CN106633555A - Polyvinyl alcohol membrane with self-repair function implemented by aid of dynamic covalent bonds and method for preparing polyvinyl alcohol membrane - Google Patents
Polyvinyl alcohol membrane with self-repair function implemented by aid of dynamic covalent bonds and method for preparing polyvinyl alcohol membrane Download PDFInfo
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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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic 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
- 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
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention belongs to the technical field of functional materials, and particularly discloses a polyvinyl alcohol membrane with a self-repair function implemented by the aid of dynamic covalent bonds and a method for preparing the polyvinyl alcohol membrane. The dynamic covalent bonds are formed by the aid of Diels-Alder reaction, so that the polyvinyl alcohol membrane can have the self-repair ability. The method includes carrying out graft reaction on polyvinyl alcohol and furan derivatives to obtain furan ring grafted and modified polyvinyl alcohol; adding certain cross-linking agents into the furan ring grafted and modified polyvinyl alcohol and carrying out Diels-Alder reaction to obtain the polyvinyl alcohol membrane with the self-repair function. Diels-Alder reaction can be carried out on the certain cross-linking agents and furan groups. The polyvinyl alcohol membrane and the method have the advantages that the polyvinyl alcohol membrane is excellent in separation performance and hydrophilic performance just like common polyvinyl alcohol membranes, and cross-linked structures of the polyvinyl alcohol membrane are excellent in temperature responsiveness and thermal reversibility; the polyvinyl alcohol membrane is excellent in self-repair ability for drawing and scratching marks under simple conditions, and the gas tightness and the water resistance of the polyvinyl alcohol membrane in wet-state environments can be obviously improved; the polyvinyl alcohol membrane prepared by the aid of the method can be used in broad fields such as the fields of permeation and evaporation membrane separation and the fields of proton exchange membrane fuel cells, catalyst carrying and ion exchange membranes.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of to realize self-repair function using dynamic covalent bond
Polyvinyl alcohol film and preparation method thereof.
Background technology
Polyvinyl alcohol（PVA）It is a kind of hydrophilic polymer, this high molecular polymer compactness is good, degree of crystallinity is high, viscous
Relay is strong, made by film flexible smooth, oil resistant, solvent resistant, abrasion performance, gas barrier it is good, it is of many uses.Polyvinyl alcohol is gathered around
Have nontoxic to human body, tasteless, harmless, there is good compatibility with natural environment, do not accumulate, free of contamination environmentally friendly spy
Point.The maximum advantage of polyvinyl alcohol film is hydrophily, and maximum shortcoming is poor water resistance.
Because PVA contains a large amount of hydrophilic radicals, using the nearly boiling-point mixture of the separable most of water of PVA film, so
PVA film is more ripe in the technology application of vapor permeable membrane industry.Although PVA film prepared by current techniques has preferable
Separation selectivity, but the penetrating power of film is poor, thus operating efficiency is not high, at the same for PVA film water phase building ring
Easily swelling or even dissolving problem, a cross-linking modified weight for being to prepare high-performance PVA infiltrating and vaporizing membrane is carried out to PVA in border
Work.Manfred etc. proposes to use silane-modified PVA as vapor permeable membrane（Manfred Antonius Geurts that, horse
Ding Boerteng Schlagles, Susan He Sheer takes sharp ElWin Sietas Shi Aoer, based on the film of polyvinyl alcohol, Chinese invention
Patent 201080015358.1,2012 year 29 days 2 months）Method improve the resistance to water of PVA film to a certain extent；Zhou Yong
Deng（Zhou Yong, Zhai Ding, height is from Congjie, a kind of preparation method of cross-linking polyvinyl alcohol furfural nanofiltration membrane, Chinese invention patent
201010103083.9, on June 16th, 2010）Polyvinyl alcohol is modified with furfural, so as to improve PVA film to a certain extent
Resistance to water.Although these work can extend to a certain extent the service life of film, but film in real work ring
More complicated and rugged environment is experienced in border, such as in long-term liquid phase separation thing processing procedure, PVA film need to frequently experience
Dry and wet state is changed, and foreign object is scratched, and in the higher mixture of process water content higher operating temperature is needed（Usually 70 DEG C
Left and right）Deng.This class process inevitably causes to damage to PVA film, which also limits the working life of PVA film and answers
Use popularity.Therefore, by carrying out the structure of special cross-linked structure to PVA film, improve its resistance to water, and be allowed to for micro-
Crackle and cut have certain self-healing properties, can extend the working life of film, reduce using and replacement cost, are
A kind of processing method economical and environmentally friendly.
