Untitled record

Installation of pollution-resistant coverage

Antifouling coating composition

Full description

Background of the invention

This invention relates to a process for physically deter fouling of a substrate in an aqueous environment using a polyorganosiloxane comprising a coating composition and a substrate coated with said coating composition.

Man-made structures such as boat hulls, drilling rigs, dry dock equipment, oil production machinery, and pipes that are submerged in water are susceptible to contamination and contamination from aquatic organisms such as green and brown algae, and aquatic organisms such as green and brown algae. , oysters, and the like. These structures are usually metal, but may also include other structural materials such as concrete. This fouling is harmful to boat hulls, because it causes increased frictional resistance during movement through water, which consequently leads to reduced speeds and increased fuel costs. It is also harmful to fixed structures such as the legs of drilling rigs and oil production machines. Firstly, the resistance of thick layers of pollution to waves and currents can cause serious stresses in the structure in a potentially unexpected manner. Secondly, because fouling makes it difficult to inspect the structure for defects such as Cracks resulting from stress and rust. It is also harmful to pipes, such as cooling water inlets and outlets, due to the lack of cross-sectional area affected by contamination, and thus flow rates decrease.

Most commercially successful methods of fouling prevention involve the use of anti-fouling coatings containing substances toxic to aquatic life, for example

Tributylin chloride or cuprous oxide. These coatings, however, are viewed with increasing disfavor due to damaging effects such as toxins that may be released into the aquatic environment. Accordingly, there is a need for pollution prevention coatings that do not release obviously toxic substances.

It has been known for many years, for example as described in patents GB 1,307,001 and US 3,702,778. Silicone rubber coatings resist contamination by aquatic organisms. It is believed that these coatings provide a surface to which aquatic organisms cannot easily adhere, and can accordingly be called pollution-free coatings rather than anti-pollution coatings. Silicone rubbers and silicone compounds are generally very low in toxicity. The disadvantage of this anti-pollution system when applied to the hulls of ships is that although the accumulation of marine organisms is reduced, ships at relatively high speeds need to remove all types of pollution. Thus, in some cases, it turns out that for effective release from the hull treated with this polymer, it is necessary to sail at a speed of at least 14 knots. For this reason, silicone rubbers have had limited commercial success and there is a need to improve the anti-pollution and pollution-free properties of these environmentally friendly coatings.

Patent US 6,906,161 describes a room-temperature antifouling coating composition comprising an organosiloxane polyorganosiloxane with at least one side group of the formula R2-Si(R3)2-O-(R4O)b-R5 bonded to a silicon atom within each molecule. In this formula b is equal to an integer from 1-30, R2 and R3 represent hydrocarbon groups with 1-6 carbon atoms, R4 represents the alkylene group with 2-4 carbon atoms, and R5 represents a hydrocarbon group with 1-8 carbon atoms or group Represented by the formula R6-SiX3, where R6 represents a hydrocarbon group with 1-6 carbon atoms and X represents a hydrolysable group.

Patent WO 2004/081121 describes an anti-fouling coating composition comprising a copolymer which is obtained by polymerizing a monomer mixture including a monomer containing a Si- with two (meth)acryl end groups containing a divalent metal atom.

It has now been found that the natural deterrent to marine pollution can be further reduced, even under constant conditions, by using a coating formulation containing a specific copolymer.

General description of the invention

Therefore, the present invention relates to a process to naturally prevent contamination, physically deter fouling, from substrates in a water-polluting environment. This process includes placing a coating composition on the substrate, before it is exposed to the aforementioned environment. The composition contains (1) an organic polyorganosiloxane template polymer, polyoxyalkylene, which is retractable. The treatment has two reactive groups

If the X groups do not react with each other, the coating composition contains an organosilicon crosslinking agent having at least two Y groups reacting with the If the copolymer is a polyorganosiloxane polyoxyalkylene copolyme that contains two reactive groups .

If the listed X groups are reactive with each other, the coating formulation contains a catalyst to promote crosslinking. In addition, it may also contain an organosilicon crosslinking agent containing at least two Y groups interacting with said X groups.

The copolymer does not require the presence of a divalent metal atom such as Mg, Zn and Cu. Hence, in a preferred embodiment, the copolymer does not contain this metal.

The coating composition is applied to a substrate and cured to form a coated substrate. The resulting coating will consist of a water-soluble, hydrophilic polymer network comprising polyoxyalkylene organopolysiloxane template copolymer chains connected to each other by crosslinking sites on the organopolysiloxane template copolymer chains. Polyoxyalkylene and/or through an organosilicon crosslinking moiety which is attached to the crosslinking sites on the copolymer chains of the organosiloxane polyorganosiloxane polyoxyalkylene template. In a preferred embodiment, the cross-linking of the copolymer chains of the polyorganosiloxane polyoxyalkylene template is largely devoid of Si-OC bonds.

Polyorganosiloxane polyoxyalkylene template copolymer Within this specification, a template copolymer is defined as a copolymer that is essentially linear with chains consisting of identical polymeric templates that are attached to each other. These templates can be connected in any way, for example alternately or randomly. Preferably, the organopolysiloxane templates contained in the template copolymer independently of each other comprise 5-30 siloxane units. More preferably, polyoxyalkylene blocks contain 2-30 oxyalkylene units.

The first preferred type of organosiloxane matrix copolymer is polyorganosiloxane polyoxyalkylene, which is a matrix copolymer terminated with polyorganosiloxane polyoxyalkylene in the form PS (A PO A PS)n, where PS represents the polyorganosiloxane matrix and PO represents the polyoxyalkylene matrix. A represents a divalent radical, and n has a value of at least 1, preferably 10-250.

