CN1310749A - Crosslinkable silicone composition useful, in particular for producing water-repellent and/or oil-repellent coating and/or impregnation with low surface energy - Google Patents
Crosslinkable silicone composition useful, in particular for producing water-repellent and/or oil-repellent coating and/or impregnation with low surface energy Download PDFInfo
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- CN1310749A CN1310749A CN99808999A CN99808999A CN1310749A CN 1310749 A CN1310749 A CN 1310749A CN 99808999 A CN99808999 A CN 99808999A CN 99808999 A CN99808999 A CN 99808999A CN 1310749 A CN1310749 A CN 1310749A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Combustion & Propulsion (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention concerns an improved perfluorinated silicone composition to obtain antifouling coating and/or impregnation provided with improved properties for adhering to substrates and with increased life span. The invention concerns a crosslinkable silicone composition useful for making various supports water-repellent and/or oil-repellent to provide them with low surface energy. Said composition comprises: at least a POS A perfluorinated by radicals selected among the carboxylic diacid perfluorinated esters capable of forming anhydrides (e.g. maleic acid- bifid graft Gf); at least a crosslinking agent B (divinyltetramethyldisiloxane) perfluorinated or not and capable of reacting with the POS A; optionally a catalyst C; optionally one or several functional additives D. The selected crosslinking system is, for example, of the SiH/Sivinyl or the COOR/oxazolidine type with R = H, alkyl, NH4<+> of Na<+>. The invention also concerns the method for producing water-repellent and/or oil-repellent coating and/or impregnation on a support, method which consists in using said A, B, C, D composition. The invention is applicable to waterproof antifouling and/or spot-repellent coating for various bases such as textiles.
Description
Technical field:
The field of the invention is to be used for base material treatment so that give the formulation of their tolerance water-baseds and oily matter performance.More specifically, the present invention relates to comprise the silicone composition of perhalogenation (preferred perfluorination) group, said composition especially can be used for the preparation of hydrophobic and/or oleophobic coating and/or be used to implement the hydrophobic and/or oleophobic dipping of various base materials.
Further specifically, the present invention relates to crosslinkable silicone composition, they can be used as in field of textiles fluoridizes the arrangement preparation and makes the fabric of processing impermeable and help to improve coloring resistance and/or resistant character, holds concurrently washing easily.
This performance also is favourable for other field except that the fabric field.For example, can mention building field, wherein use coating, lacquer or other calendering agent of waterproof and grease proofing character, that class biological pollutant or graffiti pollution of providing no bounding force surface to ice, be attached to hull, or other undesirable pollutent with rejection.
Prior art:
The silicone oil that is grafted with fluorinated units also can be used as lubricant, as the specific release agent for some tackiness agent (siloxanes that high adhesion is arranged), as the grease-proof agent or in addition as foam preventer.They also can be with various thickening material preparations so that form putty or any other leakproof and/or indication material.
The fluorosilicone of these cross-linked form can be various technique components by molding or by extrusion molding.
The present invention relates to crosslinkable silicone composition, it includes at least one by the linearity of the Siliciumatom of at least one fully-fluorinated group Rf replacement or the poly-organopolysiloxane of ring-type perhalogenation (preferred perfluorination).
The present invention also relates to the waterproof and the grease proofing perfluor silicone composition of this cross-linked form.
In the context of the present invention, also at preparing the method for hydrophobic and/or oleophobic coating and/or using above-mentioned composition to implement method hydrophobic and/or the oleophobic dipping.
At last, the present invention relates to comprise coating precursor, coating, lacquer or other calendering agent of said composition.
When specified property is offered the organic polymer objects system, halogen and especially the effect of fluorine and carbon/fluorine bond be well-known in the polymer chemistry field.Especially, known fluoridizing with more specifically saying so is incorporated into the reduction that has caused surface energy in the polymkeric substance with the perfluorination unit, the improvement of heat and chemical stability and hydrophobicity, the improvement of dredging organic property and oleophobic property.Therefore, be known that to be opposing water-based and oily matter that coating must comprise highdensity perfluorination end group Rf on the surface.Since 1970s, this by the fluoridized functionalized siloxane polymer that has been applied to, especially linearity or ring-type, the siloxane polymer of preferred linear poly-organopolysiloxane (POS) type.
About the detail of these fluorosilicones, can with reference to the title of Ogden R.Pierce the article of " Fluorosilicons ", 1970, John Wiley﹠amp; Sons Inco.1-15 page or leaf.
Mainly be dihalo-one hydrogen organosilanes such as MeHSiCl for first known strategy of the industrial synthetic that comprises the unitary siloxanes of perfluorination
2(Me=methyl) carries the unitary unsaturated compound of perfluorination " hydrosilylation ": CH with what have a following general formula
2=CH-Rf (Rf=perfluorination unit).Silane added to obtained perfluorination dihalo-organosilanes in this alkene, it can be hydrolyzed so that produce functionalized silicone, and it for example can be a cyclic tetramer.The latter might be distributed again so that obtain the linear poly-organopolysiloxane (POS) of perfluorination.It is synthetic and use the hydrosilylation reactions of various binding substancess of silicone hybrid thing and perfluorinated olefins known by the metallic compound selected with especially some VIII family metal such as platinum come catalysis to involve this class.Therefore the Pt/Sn title complex has been used as hydrosilylation catalysts-consult patent US No.4089882 (Shinestu).This synthetic method seems relative complex and is expensive therefore.
Simplify for industry, advised second synthesis strategy, it uses for example CH
2α-the fluorinated olefin of=CH-Rf type will comprise the direct hydrogenation silanization of the unitary siloxanes of SiH, and this perfluorination unit R f is directly connected in olefinic CH by the carbon atom that carries at least one fluorine atom.Here various VIII family metal catalyst (especially based on platinum) is used for this hydrosilylation reactions once more.Yet the result is that these catalyzer can not obtain very high yield.Especially, common platinum type industry hydrosilylation catalysts (for example Karstedt type) is not very efficient.In addition, can observe a large amount of by products and produce, very clear, this greatly reduces the perfluorination efficient of siloxanes.
In patent US No.5233071, use these connector elements.They come from the hydrosilylation of alpha-olefin.Yet in order to overcome the shortcoming of before used hydrosilylation catalysts, the method that is disclosed in this patent is taked cobalt type organic radical metal complexes [(Co
2CO
8Co
2CO
6) (PR
3)
3, R=alkyl, aryl].Obviously, this art proposal is not satisfied, because the reaction times that is obtained is about several days, and essential uses a large amount of catalyzer (1-2%), and this especially is unfavorable for the economy of this method.
These cobalt type title complexs be not that unessential shortcoming is, their catalysis other reaction except hydrosilylation.Especially, they can participate in polymerization process by the epoxy opening of ring.This narrow spectrum shortage is special impairment.In addition, these catalyzer are not industrial suitable.
Patent US NO.5348769 discloses linearity or the poly-organopolysiloxane of ring-type, and it comprises by formula-R
3The D siloxy units that the first perfluorination functional unit of ZRf replaces and other D siloxy units of carrying the second class functional unit of ether hydroxyl or alkyl hydroxy type.The first perfluorination functional unit's connection Si especially is made up of following group with the connector element of Rf or bridge joint base: (CH
2)
xZ, X=2 wherein, 3 or 4 and Z=NHCO, NHSO
2, O
2C, O
3S, OOHCH
3, NHCH
2CH
2Or CH
2CHOHCH
2Employed catalyzer is Platinic chloride preferably.This technology is not the simplest, because it need prepare perfluoroalkylation olefinic reagent in advance.This has obviously prolonged the time of synthetic usefulness, so this has increased the cost of this method.
