CN106883442B - A kind of preparation method of fluorided-modified polyvinyl alcohol film - Google Patents
A kind of preparation method of fluorided-modified polyvinyl alcohol film Download PDFInfo
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- C09D127/00—Coating compositions based on 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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on 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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on 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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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- C08J2427/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention discloses a kind of preparation method of fluorided-modified polyvinyl alcohol film, include the steps that spraying the surface treating composition comprising fluoride to one of surface of the film substrate comprising polyvinyl alcohol；The step of further including, spraying the priming coat of non-fluosilicic oxyalkane compound composition to the one of surface for the film substrate for including polyvinyl alcohol.The film prepared by the preparation method of fluorided-modified polyvinyl alcohol film of the invention, unmodified face maintain the property of polyvinyl alcohol ontology, and modified face waterproof performance is excellent, is not easy to be bedewed by water；The mechanical property and barrier property that preferably keep film are remained in water vapour environment.
Description
Technical field
The present invention relates to a kind of preparation methods of fluorided-modified polyvinyl alcohol film, belong to biodegradable packaging material
Hydrophobically modified technical field.
Background technique
Polyvinyl alcohol (poly- (vinyl alcohol), PVA) is a kind of biodegradable, water-soluble synthesis macromolecule
Polymer.Because it is with biological degradability, water solubility, excellent film forming, cohesiveness, while gas barrier property is excellent, special
It is not the barrier property exceptional to oxygen, has been widely used in food, medicine, pesticide and industrial packaging Material Field；Together
When by United States Department of Agriculture approval for meat, poultry product packaging.
PVA has stringent linear structure, and chemical property is stablized, and the hydrogen bond between molecule makes it have enough thermostabilizations
Property, the hydroxyl on strand make it have the hydrophily of height.But in the biggish situation of ambient humidity, in PVA film
Hydroxyl easily forms hydrogen bond with hydrone, changes so as to cause PVA aggregated structure, declines its barrier property sharply, because
This hydrophily for improving PVA film also becomes the research hotspot of people.
Currently, the hydrophilic modifying to PVA film mainly has chemical crosslinking and composite modified two major classes.Although above method energy
The water resistance and mechanical property of PVA film are improved well, but need further to recognize and deeply probe into there is also some problems.
For example the factors such as chemical crosslinking modified crosslinking temperature, crosslinking time and type of crosslinking agent decide the performance of cross linking membrane,
Therefore it needs to be accurately controlled these factors, can just obtain the PVA film of function admirable；And it is composite modified involved in system
Standby complex process, higher cost.
Patent CN102807682A discloses a kind of preparation method of single side hydrophobically modified polyvinyl alcohol film: preparing first
Then polyvinyl alcohol film sprays silane coupling agent in the modification face of film, sprays isocyanates again after air-drying, sprays again after air-drying
Fatty alcohol is applied, natural air drying obtains single side hydrophobically modified polyvinyl alcohol film.The thin-film hydrophobic face contact angle of acquisition is reachable
130 ° or so, the tensile strength of film is higher, and elongation at break is high.However, since hydrophobic surface is there are still certain adhesional wetting,
It is difficult to prevent the infiltration of steam in water vapour environment, and then declines the tensile strength of film, while can also barrier property be made to decline.
Summary of the invention
The purpose of the present invention is overcoming the prior art, a kind of preparation of fluorided-modified polyvinyl alcohol film is provided
Method, film water drenching function admirable made from this method, can preferably keep the mechanical property and resistance of film in water vapour environment
Every property.
In order to achieve the object of the present invention, it adopts the following technical scheme that
A kind of preparation method of fluorided-modified polyvinyl alcohol film, including to the film substrate comprising polyvinyl alcohol its
In surface spraying the step of including the surface treating composition of fluoride.
The surface treating composition comprising fluoride includes the hydrolyzable compound containing perfluoropolyether group, contains
There is at least one of hydrolyzable compound of perfluoro alkyl group and accounts for the organic acid of hydrolyzable compound 0.5wt%.
