under 100 ℃ of conditions, stir until producing gel (approximately stirring 3h); At room temperature leave standstill 24h again; Obtain clear solution 30 grams, containing cellulosic mass percent in the clear solution is 3%;
3) dissolving of PVDF and blend
With PVDF (FR-904; Mn=475637; Limit company is liked to be rich in Shanghai three) powder after 80 ℃ are stirred 20min and are dissolved in LiCl/DMAC organic solvent system (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system), obtain containing the PVDF mass percentage concentration and be 3% PVDF solution; To step 2) in add PVDF solution in the clear solution that obtains, at 80 ℃ of blended under agitation 40min, obtain transparent mixing solutions; The mass ratio of clear solution and PVDF solution is 97.5: 2.5;
4) cellulose film forming
Get the gram of 30 in step 3) mixing solutions and be cooled to 25 ℃ of film forming; In air, placed 1 hour after the film forming; In distilled water, soaked 12 hours then; Change distilled water 3 times; Obtain regenerated cellulose composite film, its thickness is 20um, and its electron-microscope scanning figure as shown in Figure 1; As can be seen from Figure 1, Mierocrystalline cellulose and PVDF consistency are good in the regenerated cellulose composite film of preparation.
The regenerated cellulose composite film of embodiment 1 preparation is adopted and the rupture test of percentage of elongation, tensile strength and modulus of Comparative Examples 1 identical method, and its test result sees table 1 for details.
Embodiment 2
1) cellulosic pre-treatment
With 0.9 gram Mierocrystalline cellulose (Dezhou heavenly steed Mierocrystalline cellulose company limited; Purified cotton; DP=800) join among the 100 gram DMAC; Handled 0.5 hour at 160 ℃; Again through squeezing; The squeezing condition: pressure is that 4MPa, pressing temperature are that 175 ℃, dwell time are 3min, obtains pretreated Mierocrystalline cellulose, and this process does not almost have cellulosic loss;
2) cellulosic dissolving
The pretreated 0.9 gram Mierocrystalline cellulose that obtains in the step 1) is joined in the 29.1 gram LiCl/DMAC organic solvent systems (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system); Under 100 ℃ of conditions, stir until producing gel (approximately stirring 3h); Leave standstill 24h under the room temperature again; Obtain clear solution 30 grams, containing cellulosic mass percent in the clear solution is 3%;
3) dissolving of PVDF and blend
With PVDF (FR-904; Mn=475637; Limit company is liked to be rich in Shanghai three) powder after 80 ℃ are stirred 20min and are dissolved in the LiCl/DMAC organic solvent system of getting in addition (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system), obtain containing the PVDF mass percentage concentration and be 3% PVDF solution; To step 2) in add PVDF solution in the clear solution that obtains, at 80 ℃ of blended under agitation 40min, obtain transparent mixing solutions; The mass ratio of clear solution and PVDF solution is 80: 20;
4) cellulose film forming
Get the gram of 30 in step 3) mixing solutions and be cooled to 20 ℃ of film forming, in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is 20um.
The regenerated cellulose composite film of embodiment 2 preparation is adopted and the rupture test of percentage of elongation, tensile strength and modulus of Comparative Examples 1 identical method, and its test result sees table 1 for details.
