KR20120120908A - Moisture curable antifouling coating compositions - Google Patents

Abstract

PURPOSE: A water-curable anti-fouling coating composition is provided to be moderate to be used in anti-staining coating and to provide low surface energy and improved mechanical performance. CONSTITUTION: A water-curable anti-fouling coating composition comprises 50-95 weight% of at least one silane-terminated polybutadiene-based polymer or silane-terminated polyol-based polymer, and 5-50 weight% of at least one fluoro/fluoroalkoxy-functionalized silane. The composition can form a surface of which water contact angle is larger than 101°. A coating method of a substrate comprises: a step of preparing the composition; and a step of applying the composition to a substrate and initiating a curing of the composition by exposing the same under moisture.

Description

Moisture curable antifouling coating compositions

The present invention relates to a moisture curable composition capable of forming a polybutadiene-silicon organic-inorganic hybrid network having improved mechanical strength and good fouling release properties. Such coating compositions are easy to apply in the field of antifouling coatings.

Biofouling is the accumulation of living organisms such as bacteria, algae or barnacles on the surface of a submerged marine vessel. Decontamination coatings have been developed to achieve non-stick, decontamination coating surfaces. Silica gel-based inorganic coatings capable of forming rigid crosslinked silica networks have good hydrophobicity and have improved mechanical strength. Low wettability and low critical surface tension may result in improved antifouling or fouling release properties such as reduced ulva zoospore settlement, improved drift removal, improved grad biomass removal, and improved Balanus amphitrite enables coating with the young barnacle release ability.

Polydimethylsiloxane (PDMS) based silicone rubber fouling release coatings have their unique properties such as low surface energy, low elastic modulus, high thermal oxidative stability, UV resistance and It is widely used today because of its non-toxicity. However, PDMS is too soft and the coating is mechanically weak, which limits its widespread application. Anti-fouling coatings based on silicone rubber require frequent reapplication because the silicone component is easily released, which is very cumbersome, costly and time consuming. Coatings having both good fouling release capability and mechanical strength are preferred as an alternative.

Polyurethanes blended with PDMS in foul release coatings have distinct mechanical strength, elasticity, adhesion resistance and abrasion resistance. US Pat. No. 6,313,335 B1 describes thermosetting PU-PDMS dispersions for fouling release coatings. The proposed coatings include (A) polyols; (B) polyisocyanate; (C) prepared by reacting a mixture comprising a polyorganosiloxane having functional groups capable of reacting with polyisocyanates. The resulting coating film exhibits improved mechanical and fouling release properties. However, polyurethane-PDMS coatings are two-package thermosetting systems consisting of polyols and hydroxy or amino functionalized polyorganosiloxane packages and another polyisocyanate package. Such two-package systems and heat-curing processes are inconvenient to apply to large surfaces that are particularly difficult to heat-treat. PDMS raw materials are relatively expensive.

Therefore, there is a need for novel single packaged coating compositions that reduce raw material costs and are easy to apply in practice, and preferably have better durability and allow for easy crosslinking processes such as moisture curing.

The problem addressed by the present invention is that it can self-crosslink under moisture conditions at room temperature to form an organic-inorganic hybrid network, have improved mechanical durability and excellent pollution release capability, and are applied as a single packaged marine marine paint It is to find a novel fouling release composition suitable for the following.

The present invention relates to 50 to 95 weight percent of at least one silane terminated polybutadiene based polymer or silane terminated polyol based polymer and 5 to 50 weight percent of the formula R ¹ _n Si (OR ² ) _4-n based on the dry weight of the composition. For a single packaged moisture curable composition comprising at least one fluoro / fluoroalkoxy-functionalized silane having R ¹ , wherein R ¹ has 1-18 carbon atoms, A branched or cyclic and mono- or oligo-alkyl group, R ₂ is an alkyl group (OR ² ) is a hydrolyzable group, n is an integer of 1 to 2; Wherein the silane terminated polybutadiene-based polymer is (a) present in the main chain or at least one of the two ends of the polybutadiene-based polymer backbone or in the side chain of the polybutadiene-based polymer, Polybutadiene-based polymers having at least one non-hydrolyzable organic X group selected from epoxy, maleic anhydride, thiol and acrylic ester groups, and (b) organosilanes (RO) _n Si [(CH ₂ ) _m Y] _4-n , wherein the Y group is capable of reacting with the X group and is selected from hydroxyl, amino, isocyanate, epoxy, maleic anhydride, thiol, acrylic ester and vinyl group R group is a hydrolyzable group which can participate in condensation reaction, n is an integer of 1 to 3, m is an integer of 0 to 60; Here, after moisture curing, the composition forms a surface whose water contact angle is greater than 101 °.

