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WO1990006958A1 - Polyurethanes modifies a la silicone - Google Patents

Polyurethanes modifies a la silicone Download PDF

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Publication number
WO1990006958A1
WO1990006958A1 PCT/AU1989/000537 AU8900537W WO9006958A1 WO 1990006958 A1 WO1990006958 A1 WO 1990006958A1 AU 8900537 W AU8900537 W AU 8900537W WO 9006958 A1 WO9006958 A1 WO 9006958A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
component
polysiloxane
silicone
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AU1989/000537
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English (en)
Inventor
Kenneth Roy Strudwick
Robert Charles Wallis
Robert Dean Bridges
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BRAMITE Ltd
Original Assignee
BRAMITE Ltd
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Filing date
Publication date
Application filed by BRAMITE Ltd filed Critical BRAMITE Ltd
Publication of WO1990006958A1 publication Critical patent/WO1990006958A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2270/00—Compositions for creating interpenetrating networks

Definitions

  • This invention relates to novel silicone modified polyurethanes.
  • the silicone modified polyurethanes find particular use as coating compositions and especially as marine paints.
  • the modified polyurethanes can also be moulded or cast to form a variety of articles or films.
  • the silicone modified polyurethanes have low surface energy and thus have good anti-stick properties making them suitable for fouling release paint compositions and anti-graffiti paint compositions.
  • Protective coating compositions such as paints are ever increasing in their complexity due in part to the large variety of substrates which need to be coated. Diverse articles or structures such as public buildings, aircraft, and marine vessels often require regular painting to resist environmental attack and to provide an aesthetic appearance. With large buildings in particular, maintenance of the exterior surface is both expensive and time consuming and any reduction in the maintenance of a building (ie. cleaning or painting thereof) is a distinct advantage.
  • Yet another form of painted surface comprises particles of polytetrafluoroethylene ( "TEFLON" (trade mark)) bound in a paint matrix to confer low friction qualities to a painted surface.
  • Low friction surfaces may be desirable to reduce wear in pipes or conduits carrying fluids, in particular fluids with solids in suspension.
  • the inner surface of storage hoppers, silos, road and rail freight containers may be coated with a PTFE containing paint in an endeavour to improve the flow characteristics of the particulate material over the surface of the container.
  • polymeric compositions containing anti-slip or anti-block agents are known in the art and are commonly used as mould release agents.
  • the polymer composition contains an amount of silicone oil which bleeds out from the composition to provide the mould release properties.
  • the rate of bleeding of the silicone oil can be controlled by the viscosity of the oil.
  • the silicone is not bound within the polymeric matrix and can migrate to the surface of the composition. While this is desirable for mould release properties, such "bleeding" of the silicone compound from the polymeric composition results in difficulty in an application of a protective or decorative surface finish to the moulded article.
  • a further disadvantage with these compositions is that while the presence of the silicone compound at or near the surface of the polymer composition can confer flexibility and resistance to weathering, these properties are relatively short lived due to the continual "bleeding".
  • United States Patent 4,500,688 discloses a melt processable pseudo-interpenetrating network of silicones in thermoplastic matrices.
  • the composition is formed from separate batches of thermoplastic pellets, one of which contains a vinyl siloxane complexed with a platinum catalyst and the other containing a silicone hydride composition.
  • the interpenetrating network is formed by mixing and extruding the pellets in a suitable plastics extruder. There is no disclosure of the use of liquid components and the use of the components as coatings.
  • United States Patent No. 4 , 302 , 553 describes an interpenetrating network of chemically different crosslinking polymers which do not react together.
  • the structure is described as entangled macrocylic polymeric chains.
  • the patent discloses the formation of a macrocylic structure comprising poly (dimethylsiloxane) and poly (urethane-urea) wherein aqueous emulsions of cross-linked polyurethane and hydroxy terminated poly (dimethylsiloxane) are intermixed to form an homogeneous mixture with sulphur and zinc oxide as cross-linking agents and butylated bisphenol A as an antioxidant.