Other template copolymers may be used, for example a branched template copolymer, a template copolymer terminated with polyoxyalkylene or a template copolymer containing templates terminated with polyorganosiloxane and polyoxyalkylene. In a preferred embodiment, the reactive groups More preferably, the X-reactive groups are placed in the organopolysiloxane matrix of the copolymer. X-linkable reactive groups can be placed on the terminal silicon atoms of the polyorganoslioxane polyoxyalkylene block copolymer, especially if the copolymer is in the form of PS(A PO A PS)n.

In one embodiment, the block copolymers polyorganosiloxane polyoxyalkylene has the form PS (A PO A PS)n where PS represents an alkoxy-substituted silicon seed-terminated organopolysiloxane template of the formula Si(R)(R) OR where R An alkyl group has 1 to 4 carbon atoms, and each R represents an alkyl group with 1 to 6 carbon atoms, a phenyl group or an alkoxy group with the formula OR. Examples of these groups are trimethoxysilyl, triethoxysilyl, methyldimethoxysilyl, dimethylmethoxysilyl, dimethylethoxysilyl, and dimethylethoxysilyl.

The polyorganosiloxane polyoxyalkylene block copolymer can be prepared in the form PS (A PO A PS)n in a hydrosilylation reaction by reacting an organosiloxane polyorgnosiloxane containing two Si H groups with a polyether containing two unsaturated groups. Ethylenically unsaturated groups in such an amount that the Si H groups are present in excess of the ethylenically unsaturated groups. By ethylenically unsaturated groups, we mean a group with the formula >CH=CH2. The reaction is generally carried out in the presence of a silyl hydrogen bonding catalyst such as a platinum group metal or a compound thereof. The divalent A radicals resulting from the silyl hydrogen bonding reaction are alkylene radicals, with, for example, 2 to 6 carbon atoms based on the ethylenically unsaturated groups of polyether.

The organopolysiloxane that reacts with the polyether may be branched, but preferably linear polydiorganosiloxane with a degree of polymerization (DP) of 2 to 250 siloxane units, more preferably 2 to 100 siloxane units, and most preferably of 4 to 40 siloxane units. Preferably, the organic groups for organic polysiloxane are chosen from phenyl and alkyl groups with 1 to 18, preferably 1 to 6 carbon atoms. Most preferably, at least 90% of the organic groups attached to the Si are methyl groups; For example, an organopolysiloxane is a Si H-functionalized polydimethylsiloxane. An organopolysiloxane may contain more than two Si H groups, but this most likely results in a branched organopolyoxysiloxane-polyoxyalkylene copolymer. Most preferably, the organopolyorgnosiloxane contains two Si H groups, one at each end of the organopolysiloxane chain, so that the reaction with the polyether produces a template copolymer that ends with an organopolyorgnosiloxane with reactive Si-H groups located on the terminal silicon atoms of the polycarbonate template. Organosiloxane copolymer, as shown in the reaction scheme below.

<img file="SA3115B1_D0001.tif" />

Template-type SPE terminated with SiH chloroplatinic acid

Die-type SPE terminated with SiH

Chloroplatinic acid

Organopolysiloxane compounds containing Si-H groups on the non-terminal siloxane units, or on both the non-terminal siloxane units, can be used alternatively.

In order to give the desired hydrophilic properties, it is preferable that at least 50% of the polyoxyalkylene units in the polyoxyalkylene matrix be oxyethylene units. Preferably, the polyether used to prepare the template copolymer polysiloxane organopolyoxykylene is polyethylene oxide, although the poly(oxy-ethylene oxypropylene) copolymer containing most polyoxyethylene units can also be used. The ethylene unsaturated groups of polyethers may for example be allyl, phenyl, hexenyl or isobutenyl groups. A preferred example of a polyether is polyethylene glycol diallyl ether. Polyethylene oxide preferably has a degree of polymerization of 4 to 100, more preferably 4 to 40 oxyethylene units. The molar ratio of oxyalkylene. For example, it is preferable that the ratio of oxyethylene units to siloxane units in the copolymer polyorganosiloxane polyoxyalkylene be in the range of 1:0.05 to 1:0.5.

Si-H-functional polyorganosiloxane and polyether containing ethylenically unsaturated groups react preferably with a molar ratio of Si-H- to ethylene-unsaturated groups in range 1: 1.5 to 1:6, and it is more preferable to be 1:2 to 1:4. The reaction can be performed at ambient temperature, but a higher temperature in the range of 60 to 200°C, for example 100 to 150°C, may be preferable. The reaction generally takes place in the presence of a catalyst containing a platinum group metal such as platinum or rhodium. One of the preferred platinum catalysts is hexachloroplatinic acid, or the product of the reaction of chloroplatinic acid and an organosilicon compound containing a terminal aliphatic unsaturation. The other catalyst is the complex compound platinum divinyl tetramethyl disiloxane. It is preferable that the catalyst be used in quantities ranging from 0.00001-0.5 parts platinum or rhodium per 100 parts by weight of organopolysiloxane containing Si-H-functional groups, and most preferably 0.00001-0.002 parts.

The organosiloxane groups may react with Si-H-functional polyorganosiloxane and polyether containing ethylenically unsaturated groups instead using a molar excess of polyether containing ethylenically unsaturated groups. , for example with a molar ratio of Si-H- groups to ethylene unsaturated groups in the range from 1.5:1 to 6:1, thus producing a template copolymer of the form PO-(A-PS-A-PO)n, Where PO, PS and A are defined as above and PO templates have terminal ethylene unsaturated groups. This copolymer may be crosslinked to a template by an organosilicon crosslinking agent with reactive Si-H groups, for example poly(methylhydrogensiloxane) or methyl hydrogen siloxane dimethylsiloxane copolymer, to produce a non-hydrophilic polymer network. Soluble in water according to the invention. Alternatively, the terminal ethylene unsaturated groups may react with a suitable silane to convert them into reactive groups X.

