CN106674572A - Preparation method of ultrathin modified hydrotalcite and application thereof to rubber gas barrier thin film material - Google Patents
Preparation method of ultrathin modified hydrotalcite and application thereof to rubber gas barrier thin film material Download PDFInfo
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- CN106674572A CN106674572A CN201611173788.1A CN201611173788A CN106674572A CN 106674572 A CN106674572 A CN 106674572A CN 201611173788 A CN201611173788 A CN 201611173788A CN 106674572 A CN106674572 A CN 106674572A
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 229920001971 elastomer Polymers 0.000 title claims abstract description 35
- 239000010409 thin film Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 20
- 230000004888 barrier function Effects 0.000 title abstract description 11
- 238000004528 spin coating Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 45
- 229910052599 brucite Inorganic materials 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 230000000903 blocking effect Effects 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001548 drop coating Methods 0.000 claims description 8
- 239000004816 latex Substances 0.000 claims description 8
- 229920000126 latex Polymers 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000011017 operating method Methods 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- JSLMNNPQKHONFW-UHFFFAOYSA-N benzene naphthalene-1-carboxylic acid Chemical compound C1(=CC=CC2=CC=CC=C12)C(=O)O.C1=CC=CC=C1 JSLMNNPQKHONFW-UHFFFAOYSA-N 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 11
- 229960001545 hydrotalcite Drugs 0.000 abstract description 11
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000010408 film Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 229920000459 Nitrile rubber Polymers 0.000 description 16
- 239000004927 clay Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09D109/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09D123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09D123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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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
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/02—Copolymers with acrylonitrile
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08J2323/22—Copolymers of isobutene; butyl rubber
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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
- C08J2339/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2339/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Geology (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of ultrathin modified hydrotalcite and an application thereof to a rubber gas barrier thin film material. Firstly, coprecipitation is used for preparing ultrathin hydrotalcite with a high length diameter ratio, surface modification is carried out, spin coating method technology is used, the ultrathin modified hydrotalcite and rubber are compounded in order to form a film, and finally the gas barrier thin film material is prepared by compounding the ultrathin modified hydrotalcite and the rubber. The ultrathin hydrotalcite with a nanometer sheet shaped structure has high length diameter ratio, and can be used as a filler for substantially prolonging diffusion path of oxygen molecules in a thin film material; surface modification of hydrotalcite can improve interfacial compatibility between hydrotalcite and rubber, and reduce free volume, so that the composite thin film materials has excellent gas barrier performance, good heat stability and mechanical performance. The method has wide source, low cost, and simple preparation, and accords with environmental protection requirements; and the method has wide application prospects in the fields of automobile industry, outdoor packaging and aerospace industry.
Description
Technical field
The invention belongs to inorganic/organic hybrid films field of functional materials, and in particular to a kind of ultrathin modified brucite
Prepare and its application in rubber air blocking thin film material, relate more specifically to a kind of preparation method of ultrathin modified brucite and
The preparation method of ultrathin modified brucite and rubber combined air blocking thin film material.
Background technology
Brucite (LDHs) class lamellar compound is the anionic clay that a class quickly grows in recent years, is that one kind has
The inorganic material of wide range of application.LDHs has the layer structure similar with montmorillonite cationoid clay, is cloudy by interlayer
The compound that ion and positively charged laminate are piled up, adjustable with laminate metallic element ratio, interlayer anion is commutative
The characteristics of.In recent years, in the fields such as nano composite material, functional type coated film and emulsion stabilizer are prepared, dispersibility is good
Good LDHs colloids have a wide range of applications.For nano composite material, only when original stratiform ordered arrangement structure
Dispersion is fully peeled off, the characteristic under its nanoscale could be given full play of.But due to LDHs lamina surface charge density
It is of a relatively high, while forming a large amount of hydrogen bonds between the hydroxyl in interlayer anion/hydrone and laminate, cause tool between laminate
There is very strong adhesion, therefore be difficult to peel off under conditions of being generally acknowledged that gently.The method that tradition prepares monolayer LDHs is big
Cause is divided into three steps, and the delamination brucite yield that this method is obtained is less, and process is more complicated, takes longer.On this basis, it is ultra-thin
The synthesis of brucite is not only advantageous to improve the dispersibility of brucite, and with yield it is high, the used time is short the characteristics of, greatly increase
It is added in the application in gas barrier field.