  • the mixture is cured at elevated temperatures of around 120°C whereby cross-linking is effected by chain extension of the respective polyurethane and poly (dimethylsiloxane) polymers.
  • European patent application 329375 discloses a composition to control marine fouling.
  • the composition includes a curable polyorganosiloxane, an agent capable of curing the polyorganosiloxane to an elastomer, a polyisocyanate and a polyol.
  • the cured polymer composition has a low surface energy due to the polyorganosiloxane elastomer which provides a fouling release.
  • the specification further states that the cured product generally consists of domains of polyurethane within a network of cross-linked polyorganosiloxane. The amount of polyurethane should not exceed 40% by weight as it is stated that above this value the composition will not give a sufficiently low surface energy to prevent marine fouling. It is therefore evident that the composition of European patent specification 329375 is directed to a urethane modified polysiloxane with the urethane as the minor component.
  • silicone modified polyurethanes having low surface energy can be formed with a major amount of polyurethane and a minor amount of polysiloxane.
  • the invention resides in a curable liquid silicone modified polyurethane comprising (a) a polyol, (b) a polyisocyanate or polyisothiocyanate, (c) a polysiloxane comprising silicone hydride groups and (d) an unsaturated polysiloxane, wherein the amount of (c) and (d) is between 1 to 30% by weight of the polyurethane.
  • the invention resides in a curable liquid silicone modified polyurethane comprising (a) a polyol, (b) a polyisocyanate or polyisothiocyanate, (c) 1- 30% by weight of the polyurethane of a cross-linkable and unsaturated organosiloxane polymer comprising silicone hydride groups.
  • the invention resides in a method for forming curable liquid silicone modified polyurethanes comprising premixing the unsaturated polysiloxane and polysiloxane comprising silicone hydride groups, adding the mixture to the polyol, and adding the polyisocyanate or polyisothiocyanate.
  • the silicone modified polyurethanes can be blended with other resins or fillers to confer desirable properties such as increased flexibility or strength to the silicone modified polyurethane.
  • pitch or tar can be incorporated into the silicone modified polyurethane compositions to provide increased flexibility and durability to the composition or coatings prepared therefrom.
  • the silicone modified polyurethanes can be cured by the addition of catalysts and/or heating.
  • the choice of the catalysts varies depending on the type of component used. Typically, a metal catalyst such as H 2 PtCl 6 is used to polymerise the polysiloxane components.
  • free radical producing catalysts such as organic or inorganic peroxides can be used with the application of heat to generate free radicals.
  • Polymerisation of the polyisocyanate or polyisothiocyanate component with a polyol is well known in the art, and can be catalysed by any suitable catalyst. Catalysts for this type of polymerisation comprise tertiary amines or metal salts or mixtures thereof.
  • the type of catalysts and the conditions to react the isocyanate or isothiocyanate with the polyol will be well apparent to a person skilled in the art.
  • the platinum catalyst can conveniently be premixed with the unsaturated polysiloxane before addition to the remaining compounds although this is not essential. It is preferred that the platinum catalyst is not premixed with the polysiloxane comprising the silicone hydride groups. If a free radical catalyst is used, these can suitably be premixed as described above however, additional care needs to be taken that the catalyst does not decompose into free radicals prematurely. If a catalyst is used to promote the reaction between the polyisocyanate or polyisothiocyanate and the polyol, it is preferred that this is added immediately prior to curing.
  • the unsaturated polysiloxane is suitably selected from ethylenically unsaturated components such as hexenyl or from other terminally unsaturated groups, although other forms of unsaturation are also envisaged.
  • the remaining substituents on the polysiloxane are preferably alkyl groups and an especially preferred alkyl group is the methyl group.
  • groups such as aromatic groups, long chain alkyl groups or cycloalkyl groups can advantageously be used.
  • a preferred unsaturated polysiloxane is a vinyl end grouped polydimethylsiloxane.
  • the silicone hydride containing polysiloxane is preferably a polymethylsiloxane containing a number of silicone hydride groups along the backbone of the polymer.