Self-repair material is the class intellectual material with self-healing capability in structure, and this function energy repair materials exist
The damage occurred in Long-Time Service.From most trickle microfissure to macrocrack, almost all of damage all can be different degrees of
Change calorifics, mechanics or even the acoustical behavior of material.The situation of most serious may make whole material scrap.And self-repair technology
Can then give material a certain degree of repair ability, after a series of different repair processes, they can repair itself
Damage.Such material can before degrading use the longer time, can effectively reduce due to material deterioration inside and scrap
And the loss for causing.The research of current self-repair material focuses primarily on theoretical research, and practical application is less, particularly film material
Material field, can selfreparing function film technology of preparing it is still more rare.Wang Rongguo etc.（Wang Rongguo, Hao Lifeng, Cao Zhenxing,
Can selfreparing polymethylmetacrylate resin film preparation and self-repair method, Chinese invention patent
201310079344.1, on June 15th, 2013）Invent a kind of based on golden nanometer particle photo-crosslinking reparation poly-methyl methacrylate
The method of ester film, but the golden nanometer particle that uses of the method not only preparation process is complicated, high cost, and be crosslinked the thorn for needing
Sharp condition is the ultraviolet light of specific wavelength and certain strength（Wavelength is 520nm～550nm, light intensity is 5W/cm2～50W/cm2）,
Repairing condition is complicated and harsh.Pu letter spit of fland etc.（Pu letter spit of fland, Xia Muhan, a kind of PEM with self-reparing capability and its
Preparation method, Chinese invention patent on November 25th, 201510401489.8,2015）Propose it is a kind of using self-healing polymers with
The method that the compound method of traditional proton exchange membrane material prepares selfreparing PEM, the method is to PEM material
A kind of innovation of material, but the ion bond energy of hydroxyl-boric acid reversible crosslink that the patent is used is relatively low, for pervaporation membrane
Film strength is inadequate under the use condition larger etc. water content.
Utilization Diels-Alder reactions proposed by the invention build dynamic covalent bond and prepare has the poly- of self-repair function
The method of vinyl alcohol film, combines the technology of preparing of traditional polyvinyl alcohol film and the preparation skill of novel intelligent self-repair material
Art, is the resistance to water for improving polyvinyl alcohol film, is increased the service life, and reduces diaphragm failure probability and use cost is provided separately
A kind of very effective solution.Also do not have at present and realize selfreparing using the dynamic covalent bond of Diels-Alder reaction structures
The relevant report of function film.
The content of the invention
Present invention aims to polyvinyl alcohol film poor water resistance in actual use, frequent dry and wet conversion is easily caused
Breakage, the problem of mechanically damaged rear easily failure, there is provided a kind of modified PVA membrane with self-repair function and its system
Preparation Method.
Modified PVA membrane with self-repair function proposed by the present invention, is built using Diels-Alder reactions
Dynamic covalent bond realizes self-reparing capability；There is graft reaction by polyvinyl alcohol and furan derivatives first, obtain furan nucleus and connect
The modified polyvinyl alcohol of branch；Being subsequently adding can occur the crosslinking agent of Diels-Alder reactions with furan group, carry out
Prepare after Diels-Alder reactions.
Its raw material composition includes：
100 parts of polyvinyl alcohol resin, with-CH2The gauge of-CHOH- unit materials
50-100 parts of furan derivatives, with the gauge of material；
50-100 parts of crosslinking agent, with the gauge of material；
50-150 parts of plasticizer, with the gauge of material.
Furan derivatives described in reaction raw materials of the present invention, selected from a kind of or therein several of following materials：Containing furan
Mutter ring and can on the premise of furan nucleus is not destroyed with polyvinyl alcohol chain on hydroxyl reaction compound, such as furfural, furans
Formyl chloride, furancarboxylic acid and its homologue, the acids of furans two, furfuryl alcohol etc., but it is not limited only to this.