From saying using angle, in addition to food and medicine packaging and electron device package material, with social progress and Jing
The development of Ji, substantial amounts of industrial and civilian rubber seals, Aero-Space high vacuum system rubber are similarly needed
Want rubber that there is good gas barrier property.But due to rubber molecule structure it is not fine and close enough, with larger free volume, because
This gas barrier property is poor.In recent years, the clay of lamellar structure is incorporated in rubbery system and prepares clay/rubber combined material
Material is the focus of research.The clay of lamellar structure is incorporated in polymer the barrier properties for gases that can effectively improve composite
Can, it is that gas molecule needs to bypass laminate in diffusion process to trace it to its cause, so as to extend the evolving path of molecule.But it is viscous
Some problems are yet suffered from soil/rubber composite：1. inorganic material addition crosses senior general causes the mechanical property of material to drop
It is low, and be easy to reunite, so that gas barrier property is restricted；2. there is boundary between hydrophilic clay and non-hydrophilic polymer
Face compatibility is low, weakens the problem for interacting, and then have impact on the combination property of material.Therefore, high obstructing performance is being pursued
Rubber gastight material in still there is a difficult problem and challenge.
The content of the invention
The present invention is intended to provide a kind of preparation method of ultrathin modified brucite and its application in rubber film material,
Clay addition is excessive in solve conventional clay/rubber composite causes the mechanical property of material to reduce and be easy to reunite,
So that gas barrier property is restricted；And the weaker technology of hydrophilic clay and non-hydrophilic polymer interphase interaction is asked
Topic.
The technical scheme is that：The ultra-thin brucite having compared with big L/D ratio is prepared first with coprecipitation, it is right
It is modified that it carries out surface, using spin-coating technology, by ultrathin modified brucite and rubber combined film forming, so that ultra-thin changing is obtained
Property brucite and rubber combined air blocking thin film material.
The preparation method of ultrathin modified brucite of the present invention, comprises the following steps：
A) prepare the mixing salt solution of soluble divalent metal salt and soluble trivalent metal salt, wherein divalent metal sun from
Sub- M2+Concentration be 0.02-0.04mol/L；Divalent metal M2+With trivalent metal cation M3+Molar ratio range be
2-4；The nitrate solution of Methanamide is prepared, the volume content of Methanamide is 20-40%, and the concentration of nitrate is 0.01-
0.02mol/L；Then under condition of heating and stirring, the mixing salt solution of preparation is dropwise instilled in the nitrate solution of Methanamide
Reacted, nitrate and trivalent metal cation M3+Mol ratio be 1-2, while Deca sodium hydroxide solution control reactant liquor
PH value, Deca is completed in 10-20min, be then centrifuged for washing 2-3 time, add water centrifugation, take the supernatant and obtain final product ultra-thin water
Talcum colloid solution, wherein brucite mass content are 0.05%-0.1%；
B) surface modifier of 0.2-2wt%, room temperature are added in the ultra-thin houghite colloidal solution obtained in step a)
Stirring 1-4h, obtains ultrathin modified houghite colloidal solution.
The nitrate is sodium nitrate or potassium nitrate；The temperature of the heating is 70-90 DEG C；The pH value quilt of the reactant liquor
Control is in the range of 9-11.
The divalent metal M2+Selected from Mg2+、Ni2+And Zn2+In any one；The trivalent metal cation
M3+Selected from Co3+、Al3+And Fe3+In any one.
Preferably, the surface modifier is polyvinylpyrrolidone or dodecyl sodium sulfate.
Application of the above-mentioned ultrathin modified brucite for preparing in the preparation of rubber air blocking thin film material.
The preparation method of a kind of ultrathin modified brucite of the present invention and rubber combined air blocking thin film material：By parent
Substrate after hydration process is adsorbed on whirler, when whirler rotates by ultrathin modified houghite colloidal solution
Replace for the rubber solutions of 1%-5% with mass concentration and be spin-coated in the substrate after hydrophilicity-imparting treatment；Spin coating every time completes rear chamber
The lower drying of temperature, then carries out again next spin coating operation；Repeat alternately spin coating 5-35 time, after being finally dried ultrathin modified water is obtained
Talcum and rubber combined air blocking thin film material.