Organosilicon crosslinking agent

As mentioned above, if the

In addition, the composition may contain a catalyst.

If the polyorganosiloxane polyoxyalkylene block copolymer contains only two reactive groups There are 6 interacting groups for each molecule, to help form a network (crosslinking) instead of just lengthening the chain. For example, if the organosilicon crosslinking moiety is a branched polyorganosiloxane containing at least three reactive Y groups, it may become linked to at least three polymer chains.

Examples of suitable And ethylenically unsaturated groups.

Groups Y that interact with one or more groups

When the X groups are Si-H-groups

If the reacting groups are Polysiloxane, for example, may consist of siloxane units chosen from Q units with the formula (SiO4/2), T units with the formula RcSiO3/2, D units with the formula Rb2SiO2/2, and M units with the formula Ra3SiO1/2, where the substituents Ra are chosen. The alkyl and alkenyl groups have 1 to 6 carbon atoms, Rb, Rc, and at least three Ra, Rb, and/or Rc substituents that form alkenyl units.

If the polyorganosiloxane polyoxyalkylene block copolymer is of the form PS (A PO A PS)n, where the Crosslinking is branched organic polyorganosiloxane that contains ethylenically unsaturated Y groups located on at least three branches. This branched polyorgnosiloxane generally includes Q units and/or T units, M units and optionally D units. The alkenyl groups are preferably located in the M units. Organic polysiloxane may be, for example, a branched siloxane containing one or more Q units with the formula (SiO4/2), zero to 250 D units with the formula Rb2SiO2/2, and M units with the formula RaRb2SiO1/2, where the substituents Ra and Rb are chosen. Of the alkyl and alkenyl groups with 1 to 6 carbon atoms, at least three Ra substituents in branched siloxanes are alkenyl units. If the copolymer of the polyoxykylene organopolysiloxane template has a relatively large chain length, a low molecular weight Q-branched siloxane crosslinking agent may be preferred, for example a Q-branched siloxane with a phenyl functional group containing a Q unit, four dimethyl units. Phenylsilyl M, and from 0 to 20 units dimethylsiloxane D, which may have the following formula:

<img file="SA3115B1_D0002.tif" />

If the polyoxykylene organosiloxane template copolymer contains more than two Si-H- groups, the orgnosilicon crosslinking agent need not contain more than two ethylene-unsaturated groups. For example, the crosslinking agent may be an organopolydisiloxane containing two ethylenically unsaturated groups, such as dimethylphenylsilyl-terminated polydimethylsiloxane, or it may be a mixture of such an organopolydisiloxane containing two ethylenically unsaturated groups with Branched organic polysiloxane that contains ethylenically unsaturated Y groups located on at least three branches.

If the polyorganosiloxane polyoxyalkylene block copolymer contains reactive groups A catalyst containing a platinum group metal such as platinum or rhodium. The preferred platinum catalysts are as described above. The catalyst should preferably be used in quantities ranging from 0.00001-0.5 parts platinum or rhodium per 100 parts of the polyorganosiloxane polyoxyalkylene block copolymer containing the functional group Si-H-. It is preferable that the copolymer of the polyoxyalkylene organosiloxane template containing Si-H- groups and the organosilicon crosslinking agent react in a molar ratio of Si-H- groups to the ethylene unsaturated groups in the range from 1:1.5 to 6:1. 2:1 to 4:1 is more preferred. The crosslinking reaction can be carried out at ambient temperature but takes place faster at high temperature in the range of 60 to 200°C.

Because the crosslinking reaction takes place at ambient temperature when both the polyorganosiloxane polyoxyalkylene block copolymer chains, which contain Si-H- groups, the crosslinking agent that contains ethylenically unsaturated groups, and the catalyst catalyst in contact with each other, it is preferable to fill the curable paint composition based on these reactive groups in two containers, So that the polyorganosiloxane polyoxyalkylene block copolymer, the crosslinking agent, and the catalyst are not together in the same package. The contents of the two containers may be mixed briefly before application. For example, the catalyst may be packed with a crosslinking agent containing ethylene unsaturated groups, the polyorganosiloxane polyoxyalkylene block copolymer containing the Si-H groups being in a separate container. Alternatively, the organopolyoxykylene block copolymer and the crosslinking agent may be packaged together, and the catalyst may be packaged separately, optionally with a portion of the organopolyoxylkylene block copolymer component or a portion of the crosslinking agent component.

When the X groups are Si-alkoxy groups or silanol, if the If present, it is either Si-alkoxy or silanol groups.

If the reactive groups

The coating may thus comprise the polyorganosiloxane polyoxyalkylene block copolymer chains linked together by Si-O-Si bonds derived from Si-alkoxy crosslinking sites at the ends of the polyorganosiloxane polyoxyalkylene block copolymer chains. Alkylene polyorganosiloxane polyoxyalkylene block copolymer.

The reactive groups It represents an alkyl group containing 1 to 6 carbon atoms, a phenyl group, or an alkoxy group with the formula OR. Examples of these groups are trimethoxysilyl, triethoxysilyl, methyldimethoxysilyl, dimethylethoxysilyl, dimethylethoxysilyl, and dimethylethoxysilyl.

Reacting groups Y on the crosslinking agent may exist in groups of the formula Si(R)2(OR), where R, R' have the same meanings as given above. In its simplified form, the crosslinking agent may be tetraalkyl orthosilicate, such as tetramethyl, tetraethyl, tetrapropyl, tetrabutyl orthosilicate, tert-alkoxysilane, for example alkyl tert-alkoxysilane, such as methyl tri-methoxysilane. methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, or n-octyltriethoxysilane, octyltriethoxysilane, Or dialkoxysilane, for example dimethyldiethoxysilane, such as dimethyldiethoxysilane.

If the polyorgnosiloxane polyoxyalkylene block copolymer contains two alkoxy groups linked to Si, the organosilicon crosslinking agent must contain more than two alkoxy groups linked to Si, for example, the third may be alkoxy silane. or a polysiloxane containing at least one Si(OR)3 unit, where R is defined as above, or a polysiloxane containing at least two Si(R'')(OR)2 units, Or a polysiloxane containing at least three Si(R'')2(OR) units, where "R" represents an alkyl group containing from 1 to 6 carbon atoms.

If the polyorgnosiloxane polyoxyalkylene block copolymer contains more than two alkoxy groups bonded to Si, an organosilicon crosslinking agent containing two alkoxy groups bonded to Si and/or an organosilicon crosslinking agent containing more than one alkoxy group may be used. Of the two alkoxy groups attached to Si. Alternatively, such a copolymer of a polyoxyalkylene organosiloxane template containing more than two Si-linked alkoxy groups could be processed by reacting the Si-linked alkoxy groups with each in the presence of moisture, preferably as a condensation catalyst, without Need for another crosslinking agent.

Organopolysiloxane block copolymer Polyorgnosiloxane polyoxyalkylene block copolymer containing more than two Si-alkoxy groups linked to Si is a self-crosslinking polymer that can be processed into a hydrophilic polymer network. An example of such a copolymer is a copolymer of an organopolysiloxane polyoxyalkylene template terminated with Si(R'2)(OR)2 units, where R and R' are defined as above. For example, a block copolymer of the form PS (A PO A-PS)n, where the reacting Si(R')(OR)2 units are located on the terminal silicon atoms of the polyorgnosiloxane block.

Organosiloxane polyoxyalkylene block copolymer containing alkoxy groups linked to Si-alkoxy groups may alternatively be a block copolymer of the form PO-(A-PS-A-PO)n. Such a template copolymer containing terminal ethylene unsaturated groups may be prepared as described above and may react with silane of the formula H-Si(R')2(OR), where R and R' are defined as above, to convert the unsaturated groups. Ethylenically unsaturated groups into reactive groups of the formula Si(R')2(OR) that contain one, two, or three reactive alkoxy groups each attached to a silicon atom in the copolymer of the organopolysiloxane polyoxyalkylene template. Examples of these silanes are trimethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane.

Typically, the crosslinking agent, if used, should preferably be a polydiorganosiloxane, for example an organopolydiorganosiloxane such as polydimethylsiloxane containing end units of the formula Si(R')2(OR), especially end units where At least one of the R' groups is an alkoxy group, or branched organopolysiloxane in which each branch terminates in a special group of the formula Si(R')2(OR). It will be recognized that some crosslinking between the organosiloxane polyoxyalkylene template copolymer chains ending with reactive groups of the formula Si(R')2(OR) may occur even in the presence of the crosslinking agent. It may be preferable to use a small amount of crosslinking agent to control the properties of the cured polymer formulation. For example, branched organopolysiloxanes containing Si-alkoxy groups can be added to increase the degree and/or density of the crosslinking materials, resulting in a stiffer cured polymer formulation. Alkoxy-terminated organic polydisiloxanes with a relatively large chain length, for example polydimethylsiloxanes of DP 100 up to 250 or even 500, can be added to reduce the density of the crosslinker, resulting in a more flexible cured polymer formulation. The total ratio of the copolymer alkoxy-functional polyorganosiloxane(s) to alkoxy-functional polyorganosiloxane(s) can be any value in the range from 0:100 to 99:1.

Si-alkoxy groups react with each other in the presence of moisture to form Si-O-Si bonds. This reaction may proceed, even at ambient temperature, without a catalyst, but may progress more rapidly in the presence of a siloxane condensation catalyst. Any suitable catalyst can be used for polycondensation. It includes protonated acids, Lewis acids, organic and inorganic bases, transition metal compounds, metal salts, and complex organometallic compounds.

The siloxane condensation catalyst may comprise, for example, a transition metal complex of titanium, zirconium, and hafnium. The preferred titanium compounds are titanium alkoxides, otherwise known as titanate esters. Alternatively, zirconium alkoxides (zirconate esters) or hafnium alkoxide can be used. Titanate and/or zirconate based catalysts may comprise a compound according to the general formulas Ti[OR5]4 and Zr[OR5]4, respectively, where each R5 may be the same or different and represent a primary, secondary or tertiary aliphatic hydrocarbon group. Monovalent, which may be linear or branched, contain from 1 to 10 carbon atoms. Optionally, titanate may contain partially unsaturated groups. However, preferred examples of R5 include but are not limited to methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, and a branched alkyl group such as 2,4-dimethyl. -3-pentyl. Preferably, when each R5 is identical, each R5 represents an isopropyl, a branched secondary alkyl group or a tertiaryl alkyl group, in particular, a tertiary buty. Alternatively, titanate may be chelated. Chelation may be by any suitable chelating agent such as alkyl acetylacetonate, such as methyl or ethylacetyl acetonate. Any suitable chelated titanates or zirconates can be used. Preferably, the chelating group used is a mono-keto ester such as acetyl acetone and alkyl acetoacetonate, to give chelating titanate compounds such as, for example, diisopropyldi(acetylacetonyl)titanate, diisopropyldi(ethylacetoacetonyl)titanate, diisopropoxytitanium. diisopropoxytitanium bis(ethylacetoactat), etc. Examples of suitable catalysts are further described in EP1254192 and WO200149774.