Embodiment 3
1) cellulosic pre-treatment
With 0.9 gram Mierocrystalline cellulose (Dezhou heavenly steed Mierocrystalline cellulose company limited; Purified cotton; DP=800) join among the 100 gram DMAC; Handled 0.5 hour at 160 ℃; Again through squeezing; The squeezing condition: pressure is that 4MPa, pressing temperature are that 175 ℃, dwell time are 3min, obtains pretreated Mierocrystalline cellulose, and this process does not almost have cellulosic loss;
2) cellulosic dissolving
The pretreated 0.9 gram Mierocrystalline cellulose that obtains in the step 1) is joined in the 29.1 gram LiCl/DMAC organic solvent systems (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system); Under 100 ℃ of conditions, stir until producing gel (approximately stirring 3h); Leave standstill 24h under the room temperature again; Obtain clear solution 30 grams, containing cellulosic mass percent in the solution is 3%;
3) dissolving of PVDF and blend
With PVDF (FR-904; Mn=475637; Limit company is liked to be rich in Shanghai three) powder after 80 ℃ are stirred 20min and are dissolved in the LiCl/DMAC organic solvent system of getting in addition (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system), obtain containing the PVDF mass percentage concentration and be 3% PVDF solution; To step 2) in add PVDF solution in the clear solution that obtains, at 80 ℃ of blended under agitation 40min, obtain transparent mixing solutions; The mass ratio of clear solution and PVDF solution is 60: 40;
4) cellulose film forming
Get the gram of 30 in step 3) mixing solutions and be cooled to 40 ℃ of film forming; In air, placed 1 hour after the film forming; In distilled water, soaked 12 hours then; Change distilled water 3 times; Obtain regenerated cellulose composite film; Its thickness be its electron-microscope scanning of 20um. figure as shown in Figure 2, as can be seen from Figure 2, Mierocrystalline cellulose and PVDF consistency are good in the regenerated cellulose composite film of preparation.
The regenerated cellulose composite film of embodiment 3 preparation is adopted the rupture test of percentage of elongation, tensile strength and modulus of the method for Comparative Examples 1, and its test result sees table 1 for details.
Embodiment 4
1) cellulosic pre-treatment is with embodiment 1
2) cellulosic dissolving is with embodiment 1
3) dissolving of PVDC and blend
With PVDC (Saran168; DOW chemical company) powder obtains containing the PVDC mass percentage concentration and is 3% PVDC solution after 80 ℃ are stirred 20min and are dissolved in the LiCl/DMAC organic solvent system of getting in addition (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system); To step 2) in add PVDC solution in the clear solution that obtains, at 80 ℃ of blended under agitation 40min, obtain transparent mixing solutions; The mass ratio of clear solution and PVDC solution is 97.5: 2.5;
4) cellulose film forming
Get the gram of 30 in step 3) mixing solutions and be cooled to 40 ℃ of film forming; In air, placed 1 hour after the film forming; In distilled water, soaked 12 hours then; Change distilled water 3 times; Obtain regenerated cellulose composite film, its thickness is 20um, and its electron-microscope scanning figure as shown in Figure 3; As can be seen from Figure 3, Mierocrystalline cellulose and PVDC consistency are good in the regenerated cellulose composite film of preparation.
The regenerated cellulose composite film of embodiment 4 preparation is adopted and the rupture test of percentage of elongation, tensile strength and modulus of Comparative Examples 1 identical method, and its test result sees table 2 for details.
Embodiment 5
1) cellulosic pre-treatment is with embodiment 1
2) cellulosic dissolving is with embodiment 1
3) dissolving of PVDC and blend
With PVDC (Saran168; DOW chemical company) powder obtains containing the PVDC mass percentage concentration and is 3% PVDC solution after 80 ℃ are stirred 20min and are dissolved in the LiCl/DMAC organic solvent system of getting in addition (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system); To step 2) in add PVDC solution in the clear solution that obtains, at 80 ℃ of blended under agitation 40min, obtain transparent mixing solutions; The mass ratio of clear solution and PVDC solution is 80: 20;
4) cellulose film forming
Get the gram of 30 in step 3) mixing solutions and be cooled to 30 ℃ of film forming, in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is 20um.
The regenerated cellulose composite film of embodiment 5 preparation is adopted and the rupture test of percentage of elongation, tensile strength and modulus of Comparative Examples 1 identical method, and its test result sees table 2 for details.