  • the organosiloxane component would be required to be capable of cross-linking preferably in a non-condensation reaction in the presence of a catalyst.
  • the polyol component can be chosen from any compound comprising at least two hydroxy groups which are reactive to isocyanate or isothiocyanate groups. Suitable polyols include hydroxy (meth)acrylic acid, or esters thereof, polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyester-amides all of which contain at least two reactive hydroxy groups. Branched polyalkyls with ester and ether groups may also be used. These polyols may be provided with additional functionality such as amino, thiol, or carboxylic groups.
  • the polyisocyanate or polyisothiocyanate can include acyclic, cyclic, cycloaliphatic or aromatic compounds. Additionally the isocyanate or isothiocyanate can be provided with hetero atoms in addition to the isocyanate or isothiocyanate nitrogen, and can also include unsaturated isocyanate or isothiocyanate.
  • Polyphenyl-polymethylenes polyisocyanate and polyisothiocyanate including carbodiimide, allophanate, isocyanusate, urethane, acylated urea, urea or buiret groups and polyisocyanate prepolymers or any mixtures of the above may be suitable for the invention.
  • the considered useful ratio of polysiloxane to polyurethane is between 1 - 30% by weight with a preferred ratio of about 10% by weight polysiloxane to polyurethane.
  • the silicone modified polyurethanes of the invention can be prepared by admixing the polysiloxane, polyol and polyisocyanate in any order.
  • the polyurethanes can be prepared by admixing the polysiloxane containing hydride groups, the unsaturated polysiloxane, the polyol and the polyisocyanate together in appropriate amounts.
  • the polysiloxanes can be premixed and added to the polyol after which the polyisocyanate is added.
  • one of the polysiloxane components can be premixed with the polyol while the other of the polysiloxane components can be premixed with the polyisocyanate or polyisothiocyanate and the two premixtures can be admixed together.
  • the polysiloxanes can be premixed with the polyisocyanate and the polyol added thereto.
  • the polyurethane can be in the form of a single component prepolymer composition containing the polyol and polyisocyanate or in the form of a two component composition containing the polyol and polyisocyanate as separate components.
  • the polysiloxanes can be in the form of a single component prepolymer containing both siloxanes or a two component composition containing the polysiloxane comprising hydride groups and the unsaturated polysiloxane respectively.
  • the polyurethane and polysiloxane can be admixed in any of the above manners, for instance, the two component polyurethane composition can be admixed with the single or two component polysiloxane or vice versa.
  • compositions are identified as follows:
  • DESMOPHEN 651 - A branched hydroxy containing polyester sold by BAYER AUSTRALIA
  • DESMOPHEN 670 - A slightly branched hydroxy containing polyester sold by BAYER
  • BRAMITE SILICONE 2063 - A silicone oil having a viscosity of 1000 centistokes
  • Component A Parts (% weight) 1. Desmophen 651 67% in a 1:1 mixture
  • the unsaturated polysiloxane (Bramite 2018 part A) containing a platinum catalyst and the polysiloxane comprising silicone hydride groups (Bramite 2018 part B) are premixed in the specified ratio (10:1).
  • the mixture is added to the remaining compounds of component A and is mixed for 3-10mins at ambient temperatures using low shear mixing. This mixture is left at ambient temperatures for 2-4 weeks or until the viscosity of the mixture no longer increases.
  • Component B is added to the mixture, with stirring to form the silicone modified polyurethanes.
  • the mixture can be applied to a surface and cured to form a coating. If necessary, a solvent mixture can be utilized as a thinning mixture to facilitate the formation of coating.
  • Component A Parts (% weight)
  • example 1 The method of example 1 is used with the exception that the addition of the Bramite Silicon 2063 fluid eliminates the requirement of leaving the mixture for 2-4 weeks and component B of the example can be immediately added .
  • Component A Parts (% weight) 1. Desmophen A365 65% in 3:1 ratio
  • Rutile R-HD2 22
  • Solvent - equal ratios of methoxypropyl acetate methyl isobutyl ketone, and methylethyl ketone 24
  • Component A Parts (%weight)
  • the compounds of component A were admixed and 50ppm (relative to the polysiloxane) of a platinum catalyst
  • Admixture of the above compounds gave a one pack moisture cured system.
  • This formulation is identical to example 1 without the Bramite 2018 part A and Bramite 2018 part B.
  • the solvent component is increased to 24 parts.