The hydrolyzable compound containing perfluoropolyether group can be indicated with formula (1):
PFPE-[A-(-G-Si-(OR1)3)s]lFormula (1)
Wherein, PFPE is monovalence or divalent perfluoropolyether group, and A is s+1 valence organic group, and G is bivalent organic group, R1
For C1~4Alkyl, s be 1~6 positive integer, l be 1 or 2.
The hydrolyzable compound containing perfluoro alkyl group can be indicated with formula (2):
(Rf)s’-B-Si-(OR2)3Formula (2)
Wherein, RfFor monovalence perfluoro alkyl group, the positive integer that s ' is 1~5 ,+1 valence organic group of B s ', R2For C1~4
Alkyl.
The hydrolyzable compound containing perfluoro alkyl group can be indicated with formula (3):
M(CH2CR1(-D-Rf))m(CH2CR2(-E-Si(OR3)3))n(CH2CR3(-I))pN formula (3)
Wherein, M, N are monovalent organic group, R1、R2And R3For H or CH3, R3For C1~4Alkyl, RfFor perfluoroalkyl base
Group, D are bivalent organic group, and E is bivalent organic group or covalent bond, and I is monovalent organic group, and m, n are positive integer, p be 0 or
Positive integer.
The organic acid is propionic acid or sorbic acid.
The preparation method further includes including fluorination to the spraying of one of surface of the film substrate comprising polyvinyl alcohol
Before the surface treating composition of object, non-fluorine siliconization is sprayed to one of surface of the film substrate comprising polyvinyl alcohol
The step of priming coat of polymer composition.
Further, the non-fluosilicic oxyalkane compound composition includes simultaneously containing isocyanate groups or sealing end isocyanide
Acid esters group and-Si- (OR4)3The compound of group, wherein R4For C1~4Alkyl.
Further, the non-fluosilicic oxyalkane compound composition include without containing fluoro-containing group and isocyanate groups or
Blocked isocyanate groups contain-Si- (OR5)3The silicone compounds of group, wherein R5For C1~4Alkyl.
Fluorided-modified polyvinyl alcohol film preparation method of the invention, including to the film substrate comprising polyvinyl alcohol
The step of one of surface spraying includes the surface treating composition of fluoride.Surface treating composition comprising fluoride exists
Hydrophobic layer is formed after being sprayed into film surface, it is therefore prevented that moisture avoids after film is penetrated into because of moisture to film permeation and forms hydrogen
Key leads to the variation of PVA aggregated structure, effectively maintains film to the barrier property of oxygen and the tensile strength of film.
Common preparation method includes the following steps:
1) preparation includes the film substrate of polyvinyl alcohol；
2) solution of the surface treating composition comprising fluoride is prepared；
3) 2) the middle surface treating composition solution spraying comprising fluoride prepared is included into poly- second in 1) middle preparation
One of surface of the film substrate of enol；
4) to solvent natural air drying, then room temperature curing 1h obtains fluorided-modified polyvinyl alcohol film.
The film substrate comprising polyvinyl alcohol of step 1) can be cast using pure poly-vinyl alcohol solution and be obtained, and can also be adopted
Preparation is blended with polyvinyl alcohol and various additives, modifying agent etc..
The solution of step 2) is that the surface treating composition of fluoride is dissolved in solvent appropriate to obtain, and is prepared
The concentration of solution is 0.1wt%~5wt% (mass percent), preferably 0.5wt%~3.5wt%, more preferably 0.8wt%
~1.5wt%.Solvent should select can abundant dissolved composition the organic solvent such as fluorinated solvent, solvent of class containing chlorine, not halogen
The conventional hydrocarbon solvent of element.Fluoride solvent such as perfluoro-cyclicether, 7200 (nona-fluoro butyl group ethylethers), 7100 (nona-fluoro butyl group methyl
Ether), 347 (CF3CH2OCF2CF2H)、494(CH3CH2CH2OCF2CF2H) etc..Chlorinated solvents such as methylene chloride, vinylidene chloride, three
Chloroethanes, tetrachloroethanes etc..The conventional hydrocarbon solvent being halogen-free for example butyl acetate, ethyl acetate, heptane, hexane, hexamethylene,
Petroleum ether, D40, methyl isoamyl ketone, diethylene glycol dimethyl ether etc..The preferably mixture of fluoride solvent and Conventional solvents.