The present invention introduces a silane group into a polybutadiene system different from a conventional polyorganosiloxane system, and then generates Si-O-Si bonds by hydrolysis and co-condensation to produce the organic-organic compounds described in the art. A moisture curable composition was obtained by forming an organic-inorganic hybrid network different from the hybrid network. Coating films with such networks have low surface energy and good mechanical properties.

The moisture curable composition comprises at least one silane terminated polybutadiene-based polymer. As used herein, the term "polybutadiene-based polymer" means a resin in which the polymer unit is mostly butadiene.

The silane-terminated polybutadiene-based polymer may be a reaction product of a polybutadiene having at least one functional group X group and a compound of (RO) _n Si [(CH ₂ ) _m Y] _4-n ; Where n is an integer from 1 to 3, m is an integer from 0 to 60, where X is, for example, reactive such as hydroxyl, amino, isocyanate, epoxy, maleic anhydride, thiol, acrylic ester group, or the like. Functional group; Y here means a reactive functional group capable of reacting with the X group to form a silane-terminated polymer. Suitable Y groups include, for example, hydroxyl, amino, isocyanate, epoxy, maleic anhydride, thiols, acrylic esters and vinyl groups. The reactive X group can be present at both ends of the polybutadiene backbone or at the main chain of the polybutadiene polymer.

In one embodiment, X is hydroxyl group (s) and Y is isocyanate group. Therefore, the backbone of the silane-terminated polybutadiene formed contains one or more urethane bonds.

In another embodiment, X is an isocyanate group (s) and Y is an amino group. Therefore, the backbone of the silane-terminated polybutadiene formed contains one or more urea bonds.

In another embodiment, X is an epoxy group (s) and Y is an amino group. Therefore, the backbone of the silane-terminated polybutadiene formed contains one or more epoxy bonds.

Suitable isocyanate functionalized silanes are, for example, isocyanatopropyl triethoxysilane, isocyanatopropyl trimethoxysilane, isocyanatomethyl methyldiethoxysilane, isocyanatomethyl methyldimethoxysilane and its Combinations.

The silane terminated polybutadiene-based polymer content of the moisture curable composition is 50 to 95 weight percent, preferably 80 to 95 weight percent, more preferably 80 to 90 weight percent, based on the dry weight of the composition.

The moisture curable composition comprises 5 to 50 weight percent, preferably 5 to 20 weight percent, more preferably 10 to 20 weight percent of at least one fluoro / fluoroalkoxy-functionalized based on the dry weight of the composition Contains silanes. The fluoroalkoxy-functionalized silanes can have, for example, the formula R ¹ _n Si (OR ² ) _4-n , wherein R ¹ is fluorinated linear, branched or cyclic and mono- Or an oligo-alkyl group having 1-18 carbon atoms, R ₂ is an alkyl group and (OR ² ) is a hydrolytic group. Suitable polysiloxanes include, for example, polydimethylsiloxane, polydiethylsiloxane, and combinations thereof.

Fluoro / fluoroalkoxy-functionalized silanes of the present invention are well known in the art as components of antifouling coating compositions.