Embodiment 6
1) cellulosic pre-treatment is with embodiment 1
2) cellulosic dissolving is with embodiment 1
3) dissolving of PVDC and blend
With PVDC (Saran168; DOW chemical company) powder obtains containing the PVDC mass percentage concentration and is 3% PVDC solution after 80 ℃ are stirred 20min and are dissolved in the LiCl/DMAC organic solvent system of getting in addition (mass ratio of LiCl and DMAC is 1: 9 in the LiCl/DMAC organic solvent system); To step 2) in add PVDC solution in the clear solution that obtains, at 80 ℃ of blended under agitation 40min, obtain transparent mixing solutions; The mass ratio of clear solution and PVDC solution is 60: 40;
4) cellulose film forming
Get the gram of 30 in step 3) mixing solutions and be cooled to 25 ℃ of film forming, in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is 20um.
The regenerated cellulose composite film of embodiment 6 preparation is adopted and the rupture test of percentage of elongation, tensile strength and modulus of Comparative Examples 1 identical method, and its test result sees table 1 for details.
Comparative Examples 2
1) cellulosic pre-treatment
With 1 gram Mierocrystalline cellulose (Dezhou heavenly steed Mierocrystalline cellulose company limited; Purified cotton; DP=800) join among the 100 gram DMF; Handled 0.5 hour at 155 ℃; Again through squeezing; The squeezing condition: pressure is that 4MPa, pressing temperature are that 165 ℃, dwell time are 3min, obtains pretreated Mierocrystalline cellulose, and this process does not almost have cellulosic loss;
2) cellulosic dissolving
The pretreated 0.9 gram Mierocrystalline cellulose that obtains in the step 1) is joined in the 29.1 gram LiCl/DMF organic solvent systems (mass ratio of LiCl and DMF is 1: 9 in the LiCl/DMF organic solvent system); Under 100 ℃ of conditions, stir until producing gel (approximately stirring 3h); Leave standstill 24h under the room temperature again; Obtain clear solution 30 grams, containing cellulosic mass percent in the clear solution is 3%;
3) cellulose film forming
With step 2) the 30 gram clear solutions that obtain take out, down can the striking film forming 25 ℃ of room temperatures, in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is for being about 30 microns.
Adopt universal testing machine that the regenerated cellulose composite film of Comparative Examples 2 preparations is carried out Mechanics Performance Testing.The batten standard is that 10mm is wide, and anchor clamps length is 50mm.Draw speed is 5mm/min.Its test result sees table 1 for details.
Embodiment 7
1) cellulosic pre-treatment is with Comparative Examples 2
2) cellulosic dissolving is with Comparative Examples 2
3) dissolving of PVDF and blend
With PVDF (FR-904; Mn=475637; Limit company is liked to be rich in Shanghai three) powder after 80 ℃ are stirred 20min and are dissolved in the LiCl/DMF organic solvent system of getting in addition (mass ratio of LiCl and DMF is 1: 9 in the LiCl/DMF organic solvent system), obtain containing the PVDF mass percentage concentration and be 3% PVDF solution; Add PVDF solution in the clear solution that in step 1), obtains,, obtain transparent mixing solutions at 80 ℃ of blended under agitation 40min; The mass ratio of clear solution and PVDF solution is 97.5: 2.5;
4) cellulose film forming
Get the gram of 30 in step 3) mixing solutions and be cooled to 25 ℃ of film forming, in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is 20um.
The regenerated cellulose composite film of embodiment 7 preparation is adopted and the rupture test of percentage of elongation, tensile strength and modulus of Comparative Examples 2 identical methods, and its test result sees table 1 for details.
Embodiment 8
1) cellulosic pre-treatment is with Comparative Examples 2
2) cellulosic dissolving is with Comparative Examples 2
3) dissolving of PVDF and blend
With PVDF (FR-904; Mn=475637; Limit company is liked to be rich in Shanghai three) powder after 80 ℃ are stirred 20min and are dissolved in the LiCl/DMF organic solvent system of getting in addition (mass ratio of LiCl and DMF is 1: 9 in the LiCl/DMF organic solvent system), obtain containing the PVDF mass percentage concentration and be 3% PVDF solution; Add PVDF solution in the clear solution that in step 1), obtains,, obtain transparent mixing solutions at 80 ℃ of blended under agitation 40min; The mass ratio of clear solution and PVDF solution is 80: 20;
4) cellulose film forming
Get the gram of 30 in step 3) mixing solutions and be cooled to 30 ℃ of film forming, in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is 20um.
