EP0292482A1

EP0292482A1 - Self-adhesive, drag reducing polymeric coating

Info

Publication number: EP0292482A1
Application number: EP87900406A
Authority: EP
Inventors: Keith Kent
Original assignee: Individual
Current assignee: Individual
Priority date: 1986-11-17
Filing date: 1986-11-17
Publication date: 1988-11-30
Also published as: DK398488A; NO883149D0; JP2846882B2; NO180589C; NO883149L; WO1988003930A1; EP0292482A4; JPH01501552A; DK398488D0; NO180589B

Abstract

Une composition polymère auto-adhésive est utilisée comme revêtement de réduction de la traînée et de libération de l'encrassement. Un procédé de production d'une telle composition est décrit. La composition qui est formée en mélangeant un polymère de base avec un catalyseur et en ajoutant immédiatement des quantités à l'état de traces d'un modificateur au mélange, produit un revêtement de haute intégrité avec un réseau s'étendant en surface de chaînes réticulées différentiellement qui améliorent les propriétés d'écoulement/adhésion dans la phase liquide.A self-adhesive polymer composition is used as a drag reduction and fouling release coating. A method of producing such a composition is described. The composition which is formed by mixing a base polymer with a catalyst and immediately adding trace amounts of a modifier to the mixture, produces a high integrity coating with a network extending across the surface of crosslinked chains which improve the flow / adhesion properties in the liquid phase.

Description

SELF-ADHESIVE, DRAG REDUCING POLYMERIC COATING

BACKGROUND OF THE INVENTION

The present invention relates to polymeric compositions and, more particularly, is directed towards self-adhering polymeric composition for use as a drag reducing coating.

Various coatings have been developed for reducing drag between two surfaces in relative motion. For example, U.S. Patent No. 2,937,976 discloses a drag reducing gel for a razor blade and U.S. Patent No. 4,385,134 teaches use of a drag reducing, antifouling coating for boat hulls.

The primary cause of drag on boat hulls is the growth of marine organisms on the hull. Generally, antifouling coatings contain a toxicant agent which controls the growth of marine organisms. In such coatings, it is necessary to control the amount of toxin delivered to the surface coating in order to prevent premature depletion of the antifouling agent. Other patents relating to drag reducing compositions for boat hulls include U.S. Patent Nos. 3,575,123; 3,896,753; and 3,990,381. A need has arisen for an improved drag reducing coating for marine use which does not require use of a toxicant agent.

Also, there is a need for a drag reducing composition whic can be readily manufactured in a form which can be easily applied to the surface of the object to be protected. Such a drag reducing composition should ideally be paintable or sprayable on the object surface and act to protect the underlying surface from degradation by bacterial decay, oxidation, water seepage and the like. Once such a drag reduction and/or protective coating is applied to an object surface, the coating should readily adhere to the surface, remain in such adherence, and Itself be relatively inert to ambient sources of degradation.

SUMMARY OF THE INVENTION

In accordance with the invention there is provided a method for producing a polymeric composition comprising the steps of: bulk mixing a base polymer forming material with a catalyst; immediately adding trace amounts of a cross-linking inhibitor to the bulk mixture; and curing and polymerizing the inhibited bulk mixture.

The base polymer forming material preferably includes one or more of a monomer unit of a polymer, a prepolymer of the polymer, or an unvulcanized form of the polymer which is preferably selected from the group of silicones, polyurethanes, polyacrylics, polyesters, polyolefins, polyacrylamides and polyether-urethane polymers. There is also provided a method for producing a drag reducing polymer composition comprising the steps of: selecting a base compound comprising polymer forming units having at least one hydroxyl or halogeno group bonded to silicon; bulk mixing the base silicon compound with a condensation catalyst in an amount sufficient to polymerize essentially all on the polymer forming units; and adding a cross linking inhibition agent to the bulk mixture immediately after the step of bulk mixing is carried out. The cross-linking inhibition agent is preferably added ^• in an amount sufficient to inhibit cross-linking to a predetermined degree. The mixture is typically subjected to polymerization conditions, such as heating, mixing, solution in solvent and the like, for a predetermined amount of time sufficient to effect a predetermined amount of polymerization and cross-linking.

The silicon base compound typically includes unvulcanized silicon based polymers, and the inhibition agent is preferably a metal salt of a carboxylic acid. The inhibition agent is preferably added in a trace amount. The mixture of polymer forming material may be allowed to begin polymerizing, but only to a slight degree, before the inhibition agent is added.

