CN108699246A

CN108699246A - Durable super-hydrophobic coat

Info

Publication number: CN108699246A
Application number: CN201680082334.5A
Authority: CN
Inventors: 严宏; 徐建伟; 叶群; 周慧
Original assignee: Agency for Science Technology and Research Singapore
Current assignee: Agency for Science Technology and Research Singapore
Priority date: 2015-12-23
Filing date: 2016-12-23
Publication date: 2018-10-23
Also published as: WO2017111702A9; WO2017111702A1; SG11201805366VA

Abstract

The present invention relates to polymer coatings, the polymer coating includes the nanometer additive with such as vinyl-functional of organopolysiloxane for example poly- (methyl hydrogen siloxane) (PMHS) covalently bound surface functionalization, wherein the nanometer additive includes:(a) nanometer additive base material, and (b) connector, the connector is by siloxy moieties at one end with the nanometer additive base material covalent bond and in the other end and the organopolysiloxane covalent bond.The invention further relates to manufacture the method for this coating, the purposes of this coating, the method for coating with this coating base material and obtainable by this method coat base material.

Description

Durable super-hydrophobic coat

Technical field

The present invention relates to the coating for super-hydrophobic coat.The invention further relates to the methods for manufacturing this coating.

Background technology

Super-hydrophobic textile is since it is in operation tool, medical treatment device, textile (such as swimsuit and military clothes), sea Broad range of application in thing industry and environmental applications and it is attractive.Currently, super-hydrophobic textile is commercialized main Problem be the whole manufacturing cost of height of the coating on textile substrate, low mechanical strength and difference durability.Therefore, current side Method concentrate on how the effective material of use cost come realize have enhancing long durability super-hydrophobicity.In addition, in recent years Come, the classification form for imitating lotus leaf has become the main policies for generating super-hydrophobic textile, and being related to introducing has low-surface-energy Coating or special form or pattern are generated on fiber, or both.

Currently, perfluorinated material is widely used to super-hydrophobic coat.Perfluorinated material has low cohesive energy, low surface certainly By the feature of energy and low water absorbable, this leads to chemical resistance, corrosion resistance, low friction performance and against weather.Due to these originals Cause, they are applied to the super-hydrophobic textile coating in modern industry by selection.However, they are costly, and in some feelings It is difficult to handle under condition.In addition, they are uncertain to the potential impact of health, because perfluorinated material does not have in mammals Have known metabolism, this may lead to bioaccumulation, persistently exist in the environment, and some may be it is reactive and Toxic.Therefore, the application of perfluorinated material is restricted.Therefore, efforts have been made to develop for super-hydrophobic textile coating Non- fluorine material, such as use metal oxide nano composite material, winnofil and carbon nanotube.For example, coating is aerobic Super hydrophobic surface can be generated by changing the cotton fabric of zinc nanometer rods or zinc oxide crystallite.

Another alternative solution is to use siloxane polymer, such as dimethyl silicone polymer (PDMS), poly- (methyl hydrogen silica Alkane) (PMHS) or its copolymer, they are nontoxic, inexpensive, easy to manufacture, flexible and optically transparent.With several Million small silicon silk coating fibers can obtain waterproof garment material.In addition, being obtained by two step wet-chemical paint-on techniques super Hydrophobic textile product are verified to show significant multiple self-reparing capability to physics and chemical damage, and to including that ethyl alcohol exists Interior low surface tension liquid shows excellent liquid-repellant.However, most conventional method needs perfluorinated material, toxic chemical Product and fine preparation procedure.

It has been shown that the graphene oxide (RGO) of reduction can be applied to cotton fiber surface to adjust the wetting of fiber Property so that they become super-hydrophobic, while super organic-philic material or oil.PDMS can be further applied to coated with RGO's To improve its surface wettability on cotton fiber.However, in this approach, RGO and PDMS are not chemically bonded each other, it means that Coating can only use on the material of limited kinds under limited processing method.This coating also have limited durability and Wear resistance, especially in the case of repeated washing.In addition, when textile needs to coat RGO first, high concentration is needed RGO。

Another alternative solution studied is changed for the graphene oxide (RGO) of the reduction of super-hydrophobic textile coating Property organopolysiloxane, display long-term acidproof, alkaline-resisting and hot water resistance and wear resistance.What this RGO was modified has The addition reaction that machine polysiloxane coating materials are assisted by aryl, subsequent hydrosilylation, so that very small amount of RGO gathers with organic Siloxanes covalent bonding synthesizes.Although the organopolysiloxane that RGO is modified shows excellent property, wherein there is limitation Property, including the cumbersome preparation process of vinyl-functional RGO and can be used for the limited Si -- H with polymer matrix qualitative response.

In this regard, although extensive effort has been carried out to realize super-hydrophobic textile coating, there are still challenges The problem of property, for example, the high cost, the engineering properties of coating, the chemistry of coating and environmental resistance, coating of material safety And comfort.

Accordingly, it is desirable to provide overcoming or at least improving the coating of said one or multiple shortcomings.

Invention content

In in one aspect of the present disclosure, provide polymer coating, it includes with organopolysiloxane is covalently bound receives Rice additive, wherein the nanometer additive includes:

A) nanometer additive base material, and

B) connector, the connector are covalently tied with the nanometer additive base material at one end by siloxy moieties Merge and in the other end and the organopolysiloxane covalent bond.

Advantageously, coating can be super-hydrophobic and repel water.

More advantageously, coating can not include fluorine.That is, coating can be floride-free.This means that with perfluorinated material It can be avoided by disclosed polymer coating using relevant any adverse effect.For example, disclosed coating can be Bio-compatible, because it is without possible toxic perfluorinated material.In addition, by not including perfluorinated material, it is disclosed Coating can be provided in a manner of more cost effective.

It is further advantageous that disclosed coating may include zero dimension to two-dimensional nano additive, it is only necessary to trace (<0.5 weight Measure %) nanometer additive.This can be to avoid must use the nanometer additives of a large amount of costlinesses so that coating has more cost effect Benefit.

More advantageously, disclosed coating can have high-durability under severe conditions.Disclosed coating can be to strong nothing Machine acid, strong corrosive alkali and hot water have excellent long-term tolerance, while keeping its superhydrophobic property.It is further advantageous that Even if disclosed coating can keep its super-hydrophobicity more than after the washing of 500 times (or 7 days) or if after strong etching Matter.

It is further advantageous that assigning textile substrate superhydrophobic property, assign to strong corrosive acid, strong corrosive alkali, heat The tolerance of water or chemical abrasion only needs a small amount of disclosed coating.

Advantageously, the nanometer additive base material of disclosed coating and organopolysiloxane can be with covalent bondings.It is not bound by The constraint of opinion, the favorable property of disclosed coating are attributable to be present between nanometer additive base material and organopolysiloxane Strong covalent bond.

In another aspect, the method for being used to prepare coating is provided comprising following steps:

A) silane reagent, preferred vinyl trialkoxy silane is made to be reacted with nanometer additive base material, the nanometer addition Agent base material is optionally functionalized by hydroxyl surface,

B) optionally make reaction product and organopolysiloxane or its precursor covalent bonding in the presence of a catalyst.

Advantageously, disclosed method provides the hybrid composite material for synthesizing nanometer additive and polysiloxanes Simple and easy method.It is further advantageous that compared with conventional method, the method is conducive to the large-scale production of coating, because it is suitable Together in scaled.

In another aspect, coating as defined above is provided and is used to coat base material, it is preferably natural or staple fibre Purposes.

In another aspect, coating base material, the preferably method of fiber are provided comprising following steps:

A) coating as defined above is dissolved in a solvent to form coating solution;

B) base material is immersed in the coating solution;And

C) base material is taken out from the coating solution.