The moisture curable composition furthermore comprises, in addition to the aforementioned fluoroalkoxy-functionalized silanes, at least one alkoxysilane additive up to 50 weight percent, preferably up to 30 weight percent, more preferably based on the dry weight of the composition. Up to 10 weight percent. The alkoxysilanes introduced into the composition can function in the course of moisture curing at room temperature due to the hydrolyzable groups of the alkoxysilanes. Alkoxysilanes used herein include the following general formula;

R ¹ Si (OR ² ) _4-m or Si (OR ² ) ₄

Wherein R ¹ is independently a C ₁ -C ₁₈ alkyl and / or C ₆ -C ₂₀ aryl chain, R ² is a C ₁ -C ₃ alkyl chain and (OR ² ) is, for example, hexadecyltri Hydrolyzable groups such as methoxysilane, octyltriethoxysilane, propyltriethoxysilane or tetraethoxysilane (TEOS).

Preferably, the silane terminated polybutadiene-based polymer has a number average molecular weight in the range of 500 to 200,000, more preferably 1,000 to 50,000.

In one preferred embodiment of the invention, the moisture curable composition comprises 50 to 95 weight percent of at least one silane terminated polybutadiene polymer or silane terminated polyol based polymer and 5 to 50 weight percent based on the dry weight of the composition. At least one fluoro / fluoroalkoxy-functionalized silane of.

The percentage sum of the components in the moisture curable composition is 100 percent. If there is an increase in certain components in the copolymer, the percentage of other components can be reduced by lowering their upper limit.

The term "up to" in the range means all quantities greater than zero and up to and including the limit of the range.

The water curable composition of the present invention is substantially free of water. “Substantially free of water” herein refers to that the water contained in the composition is not sufficient to initiate the moisture curing process of the composition.

The present invention also provides an antifouling coating composition comprising the moisture curable composition. The coating composition may further comprise a hydrophobic agent commonly used in the art to form a hydrophobic fouling release surface. Suitable hydrophobic agents include, for example, Si-based hydrophobic agents such as siloxanes, silanes, silicones, polydimethylsiloxanes (PDMS); Fluoro-based hydrophobic agents such as fluorosilanes, fluoroalkyl silanes, polytetrafluoroethylene, polytrifluoroethylene, polyvinyl fluoride, or functional fluoroalkyl compounds; And hydrocarbon hydrophobic agents such as reactive waxes, polyethylenes, or polypropylenes. The inventors believe that other additives in suitably concentrated form can be incorporated into the antifouling coating composition without substantially sacrificing other properties such as mechanical strength or durability. Depending on the application requirements, the coating composition may further comprise additives, including dyes, pigments, antioxidants, UV stabilizers, biocides, thickeners or viscosity enhancers in the amounts generally used.

In one preferred embodiment, the antifouling coating composition comprises, for example, copper oxide, 5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOI) sold under the trademark SEANINE ™ 211. Substantially free of such biocide compounds, or combinations thereof.

The antifouling coating compositions also include, in addition to the silane terminated polybutadiene based polymers or silane terminated polyol based polymers and fluoro / fluoroalkoxy-functionalized silanes of the moisture curable compositions described herein, for example, other polyols, It may contain a polymer binder such as an epoxy or an acrylic polymer.

Antifouling coating compositions can be prepared by techniques well known in the coating art. At least one pigment may be dispersed under high shear conditions by an IKA mixer, or alternatively at least one pre-dispersed pigment may be used.

The solids content of the antifouling coating composition is about 50 to 80 volume percent. The viscosity of the composition can be 0.05-10 Pa.s (50 cps to 10,000 cps) as measured using a Brookfield viscometer; Appropriate viscosity in different application methods is very variable.

The moisture curable composition and the coating composition prepared therefrom are stable under normal conditions and may be in the form of a single packaged product for storage, transport and application.

The moisture curable composition and the coating composition prepared therefrom can be self-cured by moisture at room temperature. In one embodiment, the hydroxyl terminated polybutadiene may be silylated alone and then mixed with fluoro / fluoroalkoxy silane or silane terminated PDMS to obtain a crosslinked coating system. In theory, fluoro / fluoroalkoxy-functionalized silanes or polysiloxanes are susceptible to covalent coupling with polybutadiene by hydrolysis and co-condensation of silane groups. In the hypothesis that is not intended to limit the present invention, the inventors have found that Si- It is believed that O-Si bonds are produced, resulting in crosslinked organic-inorganic hybrid networks. Si-O-Si inorganic bonds strengthen hybrid networks and provide improved mechanical performance. In addition, the inventors believe that polysiloxane components or fluoro / fluoroalkoxy chains with appropriate molecular weights will migrate to the surface of the coating film due to surface energy driving forces. This movement provides low surface energy to the coating film surface. Silane terminated polybutadiene, on the other hand, provides good adhesion to the substrate or primer coating and also imparts excellent mechanical properties.

