CN108752644A - A kind of the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and preparation method of high intensity - Google Patents
A kind of the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and preparation method of high intensity Download PDFInfo
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- CN108752644A CN108752644A CN201810447182.5A CN201810447182A CN108752644A CN 108752644 A CN108752644 A CN 108752644A CN 201810447182 A CN201810447182 A CN 201810447182A CN 108752644 A CN108752644 A CN 108752644A
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- cellulose
- polyvinyl alcohol
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- 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
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
The invention discloses a kind of cation modifying of high intensity nano-cellulose/composite membrane of polyvinyl alcohol and preparation methods, belong to nanocomposite preparation field.Its basic characteristics is, using modified nanometer cellulose as reinforcing agent, to be added in poly-vinyl alcohol solution after carrying out cation modifying processing to nano-cellulose, composite membrane is prepared by the tape casting technique.Cation modifying nano-cellulose/composite membrane of polyvinyl alcohol mechanical property prepared by the present invention is relatively strong and excellent optical performance, biocompatibility, the degradability for retaining composite membrane of polyvinyl alcohol simultaneously have applications well foreground in high-strength degradable packaging material.
Description
Technical field
The invention belongs to nanocomposite preparation fields, and in particular to a kind of cation modifying Nanowire of high intensity
Tie up element/composite membrane of polyvinyl alcohol and preparation method.
Background technology
Polyvinyl alcohol (PVA) is a kind of nontoxic, degradable water-soluble linear polyhydroxylated polymer, have it is good at
Film property, barrier property, biocompatibility.In recent years, polyvinyl alcohol is applied very extensive in packaging field, but due to its film strength
The defect of performance limits its development.
Nano-cellulose (cellulose nanofibers, CNF) is due to its nanoscale, with high intensity, lightweight
Feature, at the same it is renewable, biodegradable, it is widely used in enhancing composite material, filtering material, sorbing material, biology doctor
The fields such as drug material.The preparation method of nano-cellulose includes TEMPO catalytic oxidations, enzymatic treatment and high-pressure homogeneous, ultrasound
The mechanical processing methods such as processing.It is added nano-cellulose as reinforcing agent in poly-vinyl alcohol solution, high-strength complex can be prepared
Close film, but with during polyvinyl alcohol, due to electrically repelling each other, nano-cellulose be difficult to it is uniform with polyvinyl alcohol, from
And influence quality of forming film.
And this problem can be well solved by carrying out cation modifying to nano-cellulose.Cationic cellulose conduct
One of derivative of cellulose, the mainly processing by esterification, etherificate or addition reagent to nano-cellulose, in cellulose chain
Middle to introduce containing being formed prepared by the structures such as tertiary amine, quaternary ammonium salt and quaternary alkylphosphonium salt, stable nanoparticles whiles, is also accompanied by Nanowire
The new characteristic of dimension element, has application in fields such as textile printing and dyeing, environmental protections.Cation modifying nano-cellulose and the poles PVA
Similar temperament, interface compatibility is good, suffers from good biodegradable, is environmentally friendly material.Cation has high rigid
Property and high intensity, and the rigidity of PVA and intensity are relatively weak, prepare cation modifying nano-cellulose/PVA composite materials
The application of cation modifying nano-cellulose and polyvinyl alcohol can be widened significantly, especially led in high intensity solubility packaging material
Domain has broad prospect of application.
Invention content
The present invention solves the technical problem of：For the deficiency of composite membrane of polyvinyl alcohol mechanical property, to limit
Its packaging etc. fields application the problem of, it is multiple to provide a kind of cation modifying nano-cellulose/polyvinyl alcohol of high intensity
Close film and each method processed.Its basic characteristics is that it is molten that polyvinyl alcohol is added using cation modifying nano-cellulose as reinforcing agent
In liquid, relatively strong and excellent optical performance the high-strength composite film of mechanical property is prepared by the tape casting technique.
The present invention is implemented by the following technical programs：
(1) cation modifying nano-cellulose/composite membrane of polyvinyl alcohol is prepared into film liquid：Weigh polyvinyl alcohol and go from
Sub- water is mixed to get polyvinyl alcohol water solution under water-bath, and cation modifying nano-cellulose and glycerine are separately added into
Into polyvinyl alcohol water solution, water bath sonicator 2h after 5~10min is stirred at room temperature；Then water-bath stands 5~10min of defoaming, obtains
To cation modifying nano-cellulose/composite membrane of polyvinyl alcohol at film liquid.
