CN1007903B - Antifouling polymeric composite - Google Patents

Abstract

The present invention relates to an antifouling polymeric composite which comprises a strong combining layer with crosslinking siloxane rubber and exudate, and a basic impermeable layer. An acrylic gluing film is used for gluing layers together. The volume of the strong combining layer at least accounts for 60% of the volume of the composite. The antifouling polymeric composite can also comprises one or a plurality of characteristic bodies composed of crosslinking siloxane rubber and fluorescent pigment.

Description

Antifouling polymeric composite

The present invention relates to the antifouling complex body of polymer (Polymeric antifouling composition) and make the method for coating structure (structures), also relate to the structure that obtains therefrom with the antifouling complex body of this polymer.

Over past ten years, because offshore installation develop rapidly, make that the problem that how to prevent the dirty sticking device of various organic-biologicals is for example increasingly important, grass, marine alga, tender tea leaves lotus Jie, pipe snail (tubeworms) are stained with in dirt, sepula, oyster, ascidean (ascidia), moss biology (bryozoa) or the like.

Early stage habitual antifouling coating is to form with the applying coating that contains Toxic matter.For example, use the coating of cupric, tin, mercury, arsenic, lead and their derivative.Because its validity period is limited, also has relevant ecological problem, the progressively discarded now this practice.The substitute is crosslinkable silicone rubber base coating, particularly English Patent 1,307, and 001 described normal temperature crosslinked silicone rubber performance is better, after it is applied lid (coat) and goes to the equipment, prevented organic adhesion basically.

In order to improve the antifouling property of silicone rubber base coating, existing suggestion adds certain fluid in antifouling coating, these fluid utmost points are separated out from silicone rubber lentamente, thereby can stop useless organic adhesion fouling (build-up) better, suitable fluid has, English Patent 1,470, the 465 siloxanes oils of describing, English Patent 1,581,727 low-molecular-weight polyolefins of describing, polyester, the polymeric polyisocyanate class, polyurethanes, polyepoxide class, lubricated oils and softening agent class.

Though silicone rubber, particularly the silicone rubber of room temperature crosslinkable has excellent drainage, but because their genus polyporus still, so water still can flow through from structure, if in antifouling complex body, contain a basic impermeable barrier, to prevent that the structure that water flows under the antifouling coating from getting on, that will be useful.For thick film layers (high-built layer)-this class layer that can use silicone rubber on stationary structure can be suitably prefabricated.With the minute quantity tackiness agent with silicone rubber layer and basic impermeable barrier suitably bonding get up to be beneficial to make, disposal in storage and the transportation, also be very important.

Have now found that, use a kind of special adhesive of film-type as thin as a wafer, can will contain the silicone rubber thick film layers and basic impermeable barrier secure bond of liquid body exudate.

The present invention relates to the antifouling complex body of a kind of polymer, it comprises a thick film layers that contains cross-linked silicone rubber and liquid body exudate, and a basic impermeable barrier, layer is bonding with a kind of esters of acrylic acid adhesive film with interlayer, and at least 60% is thick film layers in this composite structure volume.

According to the present invention, cross-linked silicone rubber used in the antifouling complex body of polymer can be produced from siloxane glue (gums), this siloxane glue is the high-molecular weight organosiloxane polymer of height line style, main chain is made up of the silicon and the Sauerstoffatom that alternately occur substantially, and organic substituent is connected on the Siliciumatom of main polymer chain.Siloxane glue (gum), for example the silicone gums of being made up of binary replacement siloxanes basically can use various catalyzer (as peroxide) to be heating and curing, or through radiation curing, can make crosslinked silicone rubber, whole or the overwhelming majority of organic substituent can be methyl group unit, and all the other are vinyl and/or phenyl unit.

Make siloxane glue (the being called RTV glue) self-vulcanizing that contains the silanol end group, also can prepare crosslinking silicone glue, whole or most substituting groups can be alkyl in the RTV glue, (particularly methyl class), all the other can be ethyl, and the alkyl of phenyl or replacement is as chlorophenyl, fluoro propyl group, or cyanoethyl.Recommend the silicone rubber of the RTV glue of the sort of room-temperature-curable of use, wherein organic substituent is made up of the segment that does not contain siloxanes, and these segments are to be made of repeating unit (particularly polymer segment), referring to European publication (European Patent Publication 0032597).They extremely suit to be solidified into silicone rubber, as the part of the antifouling complex body of polymer.

Preferably by alkylidene group (alkylene or alkylidene) polymer segment is connected on the Siliciumatom, polymer segment should be formed by the monomer derived that contains unsaturated ethylene linkage.For example, at least a portion is made of unsaturated acid or derivatives thereof (for example, the ester class is as, the ester of vinylformic acid and/or methacrylic acid and monovalence alcohols) in the monomer, and monomer also includes or comprises vinylbenzene.Should select the basis of the multipolymer of vinylbenzene and butyl acrylate for use as polymer segment.

Can make the siloxane glue room temperature reaction prepare cross-linked silicone rubber, promptly with two kinds of different methods, single-component RTV-system (one-pack RTV-system) and two component RTV-system (two-pack RTV-system), referring to English Patent 1,581,727.

The antifouling complex body of polymer of the present invention contains liquid organic compound, and it is the part of thick film layers, and the purpose that contains liquid organic compound is to reach best for the cycle that coating is not stain.

Select for use boiling point under those normal pressures to be at least 250 ℃ compound as the liquid organic compound of transudate.For example, siloxane fluid comprises dialkyl siloxane polymer class (wherein, alkyl can be with hetero atom substituents).Alkyl can be alkyl (particularly methyl class), or wherein part or all is aryl class (a particularly phenyl class).The fluid organic compound also contains the low-molecular-weight polyolefin class, and as, ethylene/propene copolymer, available especially is molecular weight up to about 5000, for example, and 300 to 500 polyisobutene.Also can adopt other kind liquid organic compound, as, lower molecular weight polydiene hydro carbons, polyester, the polymeric polyisocyanate class, the polyepoxide class, lubricated oils such as technical white oil class and softening agent class (as, the ester class that the lipid acid of hetero atom substituents or other substituted radical is arranged, phosphoric acid ester and halogenated hydrocarbon), recommend to use polyolefins, polybutene particularly, because contain the tear strength of the antifouling complex body of polymer of these materials, tensile strength, elongation at break and shore hardness all are improved.

The consumption of liquid organic compound can change in wide region, recommend consumption be per 100 weight part cross-linked silicone rubbers with 0.1 to 100 weight part fluid organic compound, be good with per 100 weight part cross-linked silicone rubbers with 10 to 50 weight part liquid organic compound.

Basic impermeable barrier should contain or be made up of (contain or consistof) polyvinyl chloride, Resins, epoxy or urethane.Preferably adopting polyvinyl chloride is a thick film layers as the impermeable barrier material owing to the cross-linked silicone rubber layer, therefore just can reduce the thickness of impermeable barrier greatly, for example, thickness can be far smaller than 1mm, does like this and has influence can not for the property disposed (handleabilify) of whole complex body.Recommending to adopt thickness is the impermeable barrier of 50 μ to 700 μ, is good with 200 μ to 600 μ.

As preceding described, between thick film layers and basic impermeable barrier, should have enough cohesive strengths, this is very important, because the expectancy life of the antifouling complex body of polymer depends on these characteristics to a great extent.Esters of acrylic acid has excellent bond performance, thereby solved between two basal layers of the antifouling complex body of the present invention's polymer, contain one extremely thin but have the problem of the thin layer of very strong cohesive force, found that some acrylic acid or the like materials can be used to film forming, ultrathin layer, this layer even may be a unimolecular layer.

Adopt (methyl) silicon Acrylote oxyalkyl ester effective, particularly use acrylic acid low alkylsiloxane ester, as, C _1-6Alkylsiloxane ester class.Wherein manyly can buy from market as esters of acrylic acid coating.We notice, adopt snappiness binding agent (silicone rubber toluene solution) adhesion thick film layers and basic impermeable barrier, the cohesive strength that can not get suiting.

By the present invention, the typical thickness of the thick film layers of antifouling polymeric composite is 3mm to 10mm, and they account for 60% of complex body cumulative volume at least, particularly are at least 80%.

Thick film layers can comprise one or more high-visibility pigments, preferably exist with one or more words or letter (specific characters) form, this makes the polymer antifouling polymeric composite also be suitable for use as each position of Offshore Units (underwater sites particularly, for example, ship; buoy, fuel container, floatation type and fixed offshore platform and pipeline) the discriminating mark.

Fluorescent chemicals is organic or inorganic compound (a particularly dyestuff).It can be transformed into the longer light of wavelength to the incident light of certain wavelength (exciting light exciting light), and this luminous energy was launched behind a short duration.Usually, exciting light is that the light that UV-light or visible light blue end light (visible light of the blue end of the spectrum) are launched has the spectrum wavelength of visible light.The colourity of the light of launching (hue) is preferably the same with the catoptrical colourity of dyestuff, because in this case, the radiator color that produces colourity has strengthened the color color of reflection, eyes are seemed bright especially, in the used high-visibility pigment of the antifouling complex body of polymer, support by the arm into suitable organic dye, can obtain this effect.With spectrum visible light part (in other words as exciting light, show the daylight fluorescein), under its influence, the dyestuff of having supported by the arm into sends fluorescence, does being good like this, this be because, when carrying out underwater operation in this case (for example, frogman's work), with the arclight irradiation, can be clear that and identify the mark on Offshore Units surface.

Suitable pigment major part is an organic resin, has wherein mixed into dyestuff, and is general, concentration lower (for example, 1-5% weight), and this class pigment can have been bought on the market.Can reach and select pigment according to colour type by the desired coloured light intensity of the residing main environment of Offshore Units underwater portion.

By the present invention, the amount of contained high-visibility pigment is the amount doesn't matter in the antifouling complex body of polymer, optimum content be cross-linked silicone rubber 0.1 to 20%(by weight).

Do the time spent when needs make antifouling complex body play (part) mark, silicone rubber used in the antifouling polymeric composite is preferably identical, so that the whole skin of complex body all has antifouling property.

By the present invention, complex body can contain a tackiness agent undercoat, this layer energy adheres to appointed part securely with the antifouling complex body of polymer, can use suitable typical binders, as some urethane and asphaltic base compound, as pitch, the outside surface of commonly using tackiness agent is topped from adhesion zone (self-adhisive tape), before use it is peelled off, the thickness of commonly using binder layer is generally 200 μ to 2mm, according to used different substances and the incompatible definite thickness of applied field.

The invention still further relates to the method for making coating structure with the antifouling complex body of the present invention's polymer, and the coating structure that obtains therefrom.The antifouling complex body of polymer is applied to the appropriate method that appropriate configuration gets on to be comprised: cleaning is prepared the body structure surface of coating, can select protective system coating earlier for use.And, to directly be fixed on the binder layer on surface with conventional art such as the antifouling complex body of casting ready-formed polymer, perhaps will have and strip from adhesion zone on the antifouling complex body of the internally coated ready-formed polymer of tackiness agent, and it will be pressed onto desire to protect on the surface then.When under water facility of protection, can, also preferably use bail, the antifouling prefabricated complex body secure bond of polymer that will have one or several symbol is tied up bail or tie then around going to the desire protection position of equipment on it.No matter be shore facilities, as the power station pipeline, fishing ground equipment, or offshore installation can both be with the present invention's the antifouling complex body coatings of polymer.The antifouling complex body of this nontoxic polymer has special benefits, because its expectancy life prolongs to some extent.When using under environment more difficult to get access, it is of crucial importance that this advantage then seems.

Example 1

With 150 weight parts commercially available organic-polysiloxane, this polysiloxane contains with vinylbenzene (about 20-25%, weight) and butyl acrylate (about 30-40%, weight) be the polymers grafted segment on basis, 6 parts of catalyzer that contain organo-tin compound and alkyl silicate admixture, and 30 parts of molecular-weight average are 350 polyisobutene thorough mixing.(can obtain from Wacker chemie, Munich Germany) is attached to polyvinyl chloride layer with this mixture and gets on 0.4 parts by weight of acrylic ester binding agent (bonding agent).This complex body self-vulcanizing, final thickness (sheet) is about 7mm, the siloxanes top shared volume of layer adds up to about 90% of cumulative volume, this complex body secure bond to block lath (panel) gone up the antifouling property of measuring complex body with pitch (bitmastic).The antifouling property of complex body, and the bond effect of polyvinyl chloride layer and thick film silicone rubber surface layer.All make us very satisfied.

Example 2

Repeat example 1 test, but add the commercially available daylight fluorescent orange pigment of 15 weight parts in finishing coat, be cured, the finished product show comprehensive excellent antifouling property.Under irradiation, also show good visibility.

Comparative Examples

Repeat example 1 described method, the preparation complex body, but use the elastic binder of the toluene solution of curable rubber as expection.After the self-vulcanizing, need only execute a power slightly, two layers of promptly very easy being torn are so this complex body is unsuitable for further processing/test.

Claims (8)

1, the antifouling complex body of polymer, this complex body contains thick film layers and the basic impermeable barrier of being made up of cross-linked silicone rubber and liquid body exudate, it is characterized in that: with a kind of (methyl) silicon Acrylote oxyalkyl ester adhesive film above-mentioned two layer materials are combined, and the volume of thick film layers accounts for 60% of complex body volume at least.

2, complex body according to claim 1, wherein, thick film layers contains normal temperature crosslinked silicone rubber, and this rubber comprises not siliceous segment, and this segment is made of repeating unit.

3, complex body according to claim 1, wherein, basic impermeable barrier is polyvinyl chloride layer or epoxy resin layer.

4, complex body according to claim 1, wherein, thick film layers comprises one or more symbol or letters of being made up of cross-linked silicone rubber and high-visibility pigment.

5, complex body according to claim 1 wherein, scribbles one deck under the basic impermeable barrier and commonly uses tackiness agent, and binder layer is outer available topped from adhesion zone.

6, make the method for coating structure, this method comprises, goes at least one position of outside surface the antifouling complex body of any described polymer is topped in the claim 1 to 5.

7, method according to claim 6, wherein, outside surface at least a portion is topped with the antifouling complex body of any described polymer in the claim 1 to 5, it is characterized in that polymer composite is with commonly using tackiness agent or being fixed to the lip-deep of described structure with bail (Clamping bands).

8, at least a portion topped structure (structure) of any described complex body in the claim 1 to 5.