Except these connector elements, their precursor is formula CH
2The perfluoroalkylation alpha-olefin of=CH-Rf, prior art document also disclose wherein, and the olefinic precursor is CH
2The bridge joint base of=CH-L-Rf type; Chemical bond between L and Rf is an ester bond.The latter is from carboxyl functional group and perhalogenation alcohol, and preferred perfluorinated alcohols reacts and obtains.And general, above-mentioned carboxyl functional group is the hydrolysate of acid anhydrides.
Therefore, the α that discloses at the end of siloxane chain of PCT patent application WO94/12561-and ω-position on be grafted with the POS of fluorinated units separately.These α, the performance that ω-(perfluorinated alkyl ester) POS does not put up the best performance for capillary reduction and oleophobic property and hydrophobicity.
European patent application No.0640644 discloses perfluorination (Rf) silicone derivative that can be used in cosmetic ingredients with regard to its part.These perfluorination silicone derivatives are characterised in that the D siloxy units of carrying three kinds of dissimilar perfluorination grafting bodies, that is:
R wherein
2And R
3=alkyl, for example CH
3
2≤1≤16,1=3 for example; 1≤m, n≤6; ≤ p≤200;
0≤r≤50；
X and Y=singly-bound ,-CO-or C
1-C
6Alkylidene group.
Generally there is ehter bond in these perfluorination grafting (1)-(3) in the connector element that connects fully-fluorinated group Rf and silicon.
For remedy the vacancy of the chemically stable perfluorination POS that can obtain simple and economically, applicant company provides novel linear or the ring-type perfluorination POS that meets these requirements, and the latter comprises: the perfluorination grafting body Gf:C of following formula
mH
2m-Rf, wherein m 〉=2, and Rf=perfluorination residue and optional one or more other perfluorination or non-perfluorination grafting body Gf, it has two supplementary condition: first condition, grafting body Gf at least 60% by perfluorination; Second condition under the situation of m=2, then provides at least one other grafting body Gf therein, and its different in kind is defined in following formula.
These POS for example can be corresponding to following structural:
These POS can be used in lubricating oil foam preventer, release agent, the agent of reduction surface tension, stain control agent, oleophobic and/or hydrophobizing agent or prepare in the prescription of the used parent material of energy resistance to chemical attack and solvent-proof film or elastomerics.These novel perfluorination POS and their production and their application are disclosed among the french patent application No.9509269.
General introduction:
One of main purpose of the present invention be improve according to prior art and especially according to the perfluor siloxane polymer (multipolymer) of FR9509269:
-for coating and/or dipping purposes, by they and the adherent better performance of base material are provided,
-and by improving their washing fastness, wearability and resistance to abrasion, be by increasing their work-ing life in brief.
This be because, importantly the perfluor siloxane systems should tolerate outside erosion the (solubilization/extraction owing to the effect of washing or abrasive), so that keep them to reduce capillary ideal performance, this is their opacity, the source of coloring resistance and resistance to soiling function.This is to removing surperficial full-fluorine group direct effect to be arranged because above-mentioned outside is corroded.In fact, as can be seen from the above, this surface location of above-mentioned Rf group is crucial for their effectiveness.
After setting this purpose, especially the contriver is through after very long and arduous research and testing, and in complete wondrous and unexpected mode, confident confirmation might obtain this improvement by the crosslinkable silicon system that comprises the POS that carries perhalogenation, preferred fluoridized Gf grafting body is provided, and this grafting body is selected from the perfluorination ester of the dicarboxylic acid that can form acid anhydrides (for example maleic anhydride) meticulously.These Gf grafting bodies are described to two fens Rf grafting bodies.
Therefore, the present invention relates to crosslinkable silicone composition, it especially can be used for the preparation of the hydrophobic of low surface energy and/or oleophobic coating and/or be used to implement the hydrophobic and/or oleophobic dipping of low surface energy, and this based composition comprises:
.A. at least a perfluorination POS;
.B. at least a can with the perfluorination or the non-perfluorination linking agent of POS A reaction;
.C. catalyst for reaction between Ren Xuan at least a A and the B;
.D. Ren Xuan one or more functional additives;
It is characterized in that
The perfluorination Gf grafting body of → one or more following formulas, they are identical or different each other:
Wherein:
-R
1Group is independently represented hydrogen or C
1-C
6Alkyl
-Rf
1And Rf
2Be perhalogenation, preferred fully-fluorinated group, and the also more preferably linearity of following structural formula or branching perfluoroalkyl:
(II)-CqF
2Q-CF
3, q 〉=0 wherein;
Or
(III)-CqF
2Q-H, wherein q 〉=1;
-m=1-10；
-n=0-4；
→ one or more crosslinking functionality CFa, they are identical or different each other;
Should be noted that,, directly or indirectly be connected on the silicon of POS A or crosslinking agent B with the free valency of black matrix-expression as the key of all structural formulas that in this description, provide.
According to the present invention, term " low surface energy " is interpreted as and refers to total γ
s≤ 15mJ/m
2Value.By the POS that select to use crosslinkable system and replaced by the Gf perfluorination grafting body of the formula I of bisRf or Rf bi-section, the contriver has introduced the terms of settlement that is entirely satisfactory for sticking problem hydrophobic and oleophobic fluoride coating and base material.This also makes might increase the persistence of surperficial fluorine in the effect of water resisting property and oily matter aspect of performance, and these fluorosilicone coating have showed these performances with height and lasting mode ground, so is unusual ideal.
And, be not wishing to be bound by theory, as can be seen, the acquisition that the bipartite texture of the Gf grafting body of selecting according to the present invention helps anisotropy to arrange, this has promoted the unitary hydrophobic and oleophobic effects of perfluorination.
Detailed description of the present invention:
Still about Gf perfluorination grafting body, should be noted that, according to the present invention, unit price residue Rf in the formula I
1And Rf
2Preferably corresponding to-C
pF
2p-CF
3, wherein p is between 3 and 20, preferably between 5 and 20, and also more preferably between 7 and 10.
In fact, for example also may use the mixture of Rf, wherein index p equals 7,8 or 9.
According to selecting form for alternate, per molecule POS A carries:
The perfluorination Gfh grafting body of → one or more formulas (I .1), they each other can be identical or different:
Wherein:
-R
I1, Rf
3, m ' and n ' corresponding to above for R
1, Rf
1, those identical definition that m and n provide;
-Rh is linearity or branching, preferred linear C
6-C
40More preferably C
6-C
20Alkyl;
→ and the Gh grafting body of optional one or more formulas (I .2), they each other can be identical or different:
Wherein:
-R
I2, m ", n " and Rh
1And Rh
2Correspond respectively to above for R
I1, those identical definition that m ', n ' and Rh provide.
Except these specific perfluorination unit, the present invention also is based on the crosslinked ability of composition.Therefore, according to preferred form, each is selected from following combination to reactive functional CFa/CFb:
The reactive functional CFa/CFb of the first two row refers to (it is desirable to C by the Si-alkenyl in the presence of metal catalyst (preferred platinum catalysts) in the last table
2-C
10Alkenyl) the unitary hydrosilylation of unit by using Si-H comes crosslinked mechanism; And the CFa/CFb=COOR/ oxazolidine is with these two pairs of reactive functional of oxazolidine/COOR opening and come crosslinked mechanism with the reaction of the oxygen of carboxyl corresponding to Tong Guo oxazolidine ring.The R group of COOR group can be a hydrogen, and alkyl or positively charged ion for example are connected to carboxylate anion COO
-On NH
4 +Or Na
+
The detail of Guan Yu oxazolidine functional group/COOR functional group reactions, can be with reference to following reference book:
V “ oxazolidine, their preparation, reaction and application ",
John?A.Frump,Chem.Rev.,71,483(1971),
V " 2-oxazolidine chemistry ",
T.G.Gant and A.I.Meyers.,
Tetrahedron (Tetranhedron), 50 (8), 2297 (1994).
These two kinds of cross-linking methods have simple and economical advantage, are convenient to technical scale and use.Therefore, in these two kinds of methods, employed catalyzer is the standard industry catalyzer, for hydrosilylation, for example based on those of platinum, as the Karstedt catalyzer, perhaps for Daing out the oxazolidine ring, as cadmium acetate.These cheap catalyzer use with low consumption.In addition, crosslinked kinetics merits attention fully, especially for hydrosilylation.
COOR/ oxazolidine cross-linking system especially has this kinetics, so that it can use by thermal initiation in the presence of catalyst-free.
Will find that according to the present invention, each comprises at least one CFa and CFb reactive functional respectively per molecule POS A and crosslinking agent B.These CFa and CFb functional group are complementary, that is to say that they can react to each other.Do not get rid of other embodiment for necessary this characteristic of A-B bridge joint, wherein POS A and/or crosslinking agent B comprise the complementary interaction active function groups that can react to each other on same molecular: H/ alkenyl (vinyl) and/or COOR/ oxazolidine.
Yet preferably, each POS A or crosslinking agent B molecule comprise the incomplementarity reactive functional that can not react to each other.
According to first advantageous embodiment of the present invention, POS A comprises that CFa=H and crosslinking agent B are single-and/or multi-silane and/or two-and/or many siloxanes, and per molecule comprises at least two CFb=C
2-C
10Alkenyl, preferred vinyl.
Preferably, B is an organic radical sily oxide oil, for example divinyl tetramethyl disiloxane (DVTMS), and/or be selected from poly-diorganosiloxane oil, especially be selected from polydimethyl siloxane oil, they pass through the CFb=alkenyl at the end of chain, and preferred Vi (vinyl) comes functionalized.
In the scope according to first embodiment of composition of the present invention, more special use comprises the POS A of one or more corresponding following structure formula IV:
Wherein
R
2, they are same to each other or different to each other ,=methyl, propyl group or butyl;
R
3, they are same to each other or different to each other ,=linearity or branched-alkyl, preferred C
6-C
40Alkyl and more preferably C
6-C
20Alkyl;
0＜p
ⅰ, preferred 1≤p
1＜100;
0≤p
ⅱ, preferred 0≤p
ⅱ＜500;
0＜p
ⅲ, preferred 2≤p
ⅲ≤ 100;
0≤p
ⅳ, preferred 0≤p
ⅳ≤ 100;
0≤p
ⅴ, preferred 0≤p
ⅴ≤ 100;
0≤p
ⅵ, preferred 0≤p
ⅵ≤ 100;
Σ p
ⅰ-ⅵ+ 2=5-600, preferred 50-300.
In fact, might have:
p
ⅰBetween 1-50,
p
ⅱBetween 50-300,
p
ⅲBetween 5-50,
p
ⅳBetween 0-50,
p
ⅴBetween 0-50,
p
ⅵBetween 0-50.
As the alternative form of this first embodiment, POS A comprises CFa=C
2-C
10Alkenyl, preferred vinyl, and crosslinking agent B carries CFb=H, B is selected from end at chain ideally by CFb functionalized organic radical sily oxide oil and/or poly-hydrogen diorganosiloxane oil.
According to second favourable embodiment according to composition of the present invention, POS A comprises that CFa=COOR and crosslinking agent B are the compound of hydro carbons character and/or single-and/or polysilane and/or two-and/or polysiloxane, and its per molecule comprises at least two CFb=oxazolidines.B is following formula De Shuan oxazolidine preferably:
Wherein X is corresponding to alkylidene group or POS.
X=alkylidene group in this formula (V) is also more preferably corresponding to divalence C
1-C
20Alkyl, for example C
4Alkyl.
For ease of understanding, the POS A of regulation said composition is ideally corresponding to following structural formula (VII):
Wherein:
W is carboxylated hydro carbons group, is preferably selected from:
The group of ° following formula (VIII):
Wherein:
-R
I3, m and n corresponding to above to R
1, the identical definition of those definition that m and n provide;
-E
1And E
2One or another corresponding to above definition-COOR, if E
1Or E
2≠ COOR, then E
1Or E
2=R
I3
° linearity or branched-alkyl, preferred C
2-C
20Alkyl, they have at least one carboxy CO OR terminal, and are different from the group of formula (VIII);
R
4, be same to each other or different to each other=methyl, propyl group or butyl;
R
5, be same to each other or different to each other=linearity or branched-alkyl, preferred C
6-C
40Alkyl and more preferably C also
6-C
20Alkyl;
R is same to each other or different to each other ,=H, and positively charged ion or protecting group are preferably selected from alkyl and/or alkyl silane;
0＜r
ⅰ, preferred 1≤r
ⅰ≤ 100, and more preferably 1≤r also
ⅰ≤ 50,
0≤r
ⅱ, preferred 0≤r
ⅱ≤ 500, and more preferably 50≤r also
ⅱ≤ 300,
0≤r
ⅲ, preferred 2≤r
ⅲ≤ 100, and more preferably 5≤r also
ⅲ≤ 50,
0≤r
ⅳ, preferred 0≤r
ⅳ≤ 100, and more preferably 0≤r also
ⅳ≤ 50,
0≤r
ⅴ, preferred 0≤r
ⅴ≤ 100, and more preferably 0≤r also
ⅴ≤ 50,
0≤r
ⅵ, preferred 0≤r
ⅵ≤ 100, and more preferably 0≤r also
ⅵ≤ 50.
As the alternative form of second favourable embodiment according to the present invention, can mention therein POS A comprise the CFa=oxazolidine and wherein crosslinking agent B be the situation of following compound:
The diacid of formula VI or derivative under the Δ:
ROOC-X
1-COOR, wherein X
1Be the hydro carbons group, preferred C
1-C
12Alkylidene group,
Δ and/or per molecule POS carry at least two CFb=-COOR and optional one or more perhalogenation (preferred perfluorination) Gf grafting body, and the latter's structural formula is equal to the above structure formula I that provides.
The common advantageous feature of the present invention of two favourable embodiments according to the composition of above definition, except perhalogenation (preferred perfluorination) the Gf grafting body of formula I, POS A and optional crosslinking agent B per molecule can comprise perhalogenation (preferred perfluorination) Gf ' the grafting body of formula II:
(Ⅱ)
-(C
tH
2t)-Rf
3
Wherein: t 〉=2, Rf
3Corresponding to above for Rf
1And Rf
2The identical definition that provides.
In these embodiments and their alternative form, in fact, preferred POS (therefrom selecting POS A) can obtain the linear POS of the branch of 50wt% (unit except the D siloxy units) at the most alternatively, cyclic polymer or three-dimensional polymer (resin that comprises T and/Q siloxy units).Yet, in the context of the present invention, especially use the linear POS that forms by the D unit basically.
As for basic POS as the precursor of above-mentioned target grafting POS, their preferably linear poly-organic radical hydrogen siloxanes.
Can imagine various chemical route and be used for the functionalized of these precursors of POS A even B.Select the route that suits according to the character that is grafted to the group on the siloxane chain.
According to the present invention, utilize the unitary hydrosilylation of alkenyl unit and SiH.
The functionalized result that distinguishing characteristics brought of precursor can define by their preparation method characteristic according to the POS A of composition of the present invention and crosslinking agent B.
Therefore, POS A is preferably obtained by the POS that selects from poly-alkyl hydrogen siloxanes, thereafter in the presence of the hydrosilylation metal of significant quantity (preferred platinum type) catalyzer, SiH unit to the small part of these POS is used for the hydrosilylation of the olefinic precursor of following group:
All or part of Gf grafting body, if suitable, Gfh, Gh or Gf ' grafting body,
The optional group that carries at least one COOR base or can be replaced by at least one COOR base,
Optional carries at least one oxazolidinyl or can extremely be lacked the group that an oxazolidinyl replaces,
Optional at least one crosslinking functionality CFa=alkenyl, the preferred C of carrying
2-C
10The alkenyl and the more preferably group of vinyl also perhaps can be by at least one crosslinking functionality CFa=alkenyls, preferred C
2-C
10The alkenyl and the more preferably group of vinyl substituted also,
And optional R as defined above
3Or R
5Alkyl.
As for crosslinking agent B, it is made up of the POS that is selected from poly-alkyl hydrogen siloxanes (preferred polymethyl hydrogen siloxane) ideally, thereafter in the presence of the hydrosilylation metal of significant quantity (preferred platinum type) catalyzer, SiH unit to the small part of these POS is used for the hydrosilylation of the olefinic precursor of following group:
-carry at least one crosslinking functionality CFb=alkenyl, preferred C
2-C
10The alkenyl and the more preferably group of vinyl also perhaps can be by at least one crosslinking functionality CFb=alkenyls, preferred C
2-C
10The alkenyl and the more preferably group of vinyl substituted also;
-and/or the group that carries at least one crosslinking functionality CFb=COOR or can be replaced by at least one CFb=COOR of functional group;
-and/or the group that carries at least one crosslinking functionality CFb=oxazolidine or can be replaced by at least one CFb=of functional group oxazolidine;
-optional all or part of Gf grafting body, if suitable, Gfh, Gh or Gf ' grafting body;
-and optional R as defined above
3Or R
5Alkyl.
At first only a part of therein Gf, in addition Gfh, Gh or Gf ' grafting body by hydrosilylation by under the grafted situation, perhaps the introducing of remainder is carried out with one or more grafting methods that relate to any chemical reaction mechanism.This progressively functionalized other CFa for compd A and B, CFb or alkyl substituent also are feasible.
According to these aspects another, the present invention relates to the perfluor silicone composition of aforesaid cross-linked form.
The present invention also relates to as the infant industry product:
-1-per molecule carries the POS A of one or more Gf grafting bodies and one or more crosslinking functionality CFa=oxazolidines;
-2-per molecule carries the POSA of one or more Gf grafting bodies and one or more Gh grafting bodies;
-3-per molecule carries the POSA of one or more Gf grafting bodies and one or more Gfh grafting bodies;
-4-per molecule carries the POS A of one or more Gf grafting bodies and one or more Gh grafting body and one or more Gfh grafting bodies;
-5-per molecule carries one or more Gf grafting bodies, one or more crosslinking functionality CFa=oxazolidines and/or COOR, and the optional one or more Gh and/or the POSA of Gfh grafting body.
The special properties of the perfluorination grafting body of the crosslinking agent B that relies on POS A and choose wantonly and the crosslinked ability that has both make and may give the solid low surface tension that they apply or exist in persistent mode according to composition of the present invention.Therefore these compositions provide long-time stable oleophobic and/or hydrophobic performance.This result is especially favourable with attracting for the application of coating, arrangement or immersion type:
° be used for weaving,
° be used for building (coating, lacquer, anti-scribble lacquer or calendering agent),
° or be used for wanting anti-coloring and antifouling and make impervious any other goods (the anti-dirt lacquer that for example is used for ship).
These fluoro siloxane compositions according to the present invention also can be used in the prescription of putty, indication and leakproofing material, lubricant, release agent, foam preventer or grease resistance agent.
Capillary reduction by fluoro siloxane composition according to the present invention causes that is to say oleophobic and/or hydrophobic performance, can be by control by fluoridizing or alkylation grafting or the unitary ratio of non-grafted D are regulated.This is corresponding to index p in formula IV on POS A and (VII)
ⅰ-p
ⅵAnd r
ⅰ-r
ⅵVariation.
Functional additive D is according to the application of the composition of setting and difference.Make up material desire therein and be used for the preparation of fluoride coating and/or be used for fluoridizing under the situation of dipping implementing on the textile substrate, functional additive D for example can be:
-when being used to improve size and intensity or washing character or be used to introduce the resin that the heat shrinkable of rigidity to a certain degree closes;
-obtain soft feel(ing), improve character and the tenderizer that helps mechanical treatment (polishing, napping, calender process) in the Clothing industry goods;
-in various dryings and converging operation process, help the antistatic agent that the static charge of fabric accumulation flows;
-reduction combustibility and the fire retardant that prevents propagation of flame;
-prevent mouldy and septic fungicidal and bactericide;
-generally with the product of extender name expression, for example can be melamine resin by the mixture modification of lipid acid or paraffin and zirconates, and it combines with fluoro-resin and significantly improves its performance in some cases.
Composition according to the present invention prepares by the C and the D that mix various component A and B and choose wantonly.Before use or the fusion, these components can be the forms of solution, emulsion or melt in the operation batching.
According to a further aspect in the invention, POSA according to the present invention is used for the various grafting bodies of these POSA or substituently has the hydrosilylation of the olefinic precursor of at least one whole terminal double bond to prepare by imagination, but except the vinyl, that is to say:
◆ Gf, and if be fit to Gfh, Gh or Gf ';
◆ the group that carries at least one COOR base or can be replaced by at least one COOR base;
◆ carry at least one oxazolidinyl or can extremely be lacked the group that an oxazolidinyl replaces;
◆ carry at least one crosslinking functionality CFb=alkenyl, preferred C
2-C
10Alkenyl and more preferably vinyl also perhaps can be by at least one crosslinking functionality CFb=alkenyls, preferred C
2-C
10The alkenyl and the more preferably group of vinyl substituted;
◆ and corresponding to R as defined above
3Or R
5The alkyl of those types;
Crosslinking agent B itself also is to carry under the situation of the unitary POS of SiH therein, and the method for this grafting perfluorination, alkylation or crosslinking functionality also is favourable.
These hydrosilylations are carried out in the presence of the Industrial Metal catalyzer of the nickel type that is selected from, palladium type or the platinum type compound of significant quantity (preferred platinum type compound) in a manner known way.This for example can be in hydrosilylation (SiH unit) before, advantageously with in a small amount, for example use the Karstedt catalyzer with respect to the amount of about 10-50ppm of described POS compound.Hydrosilylation is well-known simple process to the person of ordinary skill in the field.Its kinetics is fast, and hydrosilylation makes may obtain extra high yield and the unitary transformation efficiency of SiH.The condition of hydrosilylation is conventional, is therefore decided by the person of ordinary skill in the field easily.
In fact, hydrosilylation occur in the different olefinic reagents that exist as many mutually in.The stirring reaction medium, and temperature is raised between 50-150 ℃.Reaction under atmospheric pressure He is generally implemented through several hours process.The unitary transformation efficiency of SiH is higher than 99% quantity.
Have been found that specified substituent is for example: Gf, Gfh, Gh, Gf ', CFa, the grafting of CFb or chain alkyl can be divided into several stages.First stage is that the SiH unit with POS will have a part of corresponding substituent precursor hydrosilylation in addition with POS.One or more other branched chain or compartmentation compound are connected to subsequently by hydrosilylation and are connected on this article one branched chain on the main chain of POS, till obtaining whole grafting body or substituting group.
Interconnecting of various branched chain can be implemented by various known chemical reactions principles, for example: esterification, addition, replacement and similar fashion.
Gf for formula I, Gfh, the situation of Gh and Gf ' grafting body can be imagined by at first by hydrosilylation a group being connected in POS and implement grafting, this group one end comprises ethylenic unsaturated bond, and the other end has two carboxyl functional groups of following form:
-COOH，
-COOR ', R '=hydro carbons character group wherein,
-COO
-X
+, X=alkali metal cation wherein,
-or ammonium.
These two carboxyl functional groups also can provide with anhydride form.
Is easy with these carboxyls or anhydride reaction active function groups with carrying insertion branched chain or the reaction of end branched chain of wishing to be grafted to the functional group on the POS.Therefore, under the situation that operation therein must be carried out article one branched chain that comprises the acid anhydrides end, can imagine:
→ at least a portion that will be connected in the anhydride functional group of POS is hydrolyzed and/or salification, so that produce the free end carboxyl, and uses subsequently and makes the reagent that may construct whole grafting body come the above-mentioned end group of esterification at least a portion,
→ and/or directly with anhydride functional group and the feasible reaction reaction that may construct whole grafting body.
As for the POS reagent that comprises vinyl-functional, they obtain by the hydrosilylation method, this method is different from above-mentioned method a bit, and difference is that the unsaturated unit of hydrosilylation is not alkene fundamental mode but alkynyl type, and catalyzer is not the platinum type ideally.For example, the crosslinking agent B of divinyl tetramethyl disiloxane type is by the preparation that is used for of acetylene and dihydro tetramethyl disiloxane.
In the middle of the POS that can be used as the preparation POS A and the parent material of the POS crosslinking agent B of choosing wantonly, for example can mention linear POS, as comprising the unitary polymethyl hydrogen siloxane of D of 10-500 SiMeH or SiMeH and SiMe type, or ring-type POS, as tetramethyl-ring siloxanes D ' 4.
According on the other hand, the present invention relates to the two-pack precursor systems of aforesaid silicone composition, being characterised in that it comprises will mix so that form two unitary part 1 and 2 of composition, this part 1 or a kind of POS A or crosslinking agent B and optional catalyzer C and/or cross-linked inhibitor D of comprising of 2.
In case mix, the part 1 and 2 of bicomponent system has formed standby perfluorination silicone composition, it especially can be with on any suitable coating or applicating implement (for example scraper or roller) the paint base material.
As another theme, the present invention also relates to be used to prepare the method for hydrophobic and/or oleophobic coating and/or be used on base material, implementing method hydrophobic and/or the oleophobic dipping, this method feature is that it mainly is:
preparation and/or use composition above definition or that obtain by the bicomponent system of above definition,
is on the said composition paint base material, so that obtain film and/or so that the dipping base material,
chooses evaporating solvent wantonly, if composition provides with the solution form,
manages to make condition, especially the temperature and pressure condition is enough to take place gratifying crosslinked.
The base material of considering can be fabric or any other solid material, for example: metal, cement, concrete, timber, plastics, matrix material and analogue.
These The Application of Technology can be included into the general knowledge of each professional application.Following embodiment has provided several illustrations of this respect.
Industrial application:
The present invention also relates to introduce the product or the formulation of wherein related composition.They are especially:
-coating precursor,
-coating,
-lacquer (anti-dirt lacquer),
-calendering agent,
-lubricant,
-reduction surface energy reagent,
-stain resistant agents,
-release agent,
-foam preventer,
-hydrophobic and/or oleophobic agent,
The parent material that-preparation resistance to chemical attack and solvent-proof elastomerics or film are used,
-textile finishing formulation.
By the film of the preparation of compositions of above definition and/or coating also within the scope of the invention.
Embodiment:
Embodiment 1: preparation can be passed through the SiH/SiVi hydrosilylation cross-linking and based on the silicone composition of various POS A and crosslinking agent B=tetramethyl divinyl disiloxane; Prepare crosslinked coating by above-mentioned composition
The employed product of I .1
a)POS?A
Employed POS is the POS that obtains by conventional redistribution reaction, and it comprises the following units:
M=(Me)
3SiO
1/4
D=(Me)
2SiO
2/4
D’=MeHSiO
2/4
Basis SiH oil is corresponding to structural formula: MD
50D '
50M.
The vinyl precursor of employed Gf grafting body is corresponding to following structural formula:
It is as follows to be used for the grafted hydrosilylation reactions:
Annotate: D ' is corresponding to its D subsequently
Rf
｜
Gf octyl group (R
3Or R
5) begin grafting with the same manner from octenyl.Prepared POS A product description is in following table 1.
B) crosslinking agent B is:
C) the catalyzer C of composition is the Karstedt catalyzer
D) composition comprises the cross-linked inhibitor as functional additive (D): ethynylcyclohexanol (FCH)
Below use sample 3,4,5,6 and 7 to prepare coating.Control sample is floride-free reference oil (contrast).
The preparation of I .2 coating
At solvent phase (C
4F
9OCH
3) in, in the presence of ECH, be coated on polyester and the glass sheet as melting materials capable and prepare coating.Evaporating solvent in advance under vacuum, system is carried out crosslinked under 90 ℃ then.Crosslinkedly monitor by the total reflection IR (disappearances of SiH bands of a spectrum) that weakens.Use the Rame-Hart A-100 protractor that is connected with image analysing computer software to measure contact angle subsequently.Used liquid probe is water and methylene iodide.Angle value is the mean value for 10 in each sample, then the feasible surface energy that may release coating of data processing.
I .3 result
The influence of I .3.1 base material and method of application (seeing table 2)
Initial from oil 5, approximately identical at glass or the income value on polyester.
These values are lower than the value (20-23mJ/m of common siloxanes
2).
The influence of I .3.2 fluorine content and network size
For the oil of fluorine at high proportion that has of all preparations, the gained result is approximately identical: see table 3.
The unitary introducing of octyl group (sample 6) has increased surface energy.
The stability of I .3.3 coating
In polar liquid-softening water, behind more or less very long dipping, how to change with regard to the surface energy of coating and to detect.These tests are carried out at three kinds of officials' energy carburetion and contrast:
The gained result provides in following table 4.
Income value with regard to sample 6 and 3 shows that after the dipping, impurity is present in (inorganic salt) in the coating, has caused the value higher than independent siloxanes in water.May get back to initial value with the simple washing of acetone is feasible.
I .3.4 single-component system
This system obtains simplifying by fluoridize this oil with fluorinated units in cross-linking process.B is different with the allylic relative reactivity of Rf.
From sample solvent phase or the initial coating for preparing of body sample.The optional washing with acetone of using after under 90 ℃ crosslinked 2 hours.
The gained result provides in following table 5.Obtained to be similar to surface energy by functionalized path gained.The stability of these coatings is not made an appraisal.
The embodiment II: preparation can Tong Guo oxazolidine/COOR cross-linking reaction and based on the silicone composition of various POS A and crosslinking agent B=Shuan oxazolidine
II .1 prepare RF-POS (A)-/the carboxylic acid silicone oil
Protect undecylenic acid with hexamethyldisilazane in advance, be grafted to silicone oil MD afterwards
50D '
50M goes forward.More than two-Rf and octyl group unit also be introduced in this oil: protection
Undecylenic acid is protected according to the method for patent EP196169.Three kinds of oil are equipped with by this protection acid, octene and two-Rf grafting system:
| Sample | Resulting structures formula (NMR) |
| ?9 | ?MD 50D Rf 30D COOSiMe3 7M |
| ?10 | ?MD 50D’ 2D Rf 5DCOOSiMe 3 5D oct 30M |
| ?11 | ?MD 50D’ 2D Rf 12D COOSiMe3 2D oct 24M |
COOSiMe
3The protection of going of group water can be successfully from three kinds of initial carrying out of above-mentioned oil.
II .2 prepares Shuan oxazolidine linking agent
Used water-soluble Shuan oxazolidine is as follows:
Three kinds of different modes with existing document description prepare:
-from hexanodioic acid with from thanomin
-from the Jia oxazolin, pass through lithiumation
-from adiponitrile with from thanomin.
Used catalyzer is a cadmium acetate under latter event.Obtained the yield of 60% distillage after 25 hours in reaction.
Need be used for linking agent and the usual vehicle that is used for the sense carburetion.Only acetone makes and may virtually completely dissolve this oil.
In the mode identical, detect in the crosslinked front or rear stability of coating in water with the embodiment I.After passing through water, the sample washing with acetone.
What obtained the results are shown in the following table 6.
Table 1
| Sample | Platinum (ppm) | Time | ???D.C. ???SiH ???(％) | The oil that is obtained (NMR) |
| ????1 | ????145 | ????7h?15 | ????8 | ????MD 50D′ 46D Rf 4M |
| ????2 | ????195 | ????72h | ????16 | ????MD 50D′ 42D Rf 8M |
| ????3 | ????1400 | ????24h | ????40 | ????MD 50D′ 23D Rf 27M |
| ????4 | ????10 | ????2h?30 | ????39 | ????MD 50D′ 30D Rf 20M |
| ????5 | ????10 | ????4h | ????65 | ????MD 50D′ 18D Rf 32M |
| ????6 | ????10 | ????5h?10 | ????70 | ????MD 50D′ 15D Rf 28Oct 7M |
| ????7 | ????10 | ????48h | ????75 | ????MD 50D′ 8D Rf 11Oct 31M |
| ????8 | ????10 | ????27h | ????92 | ????MD 50D′ 4D Rf 46M |
| Contrast | ????10 | ????5h?15 | ????52 | ????MD 50D′ 23Oct 27M |
POS A sample is stored under the situation of excluding air.
Table 2
| Base material | Method of application | Surface energy | ||
| Total γ s (mJ/m 2) | Disperse γ s d????(mJ/m 2) | Polarity γ s p????(mJ/m 2) | ||
| Glass | The Meyer rod | ????11.96 | ????11.11 | ????0.85 |
| Glass | Between two battens, shear | ????12.11 | ????8.86 | ????3.25 |
| Polyester | The Meyer rod | ????10.23 | ????8.27 | ????1.96 |
Table 3
Table 4
| Sample | Resulting structures | Dipping time | Surface energy | ||
| Total γ s????(mJ/m 2) | Disperse γ s d????(mJ/m 2) | Polarity γ s p(mJ/m 2) | |||
| Contrast | ????MD 50D′ 23Oct 27M | ????0h | ????23.3 | ????22.59 | ????0.71 |
| Contrast | ????MD 50D′ 23OCt 27M | ????24 | ????21.68 | ????20.37 | ????1.3 |
| ????5 | ????MD 50D′ 18D Rf 32M | ????0h | ????10.46 | ????9.15 | ????1.32 |
| ????5 | ????MD 50D′ 18D Rf 32M | ????24h | ????12.03 | ????8.96 | ????3.07 |
| ????5 | ????MD 50D′ 18D Rf 32M | ????6d | ????16.28 | ????12.66 | ????3.61 |
| ????5 | ????MD 50D′ 18D Rf 32M | ????13d | ????24.52 | ????19.84 | ????4.68 |
| ????6 | ????MD 50D′ 15D Rf 28OCt 7M | ????0h | ????11.34 | ????9.97 | ????1.36 |
| ????6 | ????MD 50D′ 15D Rf 28Oct 7M | ????7d | ????31.1 | ????26.8 | ????4.33 |
| ????6 | ????MD 50D′ 15D Rf 28Oct 7M | The 7d+ washing * | ????10.21 | ????8.68 | ????1.54 |
| ????3 | ????MD 50D′ 23D Rf 27M | ????0h | ????10.29 | ????8.49 | ????1.79 |
| ????3 | ????MD 50D′ 23D Rf 27M | ????7d | ????29.35 | ????27.96 | ????1.39 |
| ????3 | ????MD 50D′ 23D Rf 27M | The 7d+ washing | ????11.37 | ????9.82 | ????1.55 |
*Sample washing with acetone 3 times
Table 5
| Project organization | Medium | Handle | Surface energy | ||
| Total γ s????(mJ/m 2) | Disperse γ s d????(mJ/m 2) | Polarity γ s p????(mJ/m 2) | |||
| ?MD 50D′ 25D Rf 25M+M 2Vi | Solvent | Washing | ????14.56 | ????11.52 | ????3.04 |
| ?MD 50D′ 25D Rf 25M+M 2Vi | Solvent | Need not wash | ????15.48 | ????11.43 | ????4.05 |
| ?MD 50D′ 25D Rf 25M+M 2Vi | Solvent-free | Washing | ????10.17 | ????9.42 | ????0.74 |
| ?MD 50D′ 25D Rf 25M+M 2Vi | Solvent-free | Need not wash | ????11.41 | ????10.51 | ????0.89 |
Table 6
| (mJ/m 2) | Uncrosslinked system | Cross-linking system | ||||
| Initially | 25?h/H 2O | ?25?h/H 2The O+ washing | Initially | ????25?h/H 2O | ????25?h/H 2The O+ washing | |
| ????9 | ????11.14 | ????18.66 | ????13.7 | ????12.2 | ????11.0 | ????10.84 |
| ????10 | ????7.32 | ????18.28 | ????17.46 | ????8.3 | ????9.31 | ????8.66 |
| ????11 | ????10.32 | ????10.8 | ????- | ????12.9 | ????10.84 | ????11.03 |
The crosslinked surface energy that makes has height ideal stability.There is minimum unitary oil (sample 10) to obtain the most weak surface energy.
Claims (15)
1, crosslinkable silicone composition, it especially can be used to prepare the preparation that the hydrophobic of low surface energy and/or oleophobic coating are arranged and/or be used to implement the hydrophobic and/or oleophobic dipping of low surface energy, and this composition comprises:
.A. at least a perfluorination POS;
.B. at least a can with the perfluorination or the non-perfluorination linking agent of POS A reaction;
.C. catalyst for reaction between Ren Xuan at least a A and the B;
.D. Ren Xuan one or more functional additives;
It is characterized in that
Per molecule POS A carries: the perfluorination Gf grafting body of → one or more following formulas, and they are identical or different each other:
Wherein:
-R
1Group is independently represented hydrogen or C
1-C
6Alkyl
-Rf
1And Rf
2Be perhalogenation, preferred fully-fluorinated group, and the also more preferably linearity of following structural formula or branching perfluoroalkyl:
(II)-CqF
2Q-CF
3, q 〉=0 wherein;
Or
(III)-CqF
2Q-H, wherein q 〉=1;
-m=1-10；
-n=0-4；
→ one or more crosslinking functionality CFa, they are identical or different each other;
2,, be characterised in that per molecule POS A carries according to the composition of claim 1:
The perfluorination Gfh grafting body of → one or more formulas (I .1), they each other can be identical or different:
Wherein:
-R
I1, Rf
3, m ' and n ' corresponding to above for R
1, Rf
1, those identical definition that m and n provide;
-Rh is linearity or branching, preferred linear C
6-C
40More preferably C
6-C
20Alkyl;
→ and the Gh grafting body of optional one or more formulas (I .2), they each other can be identical or different:
Wherein:
-R
I2, m ", n " and Rh
1And Rh
2Correspond respectively to above for R
I1, those identical definition that m ', n ' and Rh provide.
3,, be characterised in that each is selected from following combination to reactive functional CFa/CFb according to the composition of claim 1 or 2;
According to each composition among the claim 1-3, be characterised in that 4, POS A comprises CFa=H and be that crosslinking agent B is single-and/or polysilane and/or two-and/or polysiloxane that per molecule comprises at least two CFa=Vi (vinyl); B is organic radical sily oxide and/or poly-diorganosiloxane preferably.
5, according to each composition among the claim 1-4, be characterised in that it comprises one or more POS A corresponding to following structural (IV):
Wherein
R
2, they are same to each other or different to each other ,=methyl, propyl group or butyl;
R
3, they are same to each other or different to each other ,=linearity or branched-alkyl, preferred C
6-C
40Alkyl and more preferably C
6-C
20Alkyl;
0＜p
ⅰ, preferred 1≤p
ⅰ＜100;
0≤p
ⅱ, preferred 0≤p
ⅱ＜500;
0＜p
ⅲ, preferred 2≤p
ⅲ≤ 100;
0≤p
ⅳ, preferred 0≤p
ⅳ≤ 100;
0≤p
ⅴ, preferred 0≤p
ⅴ≤ 100;
0≤p
ⅵ, preferred 0≤p
ⅵ≤ 100;
∑ p
ⅰ-ⅵ+ 2=5-600, preferred 50-300.
6, according to each composition among the claim 1-5, be characterised in that, POS A comprises CFa=COOR, with be that crosslinking agent B is the compound of hydro carbons character and/or single-and/or polysilane and/or two-and/or polysiloxane, its per molecule comprises at least two CFb=oxazolidines, and B is following formula De Shuan oxazolidine preferably:
Wherein X is corresponding to alkylidene group or POS.
7,, be characterised in that it comprises POS A corresponding to following structural formula (VII) according to each composition among the claim 1-6:
Wherein:
W is the connector element that the hydro carbons group is formed, and is preferably selected from:
The group of ° following formula (VIII):
Wherein:
-R
I3, m and n corresponding to above to R
1, the identical definition of those definition that m and n provide;
-E
1And E
2One or another corresponding to above definition-COOR, if E
1Or E
2≠ COOR, E so
1Or E
2=R
I3
° linearity or branched-alkyl, preferred C
2-C
20Alkyl, they have at least one end carboxy CO OR, and are different from the group of formula (VIII);
R
4, be same to each other or different to each other=methyl, propyl group or butyl;
R
5, be same to each other or different to each other=linearity or branched-alkyl, preferred C
6-C
40Alkyl and more preferably C also
6-C
20Alkyl;
R is same to each other or different to each other ,=H, and positively charged ion or protecting group are preferably selected from alkyl and/or alkyl silane;
0＜r
ⅰ, preferred 1≤r
ⅰ≤ 100, and more preferably 1≤r also
ⅰ≤ 50,
0≤r
ⅱ〉=0, preferred 0≤r
ⅱ≤ 500, and more preferably 50≤r also
ⅱ≤ 300,
0≤r
ⅲ, preferred 2≤r
ⅲ≤ 100, and more preferably 5≤r also
ⅲ≤ 50,
0≤r
ⅳ, preferred 0≤r
ⅳ≤ 100, and more preferably 0≤r also
ⅳ≤ 50,
0≤r
ⅴ〉=0, preferred 0≤r
ⅴ≤ 100, and more preferably 0≤r also
ⅴ≤ 50,
0≤r
ⅵ, preferred 0＞r
ⅵ≤≤100, and more preferably 0≤r also
ⅵ≤ 50.
According to each composition among the claim 1-6, be characterised in that 8, POS A comprises the CFa=oxazolidine and is that crosslinking agent B is:
The diacid of formula VI or derivative under the △:
ROOC-X
1-COOR, wherein X
1Be the hydro carbons group, preferred C
1-C
12Alkylidene group,
Δ and/or per molecule carry at least two CFb=-COOR and choose one or more perhalogenation, preferred perfluorination Gf grafting body wantonly, and the latter's structural formula is equal to the structure formula I that provides in claim 1.
9, according to each composition among the claim 1-8, be characterised in that, POS A is obtained by the POS that selects from poly-alkyl hydrogen siloxanes, thereafter in the presence of the hydrosilylation metal of significant quantity, preferred platinum type catalyzer, SiH unit to the small part of these POS is used for the hydrosilylation of the olefinic precursor of following group:
All or part of Gf grafting body, and if suitable, Gfh, Gh or Gf ' grafting body,
The optional group that carries at least one COOR base or can be replaced by at least one COOR base,
Optional carries at least one oxazolidinyl or can extremely be lacked the group that an oxazolidinyl replaces,
The optional group that carries at least one crosslinking functionality CFa=alkenyl, preferred vinyl, the perhaps group that can be replaced by at least one crosslinking functionality CFa=alkenyl, preferred vinyl,
And it is optional as defined R in claim 4 and 7
3Or R
5Alkyl
10, according to each composition among the claim 1-9, be characterised in that, crosslinking agent B is obtained by the POS that is selected from poly-alkyl hydrogen siloxanes, preferred polymethyl hydrogen siloxane, thereafter in the presence of the hydrosilylation metal of significant quantity, preferred platinum type catalyzer, SiH unit to the small part of these POS is used for the hydrosilylation of the olefinic precursor of following group:
-carry at least one crosslinking functionality CFb=alkenyl, perhaps can be by the group of at least one crosslinking functionality CFb=alkenyl, preferred vinyl replacement;
-and/or the group that carries at least one crosslinking functionality CFb=COOR or can be replaced by at least one CFb=COOR of functional group;
-and/or the group that carries at least one crosslinking functionality CFb=oxazolidine or can be replaced by at least one CFb=of functional group oxazolidine;
-all or part of Gf grafting body, and if suitable, Gfh, Gh or Gf ' grafting body;
-and optional as defined R in claim 4 and 7
3Or R
5Alkyl.
11, cross-linked composition is characterised in that it is obtained by each composition among the claim 1-10.
12, according to the component of the composition of claim 1, be characterised in that it is selected from:
-1-per molecule carries the POS A of one or more Gf grafting bodies and one or more crosslinking functionality CFa=oxazolidines;
-2-per molecule carries the POSA of one or more Gf grafting bodies and one or more Gh grafting bodies;
-3-per molecule carries the POSA of one or more Gf grafting bodies and one or more Gfh grafting bodies;
-4-per molecule carries the POS A of one or more Gf grafting bodies and one or more Gh grafting body and one or more Gfh grafting bodies;
-5-per molecule carries one or more Gf grafting bodies, one or more crosslinking functionality CFa=oxazolidines and/or COOR, and the optional one or more Gh and/or the POSA of Gfh grafting body.
13, and/or the method for oleophobic coating and/or method that on base material enforcement hydrophobic and/or oleophobic flood hydrophobic in preparation on the base material are characterised in that it mainly is:
preparation and/or the composition that uses among the claim 1-11 each or obtain by the bicomponent system of claim 14,
is on the said composition paint base material, so that obtain film and/or so that the dipping base material,
chooses evaporating solvent wantonly, if composition provides with the solution form,
manages to make condition, especially the temperature and pressure condition is enough to take place gratifying crosslinked.
14, the two-pack precursor systems of each silicone composition among the claim 1-11 is characterised in that, it comprises two unitary part 1 and 2 that will mix to form composition, this part 1 or a kind of POS A or crosslinking agent B and catalyzer C of comprising of 2.
15, coating precursor, coating, lacquer or calendering agent are characterised in that, they comprise among the claim 1-11 each composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9808485A FR2780407B1 (en) | 1998-06-30 | 1998-06-30 | CROSSLINKABLE SILICONE COMPOSITION FOR USE, IN PARTICULAR FOR THE PRODUCTION OF HYDROPHOBIC AND / OR OLEOPHOBIC COATING AND / OR IMPREGNATION, WITH LOW SURFACE ENERGY |
| FR98/08485 | 1998-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1310749A true CN1310749A (en) | 2001-08-29 |
Family
ID=9528190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99808999A Pending CN1310749A (en) | 1998-06-30 | 1999-06-24 | Crosslinkable silicone composition useful, in particular for producing water-repellent and/or oil-repellent coating and/or impregnation with low surface energy |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1093497A1 (en) |
| JP (1) | JP2002519470A (en) |
| CN (1) | CN1310749A (en) |
| AU (1) | AU4271499A (en) |
| BR (1) | BR9912505A (en) |
| CA (1) | CA2335926A1 (en) |
| FR (1) | FR2780407B1 (en) |
| TR (1) | TR200100347T2 (en) |
| WO (1) | WO2000000559A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956323A (en) * | 2010-10-20 | 2011-01-26 | 李竹君 | Preparation method for hydrophobic fabrics |
| CN102500241A (en) * | 2011-11-22 | 2012-06-20 | 南京工业大学 | Preparation method of anti-pollution pervaporation membrane |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3719261A1 (en) * | 1987-06-10 | 1988-12-22 | Klasen Geb Tesdorff Renate | ROAD MARKING |
| GB0112525D0 (en) * | 2001-05-23 | 2001-07-11 | Dow Corning | Polysiloxanes and gels and pastes containing them |
| US6951667B2 (en) * | 2002-01-08 | 2005-10-04 | Xerox Corporation | Fuser member coating composition and processes for providing elastomeric surfaces thereon |
| US7638589B2 (en) | 2005-12-19 | 2009-12-29 | E. I. Du Pont De Nemours And Company | Triazole-containing fluorocarbon-grafted polysiloxanes |
| KR101297368B1 (en) * | 2011-03-04 | 2013-08-19 | 부산대학교 산학협력단 | Hyhobic polymetylhydrosiloxane based hybrid for coating applications |
| EP3113757B1 (en) * | 2014-04-28 | 2020-12-16 | Dow Silicones Corporation | Cross-linked composition and cosmetic composition comprising the same |
| CN103992043B (en) * | 2014-05-15 | 2016-08-24 | 奇瑞汽车股份有限公司 | A kind of preparation method of water-repelling agent |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8621472D0 (en) * | 1986-09-05 | 1986-10-15 | Int Paint Plc | Coating compositions |
| JPH02255881A (en) * | 1988-12-28 | 1990-10-16 | Nippon Paint Co Ltd | Curable composition |
| JPH0647652B2 (en) * | 1989-04-17 | 1994-06-22 | 信越化学工業株式会社 | Curable silicone composition |
| JPH0383990A (en) * | 1989-08-28 | 1991-04-09 | Nippon Paint Co Ltd | Oxazolidine compound |
| JP3072120B2 (en) * | 1990-08-24 | 2000-07-31 | 東レ・ダウコーニング・シリコーン株式会社 | Water and oil repellent treatment agent |
| JPH05301963A (en) * | 1992-04-27 | 1993-11-16 | Toray Dow Corning Silicone Co Ltd | Fluorosilicone polymer and curable fluorosilcone polymer composition |
| FR2737215B1 (en) * | 1995-07-25 | 1997-10-17 | Rhone Poulenc Chimie | PERHALOGENATED POLYORGANOSILOXANES AND PROCESSES FOR OBTAINING SAME |
-
1998
- 1998-06-30 FR FR9808485A patent/FR2780407B1/en not_active Expired - Lifetime
-
1999
- 1999-06-24 CA CA002335926A patent/CA2335926A1/en not_active Abandoned
- 1999-06-24 JP JP2000557314A patent/JP2002519470A/en not_active Withdrawn
- 1999-06-24 CN CN99808999A patent/CN1310749A/en active Pending
- 1999-06-24 BR BR9912505-6A patent/BR9912505A/en not_active Application Discontinuation
- 1999-06-24 AU AU42714/99A patent/AU4271499A/en not_active Abandoned
- 1999-06-24 EP EP99957640A patent/EP1093497A1/en not_active Withdrawn
- 1999-06-24 TR TR2001/00347T patent/TR200100347T2/en unknown
- 1999-06-24 WO PCT/FR1999/001516 patent/WO2000000559A1/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956323A (en) * | 2010-10-20 | 2011-01-26 | 李竹君 | Preparation method for hydrophobic fabrics |
| CN102500241A (en) * | 2011-11-22 | 2012-06-20 | 南京工业大学 | Preparation method of anti-pollution pervaporation membrane |
| CN102500241B (en) * | 2011-11-22 | 2014-02-26 | 南京工业大学 | Preparation method of anti-pollution pervaporation membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2780407A1 (en) | 1999-12-31 |
| AU4271499A (en) | 2000-01-17 |
| BR9912505A (en) | 2001-05-02 |
| FR2780407B1 (en) | 2000-09-15 |
| EP1093497A1 (en) | 2001-04-25 |
| WO2000000559A1 (en) | 2000-01-06 |
| CA2335926A1 (en) | 2000-01-06 |
| JP2002519470A (en) | 2002-07-02 |
| TR200100347T2 (en) | 2001-10-22 |
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