(2) cation modifying nano-cellulose/composite membrane of polyvinyl alcohol of high intensity is prepared：It is stood above-mentioned at film liquid
After cooling, uniformly toppled over using the tape casting on a glass, air-dries for 24 hours at room temperature, obtain the cation modifying of high intensity
Nano-cellulose/composite membrane of polyvinyl alcohol.
The cation modifying nano-cellulose is etherification modified nano-cellulose.
It is 70 DEG C that the bath temperature, water-bath, which stand defoaming,.
The stirring is mechanical agitation, and rotating speed is 500r/min~600r/min.
In the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and preparation method of a kind of high intensity, sun
Ionization Modification nano-cellulose: polyvinyl alcohol: deionized water: glycerine weight ratio is (2~30): (4~5): (70~100)
: (2~3).
In the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and preparation method of a kind of high intensity, film
Thickness is 18~19 μm.
Compared with prior art, the present invention has the following advantages：
(1) present invention prepares composite membrane using the tape casting, and technological process is simple, compared to films such as blow moulding, extrusion moldings
Method, it is easier to operate, greatly reduce film cost.
(2) polyvinyl alcohol film is added by composite membrane prepared by the present invention for cation modifying nano-cellulose
In, wherein the cation modifying to nano-cellulose is handled, nano-cellulose is efficiently solved in poly-vinyl alcohol solution
The problem of easily reuniting, to promote it evenly dispersed in poly-vinyl alcohol solution so that compound film dynamic performance greatly improves.
(3) cation modifying nano-cellulose/composite membrane of polyvinyl alcohol of high intensity prepared by the present invention has excellent
Optics, mechanical property, while it is biodegradable, application of the polyvinyl alcohol membrane material in packaging, medicine and other fields can be expanded.
Specific implementation mode
Preferred embodiment of the invention is described in further detail below by specific implementation example.
1. preparing cation modifying nano-cellulose/composite membrane of polyvinyl alcohol into film liquid：4g polyvinyl alcohol is weighed, 70
It is added under DEG C water bath with thermostatic control in the beaker for filling 88ml deionized waters, 5min is defoamed in 70 DEG C of water-baths after 15min is mixed,
Poly-vinyl alcohol solution is made, the cation modifying nano-cellulose that concentration 1.0% is sequentially added in poly-vinyl alcohol solution is molten
Glue, 1g glycerine, are stirred at room temperature 10min, by mixed liquor water bath sonicator 2h, are placed in 70 DEG C of water-baths and defoam 5min, be made sun from
Sonization modified nanometer cellulose/composite membrane of polyvinyl alcohol is at film liquid；
2. preparing cation modifying nano-cellulose/composite membrane of polyvinyl alcohol of high intensity：Cation modifying is received
Rice cellulose/polyvinyl alcohol composite membrane film forming liquid cooling but, is uniformly toppled on a glass by the tape casting, is air-dried at room temperature
Obtain cation modifying nano-cellulose/composite membrane of polyvinyl alcohol of high intensity afterwards for 24 hours.
Claims (5)
1. the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and preparation method of a kind of high intensity, it is characterised in that
Following preparation process：
(1) cation modifying nano-cellulose/composite membrane of polyvinyl alcohol is prepared into film liquid：Weigh polyvinyl alcohol and deionization
Water is mixed to get polyvinyl alcohol water solution under water-bath, and cation modifying nano-cellulose and glycerine are added separately to
In polyvinyl alcohol water solution, rear water bath sonicator 2h is stirred at room temperature；Then water-bath stands defoaming, obtains cation modifying Nanowire
Element/composite membrane of polyvinyl alcohol is tieed up into film liquid.
(2) cation modifying nano-cellulose/composite membrane of polyvinyl alcohol of high intensity is prepared：Above-mentioned stood at film liquid is cooled down
Afterwards, uniformly toppled over using the tape casting on a glass, air-dry for 24 hours at room temperature, obtain the cation modifying nanometer of high intensity
Cellulose/polyvinyl alcohol composite membrane.
2. the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and system of a kind of high intensity according to claim 1
Preparation Method, it is characterised in that：The cation modifying nano-cellulose is etherification modified nano-cellulose.
3. the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and system of a kind of high intensity according to claim 1
Preparation Method, it is characterised in that：It is 70 DEG C of water-baths that step (1) water-bath, which stands defoaming temperature,.