In accordance with the invention there is also provided a blend of one or more of a selected monomer, a prepolymer of the monomer, and a polymer of the monomer; a catalyst for causing unpolymerized components of the blend to polymerize and cross-link with the catalyst being added to the blend in an amount sufficient to polymerize and cross-link essentially all of the unpolymerized components of the blend; and a trace amount of a modifier which inhibits cross-linking, wherein the modifier is added to the blend and the catalyst essentially immediately after the blend. The monomer preferably comprises a monomer unit of one or more of a silicone, polyurethane, acrylic, polyester, polyolefin, polyacrylamide or polyether -4-

urethane copolymer. The modifier is preferably a metal salt of a carboxylic acid.

An integral surface layer having pressure-sensitive adhesive properties may be formed on an otherwise fully cured polymeric body by applying a sufficient amount of a cross-linking inhibition agent to selected surfaces of a mold cavity prior to packing the cavity with uncured mono eric, prepolymeric, or unvulcanized polymeric material. The mold is then closed and the material cured. The cross-linking inhibition agent acts on the surface or surfaces of the polymer to prevent complete cross-linking thereof. The body of the polymer is otherwise completely cured and has the same properties as would be expected of a fully polymerized and cross-linked composition. Conventional additives such as fibers and fillers may be added to the uncured compound and have no effect on the integral surface layer which is formed. In applications where selected surfaces of a polymerized body are treated with inhibition agent, the surface or surfaces of the polymeric body which are cured in contact with the cross-linking inhibition agent remain tacky and possess pressure sensitive adhesive properties. The present invention deals with treatment of the bulk prepolymer rather then treatment of selected surfaces of the prepolymer.

Accordingly, it is an object of the present invention to provide a self-adhering polymeric composition for use as a drag reducing coating. Self-adhering as used in this application means that the composition will adhere to a surface to be coated without special treatment of the surface. -5-

It is another object of the present invention to provide a self-adhering polymeric composition for use as a fouling release, drag reducing coating.

It is a further object of the invention to provide a method for forming a self-adhering composition for use as a drag reducing coating. The coating is produced by inhibiting the process of curing of the superficial layers of a polymer. The method of forming the polymeric composition includes the steps of mixing a base polymer with a catalyst, and immediately adding trace amounts of a modifier to the mixture. Preferably, the resultant composition is heated to accelerate the polymerization process. The resulting composition is a high integrity coating with all the useful engineering features of the bulk polymer with a surface network of differentially cross-linked chains that reach into and control the flow/adhesion properties in the liquid phase.

Other objects, features and advantages will be apparent from the following detailed description of preferred embodiments:

DESCRIPTION OF PREFERRED EMBODIMENTS

The drag reducing polymer composition of the invention may be produced from a base polymer composition comprising any one or more of a selected unvulcanized polymer, a prepolymer thereof, a monomer unit of the selected polymer or a mixture of one or more or all of the foregoing. The polymers, prepolymers thereof and monomer units of such polymers preferred for use in producing the drag reducing composition include silicones, polyurethanes , -6-

polyacrylics, polyesters, polyolefins, polyacrylamides and polyetherurethane copolymers. The polymers presently preferred in the practice of the present invention are silicone elastomers and specifically polydimethylsiloxanes because of their ready availability.

The base polymer composition is mixed in bulk with a catalyst which catalyzes both straight chain polymerization and cross-linking. The catalyst selected is typically peculiar to catalysis of the selected monomer units of the polymers to be formed, and is preferably added in an amount sufficient to polymerize and/or cross-link essentially all of the polymer forming material of the base polymer composition. In the case, for example, where a silicone polymer composition is to be formed, the selected base polymer composition including catalyst may comprise one or more of MDX4-4210, SILGARD 194, AND SILGARD 196 silicone prepolymers commercially available from the Dow Corning Corp., GTE RTVII, a prepolymer commercially available from the General Electric Co. The catalysts employed for polymerization of such base compositions, catalyze a condensation reaction between the silicon elements which are typically bonded to one or more hydroxy or halogeno elements.

After the catalyst and base polymer forming units are mixed in bulk, a modifier, typically an inhibition agent, is added to the mixture. Preferably, the modifier is added to the mixture essentially immediately after the mixing of the catalyst and base polymer forming units. Where silicone prepolymer compositions are employed, the process is most preferably assisted by heating the base polymer/catalyst/modifier mixture to at least about 100 degrees Centrigade for at least about 20 minutes. Preferred modifiers include metal salts of carboxylic acids, most preferably stannous octoate.

The consistency of the drag reducing polymer composition may be controlled by controlling the degree of polymerization. The degree of polymerization may be controlled by accelerating or decelerating the conditions favoring polymerization such as by increasing or decreasing temperature for longer or shorter periods of time, allowing the base composition to begin polymerization to some predetermined degree before adding an inhibition agent, increasing or decreasing the amount of catalyst and the like.

The resulting drag reducing composition may range in consistency from a wax-like substance to a runny liquid depending upon the predetermined degree of polymerization allowed. Preferably the composition is produced in such a consistency that the resulting mixture may be directly painted on the surface of an object to be protected. Notwithstanding the physical consistency of the resulting mixture, the mixture may be thinned, i.e., dissolved, in conventional organic solvents such as fluorocarbons, hydrocarbons, ethers, ketones and the like, to any predetermined degree to aid in the ready application of the resulting drag reducing polymer composition. In any event, once the composition is inhibited, polymerization is permanently arrested. Application of additional catalysts, heat or other standard modalities will not cause further vulcanization of the composition. Without wishing to be limited to any specific theory or mechanism, we believe, that the application of certain agents, which we will term cross-linking inhibition agents, will inhibit the degree of cross-linking of the polymeric composition which occurs during a curing or vulcanization step. This results in a multiplicity of elastomeric polymer chains. Several suitable cross-linking inhibition agents include metal salts of carboxylic acids such as stannous octoate. Prepolymers such as MDX-4210; SILGARD 184 and 186; and SILASTIC 31-10,31-12 and 31-20 are compatable with inhibitors such as chlorinated and butyl rubbers; most other room temperature vulcanizing CRTV) silicone rubbers; sulphur containing solvents; plasticizers; and tin containing compounds. Prepolymer such as SILASTIC 382, General Electric RTV-11 are compatable with inhibitors such as oxidizing oils; linseed oils; putties; oil containing clays; and plastizers, specifically amine containing plasticizers. Those skilled in the art may determine other suitable cross-linking inhibition agents by simple testing. it will now be apparent to those skilled in the art that other embodiments, improvements, details, and uses can be made consistent with the letter and spirit of the foregoing disclosure and within the scope of this patent, which is limited only by the following claims, construed in accordance with the patent law, including the doctrine of equivalents.

Claims

-9-CLAIMS

1. A method for producing a polymeric composition comprising the steps of: bulk mixing a base polymer forming material with a catalyst; immediately adding trace amounts of a cross-linking inhibitor to the bulk mixture; and curing and polymerizing the inhibited bulk mixture.

2. The method of claim 1 wherein the base polymer forming material includes one or more of a monomer unit of a polymer, a prepolymer of the polymer, or an unvulcanized form of the polymer, the polymer being selected from the group consisting of silicones, polyurethanes , polyacrylics, polyesters, polyolefins, polyacrylamides and polyether-urethane copolymers.

3. The product of the method carried out according to claim 1.

4. A method for producing a drag reducing polymer composition comprising the steps of: selecting a base compound comprising polymer forming units having at least one hydroxyl or halogeno group bonded to silicon; bulk mixing the base silicone compound with a condensation catalyst in an amount sufficient to polymerize essentially all of the polymer forming units; and adding a cross-linking inhibition agent to the bulk mixture immediately after teh step of bulk mixing is carried out.

5. The product of the method carried out according to claim 3.

⁵ 6. The method of claim 4 wherein the cross-linking inhibition agent is added in an amount sufficient to inhibit cross-linking to a predetermined degree.

7. The method of claim 4 wherein the mixture is subjected to polymerization conditions for a predetermined lOamount of time sufficient to effect a predetermined amount of cross-linking.

8. The method of claim 7 wherein the silicon base compound further comprises ^" unvulcanized silicon based polymers.

15 9. The method of claim 8 wherein the inhibition agent is selected from the group consisting of metal salts of carboxylic acids.

10. The method of claim 9 wherein the inhibition agent is added in a trace amount.

20 11. The method of claim 4 wherein the step of bulk mixing comprises allowing the base compound to begin polymerizing before the inhibition agent is added.

12. The method of claim 8 wherein the polymerization conditions comprise heating the mixture to at least about

25100 degrees Centigrade for at least about 20 minutes.

13. A partially cross-linked polymeric composition comprising: a blend of one or more of a selected monomer, a prepolymer including the monomer, and an unvulcanized 30polymer including the monomer; a catalyst for causing unpolymerized components of the blend to polymerize and cross-link, said catalyst added to the blend in an amount sufficient to polymerize and cross-link essentially all of the unpolymerized components of the blend; and a trace amount of a modifier which inhibits cross-linking, wherein the modifier is added to the blend and the catalyst essentially immediately after the blend and the catalyst are intermixed.

14. The composition of claim 10 wherein the monomer comprises a unit of a polymer selected from the group consisting of silicones, polyurethanes, acrylics, polyesters, polyolefins, . polyacrylamides, and polyether-urethane copolymers.

15. The composition of claim 14 wherein the modifier i_s selected from the group of inhibitors consisting of cyanoacrylates and metal salts of carboxylic acids.