Antifouling coating compositions are, for example, brushing, roller application, and, for example, air-atomized spray, air-assisted airless spray, airless spray By conventional application methods such as, high volume low pressure spray, and injection methods such as air-assisted airless injection.

The antifouling coating composition can be applied to substrates such as, for example, metals, plastics, wood, stones, concrete, primed surfaces, prepainted surfaces, and cement substrates. The coating composition coated on the substrate is typically dried or may be in a dry state at a temperature of −10 ° C. to 95 ° C.

The surface energy of the coating film surface was measured to show the fouling release characteristics of the antifouling coating composition. The adhesion to the surface of the coating of marine marine organisms, such as barnacles, is generally related to the surface energy of the coating. Usually marine marine microorganisms have low adhesion to surfaces with low surface energy. Water droplets on surfaces with low surface energy will show very high static contact angles. If the contact angle is greater than 90 °, the surface is hydrophobic. For contamination release coating applications, it is desirable for the static contact angle of water to be greater than 101 °. Fluoro / fluoroalkoxy-functionalized silanes show good hydrophobicity in their natural state due to surface energy driving forces and are predominant in their tendency to exist on the coating surface. Few materials adhere well to this type of surface, and materials deposited on this type of surface are very easy to remove upside down.

The coating film formed from the coating composition of the present invention consists mainly of morphologically the strong layer of polybutadiene, the bottom layer of the Si-O-Si crosslinked network, and the fluorine rich top layer with low surface energy. All of which are advantageous for durable pollution release applications.

Advantages of polybutadiene-Si hybrid systems include the possibility of production, storage and transport of single-package forms, moisture curability at room temperature, low toxicity (without free isocyanate), environmental friendliness, good film forming ability, improved mechanical performance, and excellent Pollution release characteristics are included.

In the context of the present invention, the technical features in each of the preferred technical solutions and in the more preferred technical solutions can be combined with each other to form new technical solutions unless otherwise indicated. In short, Applicants omit the description of these combinations. However, the technical solution obtained by the combination of these technical characteristics should actually be regarded as clearly described in the specification of the present invention.

Example

Ⅰ. Raw material

 Materials used in antifouling coating materials matter function Chemical nature producer LBH-2000
PB Hydroxyl terminated polybutadiene Sartomer Company Inc LBH-2000
PB Hydroxyl terminated polybutadiene Sartomer Company Inc DWD 2080 NOP polyol Gen 1 NOP Dow Chemical IPTES Silane Isocyanatopropyl triethoxysilane TCI APTES Silane 3-aminopropyltriethoxysilane Adrich DBTL catalyst
Dibutyltin dilaurate Sinopharm Chemical Reagent Company p-toluenesulfonic acid catalyst p-toluenesulfonic acid Sinopharm Chemical Reagent Company HDI Di-isocyanate 1,6-hexamethylene diisocyanate
Propanol TCI IPDI Di-isocyanate Isophorone diisocyanate TCI Butyl acetate menstruum Butyl acetate Eastman F-silane F-silane Tridecafluorooctyltriethoxysilane Degussa TEOS Silane Tetraethoxysilane Sinopharm Chemical Reagent Company C8-TEOS Silane Octyltriethoxysilane Adrich EtOH menstruum ethanol Sinopharm Chemical Reagent Company

Ⅱ. Testing process

Pseudo-barnacle pull off strength test

This test was performed using an Elcometer ™ pull-off strength tester, as described in Kohl JG & Singer IL, Pull-off behavior of epoxy bonded to silicone duplex coatings, Progress in Organic Coatings, 1999, 36: 15-20. It was performed by modifying.