The amount of a transition metal compound such as a titanate ester present as a catalyst may be, for example, 0.01-2%, based on the weight of the organopolysiloxane-polyoxyalkylene copolymer plus the crosslinking agent.

Other condensation catalysts suitable for condensation that can be used as a catalyst for the polymerization reaction of the present invention include condensation agents including tin, lead, antimony, iron, cadmium, barium, manganese, zinc, chromium, and cobalt. cobalt, nickel, aluminum, gallium, or germanium. Examples include iron stearate, lead octoate, metal triflate compounds, organotin metal catalysts such as triethyltin tartrate, tin octoate, tin oleate, tin naphthalate, butyltin tert-2-ethylhexoate, tin butyrate, carbomethoxyphenyltin tin tert subrate. , isobutyltin tricerate, and organotin disalts, especially dicarboxylate compounds such as dibutyltin diacylate, dimethyltin dibutyrate, dibutyltin dimethoxide, dibutyltin diacetate, dibutyltin diacetate. Dimethyl tin bisneodecanoate, dibutyl tin dibenzoate, dimethyl tin dineodeconoate, dibutyl tin acetoacetonate or dibutyl tin dioctoate.

Also, the catalyst may be organobismuth or an organophosphate such as di(2-ethyl-hexyl)organo-phosphate, or it may comprise a halogenated organic acid which has at least one halogen substituent on a carbon atom which The A-position of the acid group and/or at least one halogen substituent on the carbon atom which is in the β-position of the acid group, or a derivative which is hydrolytic to form that acid under condensation reaction conditions.

The catalyst may alternatively be a Lewis acid catalyst - a Lewis acid catalyst a Lewis acid is a substance which will take an electron pair to form a covalent bond - for example, boron trifluoride, FeCl3, AlCl3, ZnCl2, ZnBr2, catalysts In the form M1R4 fX1g, where M1 represents B, Al, Ga, In or Tl, each R4 is independently identical (identical) or dissimilar and represents a monovalent aromatic hydrocarbon moiety with 6 to 14 carbon atoms, such as a monovalent aromatic hydrocarbon moiety with preferably at least one electron withdrawing element or group such as CF3 , -NO2 or CN, or substituted by at least two halogen atoms; X1 represents a halogen atom; f equals 1, 2, or 3; g equals zero, 1 or 2; Provided that f+g =3. One example of such a catalyst is B(C6F5)3.

An example of a base catalyst is an amine or quaternary ammonium compound such as tetramethylammonium hydroxide. Amine catalysts may be used alone or in combination with another catalyst such as tin carboxylate or organotin carboxylate; For example, laurylamine may be particularly effective with this lead compound.

Since the polyorganosiloxane polyoxyalkylene block copolymer containing Si-alkoxy groups and a cross-linking agent containing Si-alkoxy groups do not react in the absence of moisture, even in the presence of a catalyst, the processable composition based on them can be stored in One container, provided that the reagents are dry and the container is moisture resistant. When the container is opened, the curable composition can be applied to a surface and will generally cure in the presence of atmospheric moisture. Processing proceeds rapidly at ambient temperature in the presence of a catalyst, particularly titanium tetraalkoxide or chelated titanium alkoxide.

One type of composition processable according to the present invention includes a polyoxykylene organopolysiloxane template copolymer containing Si-alkoxy groups, optionally a crosslinking agent containing Si-alkoxy groups, and a siloxane condensation cataylst, the composition being filled in a container Moisture resistant.

Although the hydrosilylation reaction can be performed to produce a polyorgnosiloxane polyoxyalkylene block copolymer terminated by reactive Si-H groups easily under factory conditions, systems based on these copolymers do not give rapid temperature curing. surrounding. It is preferable for this to convert the Si-H-terminated organosiloxane-polyoxyalkylene copolymer into a copolymer terminated with another reactive group. Si-H groups may generally react with a compound containing an ethylene unsaturated group which reacts with a Si-H group and another reactive group, such as Si-alkoxy, which does not react with Si-H but forms the X-reactive groups of the resulting polymer. For example, reactive groups of the formula -Si(R)2(OR), where R and R' do not have the previously given meanings, can be introduced into the copolymer with the Si-H functional group, for example by reaction with an ethylene-unsaturated alkoxysilane of the formula Z-Si(R)2(OR), where Z represents an ethylene unsaturated group such as vinyl, allyl, isobutenyl or 5-hexenyl. Examples of ethylenically unsaturated alkoxysilanes are phenyltrimethoxysilane, allyltrimethoxysilane, and methylphenyldimethoxysilane. If the Si-H-terminated organopolyoxyalkylene block copolymer has the formula PS(APO-A-PS)n as previously defined, then the Si-terminated polyoxykylene organosiloxane block copolymer with the formula PS(APOA-PS) can be produced. n, where PS' represents an organopolysiloxane template terminating with an alkoxy-substituted silicon atom with the formula -Si(R)2(OR), PO represents a polyoxyalkylene template, A represents a divalent radical, and n has a value of at least 1. The copolymer reaction of the Si-H-terminated organopolysiloxane polyoxyalkylene template with ethylene-unsaturated polyethylene oxysilane can be performed using the same catalysts and reaction conditions as described above for the reaction of Si-H-terminated organopolysiloxanes with ethylene-unsaturated polyether.

The crosslinking group, if used, can also be prepared by a hydrosilylation reaction. For example, a Si-H-terminated polyorgnosiloxane may react with ethylenically unsaturated alkoxysilane. Alternatively, organopolysiloxanes containing ethylene-unsaturated groups may react with polysiloxanes containing at least one Si-H group and at least one Si-alkoxy group.

The reactive group-terminated polyoxysiloxane polyoxykylene copolymer of the formula Si(R)(OR)2 contains 2 or 3 reactive Si-linked alkoxy groups at each end of the copolymer chain. It does not need to interact with a highly functional or branched crosslinking material to form a network. The crosslinking material used with the copolymer is an organopolysiloxane/polyoxyalkylene. This may be, for example, an organopolydisiloxane, for example, a polydimethylsiloxane, terminating with Si-alkoxy groups such as groups of the formula -Si(R)(OR)2.

Alkoxy-terminated organopolydisiloxanes can be prepared by reacting Si-H-terminated organopolydisiloxanes with ethylene-unsaturated alkoxy-silane of the formula Z-Si(R)(OR)2 in the presence of a platinum group metal catalyst. The organopolydisiloxane may be, for example, polydimethylsiloxane with a DP in the range from 4 to 500 siloxane units.

The crosslinking agent for the organopolysiloxane polyoxyalkylene copolymer terminated with reactive groups of the formula -Si(R)(OR)2 may alternatively or additionally comprise an organopolysiloxane containing -Si(R)2(OR) groups, wherein is defined R and R' As above, the branched organic polysiloxane may for example be a Q-branched polysiloxane in which each branch terminates in a -Si(R)2(OR) group. Branched organopolysiloxane groups can be formed by reacting ethylene-unsaturated branched organosiloxanes, for example the Q-branched siloxane with a vinyl functional group described previously, with a short-chain polyorgnosiloxane containing a Si-H group and a Si(R) group with the formula )2(OR), for example polysiloxane with the formula

<img file="SA3115B1_D0003.tif" />

In the presence of a platinum group metal catalyst, the branched organopolyorgnosiloxane crosslinking agent can be prepared alternatively from branched organopolysiloxanes containing Si-H groups, for example Q-branched polysiloxane having terminal dimethylsilyl groups. , with ethylene-unsaturated alkoxysilane with the formula Z-Si(R)(OR)2.

It may be preferable to use a mixture of alkoxy-terminated organic polydisiloxane and alkoxy-terminated Q-branched polysiloxane.

Additional components

The coating composition used in the present invention may also include one or more excipients and/or fillers, one or more pigments or colors, moisture scavengers, and non-reactive fluids.

Examples of suitable excipients or fillers are barium sulphate, calcium sulphate, calcium carbonate, silica or silicate groups (e.g., feldspar, talc, feldspar and china clya), including pyrogenic silica, bentonite and other clays, and solid silicone resins, which are generally branched polysiloxanes, such as a siloxane resin having Q units of the formula SiO4/2 and M units of the formula Rm3SiO1/2, where The Rm substituents are chosen from alkyl groups with 1 to 6 carbon atoms and the ratio of M units to Q units is in the range 1:0.4 to 1:1.

Examples of pigments include black iron oxide, titanium dioxide, foil materials (eg aluminum flakes), other pigments or so-called barrier pigments or anti-corrosion pigments such as zinc dust or zinc alloy. It is preferable that the dye concentration be in the range of 5-25%.

Suitable unreactive fluids are silicone oils such as methylphenyl silicone oil, petroleum oils, polyolefin oils, polyaromatic oils, fluoro resins such as polytetrafluoroethylene or alkyl-containing polymers. Fluoro-linked or alkoxy-containing, or combinations thereof. The preferred non-reactive fluid is methylphenyl silicone oil. The unreacted fluid percentage is preferably 5-25 wt%, more preferably 5-10 wt%, based on the solids content of the coating composition.

Preferably, the paint composition should have a solids content, defined as the weight percentage of volatile matter, of 35%, more preferably at least 35 weight%, and more preferably at least 70 weight%. The solids content range may be up to 100 wt%, preferably up to 95 wt%, most preferable up to 90 wt%, and most preferable up to 80 wt%.

Paint

The coating composition according to the present invention allows the formation of a cured coating which is essentially insoluble in water and has hydrophilic properties.

The thickness of the paint layer when dry is preferable to be in the range from 50 to 400 microns, most preferably in the range from 75 to 250 microns, and preferably 100 to 200 microns.

The coating is particularly suitable for the physical prevention of fouling by aquatic organisms such as algae, barnacles, and mussels on underwater structures, such as ship hulls, cooling water inlets for power plants, fish farming equipment, and the surfaces of the underwater area and the droplet area of production platforms. Oil.

Detailed description

Examples

Example 1

37.5 g of polyethylene glycol diallyl ether with an average DP of 10 in 31.20 g of toluene was placed in a three-necked flask and heated to 65°C in an atmosphere of pterogen, followed by 165 μl of chloroplatinic acid catalyst, then added. 100 g liquid polydimethylsiloxane terminated with dimethylhydrogensilyl with an average DP of 6.7 drip. The ratio of Si:H groups to allyl groups was 1:3. The mixture was heated for 1 h at 80˚C, then cooled to form a solution of a Si-H-terminated polysiloxane-polyoxyethylene template copolymer to a Si-H content of 5.36%.

The previously produced polymer solution was mixed with 2 by weight platinum vinyl siloxane complex dissolved in vinyl siloxane copolymer at 0.5% platinum and with a Q-branched polysiloxane terminated in vinyl with the formula

<img file="SA3115B1_D0004.tif" />

It contains a total of 100 D-siloxane units to give the molar ratio of the Si - H groups of the template copolymer polysiloxane polyoxyethylene terminated with Si - H to the vinyl groups 1:1.4. The mixture was applied to the surface of a test dish and left for 1 hour at ambient temperature. The formulation has been processed into a water-insoluble coating.

Example 2

Example 1 was repeated, replacing the Q-branched crosslinking agent with a Q-branched polysiloxane with the same general formula but containing a total of 225 D-siloxane units, keeping the Si-H to vinyl molar ratio at 1:1.4. The mixture was applied to the surface of the test dish and left for 1 hour at ambient temperature. The resulting coating was harder and more brittle than the cured composition of Example 1.

Examples 4 and 5

The Si-H-terminated polysiloxane polyoxyethylene black block copolymer obtained in Example 1 was mixed with an equal weight of Si-H-terminated polydimethylsiloxane with substantially the same Si-H content. The mixture was mixed with 2% by weight platinum vinylsiloxane complex dissolved in vinylsiloxane copolymer at a rate of 5% platinum and with Q-branched polysiloxanes terminated with vinyl to give a Si-H to vinyl ratio of 1:1.4. The branched polysiloxane Q contained 100 siloxane units (Example 4) or 225 siloxane units Q (Example 5). The resulting compositions were applied to the test surface and treated as described in Example 1. Water-insoluble coatings were produced.

Examples 6 to 8

The Si-H-terminated polysiloxane polyoxyethylene black copolymer obtained in Example 1 was mixed with Si-H-terminated polydimethylsiloxane with substantially the same Si-H content in weight ratios of 50:50 (Example 6 ), 70:30 (Example 7), and 90:10 (Example 8). Each of these mixtures was mixed with 2% by weight platinum vinylsiloxane complex dissolved in vinylsiloxane copolymer at a rate of 0.5% platinum and with Q-branched vinyl-terminated polysiloxane for Example 3 to give a Si-H to vinyl ratio of 1:1.4. The resulting compositions were applied to a test surface and treated as described in Example 1. Hydrophilic water-insoluble hydrophilic coatings were produced.

Examples 9 to 11

A polysiloxane polyoxyethylene black copolymer ending with Si-H was prepared as described in Example 1, but by replacing the polydimethylsiloxane fluid with a polydimethylsiloxane fluid with an average DP of 19 and substituting Polyethylene glycol di-allyl ether with 6.20 g Polyethylene glycol di-allyl ether with an average DP of 4.5 (Si-H:allyl ratio 1:3). The resulting polysiloxane polyoxyethylene block copolymer has a Si-H content of 2.85%.

In Examples 9-11, the polysiloxane polyoxyethylene template copolymer is processed with Q-branched vinyl-terminated polysiloxane polyoxyethylene black copolymers of Examples 1, 2, and 3, respectively. The amount of vinyl-terminated polysiloxane was such that it gave a Si-H to vinyl ratio of 1.2 (Examples 9 and 10) or 1.4 (Example 11). A water-insoluble hydrophilic coating was produced in each example. In general, the coatings were somewhat stiffer than the corresponding coatings of Examples 1 to 3.

Examples 12 to 14

The Si-H-terminated polysiloxane polyoxyethylene black copolymer obtained in Example 9 was mixed with Si-H-terminated polydimethylsiloxane with substantially the same Si-H content in weight ratios of 50:50 (Example 12 ), 70:30 (Example 13), and 90:10 (Example 14). Each of these mixtures was mixed with 2% by weight platinum vinylsiloxane complex dissolved in vinyl siloxane copolymer at a rate of 0.5% platinum and with Q-branched polysiloxanes terminated with vinyl for Example 3 to give a Si-H to vinyl ratio of 1:1.4. The resulting compositions were applied to the test surface and cured as described in Example 1. Water-insoluble hydrophilic coatings were produced.

Example 15

A Si-H-terminated polysiloxane polyoxyethylene black copolymer was prepared as described in Example 9. The template copolymer had a Si-H content of 2.42% and contained a precipitated catalyst. 100 g of Si-H-terminated polysiloxane polyoxyethylene template copolymer in 30 g toluene was placed in a three-necked flask and heated to 65 °C in a nitrogen atmosphere. 37.16 g phenyl trimethoxysilane was added dropwise. The ratio of Si:H groups to vinyl groups was 3:1. The mixture was heated for 1 h at 80 °C, then cooled to form a solution of the polysiloscan-polyoxyethylene template copolymer terminated with Si(CH3)2-CH2CH2-Si(OCH3)3 groups. This copolymer had an average molecular weight Mn of 3.535 and contained 6.95% by weight of methoxy groups.

The methoxy-terminated Si-terminated copolymer of example 15 was mixed with a titanium tetra-n-butoxide catalyst to a level of 0.1 wt% Ti based on the copolymer, applied to the test surface, and allowed to cure in a humid atmosphere at ambient temperature. A hydrophilic coating was produced.

Example 16

Reaction of the vinyl-terminated Q-branched polysiloxane from Example 3 with polydimethylsiloxane with the trimethoxysilyl functional group ending with

H in the form

<img file="SA3115B1_D0005.tif" />

It has a DP, in the presence of 2% by weight platinum vinyl siloxane complex A complex dissolved in a vinyl siloxane copolymer at 0.5% platinum to produce a crosslinking material with a branched S-methoxy functional group with Mn 1.657 and a methoxy content of 25.55% by weight.

The Si-terminated copolymer of example 15 (9.09 g) was blended with 0.91 g of Si-terminated methoxy crosslinking material and a titanium tetra-n-butoxide catalyst to a level of 0.1 wt% Ti on a total siloxane basis, and Apply the mixture to the test surface and allow to cure in a humid environment at ambient temperature. A hydrophilic coating is produced.