The regenerated cellulose composite film of embodiment 8 preparation is adopted and the rupture test of percentage of elongation, tensile strength and modulus of Comparative Examples 1 identical method, and its test result sees table 1 for details.
Comparative Examples 3
1) cellulosic pre-treatment
With 1 gram Mierocrystalline cellulose (Dezhou heavenly steed Mierocrystalline cellulose company limited; Purified cotton; DP=800) join among the 100 gram DMSO; Handled 0.5 hour at 165 ℃; Again through squeezing; The squeezing condition: pressure is that 4MPa, pressing temperature are that 165 ℃, dwell time are 3min, obtains pretreated Mierocrystalline cellulose, and this process does not almost have cellulosic loss;
2) cellulosic dissolving
The pretreated 0.9 gram Mierocrystalline cellulose that obtains in the step 1) is joined in the 29.1 gram LiCl/DMSO organic solvent systems (mass ratio of LiCl and DMSO is 1: 9 in the LiCl/DMSO organic solvent system); Under 100 ℃ of conditions, stir until producing gel (approximately stirring 3h); Leave standstill 24h under the room temperature again; Obtain clear solution 30 grams, containing cellulosic mass percent in the clear solution is 3%;
3) cellulose film forming
With step 2) clear solution that obtains takes out, down can the striking film forming 25 ℃ of room temperatures, in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is for being about 30 microns.
Adopt universal testing machine that the regenerated cellulose composite film of Comparative Examples 3 preparations is carried out Mechanics Performance Testing.The batten standard is that 10mm is wide, and anchor clamps length is 50mm.Draw speed is 5mm/min.Its test result sees table 1 for details.
Embodiment 9
1) cellulosic pre-treatment is with Comparative Examples 3
2) cellulosic dissolving is with Comparative Examples 3
3) dissolving of PVDF and blend
With PVDF (FR-904; Mn=475637; Limit company is liked to be rich in Shanghai three) powder after 80 ℃ are stirred 20min and are dissolved in the LiCl/DMSO organic solvent system of getting in addition (mass ratio of LiCl and DMSO is 1: 9 in the LiCl/DMSO organic solvent system), obtain containing the PVDF mass percentage concentration and be 3% PVDF solution; Add PVDF solution in the clear solution that in step 1), obtains,, obtain transparent mixing solutions at 80 ℃ of blended under agitation 40min; The mass ratio of clear solution and PVDF solution is 97.5: 2.5;
4) cellulose film forming
Get 25 ℃ of film forming of the gram mixing solutions cool to room temperature of 30 in the step 3), in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is 20um.
The regenerated cellulose composite film of embodiment 9 preparation is adopted and the rupture test of percentage of elongation, tensile strength and modulus of Comparative Examples 3 identical methods, and its test result sees table 1 for details.
Embodiment 10
1) cellulosic pre-treatment is with Comparative Examples 3
2) cellulosic dissolving is with Comparative Examples 3
3) dissolving of PVDF and blend
With PVDF (FR-904; Mn=475637; Limit company is liked to be rich in Shanghai three) powder after 80 ℃ are stirred 20min and are dissolved in the LiCl/DMSO organic solvent system of getting in addition (mass ratio of LiCl and DMSO is 1: 9 in the LiCl/DMSO organic solvent system), obtain containing the PVDF mass percentage concentration and be 3% PVDF solution; Add PVDF solution in the clear solution that in step 1), obtains,, obtain transparent mixing solutions at 80 ℃ of blended under agitation 40min; The mass ratio of clear solution and PVDF solution is 60: 40;
4) cellulose film forming
Get 25 ℃ of film forming of the gram mixing solutions cool to room temperature of 30 in the step 3), in air, placed 1 hour after the film forming, in distilled water, soaked 12 hours then, change distilled water 3 times, obtain regenerated cellulose composite film, its thickness is 20um.