  • This formulation is identical to example 2 without the Bramite 2018 part A and Bramite 2018 part B and Bramite Silicone 2063.
  • the solvent component is increased to 16 parts.
  • Bramite Silicone 2063 can be partially or totally substituted by polyphenylmethyl siloxane fluids or fluorinated hydrocarbons with low surface energy.
  • silicone elastomers such as RTV3110 (produced by DOW CORNING as a two part mixture) can be used. These silicones are catalysed by dibutyltin dilaurate or stannous octanoate. Although the silicones are of high viscosity, thinning with appropriate solvents can be carried out prior to incorporation into the polyol.
  • the silicone modified polyurethanes can be formed as a single component by inclusion of a polyurethane prepolymer which cures by reaction with atmospheric moisture.
  • a suitable prepolymer is Desmodur E21 sold by BAYER AUSTRALIA LTD.
  • a one component moisture cured silicone modified polyurethane can be formed based on an aliphatic polyisocyanate such as Desmodur N75.
  • hydroxy containing polyacrylates and other polyol compounds sold by BAYER AUSTRALIA
  • these compounds may be substituted by hydroxy containing polyacrylates from HOECHST AUSTRALIA LTD under the trade mark MACRYNAL SM series and hydroxy containing polyacrylates from CRAY VALLEY PRODUCTS LTD U.K. which are sold under the trade name SYNOCURE.
  • an aliphatic polyisocyanate designated as HARTBEN A75 sold by A VICTOR LEGGO AND CO PTY LTD is considered a suitable alternative to Desmodur N75.
  • the silicone modified polyurethane system of example 3 containing a small percentage of Desmophen 670 has been used for coating a product sold by FERRO CORPORATION (AUST) PTY LTD under the trade name VULKEM which is used to provide a very flexible substrate on pools.
  • silicone modified polyurethane compositions of example 5 incorporating the pitch provides heavy duty coatings with improved weathering properties in terms of gloss retention.
  • Polyurethane pitch or tar formulations not including silicone modification suffer from loss of gloss within six months of exposure.
  • the silicone modified polyurethanes of the examples can be unpigmented and these formulations usually have UV stabilizers present as well as the levelling agent MODAFLOW.
  • Suitable stabilizers include Tinuvin 292 and Tinuvin 900 (trade mark CIBA-GEIGY AUSTRALIA LTD) as a 10% solution in xylene and which are added in two parts and four parts respectively to the formulation.
  • An alternative method of forming the silicone modified polyurethane compositions of the examples is to premix the polyol and polyisocyanate or polyisothiocyanate at ambient temperature together with the desired solvent mixture and additives using low shear mixing conditions.
  • the unsaturated polysiloxane (containing platinum catalyst) and the polysiloxane containing silicone hydride groups are premixed and then added to the polyol/isocyanate or isothiocyanate mixture over a period of 3-10 minutes at ambient temperatures and using low shear mixing conditions. This mixture can be applied to a substrate in the form of a coating to cure at room temperature.
  • Table 1 lists various properties of certain of the exemplified silicone modified polyurethanes compared with identical polyurethanes not containing ⁇ ilicone. Unless otherwise specified, the silicone modified polyurethane coatings have been tested to Australian Standards 2602-Paints for steel structures: full gloss polyurethanes. The tests were carried out in accordance with Australian Standards 1580 - Methods of Test for Paints and Related Materials.
  • silicone polymers prepared by Bramite Limited, Dow Corning and General Electric for use in the examples above are generally similar in properties, the polymers manufactured by Bramite Limited are preferred in practice.
  • AS2602 requires testing to AS1580-214.1.
  • Modified coatings can be applied by brushing, conventional air spraying and roller coating without any evidence of film defects.
  • the presence of the silicone aids the flow, spreading, levelling and lapping properties compared to the unmodified coating.
  • the curing properties of the polyurethanes is assessed by measuring the scratch resistance; the film having cured for 7 days in accordance with AS1580-403.1 should withstand a load of 1.5kg.
  • the scratch resistance of the product of Example 1 is slightly down from all other coatings trialled.
  • the abrasion resistance of all the coatings was excellent.
  • the test method used is a variation of ASTM D4581 in that a 500gm vertical load was placed on each coated coupon through a 9.5mm diameter steel ball.
  • the coated coupon sample was mounted on a flat steel plate that could advance on low friction bearings.