Crosslinking agent described in reaction raw materials of the present invention is divided into two classes：（1）Diels-Alder reactions can occur with furan nucleus
Polymaleimide class crosslinking agent, specifically refer to the small molecule crosslinking agent containing multiple maleimide base groups, such as penylene is double
Maleimide, hexa-methylene BMI etc., but it is not limited only to this；（2）Diels-Alder can occur with furan nucleus anti-
The styrene base class crosslinking agent answered, specifically refers to the small molecule crosslinking agent containing multiple styrene groups, such as divinylbenzene, 1,
2,4- trivinylbenzenes etc., but it is not limited only to this.
Plasticizer described in reaction raw materials of the present invention refers to and adds to improve the pliability of film, film is risen
The additive of plasticization, such as dibutyl phthalate, tributyl phosphate, but it is not limited only to this.
The preparation method of the modified PVA membrane with self-repair function proposed by the present invention, concretely comprises the following steps：
Step 1,100 parts of polyvinyl alcohol are dissolved in 500 ~ 1000 parts of DMSO at 80 ~ 100 DEG C, are subsequently adding 50 ~ 100 parts
Furan derivatives, under the conditions of certain reaction temperature（If raw material is that furoyl chloride condition is ice-water bath, raw material is furfural, furan
Mutter formic acid or furfuryl alcohol etc., then condition is to be heated to 80 ~ 120 DEG C）, stir and be incubated more than 12h（Such as 12-24h）, make polyvinyl alcohol
There is graft reaction with furan derivatives, after the completion of reaction, add 500 ~ 1000 parts of ethanol precipitations to obtain product, and use ethanol rope
Carry more than 12h（Such as 12-24h）Purified product；
Step 2, the product that step 1 is obtained is redissolved in 500 ~ 1000 parts of DMSO, is subsequently adding 50 ~ 100 parts of crosslinking agents,
2h-4 h are stirred under normal temperature, is scratched in polytetrafluoroethylene film frame, carry out Diels-Alder thermal reversion reactions；Dry out solvent, prepares
The required modified PVA membrane with self-repair function.
In step 1 of the present invention, there is graft reaction in the polyvinyl alcohol resin with furan derivatives, and its reaction scheme is：
Wherein, R1For can be with the group of hydroxyl reaction, R in furan derivatives2For R1With the group generated after hydroxyl reaction.
In step 2 of the present invention, the reaction of product and crosslinking agent after the polyvinyl alcohol resin grafting furan derivatives, root
Species according to crosslinking agent is different, is divided into two kinds of reaction schemes：
The modified polyvinylalcohol of the furans of reaction scheme 1. grafting can with the Diels-Alder heat of polymaleimide class crosslinking agent
Back reaction：
Wherein, described Diels-Alder thermal reversions reaction, the condition of positive reaction is 50 ~ 70 DEG C of low temperature and is incubated 12 ~ 24h；It is inverse
The condition of reaction is 100 ~ 130 DEG C of high temperature and is incubated 2h ~ 4h.
The modified polyvinylalcohol of the furans of reaction scheme 2. grafting can with the Diels-Alder heat of styrene base class crosslinking agent
Back reaction：
Wherein, described Diels-Alder thermal reversions reaction, the condition of positive reaction is 50 ~ 70 DEG C of low temperature and is incubated 12 ~ 24h；It is inverse
The condition of reaction is 100 ~ 130 DEG C of high temperature and is incubated 2h ~ 4h.
The polyvinyl alcohol film that self-reparing capability is realized using dynamic covalent bond of the present invention, its selfreparing is needed suitable
When environmental stimuli under carry out.In addition to heating, cooling and isothermal holding is carried out, according to selective system, in addition it is also necessary to certain ring
Border humidity, small patch and pressure etc..These stimulations can be just realized generally under simple condition, repairing condition is relatively simple.
Self-healing properties of the present invention are realized by procedure below：When film is impaired, cross-linked structure is by broken
After bad, high temperature/low-temperature circulating process is carried out to film, above-mentioned reaction 1 or reaction 2 occurs, make film regenerate crosslinking knot
Structure, so as to complete the reparation to breakage of thin film applied structure.
Self-reparing capability of the present invention, refer mainly to material it is mechanically damaged after, it is maximum under certain repairing condition
The reparation wound of degree simultaneously recovers mechanical property or the ability of other performances.