High-pressure spray gun completion can be used in step 3), and gas auxiliary is higher than spray gun gas pressure, Ventilation Rate etc. should basis
Concrete application situation is suitably adjusted, and specific quantity for spray can be adjusted according to nozzle diameter and spray rate.
Surface treating composition comprising fluoride includes the hydrolyzable compound containing perfluoropolyether group, contains perfluor
At least one of hydrolyzable compound of alkyl group.The hydrolyzable compound of the perfluoropolyether group contains perfluor
The hydrolyzable compound of alkyl group contains the siloxane group of hydrolyzable crosslinking, can be anti-with the hydroxyl in polyvinyl alcohol film
It answers, forms chemical bonding.
Perfluoropolyether group is such as: F (CF (CF3)CF2O)aCF(CF3)-、F(CF(CF3)CF2O)aCF2CF2-、CF3O
(CF2CF2O)aCF2-、CF3O(CF2O)b(CF2CF2O)aCF2-、-CF(CF3)O(CF(CF3)CF2O)aCF(CF3)-、-CF2CF2(CF
(CF3)CF2O)aCF2CF2-、-CF2O(CF2CF2O)aCF2-、-CF2O(CF2O)b(CF2CF2O)aCF2Etc., wherein a, b be 1 to
100 integer.Alkyl group is such as: CH3、CH2CH3、CH(CH3)2、C(CH3)3Deng.Formula contains perfluoropolyether group shown in (1)
Compound can be listed below: PFPE-CONHCH2CH2CH2-Si(OCH3)3、PFPE-CH2OCH2CH2CH2-Si(OCH3)3、
PFPE-CH2OCH2CH2CH2-Si(OC2H5)3、PFPE-CH2OCH2CH2CH2Si(CH3)2OSi(CH3)2CH2CH2-Si(OCH3)3、
PFPE-CH2OCONHCH2CH2CH2-Si(O CH3)3、PFPE-CONHCH2CH2OCONHCH2CH2CH2-Si(OCH3)3、PFPE-
CH2OCOCH2CH2N(CH3)CH2CH2CH2-Si(OCH3)3、PFPE-CH2OCH2CH2CH2Si(CH2CH2CH2Si(OCH3)3)3、
PFPE-CONHCH(CH2OCONHCH2CH2OOCCH2CH2N(CH2CH2CH2Si(OCH3)3)2)2、PFPE-CH2OCH2CH2CH2Si
(CH3)O(Si(CH3)(CH2CH2CH2Si(OCH3)3)O)3、(H3CO)3SiCH2CH2CH2NHOC-PFPE-CONHCH2CH2CH2Si
(OCH3)3、((H3CO)3SiCH2CH2CH2)2NCO-PFPE-CON(CH2CH2CH2Si(OCH3)3)2。
Perfluoro alkyl group is such as: CF3(CF2)c、(CF3)2CF(CF2)c、CF3Deng the integer that wherein c is 0~20.Alkyl base
It rolls into a ball such as: CH3、CH2CH3、CH(CH3)2、C(CH3)3Deng.Compound containing perfluoro alkyl group shown in formula (2) can enumerate as
Under: CF3(CF2)3CH2CH2Si(OCH3)3、CF3(CF2)5CH2CH2Si(OCH3)3、CF3(CF2)3CH2CH2Si(OCH2CH3)3、CF3
(CF2)5CH2CH2Si(OCH2CH3)3、(CF3)2CF(CF2)3CH2CH2Si(OCH3)3、CF3CH2CH2Si(O CH3)3、
CF3CF2CH2OCH2CH2CH2Si(OCH2CH3)3、CF3(CF2)3CH2CH2OCH2CH2CH2Si(OCH3)3、CF3(CF2)3CH2CH2OCONHCH2CH2CH2Si(OCH3)3、(CF3(CF2)5CH2CH2)2NCH2CH2CH2Si(O CH3)3、(CF3(CF2)5CH2CH2)2NCH2CH2N(CH2CH2(CF2)5CF3)CH2CH2CH2Si(OCH3)3。
The compound containing perfluoro alkyl group that formula (3) indicates is usually by with unsaturated double-bond containing by perfluoroalkyl
Monomer is obtained with siloxanyl monomers with unsaturated double-bond through free-radical polymerized, and Third monomer component can also be added.Have
Unsaturated double-bond contains by perfluoroalkyl monomeric such as CH2=C (R) COOCH2CH2(CF2)dCF3、CH2=C (R) COOCH2CH2N