The regenerated cellulose composite film of embodiment 10 preparation is adopted and the rupture test of percentage of elongation, tensile strength and modulus of Comparative Examples 3 identical methods, and its test result sees table 1 for details.
Table 1
Can know by table 1; The regenerated cellulose composite film of embodiment 1～6 preparation is compared with the regenerated cellulose film of Comparative Examples 1 preparation, the regenerated cellulose composite film of embodiment 7～8 preparations is compared with the regenerated cellulose film of Comparative Examples 2 preparations compares with the regenerated cellulose film of Comparative Examples 3 preparations with the regenerated cellulose composite film of embodiment 9～10 preparations; Under the situation that intensity and modulus are maintained, the elongation at break of the regenerated cellulose composite film of embodiment 1～10 preparation has generally improved 3～4 times.
Claims (10)
1. regenerated cellulose composite film, form by following component by mass percent:
Mierocrystalline cellulose 60%～97.5%;
Halo polymer 2.5%～40%.
2. regenerated cellulose composite film according to claim 1; Its spy is being, described Mierocrystalline cellulose is a kind of or two or more in seaweed fiber element, bacteria cellulose, short velveteen, flax, hemp, wood pulp, Microcrystalline Cellulose, cotton, timber, bamboo powder, the bagasse.
3. regenerated cellulose composite film according to claim 1, its spy is being, described halo polymer is a kind of in polyvinylidene difluoride (PVDF), the polyvinylidene dichloride or two kinds.
4. according to the preparation method of each described regenerated cellulose composite film of claim 1～3, may further comprise the steps:
1) Mierocrystalline cellulose is joined in the pre-treatment organic solvent, handle 0.5h～1h, through squeezing, obtain pretreated Mierocrystalline cellulose again at 155 ℃～165 ℃;
2) the pretreated Mierocrystalline cellulose that obtains in the step 1) is joined be dissolved with altogether in the machine solvent system, until producing gel, leave standstill 12h～30h again, obtain clear solution 70 ℃～100 ℃ stirrings;
3) to step 2) in add the halo polymer in the clear solution that obtains, at 70 ℃～100 ℃ blended under agitation 15min～40min, obtain mixing solutions;
4) mixing solutions that step 3) is obtained obtains regenerated cellulose composite film through film forming and film forming aftertreatment.
5. the preparation method of regenerated cellulose composite film according to claim 4 is characterized in that, in the step 1), described pre-treatment organic solvent is a kind of in N,N-DIMETHYLACETAMIDE, dimethyl formamide, the dimethyl sulfoxide (DMSO).
6. the preparation method of regenerated cellulose composite film according to claim 4 is characterized in that, in the step 1), and squeezing condition: pressurize 1min～5min under 3MPa～10MPa pressure and 165 ℃～210 ℃ conditions.
7. the preparation method of regenerated cellulose composite film according to claim 4; It is characterized in that; Step 2) in, the described machine solvent system that is dissolved with altogether is a kind of in lithium chloride and N,N-DIMETHYLACETAMIDE organic solvent system, lithium chloride and dimethyl formamide organic solvent system, lithium chloride and the dimethyl sulfoxide (DMSO) organic solvent system.
8. the preparation method of regenerated cellulose composite film according to claim 4 is characterized in that, in the step 3), described halo polymer adds with form of powder.
9. the preparation method of regenerated cellulose composite film according to claim 4; It is characterized in that; In the step 3), the high molecular powder of described halo stirs at 70 ℃～100 ℃ and adds in the clear solution after 10min～30min is dissolved in the machine that is dissolved with the altogether solvent system of getting in addition again.