It is an advantage of the current invention that：By polymer crosslinking technology, crosslinking agent is added to build the reversible common of temperature response type
Valence link cross-linked structure, obtaining can be with the polyvinyl alcohol film of selfreparing.The modified PVA membrane after mechanically damaged, one
Determine that self-regeneration can be realized under environmental stimuli, farthest recover initial mechanical and other performances, and to a certain extent
Make damage location up, and with good water resistance, can effectively extend polyvinyl alcohol film service life.The invention most preferably should
It is osmotic evaporating and separating membrane field with field, secondly can also be used in Proton Exchange Membrane Fuel Cells, catalyst carrying, ion friendship
Change the fields such as film, be the reliability of equipment using providing safeguard, while maintenance, replacement cost can be substantially reduced, with very excellent
The reference value and application prospect of show.
Description of the drawings
The polyvinyl alcohol nuclear magnetic resonance map of Fig. 1 graft modifications.
The polyvinyl alcohol structures formula of Fig. 2 thermally reversibles.
Diagram before and after the polyvinyl alcohol film reparation of Fig. 3 self-repair functions.Wherein,（a）、（c）To there is depth cut
Damaged film,（b）、（d）For the film that cut after reparation disappears.
Tensile strength is tested before and after Fig. 4 films are repaired.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the present invention is further detailed explanation.Following examples are used to illustrate this
Invention, but should not be construed as limiting the invention.
Polyvinyl alcohol in embodiment（PVA-124, Mw ~ 195000）, furoyl chloride (98%), p-methyl benzenesulfonic acid (98%), diethyl
Alkene benzene（AR, >=99%）Buy in Aladdin reagent；N, N '-hexa-methylene BMI（＞ 97%）, phthalic acid two
Butyl ester（＞ 97%）Buy in lark prestige reagent；Absolute ethyl alcohol（AR, >=99%）, furfural（AR, >=99%）, N, N- dimethyl formyls
Amine（DMF AR, >=99%）, dimethyl sulfoxide (DMSO)（DMSO AR, >=99%）Etc. buying in Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
The preparation for building the polyvinyl alcohol film that dynamic covalent bond realizes selfreparing is reacted using Diels-Alder：
（1）11g polyvinyl alcohol is mixed with 200mL DMSO, stirs transparent to solution under the conditions of 70 DEG C ~ 80 DEG C；It is right to add
Toluenesulfonic acid 2g stir dissolving after add furfural 20mL, 70 DEG C ~ 80 DEG C stirring reactions 12h, by product with ethanol precipitation simultaneously
Rope puies forward 5h post-dryings and obtains product, that is, obtain the polyvinyl alcohol of furan nucleus graft modification；
（2）Take（1）In the polyvinyl alcohol 0.7g of graft modification that obtains, during 30mL DMSO are dissolved at 70 ~ 80 DEG C, be cooled to often
Temperature, adds 0.2g N, N '-hexa-methylene BMI, is stirred until homogeneous, and obtains the modified PVA with self-healing properties
Film liquid.Gained film liquid is scratched in size is for the poly tetrafluoroethylene frame of 10cm*10cm, 60 DEG C of baking oven 12h are placed in, solvent is treated
After drying, it is obtained by Diels-Alder reactions and builds the polyvinyl alcohol film that dynamic covalent bond realizes selfreparing.
Selfreparing condition：Take out the film of existing depth cut（Depth cut is that scalpel applying certain force is marked）, in cut
Place applies slight pressure（≤70Pa）, 100 DEG C of insulation 30min are warming up to, 60 DEG C of insulation 3h are cooled to, reparation is completed.
Repairing effect is tested：（1）Observing effect before and after reparation is as shown in Fig. 2 the vestige of depth cut is before and after reparation
Substantially completely disappear, and film does not have the change of shape before and after repairing；（2）To the Mechanics Performance Testing before and after reparation, use
Puller system（Shenzhen Suns Technology Stock Co.LTD）Tested according to GB GB/T13022-1991,
By the complete thin film mechanics intensity without scratching with through scratching and repair after thin film mechanics intensity carry out
Contrast, as a result as shown in figure 4, Fig. 4 shows the remediation efficiency of the film substantially more than 50%.