(R’)SO2(CF2)dCF3Deng wherein R and R ' is the alkyl of H or C1~4, and the integer that d is 0~20 is specific enumerable as follows: CH2
=C (CH3)COOCH2CH2N(CH3)SO2C4F9、CH2=C (CH3)COOCH2CH2N(CH3)SO2C6F13、CH2=C (CH3)
COOCH2CH2C6F13、CH2=CHCOOCH2CH2C4F9、CH2=CHCOO CH2CH2C8F17.Siloxanes with unsaturated double-bond
Monomer such as CH2=CHSi (OR3)3、CH2=CHCH2Si(OR3)3、CH2=C (R ") COOCH2CH2CH2Si(OR3)3Deng wherein R3With
Same as before, R " is C1~4Alkyl.Third component monomer is such as: (methyl) acrylic acid non-fluorine Arrcostab, (methyl) acrylic acid chloro
Arrcostab, styrene, vinyl chloride, vinylidene chloride, (methyl) glycidyl acrylate etc..
Simultaneously containing isocyanate groups or blocked isocyanate groups and-Si- (OR4)3The compound of group, wherein R4
For C1~4Alkyl, can be listed below: OCNCH2CH2CH2Si(OCH)3、OCN-T-NHCONHCH2CH2CH2Si(OCH)3、OCN-
T-NHCONHCH2CH2CH2Si(OCH2CH)3、Y-CONH-T-NHCONHCH2CH2CH2Si(OCH)3、(OCN)2-Q-
NHCONHCH2CH2CH2Si(OCH)3、(Y-OCONH)2-Q-NHCONHCH2CH2CH2Si(OCH)3Deng, wherein T be hexamethyl two it is different
Cyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isoflurane chalcone diisocyanate etc. remove diisocyanate
Residue after group, Q are hexamethylene diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone
The tripolymer or triphenylmethane triisocyanate of diisocyanate etc. remove the residue after triisocyanate group, and Y is 2- first
Base imidazoles, methyl ethyl ketoxime etc. remove the residue after glass hydrogen living.
Without containing fluoro-containing group and isocyanate groups or blocked isocyanate groups, contain-Si- (OR5)3The silicon of group
Oxygen alkane, wherein R5For C1~4Alkyl, can be listed below: ethyl orthosilicate (Si (OCH2CH3)4), methyltrimethoxysilane
(CH3Si(OCH3)3), ethyl trimethoxy silane (CH3CH2Si(OCH3)3), cyclohexyl trimethoxy silane, three second of isobutyl group
Oxysilane, n-hexyl triethoxysilane, n-butyltrimethoxysilane, n-octyl trimethoxy silane, three second of n-octyl
Oxysilane, dodecyltrimethoxysilane, hexadecyl trimethoxy silane, three ethoxy of 3- glycydoxy
Base silane, phenyltrimethoxysila,e etc..
Non- fluosilicic oxyalkane compound composition should usually dissolve to be sprayed in a solvent, and the concentration for preparing solution is
0.1wt%~5wt%, preferably 1wt%~4wt%, more preferably 1.5wt%~2.5wt%.Solvent should be selected can be sufficiently molten
Solve the fluorine-free organic solvent of composition, such as esters, ketone, ethers, hydro carbons, nitrogen-containing solvent.It is specific enumerable as follows: acetic acid
Butyl ester, ethyl acetate, heptane, hexane, hexamethylene, petroleum ether, D40, methyl isoamyl ketone, diethylene glycol dimethyl ether, N, N- diformazan
Base formamide etc. can be one of which, or mixture.