4. the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and system of a kind of high intensity according to claim 1
Preparation Method, it is characterised in that：Cation modifying nano-cellulose in composite membrane: polyvinyl alcohol: deionized water: glycerine weight
Than for (2~30): (4~5): (70~100): (2~3).
5. the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and system of a kind of high intensity according to claim 1
Preparation Method, it is characterised in that：Step (2) cation modifying nano-cellulose/composite membrane of polyvinyl alcohol thickness be 18~
19μm。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810447182.5A CN108752644A (en) | 2018-05-11 | 2018-05-11 | A kind of the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and preparation method of high intensity |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810447182.5A CN108752644A (en) | 2018-05-11 | 2018-05-11 | A kind of the cation modifying nano-cellulose/composite membrane of polyvinyl alcohol and preparation method of high intensity |
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| CN108752644A true CN108752644A (en) | 2018-11-06 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111119A (en) * | 2020-09-21 | 2020-12-22 | 桂林理工大学 | Polyvinyl alcohol nanocomposite with excellent performance and preparation method thereof |
| CN113042112A (en) * | 2021-03-16 | 2021-06-29 | 福建师范大学 | Preparation method of functionalized cation exchange membrane |
| CN114957753A (en) * | 2022-06-30 | 2022-08-30 | 郑州职业技术学院 | High-strength copper sulfide/nanocellulose/polyvinyl alcohol near-infrared shielding heat-insulating film and preparation method and application thereof |
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| CN103387685A (en) * | 2013-08-19 | 2013-11-13 | 南京林业大学 | Preparation method of cellulose nano-fiber/polyvinyl alcohol composite membrane |
| CN103866487A (en) * | 2014-03-27 | 2014-06-18 | 同济大学 | Method for preparing NCC/CS/PVA composite nano-membrane |
| CN104629067A (en) * | 2015-02-16 | 2015-05-20 | 东北林业大学 | Preparation method of regenerative and antibacterial cellulose-polyvinyl alcohol composite membrane |
| CN106832725A (en) * | 2016-12-20 | 2017-06-13 | 安徽省阜阳市国泰彩印包装有限公司 | Enhanced degradable plastic sheeting composite of a kind of nano-cellulose and preparation method thereof |
| CN106867042A (en) * | 2017-03-14 | 2017-06-20 | 天津科技大学 | The tape casting prepares nano-cellulose/chitosan/polyvinyl alcohol composite membrane and its application in biological antibiotic film |
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2018
- 2018-05-11 CN CN201810447182.5A patent/CN108752644A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387685A (en) * | 2013-08-19 | 2013-11-13 | 南京林业大学 | Preparation method of cellulose nano-fiber/polyvinyl alcohol composite membrane |
| CN103866487A (en) * | 2014-03-27 | 2014-06-18 | 同济大学 | Method for preparing NCC/CS/PVA composite nano-membrane |
| CN104629067A (en) * | 2015-02-16 | 2015-05-20 | 东北林业大学 | Preparation method of regenerative and antibacterial cellulose-polyvinyl alcohol composite membrane |
| CN106832725A (en) * | 2016-12-20 | 2017-06-13 | 安徽省阜阳市国泰彩印包装有限公司 | Enhanced degradable plastic sheeting composite of a kind of nano-cellulose and preparation method thereof |
| CN106867042A (en) * | 2017-03-14 | 2017-06-20 | 天津科技大学 | The tape casting prepares nano-cellulose/chitosan/polyvinyl alcohol composite membrane and its application in biological antibiotic film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111119A (en) * | 2020-09-21 | 2020-12-22 | 桂林理工大学 | Polyvinyl alcohol nanocomposite with excellent performance and preparation method thereof |
| CN113042112A (en) * | 2021-03-16 | 2021-06-29 | 福建师范大学 | Preparation method of functionalized cation exchange membrane |
| CN114957753A (en) * | 2022-06-30 | 2022-08-30 | 郑州职业技术学院 | High-strength copper sulfide/nanocellulose/polyvinyl alcohol near-infrared shielding heat-insulating film and preparation method and application thereof |
| CN114957753B (en) * | 2022-06-30 | 2024-01-05 | 郑州职业技术学院 | High-strength copper sulfide/nanocellulose/polyvinyl alcohol near-infrared shielding heat insulation film and preparation method and application thereof |
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