Examples 17 to 19

Example 16 is repeated, except that the Si-terminated copolymer of Example 15 is partially replaced by Si-terminated polydimethylsiloxane in weight ratios of 50:50 (Example 17), 70:30 (Example 18), and 90:10 (Example 19). The polydimethylsiloxane was terminated with Si(CH3)2-CH2CH2-Si(OCH3)3 groups and had a molecular weight and methoxy content similar to the copolymer of Example 15. Each composition was processed into a hydrophilic coating.

Example 20

Following the method of Example 15, react the Si-H-terminated Si-methoxy terminated copolymer prepared in Example 1 with 85.46 g vinyltrimethoxysilane (Si-H to vinyl ratio 3:1) to produce the template copolymer Polyoxyethylene polysiloxane with Mn 1.754 ends with Si(CH3)2-CH2CH2-Si(OCH3)3 groups and has a methoxy content of 18.47% by weight.

The Si-terminated methoxy copolymer of Example 20 was mixed with a titanium tetra-n-butoxide catalyst to a level of 0.1 wt% titanium, applied to the test surface, and allowed to cure in a humid atmosphere at ambient temperature. A hydrophilic coating was produced.

Example 21

The Si-terminated copolymer of Example 20 (9.03 g) was blended with 0.97 g of the Si-terminated cross-linking material described in Example 16 and a titanium tetra-n-butoxide catalyst to a level 0.1% by weight Ti, and the mixture was applied to the test surface and allowed to cure in a humid atmosphere at ambient temperature. A hydrophilic coating was produced.

Examples 22 to 24

Example 21 is repeated, except that the Si-terminated copolymer of Example 20 is partially replaced by Si-terminated polydimethylsiloxane in weight ratios of 50:50 (Example 22), 70:30 (Example 23), and 90:10 (Example 24). The polydimethylsiloxane was terminated with Si(CH3)2-CH2CH2-Si(OCH3)3 groups and had a molecular weight and methoxy content similar to the copolymer of Example 20. Each mixture was mixed with a titanium tetra-n-butoxide catalyst to a level of 0.1% by weight. Ti, apply it to the test surface, and allow to cure in a humid atmosphere at ambient temperature. Each formulation has been processed into a hydrophilic coating.

Example 25

100 g dimethyl hydrogen silyl-terminated polydimethylsiloxane fluid with an average DP of 11.8 was placed in 50 g of toluene in a three-neck flask and heated to 80°C in a nitrogen atmosphere. A drop of polyethylene glycol diallyl ether with an average DP of 7 was added followed by 30 μL chloroplatinic acid catalyst, then 12.76 g of polyethylene glycol diallyl ether was added dropwise. The molar ratio of Si:H groups to allyl groups was 1:3. The mixture was heated for 1 h at 80 °C and then cooled to form a solution of a Si-H-terminated polysiloxane-polyoxyethylene template copolymer with a Si-H content of 3.10%.

100 g of this Si-H-terminated polsiloxane polyoxyethylene block copolymer was placed in 50 g of toluene in a three-necked flask and heated to 80 °C in a nitrogen atmosphere. 30 μL of chloroplatinic acid catalyst, then 54.75 g of phenyltrimethoxysilane were added dropwise. The molar ratio of Si:H groups to vinyl groups was 1:3. The mixture was heated for 1 h at 80 °C and then cooled to form a solution of a polysiloxane-polyoxyethylene template copolymer terminated with Si(CH3)2-CH2CH2-Si(OCH3)3 groups. This copolymer has an average molecular weight of Mn 2.611 and contains 10.26% by weight of methoxy groups.

The Si-terminated methoxy copolymer of Example 25 was mixed with a titanium tetra-n-butoxide catalyst to a level of 0.1 wt% titanium based copolymer, applied to the test surface, and allowed to cure in a humid atmosphere at ambient temperature. A hydrophilic polymer coating was produced.

Example 26: Anti-fouling test

The coating compositions for Examples 11-14 were applied by brush (to a dry film thickness of ~300 µm) to 60cm x 60cm marine plywood panels, which were filled with two coats of epoxy primer and acrylic paint. 6 samples of each coating formulation were applied. Standard anti-fouling coatings and non-toxic controls were applied as references to evaluate the relative performance, abundance and diversity of fouling settlement on the coatings in accordance with the invention.

The test panels were submerged from buoys designed to submerge experimental test surfaces and conditions were representative of those experienced in the hulls of pleasure boats or ships.

The panels were attached to the test frames and suspended vertically between 0.5 and 1.5 m below the water surface at each test location. Plates were checked regularly for existing biofouling and paint integrity.

Test sites included: Changi, Singapore and Newton Ferrers, UK, which show fouling typical of all basic fouling types.

Dirt coverage was assessed in four major environmentally derived contamination categories: contamination by microorganisms, herbivores, soft-bodied animals, and hard-bodied animals. A visual analysis was performed on these four contamination categories. This provides sufficient information to differentiate the performance of the coatings while allowing some general comparisons to be made. between testing sites. The results are shown in the table below. Data in this table indicate total contamination coverage of test panel surfaces, in percentages.

Schedule

Changi, Singapore,

17 week

Newton Ferrers, UK,

26 week

Example 11

64.0

5.3

Example 12

45.0

3.0

Example 13

34.0

15.0

Example 14

58.0

26.3

Standard anti-pollution paint

83.0

20.0

Anti-abrasion lining only

93.0

95.0

This table shows that after four months of immersion in Singapore waters and six months of immersion in the United Kingdom, the accumulated fouling was significantly lower than that of the control substrates coated only with the anticorrosive pimer, and lower than that of the standard substrate. Any fouling on the coatings in Examples 11-14 can be removed very easily by light rubbing, while fouling accumulated on the control substrates cannot be removed in the same way.