As a result of the above technical solution, the following beneficial effects are obtained:
The film prepared by fluorided-modified polyvinyl alcohol film of the invention, unmodified face maintains polyvinyl alcohol ontology
Property, modified face waterproof performance is excellent, is not easy to be bedewed by water；The mechanical property for preferably keeping film is remained in water vapour environment
And barrier property；Modified face also has the function of grease proofing antifouling.
Detailed description of the invention
The whole electron-microscope scanning figure figure one of Fig. 1 embodiment of the present invention 4；
The local electron-microscope scanning figure figure two of Fig. 2 embodiment of the present invention 4；
The whole electron-microscope scanning figure figure three of Fig. 3 comparative example 7 of the present invention；
The local electron-microscope scanning figure figure four of Fig. 4 comparative example 7 of the present invention；
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
(a) synthesis of perfluoropolyether siloxanes shown in formula (1)
Perfluoropolyethercarboxylate (PFPE-COOCH3Purchased from Su Wei) through sodium borohydride reduction perfluoropolyether alcohol (PFPE- is made
CH2OH), it is obtained to carry out etherification reaction with allyl bromide, bromoallylene (being purchased from Ti Xiai chemical conversion industry Development Co., Ltd) again for perfluoropolyether alcohol
Perfluoropolyether allyl ether (PFPE-CH2OCH2CH=CH2), last perfluoropolyether allyl ether and trimethoxy hydrogen silicon are through silicon hydrogen
Perfluoropolyether siloxanes (PFPE-CH is made in addition reaction2OCH2CH2CH2Si(OCH3)3)。
(b) synthesis of perfluoropolyether siloxanes shown in formula (1)
Perfluoropolyethercarboxylate (PFPE-COOCH3Purchased from Su Wei) and bis- (trimethoxy-silylpropyl) amine (NH
(CH2CH2CH2Si(OCH3)3)2Purchased from Nanjing Neng De Chemical Co., Ltd.) through amidation process Perfluoropolyether silanes oxygen alkane is made
(PFPE-CON(CH2CH2CH2Si(OCH3)3)2)。
(c) synthesis of perfluoropolyether siloxanes shown in formula (1)
With the perfluoropolyethercarboxylate (CH of both-end3OOC-PFPE-COOCH3Purchased from Su Wei) replace (a) in single-ended perfluor
Perfluoropolyether silanes oxygen alkane ((H is made in polyether ester3CO)3SiCH2CH2CH2OCH2-PFPE-CH2OCH2CH2CH2Si(OCH3)3)。
(d) perfluoroalkylsilane compound (CF shown in formula (2)3(CF2)5CH2CH2Si(OCH3)3Collect purchased from hugeization
Group)
(e) synthesis of perfluoroalkylsilane compound shown in formula (2)
By perfluorohexyl ethylene (C6F13CH=CH2) and 3- aminopropyl trimethoxysilane (H2NCH2CH2CH2Si(OCH3)3
Purchased from Nanjing Neng De Chemical Co., Ltd.) through Michael's addition perfluoroalkylsilane ((C is made6F13CH2CH2)2NCH2CH2CH2Si(OCH3)3)。
(f) synthesis of the compound containing perfluoro alkyl group shown in formula (3)
By CH2=C (CH3)COOCH2CH2(CF2)5CF5(inspiring confidence in being purchased from), CH2=CHCOOCH2(CH2)10CH3(it is purchased from lake
Bei Jusheng Science and Technology Ltd.) and CH2=CHCH2Si(OCH3)3It is obtained according to the mass ratio of 6:2:2 by free radical solution copolymerization
?.
(g) conjunction of the compound simultaneously containing isocyanate groups or blocked isocyanate groups and alkoxysilyl group group
At
By (the NH of compound containing amino silicone2CH2CH2CH2Si(OCH)3Purchased from Nanjing Chemical Co., Ltd. forward) with etc.
Mole isoflurane chalcone diisocyanate (be purchased from Dow) reacted through isocyanation esterification (OCN-T- be made
NHCONHCH2CH2CH2Si(OCH)3, T is the isoflurane chalcone diisocyanate residue removed after two isocyanate groups).