  • the plate was pulled forward at a speed of 50mm/minute by the cross-head of a JJ Lloyd testing machine by means of a nylon cord.
  • the force required to propel the plate was measured by means of a load cell. Results clearly show a significant reduction in surface friction coefficient of the silicone modified polyurethane coatings.
  • Specular gloss was measured for those samples prepared for accelerated QUV weathering. All coatings met the minimum requirement of AS2602, in that specular gloss shall not be less than 85 gloss units.
  • Example 2 the effectiveness of the silicone-modified polyurethane coating of Example 2 in improving the water resistance rating (with respect to blistering) of a gelcoated laminate was ascertained.
  • the procedure differed to AS1838 in that a temperature of 65°C was maintained for 300 hours and not 100°C for 100 hours.
  • the gel-coat laminate was known to have a degradation rating of 5 or, as assessed by AS1580-481.2, a rating of 4C.
  • the silicone modified polyurethane coating significantly improved the blister rating of the gel-coat and showed an improvement with respect to the polyurethane system of the Comparative Examples. It should be noted that there was no sign of blistering or any other film defect when coatings were applied to polyester DMC (dough moulded compound) panels. Results indicate improved water resistance of the silicone modified coating and suggests that the application of such coatings to fibreglass vessels will provide increased protection with respect to osmosis.
  • Re sul t s were obtained after plaques were prepared approximately 1mm thick.
  • Results indicate an increase in flexibility of the silicone modified polyurethane. These values can be compared with an unpigmented silicone elastomer (110%), the unpigmented polyurethanes of Comparative Examples 1 or 2 (59%) and the unpigmented silicone modified polyurethanes of Examples 1,2,3 and 8 (66%).
  • results indicate a decrease in tear strength for the silicone modified polyurethanes. These results can be compared with an unpigmented silicone elastomer (6.7), the unpigmented polyurethanes of Comparative Examples 1 or 2 (12.8) and the unpigmented silicone modified polyurethanes of Examples 1,2,3 and 8 (11.5).
  • a particular advantage of the coatings of the examples resides in their low surface energy properties.
  • silicone modified polyurethane compositions as a means of effectively and safely managing the effects of marine growth on vessels such as commercial ships, pleasure craft, ferries and the like as well as static marine structures such as oil rigs, jetty piles, etc.
  • these silicone modified polyurethane compounds are inherently non toxic to marine organisms and otherwise preserve the integrity of the marine environment, their low surface energy characteristics provide a fouling release coating which inhibits the degree of adhesion of marine organisms. This in turn permits simple and inexpensive underwater cleaning operations to be carried out or otherwise less time consuming slipping of vessels for removal of marine growth.
  • the fouling release coatings enable ready removal of marine growth by less rigorous scrubbing or high pressure hosing without damaging the coating surface. Few organic substances will bond strongly to the surface of the coatings and thus the coating can be used as anti-graffiti coatings on buildings, railway carriages or other surfaces likely to be disfigured by graffiti artists. In addition they may be used as fouling release coatings on marine vessels. Dirt pick up is reduced and therefore surface tracking is also reduced.
  • the coatings When used as a decorative and/or protective coating on buildings, the coatings have a low coefficient of friction and together with the reduced adhesion of dirt of other particles the coating is easily cleansed by rain or washing.
  • the coatings are more flexible and softer than conventional cross-linked paint coatings and thus exhibits improved scratch resistance.
  • the coatings while having an anti-stick surface can be recoated with a second coat having good adhesion properties to the first coat. Thus, it is not necessary to strip the first coat. Further, the coatings can be applied directly to a substrate without requiring primer coats or
  • Thermal Analysis Thermal analysis using a differential spectral calorimeter showed that the glass transition state (Tg) of the silicone elastomer, the modified and the unmodified urethane acrylic compositions were substantially identical. Physical Tests Tensile elongation and tear strength measurements all showed reduced values for silicone modified systems.