10. the preparation method of regenerated cellulose composite film according to claim 4 is characterized in that, in the step 4); Described film forming and film forming aftertreatment comprise: 20 ℃～40 ℃ following film forming; Place 0.5h～3h after the film forming, in water, soak 10h～20h again, change water 2～8 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110215330 CN102304238B (en) | 2011-07-29 | 2011-07-29 | Renewable cellulose composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110215330 CN102304238B (en) | 2011-07-29 | 2011-07-29 | Renewable cellulose composite film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102304238A true CN102304238A (en) | 2012-01-04 |
| CN102304238B CN102304238B (en) | 2013-01-30 |
Family
ID=45378163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110215330 Active CN102304238B (en) | 2011-07-29 | 2011-07-29 | Renewable cellulose composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102304238B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730307A (en) * | 2012-07-12 | 2012-10-17 | 云南绅博源生物科技有限公司 | Degradable transparent packaging material for cigarettes |
| CN103554534A (en) * | 2013-10-24 | 2014-02-05 | 华南理工大学 | Preparation method of wood fiber biomass film |
| CN106397839A (en) * | 2016-09-27 | 2017-02-15 | 河南工程学院 | Completely degraded waterproof food packaging material and preparation method thereof |
| CN106432807A (en) * | 2016-09-27 | 2017-02-22 | 河南工程学院 | Completely degradable waterproof packaging material and method for preparing same |
| CN107603178A (en) * | 2017-09-30 | 2018-01-19 | 四会市启德信息咨询服务有限公司 | A kind of heat-resisting biodegradable plastic material |
| CN107840977A (en) * | 2017-10-20 | 2018-03-27 | 天津市宝德包装有限公司 | A kind of fresh-keeping preparation method with oxygen flow moisture-inhibiting packaging film of vegetables and fruits |
| CN111617639A (en) * | 2020-05-28 | 2020-09-04 | 中国科学院合肥物质科学研究院 | Biomass cellulose modified PVDF hollow fiber microfiltration membrane and preparation method and application thereof |
| CN114381079A (en) * | 2022-01-27 | 2022-04-22 | 陕西科技大学 | BT nanoparticle/regenerated cellulose/PVDF composite material and preparation method thereof |
| CN116249614A (en) * | 2020-06-01 | 2023-06-09 | 得克萨斯技术大学联合体 | Method for producing cellulose bioplastic |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088225A (en) * | 1992-12-18 | 1994-06-22 | 中国国际科技促进会 | Vegetable fibre film product and technology thereof |
| JP2010094670A (en) * | 2008-09-19 | 2010-04-30 | Toray Ind Inc | Polyvinylidene fluoride-based multiple membrane and method for producing the same |
| CN102035043A (en) * | 2009-09-25 | 2011-04-27 | 上海比亚迪有限公司 | Polymer porous membrane, preparation method thereof, polymer electrolyte, polymer battery and preparation method of battery |
-
2011
- 2011-07-29 CN CN 201110215330 patent/CN102304238B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088225A (en) * | 1992-12-18 | 1994-06-22 | 中国国际科技促进会 | Vegetable fibre film product and technology thereof |
| JP2010094670A (en) * | 2008-09-19 | 2010-04-30 | Toray Ind Inc | Polyvinylidene fluoride-based multiple membrane and method for producing the same |
| CN102035043A (en) * | 2009-09-25 | 2011-04-27 | 上海比亚迪有限公司 | Polymer porous membrane, preparation method thereof, polymer electrolyte, polymer battery and preparation method of battery |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730307A (en) * | 2012-07-12 | 2012-10-17 | 云南绅博源生物科技有限公司 | Degradable transparent packaging material for cigarettes |
| CN103554534A (en) * | 2013-10-24 | 2014-02-05 | 华南理工大学 | Preparation method of wood fiber biomass film |
| CN103554534B (en) * | 2013-10-24 | 2017-02-08 | 华南理工大学 | Preparation method of wood fiber biomass film |
| CN106397839A (en) * | 2016-09-27 | 2017-02-15 | 河南工程学院 | Completely degraded waterproof food packaging material and preparation method thereof |