The above-mentioned operating procedure that hydrophilicity-imparting treatment is carried out to substrate is included successively respectively with ethanol, acetone, water ultrasonic cleaning
Substrate 10-30min, then cleans up substrate deionized water, is dried at room temperature.
Preferably, the substrate is polyethylene terephthalate.
The rubber solutions are added water by NBR latex or butyl latex and are formulated；During the ultra-thin houghite colloidal solution of drop coating
The rotary speed of whirler is 1500-2500 rev/min, and the rotary speed of whirler is during drop coating rubber solutions
3000-5000 rev/min.
Ultrathin modified brucite and rubber combined air blocking thin film material according to obtained in preparation method mentioned above.
The invention has the beneficial effects as follows：The ultra-thin brucite prepared in the present invention is flaky nanometer structure, with larger
Draw ratio, as filler the evolving path of the oxygen molecule in thin-film material can be significantly extended, and hydrotalcite surface changes
Property can improve the interface compatibility of brucite and polymer for example between rubber, free volume is reduced, so that THIN COMPOSITE
Membrane material has superior in gas barrier property, good heat stability and mechanical performance.Wide material sources of the present invention, it is with low cost,
Prepare simply, meet environmental requirement, before auto industry, outdoor encapsulation and aerospace industry field have a wide range of applications
Scape.
Description of the drawings
Fig. 1 is the XRD figure of the ultra-thin hydrotalcite sample obtained by step A of the embodiment of the present invention 1；Wherein abscissa is
2Theta, unit is degree；Vertical coordinate is intensity.
Fig. 2 is the TEM figures of the ultra-thin hydrotalcite sample obtained by step A of the embodiment of the present invention 1.
Fig. 3 is the FT-IR figures of the ultrathin modified hydrotalcite sample obtained by step B of the embodiment of the present invention 1.
Fig. 4 is the air blocking thin film material that the ultrathin modified brucite obtained by step D of the embodiment of the present invention 1 is combined with nitrile rubber
Material sample XRD figure, wherein abscissa be 2Theta, unit：Degree, vertical coordinate is intensity.
Fig. 5 is the air blocking thin film material that the ultrathin modified brucite obtained by step D of the embodiment of the present invention 1 is combined with nitrile rubber
The SEM plane graphs of material sample.
Fig. 6 is the air blocking thin film material that the ultrathin modified brucite obtained by step D of the embodiment of the present invention 1 is combined with nitrile rubber
The SEM sectional views of material sample.
Fig. 7 is the air blocking thin film material that the ultrathin modified brucite obtained by step D of the embodiment of the present invention 1 is combined with nitrile rubber
The thermal multigraph of material sample.
Fig. 8 is the air blocking thin film material that the ultrathin modified brucite obtained by step D of the embodiment of the present invention 1 is combined with nitrile rubber
The stress-strain curve diagram of material sample.
Specific embodiment
Below in conjunction with the accompanying drawing in embodiments of the invention and embodiment, the technical scheme in the embodiment of the present invention is entered
Clear, the complete description of row, it is clear that described embodiment is only a part of embodiment of the invention, rather than the reality of whole
Apply example.Based on the embodiment in the present invention, those of ordinary skill in the art are obtained under the premise of creative work is not made
Every other embodiment, belong to the scope of protection of the invention.
Embodiment 1：
A. 0.512g Mg (NO are weighed3)2·6H2O and 0.375g Al (NO3)3·9H2O be dissolved in 100mL deionized waters with
Prepared mixing salt solution, weighs 1g NaOH and is dissolved in 100mL deionized waters NaOH solution is obtained, and prepares formyl containing 25vol%
The NaNO of amine3Solution 100mL, sodium nitrate concentration 0.01mol/L；Under conditions of 80 DEG C of mechanical agitation, the salt-mixture that will be prepared
Solution and NaOH solution are added dropwise to the NaNO of the Methanamide prepared3Reacted in solution, it is anti-using NaOH solution control
The pH value answered completes Deca 10 or so, in 10min, is then centrifuged for washing 2 times, adds water centrifugation, takes the supernatant and obtains final product
Ultra-thin houghite colloidal solution, wherein hydrotalcite levels are 0.05wt%.Referring to Fig. 1 and 2, ultra-thin brucite sample is respectively illustrated
The XRD figure of product and TEM scheme.
B. polyvinylpyrrolidone (0.5wt%) is added in the ultra-thin hydrotalcite nano piece solution obtained by step A, magnetic
Power stirs 2h, obtains the ultrathin modified hydrotalcite nano piece colloid solution of clear.Referring to Fig. 3, ultrathin modified water is shown
The FT-IR figures of talc sample.
C. the PET substrate by thickness for 180nm is cleaned by ultrasonic successively with ethanol, acetone, water
10min, then cleans up the substrate deionized water after ultrasonic cleaning, is dried at room temperature, to obtain the base handled well
Bottom；
D. the substrate handled well is adsorbed on whirler, then when whirler rotates by obtained by step B
Ultra-thin houghite colloidal solution and solid content replace for the nitrile rubber solution (added water by NBR latex and be formulated) of 1wt%
Be spin-coated in the substrate handled well, wherein drop coating ultra-thin houghite colloidal solution when whirler rotary speed be 2500
Rev/min, the rotary speed of whirler is 4500 revs/min during drop coating NBR latex；Every time after the completion of spin coating under room temperature
It is dried, next spin coating operation is then carried out again；Repeat alternately spin coating 30 times, it is final be dried after obtain ultrathin modified brucite with
The compound air blocking thin film material of nitrile rubber.
Fig. 4 shows the air blocking thin film material sample that the ultrathin modified brucite of the gained of embodiment 1 is combined with nitrile rubber
XRD figure；Fig. 5 shows the air blocking thin film material sample that the ultrathin modified brucite of the gained of embodiment 1 is combined with nitrile rubber
SEM plane graphs.Fig. 6 shows the air blocking thin film material that the ultrathin modified brucite of the gained of embodiment 1 is combined with nitrile rubber
The SEM sectional views of sample.Fig. 7 shows the air blocking thin film that the ultrathin modified brucite of the gained of embodiment 1 is combined with nitrile rubber
The thermal multigraph of material sample.Fig. 8 shows the air blocking thin film that the ultrathin modified brucite of the gained of embodiment 1 is combined with nitrile rubber
The stress-strain curve diagram of material sample.
Structure and morphology, the oxygen-barrier property of the air blocking thin film material by being combined to ultrathin modified brucite and nitrile rubber
Energy, heat stability and mechanical performance are tested, and are as a result shown：The oxygen transit dose of the thin film is 0.63cm3m-2day-1, and its
With good heat stability and mechanical stability.
Embodiment 2：
A. 1.024g Mg (NO are weighed3)2·6H2O and 0.375g Al (NO3)3·9H2O be dissolved in 100mL deionized waters with
Prepared mixing salt solution, weighs 1g NaOH and is dissolved in 100mL deionized waters NaOH solution is obtained, and prepares formyl containing 35vol%
The NaNO of amine3Solution 100mL, sodium nitrate concentration 0.02mol/L；Under conditions of 90 DEG C of mechanical agitation, the salt-mixture that will be prepared
Solution and NaOH solution are added dropwise to the NaNO for preparing3In solution, the pH value of reaction is controlled 11 or so using NaOH solution,
Deca is completed in 20min；Washing 3 times is then centrifuged for, centrifugation is added water, taking the supernatant, to obtain final product ultra-thin brucite colloid molten
Liquid, wherein hydrotalcite levels are 0.07wt%.
B. dodecyl sodium sulfate (1wt%) is added in the ultra-thin hydrotalcite nano piece solution obtained by step A, magnetic force
Stirring 3h, obtains the ultrathin modified hydrotalcite nano piece colloid solution of clear.
C. the PET substrate by thickness for 180nm is cleaned by ultrasonic successively with ethanol, acetone, water
10-30min, then cleans up the substrate deionized water after ultrasonic cleaning, is dried at room temperature, to obtain what is handled well
Substrate；
D. the substrate handled well is adsorbed on whirler, then when whirler rotates by obtained by step B
Ultra-thin houghite colloidal solution and solid content replace for the butyl rubber solution (added water by butyl latex and be formulated) of 2wt%
Be spin-coated in the substrate handled well, wherein when coating preferred drop coating ultra-thin houghite colloidal solution whirler rotary speed
For 1500 revs/min, the rotary speed of whirler is 3500 revs/min when coating preferred drop coating butyl latex；Rotation every time
Painting completes drying under rear chamber temperature, and next spin coating operation is then carried out again；Repeat alternately spin coating 20 times, surpassed after being finally dried
The air blocking thin film material that thin modified hydrotalcite is combined with butyl rubber.
Structure and morphology, the oxygen-barrier property of the air blocking thin film material through being combined to ultrathin modified brucite and butyl rubber
Energy, heat stability and mechanical performance are tested, and are as a result shown：The oxygen transit dose of the thin film is 1.574cm3m-2day-1, and
It has good heat stability and mechanical stability.
The foregoing is only presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
Any modification, equivalent and improvement for being made within principle etc., should be included within the scope of the present invention.Therefore,
Protection scope of the present invention should be defined by the scope of the claims.
Claims (10)
1. a kind of preparation method of ultrathin modified brucite, it is characterised in that comprise the following steps：
A) mixing salt solution of soluble divalent metal salt and soluble trivalent metal salt, wherein divalent metal M are prepared2+
Concentration be 0.02-0.04mol/L；Divalent metal M2+With trivalent metal cation M3+Molar ratio range be 2-4；
The nitrate solution of Methanamide is prepared, the volume content of Methanamide is 20-40%, and the concentration of nitrate is 0.01-0.02mol/
L；Then under condition of heating and stirring, carry out in the nitrate solution that the mixing salt solution of preparation is dropwise instilled Methanamide anti-
Should, nitrate and trivalent metal cation M3+Mol ratio be 1-2, while Deca sodium hydroxide solution control reactant liquor pH
Value, completes Deca in 10-20min, is then centrifuged for washing 2-3 time, adds water centrifugation, takes the supernatant and obtains final product ultra-thin brucite
Colloid solution, wherein brucite mass content are 0.05%-0.1%；
B) surface modifier of 0.2-2wt% is added in the ultra-thin houghite colloidal solution obtained in step a), is stirred at room temperature
1-4h, obtains ultrathin modified houghite colloidal solution.
2. preparation method according to claim 1, it is characterised in that the nitrate is sodium nitrate or potassium nitrate；It is described
The temperature of heating is 70-90 DEG C；The pH value of the reactant liquor is controlled in the range of 9-11.
3. the preparation method according to any claim in claim 1-2, it is characterised in that the divalent metal sun from
Sub- M2+Selected from Mg2+、Ni2+And Zn2+In any one；The trivalent metal cation M3+Selected from Co3+、Al3+And Fe3+In
Any one.
4. the preparation method according to any claim in claim 1-2, it is characterised in that the surface modifier is
Polyvinylpyrrolidone or dodecyl sodium sulfate.
5. the ultrathin modified brucite that preparation method according to claim 1 is obtained is in the preparation of rubber air blocking thin film material
Application.
6. the preparation method of a kind of ultrathin modified brucite and rubber combined air blocking thin film material, it is characterised in that include with
Lower step：
Substrate after hydrophilicity-imparting treatment is adsorbed on whirler, when whirler rotates by ultrathin modified brucite
Colloid solution and mass concentration replace for the rubber solutions of 1%-5% and are spin-coated in the substrate after hydrophilicity-imparting treatment；Spin coating every time
After the completion of be dried under room temperature, next spin coating operation is then carried out again；Repeat alternately spin coating 5-35 time, surpassed after being finally dried
Thin modified hydrotalcite and rubber combined air blocking thin film material.
7. preparation method according to claim 6, it is characterised in that the operating procedure bag of hydrophilicity-imparting treatment is carried out to substrate
Include successively respectively with ethanol, acetone, water ultrasonic cleaning substrate 10-30min, then clean up substrate deionized water, in
It is dried under room temperature.
8. the preparation method according to any claim in claim 6-7, it is characterised in that the substrate is for poly- to benzene
Naphthalate.