Advantageously, disclosed method is conducive to easily coat base material with coating as defined above.Further have Sharp ground, the method allow coating to be applied to various natural or staple fibres to realize similar super-hydrophobicity.Further have Sharp ground, need not be further processed base material after the coating process so that the application of coating is simple and effective.

In another aspect, the painting with superhydrophobic property that can be obtained by any method as defined above is provided Cover base material.

Advantageously, physicochemical properties, color or the feel of the base material coated with disclosed coating can not change.More have Sharp ground, coating can be stain resistant, it means that any base material coated with disclosed coating can be easy to carry out clearly It washes.It is further advantageous that coating can be applied on the base material of wide scope, including cotton, polyester, nylon and Nomex, while keeping super Hydrophobic property.Even it is further advantageous that even if the property of base material itself can assign base material similar super-hydrophobicity if different Matter.More advantageously, even if the permeability of primary substrate can be kept if after with disclosed coating coating base material.

In another aspect, polymer nanocomposite additive composite material is provided, it includes covalently tied with organopolysiloxane The nanometer additive of conjunction,

The wherein described nanometer additive includes:

A) nanometer additive base material, and

B) connector, the connector are covalently tied with the nanometer additive base material at one end by siloxy moieties Merge and in the other end and the organopolysiloxane covalent bond;

And the wherein described organopolysiloxane includes the non-end list of one or more formulas (III) in polymer chain Member:

Wherein

R¹Independently selected from hydrogen, C₁To C₁₀Alkyl, C₁To C₁₀Alkenyl, C₁To C₁₀Alkyl-C₆To C₁₀Aryl or C₆To C₁₀Virtue Base;And R¹Preferably methyl;

And X is the key combined with the connector.

Brief description of drawings

Disclosed embodiment and the principle for explaining disclosed embodiment are illustrated.However, answering Understand, attached drawing is designed only for the purpose of explanation, not as the definition of the limitation of the present invention.

Fig. 1

[Tu1 ]The schematic diagram for being silane hydrolyzate and being then condensed on hydration surface.

Fig. 2

[Tu2 ]It is the schematic diagram of PMHS and silanization-polymerization process of the nanometer additive of various vinyl-functionals.

Fig. 3

[Tu3 ]It is the photo of (a) original clay and the functionalized clay of (b) vinyl silanes in (A) water and (B) THF.

Fig. 4

[Tu4 ]It is the FTIR spectrum of (a) octavinyl-POSS and (b) PMHS@POSS.

Fig. 5

[Tu5 ]It is the FTIR spectrum of (a) SiNP, the functionalized SiNP of (b) vinyl silanes and (c) PMHS@SiNP.

Fig. 6

[Tu6 ]Be (a) thick carbon nanotube (CNT), the functionalized CNT of (b) vinyl silanes and (c) PMHS@CNT FTIR Spectrum.

Fig. 7

[Tu7 ]It is the FTIR spectrum of (a) spavin, the functionalized clay of (b) vinyl silanes and (c) PMHS@clays.

Fig. 8

[Tu8 ]It is the FTIR spectrum of (a) GO, the functionalized GO of (b) vinyl silanes and (c) PMHS@GO.

Fig. 9

[Tu9 ]It is the FTIR spectrum of (a) RGO, the functionalized RGO of (b) vinyl silanes and (c) PMHS@RGO.

Figure 10

[Tu10 ]It is the TEM microphotos of the functionalized SiNP of vinyl silanes.

Figure 11

[Tu11 ]It is the TEM microphotos of (a) GO and the functionalized GO of (b) vinyl silanes.

Figure 12

[Tu12 ]It is the TEM microphotos of the functionalized RGO of vinyl silanes.

Figure 13

[Tu13 ]It is the TEM microphotos of the sample of (A) spavin and the functionalized clay of (B) vinyl silanes.

Figure 14

[Tu14 ]It is shown in the wetting of the water droplet on the cotton fabric for the coating coating for being used as the embodiment of the application The image of behavior.Image is shown in (A) PMHS@POSS, (B) PMHS@SiNP, (C) PMHS@CNT, (D) PMHS@clays, (E) 5 μ l water droplets on PMHS@GO and (F) PMHS@RGO.

Figure 15

[Tu15 ]Be (A) it is uncoated, (B) coated with PMHS@SiNP, (C) coated with PMHS@POSS and (D) apply It is covered with the SEM image of the cotton fabric of PMHS@clays.

Figure 16

[Tu16 ]Be shown in various cospinnings (comcemtial) textile substrate (1) braided fabric, (2) non-woven fabric and (3) image of the wetting behavior of the water droplet on weaven goods.Image be shown in (A) it is uncoated, (B) coated with PMHS@POSS, (C) be coated with PMHS@Silica, (D) coated with PMHS@CNT, (E) coated with PMHS@GO, (F) be coated with PMHS@ The water droplet of RGO being coated with (G) on textile of PMHS@clays.

Figure 17

[Tu17 ]It is the graphical representation of the super-hydrophobic textile coating of the PMHS@nanometer additives on textile substrate.

Figure 18

[Tu18 ]It is the stain resistant behavior that (A) shows (a) uncoated mitten that PMHS@clays are coated with (b) Image, (B) is shown before (a) coating and (b) uses the image of the color of the base material after PMHS@clay coateds, (C) to show (a) Uncoated and (b) is coated with the image of the antibacterial behavior of the textile substrate of PMHS@clays, and the sum that (D) (a) is uncoated (b) it is coated with the automatical cleaning ability of the textile substrate of PMHS@clays.

Figure 19

[Tu19 ]It is shown in acid solution and impregnates (A) 1 week, (B) 2 weeks, (C) 3 weeks and (D) 4 weeks later coated with PMHS@ The image of the wetting behavior of water droplet on the wollen fabrics base material of clay.

Figure 20

[Tu20 ]It is shown in and impregnates (A) in aqueous slkali 1 week and (B) 2 weeks wollen fabrics for being coated with PMHS@clays later The image of the wetting behavior of water droplet on base material.

Figure 21

[Tu21 ]It is shown in washing (A) 1 day, (B) 2 days, (C) 5 days and (D) are coated with cottons of PMHS@clays after 7 days The image of the wetting behavior of water droplet on textile substrate.

Figure 22

[Tu22 ]It is shown in washing (A) 1 day, (B) 2 days, (C) 5 days and (D) are coated with cottons of PMHS@clays after 7 days The SEM image of the form of textile substrate.

Specific implementation mode

Definition

Following word and term used herein should have indicated meaning:

Unless otherwise stated, " alkyl " of the part as group or group refers to linear chain or branched chain aliphatic hydrocarbon Base, preferably C₁-C₁₂Alkyl, more preferable C₁-C₁₀Alkyl, most preferably C₁-C₆Alkyl.Suitable straight chain and branch C₁-C₆Alkyl replaces The example of base includes methyl, ethyl, n-propyl, 2- propyl, normal-butyl, sec-butyl, tertiary butyl, hexyl etc..The group can be with It is end group or bridged group.

" alkenyl " of a part as group or group indicates containing at least one carbon-to-carbon double bond and preferred in normal chain With 2-12 carbon atom, more preferable 2-10 carbon atom, most preferably 2-6 carbon atom can be linear chain or branched chain aliphatic series Alkyl.The group can contain multiple double bonds in normal chain, and the orientation of each double bond independently is E or Z.Exemplary alkene Base includes but not limited to vinyl, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl and nonenyl.The base Group can be end group or bridged group.

" aryl " of a part as group or group indicates the monocycle or condensed polycyclic that (i) is optionally substituted Carbocyclic ring (ring structure of all carbon of annular atom), preferably each ring have 5 to 12 atoms.The example of aryl includes phenyl, naphthalene Base etc.;(ii) the bicyclic aromatic isocyclic part for the fractional saturation being optionally substituted, wherein phenyl and C_5-7Naphthenic base or C_5-7Ring Alkenyl is fused together to form cyclic structure, such as tetralyl, indenyl or indanyl.The group can be end group Or bridged group.Typically, aryl is C₆-C₁₈Aryl.

" alkylaryl " refers to that alkyl-aryl-group, wherein aryl and moieties are as defined herein.Preferred alkane Base aryl contains C_1-10Moieties.The group can be end group or bridged group.If the group is terminal groups Group, then it is bonded to the rest part of molecule by aryl.

For the purpose of this disclosure, term " PMHS@POSS " refers to " functionalized with the crosslinked vinyl silanes of PMHS POSS".Term PM HS@SiNP, PMHS@CNT, PMHS@clays, PMHS@RO, PMHS@RGO should be explained correspondingly.

For the purpose of this disclosure, PDMS/PMHS refers to the copolymer of PDMS and PMHS.Therefore, term " PDMS/PMHS@ POSS " refers to " the functionalized POSS of vinyl silanes with the crosslinking copolymers of PDMS and PMHS ".Term PDMS/PMHS@ SiNP, PDMS/PMHS@CNT, PDMS/PMHS@clays, PDMS/PMHS@RO and PDMS/PMHS@RGO should be solved correspondingly It releases.

For the purpose of this disclosure, zero dimension (0D) nanostructure (such as nano particle) have on nanoscale there are three dimension Degree, usually less than 100nm.One-dimensional (1D) nano material (such as nanometer rods, nano wire, nanobelt and nanotube) is in nanoscale There are two dimensions, usually less than 100nm for upper tool.Two-dimentional (2D) nano material (such as nanometer sheet and nano-plates) is on nanoscale There are one dimensions, usually less than 100nm for tool.

Word " substantially " is not excluded for " fully ", such as the composition of substantially free Y can be entirely free of Y.It is necessary When, word " substantially " can be omitted from the definition of the present invention.

Unless otherwise stated, term " including (comprising and comprise) " and its grammatical variants are intended to indicate Open to the outside world or " inclusive " term so that they include not only cited element, but also allow to include other unrequited Element.

As used herein, term " about " generally means that +/- the 5% of described value under the background of the concentration of the component of preparation, More generally +/- the 4% of described value, more generally +/- the 3% of described value, more generally +/- the 2% of described value, in addition it is more generally described +/- the 1% of value, and even more generally +/- the 0.5% of described value.

Interior in the whole text in the disclosure, certain embodiments can be disclosed with range format.It will be appreciated that in range format description only It is merely for convenience and succinct and be not construed as unmodifiable limitation to the scope of disclosed range.Therefore, right The description of one range should be considered having specifically disclosed all possible subrange in the range and single Numerical value.For example, range should such as be considered specifically disclosing subrange from 1 to 6 description, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to the 6, single number from 3 to 6 etc. and within the scope of this, such as 1,2,3,4,5 and 6.This independent of The range of range and be applicable in.

Certain embodiments can also widely and be in general manner described herein.It falls in the open model of generality Each of in enclosing a part of this disclosure is also constituted compared with the species of narrow sense and subgenus group.This includes with collateral condition or negative limit The general description of the embodiment of system, the collateral condition or negative limitation remove any theme but regardless of deletion from generic Whether material has carried out specific narration herein.

The specific disclosure of optional embodiment

Now by exemplary, the non-limiting embodiments of open polymer substrate.

The hydridization of nanometer additive and polymer substrate represents a kind of brand-new material, is for super-hydrophobic textile coating It is promising, because they incorporate the inherent characteristic of both organic polymer matrix and nanometer additive.However, many researchs Show that the performance of hydridization super hydrophobic material may be limited by two factors:

1) compatibility of nanometer additive and polymer substrate.

Due to the trend of nanometer additive aggregation or precipitation during hydridization is reacted, the incompatibility of two kinds of substances is still Prepare the major obstacle of hybridized nano composite material.

2) efficiency being chemically bonded between nanometer additive and polymer substrate.

Reactivity between functionalization nanometer additive and polymer substrate rises in terms of the stability for facilitating gained coating Key effect.In general, coating film can be significantly increased by generating strong chemical bonding between nanometer additive and polymer substrate Machinery and physical property.

Graphene oxide (RGO) hybrid polymeric material of organopolysiloxane-reduction has been prepared for super-hydrophobic Fabric coating.Such material makes RGO and poly- (methyl hydrogen silica by the hydrosilylation of the addition reaction assisted via aryl Alkane) it is prepared by (PMHS) crosslinking.Have shown that these organopolysiloxanes being modified by two-dimension nano materials such as RGO with non- All chemically and physically tolerances.However, the preparation method of the RGO of vinyl-functional and can be used for and polymer matrix qualitative response Limited Si -- H make this method cumbersome and inefficient.

The preparation method phase of the addition reaction assisted by aryl with the alternative materials of the RGO of such as vinyl-functional Instead, in the disclosure, zero-dimensional polyhedron oligomeric silsesquioxane (POSS) and nano SiO 2 particle (SiNP), one-dimensional are come from A series of nanometers of carbon nanotube (CNT) and two-dimensional graphene oxide (GO), the graphene oxide (RGO) and clay that restore Additive uses silane reagent, such as tetraethoxysilane (TEOS) first, is handled, is then reacted with PMHS, to generate zero It ties up to the additive agent modified PMHS polymer of two-dimensional nano.Nanometer additive such as POSS, SiNP, GO, RGO and clay have can The size of tune, and different forms provides many chances for different applications.Nanometer additive is easy to scale and is combined to, because This avoids the multi-step sequence polymerizeing on textile surface.In addition, nano-additive agent modified polymer material can spun Film is formed on fabric base material, the film can also even be stablized in a long time under severe conditions.In the disclosure, this A little nanometer additives are designed to be used to form the crosslinking agent of polymer coating.

Vinyl the whole process on nanometer additive is fixed on by silanization to be shown in FIG. 1.Group R is to promote With the organic group (substituted vinyl) of organic resin and the non-hydrolysable of polymer-bound.Silanol group is usually can water Group, typically trimethoxysilyl or triethoxysilyl are solved, participation is reacted with nanometer additive base material. Therefore, in the disclosure, the hydrolysis of trimethoxysilyl, subsequent silanol condensation, causes vinyl to be covalently attached Onto nanometer additive surface.

PDMH is reacted with the nanometer additive comprising SiNP, POSS, CNT, GO, RGO and the vinyl-functional of clay, with Polymer composites as shown in Figure 2 are provided.Nano-additive agent modified PDMH be directly used in fabric coating without It is any to be further processed.

A variety of crosslinking nano reagents can provide the chance to form fine and close crosslinked polymeric materials, super thin to generate high-performance Water fabric coating.In addition, the ability for the active component that distribution is grafted in polymer network can provide improvement stability of material And then optimize the chance of performance.

Disclosed polymer coating may include with the covalently bound nanometer additive of organopolysiloxane, received wherein described Rice additive include:

A) nanometer additive base material, and

The organopolysiloxane may include that hydrophobic grouping, the hydrophobic grouping are preferably selected from alkyl, alkenyl, alkylaryl Or aryl, most preferably C₁To C₁₀Alkyl, C₁To C₁₀Alkenyl, C₁To C₁₀Alkyl-C₆To C₁₀Aryl or C₆To C₁₀Aryl.

Alkyl can be the methyl of linear chain or branched chain, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or Decyl.Alkenyl can be the vinyl of linear chain or branched chain, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, Nonenyl or decene base.Aryl can be phenyl, naphthalene, tetraphenyl naphthalene, indenyl or indanyl.Alkylaryl can be 2- first Base benzene, 3- methylbenzenes, 4- methylbenzenes, 2- ethylo benzenes, 3- ethylo benzenes, 4- ethylo benzenes, 2- propylbenzenes, 3- propylbenzenes, 4- propylbenzenes, 2- butyl benzenes, 3- butyl benzenes, 4- butyl benzenes, 2- amylbenzenes, 3- amylbenzenes, 4- amylbenzenes, 2- hexyl benzenes, 3- hexyl benzenes, 4- oneself Base benzene, 2- heptyl benzenes, 3- heptyl benzenes, 4- heptyl benzenes, 2- octyls benzene, 3- octyls benzene, 4- octyls benzene, 2- nonyl benzenes, 3- nonyl benzenes, 4- nonyl benzenes, 2- decyls benzene, 3- decyls benzene, 4- decyls benzene, 2- vinyl benzenes, 3- vinyl benzenes, 4- vinyl benzenes, 2- acrylic Benzene, 3- propenylbenzenes, 4- propenylbenzenes, 2- cyclobutenyls benzene, 3- cyclobutenyls benzene, 4- cyclobutenyls benzene, 2- pentenyls benzene, 3- pentenyls Benzene, 4- pentenyls benzene, 2- hexenyls benzene, 3- hexenyls benzene, 4- hexenyls benzene, 2- heptenyls benzene, 3- heptenyls benzene, 4- heptenyls Benzene, 2- octenyls benzene, 3- octenyls benzene, 4- octenyls benzene, 2- nonenyls benzene, 3- nonenyls benzene, 4- nonenyls benzene, 2- decene bases Benzene, 3- last of the ten Heavenly stems alkenyl benzene or 4- last of the ten Heavenly stems alkenyl benzenes.

Relative to organopolysiloxane, the content of nanometer additive base material is smaller than about 3 weight %, and preferably less than about 0.5 Weight %, most preferably from about 0.005 weight % are to 0.5 weight %.

Relative to organopolysiloxane, the content of nanometer additive base material can be about 0.001 weight % to about 5 weights Measure %, about 0.001 weight % to about 0.005 weight %, about 0.001 weight % to about 0.01 weight %, about 0.001 weight % extremely About 0.05 weight %, about 0.001 weight % are to about 0.1 weight %, about 0.001 weight % to about 0.5 weight %, about 0.001 weight Measure % to about 1 weight %, about 0.001 weight % to about 3 weight %, about 0.005 weight % to about 0.01 weight %, about 0.005 Weight % to about 0.05 weight %, about 0.005 weight % to about 0.1 weight %, about 0.005 weight % to about 0.5 weight %, about 0.005 weight % to about 1 weight %, about 0.005 weight % to about 3 weight %, about 0.005 weight % to about 5 weight %, about 0.01 weight % to about 0.05 weight %, about 0.01 weight % to about 0.1 weight %, about 0.01 weight % to about 0.5 weight %, About 0.01 weight % to about 1 weight %, about 0.01 weight % to about 3 weight %, about 0.01 weight % to about 5 weight %, about 0.05 weight % to about 0.1 weight %, about 0.05 weight % to about 0.5 weight %, about 0.05 weight % to about 1 weight %, about 0.05 weight % to about 3 weight %, about 0.05 weight % are to about 5 weight %, about 0.1 weight % to about 0.5 weight %, about 0.1 Weight % to about 1 weight %, about 0.1 weight % to about 3 weight %, about 0.1 weight % to about 5 weight %, about 0.5 weight % extremely About 1 weight %, about 0.5 weight % to about 3 weight %, about 0.5 weight % to about 5 weight %, about 2 weight % to about 3 weight %, About 1 weight % to about 5 weight % or about 3 weight % to about 5 weight %.

Advantageously, it is only necessary to the nanometer additive of trace, so as to avoid needing using a large amount of expensive nanometer additives.

Polymer organic polysiloxanes with connector covalent bonding before may include repeat silicon-hydrogen partial.

Polymer organic polysiloxanes with connector covalent bonding before, one or more is may include in polymer chain It is a, the preferred unit of 3 to 200 formulas (I) or (Ia):

Wherein

R¹At each occurrence independently selected from C₁To C₁₀Alkyl, C₁To C₁₀Alkenyl, C₁To C₁₀Alkyl-C₆To C₁₀Aryl or C₆To C₁₀Aryl;And R¹Preferably methyl.

Polymer organic polysiloxanes with connector covalent bonding before, one or more is may include in polymer chain The unit of formula (I) or (Ia).Polymer organic polysiloxanes with connector covalent bonding before, may include in polymer chain The unit of 1 to 300 formula (I) or (Ia), 1 to 3 unit, 1 to 10 unit, 1 to 20 unit, 1 to 50 unit, 1 to 100 units, 1 to 200 unit, 3 to 10 units, 3 to 20 units, 3 to 50 units, 3 to 100 units, 3 to 200 units, 3 to 300 units, 10 to 20 units, 10 to 50 units, 10 to 100 units, 10 to 200 units, 10 to 300 units, 20 to 50 units, 20 to 100 units, 20 to 200 units, 20 to 30 units, 50 to 100 Unit, 50 to 200 units, 50 to 300 units, 100 to 200 units, 100 to 300 units or 200 to 300 lists Member.

R¹Preferably it is selected from alkyl, alkenyl, alkylaryl or aryl, most preferably C₁To C₁₀Alkyl, C₁To C₁₀Alkenyl, C₁Extremely C₁₀Alkyl-C₆To C₁₀Aryl or C₆To C₁₀Aryl.

Work as R¹When being alkyl, alkyl can be the methyl of linear chain or branched chain, ethyl, propyl, butyl, amyl, hexyl, heptan Base, octyl, nonyl or decyl.Work as R¹When being alkenyl, alkenyl can be the vinyl of linear chain or branched chain, acrylic, cyclobutenyl, penta Alkenyl, hexenyl, heptenyl, octenyl, nonenyl or decene base.Work as R¹When being aryl, aryl can be phenyl, naphthalene, four Phenyl napthyl, indenyl or indanyl.Work as R¹When being alkylaryl, alkylaryl can be 2- methylbenzenes, 3- methylbenzenes, 4- methyl Benzene, 2- ethylo benzenes, 3- ethylo benzenes, 4- ethylo benzenes, 2- propylbenzenes, 3- propylbenzenes, 4- propylbenzenes, 2- butyl benzenes, 3- butyl benzenes, 4- Butyl benzene, 2- amylbenzenes, 3- amylbenzenes, 4- amylbenzenes, 2- hexyl benzenes, 3- hexyl benzenes, 4- hexyl benzenes, 2- heptyl benzenes, 3- heptyl Benzene, 4- heptyl benzenes, 2- octyls benzene, 3- octyls benzene, 4- octyls benzene, 2- nonyl benzenes, 3- nonyl benzenes, 4- nonyl benzenes, 2- decyls benzene, 3- Decyl benzene, 4- decyls benzene, 2- vinyl benzenes, 3- vinyl benzenes, 4- vinyl benzenes, 2- propenylbenzenes, 3- propenylbenzenes, 4- propylene Base benzene, 2- cyclobutenyls benzene, 3- cyclobutenyls benzene, 4- cyclobutenyls benzene, 2- pentenyls benzene, 3- pentenyls benzene, 4- pentenyls benzene, 2- hexenes Base benzene, 3- hexenyls benzene, 4- hexenyls benzene, 2- heptenyls benzene, 3- heptenyls benzene, 4- heptenyls benzene, 2- octenyls benzene, 3- octenes Base benzene, 4- octenyls benzene, 2- nonenyls benzene, 3- nonenyls benzene, 4- nonenyls benzene, 2- last of the ten Heavenly stems alkenyl benzene, 3- last of the ten Heavenly stems alkenyl benzene or the 4- last of the ten Heavenly stems Alkenyl benzene.

Advantageously, multiple reaction sites of organopolysiloxane provide strong between nanometer additive and polymer substrate Covalent bonding, to prevent the phase separation in final hybrid material.

Polymer organic polysiloxanes can be poly- (methyl hydrogen siloxane) (PMHS).

Advantageously, PMHS can have more reaction sites (Si -- H), to promote more durable coating, because of energy It is enough that stronger key is formed between polymer substrate and nanometer additive.

Poly- (methyl hydrogen siloxane) can be representative formula (II):

Wherein R¹Indicate methyl, and n is to be selected so that poly- (methyl hydrogen siloxane) has about 390 to about 10,000 The integer of molecular weight ranges.

N can be selected so that poly- (methyl hydrogen siloxane) has the integer of following molecular weight ranges:About 350 to about 15,000, about 350 to about 390, about 350 to about 500, about 350 to about 1000, about 350 to about 5000, about 350 to about 10,000, About 390 to about 500, about 390 to about 1000, about 390 to about 5000, about 390 to about 10,000, about 390 to about 15,000, about 500 to about 1000, about 500 to about 5000, about 500 to about 10,000, about 500 to about 15,000, about 1000 to about 5000, about 1000 to about 10,000, about 1000 to about 15,000, about 5000 to about 10,000, about 5000 to about 15,000 or about 10,000 to About 15,000.

Nanometer additive base material can use vinyl before being connect with organopolysiloxane, preferably by using trimethoxy (vinyl) silane carries out surface functionalization as silane reagent.

Advantageously, promote the strong covalent bond between nanometer additive and polymer using the surface functionalization of vinyl.

Nanometer additive base material can be particles of the 10nm to 10 μ m in size.Nanometer additive base material can be following size Particle:About 5nm to about 15 μm, about 5nm to about 10nm, about 5nm to about 50nm, about 5nm to about 100nm, about 5nm is to about 500nm, about 5nm to about 1 μm, about 5nm to about 5 μm, about 5nm to about 10 μm, about 10nm to about 50nm, about 10nm to about 100nm, About 10nm to about 500nm, about 10nm to about 1 μm, about 10nm to about 5 μm, about 10nm to about 10 μm, about 10nm to about 15 μm, about 50nm to about 100nm, about 50nm to about 500nm, about 50nm to about 1 μm, about 50nm to about 5 μm, about 50nm to about 10 μm, about 50nm to about 15 μm, about 100nm to about 500nm, about 100nm to about 1 μm, about 100nm to about 5 μm, about 100nm to about 10 μm, About 100nm to about 15 μm, about 500nm to about 1 μm, about 500nm to about 5 μm, about 500nm to about 10 μm, about 500nm to about 15 μ M, about 1 μm to about 5 μm, about 1 μm to about 10 μm, about 1 μm to about 15 μm, about 5 μm to about 10 μm, about 5 μm to about 15 μm or about 10 μ M to about 15 μm.

Nanometer additive base material can be selected from the group being made up of:Carbon nanotube, graphene oxide and the graphite of reduction Olefinic oxide, clay, nano SiO 2 particle or polyhedral oligomeric silsesquioxane.

Advantageously, different types of nanometer additive can be used in coating.Nanometer additive can be zero dimension, it is one-dimensional or It is two-dimensional.

Siloxy connector may include non-hydrolysable part, preferred vinyl, Yi Jijia before forming covalent bond Siloxy part.

Advantageously, this may insure that nanometer additive is bonded with the selectivity of organopolysiloxane.It is further advantageous that this It may insure that gained coating has long-term tolerance to strong acid, alkali and hot water, because there is no hydrolyzable groups Less chemical reaction can occur.

Siloxy moieties can be via silicyl-ether bridge and nanometer additive base material covalent bond.

Advantageously, silicyl-ether bridge can provide the strong chemical bond between nanometer additive and polymer substrate, in turn Significantly increase the machinery and physical property of coating.

Non-hydrolysable part, preferred vinyl can be with polymer organic polysiloxanes covalent bond.

The method for being used to prepare coating may include following steps:

Silane reagent can be any reagent for including silane.

Vinyl trialkyl oxysilane can be vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Tripropoxy silane or vinyltributoxysilane.

Catalyst can be selected from the 10th race's element.10th race's element can be nickel, palladium or platinum.

Catalyst may include platinum.Catalyst can be platinum (0) -1,3- divinyl -1,1,3,3- tetramethyl disiloxanes; For the catalyst of classical Pt catalysis, such as Speier or Karstedt catalyst;For the catalyst of the catalysis based on Rh, example Ru [Rh(cod)₂]BF₄Huo [RhCl(nbd)]₂;Or the catalyst for the catalysis based on Ru, such as Wilkinson catalyst, Grubb first generation catalyst ,s [Ru (benzene) Cl₂]₂Huo [Ru (p- cymol) Cl₂]₂),[Cp*Ru(MeCN)₃]PF₆。

Advantageously, organopolysiloxane can be PMHS, and nanometer additive base material can be vinyl silanes function Change.By disclosed method, the reaction between organopolysiloxane and nanometer additive base material can be easily controlled, and Complicated intermediate need not be introduced.

Coating as defined above can be used for coating base material, preferably natural or staple fibre.

Base material can be textile.The flexible material that textile can be made of the network of natural or artificial (artificial) fiber Material.Natural or staple fibre may include hair, fur, skin, silk, wool, flax, cotton, grass, rush, hemp, sisal hemp, Coir, straw, bamboo, pulpwood, rice, nettle, jute, Modal fibre (modal), lace bark (lacebark), acetate fiber, seaweed, Lyocell fibers (lyocells), asbestos, basalt, glass, metal, polyester, virtue Synthetic fibre, acrylic fiber, nylon, spandex, alkene, English gill fiber (ingeo), metallized thread (lucrex), milk fibre or carbon fiber Dimension.

Advantageously, coating can be used on a variety of different base materials, but imparting base material is identical when coating base material with coating Superhydrophobic property.

The method of coating base material (preferably fiber) may include following steps:

A) coating as defined above is dissolved in a solvent to form coating solution;

B) base material is immersed in coating solution;And

C) base material is taken out from coating solution.

The method can further comprise the step of dry base material from step (c) is to remove solvent (d).

Used solvent can be any solvent that can dissolve coating as defined above.Used solvent can It is preferably selected from the group being made of toluene, dichloromethane and chloroform.

Coating base material with superhydrophobic property can be obtained by any method as defined above.

The water contact angle (WCA) within the scope of about 150 ° to about 170 ° can be had by coating base material.

Coating base material can be used for textile process, packaging material, paper industry, antifouling clothes, gym suit and sail.

Polymer nanocomposite additive composite material may include with the covalently bound nanometer additive of organopolysiloxane,

The wherein described nanometer additive includes:

A) nanometer additive base material, and

Wherein

And X is the key combined with the connector.

Organopolysiloxane with connector covalent bonding before can be representative formula (II) poly- (methyl hydrogen Siloxanes):

Wherein R¹It indicates methyl, and n is integer, is selected to indicate so that poly- (methyl hydrogen siloxane) has about The integer of the molecular weight ranges of 390 to about 10,000.

Embodiment

The present invention is more fully described in specific embodiment non-limiting embodiment and comparing embodiment will be referred to further, It is not necessarily to be construed as limiting the scope of the invention in any way.

Embodiment 1:Material and method

Material

Poly- (methyl hydrogen siloxane) (average Mn is 1,700-3,200, PMHS), poly- (dimethyl siloxane -co- methyl hydrogen Siloxanes) (trimethyl silyl sealing end, (PDMS/PMHS), (Mn is about 13,000, and methyl hydrogen siloxane accounts for 3- 4mol%) it is purchased from Sigma-Aldrich.Used clay is alkyl quaternary ammonium salts bentonite " CLOISITE 30B ".Otherization Product are purchased from Sigma-Aldrich and use as former state.Carry out purified water using Millipore Milli-Q water systems.

Method

Scanning electron microscope (SEM) image uses the JEOLJSM 6700F operated under the accelerating potential of 5.0kV to clap It takes the photograph.Contact angle (CA), which is measured, to be carried out on ram é-hart contact angle angular instruments using the drop that volume is 5 μ L.Fourier transformation Infrared (FTIR) spectrum is on 70 instruments of Bruker VERTEX with ATR patterns with 4cm^-1Resolution ratio record, accumulation scanning 32 It is secondary.

Embodiment 2:Synthesis

Embodiment 2A:The preparation of the functionalized nano SiO 2 particle of vinyl silanes (SiNP)

In short, tetraethoxysilane (TEOS, 10mL) and ammonium hydroxide (10mL) are dissolved in ethanol/water (428mL/ 60mL, v/v) solution in, and be gently mixed 2 hours at 30 DEG C.White product is used into ethyl alcohol and distilled water flushing 4 times respectively. The SiNP of gained surfactant-free is dried overnight in 40 DEG C of vacuum drying oven to remove remaining solvent.Then, will SiNP (1.00g) flows back in the 80.00mL dry toluenes with 0.25mL (1.00mmol) trimethoxy (vinyl) silane 20 hours, to generate the functionalized SiNP of vinyl silanes.

Embodiment 2B:The preparation of the functionalized multi-walled carbon nanotube of vinyl silanes (MWCNT)

150mL H are added in MWCNT (0.5g)₂SO₄(98%) it in, is then ultrasonically treated 30 minutes in room temperature.50mL is dense HNO₃It is slowly added in solution, and is vigorously stirred 30 minutes in room temperature.80 DEG C are heated the mixture to, is kept for 1 hour.Hereafter, Mixture is cooled to room temperature, Milli-Q water is used in combination slowly to dilute.Mixture is filtered, is used in combination methanol and distilled water by 0.2 μm filter paper washs 4 times.After being dried in vacuo filtrate, the MWCNT (MWCNT-OH) of hydroxy-functional is obtained.

The MWCNT (0.05g) of hydroxy-functional produced as described above is dispersed in 40mL by being ultrasonically treated 10 minutes In toluene.After excessive trimethoxy (vinyl) silane is added, by suspension in N₂Under in 100 DEG C flow back 6 hours.Reaction Afterwards, gained filtrate is washed repeatedly with methanol, to remove remaining trimethoxy (vinyl) silane.The solid product of acquisition is existed Dried overnight under vacuum.

Embodiment 2C:The preparation of the functionalized clay of vinyl silanes

By clay (5.0g) and 1,2.5 or 3.5M H₂SO₄Solution (100mL) mixes.By gained suspension in 80 ± 2 DEG C Continuously stir lower heating 2 hours.After acid activation, precipitation is filtered and thoroughly washed with distilled water, until filtrate not sulfur-bearing Acid ion (uses BaCl₂Solution testing).Then, the clay of acid activation is suspended in the concentration of 10g/L in toluene, and by institute Trimethoxy (vinyl) silane of requirement is introduced into reaction flask, and mixture is flowed back 6 hours.Grafting clay is filtered, It is fully washed with toluene to remove excessive silane, and is dried overnight in 40 DEG C of vacuum drying oven, then used.Fig. 3 is (a) The image of original clay and the functionalized clay of (b) vinyl silanes in (A) water and (B) THF, and show in vinyl Changes in solubility of the clay in water and THF before and after silane treatment.

Embodiment 2D:The graphene oxide (RGO) of the functionalized graphene oxide of vinyl silanes (GO) and reduction Preparation

It is prepared by the methods of GO and RGO according to the literature.By GO or RGO (0.5mg mL^-1) and NaOH (0.25mL, 2M) plus Enter in round-bottomed flask, then on coated with ultra-pure water to obtain the final volume of 100mL.Solution is vigorously stirred 30 points at 80 DEG C Clock.The CTAB (10mL, 0.56M) of heat is added in solution, and stirs the mixture for other half an hour.When temperature is stablized 80 DEG C when, TEOS (2mL) is added dropwise into solution, then over the course of 15 mins be added trimethoxy (vinyl) silane (0.5mL). Solution is set to be incubated again at 80 DEG C 4 hours.Final product is used in combination HCl (1M) and MeOH to wash 3 times, is used every time by being collected by centrifugation Then isometric HCl (1M) and MeOH is washed 3 times with pure MeOH.The solid product of acquisition is dried under vacuum overnight.

Embodiment 2E:The preparation of the polymer coating of the various crosslinked PMHS of nanometer additive

PMHS or PDMS/PMHS (6g) are dissolved in toluene, the nanometer containing ethyleneoxy prepared by 30mg is then added Additive (being respectively POSS, SiNP, CNT, GO, RGO or clay).By platinum (0) -1,3- divinyl -1,1,3,3- tetramethyls Disiloxane complex solution (100 μ L) is dissolved in minimal amount of toluene, and in N₂Under be slowly added in above-mentioned solution.Once adding It adds into, mixture solution is stirred 4 hours at 80 DEG C.Then solution is diluted to further use.The product of acquisition is distinguished For PMHS@POSS, PMHS@SiNP, PMHS@CNT, PMHS@clays, PMHS@RO, PMHS@RGO, PDMS/PMHS@POSS, PDMS/PMHS@SiNP, PDMS/PMHS@CNT, PDMS/PMHS@clays, PDMS/PMHS@RO or PDMS/PMHS@RGO.

Embodiment 3:The characterization of coating

Embodiment 3A:FTIR

Fig. 4 to 9 shows that the functionalized nanometer additive of original nanometer additive, vinyl silanes and nanometer additive change One group of representativeness FTIR spectrum of the PMHS of property.Fig. 4 shows the FTIR spectrum of (a) octavinyl-POSS and (b) PMHS@POSS, Fig. 5 shows that the FTIR spectrum of (a) SiNP, the functionalized SiNP of (b) vinyl silanes and (c) PMHS@SiNP, Fig. 6 show (a) The FTIR spectrum of SiNP, the functionalized SiNP of (b) vinyl silanes and (c) PMHS@SiNP, Fig. 7 show (a) spavin, (b) second The FTIR spectrum of the functionalized clay of alkenyl silanes and (c) PMHS@clays, Fig. 8 show (a) GO, (b) vinyl silanes functionalization GO and (c) PMHS@GO FTIR spectrum, and Fig. 9 shows (a) RGO, the functionalized RGO of (b) vinyl silanes and (c) The FTIR spectrum of PMHS@RGO.

All FTIR spectrums are shown in about 2950cm^-1The band at place, is designated as-CH₃With-CH₂C-H flexible shake It is dynamic.The characteristic features of the vinyl-functional of nanometer additive are shown in about 1629cm^-1The band at place stretches with C=C and shakes Dynamic characteristic absorption peak is related.By about 1168cm^-1And 1089cm^-1The band at place is respectively designated as Si-O-C asymmetry and Si-O- C symmetrical stretching vibrations absorb.About 941cm^-1The band at place is related with symmetrically stretching for Si-C keys.And it will about 1072cm^-1Peace treaty 806cm^-1The band at place is appointed as Si-O-Si symmetrical stretching vibrations.

Embodiment 3B:TEM

One group of the functionalized nanometer additive of vinyl silanes that the displays of Figure 10 to 13 are prepared by silanization is representative TEM image.Figure 10 shows that the TEM microphotos of the functionalized SiNP of vinyl silanes, Figure 11 show (a) GO and (b) vinyl The TEM microphotos of silane-functionalised GO, Figure 12 show the TEM microphotos of the functionalized RGO of vinyl silanes, and scheme The TEM microphotos of the sample of 13 display (A) spavins and the functionalized clay of (B) vinyl silanes.In nanometer additive example As being found that characteristic silica shell respectively on the surface of CNT, GO, RGO and clay.

Embodiment 4:The super-hydrophobic coat of base material

Simple " one kettle way " synthesis of nano-additive agent modified polymer material is schematically depicted in Fig. 2.Ethylene The functionalized nanometer additive of base (202) in the presence of the Pt catalyst of catalytic amount in toluene with polymethyl hydrogen siloxane (PMHS) (204) reaction is to form nanocomposite (206).Nanometer additive includes POSS (212), SiNP (214), CNT (216), GO or RGO (218) and clay (220).PMHS is used as polymer substrate, has 25 to 50 in its polymer architecture Methylhydrogensiloxane units.Multiple reaction sites provide the strongly covalent bonding between nanometer additive and polymer substrate, from And prevent the phase separation in final hybrid material.

Nano-additive agent modified PMHS materials are distributed in toluene to form coating solution.It can use dip-coating that will apply Material solution is applied directly on textile substrate.The textile substrate of coating is dried into a few houres in draught cupboard, is subsequently placed with It is dried overnight in an oven at 60 DEG C.

Water contact angle measurement shows that the cotton fabric for being coated with nanometer additive-PMHS hybrid materials as shown in Figure 14 is aobvious Intimate spherical water droplet is shown.It is viscous that image is shown in (A) PMHS@POSS, (B) PMHS@SiNP, (C) PMHS@CNT, (D) PMHS@ 5 μ l water droplets on soil, (E) PMHS@GO and (F) PMHS@RGO.It was found that nanometer additive significantly affects the super thin of coating textile It is aqueous.With on PMHS@SiNP, PMHS@POSS, PMHS@CNT, PMHS@RGO, PMHS@clays and the cotton surface of PMHS@GO coatings Average contact angle be respectively about 130 °, about 150 °, about 160 °, about 160 °, about 170 ° and about 170 °.It is worth noting that, with It nanometer additive and is changed to two-dimensional structure from zero-dimension structural, contact angle increases.

This trend can be explained by the crosslink density of linear polymer matrix and two-dimensional nano additive, described two Nanometer additive is tieed up with the surface area than zero-dimension nano additive bigger.Spherical water droplets (5 μ L) are stable, and can be Their spherical morphology is kept on coating base material, until they are evaporated.However, when pure water being dropped onto on uncoated base material When, contact angle is not observed, water drawout and is absorbed into base material in this case.In contrast, for identical The textile substrate of the pure PMHS coatings of concentration, it is observed that small contact angle.The size and surface area of nanometer additive and it Cross-linking efficiency and physical property it is closely related.It observes, as textile substrate zero-dimension nano additive POSS and SiNP When hybrid material coats, detects that oiliness is felt, show the incomplete crosslinking between nanometer additive and polymer.

Embodiment 5:The characterization of super-hydrophobic coat

Check the form and surface nature of the textile for coating useful nano-additive agent modified PMHS.Figure 15 shows one group Representative SEM image, the SEM image show that the form of cotton fiber before and after the various coating coating with the disclosure becomes Change, wherein (A) is uncoated, (B) is coated with PMHS@SiNP, and (C) is coated with PMHS@POSS, and (D) is glued coated with PMHS@ Soil.As shown in Figure 15 (A), original uncoated textile substrate has quite thick surface.It is consistent with contact angle analysis, lead to It crosses SEM image and observes one group of smooth silica casing krofile different from the original-shape of textile fabric, correspond to polymerization The coating of object hybrid material.

Coating solution is applied to various natural or staple fibres, such as polyester, cotton, asbestos using identical dip-coating method Cloth etc..As shown in Figure 16, in the textile of three kinds of different woven types, i.e., (1) braided fabric, (2) non-woven fabric and (3) are knitted Also super-hydrophobicity is observed on the divine force that created the universe.Image be shown in (A) it is uncoated, (B) coated with PMHS@POSS, (C) be coated with PMHS@Silica, (D) coated with PMHS@CNT, (E) coated with PMHS@GO, (F) coated with PMHS@RGO and (G) Water droplet on textile coated with PMHS@clays.The Weaving pattern of textile has significant impact to water contact angle.With one The additive agent modified polymer of peacekeeping two-dimensional nano shows consistent water contact angle on various types of textiles.On the contrary, It is significantly correlated with the water contact angle of the modified polymer of zero-dimension nano additive (POSS and SiNP) and the form of textile.Especially Ground, for the textile substrate sparsely woven, water contact angle is reduced to 90-130 °.

How the above results have the mechanism of hydrophobic property related to the lotus leaf reported.With the painting for being applied to flat surfaces Layer is compared, and the coating of the disclosure utilizes the intrinsic form of the textile substrate on a microscopic scale with classification roughness respectively to different Property, to further enhance surface hydrophobic.Based on this super-hydrophobic feature, as shown in Figure 17, it is proposed that the coating of the disclosure The mechanism how to work.It is without being bound by theory, propose the surface roughness and table of the coating enhancing textile substrate of the disclosure Face chemical property is to simulate lotus leaf.

The super-hydrophobic textile coating for assigning the properties such as base material stain resistance to be coated and automatical cleaning ability exists Various applications are obtained in textile industry.Coating solution is applied to fiber, such as polyester, cotton, stone using identical dip-coating method Cotton etc..In control experiment, the textile substrate of coating is also dyed with the water of coloring to test stain resistance.Such as Figure 18 (A) Shown in, the mitten of PMHS@clays is coated with after immersing in staining solution, is easy to be cleaned by being rinsed with water.

In addition, Figure 18 (B) is shown, different from this kind of conventional coating, coating PMHS@clays disclosed herein do not change The white of textile substrate.

The performance of biomedical implants and device can be changed in the absorption of polluter, is infected so as to cause patient, durable Property shorten and device replace health care cost increase.Currently, organopolysiloxane elastomers are most widely used for non-biocidal Nonpolluting coating in, without toxic chemical is discharged into organism or marine environment.The results show that PMHS@clays apply The cotton covered has staphylococcus aureus the antibacterial activity of strength.Pass through scraps of paper method of diffusion (disk-diffusion Method Bacteria suppression of the cotton to staphylococcus aureus of PMHS@clay coateds) is tested.As a result it is shown in Figure 18 (C).Make As a contrast with the cottons of uncoated PMHS@clay coateds.According to Figure 18 (C), in the bacterium handled with the wollen fabrics of coating Seldom inhibition is observed on tablet.The excellent antibacterial ability of coating shows it for knitting in the antifouling application of organic contamination herein Object has huge potentiality.

Figure 18 (D) shows that the self-cleaning-test of the cotton of PMHS@clay coateds is dropped in uncoated cotton when tilting 10o Shipwreck on surface is to take away dust.However, as shown in Figure 18 (D), when the cotton of PMHS@clay coateds tilts 10o, water droplet It can easily tumble, leave clean surface.Since the contact area of dirty particle and the cotton of PMHS@clay coateds reduces, dirty Adhesion strength between grain and the cotton surface of PMHS@clay coateds also reduces, therefore the dirt on nano structural material is easier It is taken away by the water.The self-cleaning-test verifies developed method and has succeeded the automatically cleaning mechanism of simulation lotus leaf.

Embodiment 6:The stability of super-hydrophobic coat

It checks under adverse circumstances and laundry situation, PMHS@clay hybrid materials are as the steady in a long-term of super-hydrophobic coat Property.In the textile substrate that will be coated in H₂SO₄Dipping still observes that average contact angle is about after 1 month in aqueous solution (pH=1) 170 ° of spherical water droplets (Figure 19).In addition, when being handled with KOH aqueous solutions (pH=14), superhydrophobic property keeps one week (figure 20)。

In addition, super-hydrophobic coat also shows the good tolerability to boiling water.Experimental result is shown, by the textile of coating After base material boils 2 hours in water, the ultra-amphosphobic (superamphiphobicity) of the textile substrate of coating does not become Change.Therefore, coating not only assigns textile substrate super water repellent property, but also shows excellent chemical resistance.

In addition, checking super-hydrophobic stability of the coating under laundry situation.As shown in Figure 21, PMHS@clays are coated with The contact angle of fiber slightly reduce, but even using oval stirring rod (3/4 × 1 5/8 inches) 160 ° are remained greater than after being stirred 1 week with 900rpm in 500mL water.It is special that this shows that coating not only assigns the super water repellent of textile substrate Sign, but also show excellent washability and wear resistance.

Figure 22 shows that one group of metamorphosis of the cotton fiber coated with PMHS@clays after washing different time is representative SEM image.Although silica shell ruptures, especially the silica shell on fiber junction, single fiber is still able to It keeps.The water contact angle measured in configuration of surface and Figure 21 is qualitative consistent.

Industrial feasibility

The coating of the disclosure and base material coated with the coating (such as are swum in operation tool, medical treatment device, textile Clothing and military clothes), maritime affairs industry and environmental applications in have a wide range of applications.

Specifically, the application in agricultural may include seed/vegetation object, bag, shade material, irrigation system, pond Lining and hose, the application in clothes may include vamp and lining, artificial leather/bag/band, raincoat, garment lining, backing/reinforcement Part, gloves and cap, the application in geotextile may include settling tank lining, irrigate lining, garbage loading embeading lining and covering, Soil stabilizer may include safe fence, hurricane globe, safety vest, conveyer belt and truck with barrier, the application in building is corroded Covering, the application in household items may include indoor decoration, decoration, carpet backing, curtain backing, bedding and artificial Leather, the application in industry may include conveyer belt, filtering, barrier material, place covering, grinding backing and mechanical rubber good, And the application in Medical Devices, tent, transport, movement, leisure, packaging and safeguard.

The coating of the disclosure and base material coated with the coating can be applied to need antifouling, antipollution, antibacterial, anti-icing In the material of automatically cleaning property.

It is readily apparent that without departing from the spirit and scope of the present invention, read above disclosure it Afterwards, various other modifications of the invention and adjustment will be apparent those skilled in the art, and all such Modification and adjustment are intended within the scope of the appended claims.

Claims

1. a kind of polymer coating, it includes with the covalently bound nanometer additive of organopolysiloxane, wherein the nanometer adds The agent is added to include:

A) nanometer additive base material, and

B) connector, the connector by siloxy moieties at one end with the nanometer additive base material covalent bond simultaneously And in the other end and the organopolysiloxane covalent bond.

2. coating according to claim 1, wherein the organopolysiloxane includes hydrophobic grouping, the hydrophobic grouping is excellent Choosing is selected from alkyl, alkenyl, alkylaryl or aryl, most preferably C₁To C₁₀Alkyl, C₁To C₁₀Alkenyl, C₁To C₁₀Alkyl-C₆To C₁₀ Aryl or C₆To C₁₀Aryl.

3. coating according to any one of the preceding claims, wherein relative to the organopolysiloxane, the nanometer The content of additive base material is less than about 3 weight %, preferably less than about 0.5 weight %, most preferably from about 0.005 weight % to 0.5 weight Measure %.

4. coating according to any one of the preceding claims, wherein the polymer organic polysiloxanes with the company Include the silicon-hydrogen partial repeated before junctor covalent bonding.

5. coating according to any one of the preceding claims, wherein the polymer organic polysiloxanes with the company Before junctor covalent bonding, one or more, the preferably unit of 3 to 200 formulas (I) or (Ia) are included in polymer chain:

Wherein

R¹At each occurrence independently selected from C₁To C₁₀Alkyl, C₁To C₁₀Alkenyl, C₁To C₁₀Alkyl-C₆To C₁₀Aryl or C₆Extremely C₁₀Aryl;And R¹Preferably methyl.

6. the coating according to preceding claims 4 or 5, wherein the polymer organic polysiloxanes is poly- (methyl hydrogen silicon Oxygen alkane) (PMHS).

7. the coating according to any one of claim 4 to 6, wherein poly- (methyl hydrogen siloxane) is representative Formula (II):

8. coating according to claim 1, wherein the nanometer additive base material is connect with the organopolysiloxane Before, with vinyl, surface functionalization is preferably carried out as silane reagent by using trimethoxy (vinyl) silane.

9. coating according to claim 1, wherein the nanometer additive base material is particles of the 10nm to 10 μ m in size.

10. coating according to claim 8 or claim 9, wherein the nanometer additive base material is selected from the group being made up of:Carbon Nanotube, graphene oxide and the graphene oxide of reduction, clay, nano SiO 2 particle or polyhedral oligomeric sesquialter Siloxanes.

11. coating according to claim 1, wherein the siloxy connector includes not before forming covalent bond Hydrolyzable moiety, preferred vinyl and siloxy moieties.

12. coating according to claim 11, wherein the siloxy moieties via silicyl-ether bridge with it is described Nanometer additive base material covalent bond.

13. coating according to claim 12, wherein the non-hydrolysable part, preferred vinyl, with the polymer Organopolysiloxane covalent bond.

14. a kind of method being used to prepare coating comprising following steps:

A) silane reagent, preferred vinyl trialkoxy silane is made to be reacted with nanometer additive base material, the nanometer additive base Material is optionally functionalized by hydroxyl surface,

15. according to the method for claim 14, wherein the catalyst is selected from the 10th race's element.

16. according to the method for claim 15, wherein the catalyst includes platinum.

17. a kind of coating according to any one of the preceding claims is used to coat the purposes of base material, the base material is preferred Natural or staple fibre.

18. a kind of method of coating base material, the preferred fiber of base material comprising following steps:

A) coating according to any one of the preceding claims is dissolved in a solvent to form coating solution;

B) base material is immersed in the coating solution;And

C) base material is taken out from the coating solution.

19. according to the method for claim 18, further comprising the dry base material from step (c) to remove The step of stating solvent (d).

20. according to the method for claim 19, wherein the solvent used is selected from by toluene, dichloromethane and chloroform group At group.

21. a kind of painting with superhydrophobic property that can be obtained by the method according to any one of claim 18 to 20 Cover base material.

22. coating base material according to claim 21 is used for textile process, packaging material, paper industry, antifouling clothes Dress, gym suit and sail.

23. a kind of polymer nanocomposite additive composite material, it includes with the covalently bound nanometer additive of organopolysiloxane,

The wherein described nanometer additive includes:

A) nanometer additive base material, and

B) connector, the connector by siloxy moieties at one end with the nanometer additive base material covalent bond simultaneously And in the other end and the organopolysiloxane covalent bond;

And the wherein described organopolysiloxane includes the non-end unit of one or more formulas (III) in polymer chain:

Wherein

R¹Independently selected from hydrogen, C₁To C₁₀Alkyl, C₁To C₁₀Alkenyl, C₁To C₁₀Alkyl-C₆To C₁₀Aryl or C₆To C₁₀Aryl;And And R¹Preferably methyl;

And X is the key combined with the connector.

24. polymer nanocomposite additive composite material according to claim 23, wherein the organopolysiloxane with It is poly- (methyl hydrogen siloxane) of representative formula (II) before the connector covalent bonding:

Wherein R¹It indicates methyl, and n is integer, is selected to indicate so that poly- (methyl hydrogen siloxane) has about 390 To the integer of about 10,000 molecular weight ranges.

25. polymer nanocomposite additive composite material according to claim 23, wherein the nanometer additive be selected from by Group consisting of:Carbon nanotube, graphene oxide and the graphene oxide of reduction, clay, nano SiO 2 particle Or polyhedral oligomeric silsesquioxane.