  • the silicone modified polyurethanes of the invention comprise domains of at least partially cured polysiloxanes within a network of polyurethane. It is possible that an amount of inter-penetration and/or chemical bonding occurs along the interface between the silicone domains and the polyurethane. However, it is also possible that some degree of chemical coupling occurs between the silicone and polyurethane to give cross-linked, and/or graft polymers or block polymers.
  • the polyol may react with a silicone hydride functionality to link at least a portion of the polyurethane resin to the polysiloxane domains.
  • the silicone hydride containing polysiloxane may react with a polyol to form polar segments which may aggregate into micelle-like particles with silicone polymer chains extending into the surrounding polyurethane matrix.
  • the respective densities and polarities of the polysiloxanes and the polyol may have a profound bearing on the type of product formed.
  • the polysiloxanes typically have a low solubility in the polyol/solvent mixture and thus tend to form an emulsion or colloidal suspension of fine droplets of the silicone in the polyol upon mixing.
  • the hydroxy containing polyacrylates typically have a low solubility in the polyol/solvent mixture and thus tend to form an emulsion or colloidal suspension of fine droplets of the silicone in the polyol upon mixing.
  • polysiloxane eg. Bramite 2018 Part A
  • silicone hydride containing polysiloxane eg. Bramite 2018 part B
  • the polyurethane system comprises a polyol with a number of hydroxyl groups which normally react with the isocyanate groups, it is possible that some of these hydroxyl groups react with hydrosilane functional groups to chemically bond the silicone domains within the polyurethane matrix.
  • these could be formed as polymer chains having a polyurethane function at one end and a silicone function at the other.
  • a further postulation is that through inhibition of polymerisation of the silicone monomers, the proportion of uncross-linked silicone monomer may be free to migrate through the polyurethane matrix. That being the case, it is likely through surface tension effects, that there occurs a greater concentration of silicone monomers near the exposed surface of the polyurethane matrix. This concentration may then allow cross-linking of the silicone monomers in an interpenetrating network as steric inhibition is reduced.
  • silicone modified polyurethane systems According to the invention, the most likely structure is believed to comprise micelle-like domains of silicone polymer with silicone chains extending into the surrounding polyurethane matrix. These extended silicone chains probably bind to the polyurethane matrix by a combination of chemical bonding between silicone hydride and the polyol hydroxy groups as well as interpenetration of the polyurethane molecules.
  • the silicone modified polyurethane compositions according to the invention may have application in a wide range of fields.
  • the silicone modified polyurethanes have particular application as non-toxic environmentally safe fouling release coatings for marine applications including all manners of marine vessels and marine structures such as oil rigs and the like.
  • Heavy duty coatings comprising pitch or tar may be used as anti-corrosion coatings in marine and land based structures particularly where marine fouling release properties are required.
  • Non-toxic low friction coatings are also suitable for the interior of pipes and other conduits. These non-toxic coatings could be used for example in the pumping of town water or in the food industry such as in conveyancing of beverages. In other applications such as the pumping of cooling water in condensers of power stations, substantial improvement in pump efficiency by reduction of head losses can be expected.
  • silicone modified polyurethane coatings according to the invention in aeronautic applications is expected to lead to increased fuel savings due to reduced air drag on aeroplanes and the like.
  • compositions according to the invention provide a means of overcoming, many of the traditional gel coat problems such as cracking, blistering, osmosis and water absorption.
  • the greater flexibility and improved resistance to moisture absorption impart improved impact resistance, resistance to abrasion which otherwise in more brittle polyester gel coats leads to "star" cracking which in turn allows water to penetrate the gel coat/fibreglass structure, often with disastrous effects.
  • the low surface energy of the compositions provides an environmentally sound, nontoxic fouling release surface for above and below water surfaces.
  • mouldable or castable silicone modified polyurethane compositions applicable in the field of medicine, such as surgical prostheses, or in other fields such as automotive components, cast films, polymeric laminates for automotive and domestic upholstery and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