Embodiment 2
The preparation of the polyvinyl alcohol film of high grafting degree dynamic covalent bond selfreparing：
（1）11g polyvinyl alcohol is mixed with 200ml DMSO, stirs transparent to solution under the conditions of 70 DEG C ~ 80 DEG C；It is right to add
Toluenesulfonic acid 2g stir dissolving after add furfural 20ml, 70 DEG C ~ 80 DEG C stirring reactions 12h, by product with ethanol precipitation simultaneously
Rope puies forward 5h post-dryings and obtains first step product.Take and be dissolved in 100ml DMSO at 70 ~ 80 DEG C of 2g first steps product, ice-water bath
It is added dropwise 3ml furoyl chlorides in 30min, normal-temperature reaction 4h, deionized water precipitation is washed and dried and obtains second step product, is obtained final product
To the polyvinyl alcohol that novel graft is modified；
（2）Take（1）In the polyvinyl alcohol 0.7g of graft modification that obtains, during 30ml DMSO are dissolved at 70 ~ 80 DEG C, be cooled to often
Temperature, adds 0.2g N, N '-hexa-methylene BMI, is stirred until homogeneous, and obtains the modified PVA film film of high grafting degree
Liquid.Gained film liquid is scratched in size is for the poly tetrafluoroethylene frame of 10cm*10cm, 60 DEG C of baking oven 12h are placed in, treats that solvent is done
After dry, the polyvinyl alcohol film that high grafting degree realizes selfreparing using dynamic covalent bond is obtained.
Take（2）In the modified PVA membrane liquid that obtains take 50mg, with 0.5mL DMSO-d6 Solution is configured to, nuclear-magnetism is done
Analysis, obtains the modified polyvinyl alcohol nuclear magnetic spectrum of novel graft as shown in figure 1, each in Fig. 1 nuclear magnetic spectrums goes out peak position
Show that the modified polyvinylalcohol structure for finally giving is completely the same with chemical formula with intensity, and from two kinds of furans of furfural and furoyl chloride
Mutter functional group ratio be 1：0.5, basically identical with rate of charge, the percent grafting of furans functional group is 70%.
Selfreparing condition：The film of existing depth cut is taken out, slight pressure is applied at cut（≤70Pa）, it is warming up to 100
DEG C insulation 30min, is cooled to 60 DEG C of insulation 3h, and reparation completes.
Repairing effect test is similar to Example 1.
Embodiment 3
The preparation of the polyvinyl alcohol film of dynamic covalent bond selfreparing：
（1）11g polyvinyl alcohol is mixed with 200mL DMSO, stirs transparent to solution under the conditions of 70 DEG C ~ 80 DEG C；It is right to add
Toluenesulfonic acid 2g stir dissolving after add furfural 20mL, 70 DEG C ~ 80 DEG C stirring reactions 12h, by product with ethanol precipitation simultaneously
Rope puies forward 5h post-dryings and obtains first step product；
（2）Take and be dissolved in 100mL DMSO at 70 ~ 80 DEG C of 2g first steps product, add divinylbenzene 0.5g, be stirred until homogeneous,
There must be the modified PVA film film liquid of self-healing properties.Gained film liquid is scratched into the poly tetrafluoroethylene in size for 10cm*10cm
In frame, 60 DEG C of baking oven 12h are placed in, the modified polyvinylalcohol osmotic evaporation film with self-reparing capability is obtained after solvent seasoning.
Repairing effect test is similar to Example 1.
Embodiment 4
Plus the preparation of the selfreparing polyvinyl alcohol osmotic evaporation film of plasticizer：
（1）Modified PVA osmotic evaporation film film liquid is prepared by the method for operating of embodiment 1；
（2）Take and be dissolved in 100mL DMSO at 70 ~ 80 DEG C of 2g first steps product, add 0.4g penylene BMIs, stir
Mix to uniform, add 0.5g dibutyl phthalates, obtain modified PVA osmotic evaporation film film liquid.Gained film liquid blade coating is existed
During size is for the poly tetrafluoroethylene frame of 10cm*10cm, 60 DEG C of baking oven 12h are placed in, after solvent seasoning, are obtained with selfreparing
The modified polyvinylalcohol osmotic evaporation film of ability.
Selfreparing condition：The film of existing depth cut is taken out, slight pressure is applied at cut（≤70Pa）, it is warming up to 120
DEG C insulation 30min, is cooled to 60 DEG C of insulation 3h, and reparation completes.
Repairing effect test is similar to Example 1.
Claims (10)
1. a kind of polyvinyl alcohol film with self-repair function, it is characterised in that build dynamic altogether using Diels-Alder reactions
Valence link realizes self-reparing capability；There is graft reaction by polyvinyl alcohol and furan derivatives first and obtain furan nucleus graft modification
Polyvinyl alcohol；Being subsequently adding can occur the crosslinking agent of Diels-Alder reactions with furan group, carry out Diels-Alder
Prepare after reaction；Its raw material components is calculated as by the amount of material：
100 parts of polyvinyl alcohol resin, with-CH2- CHOH- unit meters
50-100 parts of furan derivatives；
50-100 parts of crosslinking agent；
50-150 parts of plasticizer.
2. the polyvinyl alcohol film with self-repair function according to claim 1, it is characterised in that described furans derives
Thing is a kind of or therein several selected from following materials：Containing furan nucleus and can on the premise of furan nucleus is not destroyed with polyethylene
The compound of the hydroxyl reaction on alcohol chain.
3. the polyvinyl alcohol film with self-repair function according to claim 1, it is characterised in that described furans derives
Thing is a kind of or therein several selected from following materials：Furfural, furoyl chloride, furancarboxylic acid and its homologue, furans diacid
Class, furfuryl alcohol.
4. the polyvinyl alcohol film with self-repair function according to claim 1,2 or 3, it is characterised in that described friendship
Connection agent is divided into two classes：（1）The polymaleimide class crosslinking agent of Diels-Alder reactions can occur with furan nucleus, specifically refer to
Small molecule crosslinking agent containing multiple maleimide base groups,（2）The styrene of Diels-Alder reactions can occur with furan nucleus
Base class crosslinking agent, specifically refers to the small molecule crosslinking agent containing multiple styrene groups.
5. the polyvinyl alcohol film with self-repair function according to claim 4, it is characterised in that described More Malay acyl
Imines crosslinking agent is selected from penylene BMI, hexa-methylene BMI；Described styrene base class crosslinking agent
Selected from divinylbenzene, 1,2,4- trivinylbenzenes.
6. the polyvinyl alcohol film with self-repair function according to claim 1,2,3 or 5, it is characterised in that described
Plasticizer is selected from dibutyl phthalate, tributyl phosphate.
7. a kind of preparation method of the polyvinyl alcohol film with self-repair function according to one of claim 1-6, its
It is characterised by, concretely comprises the following steps：
Step 1,100 parts of polyvinyl alcohol are dissolved in 500 ~ 1000 parts of DMSO at 80 ~ 100 DEG C, are subsequently adding 50 ~ 100 parts
Furan derivatives, under the conditions of certain reaction temperature, stir and are incubated more than 12h, polyvinyl alcohol is occurred with furan derivatives
Graft reaction；After the completion of reaction, add 500 ~ 1000 parts of ethanol precipitations to obtain product, and more than 12h purifications are proposed with ethanol rope and produce
Thing；
Step 2, the product that step 1 is obtained is redissolved in 500 ~ 1000 parts of DMSO, is subsequently adding 50 ~ 100 parts of crosslinking agents,
2h-4 h are stirred under normal temperature, is scratched in polytetrafluoroethylene film frame, carry out Diels-Alder thermal reversion reactions；Dry out solvent, prepares
The required modified PVA membrane with self-repair function.
8. the preparation method of the polyvinyl alcohol film with self-repair function according to claim 7, it is characterised in that step
There is graft reaction in polyvinyl alcohol resin described in 1, its reaction scheme is with furan derivatives：
Wherein, R1For can be with the group of hydroxyl reaction, R in furan derivatives2For R1With the group generated after hydroxyl reaction.
9. the preparation method of the polyvinyl alcohol film with self-repair function according to claim 7, it is characterised in that step
Certain reaction temperature condition described in 1, for furan starting material formyl chloride, temperature conditionss are ice-water bath, for raw material be furfural,
Furancarboxylic acid, furfuryl alcohol, temperature conditionss are 80 ~ 120 DEG C.