A 10 mm diameter aluminum stud was designed for the Elcometer ™ instrument. Epoxy adhesive (Araldite ™ resin) was used to attach the studs to the coated panel surface. Epoxy remaining after curing for about 1 hour was removed. Then, it was left at room temperature for 3 days to harden the epoxy resin. The studs were then pulled off with an Elcometer ™ instrument until the studs detached from the coating surface. For each test, at least three replicate samples were used and the average value for pull off intensity (MPa) was recorded. If the pseudo-barnacle pull-off strength is 0.5 MPa or less, this means that the coating has good fouling release properties.

Impact resistance test

To evaluate the mechanical strength of PB-Si hybrid coatings, impact resistance tests were performed according to ASTM D 2794-93. The coating was applied to steel panels and moisture cured at room temperature. After the coating had fully cured, the coated steel panel was placed under a 2-lb load with a 0.5 inch diameter round tip. The rod was lifted to a certain height and then dropped to impact the coating and steel panels. If the raised rod was higher than a certain value, the coating was damaged by the impact formed by the falling rod. The value was recorded to assess the impact resistance of the coating.

Example 1

Preparation of Silane Terminated Polybutadiene: 10.5 g of α, ω-hydroxyl terminated polybutadiene Krasol ™ LBH-2000 was introduced into a 250 mL round bottom flask with a mechanical stirrer. 2.73 g of IPTES and 5.67 g of butyl acetate were added to the round bottom flask. At 75 ° C. the mixture was stirred under nitrogen protection. 0.1 weight percent catalyst DBTL was added. The reaction proceeded until IR analysis confirmed complete disappearance of the isocyanate functional groups. The final sample of modified polybutadiene was clear and stable at room temperature.

Synthesis of PB-Si Gel Hybrid Coatings: In a glass jar, 5 g of silane functionalized polybutadiene solution (70% solids) was mixed with 0.35 g of tridecafluorooctyltriethoxysilane with a straight magnetic stir bar. 0.2 weight percent of p-toluenesulfonic acid was added to the solution as a catalyst for the hydrolysis and condensation reaction of the silane groups and the solution was stirred vigorously for 20 minutes. The formulation was coated on an aluminum panel (H. J. Unkel LTD. Company) using a blade coater. A wet coating with a thickness of 300 μm was applied to a clean aluminum panel (H. J. Unkel LTD. Company). The coated panels were dried for at least 2 days prior to contact angle measurements and pseudo-barnacle pull off strength tests at room temperature. Contact angles were measured using an OCA 20 contact angle instrument (DataPhysics Company). Coating surfaces with good fouling release properties exhibited static contact angles in excess of 101 °.

Pseudo-barnacle pull off tests have shown that the coating has a very good fouling release capability, with a pseudo-barnacle pull off strength of 0.2 to 0.5 MPa.

The moisture curable sol-gel based coating formulations are listed in Table 1. In all formulations, PTES / polyol was terminated using IPTES as functionalized silane.

Moisture Curable PB / Polyol-Si Coating Composition Coating samples PB / Polyol Silylated
PB / Polyol
(Solid weight%) F-silane
(Solid weight%) TEOS
(Solid weight%) Contact angle
(˚) Doctor-Barnacle Pull Off
Strength (MPa) One LBH-2000 95 5 0 105 0.5 2 LBH-2000 90 10 0 110 0.2 3 LBH-2000 80 10 10 109 0.3 4 LBH-2000 70 10 20 108 0.4 5 LBH-2000 80 20 0 120 0.2-0.3 6 LBH-2000 50 50 0 122 0.2-0.3 7 LBH-3000 90 10 0 112 0.2 ^a comparison sample 1 LBH-2000
100 0 0 85 > 3 ^b comparison sample 2 References (Ying Tang et sol-gel coating according to al ., Biofouling , 2005, 21 : 59-71). 106 0.6 ^c comparison sample 3 Modified by tridecafluorooctyltriethoxysilane
Sol-gel coating 118 0.4 ^d comparison sample 4 2 packaged PU-PDMS coating as described in US Pat. No. 6,313,335 B1 107 0.2

^a Comparative Sample 1 is a silylated pure PB coating prepared by the method described in Example 1.