(h) compound containing isocyanate groups or blocked isocyanate groups and alkoxysilyl group group simultaneously
(OCNCH2CH2CH2Si(OCH)3Purchased from Nanjing energy moral)
(i) conjunction of the compound simultaneously containing isocyanate groups or blocked isocyanate groups and alkoxysilyl group group
At
By hexamethylene diisocyanate trimer (being purchased from BASF) first and equimolar NH2CH2CH2CH2Si(OCH)3
Then reaction is blocked again with methyl ethyl ketoxime (being purchased from Zhejiang Sheng An Chemical Co., Ltd.) and Y-OCONH is made)2-Q-
NHCONHCH2CH2CH2Si(OCH)3(Q is that hexamethylene diisocyanate tripolymer removes the residue after triisocyanate group, Y
Residue after removing glass hydrogen living for methyl ethyl ketoxime etc.).
(j)Si(OC2H5)4(being purchased from Changzhou Wujin Heng Ye Chemical Co., Ltd.)
(k)CH3Si(OCH3)3(being purchased from Nanjing Chemical Co., Ltd. forward)
Examples 1 to 10 and comparative example 1~2
Fluorided-modified polyvinyl alcohol film preparation step is as follows:
1) polyvinyl alcohol (being purchased from Shanghai Kai Du industry development Co., Ltd) is dissolved into 7% aqueous solution, be then cast
Film forming, is prepared into film substrate；
2) surface treating composition (being mass parts ratio in table) comprising fluoride is prepared according to the formula in table 1,
Middle Examples 1 to 7 and comparative example 1 are also gone back containing propionic acid, embodiment 8~10 and the comparative example 2 for accounting for hydrolyzable compound 0.5wt%
Containing the sorbic acid for accounting for hydrolyzable compound 0.5wt%, the composition is then dissolved in perfluoro-cyclicether and butyl acetate quality
Than the mixed solvent for 1:1, it is configured to the solution that concentration is 1%；
3) 2) the middle surface treating composition solution spraying comprising fluoride prepared is made 1) middle using high-pressure spray gun
One of surface of the standby film substrate comprising polyvinyl alcohol；
4) to solvent natural air drying, then room temperature curing 1h obtains fluorided-modified polyvinyl alcohol film.
Table 1
| a | b | c | d | e | f | |
| Embodiment 1 | 9 | 1 | ||||
| Embodiment 2 | 1 | 9 | ||||
| Embodiment 3 | 4 | 4 | 2 | |||
| Embodiment 4 | 5 | 5 | ||||
| Embodiment 5 | 7 | 3 | ||||
| Embodiment 6 | 4 | 2 | 2 | 2 | ||
| Embodiment 7 | 4 | 2 | 2 | 2 | ||
| Embodiment 8 | 7 | 2 | 1 | |||
| Embodiment 9 | 5 | 1 | 3 | 1 | ||
| Embodiment 10 | 7 | 1 | 1 | 1 | ||
| Comparative example 1 | 10 | |||||
| Comparative example 2 | 10 |
Embodiment 11~20 and comparative example 3~4
Fluorided-modified polyvinyl alcohol film preparation step is as follows:
1) polyvinyl alcohol (being purchased from Shanghai Kai Du industry development Co., Ltd) is dissolved into 7% aqueous solution, be then cast
Film forming, is prepared into film substrate；
2) non-fluosilicic oxyalkane compound composition (being mass ratio in table) is prepared according to the formula in table 2, then by the group
Close object and be dissolved in the mixed solvent that butyl acetate and n,N-Dimethylformamide mass ratio are 1:1, be configured to concentration be 2% it is molten
Liquid；
3) use high-pressure spray gun by the primary coat solution spraying of 2) the middle non-fluosilicic oxyalkane compound composition prepared in 1)
One of surface of the film substrate comprising polyvinyl alcohol of preparation；
4) surface treating composition (being mass ratio in table) comprising fluoride is prepared according to the formula in table 2, wherein real
Example 11~17 and comparative example 3 is applied also to go back containing propionic acid, embodiment 18~20 and the comparative example 4 for accounting for hydrolyzable compound 0.5wt%
Containing the sorbic acid for accounting for hydrolyzable compound 0.5wt%, the composition is then dissolved in perfluoro-cyclicether and butyl acetate quality
Than the mixed solvent for 1:1, it is configured to the solution that concentration is 1%；
5) after the solvent volatilization in 3), the surface treatment combination comprising fluoride that will be prepared in 4) using high-pressure spray gun
Object solution spraying is in base coating surface；
6) to solvent natural air drying, then room temperature curing 1h obtains fluorided-modified polyvinyl alcohol film.