9. preparation method according to claim 6, it is characterised in that the rubber solutions are by NBR latex or butyl latex
Add water and be formulated；The rotary speed of whirler is 1500-2500 rev/min during drop coating ultra-thin houghite colloidal solution,
The rotary speed of whirler is 3000-5000 rev/min during drop coating rubber solutions.
10. a kind of ultrathin modified brucite and rubber combined air blocking thin film material, it is characterised in that the ultrathin modified neatly
Stone is obtained by preparation method according to claim 6 with rubber combined air blocking thin film material.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501815A (en) * | 2017-08-11 | 2017-12-22 | 绍兴福膜新材料有限公司 | A kind of scratch-resistant polyvinylidene difluoride film of high water resistant and preparation method thereof |
| CN108126206A (en) * | 2017-12-29 | 2018-06-08 | 北京化工大学 | Drug loading is with mixing gadolinium individual layer hydrotalcite and preparation method thereof and a kind of anticancer drug and preparation method thereof |
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| CN111423685A (en) * | 2020-03-11 | 2020-07-17 | 上海工程技术大学 | Polyacrylonitrile/hydrotalcite composite film and preparation method and application thereof |
| CN112055696A (en) * | 2018-05-14 | 2020-12-08 | Scg化学有限公司 | Surface-modified layered double hydroxides |
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| CN112724463A (en) * | 2020-12-30 | 2021-04-30 | 北京化工大学 | Modified hydrotalcite, preparation method and application thereof, stretchable gas barrier film and preparation method thereof |
| CN116144122A (en) * | 2022-12-12 | 2023-05-23 | 湖北华强科技股份有限公司 | Transparent brominated butyl rubber for gasket for pen-type injector and preparation method thereof |
| US11993519B2 (en) | 2017-03-06 | 2024-05-28 | Oxford University Innovation Limited | Layered double hydroxide precursor, their preparation process and catalysts prepared therefrom |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374153A (en) * | 2013-06-30 | 2013-10-30 | 北京化工大学 | Preparation method of supermolecule/rubber airtight materials |
| CN104788704A (en) * | 2015-05-02 | 2015-07-22 | 北京化工大学 | Preparation of multi-stage structured hydrotalcite and application of multi-stage structured hydrotalcite in gasbarrier packaging material |
| CN104877204A (en) * | 2015-05-31 | 2015-09-02 | 北京化工大学 | Preparation method of hydrotalcite masterbatch/halogenated butyl rubber high-gas obstruction composite materials |
-
2016
- 2016-12-16 CN CN201611173788.1A patent/CN106674572B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374153A (en) * | 2013-06-30 | 2013-10-30 | 北京化工大学 | Preparation method of supermolecule/rubber airtight materials |
| CN104788704A (en) * | 2015-05-02 | 2015-07-22 | 北京化工大学 | Preparation of multi-stage structured hydrotalcite and application of multi-stage structured hydrotalcite in gasbarrier packaging material |
| CN104877204A (en) * | 2015-05-31 | 2015-09-02 | 北京化工大学 | Preparation method of hydrotalcite masterbatch/halogenated butyl rubber high-gas obstruction composite materials |
Non-Patent Citations (2)
| Title |
|---|
| JINGFANG YU ET AL.: ""One-step direct synthesis of layered double hydroxide single-layer nanosheets"", 《NANOSCALE COMMUNICATION》 * |
| 徐金芳等: ""阴-非离子表面活性剂复合改性水滑石的表面性质研究"", 《无机化学学报》 * |
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| CN108126206B (en) * | 2017-12-29 | 2020-04-28 | 北京化工大学 | Gadolinium-doped single-layer hydrotalcite for drug loading and preparation method thereof, and anticancer drug and preparation method thereof |
| CN112055696A (en) * | 2018-05-14 | 2020-12-08 | Scg化学有限公司 | Surface-modified layered double hydroxides |
| CN108993377A (en) * | 2018-08-13 | 2018-12-14 | 武汉理工大学 | Ultra-thin zinc-aluminum gavite nanometer sheet and its preparation method and application |
| CN111423685B (en) * | 2020-03-11 | 2022-03-25 | 上海工程技术大学 | Polyacrylonitrile/hydrotalcite composite film and preparation method and application thereof |
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