10. the preparation method of the polyvinyl alcohol film with self-repair function according to claim 7, it is characterised in that step
The reaction of product and crosslinking agent after the grafting furan derivatives of polyvinyl alcohol resin described in rapid 2, according to the species of crosslinking agent not
Together, it is divided into two kinds of reaction schemes：
The modified polyvinylalcohol of the furans of reaction scheme 1. grafting can with the Diels-Alder heat of polymaleimide class crosslinking agent
Back reaction：
Wherein, described Diels-Alder thermal reversions reaction, the condition of positive reaction is 50 ~ 70 DEG C of low temperature, is incubated 12 ~ 24h；It is inverse
The condition of reaction is 100 ~ 130 DEG C of high temperature, is incubated 2h ~ 4h；
The modified polyvinylalcohol of the furans of reaction scheme 2. grafting is anti-with the Diels-Alder thermal reversions of styrene base class crosslinking agent
Should：
Wherein, described Diels-Alder thermal reversions reaction, the condition of positive reaction is 50 ~ 70 DEG C of low temperature, is incubated 12 ~ 24h；It is inverse
The condition of reaction is 100 ~ 130 DEG C of high temperature, is incubated 2h ~ 4h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610824068.0A CN106633555A (en) | 2016-09-14 | 2016-09-14 | Polyvinyl alcohol membrane with self-repair function implemented by aid of dynamic covalent bonds and method for preparing polyvinyl alcohol membrane |
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| CN201610824068.0A CN106633555A (en) | 2016-09-14 | 2016-09-14 | Polyvinyl alcohol membrane with self-repair function implemented by aid of dynamic covalent bonds and method for preparing polyvinyl alcohol membrane |
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| CN108598531A (en) * | 2018-01-24 | 2018-09-28 | 辽宁石油化工大学 | A kind of dibenzo 18 is preced with the preparation method of 6 grafting polyvinyl alcohol microporous barriers |
| CN108997687A (en) * | 2018-07-27 | 2018-12-14 | 江苏坦能纳米材料科技有限公司 | A kind of transparence display film capable of self-healing and its preparation method and application |
| WO2019119779A1 (en) * | 2017-12-22 | 2019-06-27 | 中天储能科技有限公司 | Solid polymer electrolyte, preparation method therefor, and lithium secondary battery |
| CN110054795A (en) * | 2018-01-19 | 2019-07-26 | 清华大学 | Thermoset macromolecule material processing, healing and welding method |
| CN112480572A (en) * | 2020-12-02 | 2021-03-12 | 宜兴市光辉包装材料有限公司 | Packaging PVC heat-shrinkable label film resistant to bundling |
| CN112777447A (en) * | 2019-11-07 | 2021-05-11 | 奥的斯电梯公司 | Self-repairing elevator load bearing member |
| CN113410496A (en) * | 2021-06-16 | 2021-09-17 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
| CN113831178A (en) * | 2021-09-07 | 2021-12-24 | 山东大学 | Slow-release coated fertilizer and preparation method thereof |
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| WO2019119779A1 (en) * | 2017-12-22 | 2019-06-27 | 中天储能科技有限公司 | Solid polymer electrolyte, preparation method therefor, and lithium secondary battery |
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| CN108997687A (en) * | 2018-07-27 | 2018-12-14 | 江苏坦能纳米材料科技有限公司 | A kind of transparence display film capable of self-healing and its preparation method and application |
| CN112777447A (en) * | 2019-11-07 | 2021-05-11 | 奥的斯电梯公司 | Self-repairing elevator load bearing member |
| CN112480572A (en) * | 2020-12-02 | 2021-03-12 | 宜兴市光辉包装材料有限公司 | Packaging PVC heat-shrinkable label film resistant to bundling |
| CN113410496A (en) * | 2021-06-16 | 2021-09-17 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
| CN113410496B (en) * | 2021-06-16 | 2023-02-14 | 东北大学秦皇岛分校 | All-solid-state trace water-containing low-temperature applicable proton exchange membrane and preparation method thereof |
| CN113831178A (en) * | 2021-09-07 | 2021-12-24 | 山东大学 | Slow-release coated fertilizer and preparation method thereof |
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Application publication date: 20170510 |