Table 2
Beneficial effects of the present invention are verified using following test method:
1, waterproofing tests
Waterproofing property evaluation standard is executed by GB/T 4745-1997 " textile fabric surface moisture resistance measures dip experiment "；
3 waterproofing property evaluation standard of table
| Waterproofing grade | State |
| 5 | Surface is without wet |
| 4 | Surface moistens on a small quantity |
| 3 | Surface portion is wet |
| 2 | Surface wettability |
| 1 | Surface is all wet |
2, grease proofness is tested
Grease proofness evaluation criterion is executed by GB/T 19977-2005 " the anti-hydrocarbon test of textile oil repellent ".
4 grease proofness evaluation criterion of table
| Number | Experimental liquid composition | Surface tension (N/m, 25 DEG C) |
| 8 | Normal heptane | 0.0198 |
| 7 | Normal octane | 0.0214 |
| 6 | N-decane | 0.0235 |
| 5 | N-dodecane | 0.0247 |
| 4 | N-tetradecane | 0.0264 |
| 3 | Hexadecane | 0.0273 |
| 2 | 35/ white mineral oil of hexadecane, 65 mixed liquor | 0.0296 |
| 1 | White mineral oil | 0.0315 |
3, antipollution assessment
Oil pen's test: drawing a line with oil pen on modified surface, then examines ink traces and changes, and with
Standard is evaluated below
E: ink rapid desufflation
F: ink portions are shunk
NG: ink is not shunk substantially
4, tensile strength
It is measured using puller system, batten width is 5cm.
Table 5
Note: comparative example 5 is the method preparation according to embodiment 1 in patent CN102807682A.Comparative example 6 is removed and has not been added
Machine acid is outer, remaining is identical with embodiment 17.Comparative example 7 is non-modified processed film.The test sample of tensile strength needs
To pass through double treatment, processing refers to that the film for crossing double treatment is placed in the environment that humidity is 80% in water vapour environment
24h.The unit of tensile strength is MPa/50um, refers to the tensile strength for being converted to film when film thickness is 50um.
As seen from the above table, the fluorided-modified polyvinyl alcohol film sample of 1-20 of embodiment of the present invention preparation gained, waterproof,
Oil preventing performance is excellent；The mechanical property and barrier property that preferably keep film are remained in water vapour environment；Among these, in embodiment 4
When perfluoropolyether silicone compounds are 5:5 with perfluoroalkylsilane compound quality number, effect is optimal；And comparative example
Mechanical property and barrier property are relatively initial poor in sample water vapour environment obtained by 1-6；It can be seen that of the invention is fluorided-modified
The unmodified face of polyvinyl alcohol film maintains the property of polyvinyl alcohol ontology, and modified face waterproof performance is excellent, is not easy to be bedewed by water；
The mechanical property and barrier property that preferably keep film are remained in water vapour environment；Modified face also has the function of grease proofing antifouling.
The environmental scanning electron microscope of the fluorided-modified polyvinyl alcohol film of embodiment 4 is as shown in Figure 1, 2, can from Fig. 1
To find out, fluorided-modified polyvinyl alcohol film film is integrally smooth, without obvious bulky grain protrusion；Figure it is seen that fluorination
It is also smoother at object modified polyvinylalcohol foamed film surface detail, without obvious concave-convex.Non-modified polyvinyl alcohol film is (right
Ratio 7) environmental scanning electron microscope it is as shown in Figure 3, Figure 4, from figure 3, it can be seen that unmodified film overall surface is coarse,
There is obvious protrusion；From fig. 4, it can be seen that there is the obvious plane of disruption at raised brim.
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to realize essentially identical technical effect, made ground simple change, equivalent replacement or modification etc. are all covered
Among protection scope of the present invention.