^b Comparative Sample 2 is a sol-gel based fouling release coating according to Ying Tang et al., Biofouling , 2005, 21, 59-71. 2.76 g C8-TEOS, 2.08 g TEOS and 5 mL EtOH were mixed and 1.6 ml 0.1N HCL was added and stirred at room temperature for 2 hours. The coating was prepared as described in Example 1. Sol-gel coatings showed poor fouling capacity.

^c Comparative Sample 3 is a sol-gel coating further modified with tridecafluorooctyltriethoxysilane to provide lower surface energy. 0.2 g of tridecafluorooctyltriethoxysilane, 2.08 g of TEOS and 5 mL of EtOH were mixed and 1.6 mL of 0.1N HCL was added and stirred at room temperature for 2 hours. The coating was prepared as described in Example 1.

^d Comparative Sample 4 is a two-packaged PU-PDMS coating made according to US Pat. No. 6,313,335 B1 with the following process: 1.7 g of natural seed oil having an equivalent weight of 170 g / mol and functionality 3. , PDMS, solvent, and catalyst were weighed and added to a 1 ounce glass jar with magnetic stir bar. The solution was mixed at room temperature for 10 minutes and then HDI trimer was added to the mixture. The mixture was stirred for 20 minutes and then coated on an aluminum panel as described in Example 1 above.

As shown in the pseudo-barnacle pull off strength test, Comparative Sample 1 has a low water contact angle and poor pollution release capability. Although Comparative Sample 2 showed a good water contact angle, the pseudo-barnacle pull off strength is higher than that of the PB-Si-F hybrid coating. Further modification with tridecafluorooctyltriethoxysilane can make the sol-gel coating more hydrophobic and have an acceptable level of pseudo-barnacle pull off strength as shown in Comparative Sample 3. Coating films made from pure inorganic Si-O-Si have been observed to be very unstable and easily cracking, especially when the coating is 300 μm thick in wet films. However, PB-based hybrid coatings are elastic and exhibit much better impact resistance as shown in Table 2. Single-packaged coating compositions Samples 1-7 have mechanical properties and fouling release capability as good as two-packaged PU-PDMS coatings (comparative sample 4).

Impact resistance results of coating Coating samples Impact resistance (cm) 2 50 7 50 Comparative Sample 2 <10 Comparative Sample 3 <10 Comparative Sample 4 25

Example 2

Preparation of Silane Terminated Polybutadiene-based Polyurethane Polymer.

In order to increase the molecular weight of the polybutadiene-based polymer, an excess of diisocyanate reaction with hydroxyl terminated polybutadiene and a molar ratio of NCO / OH = 2 was performed. Isocyanate terminated polyurethane prepolymers were designed to react with amino functionalized silanes to obtain silane terminated polybutadiene-based polymers.

10.5 g of α, ω-hydroxyl terminated polybutadiene Krasol ™ LBH-2000 was introduced into a 250 mL round bottom flask equipped with a mechanical stirrer. 1.68 g of 1,6-hexamethylene diisocyanate and 5.20 g of butyl acetate were introduced into a round neck flask and 0.1 weight percent DBTL was added. The mixture was stirred at 75 ° C. for 1 hour under nitrogen protection. 2.26 g of APTES was carefully added to the flask without exposure to air. The reaction proceeded until IR analysis confirmed complete disappearance of the isocyanate functional groups. The final sample was clear and stable at room temperature.

Synthesis of Hybrid Coating: 5 g of silane terminated polybutadiene polyurethane solution (70% solids) was mixed with 0.35 g of tridecafluorooctyltriethoxysilane in a glass jar with a straight magnetic stir bar. 0.2 weight percent of p-toluenesulfonic acid was added to the solution as a catalyst for the hydrolysis and condensation reaction of the silane groups and the solution was stirred vigorously for 20 minutes. The coating was prepared as in Example 1. The coating surface exhibited a static contact angle of 113 ° and a pseudo-barnacle pull off strength of 0.2 MPa.