Les compositions de polyuréthane modifiées à la silicone décrites, qui se caractérisent par une faible énergie superficielle, comprennent une matrice de polyuréthanes dans laquelle est dispersé 1 à 30 % d'un composé de silicone. La faible énergie superficielle qui caractérise les revêtements de surface contenant de tels polyuréthanes modifiés à la silicone permet de gérer, de façon efficace et sûre pour l'environnement, les effets de la prolifération d'organismes marins sur les navires et les structures marines statiques, grâce à la formation d'une surface d'élimination du fouling, laquelle permet de retirer de façon simple et efficace les organes marins sans endommager le revêtement de surface. Les polyuréthanes modifiés à la silicone de la présente invention constituent également une alternative utile à l'emploi d'enduits en gel de polyester dans les bateaux en plastique renforcé par des fibres de verre et dans toute autre structure similaire.
PCT/AU1989/000537 1988-12-14 1989-12-14 Polyurethanes modifies a la silicone Ceased WO1990006958A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPJ1952 1988-12-14
AUPJ195288 1988-12-14

Publications (1)

Publication Number Publication Date
WO1990006958A1 true WO1990006958A1 (fr) 1990-06-28

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Application Number Title Priority Date Filing Date
PCT/AU1989/000537 Ceased WO1990006958A1 (fr) 1988-12-14 1989-12-14 Polyurethanes modifies a la silicone

Country Status (4)

Country Link
EP (1) EP0404895A4 (fr)
CA (1) CA2005546A1 (fr)
NZ (1) NZ231770A (fr)
WO (1) WO1990006958A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0442272A3 (en) * 1990-02-15 1992-03-18 Beutelrock, Carolin Means of coating substrates with a paint-proof layer
WO1997019128A1 (fr) * 1995-11-21 1997-05-29 Imperial Chemical Industries Plc Film antiadherent
FR2755695A1 (fr) * 1996-11-08 1998-05-15 Rhodia Chimie Sa Compositions reticulables contenant des huiles silicones fonctionnalisees et utilisation de ces compositions pour preparer des films polyurethannes
WO1998021257A1 (fr) * 1996-11-08 1998-05-22 Rhodia Chimie Compositions reticulables contenant des huiles silicones fonctionnalisees et utilisation de ces compositions pour preparer des films polyurethannes
EP0806342A3 (fr) * 1996-05-06 1998-07-29 The B.F. Goodrich Company Système de dégivrage pneumatique avec protection contre les grosses particules d'eau en surfusion
US5932352A (en) * 1995-11-21 1999-08-03 Higgins; David Edward Release film
US6071564A (en) * 1996-06-10 2000-06-06 Ausimont S.P.A. Coatings based on perfluoropolyethers
US7875672B2 (en) 2007-08-24 2011-01-25 Perstorp France Two component waterborne polyurethane coatings for anti-graffiti application
WO2011072056A2 (fr) 2009-12-08 2011-06-16 Dow Corning Coporation Régulation de la vitesse de durcissement pour des polymères à terminaison bloquée par un alcoxysilyle
EP2813554A3 (fr) * 2013-06-13 2015-07-29 Eczacibasi Yapi Gerecleri Sanayi Ve Ticaret Anonim Sirketi Mélange/composition permettant de former une surface antidérapante, procédé de préparation et application du mélange et produits sur lesquels est appliquée cette composition
US9145500B2 (en) 2012-12-31 2015-09-29 Dow Global Technologies Llc Siloxane-urethane foul release coatings
CN106795369A (zh) * 2014-08-12 2017-05-31 玛尔提贝斯股份有限公司 热塑性聚氨酯有机硅弹性体
WO2021013421A1 (fr) * 2019-07-23 2021-01-28 Konrad Hornschuch Ag Procédé de production d'un film polyuréthane
CN114539785A (zh) * 2022-04-01 2022-05-27 郑州轻工业大学 一种聚氨酯改性的橡胶复合材料、制备方法及其在避雷器复合外套中的应用
CN116693800A (zh) * 2023-07-04 2023-09-05 广东领跑新材料科技有限公司 一种抗老化塑胶跑道用硅pu材料及其制备方法
CN117050321A (zh) * 2023-06-29 2023-11-14 广州市斯洛柯高分子聚合物有限公司 反应型有机硅表面助剂、水性uv光固化抗涂鸦涂料及其制备方法与应用
CN118027736A (zh) * 2023-12-15 2024-05-14 广州海豚新材料有限公司 一种水性抗蚀刻油墨及其制备方法与应用