Claims (7)
1. a kind of preparation method of fluorided-modified polyvinyl alcohol film, it is characterised in that: including
Polyvinyl alcohol is configured to aqueous solution, then casting film-forming, is prepared into polyvinyl alcohol film substrate by step (1)；
The surface treating composition of fluoride is dissolved in perfluoro-cyclicether and butyl acetate mass ratio is the mixed of 1:1 by step (2)
In bonding solvent, it is configured to the solution that concentration is 1wt%；
Step (3) sprays solution made from step 2 to a surface of film substrate made from step 1, to solvent natural wind
Dry, then room temperature curing 1h obtains fluorided-modified polyvinyl alcohol film；
Wherein, the surface treating composition comprising fluoride of the step (2) includes the hydrolyzable of perfluoro-polyether group
It closes object and hydrolyzable compound containing perfluoro alkyl group and accounts for the organic acid of hydrolyzable compound 0.5wt%, described contains
The hydrolyzable compound of perfluoropolyether group is indicated with formula (1):
PFPE-[A-(-G-Si-(OR1)3)s]lFormula (1)
Wherein, PFPE is monovalence or divalent perfluoropolyether group, and A is s+1 valence organic group, and G is bivalent organic group, R1For
C1~4Alkyl, s be 1~6 positive integer, l be 1 or 2；
The mass parts ratio of the hydrolyzable compound of the perfluoro-polyether group and the hydrolyzable compound containing perfluoro alkyl group
For any one mass parts ratio in 9:1 or 1:9 or 4:6 or 5:5 or 7:3 or 8:2 or 6:4.
2. the preparation method of fluorided-modified polyvinyl alcohol film according to claim 1, it is characterised in that: the step
(3) hydrolyzable compound containing perfluoro alkyl group is indicated with formula (2):
(Rf)s’-B-Si-(OR2)3Formula (2)
Wherein, RfFor monovalence perfluoro alkyl group, the positive integer that s ' is 1~5 ,+1 valence organic group of B s ', R2For C1~4Alkane
Base.
3. the preparation method of fluorided-modified polyvinyl alcohol film according to claim 1, it is characterised in that: the step
(3) the hydrolyzable compound containing perfluoro alkyl group is indicated with formula (3):
M(CH2CR1(-D-Rf))m(CH2CR2(-E-Si(OR3)3))n(CH2CR3(-I))pN formula (3)
Wherein, M, N are monovalent organic group, R1、R2And R3For H or CH3, R3For C1~4Alkyl, RfFor perfluoro alkyl group, D is
Bivalent organic group, E are bivalent organic group or covalent bond, and I is monovalent organic group, and m, n are positive integer, and p is 0 or just whole
Number.
4. the preparation method of fluorided-modified polyvinyl alcohol film according to claim 1, it is characterised in that: the step
(3) organic acid in is propionic acid or sorbic acid.
5. the preparation method of fluorided-modified polyvinyl alcohol film according to claim 1, it is characterised in that: the preparation side
Method further includes including fluoride to the spraying of one of surface of the film substrate comprising polyvinyl alcohol in the step (3)
Before surface treating composition, non-fluosilicic oxyalkane compound is sprayed to one of surface of the film substrate comprising polyvinyl alcohol
The step of priming coat of composition.
6. the preparation method of fluorided-modified polyvinyl alcohol film according to claim 5, it is characterised in that: described is non-
Fluosilicic oxyalkane compound composition includes simultaneously containing isocyanate groups or blocked isocyanate groups and-Si- (OR4)3Group
Compound, wherein R4For C1~4's.
7. the preparation method of fluorided-modified polyvinyl alcohol film according to claim 5, it is characterised in that: described is non-
Fluosilicic oxyalkane compound composition include without containing fluoro-containing group and isocyanate groups or blocked isocyanate groups, containing-
Si-(OR5)3The silicone compounds of group, wherein R5For C1~4Alkyl.
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| CN102807682B (en) * | 2012-08-24 | 2014-02-19 | 东北林业大学 | Method for preparing modified single hydrophobic polyvinyl alcohol film |
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