| CN106432807A (en) * | 2016-09-27 | 2017-02-22 | 河南工程学院 | Completely degradable waterproof packaging material and method for preparing same |
| CN106432807B (en) * | 2016-09-27 | 2018-09-11 | 河南工程学院 | A kind of water proof type packaging material and preparation method thereof that can be degradable |
| CN106397839B (en) * | 2016-09-27 | 2018-10-09 | 河南工程学院 | A kind of water proof type food packaging material and preparation method thereof that can be degradable |
| CN107603178A (en) * | 2017-09-30 | 2018-01-19 | 四会市启德信息咨询服务有限公司 | A kind of heat-resisting biodegradable plastic material |
| CN107840977A (en) * | 2017-10-20 | 2018-03-27 | 天津市宝德包装有限公司 | A kind of fresh-keeping preparation method with oxygen flow moisture-inhibiting packaging film of vegetables and fruits |
| CN111617639A (en) * | 2020-05-28 | 2020-09-04 | 中国科学院合肥物质科学研究院 | Biomass cellulose modified PVDF hollow fiber microfiltration membrane and preparation method and application thereof |
| CN116249614A (en) * | 2020-06-01 | 2023-06-09 | 得克萨斯技术大学联合体 | Method for producing cellulose bioplastic |
| CN114381079A (en) * | 2022-01-27 | 2022-04-22 | 陕西科技大学 | BT nanoparticle/regenerated cellulose/PVDF composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102304238B (en) | 2013-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102304238B (en) | Renewable cellulose composite film and preparation method thereof | |
| Tu et al. | Recent progress in high‐strength and robust regenerated cellulose materials | |
| CN100400579C (en) | Method for preparing functional material of regenerated cellulose | |
| Li et al. | All-cellulose composites based on the self-reinforced effect | |
| CN1261496C (en) | Cellulose solution and its preparing method | |
| CN109553945B (en) | Environment-friendly heat-insulating plastic film and preparation process thereof | |
| CN103552353B (en) | A kind of method preparing holocellulos composite laminates | |
| CN109517212B (en) | Preparation method of cellulose-graphene oxide-chitosan ternary composite aerogel | |
| CN103469588B (en) | The preparation method of the agent of sisal fiber surface size and sisal fiber composite | |
| CN103866487A (en) | Method for preparing NCC/CS/PVA composite nano-membrane | |
| CN106955599B (en) | A kind of aramid nano-fiber modification of chitosan composite membrane and its preparation and application | |
| CN107955984B (en) | Graphene grafted polysaccharide Lyocell fiber and preparation method thereof | |
| CN109402774B (en) | Anti-fibrillation cellulose fiber and preparation method thereof | |
| CN111910282B (en) | Waste feather regenerated pure keratin fiber and preparation method thereof | |
| CN105153660A (en) | Full-biodegradation bacterial cellulose/polylactic acid composite material and preparing method thereof | |
| CN105801883A (en) | Method for preparing cellulose solution | |
| CN103435839A (en) | Green recovery method for converting abandoned clothing into regenerant | |
| CN108160053B (en) | Nano cellulose gel and preparation method and application thereof | |
| CN104262642A (en) | Method for dissolving cellulose in aqueous solution of NaOH/thiourea at normal temperature | |
| CN108034205A (en) | A kind of preparation method of peanut shell fibre modification polylactic acid | |
| CN101168602B (en) | Corn protein/cellulose mixed solution, and preparation method and use thereof | |
| CN105463846B (en) | A kind of water-soluble sizing agent composition for carbon fiber and preparation method thereof | |
| CN1289587C (en) | Cellosolve and its use | |
| CN101168603A (en) | Soybean separation protein/cellulose mixed solution, and preparation method and use thereof | |
| CN1125845C (en) | Solvent composition and its use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |