CN101534786A - Polysiloxane based in situ polymer blends-compositions, articles and methods of preparation thereof - Google Patents

Abstract

Stable blend compositions composed of mixtures of polysiloxane(s) and organic polymer(s) are claimed. These polymer blends are white and opaque indicating the presence of phase separation on the micron scale. Such blends can be stored for long periods of time (years) without exhibiting evidence of macroscopic phase separation. These stable blends are achieved without substantial crosslinking as evidenced by the fact that the polymer blend is readily dissolved in a suitable organic solvent for molecular weight characterization. The stable blends of the present invention have particular utility as fouling release coatings for marine applications.

Description

In-situ polymerization polymer blends thing-its constituent, article and preparation method based on polysiloxanes

U.S. patent application case

The novel patent application case that U.S.C.35 bar § 111 (a) is proposed is abideed by by this U.S. patent application case system.

The related U.S. patent application case

This U.S. patent application case system is relevant for the U.S. Provisional Patent Application case the 60/832nd proposition on July 25 in 2006, No. 971, and advocate the priority of this case, wherein, the name of this temporary patent application case is called " based on the in-situ polymerization polymer blends thing (Polysiloxane-Based In-situ Polymer Blends) of polysiloxanes ".This U.S. patent application case is also relevant for the U.S. Provisional Patent Application case the 60/832nd proposition on July 25 in 2006, No. 972, and advocate the priority of this case, wherein, the name of this temporary patent application case is called " based on the preparation method (Method for PreparingPolysiloxane-Based In-situ Polymer Blends) of the in-situ polymerization polymer blends thing of polysiloxanes ".

The incorporated by reference document

Each application case that Ben Neiwen quoted and patent case and the file of in each application case and patent case, being quoted from or (be included in during each has checked and approved the program of patent with reference to case; " application case reference document "), corresponding with any one of these application cases and patent case and/or state PCT and the foreign application case or the patent case of its priority, and the file of in each application case reference document, quoting from or addressing, all incorporate this paper into way of reference.Haply, file and be set forth in interior literary composition with way of reference with reference to case system, may be set forth in the list of references forms or be set forth in of literary composition itself; Each file of being quoted from each file or the list of references quoted with reference to case (" list of references that this paper quotes ") and each this paper or all incorporate this paper into way of reference with reference to case (comprise and appoint a description of closing manufacturer, indication etc.).

Background technology

The object that is immersed in fresh water or sea water below such as boats and ships, naval vessels, buoy, water introduction tube and water discharge spout etc. all can be subjected to the invasion of aquatile such as barnacle class, mussel class, pipe Vermes and algae.The existence of " ocean dirty (marine fouling) " causes serious problems, comprises the forfeiture aesthetic appearance, reduces operating efficiency etc.Therefore, normal traditionally the use prevents that dirty (antifouling) coating applies the surface of these objects.

To so far, these anti-dirty coating are blending toxicity tin compound or toxicity copper compound usually.Because environmental issue, (tin-based coating) is in fact disabled for tinbase coating.With copper is that based coating is widely used at present, but effect is good not as stannum, and service life is shorter, and because environmental protection is considered, is under pressure gradually in the use.

In recent years study polysiloxane-based (polysiloxane) or silicone (silicone), particularly gather (dimethyl siloxane) (PDMS), with the anti-dirty coating as maritime applications, or more suitable name is called the dirty release coat.The distinctive releasing properties of these materials can reduce to minimum with dirty under the situation of not using toxic metal.Some dirty control coating based on poly-silica elastomer have been known since the 1970's are early stage.For example, the prescription system based on poly-silica is disclosed in United States Patent (USP) case the 4th, 025,693; 4,080,190; 4,227, No. 929 etc.The Japanese patent application case also discloses a kind of silicone and anti-dirty coating with mixture of holding the poly-silicone rubber of last hydroxyl and so on oligomer of using for No. 96830/76 in addition.Unfortunately, silicone since durability issues and be difficult between poly-silica layer and base material to form the problem of brute force bonding hindered in the use.

The present invention's explanation contains the preparation of the stable polymer blend of silicone.These admixtures can be used for forming the coating with good plate out resistance matter, more tough and more durable more than poly-silica release coat such as RTV11, RTV11 is for gathering the poly-silica elastomer with independent dibutyltin dilaurate catalyst of silica company (GE Silicones) available from New York watt Buddhist GE.So, these admixtures can be used as tough anti-dirty top coat, or these admixtures can be used as bonding coat or the binding coating is extremely gathered the silica top coat to bind, and the toughness of improvement and the anti-adhesion of enhancing are provided.

Summary of the invention

In an aspect, the present invention is contained a kind of dirty that comprises at least a polysiloxane polymer and a kind of organic polymer and is discharged binding coated polymeric admixture (fouling release tiecoat polymer blend), wherein, this organic polymer is made up of the monomer that aggregates into monochain polymer, and wherein this organic polymer does not comprise crosslinked polyfunctional monomer (crosslinkingmultifunctional monomer).

In another specific embodiment, this binding coated polymeric fusion system comprises and has typical weight average molecular weight and serve as reasons about 50,000 to about 500,000 and better for about 120,000 to about 160,000 polymer.

In another specific embodiment, the polysiloxane polymer of this binding coated polymeric admixture has the following formula repetitive

R wherein ₁And R ₂System is C1-C3 alkyl that is substituted or is unsubstituted or the aryl that is substituted or is unsubstituted respectively independently, wherein if these substituent groups are other group that is selected from cyano group, halogen or another binding functionality (linking functionality) is not provided when existing.

In another specific embodiment again, at least one end of this polysiloxane polymer has terminal-reactive group (terminal reactive group); Preferable this terminal-reactive group is hydroxyl, alkoxyl, aryloxy group, amino, amide groups, halogen or vinyl; Better this polysiloxane polymer is through hydroxy-end capped dimethyl siloxane (hydroxyl terminateddimethylsiloxane).

In another specific embodiment, this binding coated polymeric admixture further comprises the organic monomer that can carry out Raolical polymerizable under the free radical existence that original position produced; Be preferably monoene and belong to monomer; Be more preferred from vinyl monomer, propylene monomer, butene monomers, Vinyl Chloride Monomer, fluoride monomers, the perfluoroalkyl acrylate esters, vinyl acetate monomer, styrene monomer, the styrene monomer that ring is substituted, the ethenyl pyrrolidone monomer, the vinyl naphthalene monomer, N-VCz monomer (N-vinylcabazole monomers), the N-vinylpyrrolidone monomer, acrylic monomers, methacrylic acid monomer, acrylonitrile monemer, the metering system nitrile monomer, vinylidene fluoride monomers, vinylidene chloride monomer, the acrylic aldehyde monomer, the methylacrolein monomer, the maleic anhydride monomer, the stilbene monomer, the indenes monomer, the maleic acid monomer, or fumaric acid monomer.

In another specific embodiment again, this organic polymer is styrene, butyl acrylate, other alkyl acrylate esters or its mixture.

In another specific embodiment again, the free base system of this original position generation causes by adding benzoyl peroxide or di-t-butyl peroxide, cumyl hydroperoxide and tert-butyl hydroperoxide.

In another aspect of the present invention, this binding coated polymeric admixture comprises can be further through atomizing and extremely surperficial through spray application.In another aspect again, this binding coated polymeric admixture further comprises the siloxanes fluids of the sprayability that can improve this admixture.

In another specific embodiment again, this binding coated polymeric further can form tight covalent bond matrix (matrix) with its surface of using.

In another aspect of the present invention, this binding coated polymeric admixture has viscosity in the time of about 25 ℃ be about 40,000 to about 400,000 centipoises (centipoise); It is preferable that to have viscosity in the time of 25 ℃ be about 80,000 to about 250,000 centipoises; And better to have viscosity in the time of 25 ℃ be about 95,000 to about 150,000 centipoises.

In another aspect of the present invention, face coat has viscosity and is about 8,000 to about 18,000 centipoises in the time of 25 ℃; It is preferable that to have viscosity in the time of 25 ℃ be about 9,000 to about 15,000 centipoises; It is better that to have viscosity in the time of 25 ℃ be about 10,000 to about 12,000 centipoises.

In the present invention's another aspect, this binding coated polymeric admixture comprises firming agent again, this firming agent is non-to be tin-based catalyst, be preferably N, N '; N " the catalyst of-thricyclohexyl-1-methyl-monosilane triamine, platino plinth or Ti-base catalyst or other non-tin-based catalyst or organic group catalyst, for example cross-linking agent CA-40 (Brunswick chemical company (Wacker Chemie)).

In another aspect, a kind of dirty delivery system is contained in the present invention, this system comprises the anticorrosion epoxy layer (epoxy layer) that is applied to base material, be applied to the binding coated polymeric admixture as described herein of this epoxy layer, and the poly-silica face coat that is applied to this binding coated polymeric admixture, wherein this epoxy layer comprises the silane coupler with primary amine or secondary amine.

In some specific embodiments of dirty delivery system, this binding coated polymeric admixture further comprises siloxanes fluids.

In another specific embodiment of dirty delivery system, before the applying corrosion protection epoxy layer, this base material system is through cleaning; Preferable before the applying corrosion protection epoxy layer, this base material system is through blasting treatment (grit-blasted).

In other specific embodiment of dirty delivery system, this poly-silica face coat further comprises release oil (release oil).

In another aspect, a kind of dirty release polymers system is contained in the present invention, this system comprises the first anticorrosion epoxy layer that is applied to base material, be applied to the second anticorrosion epoxy layer of this first anticorrosion epoxy layer, be applied to the binding coated polymeric admixture as described herein of this second anticorrosion epoxy layer, and the poly-silica face coat that is applied to this binding coated polymeric admixture, wherein this second anticorrosion epoxy layer further comprises the silane coupler with primary amine class.

In some specific embodiments of dirty delivery system, this binding coated polymeric admixture further comprises siloxanes fluids.

In another specific embodiment of dirty delivery system, before the applying corrosion protection epoxy layer, this base material system is through cleaning; Preferable before the applying corrosion protection epoxy layer, this base material system is through blasting treatment.

In other specific embodiment again of dirty delivery system, poly-silica face coat further comprises release oil.

In another aspect, a kind of dirty release polymers system is contained in the present invention, and this system comprises the anticorrosion epoxy layer that is applied to base material; Be applied to the releasing layer of this anticorrosion epoxy layer, this releasing layer comprises poly-silica face coat admixture; And binding coated polymeric admixture as described herein, wherein this anticorrosion epoxy layer further comprises the silane coupler with primary amine class.

In some specific embodiments of dirty delivery system, link the coated polymeric admixture and further comprise siloxanes fluids.

In another specific embodiment of dirty delivery system, before the applying corrosion protection epoxy layer, this base material system is through cleaning; Preferable before the applying corrosion protection epoxy layer, this base material system is through blasting treatment.

In other specific embodiment again of dirty delivery system, this poly-silica face coat further comprises release oil.

In other specific embodiment of dirty delivery system, the single administration layer can be reached and link the two function of coating and dirty releasing layer.This kind single administration layer is called single worker's layer (monoplex), be blending link coating admixture material and top coat material both.The content of the binding coating admixture resin in single worker's layer is 5% to 99%, or is preferably 50% to 99%, and the best is 75% to 95%.On the contrary, the content of the top coat resin of blending in single worker's layer is 1% to 95%, or preferable 1% to 50%, and best 5% to 25%.

In another aspect, a kind of method of preparation constituent is contained in the present invention, this method comprises makes organopolysiloxane contact with a kind of organic polymer, and wherein this organic polymer is made up of the monomer that aggregates into monochain polymer, and wherein this organic polymer does not comprise crosslinked polyfunctional monomer.

In a specific embodiment, this method further comprises makes radical initiator contact with organopolysiloxane and/or organic monomer.

In some specific embodiments, this radical initiator is azo group-two-alkyl nitrile (azo-bis-alkylnitrile); Be preferably AIBN.In other specific embodiment, this radical initiator is a peroxide; Be preferably benzoyl peroxide, di-t-butyl peroxide, cumyl hydroperoxide or tert-butyl hydroperoxide.

In another specific embodiment, polysiloxane polymer has the following formula repetitive

R wherein ₁And R ₂System is the C1-C3 alkyl that is substituted or is unsubstituted or the aryl that is substituted or is unsubstituted respectively independently, and wherein if these substituent groups are other group that is selected from cyano group, halogen or another binding functionality is not provided when existing.

In another specific embodiment, at least one end of polysiloxane polymer has the terminal-reactive group; Preferable this terminal-reactive group is hydroxyl, alkoxyl, aryloxy group, amino, amide groups, halogen or vinyl; Better this polysiloxane polymer is through hydroxy-end capped polydimethylsiloxane.In other specific embodiment, this has viscosity for being lower than 100 centistokes (centistokes) through hydroxy-end capped polydimethylsiloxane during in 25 ℃.In other specific embodiment, this has viscosity through hydroxy-end capped polydimethylsiloxane during in 25 ℃ is 2000 to 8000 centistokes.Again, in other specific embodiment, this has viscosity through hydroxy-end capped polydimethylsiloxane during in 25 ℃ is 10,000 to 50,000 centistokes.

In another specific embodiment, this binding coated polymeric admixture further comprises the organic monomer that can carry out Raolical polymerizable under the free radical existence that original position produced; Be preferably monoene and belong to monomer; Be more preferred from vinyl monomer, propylene monomer, butene monomers, Vinyl Chloride Monomer, fluoride monomers, the perfluoroalkyl acrylate esters, vinyl acetate monomer, styrene monomer, the styrene monomer that ring is substituted, the ethenyl pyrrolidone monomer, the vinyl naphthalene monomer, N-VCz monomer, the N-vinylpyrrolidone monomer, acrylic monomers, methacrylic acid monomer, acrylonitrile monemer, the metering system nitrile monomer, vinylidene fluoride monomers, vinylidene chloride monomer, the acrylic aldehyde monomer, the methylacrolein monomer, the maleic anhydride monomer, the stilbene monomer, the indenes monomer, the maleic acid monomer, or fumaric acid monomer.

In another specific embodiment again, this organic polymer is styrene, butyl acrylate, other alkyl acrylate esters or its mixture.

In another specific embodiment, the polymer of this method has typical weight average molecular weight and serves as reasons about 80,000 to about 250,000, and better for about 120,000 to about 160,000.

Again in another specific embodiment, this method lies in the atmosphere of nitrogen sprinkling carries out.

In another specific embodiment, this method further comprises with difunctionality mooring agent (bifunctional tethering agent) and contacts; Preferable this difunctionality mooring agent comprises primary amine functional group and/or secondary amine functional group and class siloxanes functional group (siloxane-like functionality).

In another specific embodiment, the initiator of this method system is imported into organopolysiloxane and/or organic monomer with multi-agent.In another specific embodiment, the initiator of this method system is imported into organopolysiloxane and/or organic monomer with single agent.

In another specific embodiment, this method further comprises with firming agent and contacts, and wherein this firming agent is non-is tin-based catalyst.

Again in another specific embodiment, during polyreaction in order to form expection shear rate (shear rate) canonical system that links the coated polymeric admixture between by about 10 minutes ^-1(min ^-1) to about 1,500min ^-1, and better for about 100min ^-1To about 1,000min ^-1Scope.

In another specific embodiment, the product of this method manufacturing of mat does not have the polymer morphology of elongated shape microphase-separated (elongated microphase separated polymermorphology) again.

In another specific embodiment again, this method further comprises interpolation water.

In another aspect, the method that a kind of preparation has the surface of dirty releasing properties is contained in the present invention, comprises to use dirty release binding coated polymeric admixture as described herein to the surface.

In another aspect, the method that a kind of preparation has the surface of dirty releasing properties is contained in the present invention, comprises to use dirty delivery system as described herein to the surface.

In one of the method for preparing surface specific embodiment, this surface is for comprising the base material of anticorrosion epoxide (epoxy).

In another specific embodiment of the method for preparing the surface, this method further comprises the application surface coating; Be preferably poly-silica face coat.

In another aspect, the present invention is contained a kind of by making the product of the method manufacturing that organopolysiloxane contacts with a kind of organic polymer, wherein this organic polymer is made up of the monomer that aggregates into monochain polymer, and wherein this organic polymer does not comprise crosslinked polyfunctional monomer.

In a specific embodiment, the manufacture method of this product system further comprises makes radical initiator contact with organopolysiloxane and/or organic monomer.In another specific embodiment, in the manufacture method of this product, this contact lies in the atmosphere of nitrogen sprinkling to be carried out.

In another specific embodiment again, the manufacture method of this product system further comprises interpolation water.

Description of drawings

Fig. 1 shows the sketch map of the duplexing dirty delivery system that comprises first and second anticorrosion epoxy layer, and this second epoxy layer is coupled to and links the coated polymeric admixture, should link the coated polymeric admixture then and apply through poly-silica face coat.

Fig. 2 shows the sketch map of the duplexing dirty delivery system that comprises simple layer, and wherein this corrosion-resistant coating is coupled to and links the coated polymeric admixture, should link the coated polymeric admixture then and apply through poly-silica face coat.

Fig. 3 shows the base material of handling coating with known poly-silica, with respect to how much patterns of disbonded test of the base material that gathers the silica surface-coated with duplex.

The specific embodiment

Definition

Be easier to understand the present invention for making, at first be with some term definitions and gather in herein in the hope of convenient.Other definition system comes across literary composition in the whole case.

In this disclosure, " comprising ", " containing " reach the definition that speech such as " having " has defined in united states patent law, and can represent " comprising " etc.; " mainly by ... form " or equally also have " the main composition " definition of defined in united states patent law, this term is open, allow to have contained scope with epigenesist, as long as the basic or novel characteristics of contained scope can be owing to contained scope change with existing of epigenesist, but eliminating prior art specific embodiment.

As used herein, " anti--dirty ", " anti-dirty ", " dirty release ", " release of dirty thing " reach system such as " release of dirty organism " speech and are used interchangeably, and being used for expression removes or prevents microorganism, plant, Zao class and animal on the structure of submergence, particularly the method gathered of the non-expectation on shell.

" dirty discharge link coated polymeric admixture " or " linking the coated polymeric admixture " waits speech to mean can be bonded to base material or other surperficial and the polymer blend of toughness and/or rigidity is provided, when being exposed to ocean dirty material, it can hinder ocean dirty material combination again and/or prevent gathering of these ocean dirty materials.This paper uses it " dirty delivery system " speech to mean the surface that has the dirty releasing properties with multiple coating.These examples comprise but non-being limited to: first and second anticorrosion epoxy layer, this second epoxy layer are coupled to and link the coated polymeric admixture, and this links the coated polymeric admixture and is covered through face coat; Epoxide coating agent and the epoxide barrier that comprises mooring agent, binding coated polymeric admixture and face coat; Or comprise the mooring agent, link the epoxide barrier of coated polymeric admixture and face coat.

" crosslinked polyfunctional monomer " speech means when the fashionable monomer that forms the cross linked polymer chain of homopolymerization.

" halogen " speech means fluorine, chlorine, bromine or iodine.

As used herein, " alkyl " speech means straight chain or the branched chain alkyl that contains 1 to 50 carbon atom.The example of alkyl comprises but non-methyl, ethyl, n-pro-pyl, isopropyl, tributyl, and the n-pentyl of being limited to.Alkyl can optionally replace through one or more substituent groups.

" C1-C3 alkyl " speech means and only contains carbon atom and hydrogen atom, has 1 to 3 carbon atom, and be to be attached to the straight chain of remainder of molecule or the hydrocarbon chain base of branched chain by singly-bound, for example methyl, ethyl, n-pro-pyl, and 1-Methylethyl (isopropyl).

" aryl " speech means hydrocarbon monocycle, bicyclo-or tricyclic aromatic ring system.Aryl can optionally replace through one or more substituent groups.In a specific embodiment, 0,1,2,3,4,5 or 6 atom of each ring of aryl can be substituted base and replace.The example of aryl comprises phenyl, naphthyl, anthryl, fluorenyl, indenyl, azulene base etc.In addition, " aryl " speech means that wherein at least one ring is the monocyclic, bicyclic or tricyclic bridge joint ring system of hydrocarbon of aromatic rings.

" alkoxyl " speech means-the O-alkyl." aryloxy group " speech means-the O-aryl." amide groups " is-C (O) NH ₂

This paper uses it " substituent group " or " being substituted " to be shown in the last hydrogen group system of chemical compound or group (such as alkyl, thiazolinyl, alkynyl, stretch alkyl, aryl, aralkyl, heteroaryl, heteroarylalkyl, cycloalkyl, cyclic group, Heterocyclylalkyl or heterocyclic radical) anyly to be desired group displacement with what can not cause harmful effect in fact to the stability of chemical compound.The example of substituent group comprises but non-being limited to, halogen (F, Cl, Br or I), hydroxyl, amino, alkyl amine group, arylamine group, dialkyl amino, the diaryl amido, the alkylaryl amido, cyano group, nitro, sulfydryl, sulfenyl, imido grpup, the first anilide, the amine formamido, amido first anilide, carboxyl, ghiourea group, the sulfur cyanato-, the sulfonic acid amides base, sulphur anilide alkyl, sulphur anilide aryl, alkyl, thiazolinyl, alkoxyl, the sulfydryl alkoxyl, aryl, heteroaryl, cyclic group, heterocyclic radical, wherein alkyl, thiazolinyl, alkoxyl, alkoxyalkyl, aryl, heteroaryl, cyclic group, and the heterocycle base system is optionally through alkyl, aryl, heteroaryl, halogen, hydroxyl, amino, sulfydryl, cyano group, nitro, ketone group (=O), the thioketone base (=S), or imido grpup (=NR) replace.

" terminal-reactive group " speech means the group that is bonded to the polysiloxane polymer end, and it can further produce chemical reaction with another chemical compound or contiguous reactive group.The terminal-reactive group comprises but non-being limited to, hydroxyl, alkoxyl, aryloxy group, amino, amide groups, halogen or vinyl.

A speech means the polymer that is formed by organic monomer " to carry out the organic monomer of Raolical polymerizable under can existing in the free radical of original position generation ", these organic monomers can form polymer by the radical reaction that is produced with monomer itself, but not form polymer by producing the agent reaction with the external freedom base.

" monoene belongs to (mono-olefinic) ", a speech meant the monomer that only has a reactive carbon-to-carbon double bond.Among the present invention, but a reactive carbon-to-carbon double bond is owing to bond to two a contiguous monomer, so the difunctionality of being actually.Monoene belongs to that monomer comprises but the non-vinyl monomer that is limited to, propylene monomer, butene monomers, Vinyl Chloride Monomer, fluoride monomers, the perfluoroalkyl acrylate esters, vinyl acetate monomer, styrene monomer, the styrene monomer that ring is substituted, vinylpyridine alkane monomer, the vinyl naphthalene monomer, N-VCz monomer, the N-vinylpyrrolidone monomer, acrylic monomers, methacrylic acid monomer, acrylonitrile monemer, the metering system nitrile monomer, vinylidene fluoride monomers, vinylidene chloride monomer, the acrylic aldehyde monomer, the methylacrolein monomer, the maleic anhydride monomer, the stilbene monomer, the indenes monomer, the maleic acid monomer, or fumaric acid monomer.

" difunctionality mooring agent (bifunctional tethering agent) " speech means in order to form the chemical compound of molecule bridge between binding coating and epoxy layer by the covalency bond.In some specific embodiments, difunctionality mooring agent comprises one-level and/or secondary amine functional group and class siloxanes functional group's combination." class siloxanes functional group " speech typically means triethoxysilane and trimethoxy silane.

" elongated condition (morphology) " speech mean in be separated or the material of microphase-separated in, the morphological characteristic with bar-shaped or needle-like.

" siloxanes fluids " speech means fluent material or the free-flowing material based on poly-silica, when being added into polymer, can reduce the viscosity of this polymer, increase this polymer mat strong nozzle and be injected into the ability on surface, also can improve the dirty releasing properties simultaneously.Siloxanes fluids comprises but non-SF69 of being limited to and SF1147.

" firming agent " speech means can be by solidifying organic catalyst or organic catalyst or other material of this binding coating resin with holding last Si-OH radical reaction.Firming agent comprises but the non-N of being limited to, N ', N "-thricyclohexyl-1-methyl-monosilane triamine, tin-based catalyst, platinum based catalyst or other non-tin-based catalyst.

" anticorrosion epoxy layer " speech means thermosetting polymer; it is to solidify by epoxide functional base and amine functional group reaction; provide the corrosion protection effect to metal, concrete barrier and waterproof invasion barrier; and can further be used as the tackness of priming coat (primer) with improvement maritime affairs coating; especially the tackness of maritime affairs coating on the metal surface, the anticorrosive property of this metal surface (rust-preventing characteristic) is quite important.

" base material " reaches " surface " speech and is used interchangeably in this paper, and means kinds of surface, comprises but the non-ice removal that is limited to boats and ships, naval vessels, submarine, power plant, pipe of cement, plumbing drain and subterranean pipe line, lawn sprinkler systems and electric wire and windmill.These surfaces comprise maritime affairs environment and industrial environment, comprise the application of marine ship and power plant cooling water water inlet.Additional application comprises that the water from environment is used for industrial process.More particular words it, the surface comprises shell, outer driver, rudder and tab.These surfaces comprise but non-glass fibre, foamed glass fiber, timber, Wood shell, existing coating, steel, steel shell, aluminum and the metal spare part of being limited to comprises metal spare part under water.Other base material comprises building, roof, water purification system and desalination system.

" discharge oil " vocabulary shows a kind of material, when being blended into fluoropolymer resin or poly-silica surfacing, along with the process of time slowly diffuses out, or stays the surface, improves the dirty releasing properties of material by this.Discharge oil and comprise but non-being limited to, based on oils, SF1147, SF1154, DMSC 15 and the DBE 224 of the poly-silica of low-molecular-weight.

Also must understand the term that this paper uses, only be used to illustrate specific embodiment, but non-be intended to be used for the restriction.Odd number shape " ", " one " as description and claim use reach " being somebody's turn to do ", unless understand indication separately, otherwise comprise plural shape.So for example addressing " a victory peptide " comprises multiple victory peptide, addresses " spacing body " and comprises two or more spacing bodies.

Unless otherwise defined, otherwise all technology of this paper use and scientific terminology are all the identical definition of the general understanding of personage of field skill under the present invention of being familiar with.Under the situation of conflict, will be defined as the master with this case or its.All open cases described herein, patent application case, patent case and other list of references all are to incorporate this paper into way of reference.

Link the coating constituent

The present invention's binding coating constituent contains the monomer that can be grouped to monochain polymer and do not contain crosslinked polyfunctional monomer.This kind link coating for by polymer blend (the mat graft copolymer gives stabilization) but not simple graft polymers forms stabilize graft polymers and copolymer.

The present invention's binding coating had not had before the elongated condition (referring to for example US5,449,553 and US 5,593,732) of announcement once.The present invention's binding coating need not high shearing and obtains the high tenacity form, only needs enough shearings and reaches the homogenizing admixture of starting material and be used for polyreaction.In linking the coating composite, observe spherula particle shape (mat electron microscope observation), it can reach toughness certain degree or preferable degree, with in absorbing mechanical shock during the ship operation and under other abrasive environment, and the chemical bonded refractory between mat surface and binding coating (silicon, butyl acrylate and polystyrene-block copolymer), this toughness provided give face coat.This binding coating forms tight covalency matrix, provides toughness to give the silicon face coating, and does not reduce the dirty releasing properties of silicon top coat.Though it is impaired to understand bending mechanism or other dirty releasing mechanism of silicon top coat, but the victory peptide that animal discharged or other viscose to stick together character then impaired, so the decay of the bond between animal and surface, this bond may be solidified or be still uncured or be completely fixed.

The advantage that system had that links coating or adopt the present invention to link coating comprises dependable performance (when being applied to marine ship, but having excellent releasability and fuel saving); Owing to do not contain heavy metal and Biocide, so avirulence; Environmental safety (the waste material innocuousness, after removing by shell or other device, can allow to abandon be used for sanitary landfills); The releasing properties of excellence, but comprise that mat water sprays or self-cleaning removes dirty; Using fast (uses the no air-atomizing device of the poly-silica spraying of known utilization pipeline to use); And operation is gone up durable and layer adhesion.

Contain the mooring agent to form the anticorrosion epoxide coating of poly-silica to poly-silica bond

In other aspect of the present invention, the anticorrosion epoxy layer further comprises and has amine, for example the silane coupler of primary amine and/or secondary amine.The series of compounds that for example is called SCM 501C is added into epoxy layer (if use more than one deck epoxy layer, then SCM 501C being added into outermost layer or last applied layer).Referring to No. the 6th, 391,464, United States Patent (USP) case, title " epoxide coating and the surface (Epoxy Coatings and Surfaces CoatedTherewith) of using its coating ".The inventor finds that subsequently other several agents system sees through poly-silica to poly-silica (silicone-to-silocone) bond and improves this kind bonding, and can use more a spot of in fact material reagent.These novel agents comprise but non-being limited to: methyl amido propyl trimethoxy silicane, N-phenyl amido propyl trimethoxy silicane, and cyclohexyl amido propyl trimethoxy silicane.

Be applied to the surface

In some specific embodiments, link and to be coated with series of strata and to contain the siloxanes fluids blending and spray application is more prone in end product.This fluid can about 1% to about 30% the volume blending, be volume blending in some specific embodiments with 15%.

In a specific embodiment, binding is coated with series of strata and binds to face coat.The present invention's binding is coated with series of strata and binds to face coat by linking poly-between coating and face coat silica being crosslinked.The adherent covalent bond and very tough that is in the nature of this kind.The essential system of this kind bonding is with two-layer " integrating ".This kind " integrates " and makes toughness be passed to face coat by linking coating, allows whole system to reach the poly-unexistent toughness of silica coating of tradition.Face coat with this kind toughness provides than the poly-silica dirty releasable material of standard to have more elastic surface, keeps required dirty release characteristics simultaneously.This causes having the coating of excellent anti damageability, stripper-resistance and long-life.

In another specific embodiment, the invention provides a kind of binding coating of binding to epoxide.This binding is coated with series of strata with physical/mechanical means and chemical means and bind to epoxide.In addition, be to add difunctionality mooring agent, with a end amine functional group is arranged in molecule, in the other end class siloxanes functional group is arranged.Because silicone forms low-yield surface, therefore some siloxanes functional groups are increased to epoxide surface (being referred to as " oneself's assembling (self-assembling) " herein) and prepare to be coated with strata silica functional group with binding and produce bond.The amine official can base system bond to the epoxide functional base of epoxy layer, the poly-silica molecule of the surface layer oneself assembling of epoxy layer then bond gather the silica molecule to what link coating.The example of the difunctionality mooring agent that the present invention's expection is contained comprises SCM 501C, aminocarbonyl propyl triethoxysilane, aminocarbonyl propyl trimethoxy silane, methyl amido propyl trimethoxy silicane and cyclohexyl amido propyl trimethoxy silicane.See table 1.

The present invention further contemplates that contains a kind of binding coating of binding to epoxide, and this epoxide binds to base material; And a kind of bonding is to the top coat that links coating, and this binding is coated with series of strata and binds to epoxide, and this epoxidation system binds to base material.

Polysiloxane-based

This method use polysiloxane-based for meeting the polymer of following general formula repetitive

R wherein ₁And R ₂Be organic group, be in particular the alkyl that contains 1 to 3 carbon atom that can be substituted and can be identical or different, R under the simplest situation ₁And R ₂(promptly this polymer is poly-(dimethyl siloxane), PDMS) for methyl.R ₁Group and R ₂Group also can be other monovalent alkyl or aromatic yl group, maybe can be substituted, and for example, replaces with halogenic substituent or cyano group.The polysiloxane chain terminal has the terminal-reactive group, such as hydroxyl, alkoxyl, aryloxy group, amino, amide groups, halogen and vinyl.These end group systems are used for the fixing of polysiloxanes admixture or solidify, and/or the layer that is used for containing these structures binds to polysiloxanes top coat such as RTV11 or mooring agent.

The polysiloxane-based example of suitable end-functionalization that is used to form the present invention's stable polymer blend is through hydroxy-end capped siloxanes fluids.The viscosity of the fluid of use is between about 500cps to 50 in the time of 25 ℃, and 000cps is better for 1,000cps to 20, the scope of 000cps.

The monoene that can be any polymerizable through the monomer of radical polymerization belongs to monomer, such as ethylene, propylene, butylene, vinyl chloride, fluorothene, vinyl acetate, styrene, the phenylethylene that ring is substituted, vinylpyridine alkane, vinyl naphthalene, the N-VCz, the N-vinyl pyrrolidone, acrylic acid and methacrylic acid, its derivant comprises salt, esters and vinegar amine, acrylonitrile, methacrylonitrile, vinylidene, vinylidene chloride, acrylic aldehyde, methylacrolein, maleic anhydride, stilbene, indenes, maleic acid, and fumaric acid and derivant thereof, and conjugated diene such as butadiene and isoprene.In some specific embodiments, monomer can comprise the fluorinated analogues of monomer that preamble provides.Can there be independent polymerization down in these monomers in polysiloxanes and free radical source, or with two or more polymerization mixs.(weight that belongs to monomer in monoene is benchmark though multifunctional " cross-linking monomer " such as divinylbenzene, ethylene glycol dimethacrylate, trihydroxy propane trimethyl acrylic ester, tetramethylolmethane tetramethyl acrylate etc. can the indivisible the present invention of being used for, be lower than about 5%, and goodly be lower than 1%), but preferable system only uses the monomer that contains single kind of polymerizable olefinic group, in case gelatine allows in single batch radical initiator to be added into reactant with a cooking-pot type processing procedure (one-pot process) simultaneously.

The usage ratio of organopolysiloxane can change in broad limit range, but preferable system accounts for 25 weight % to 60 weight % of reactant.

The free radical initiating method can relate to common radical initiator, such as peroxide or azodiisobutyronitrile (AIBN), redox initiator, light trigger or by heat treatment or use free radiation to form free radical.Preferable initiator is the peroxide or the hydroperoxide kind of formula ROOR, ROOH and RCOOOR (wherein each R system is alkyl or aryl respectively independently), such as peroxidating benzene first vinegar, tributyl hydrogen peroxide, cumyl peroxide, benzylhydroperoxide tributyl etc., and AIBN.

The consumption typical case of radical initiator is a benchmark in the combination weight of organopolysiloxane and monomer, is the scope between 0.005% to 2%.Usually single initiator will be used, but also two or more initiators can be used.Usually initiator system adds when polymerization process begins with single batch, but also can add initiator by increment.

The temperature of Raolical polymerizable there is no particular restriction, but must change the proper temperature that makes selected decomposition of initiator with generation.Usually this temperature is the scope between 50 to 150 ℃.

The radical polymerization effect is preferable to lie in the noble gas, in the presence of the liquid of scope boiling that can in 50 to 150 ℃, carries out with alr mode.This kind liquid should have little chain transfer constant, limits the chemical reaction that its participation is taken place.Preferably,, can make water, even water does not dissolve polysiloxane-based or most of vinyl monomer for reaching this purpose.

Generally consider the stable polymer blend that needs crosslinked generation the " IPN formula polymer network " type.A stable vocabulary shows that polymer blend can not separate (de-mix) when storing.This has illustrated that Griffith (United States Patent (USP) case #5,449,553, its content is incorporated this paper into way of reference) uses " multifunctional (crosslinked) monomer " to prepare the similar releasing layer based on organopolysiloxane.In the present invention, the inventor can produce the polymer blend of Non-crosslinked, this fusion system gives stabilization by the graft copolymer of original position generation, and the graft copolymerization system of this original position generation is used as the admixture that the giant molecule interfacial agent is stablized the polymer of the polysiloxanes that is pre-formed and free-radical generating.In course of reaction, the free radical of generation can form by polysiloxane backbone and mat chain and be transferred to the graft copolymer that the side chain of polysiloxanes is formed, and wherein this side chain is the monomer through radical polymerization.But the product of free radical method is a polymer blend obviously, but not the graft copolymer that is separated, being separated and can demonstrate,proving by micron length scale (micrometer lemgth scale).The graft copolymerization system with number how meter level how meter level carries out microphase-separated to hundreds of, yet even polymer blend mat copolymer interfacial agent is stabilized, still represent micron order or bigger being separated.Opaque (white) outward appearance of the product of method disclosed herein provides the strong evidence of the polymer blend that forms the micron length scale, but therefore scattered light, but not form with graft copolymer as primary product.

The present invention exceed unexpected aspect for no crosslinked in the presence of, the long-term stability of novel polymeric admixture.The admixture of incompatible polymer is separated when storing, and it is invalid for stability usually to add block copolymer, and reason is that most of block copolymer that is added all forms the event of micelle (micelle).But in this example, the polymer blend that is produced can be dissolved in appropriate solvent fully, and expression does not have crosslinked, and has stored and do not have macroscopic more than the time in 2 years and be separated.

In a specific embodiment,, make that linking coating can provide mechanical strength and toughness to top coat owing to link chemical constitution, physical property and the form of coating.Link one of coating example and comprise that its randomcopolymer with n-butyl acrylate and styrene is partially grafted through hydroxy-end capped poly-(dimethyl siloxane).This kind structural formula shows below:

The illustration composition that links coating is the graft copolymer of grafted chain with polydimethylsiloxane (PDMS) main chain and poly-(styrene-common-n-butyl acrylate).These chemical species (species) provide the covalent bond between poly-silica functional group and styrene/acrylic based polymer group, and the effect of this graft copolymer is the heterogeneity in the stabilization binding coating and prevents to link heterogeneity in the coating and carry out macroscopic and be separated.Free hydroxyl group allow bond to poly-silicone rubber top coat and bond to the epoxide base material and bond to the mooring agent.In addition, free hydroxyl group allows and the silane coupler reaction, and silane coupler system is added into the epoxide protective finish, the epoxide priming coat is provided and links the brute force that is coated with interlayer and stick together.In addition, hydroxyl can react and binding to the cross-linked network of top coat.This kind bond allows the effective stress transfer of two interlayers and the efficient hardening of material.

The glass transition temperature T of poly-silicone rubber face coat _gSystem is preferably approximately-120 ℃ between about-150 ℃ to about-60 ℃ scope, forms soft face coat.But the present invention's binding coating contains the polymer based on styrene, such as poly-(styrene-be total to-n-butyl acrylate) copolymer, contain the 75wt% n-butyl acrylate of having an appointment, have quite high Tg, Tg system is preferably approximately-20 ℃ between making an appointment with-50 ℃ to about 0 ℃ scope.Higher glass transition temperature provides the toughness of material, allows the mechanical energy of absorbed impact and scraping.Bond to the poly-silica official who links coating can base system to greatest extent mechanical energy is passed to the binding coating by fragile top coat, make this mechanical energy be absorbed and dissipate in linking the coating place.

Monolayer dirty delivery system

Another aspect of the present invention discharges the simplex system (monoplex syatem) of constituent bonding to below base material (for example shell, tunnel, flexible pipe or pipeline surface, windmill surface, electric wire etc.) for the dirty that can promote this paper.This simplex system provides the bonding of the dirty release coat of enhancing to below base material (shell or feeding tunnel, power plant (utility intake tunnel) etc.).

Simplex system comprises unique composite and it " oneself's assembling " chemical property of face coat that links coating.This kind simplex system is when assembling and curing, the face coat of level and smooth and so on polysiloxanes RTV is provided, have very effective dirty releasing properties and ruggedness, this ruggedness is constituted by the binding coating chemical property that surface dirt discharges the chemical property below.

Simplex system is made up of the mixed layer of itself, has the coating of binding and top surface functional group, and it needs the single administration layer.In case when being applied to the surface, the top paint ingredient raises towards the surface, move towards the below epoxide and link coating composition.Even simplex system does not have the layer of clearly defining yet after self-assembly program has appearred in setting up period.The binding coating material is rich in the bottom, and coating material is rich at the top, changes in forming gradually from bottom to the top (oneself's assembling).This kind oneself assembling release coat allows easier using and easier maintenance.

In an aspect, simplex system comprises the anticorrosion epoxy layer that is applied to base material, and is applied to single worker's layer of this anticorrosion epoxy layer, and this anticorrosion epoxy layer comprises poly-silica coating material and the admixture that links coating material.In other aspect, the anticorrosion epoxy layer further comprises and has amine, such as the silane coupler of primary amine and secondary amine.For example, the material that is referred to as SCM 501C is to be added into epoxy layer (if use more than one deck epoxy layer, then SCM 501C system is added into outermost layer or last applied layer).Referring to No. the 6th, 391,464, United States Patent (USP) case, title " epoxide coating and the surface of using its coating ".The inventor finds some other reagent that improve this kind bonding subsequently, and can use more a spot of material reagent in fact.These novel agents comprise but non-being limited to: methyl amido propyl trimethoxy silicane, N-phenyl amido propyl trimethoxy silicane, and cyclohexyl amido propyl trimethoxy silicane.

In single worker's monolayer specific embodiment, blending in the admixture of face coat resin in the content of binding coating resin be 5% to 99%, or be preferably 50% to 99%, and the best is 75% to 95%.On the contrary, blending is 1% to 95% in the content of the face coat resin of fusion monolayer, or preferable 1% to 50%, and best 5% to 25%.In some specific embodiments, the content that links coating resin is about 85%, and the content of face coat is about 15%.

Can use to discharge the similar fashion of oily blending, will discharge oily blending in simplex system in the face coat of duplex system.Discharge oils and comprise SF1147, SF1154, DMSC15 and DBE224.The content that links coating material and coating material in mixing is benchmark, and discharging oils can be present in simplex system by 0.1% to 40% content.In some specific embodiments, be to add the sprayability that siloxanes fluids is assisted single worker's coating.In a specific embodiment, this siloxanes fluids system is selected from SF69 and SF1147 again.

In other aspect, link coated polymeric fusion system through upgrading with blending perfluorinate acrylate or perfluorinate methacrylate (or some other fluorinated monomers).Fluoropolymer is blended into and links coating and can improve the dirty releasing properties that links coating, and can allow to link coating and be used as face coat.

In addition, when the binding coating is applied to the glass fibre that is filled with glass, bind very tough.Need not coupling agent or surface treatment.This can be extended to other surface, for example polyurethane class or acrylic compounds etc.So the mixed layer of simplex system can be applied directly to base material under the situation that does not have the anticorrosion epoxy layer in some aspects.

Duplex dirty delivery system

Another aspect of the present invention discharges the duplex system (duplexsystem) of constituent bonding to below base material (shell, tunnel, flexible pipe or pipeline surface, windmill surface, electric wire etc.) for promoting dirty.This duplex system provides the dirty release coat to the enhanced bonding of below base material (shell or feeding tunnel, power plant etc.).

The series of compounds that is referred to as SCM 501C is added into second epoxy layer (if only use one deck epoxy layer, then SCM 501C system is added into this layer).Referring to No. the 6th, 391,464, United States Patent (USP) case, title " epoxide coating and the surface of using its coating ".The inventor finds some other reagent of improveing this kind bonding subsequently, can use more a small amount of in fact material reagent simultaneously.These novel agents comprise but non-methyl amido propyl trimethoxy silicane, N-phenyl amido propyl trimethoxy silicane, and the cyclohexyl amido propyl trimethoxy silicane of being limited to.

Because its difunctionality character, these reagent can unique machine be transmitted wave effect, and by this: 1. because silane-functional, reagent goes out fluid (bloom) to the epoxide surface, expose by this silane-functional base with the covalency bond to linking coating.In some specific embodiments, fluid goes out to lie in and betided epoxide afterwards, and wherein the demand of multifunctional reagent disappears.Epoxide is crosslinked.2. amine official energy covalency bond is to the epoxide functional base of epoxy layer.3. these reagent can be low to moderate 1% or exist and reach tight bonding with purgation concentration.The inventor obtain good result, but low concentration 1% can provide remarkable cost advantage with up to 30% concentration determination.

In addition, when linking coating and be applied to the glass fibre of filling or ethylene and be esters, bind very powerful through glass.Need not coupling agent, epoxy layer or surface treatment.This can be extended to other surface, for example polyurethane class or acrylic acid series class etc.So in some aspects, duplex system can directly be applied to base material under the situation that does not have the anticorrosion epoxy layer.In aforementioned will link coating directly bind to glass fibre or ethylene be under the situation of ester, link the tackness of coating and it binds to the tackness of second epoxy layer that contains the mooring agent good on an equal basis in the standard duplex system.

Duplex system is particularly suitable for being applied to small-sized pipeline, such as be used for irrigating, fire extinguishing, building water are carried, and the pipe of other similar applications; The bedding roof; Wind turbine/windmill; Aircraft; Circuit (high-tension electric wire, telephone wire, fax lead); Building and ground (salt corrosion inhibitor); Power plant efficiency; The dock surface; Oil derrick (dirty causes and the intensity of piling " excessively need be built (overbuild) "); " antifreeze " purposes comprises roof, windmill, aircraft wing, boats and ships and oil derrick fence, reaches no step surface (non-step surface) (no matter being to be used for antifreeze or snow defence).

In addition, duplexing dirty delivery system has powerful electrical insulation property and good heat resistance.Therefore this system also is suitable for insulation applications and fire-retardant purposes.

Object and coating

When viscosity drop to 10, during 000 to 12,000 centipoise, the poly-silica viscosity of face coat is facilitated the spray characteristics of improvement.In this range of viscosities, the constituent of this paper has the spray characteristics of being desired, but balance spraying ability and the coating layer thickness of being reached.In the difficult spraying of viscosity of 18,000 centipoise scopes, and need a large amount of solvents of interpolation to reach sprayability.When using a large amount of solvent, then be difficult to reach desired coating layer thickness (piling up (build)), and the solvent of extra interpolation can cause the problem of rules aspect owing to volatile organic solvent (VOC) content.The constituent of this paper provides enhanced ability that face coat is applied to large-scale plant (big ship and tunnel, power plant) and reaches desired thickness.This makes duplex system and simplex system very friendly to user, and application purpose is more consistent.

Repair the external member group

In some specific embodiments, binding coat system and dirty delivery system can be reparation external member group form to be provided, to be used for patchery or to repair previous set dirty delivery system.This kind external member group comprises:

One or more oceans epoxide corrosion barrier comprises but the non-A Molong of being limited to (Ameron) 235 (PPG company), A Molong 400 (PPG company), Xi Jia (SeaGuard) 5000 (snow grace William company (Sherwin Williams)), good 6000 (the snow grace William companies) in west;

One or more ocean epoxide, this oxycompound contains one or more mooring agent, comprises but the non-SCM of being limited to 501C or aminocarbonyl propyl triethoxysilane, aminocarbonyl propyl trimethoxy silane, methyl amido propyl trimethoxy silicane, cyclohexyl amido propyl trimethoxy silicane or N-phenyl amido propyl trimethoxy silicane;

Link coating, comprise for sprayability and dirty and discharge silicone such as SF 69 ((the Momentive Performance Materials of momentum performance materials company that uses, Inc.)), and stick together promoter GF-91 (momentum performance materials company), reach firming agent such as CA-40 (Brunswick chemical company); And

Face coat comprises the poly-silica that is used for dirty releasing properties and sprayability and discharges oil such as SF 1147 (momentum performance materials company), and firming agent such as DBT, dibutyl tin laurate (momentum performance materials company) or its equivalent.

The appropriate combination of the mooring agent of using in second epoxy layer comprises but non-ly is limited to following table 1 cited person.

Table 1: the example of the mooring agent that second epoxy layer is used

Numbering	Explanation
		1	Epoxide+30% SCM 501C
2	Epoxide+15% SCM 501C

3	Epoxide+5% SCM 501C
		4	Epoxide+6% aminocarbonyl propyl triethoxysilane
5	Epoxide+3% aminocarbonyl propyl triethoxysilane
		6	Epoxide+1% aminocarbonyl propyl triethoxysilane
7	Epoxide+6% aminocarbonyl propyl trimethoxy silane
		8	Epoxide+3% aminocarbonyl propyl trimethoxy silane
9	Epoxide+1% aminocarbonyl propyl trimethoxy silane
		10	Epoxide+6% methyl amido propyl trimethoxy silicane
11	Epoxide+3% methyl amido propyl trimethoxy silicane
		12	Epoxide+1% methyl amido propyl trimethoxy silicane
13	Epoxide+6% cyclohexyl amido propyl trimethoxy silicane
		14	Epoxide+3% cyclohexyl amido propyl trimethoxy silicane
15	Epoxide+1% cyclohexyl amido propyl trimethoxy silicane
		16	Epoxide+6%N-phenyl amido propyl trimethoxy silicane
17	Epoxide+3%N-phenyl amido propyl trimethoxy silicane
		18	Epoxide+1%N-phenyl amido propyl trimethoxy silicane

The present invention's reparation external member group can be used by any rational method.For following material such as steel, aluminum, other metal, glass fibre, wooden and other non-porous material or less porous material, can utilize following method.

At first, the clean surface, this surface is preferably the material that do not get loose and comes out.For taking off glutinous zone (debonded area), can take off glutinous material and remove by using suitable instrument such as blade scraping coating, return intact coating.

Pull-up is glutinous to extend to substrate surface if be coated with, and then epoxide first coating in ocean can be applied to the exsiccant exposure substrate surface of cleaning.If the area that desire applies is little,, be good then with the manual application of using brush or running roller less than about 100 squares of Foot to 200 square of Foot.All coatings all can manual mode use or use no air or other suitable spraying apparatus to use, and use according to the preference of user.For plant more than repairing the external member group use for, this epoxide first coating can be manually or spray application reach 6 millimeters to 9 millimeters thickness (wet-film thickness).

In case epoxide first coating in ocean is in " do glutinous (dry tack) " stage, the assessment mode in this stage is, for example by allowing dorsal surfaces of fingers press on the epoxide, removes finger and acyclic oxide paint is attached to finger, but should the surface be stickiness; Can use epoxide second coating that contains the mooring agent then.In some application of repairing the external member group, can dissipate and reached a few days in this stickiness, preferable lying in 24 hours carried out using of the second epoxide coating.Containing the second epoxide coating of mooring agent can manual application or use no air-atomizing equipment or other suitable spraying apparatus to use, and uses according to the preference of user.For kind is used more than repairing the external member group, the second epoxide coating will reach 6 millimeters to 9 millimeters thickness (wet-film thickness) with manual or spray application.

In case used the second epoxide coating that contains the mooring agent, in case the second epoxide coating reaches as preamble its " dried glutinous " state is described, then can use the binding coating.In addition, in use can wait 24 hours before linking coating or more than, reason is that the mooring part is transportable or stays the second epoxide surface, waits bond to linking coating.Link and to be coated with series of strata and to use and reach 10 millimeters to 16 millimeters thickness (wet-film thickness).Link that coating can be used brush or the running roller mat is manual uses, but or the mat high pressure do not have air-atomizing equipment, for example your (Graco Premier) aerosol apparatus of Ge Leikepu honey is used (45 to 1 or stronger pressurization).

Reached and done glutinous (about 1 to 2 hour) in case link coating, but application surface coating then.In addition, before the application surface coating, can wait 24 hours or more than, reason is that the two bonds systems that are coated with interlayer see through to be present in and links the two poly-silica-poly-silica reciprocal action of coating and face coat.Face coat system uses and reaches 16 millimeters to 20 millimeters thickness (wet-film thickness).Face coat can use that brush or running roller mat are manual to be used, but or the mat high pressure do not have air-atomizing equipment, for example your aerosol apparatus of Ge Leikepu honey is used (56 to 1 pressurizations).

At last, in case face coat drying (1 to a few hours, apparent temperature and humidity), the surface can be prepared in the submergence entry.In some application of repairing the external member group, allow whole system to solidify 1 to 3, damage in solidified commitment to prevent coating.

For for materials such as concrete or other highly porous material, ocean barrier epoxide first coating can be replaced such as the coating of A Molong Nuck Rider (Ameron NuKlad) 105A or its equivalent by the concrete coating agent.This kind concrete coating agent can use brush or running roller to use with manual, or in addition, can use the standard spraying apparatus or does not have air-atomizing equipment and use.

Synthetic method

The binding of previous announcements is coated with series of strata and manufactures and have elongated condition, and it is interior with the high-rate of shear manufacturing that this coating lies in reaction vessel.Through finding, not needing to reach by the elongated condition that links coating to provide the binding of suitable intensity and ruggedness coating.The method that this manufacture method of gained had more before disclosed is simpler, can reduce manufacturing cost and make burden.The gained form is not an elongated condition, and big stability can be provided.

In one of manufacture method specific embodiment, be that water is dispelled the heat between synthesis stage in linking coating.The method for making that links coating will cause heat release, and reason is that reaction can produce heat.The controlled effusion that heats of some modes is arranged, comprise the existence or the immiscible mixed fluidic existence of solvent.Two kinds of character of water are all ideal to this method.First character is that the boiling point of water is 100 ℃.Inventor's expectation is maintained at temperature of reactor near 100 ℃, reaches complete reaction, and does not cause the polymer in the construction overheated.In addition, the inventor expects to use the friendly and inexpensive coolant fluid as environmental protection.The inventor is found on control reaction and the reactor, and the effect of water is very good.After reaction was finished, most of water was removed by decant, then material was heated to 100 ℃ to remove surplus water.

In another specific embodiment, radical initiator such as peroxidating benzene first vinegar system is used for graft reaction.Initiator is added into response blend two kinds of methods are arranged: (i) low add initiator, typically this kind method system is used for reaching the close control of reaction, but need discretion monitor, and need to carry out measuring along with the process of time in the process in reaction the equipment of the definite quantity of initiator; And (ii) once add initiator, the reaction control of this kind initiator adding method is not good, and not good in polymer chain length and concordance control.But this is the more or less freely method that is used for extensive manufacturing.

In other specific embodiment, measure elongated condition and shear rate and can not cause harmful effect the present invention's binding coating.

The bond that links coating and surface

The present invention's binding coating and system can be used for suffering the various surfaces and the structure of environment and ecological abrasion and infringement (that is dirty, biomembrane, algae, antibacterial), comprise but non-be limited to naval vessels, boats and ships, submarine, dock, bridge pier, piling, fishnet, power plant and desalination plants comprise its relevant equipment with structure, pipe of cement, soil pipe and foggara, lawn sprinkler systems, roof, building, turbine, reach the antifreeze of electric wire, windmill and aircraft.These surfaces comprise maritime affairs environment and industrial environment, comprise boats and ships and power-plant cooling water feeding application.Additional application comprises that the water that comes from environment is used for industrial treatment, commercial processes or amusement and handles or contact with equipment or structure.

More specifically, the present invention's binding coating can be used on shell, peripheral driver, rudder and the tab.These surfaces comprise but non-glass fibre, foamed glass fiber, timber, Wood shell, existing coating, steel, steel shell, aluminum and the metal spare part of being limited to comprises metal spare part under water.The present invention's binding is coated with series of strata bond to a surface, and wherein the covalent bond between poly-silicon-oxygen polymer main chain that links coating and hydrocarbon polymer grafting is the important document of the reaction compatibility of polymer blend.In a specific embodiment, silane coupler system is used for this epoxy layer bond is linked coating to this.One of silane coupler example is SCM 501C (a momentum performance materials company), and this SCM 501C has the epoxide group of primary amine groups bond to the epoxide coating; And has poly-silica functional group bond to the poly-silica end group (hydroxyl) that links coating.In addition, the Si-OH group that links in the coating is bond influences two interlayers to the poly-silica end group of face coat a bond.

In another specific embodiment, discharging on the oily entity is to be mixed into face coat, and along with the process of time slowly diffuses out.Discharge oil and comprise SF1147, SF1154, DMSC15 and DBE224.In a specific embodiment, the surface tension of face coat is extremely low; Be about 20 to 25 dynes per centimeter (dyne/cm).In another specific embodiment, coating layer thickness system is between the scope of about 8 mils (mil) to about 16 mils, and is preferable between by the scope of about 10 mils to about 14 mils.

In some specific embodiments, be to add siloxanes fluids to assist the sprayability that links coating.In another specific embodiment, siloxanes fluids system is selected from SF69 and SF1147.

In another specific embodiment, the viscosity of resin has determined the spraying degree of coating.The inventor finds when viscosity drop to 10,000 centipoise to 12, and during 000 centipoise, the viscosity of the poly-silica of face coat can significantly improve spray characteristics.In the then difficult spraying of viscosity of 18,000 centipoise scopes, reach sprayability and must add a large amount of solvents.When using a large amount of solvent, then be difficult to reach required coating layer thickness (accumulation), and because volatile organic solvent (VOC) content, the solvent system of extra interpolation causes the problem of rules aspect.This discovery provides the increase ability that face coat is applied to large-scale plant (large-scale ships and tunnel, power plant) and reaches institute's required thickness.

Oneself's assembling-poly-silica is to poly-silica bond

Though the inventor does not wish to be subject to the theory of any particular chemical reaction or machine commentariess on classics, when the coating of believing the present invention does not contain cross-linking agent in linking coating, can provide the oneself of poly-silica part to assemble.The epoxy layer that is used as the base material that links coating contains coupling agent such as SCM501C, discuss as preamble, SCM 501C contain amine functional group and siloxanes functional group both.When SCM 501C mixes with epoxide and is coated on the base material, because poly-silica surface energy is low, so has some poly-silica partly to tend to migrate to the surface in the admixture, the epoxy functional base of amido bond to the admixture simultaneously.This poly-silica group that equals the epoxy layer surface can form chemical bond with the some-Si-OH group that is present in the binding coating formula subsequently.This provides epoxy layer and links the powerful interface bond that is coated with interlayer.And the lip-deep mooring agent reaction of some poly-silica functional group in the binding coating and epoxy layer, (the XPS experiment shows that the binding coating surface is rich in silicone) is shown in the setting up period that links coating on evidence also oneself's assembling tendency (gather silica and migrate to the surface tendency).This is driven by the low-surface-energy on poly-silica surface once again, and lacks crosslinked assisting in the coated polymeric admixture by linking.Haply, salty believe link in the coating and use the poly-silica part in the epoxide coating that the mooring agent according to the present invention allocated all to tend to the air surface side that the oneself is assembled to coating, with surface energy and the interfacial tension between (a) reduction applied layer; And (b) in the poly-silica functional group of mooring agent with link gathering between the silica functional group of coating and form chemical bonded refractory.Because the result of the self-assembling characteristic of this kind, believe that being bonded to the epoxide coating that links coating no longer is limited to the simple excessively assembling that hydrogen bond and the intermolecular attraction of Fan Dewaer occur, be because the self-assembling characteristic of this kind on the contrary according to the present invention, and be coated with interlayer and in linking between coating and face coat, comprise that uniquely poly-silica is to poly-silica bond in the epoxide coating that contains the mooring agent and binding.

Must understand the present invention's coating or complex, be in particular the epoxide coating that contains the mooring agent, link coating, and face coat, for low surface energy coat and comprise having natural free volume in poly-silicon-oxygen polymer matrix wherein, have silicone in this free volume, and because the slight gradient of the air surface side of face coat will make silicone slowly be diffused out by this free volume.

In addition, the invention is intended to contain the present invention's coating or complex, for example the free volume in face coat can be injected the plate out agent of effective dose, anti-algae agent, antibacterial (antibacterial and antibacterial), the antibiont film forms agent, Biocide, press down biological agent and other similar medicament (plate out agent), such as they those disclosed herein in following document: United States Patent (USP) case the 7th, 087, No. 106, title " inhibition is exposed to the material and the method (Materials andMethods for Inhibiting Fouling of Surfaces Exposed to AquaticEnvironments) of the surface dirt of aquatic environment "; No. the 5th, 314,932, United States Patent (USP) case, title " anti-dirty coating and using method (Antifouling Coating and Method for Using Same) thereof "; United States Patent (USP) case the 5th, 259, No. 701, title " the anti-dirty coating constituent that comprises furan compound; protect the method for aquatic structure and the object that protection avoids the evil of dirty organism (Antifouling CoatingComposition Comprising Furan Compounds; Method for ProtectingAquatic Structures, and Articles Protected against Fouling Organisms) "; No. the 5th, 252,630, United States Patent (USP) case, title " anti-dirty coating and using method thereof (AntifoulingCoating and Method for Using Same) "; United States Patent (USP) case the 5th, 248, No. 221, title " the anti-dirty coating constituent that comprises lactone compound; protect the method for aquatic structure and the object that protection avoids the evil of dirty organism (Antifouling Coating CompositionComprising Lactone Compounds; Method for Protecting Aquatic Structures, and Articles Protected against Fouling Organisms) "; No. the 4th, 788,302, United States Patent (USP) case, title " anti-dirty chemical compound and using method thereof (Anti-fouling Compound andMethod of Use) "; No. the 20060110456th, U.S. Patent Publication application case, title " kill livestock thing and/or press down bioremediation and be used for the constituent (Method for Biocidaland/or Biostatic Treatment and Compositions therefore) of this purpose "; No. the 20050159454th, U.S. Patent Publication application case, title " inhibition is exposed to the material and the method (Materials and Methods for Inhibiting Fouling of SurfacesExposed to Aquatic Environments) of the surface dirt of aquatic environment "; No. the 20040235901st, U.S. Patent Publication application case, title " inhibition is exposed to the material and the method (Materials and Methods for Inhibiting Fouling of Surfaces Exposed toAquatic Environments) of the surface dirt of aquatic environment "; (Poseidon Ocean SciencesInc ' natural biological product (NB) s) comprises eastern NB17 in general west and NB16 chemical compound to ocean, Pu Xi East Sea scientific company, as be reported in " life in the ocean; the life on the ocean wave (Life on the Ocean; Life on theOcean Wave) ", Jonathan doctor R.Matias, CEO, ocean, Pu Xi East Sea scientific company, http://www.poseidonsciences.com/oceanwave_ppcj.; Rittschof, D.1999, dirty and natural prodcuts plate out agent (Fouling and natural productantifoulants.), in: the in recent years development (Recent Advances in MarineBiotechnology) of maritime affairs biotechnology, the II volume, M.Fingerman, R.Nagabhushanam, and M.-F.Thompson (editor), xx page or leaf, New Delhi: Oxford and IBH publishing company; And Rittschof, D.1999, natural prodcuts plate out agent: the perspective (Natural productantifoulants:One perspective on the challenges related to coatingsdevelopment) of relevant coating development challenge, biological dirty (Biofouling) (special issue).

Time of application

Constituent of the present invention has the character of using easily.But constituent mat spray method is used, the spraying of constituent as traditional epoxide coating easily.So, constituent of the present invention atomizes in the spraying program easily, the ability improvement that obtains more even spray application and reach required ulking thickness.The mooring agent provides the binding coating of using subsequently bigger time window, by 24 hours to longer, the selection of using so is provided.Additional advantage comprises that the epoxide coating that need not mat spraying " activation " or the vaporific coating of other epoxide are to activate once again.

Hardening time

Constituent of the present invention can be laminated to and reaches on each layer in " doing glutinous " stage, does the assessment mode in glutinous stage, is for example will point dorsal part to be pressed on the epoxide, removes to point and do not have any epoxide coating and be attached to finger.Perhaps, before using the second layer, each layer be curable to reach a few days.Under most of situation, the constituent layer can be in 24 hours that use with interior curing.

Coating layer thickness

Constituent of the present invention can be all thickness and use.Each coating can be used by hand, or mat does not have air-atomizing equipment or other suitable spraying apparatus is used, and is to use according to the preference of user.Usually, respectively being coated with series of strata, to be applied to wet-film thickness be about 2 mils to about 30 mils, and preferable about 4 mils are to about 25 mils, and better about 6 mils are to about 20 mils.In addition, to about 12 mils, preferable about 4 mils are to about 10 mils with about 2 mils of wet-film thickness for the common system of epoxy layer, and better about 6 mils to about 9 mils are used.To about 30 mils, preferable about 13 mils are about 25 mils extremely with about 10 mils of wet-film thickness for the common system of dirty release binding coating and face coat, and better about 16 mils extremely about 20 mils are used.The best, binding are coated with series of strata to be used to the wet-film thickness of about 14 mils by about 12 mils, and face coat system is to be used by about 16 mils to the wet-film thickness of about 20 mils.

Total wet-film thickness of the present invention's dirty delivery system (comprising two-layer epoxy layer) usually by about 8 mils to about 90 mils, preferable about 9 mils are to about 75 mils, and better about 20 mils are to about 60 mils.

Other advantage

The present invention's binding coat system and coating provide the advantage that is better than the dirty release coat, comprise that ruggedness increases; Environmental protection (not containing heavy metal or Biocide); Environmental security (can be used for sanitary landfills, do not contain the EPA report) in accordance with FIFRA in accordance with VOC, garbage; Use (using known no air-atomizing pipeline to use poly-silica spraying) easily; (can exempt labour-intensive strike off, cleaning procedure streaming) safeguarded in saving; Release from excellence (spray with non-pressurized water and to remove, or to be low to moderate the constant current self-cleaning of per second 7 Foot); Effectively release from (speed is low to moderate 12 joints (knots) or is low to moderate 8 joints); Fuel saving (by about 6% to about 10%); According to operative temperature, reached service life 3 to 5 years or above (because present coating was promptly lost effect in 18 months, so can shorten half dry dock repair time).

Embodiment

For asking more complete understanding the present invention, be that the following example is provided.Must understand these embodiment and only be used to illustrate purpose, and be considered as the limit the present invention that limits absolutely not.So the present invention is a more complete description of mat following non-limiting examples.

Analytical method

Following method can be used for determining the architectural feature of an embodiment more than the present invention, and dirty material and other are attached to the effect of the pollutant of various base materials.

Sieve chromatography or gel permeation chromatography

Use oxolane as mobile phase, mat SEC/GPC measures molecular weight and the polydispersity (polydispersity) that links coating in 30 ℃ in oxolane.Use the linear polystyrene class as standard substance, carry out the wsw calibration.

Viscosity

The viscosity system that links coating resin uses Brooker striking (Brookfield) RTV viscosity to take into account large-scale axle and measures.

Solid appearance

The present invention's polymer can use solid appearance such as color and transparency to discern.The skill of being familiar with personage is the solid appearance difference between identification sample and standard substance easily, this information can be applied to identifying purpose.

Elementary analysis

Elementary analysis is by this laboratory of ko-hemp cloth (Galbraith Laboratories), and Tennessee State Nuo Kewei carries out.

Disbonded test is analyzed

Disbonded test can provide the mensuration of the tack strength (sticking together energy) of each interlayer in the system.This test lies in this paper explanation and measures second epoxy layer (containing the mooring agent) and link the tack strength that is coated with interlayer being used to.5 o'clock wide nylon wire rectangular (being used for dry wall type) be to be embedded in the interface that second epoxy layer and binding are coated with interlayer, method for embedding is for to be positioned over net on the stickiness epoxy layer, apply the binding coating then, subsequently top coat is coated on the top that links coating.Rectangular the letting alone of the screen cloth of 8 durations stretches out from the interface, and surpasses ceramic tile form (tile form) edge pull in the test to be clamped.

Ceramic tile is clamped to because of Strong (Instron) tension test motor spindle, uses conduit and anchor clamps to strengthen, and the rectangular mat of screen cloth is upwards pullled because of the Strong testing machine.Because of the Strong testing machine is measured pulling force that is applied and the distance of being pullled simultaneously.Pulling force below area divided by the rectangular area integral of screen cloth, obtains the interface energy of per unit area with respect to displacement curve, and this is the advantage data that recorded by test.

Following table shows energy/area (E/A) result of all tests carried out, with joule/square metre be unit representation.To each group sample, calculate average E/A value and standard deviation.

Table: pull the result of the test table

Contain the functional of the sample 1 of 30% and 15% SCM 501C and sample 2 respectively, do not have statistics and go up the significance difference opposite sex.The interface energy of sample 3 that contains 5% SCM 501C is lower, in other words, shows not goodly, and the tool statistics goes up significant difference.

In other mooring additive, sample 6 (1% aminocarbonyl propyl triethoxysilane) and sample 9 (1% aminocarbonyl propyl trimethoxy silane) produce optimum, are identical with sample 1 and sample 2 (30% and 15% 501C) in the experimental error scope.The poor effect of other reagent of sample 12 and sample 15.Other mooring agent of sample 18 obtains highest energy/area result, but has only three samples through successfully test, and the error of this data acquisition system is high.Therefore sample 18 is difficult to final conclusion.

Dirty material-range estimation is inspected

The trial zone can be coated with the present invention's dirty delivery system, and uses visual inspection and undressed trial zone to make comparisons.Can test that zone comprises but non-ly be limited to material that pipe of concrete or other be exposed to movable sea water, place the glass mat of static sea water and place the shell that is exposed to water and other substrate material by water.Range estimation is inspected and can be carried out after various time histories, or uses various water speeds to carry out, and can be changed by the skill personage that is familiar with easily.

The following example is only for the usefulness that illustrates, but not is considered as limiting the present invention; Or can not make multiple significant change departing from the present invention's marrow and scope.

Surface roughness analysis

(Atomic Force Microscopy, AFM) technology system utilizes a ultra fine needle tip to measure the technology of its pattern by sample surface to atomic force microscope.Present technique can obtain the pattern image of surface roughness, and the average measurement value of surface roughness can be provided.Quote two numerical value that is Z scope and RMS.The Z scope is by the vertical dimension of peak to minimum point on the scanning area surface.RMS is the root-mean-square mean roughness on the whole image.The AFM test shows that duplexing dirty delivery system has the Z scope and serves as reasons about 0.5 micron (microns) to about 70 microns, is more preferred from about 1.2 microns; And rms roughness system how rice (nm) is to about 1 micron scope between about 40; And be more preferred from about 80 rice how.

Embodiment 1

Synthetic based on the in-situ polymerization polymer blends thing of polysiloxanes

Admixture reaction lies in uses the 3 neck round-bottomed flasks that are equipped with condenser and mechanical agitator and use nitrogen sweep to remove continuously to carry out in the convulsion cabinet.For example, will have viscosity in 25 ℃ be 8,32 milliliters of 000cSt add reactor, admixture high degree of agitation 20 minutes through hydroxy-end capped polydimethylsiloxane and 0.386 gram peroxidating benzene first vinegar.12.3 milliliter styrene and 35.4 milliliters of n-butyl acrylates are added into reactor, admixture continuous stirring 20 minutes.Add 20 ml deionized water, and this system stirred 20 minutes.Reactor soaks in the water-bath of 100 ℃ of temperature then.Color changed into canescence in 10 minutes, and color and viscosity increase during entire reaction continuously.Afterreaction was finished in 2 to 3 hours.Removed condenser in last 15 minutes in order to do removing most water.Collect white sticky polymer, further dry in vacuum drying oven.

Embodiment 2

Synthetic based on the in-situ polymerization polymer blends thing of polysiloxanes

Reaction system carries out as described above, but use have viscosity in 25 ℃ be 20,32 milliliters of 000cSt through hydroxy-end capped polysiloxanes and 18.5 milliliters of styrene, 52.6 milliliters of n-butyl acrylates, 0.836 gram peroxidating benzene first vinegar and 20 ml deionized water.Embodiment 1 and embodiment 2 can carry out in multiple solvent, comprise but non-toluene, ether, oxolane (THF), benzene, the dichloromethane Radix Chloranthi Serrati alkanes of being limited to.Polysiloxane-based viscosity can be between about 10 scopes to about 100cSt in the time of 25 ℃, in the time of 25 ℃ between about 2,000 to about 8, the scope of 000cSt and in the time of 25 ℃ between about 10,000 to about 50, the scope of 000cSt.In certain specific embodiments, the viscosity of polysiloxanes is 3,500cSt.In addition, initiator comprises but non-peroxidating benzene first vinegar, two-Di tributyl peroxide, cumyl hydroperoxide, tert-butyl hydroperoxide, AIBN, azo-two-alkyl nitrile and the di-t-butyl peroxide of being limited to.

Embodiment 3

The binding coating of illustration and top coat prescription

The exemplary prescription of binding coating described herein and top coat is to be shown in following table 2, but non-limiting.In each coating, before mixing, material is divided into two parts (A and B).

Table 2: link coating and top coat prescription (A and B prescription are represented with metric unit)

Link coating	Composition	1000 milliliters	500 milliliters	250 milliliters	100 milliliters
						A	Link coating resin	444.622	222.311	111.156	44.462
	Hexane	244.422	122.211	61.106	24.442
							SF-69	110.955	55.478	27.739	11.096
	Total A	800.000	400.000	200.000	80.000
B	CA-40	110.955	55.478	27.739	11.096
							Hexane	88.844	44.422	22.211	8.884
	GF-91	0.200	0.100	0.050	0.020
							Total B	200.000	100.000	50.000	20.000
							It is total to link coating	1000.000	500.000	250.000	100.000

	A+B
Top coat	Composition	1000 milliliters	500 milliliters	250 milliliters	100 milliliters
						A	RTV-11	766.871	383.436	191.718	76.687
	SF-1147	92.025	46.012	23.006	9.202
							Na Pusa (Naptha)	69.018	34.509	17.255	6.902
	Total A	927.914	463.957	231.979	92.791
B	DBT	3.067	1.534	0.767	0.307
							Na Pusa	69.018	34.509	17.255	6.902
	Total B	72.086	36.043	18.021	7.209
	The total A+B of top coat	1000.000	500.000	250.000	100.000

Embodiment 4

Duplex is linked coating be applied to the water tunnel

Present embodiment explanation is applied to concrete surface with the present invention's duplexing dirty delivery system, and concrete surface is to be used for cooling water is guided to test sticking patch (test patch) in the tunnel in power plant by the ocean.

Concrete uses the sealing of two parts of formula epoxide of inferior U.S. coating (Americoat) Ya Meiluoke (Amerlock) concrete coating agent.Coating agent system uses 1/4 o'clock flour roller wheel rolling.The application conditions of coating agent: temperature=60 ℃, 60% relative humidity.Concrete surface seals back 18 hours, uses 1/4 o'clock flour roller wheel that two parts of formula epoxide Ya Meiluoke 400 ocean coating are applied on this surface.Allow the anticorrosion epoxy layer to solidify 24 hours.

Tough and tensile binder couse resins is as follows.2 liters of reactive stabilization organopolysiloxane fusion systems are according to embodiment 1 preparation, and this organopolysiloxane system significantly reduces with the viscosity that 1.5 liters of hexanes are mixed to organopolysiloxane.After 10 minutes, add 500 milliliters of Brunswick CA40 firming agent, mix two materials.Use the binding coating with 1/4 o'clock flour roller wheel, use and finished the back about 2 hours, the dirty releasing layer is applied to links above the coating in linking coating.The poly-silica release layer materials of 4 liters of momentum performance materials RTV-11 system mixes with tin-based catalyst and uses at once.

Allow applied layer solidify 2, the tunnel floods with sea water once again subsequently.Water in the tunnel regularly drains, the checkout facility sticking patch.Find that the test sticking patch does not contain ocean dirty organism, yet organism infects the remainder of tunnel surface.When checking individually in 1 year and the 3rd year, find that the physical state of coating is excellent.

Embodiment 5

Single worker is linked coating be applied to the water tunnel

This example explanation is applied to concrete surface with single worker's dirty delivery system of the present invention, and concrete surface is to be used for cooling water is guided to test sticking patch in the tunnel in power plant by the ocean.

Concrete uses the sealing of two parts of formula epoxide of inferior U.S. coating Ya Meiluoke concrete coating agent.Coating agent system uses 1/4 o'clock flour roller wheel rolling.The application conditions of coating agent: temperature=60 ℃, 60% relative humidity.Concrete surface seals back 18 hours, uses 1/4 o'clock flour roller wheel that two parts of formula epoxide Ya Meiluoke 400 ocean coating are applied on this surface.Allow the anticorrosion epoxy layer to solidify 24 hours.

Tough and tensile binding coating/surface coating hybrid resin is prepared as follows.4 liters of reactive stabilization organopolysiloxane fusion systems are according to embodiment 1 preparation, and the viscosity that this organopolysiloxane and 1.5 liters of hexanes are mixed to organopolysiloxane significantly reduces.Further add the poly-silica release layer materials of 1 liter of momentum performance materials RTV-11, stirred 10 minutes.After 10 minutes, add 500 milliliters of Brunswick CA40 firming agent, with material mixing.CA40 can be used to solidify two kinds of compositions of simplex system.Perhaps, DBT (face coat firming agent) also can be used to solidify two kinds of compositions of simplex system.In certain specific embodiments, when using DBT to solidify, system is for slightly good.Linking coating/surface coating resin system uses the pressure atomization dispensing device and is applied to the surface.

Allow applied layer solidify 2, the tunnel floods with sea water once again subsequently.Water in the tunnel regularly drains, the checkout facility sticking patch.

Embodiment 6

Method with the present invention's binding coating coating surface

Before coating surface, should carry out following preparation: test sticking patch or comprehensive application system; Reach the spot, check that desire applies the situation of items, affirmation substrate is timber, steel, glass fibre, or whether the surface preparation is complete, or does not need any repairing; Confirm container demand or ventilation requirement; Whether self-criticism needs pressurization washing, the quick-fried spray of abradant or the quick-fried spray of soda; Confirm area and estimate required coating content; Whether judge needs special access requirement; Record devices needed and material; Enumerate the testing equipment that needs and check operation, whether test film also needs to apply; To help the Pu coated with epoxide, binding coating, face coat; Whether measure has enough spraying pipeline, spray gun, top end and replacement part; Check that schedule defines enough drying times and applies the time again; Check weather forecast; Whether at the scene to check coating, check its quantity and lot number; Use the time-histories table with user discussion; And the spraying group Pu and the pipeline of separately epoxide, binding coating and face coat special use.

First, check ambient conditions (temperature, dew point, humidity, surface temperature and weather forecast).Data logging is become to use form.Check the whether possible spray problem of crossing of adjacent area.The surface that need not to apply is attached with adhesive tape.Running air line and layout coating pipeline.Bring up to the coating and the diluent of desire coating.Fully whether the judgement repairing (concrete may need coating agent).Judge whether the surface totally prepares to accept to apply (solvent is smeared and wiped away, blows off).Guarantee to have sufficient solvent to clean group Pu, spraying pipeline and spray gun.According to recommendation hybrid ring oxidation thing coating 1 material of manufacturer, optionally check viscosity.Release coating (acute angle, corner, compact zone) optionally.Use coating, check wft (wet-film thickness), use even pattern and intersection and use.Brush falls or rolling is removed mobile, sagging.Supply holiday.

At once clean spraying apparatus.In recommend the drying time/apply the time check coating again.Obtain build measured value (5 to 7 mil) and record.If coating slightly softness is then used plastics shim (determining to deduct the thickness of shim from measured value).If ambient conditions for accepting, carries out a time coating when coating touches to drying.About coating 2 (epoxide-mooring agent), be to mix an amount of mooring agent and epoxide.Mix each composition fully, allow it that arranged 10 to 15 minutes surface water setting time before using.Check the cleannes (visual inspection) of desiring coating surface, optionally clean.On last coating, use new coating.Owing to add the mooring agent, can increase dry weight and newly apply the time.Check the wet film measured value.When work is carried out, brush outflow, sagging situation, supply holiday.Cleaning equipment.The first and second epoxide coatings lie in usually to be used in same day.If do not use the binding coating next day, then use the extra loop oxide coating that contains the mooring agent.

On 1st, check and the record ambient conditions, check the curing situation of coating, check surface cleanness (visual inspection).Spanning equipment.Coating material is placed the scene.For linking coating, be that the binding coating composition is mixed, use flow cup and code table to check the viscosity of coating (using usually and praising cup (Zahn cup) for No. 5 is 20 to 25 seconds).This coating need not attenuate.In the middle of carrying out, use spraying to remove sharpened edge, corner and the compact zone of coating.Check wet-film thickness judges whether need repeatedly bout (10 to 14dft).Optionally check and supply holiday.When generation is flowed or be sagging, slightly brush mobile, sagging.At once cleaning spraying group Pu, pipeline and spray gun.Do not allow coating to be deposited in the spraying pipeline.Coating is solidified comparatively quick during higher temperatures.

Before using, face coat allows 1 to 2 hour drying time.Before the application surface coating, coating must the sensation drying when touching.Check and the record ambient conditions.Check surface cleanness (range estimation).Check and record binding coating dry film thickness measurements (with reference to plastics shim method).Spanning equipment.Place coating material.For face coat, be pre-mixed A part surface coating.Optionally add diluent reach praise for No. 5 the cup 40 to 45 seconds.About 15%.After reaching proper viscosity, add part B (sclerosing agent).In carrying out, use and spray sharpened edge, corner and the compact zone of removing coating.When occurring sinking, brush gently when flowing.The environment temperature height can quicken hardening time.The inspection wet-film thickness is judged to be needed by several bouts (12 to 14dft).At once cleaning spraying group Pu, spraying pipeline, spray gun.Do not allow coating to be piled up in the spraying pipeline.Collecting whole coating refuses suitably abandons.

Remove before the shielding material, allow coating to solidify at least 1.Before removing, cut gently along the adhesive tape line.Do not cut base material.Allow the sufficiently dry time (2 days) before in removing frame (jack stand).Use complete four coat systems to supply shelf position.If need, with the solvent wiping base material.It is preferable that surface-coated is carried out in the mat spraying.Preferablely when using frame, make ladder and apply around frame.Epoxide, epoxide+mooring agent and binding are coated with that series of strata are applied to existing coating but are not overlapping.Face coat must slightly overlapping existing face coat.

Embodiment 7

Use: duplexing dirty delivery system, full shell are used, spray application

Boats and ships: Hank profit (Hinckley) picnic ship-length: 36 Foot, sail Yan: 12 Foot

Duplex dirty delivery system (DFRS) is to be applied to the sharp 36 Foot picnic of Hank ship.This is the yacht that mat water sprays the power supply of (Water Jet) engine.Shell is made by carbon fibre/Kai Fule (Kevlar)/epoxide/e-glass composite material.These boats and ships carry out the sea water test, measure the performance of existing copper ablation anti-dirty bottom before copper ablation coating peels off, and duplexing dirty delivery system is installed.Before using DFRS to apply, the maximum of shell can reach speed, is about 27.4 joints in 2 monthly age copper bottoms.

Use ocean coating to use well-known standard spray application technology on the skill circle practice and use DFRS.Use as follows:

Place the open air through the space, shipyard of overprotection the boats and ships haul, be supported on the keel, each port and starboard is erect so that three jack stands are fixing.Each layer DFRS system uses spray technique with intersection described herein, uses with no air-atomizing equipment.

Use the sodium bicarbonate sandblast copper removal abrasion primer of making a return journey.Hull bottom to bootopping branch cleans to composite material surface.

The ground floor epoxide lies in to be used in first day that DFRS installs.Weather is bright and clear drying, and temperature is for being higher than the scope that 70 ℉ are lower than 80 ℉, and humidity is about 50%.The ground floor epoxide comprises the west good 5000 that derives from snow grace William company.These series of strata are to use in the 36:1 of 60psi operation solid injection device (but Ge Lei company).The ground floor epoxide is used about 15 minutes (8 to 9 mil wet-film thickness), allows it be dried to glutinous state, reaches the state of using once again in 4 hours consuming time approximately.

Second layer epoxy layer comprises the west that derives from snow grace William company and praises 5000, contains the SCM 501C that 15 volume % derive from momentum performance materials company.These series of strata are used identical 36:1 solid injection device (but Ge Lei company), use with the uniform pressure operation.This epoxy layer is used about 15 minutes (8 to 9 mil wet-film thickness), places overnightly, uses DFRS inferior morning and links coating.Attention: this second epoxy layer allows to reach the glutinous state of doing, and takes about 4 hours before using the binding coating.For asking user convenient, the binding coating lies in to be used next day.

That installs in DFRS used the binding coating in second day.Weather is bright and clear drying, and temperature is for being higher than the scope that 70 ℉ are lower than 80 ℉, and humidity is about 50%.These series of strata are used in the 54:1 solid injection device (but Ge Lei company) of about 60psi operation and use.Link coating and used about 15 minutes, allow it be dried to the state of sticking, reached the state of using once again in about 1.5 hours consuming time.

Reach the state of sticking of doing in case link coating, in second day application surface coating of DFRS installation.These series of strata are to use in the 54:1 of about 75psi operation solid injection device (but Ge Lei company).Face coat was used about 15 minutes.

Face coat was used back 2 days, removed frame (jack stand), and the unprocessed district that frame covered uses the DFRS repair system to apply.Repair system is used as follows:

A. use brush the good 5000 ocean epoxide in west to be applied to the clean section of shell.This first epoxide coating is applied to about 9 mil wet-film thickness, allows it to proceed to and does glutinous drying regime.Be about 3 hours drying time.

B. the west good 5000 of containing 15% SCM501C is with the manual first epoxide coating (being set forth in as above (a) section) that is applied to.Second epoxide is coated with series of strata and is applied to about 9 mil wet-film thickness, allows it proceed to and does glutinous degree of drying.Be about 3 hours drying time.

C.DFRS links coating and uses the manual second epoxide coating that is applied to of brush.This links coating and is applied to about 16 mil wet-film thickness, allows it proceed to and does glutinous degree of drying.Be about 1.5 hours drying time.

The d.DFRS face coat uses brush with the manual binding coating surface that is applied to.This face coat is applied to about 18 mil wet-film thickness, allows it proceed to drying.

The sharp picnic of Hank that DFRS was installed after using reparation external member group on the 2nd launches a ship.

The sharp picnic of the Hank ship that duplexing dirty delivery system is installed is accepted the ocean test before setting out.During in June, 2007 and July 30 days, boats and ships are kept in the Qi Sapi bay and are not contained hard dirty.Be biological dirty very highly season this season, has the boats and ships of copper ablative coating hard dirty to occur in same period.In addition, after using DFRS, the sharp picnic of Hank ship can repeat to reach the speed of 30.5 joints.Compare with new copper ablative coating, shell speed improves about 11.3%.

Embodiment 8

Use: antifogging coating, test sticking patch, the manual duplexing dirty delivery system of using are arranged

Boats and ships: San Juan Jax bridge test: 150 squares of Foot sticking patch (approximation)

Duplex dirty delivery system (DFRS) is advanced with about 8 joint speed in 700 Foot scows, and duplexing dirty delivery system (DFRS) is applied to waterline position fore harbour section.This is to navigate by water to tie up the extremely ship of Peurto Rican San Juan in the Fla. Jackson.Ship hull is a steel.Select for use and should assess DFRS with purposes and be used for the usefulness of boats and ships that headway is lower than 12 joints.

DFRS system uses the well-known normal manual application technique of personage with the ocean coating of being familiar with and uses.Should be with as follows:

Before thorough reparation, boats and ships are to place dry dock, thoroughly repair to comprise that using standard copper ablates anti-dirty coating on whole shell, and DFRS tests except the sticking patch position, and coating is applied to Os Draconis by waterline.Each layer DFRS system uses the running roller coating technology to use.

Housing is prepared by sandblast to reference white polishing.Whole DFRS system lies on the same day and uses.

The first epoxide series of strata are used about 1 micromicron (PM).The bright and clear drying of weather, temperature are 90 ℉ intermediate ranges, and humidity is about 85% to 90%.First epoxy layer comprises A Molong 235 (A Molong company).The first epoxide coating is used about 15 minutes (8 to 9 mil wet-film thickness), allows it be dried to glutinous state, but reaches the repetitive administration state in 2 hours consuming time.

Second epoxy layer comprises A Molong 235 (A Molong company).The first epoxide coating is used about 15 minutes (8 to 9 mil wet-film thickness), allows it be dried to glutinous state, but reaches the repetitive administration state in 2 hours consuming time.

In case the second epoxide coating reaches dried glutinous state then uses antifogging coating.Antifogging coating was used about 15 minutes, and it is glutinous to allow it be dried to, but reaches the repetitive administration state in 30 minutes consuming time.

In case antifogging coating reaches dried glutinous state then uses the binding coating.Link coating and used about 15 minutes, it is glutinous to allow it be dried to, but reaches the repetitive administration state in 1 hour consuming time.

Reach dried glutinous state, then application surface coating in case link coating.Face coat was used about 15 minutes.

After being finished, the extra repairing of shell makes ship launching (in DFRS test sticking patch the back is installed and surpassed for 1 week).

In 1 year after using, check for several times is equipped with the San Juan Jax bridge of duplexing dirty delivery system test sticking patch.Behind the first water down, Fan Lakuzi additionally repaired boats and ships in Mexico by harbour in about 1 month consuming time.During this, as expected, hard dirty is attached to DFRS test sticking patch.During this, boats and ships meet with fierce storm wind in quayside, and starboard side is badly damaged and comprises that DFRS test sticking patch district also is badly damaged.Tie up inspection in the Florida State Jackson after one month, find that DFRS test sticking patch has only slight scratch, till the copper ablative coating on DFRS test sticking patch both sides then is removed to the shell of steel.So the damage of checking DFRS impact has splendid patience.

In addition, boats and ships are navigated by water to Peurto Rican San Juan back and forth by Florida State Jackson dimension, because the ship navigation can simply discharge the hard dirty of DFRS test sticking patch, so confirm that saving velocity interval DFRS in about 8 has effective dirty releasability.DFRS test sticking patch is still kept well in using above 1 year, does not contain hard dirty.

Embodiment 9

Use: duplexing dirty delivery system, test sticking patch (about 200 squares of Foot), manual running roller is used

Boats and ships: Ai Ermoluo (E1 Moro)-length: 700 Foot, sail Yan: 60 Foot

Duplex dirty delivery system (DFRS) is applied to ocean counter wheel.Shell is a steel.

Each layer of DFRS all used with the well-known standard manual running roller of ocean coating skill circle personage application technique.Use as follows:

Boats and ships place outdoor dry dock.

Use sandblast to remove copper ablation primer.Be cleaned to the steel surface by hull bottom to waterline.

Be installed in DFRS and used first epoxy layer on the 1st.Weather is cloudy drying, and temperature is in the scope of 80 ℉ to 90 ℉, humidity about 70% to 80%.First epoxy layer comprises A Molong 235 (A Molong company, be PPG company today).The first epoxide coating is used about 15 minutes (8 to 9 mil wet-film thickness), allows it be dried to glutinous state, but reaches the repetitive administration state in about 4 hours consuming time.

Second epoxy layer (in case first epoxide reaches when doing the state of sticking, using on 1st) comprises A Molong 235 (A Molong company), contains the SCM 501C of the momentum performance materials company of 15% volume ratio.This epoxy layer is used about 15 minutes (8 to 9 mil wet-film thickness), places overnightly, uses DFRS inferior morning and links coating.Attention: second epoxy layer reaches does glutinous state, needs 4 hours approximately, just can use the binding coating.During this is used, convenient for asking user, use the binding coating next day.

Used the binding coating in second day that DFRS is installed.Weather is sunny drying, and temperature lies in the scope of 80 ℉ to 90 ℉, humidity about 80%.Link coating and used about 15 minutes, allow it be dried to glutinous state, but reached the repetitive administration state in about 1.5 hours consuming time.

Reach the state of sticking of doing in case link coating, in the application surface coating on the secondth that DFRS is installed.Face coat was used about 15 minutes.Use back a few days ship launching.

Suggestion is in case use DFRS, then gives 3 day time to allow DFRS solidify just to allow ship launching.

Till this case applying date, Ai Ermoluoshang does not reach and checks the harbour.Therefore the comment of still not having relevant its performance so far.

Embodiment 10

Power-plant cooling water feeding tunnel: Dutch An Xuefen

Use: the duplexing dirty of used antifogging coating, test sticking patch, using by hand discharges system System

Shellfish (Electrabel) electric station, a Yi Lai left side that duplex dirty delivery system (DFRS) lies in Dutch An Xuefen is applied to the section in tunnel 6.Assess the performance that DFRS is used for the concrete cooling unit originally to use, this cooling unit tunnel uses the water (cold water environment) from the North Sea, and suffers the Asia Concha Ostreae and from the dirty of other hard dirty kind in the North Sea.To lie in dirty season be benchmark with the every month in this tunnel in addition, accepts the anti-dirty of hot water (43 ℃) and handle.

DFRS system uses the well-known normal manual application technique of skill circle with ocean coating and uses.Use as follows:

The tunnel is anhydrated, and the mat high-pressure washing removes existing dirty organism.All each layer DFRS system uses with the running roller paint-on technique.

Tunnel wall acceptance line brush is handled and is removed any remains that get loose.

Use ground floor, epoxide concrete coating agent Nuck Rider (NuKlad) 105A (A Molong company).Environmental condition when using in the tunnel is about 60 ℉ of temperature and humidity about 50%.Tunnel wall is dry, but bottom surface, tunnel back water slightly.Use about 15 minutes first epoxy layer (8 to 9 mil wet-film thickness), make its drying overnight.

The next day of using DFRS, use epoxy layer and comprise A Molong 235 (A Molong company).This epoxy layer is used about 15 minutes (8 to 9 mil wet-film thickness), allows it be dried to glutinous state, and about 3 hours consuming time, but reach the repetitive administration state.

Do glutinous state in case the second epoxide coating reaches, then use antifogging coating.Antifogging coating was used about 15 minutes, and it is glutinous to allow it be dried to, but reaches the repetitive administration state in about 30 minutes consuming time.

In case antifogging coating reaches dried glutinous state then uses the binding coating.Link coating and used about 15 minutes, it is glutinous to allow it be dried to, but reaches the repetitive administration state in 1 hour consuming time.

Reach dried glutinous state, then application surface coating in case link coating.Face coat is used about 15 minutes clock times.

After being installed, DFRS about 1 week the tunnel is installed back the operating position.

Install and check twice of DFRS test sticking patch in back 3 years.In this triennial, DFRS keeps good and does not have hard dirty, confirms to there is no detectable abrasion, and has extremely strong protection effect for being subjected to the organic dirty of the hard dirty of Asia Concha Ostreae and other North Sea.In addition, customary hot water treatment can the not detract service life or the dirty releasing properties of coating of using.The uncoated in tunnel comprehensive dirty partly occurs and comprises that the Asia Concha Ostreae reaches at about 6 o'clock or above diameter.

Embodiment 11

The ceramic tile that zebra shellfish dirty releasing research is used

The ABS plastic ceramic tile of thickness is used coated with the dirty releasing research during 70 20 * 20 cm x 1/4 anti-dirty prescription of duplex and the anti-dirty prescription of single worker.

1. duplex system/stannum solidifies/contains release oil (modular system).

2. duplex system/stannum solidifies/contains and discharges oil/contain pigment.

3. duplex system/stannum is solidified/oil-containing not.

4. duplex system/stannum is solidified/oil-containing/contain pigment not.

5. the stanniferous of duplex system/or not contain discharges oil.

6. the oil-containing of the stanniferous of duplex system/or not.

7. single worker (85% links coating/15% top coat)/stannum solidifies/contains release oil.

8. single worker (85% link coating/15% top coat)/stannum solidifies/oil-containing not.

9. the stanniferous of single worker (85% link coating/15% top coat)/or not contain discharges oil.

10. the oil-containing of the stanniferous of single worker (85% link coating/15% top coat)/or not.

11. the stanniferous of single worker (85% link coating/15% top coat)/or not contain discharges oil.

Discharge oil 12. contrast/have only binding coating/contain.

13. contrast/have only the oil-containing of binding coating/not.

14. contrast/only contain the ocean epoxide.

The two all is to use CA-40 to solidify to linking coating and top coat in the system that is denoted as " Wuxi ".The system that is denoted as " single worker " is with the top coat of prescribed volume percentage ratio and link coating (for example 85% links coating material and 15%# coating) and mix, and is monolayer and uses and use tin catalyst (7 and 8) or use CA-40 (9 to 11) to solidify.

The caking that links coating can effectively be eliminated by following manner: with (with being used for diluting the same solvent that the links coating resin) dilution in advance in hexane of CA-40 firming agent, and the firming agent after will diluting is added into during the binding coating resin use electric drill driving high speed shearing mixer.In two partially mixed together before, be added into the hexane total amount that links coating resin and be added into the CA-40 resin, by volume system equals to link only the amount of coating resin.

The plastics ceramic tile is immersed in the Bo Lindun bay of contiguous Lake Ontario, dirty season autumn in summer of experience zebra shellfish.Observation is assessed the dirty releasing properties up to the removal situation of zebra shellfish in 10 miles/hour the circulating water.Standard duplex system prescription and simplex system recipe ratio all can reduce the invasion quantity of zebra shellfish than matched group (sample 12,13 and 14).Be present in zebra shellfish on duplexing plastic tile and the single worker's plastic tile easily with up to per hour 10 miles or remove with the purgation water flow velocity.Even the zebra shellfish that is attached on the check sample also can't be removed with the highest water flow velocity.On duplexing top coat or single worker, have the oily SF1147 of release, can promote the releasing effect of coating, further reduce the invasion quantity of zebra shellfish, or the required water flow velocity of reduction removal zebra shellfish invasion is low to moderate 2 miles/hour.

Equivalent

The skill of being familiar with personage need not to surpass the experiment of routine can identification or confirm an equivalent more than the present invention's described herein certain specific embodiments.These equivalent systems are intended to be covered by following claim.Though so with regard to specific embodiment and embodiment the present invention is described, the skill of being familiar with personage should be appreciated that and can make other modification and variation under not departing from the present invention's spirit and scope.In view of the above, being intended to absolutely not the present invention's scope limited is limited to the particular range of aforementioned specific embodiment and embodiment explanation, and the present invention's that the claim of only being enclosed defines scope is limit.

Claims (79)

1, a kind of dirty discharges and links the coated polymeric admixture, it comprises at least a polysiloxane polymer and a kind of organic polymer, wherein this organic polymer is made up of the monomer that aggregates into monochain polymer, and wherein this organic polymer be can't help crosslinked polyfunctional monomer and formed.

2, binding coated polymeric admixture as claimed in claim 1, wherein to have weight average molecular weight be about 50,000 to 500,000 to this polymer.

3, binding coated polymeric admixture as claimed in claim 1, wherein this polysiloxane polymer has the following formula repetitive

R wherein ₁And R ₂Independently for being substituted or unsubstituted C ₁-C ₃Alkyl or be substituted or unsubstituted aryl R ₁And R ₂Each can or not provide another group of another binding functionality to replace by cyano group, halogen.

4, binding coated polymeric admixture as claimed in claim 3, wherein at least one terminal of this polysiloxane polymer has the terminal-reactive group.

5, binding coated polymeric admixture as claimed in claim 4, wherein this terminal-reactive group is hydroxyl, alkoxyl, aryloxy group, amino, amide groups, halogen or vinyl.

6, binding coated polymeric admixture as claimed in claim 5, wherein this polysiloxane polymer is hydroxy-end capped polydimethylsiloxane.

7, binding coated polymeric admixture as claimed in claim 1, the following monomer that carries out radical polymerization of free radical existence that it further comprises organic monomer or can produce in position.

8, binding coated polymeric admixture as claimed in claim 7, wherein this organic polymer belongs to monomer by monoene and forms.

9, binding coated polymeric admixture as claimed in claim 8, wherein to belong to monomer be vinyl monomer to this monoene, propylene monomer, butene monomers, Vinyl Chloride Monomer, fluoride monomers, the perfluoroalkyl acrylate esters, vinyl acetate monomer, styrene monomer, cyclosubstituted styrene monomer, the ethenyl pyrrolidone monomer, the vinyl naphthalene monomer, N-VCz monomer, N-vinylpyridine noise made in coughing or vomiting alkane one monomers, acrylic monomers, methacrylic acid monomer, acrylonitrile monemer, the metering system nitrile monomer, vinylidene fluoride monomers, vinylidene chloride monomer, the acrylic aldehyde monomer, the methylacrolein monomer, the maleic anhydride monomer, the stilbene monomer, the indenes monomer, the maleic acid monomer, or fumaric acid monomer.

10, binding coated polymeric admixture as claimed in claim 9, wherein this organic polymer is made up of styrene, butyl acrylate, other alkyl acrylate esters or its mixture.

11, binding coated polymeric admixture as claimed in claim 7, wherein the free radical of this original position generation causes by adding benzoyl peroxide or di-t-butyl peroxide, cumyl hydroperoxide and tert-butyl hydroperoxide.

12, binding coated polymeric admixture as claimed in claim 1, it can further be atomized and spray and be applied to the surface.

13, binding coated polymeric admixture as claimed in claim 12, it further comprises the siloxanes fluids of the sprayability that can improve this admixture.

14, binding coated polymeric admixture as claimed in claim 1, it can further form tight covalent bond matrix with the surface of being used.

15, binding coated polymeric admixture as claimed in claim 1, it has about 40,000 viscosity to about 400,000 centipoises under 25 ℃.

16, binding coated polymeric admixture as claimed in claim 15, it has about 80,000 viscosity to about 250,000 centipoises under 25 ℃.

17, binding coated polymeric admixture as claimed in claim 16, it has about 95,000 viscosity to about 150,000 centipoises under 25 ℃.

18, binding coated polymeric admixture as claimed in claim 1, it further comprises firming agent, and wherein this firming agent is not a tin-based catalyst.

19, binding coated polymeric admixture as claimed in claim 18, wherein this firming agent is methyl three (hexamethylene amino) silane, tin-based catalyst, platinum based catalyst or Ti-base catalyst or other non-tin-based catalyst or organic group catalyst.

20, a kind of dirty delivery system, it comprises: the anticorrosion epoxy layer that is applied to base material, be applied to the binding coated polymeric admixture as claimed in claim 1 of this epoxy layer, and the siloxane surface coating that is applied to this binding coated polymeric admixture, wherein this epoxy layer comprises the silane coupler with primary amine.

21, dirty delivery system as claimed in claim 20, wherein this binding coated polymeric admixture further comprises siloxanes fluids.

22, dirty delivery system as claimed in claim 20, wherein this base material cleaned before using this anticorrosion epoxy layer.

23, dirty delivery system as claimed in claim 22, wherein this base material sandblast before using this anticorrosion epoxy layer.

24, dirty delivery system as claimed in claim 20, wherein this siloxane surface coating further comprises release oil.

25, a kind of dirty delivery system, it comprises: the first anticorrosion epoxy layer that is applied to base material, be applied to the second anticorrosion epoxy layer of this first anticorrosion epoxy layer, be applied to the binding coated polymeric admixture as claimed in claim 1 of this second anticorrosion epoxy layer, and the siloxane surface coating that is applied to this binding coated polymeric admixture, wherein this second anticorrosion epoxy layer further comprises the silane coupler with primary amine and/or secondary amine.

26, dirty delivery system as claimed in claim 25, wherein this binding coated polymeric admixture further comprises siloxanes fluids.

27, dirty delivery system as claimed in claim 25, wherein this base material cleaned before using this first anticorrosion epoxy layer.

28, dirty delivery system as claimed in claim 27, wherein this base material sandblast before using this first anticorrosion epoxy layer.

29, dirty delivery system as claimed in claim 25, wherein this siloxane surface coating further comprises release oil.

30, a kind of dirty delivery system, it comprises: the monolayer of fulfiling the combination function that links coating and releasing layer in a monolayer that is applied to the anticorrosion epoxy layer of base material and is applied to this anticorrosion epoxy layer, this monolayer comprises the admixture of siloxane surface coating material and binding coating material as claimed in claim 1, and wherein this anticorrosion epoxy layer further comprises the silane coupler that contains primary amine and/or secondary amine.

31, dirty delivery system as claimed in claim 30, wherein this binding coated polymeric admixture further comprises siloxanes fluids.

32, dirty delivery system as claimed in claim 30, wherein this base material cleaned before using this first anticorrosion epoxy layer.

33, dirty delivery system as claimed in claim 32, wherein this base material sandblast before using this first anticorrosion epoxy layer.

34, dirty delivery system as claimed in claim 30, wherein link the coated polymeric admixture for about 5 weight % of this mixed layer to about 99 weight %.

35, dirty delivery system as claimed in claim 34, wherein link the coated polymeric admixture for about 50 weight % of this mixed layer to about 99 weight %.

36, dirty delivery system as claimed in claim 35, wherein link the coated polymeric admixture for about 75 weight % of this mixed layer to about 95 weight %.

37, dirty delivery system as claimed in claim 30, wherein this siloxane surface coating further comprises release oil.

38, a kind of method for preparing constituent, this method comprise organopolysiloxane are contacted with a kind of organic polymer, and wherein this organic polymer is formed by aggregating into the polymeric monomer of strand, and wherein this organic polymer be can't help crosslinked polyfunctional monomer and formed.

39, method as claimed in claim 38, it further comprises radical initiator is contacted with this organopolysiloxane and/or organic polymer.

40, method as claimed in claim 39, wherein this radical initiator is azo-two-alkyl nitrile.

41, method as claimed in claim 40, wherein this radical initiator is an azodiisobutyronitrile.

42, method as claimed in claim 39, wherein this radical initiator is a peroxide.

43, method as claimed in claim 42, wherein this radical initiator is benzoyl peroxide, di-t-butyl peroxide, cumyl hydroperoxide, reaches tert-butyl hydroperoxide.

44, method as claimed in claim 38, wherein this polysiloxane polymer has the following formula repetitive

R wherein ₁And R ₂Independently for being substituted or unsubstituted C ₁-C ₃Alkyl or be substituted or unsubstituted aryl, wherein this substituent group is if exist, and then is selected from cyano group, halogen or another group of another binding functionality is not provided.

45, method as claimed in claim 38, wherein at least one terminal of this polysiloxane polymer has the terminal-reactive group.

46, method as claimed in claim 45, wherein this terminal-reactive group is hydroxyl, alkoxyl, aryloxy group, amino, amide groups, halogen or vinyl.

47, method as claimed in claim 45, wherein this polysiloxane polymer is hydroxy-end capped polydimethylsiloxane.

48, method as claimed in claim 47, wherein this hydroxy-end capped polydimethylsiloxane is lower than 100 centistokes under 25 ℃.

49, method as claimed in claim 47, wherein this hydroxy-end capped polydimethylsiloxane is 2000 to 8000 centistokes under 25 ℃.

50, method as claimed in claim 47, wherein this hydroxy-end capped polydimethylsiloxane is 10,000 to 50,000 centistokes under 25 ℃.

51, method as claimed in claim 38, it further comprises the free radical that can produce in position and has the organic monomer that carries out radical polymerization down.

52, method as claimed in claim 38, wherein this organic polymer belongs to monomer by monoene and forms.

53, method as claimed in claim 52, wherein to belong to monomer be vinyl monomer to this monoene, propylene monomer, butene monomers, Vinyl Chloride Monomer, fluoride monomers, the perfluoroalkyl acrylate esters, vinyl acetate monomer, styrene monomer, cyclosubstituted styrene monomer, the ethenyl pyrrolidone monomer, the vinyl naphthalene monomer, N-VCz monomer, N-vinylpyridine noise made in coughing or vomiting alkane one monomers, acrylic monomers, methacrylic acid monomer, acrylonitrile monemer, the metering system nitrile monomer, vinylidene fluoride monomers, vinylidene chloride monomer, the acrylic aldehyde monomer, the methylacrolein monomer, the maleic anhydride monomer, the stilbene monomer, the indenes monomer, the maleic acid monomer, or fumaric acid monomer.

54, method as claimed in claim 38, wherein this organic polymer is styrene, butyl acrylate, other alkyl acrylate esters or its mixture.

55, method as claimed in claim 38, wherein to have weight average molecular weight be about 50,000 to 500,000 to this polymer.

56, as claim 38 or 39 described methods, wherein this contact is carried out in the drum blanket of nitrogen.

57, method as claimed in claim 38, it further comprises with difunctionality mooring agent and contacts.

58, method as claimed in claim 57, wherein this difunctionality mooring agent comprises amine functional group and class siloxanes functional group.

59, method as claimed in claim 39 is wherein introduced this organopolysiloxane and/or organic polymer with this initiator with multiple dose.

60, method as claimed in claim 39 is wherein introduced this organopolysiloxane and/or organic polymer with this initiator with single dose.

61, method as claimed in claim 38, it further comprises with firming agent and contacts, and wherein this firming agent is not a tin-based catalyst.

62, method as claimed in claim 38, wherein used shear rate is about 10 minutes between polymerization period ^-1To about 1500 minutes ^-1

63, method as claimed in claim 38, the product that wherein makes do not have elongated being separated or the polymer morphology of microphase-separated.

64, method as claimed in claim 38, it further comprises interpolation water.

65, a kind of preparation method with surface of dirty releasing properties, this method comprise compositions as claimed in claim 1 are applied to the surface.

66,, should the surface be the base material that comprises the anticorrosion epoxide wherein as the described method of claim 65.

67, a kind of preparation method with surface of dirty releasing properties, this method comprise compositions as claimed in claim 20 are applied to the surface.

68,, should the surface be the base material that comprises the anticorrosion epoxide wherein as the described method of claim 67.

69, a kind of preparation method of any described surface as claim 65 or 67, this method further comprises the application surface coating.

70, as the described method of claim 69, wherein this face coat is the siloxane surface coating.

71, a kind of product that makes by the method that organopolysiloxane is contacted with a kind of organic polymer, wherein this organic polymer is made up of the monomer that aggregates into monochain polymer, and wherein this organic polymer be can't help crosslinked polyfunctional monomer and is formed, and this organic polymer makes by the free radical that is exposed to the original position generation in the presence of this polydimethylsiloxane.

72, as the described product of claim 71, it further comprises radical initiator is contacted with this organopolysiloxane and organic monomer.

73, as the described product of claim 71, wherein this contact is carried out in the drum blanket of nitrogen.

74, as the described product of claim 71, wherein this method further comprises interpolation water.

75, as claim 20, each described dirty delivery system of 25 or 30, wherein this epoxide coating comprises the mooring agent, and this binding coating be can't help cross-linking agent and formed.

76, as claim 20, each described dirty delivery system of 25 or 30, wherein this epoxide coating and this binding coating are self assembly.

77, as the described system of claim 76, wherein this self assembly is interacted by siloxanes-siloxanes and causes.

78, as claim 20, each described dirty delivery system of 25 or 30, wherein this face coat and this binding coating are self assembly.

79, as the described system of claim 78, wherein this self assembly is interacted by siloxanes-siloxanes and causes.

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