The moisture curable sol-gel based coating formulations are listed in Table 3. In all formulations, HDI was used as the diisocyanate (initial molar ratio of NCO / OH = 2) and APTES was used as the functionalized silane to terminate the prepolymer.

Moisture Curable PB / Polyol-Si Coating Composition Coating samples PB / Polyol Silylated PB / polyols
(Solid weight%) F-silane
(Solid weight%) Contact angle
(˚) Pseudo-barnacle pull-off strength (MPa) 8 LBH-2000 90 10 113 0.2 9 LBH-3000 90 10 115 0.2

Example 3

The same procedure as in Example 2 was carried out except that the molar ratio of NOP and diisocyanate was NCO / OH = 0.5. The silylation process was carried out by reacting isocyanatopropyl triethoxysilane with hydroxyl terminated PB prepolymer. The coating was prepared as in Example 2.

Formulations for moisture curable sol-gel based coatings are listed in Table 4. In all formulations, HDI was used as diisocyanate (initial molar ratio of NCO / OH = 0.5) and IPTES was used as the functionalized silane to terminate the prepolymer.

Moisture Curable PB / Polyol-Si Coating Composition Coating samples PB / Polyol Silylated PB / polyols
(Solid weight%) F-silane
(Solid weight%) Contact angle
(˚) Pseudo-barnacle Pull-off Strength (MPa) 10 LBH-2000 90 10 114 0.3 11 LBH-3000 90 10 115 0.3

Claims (10)

At least one fluoro / fluoro having from 50 to 95 weight percent of at least one silane terminated polybutadiene based polymer and from 5 to 50 weight percent of the formula R ¹ _n Si (OR ² ) _4-n based on the dry weight of the composition A single packaged moisture curable composition comprising an alkoxy-functionalized silane,
Wherein R ¹ is a fluorinated linear, branched or cyclic and mono- or oligo-alkyl group having 1-18 carbon atoms, R ₂ is an alkyl group and (OR ² ) is a hydrolyzable group , n is an integer of 1 to 2;
Silane-terminated polybutadiene-based polymers may comprise (a) hydroxyl, amino, isocyanate, epoxy, maleic anhydride (a) in the main chain or at least one of the two ends of the polybutadiene-based polymer backbone or on the side chain of the polybutadiene-based polymer ( maleic anhydride), a polybutadiene-based polymer having at least one non-hydrolyzable organic X group selected from thiol and acrylic ester groups, and (b) organosilanes (RO) _n Si [(CH ₂ ) _m Y] _4-n Wherein the Y group can react with the X group and is selected from hydroxyl, amino, isocyanate, epoxy, maleic anhydride, thiol, acrylic ester and vinyl groups, and the R group can participate in the condensation reaction A hydrolyzable group, n is an integer from 1 to 3, m is an integer from 0 to 60;
After moisture curing, the composition forms a surface with a water contact angle greater than 101 °. The composition of claim 1 wherein the polybutadiene is the product of 1,2 polymerization or 1,4 polymerization of 1,3-butadiene or combinations thereof. The composition of claim 1 wherein the X group is a hydroxyl group and the Y group is an isocyanate group, or the X group is an isocyanate group and the Y group is an amino group, or the X group is an epoxy group and the Y group is an amino group. The fluorinated compound of claim 1, wherein the fluoro / fluoroalkoxy-functionalized silane has the formula R ¹ _n Si (OR ² ) _4-n , wherein R ¹ has 1-18 carbon atoms A linear, branched or cyclic and mono- or oligo-alkyl group, R ₂ is an alkyl group and (OR ² ) is a hydrolyzable group. The composition of claim 1 wherein the amount of silane terminated polybutadiene-based polymer is from 50 to 90 weight percent. The composition of claim 1 wherein the amount of fluoro / fluoroalkoxy-functionalized silane is 10-50 weight percent. The composition of claim 1 wherein the silane terminated polybutadiene-based polymer has a number average molecular weight in the range of 500 to 200,000. A coating composition comprising the moisture curable composition of claim 1. (a) providing a composition of claim 1; And
(b) applying the composition to the substrate and exposing to moisture to initiate curing of the composition. A coating film derived from the moisture curable composition of claim 1.