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Cited By (22)

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Publication number Priority date Publication date Assignee Title
EP0442272A3 (en) * 1990-02-15 1992-03-18 Beutelrock, Carolin Means of coating substrates with a paint-proof layer
WO1997019128A1 (fr) * 1995-11-21 1997-05-29 Imperial Chemical Industries Plc Film antiadherent
US5932352A (en) * 1995-11-21 1999-08-03 Higgins; David Edward Release film
CN1070205C (zh) * 1995-11-21 2001-08-29 美国杜邦泰津胶片合伙人有限公司 隔离膜
EP0806342A3 (fr) * 1996-05-06 1998-07-29 The B.F. Goodrich Company Système de dégivrage pneumatique avec protection contre les grosses particules d'eau en surfusion
US6247669B1 (en) 1996-05-06 2001-06-19 The B. F. Goodrich Company Airfoil low ice adhesion surface
US6071564A (en) * 1996-06-10 2000-06-06 Ausimont S.P.A. Coatings based on perfluoropolyethers
FR2755695A1 (fr) * 1996-11-08 1998-05-15 Rhodia Chimie Sa Compositions reticulables contenant des huiles silicones fonctionnalisees et utilisation de ces compositions pour preparer des films polyurethannes
WO1998021257A1 (fr) * 1996-11-08 1998-05-22 Rhodia Chimie Compositions reticulables contenant des huiles silicones fonctionnalisees et utilisation de ces compositions pour preparer des films polyurethannes
US7875672B2 (en) 2007-08-24 2011-01-25 Perstorp France Two component waterborne polyurethane coatings for anti-graffiti application
WO2011072056A2 (fr) 2009-12-08 2011-06-16 Dow Corning Coporation Régulation de la vitesse de durcissement pour des polymères à terminaison bloquée par un alcoxysilyle
US9145500B2 (en) 2012-12-31 2015-09-29 Dow Global Technologies Llc Siloxane-urethane foul release coatings
EP2813554A3 (fr) * 2013-06-13 2015-07-29 Eczacibasi Yapi Gerecleri Sanayi Ve Ticaret Anonim Sirketi Mélange/composition permettant de former une surface antidérapante, procédé de préparation et application du mélange et produits sur lesquels est appliquée cette composition
CN106795369A (zh) * 2014-08-12 2017-05-31 玛尔提贝斯股份有限公司 热塑性聚氨酯有机硅弹性体
US10253180B2 (en) 2014-08-12 2019-04-09 Multibase Sa Thermoplastic polyurethane silicone elastomers
CN106795369B (zh) * 2014-08-12 2019-09-06 玛尔提贝斯股份有限公司 热塑性聚氨酯有机硅弹性体
WO2021013421A1 (fr) * 2019-07-23 2021-01-28 Konrad Hornschuch Ag Procédé de production d'un film polyuréthane
CN114539785A (zh) * 2022-04-01 2022-05-27 郑州轻工业大学 一种聚氨酯改性的橡胶复合材料、制备方法及其在避雷器复合外套中的应用
CN114539785B (zh) * 2022-04-01 2023-11-17 郑州轻工业大学 一种聚氨酯改性的橡胶复合材料、制备方法及其在避雷器复合外套中的应用
CN117050321A (zh) * 2023-06-29 2023-11-14 广州市斯洛柯高分子聚合物有限公司 反应型有机硅表面助剂、水性uv光固化抗涂鸦涂料及其制备方法与应用
CN116693800A (zh) * 2023-07-04 2023-09-05 广东领跑新材料科技有限公司 一种抗老化塑胶跑道用硅pu材料及其制备方法
CN118027736A (zh) * 2023-12-15 2024-05-14 广州海豚新材料有限公司 一种水性抗蚀刻油墨及其制备方法与应用

Also Published As

Publication number Publication date
EP0404895A1 (fr) 1991-01-02
NZ231770A (en) 1991-08-27
CA2005546A1 (fr) 1990-06-14
EP0404895A4 (en) 1991-05-15

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