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  • 10 512 940 Amino Functional Polysiloxane

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    Eddy Wibowo
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    The present invention relates to an amino-functional polysiloxane of formula (1) where each Rl is independently selected from alkyl or aryl radicals. N is selected so that the molecular weight for the functional polysilicone is in the range of from 400 to 10,000. The present invention further relates to a composition which includes an aminopolysiloxanes hardener component.

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    10_512_940_Amino_functional_polysiloxane

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    The present invention relates to an amino-functional polysiloxane of formula (1) where each Rl is independently selected from alkyl or aryl radicals. N is selected so that the molecular weight for the functional polysilicone is in the range of from 400 to 10,000. The present invention further relates to a composition which includes an aminopolysiloxanes hardener component.

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    163 views29 pages

    10 512 940 Amino Functional Polysiloxane

    Uploaded by

    Eddy Wibowo
    The present invention relates to an amino-functional polysiloxane of formula (1) where each Rl is independently selected from alkyl or aryl radicals. N is selected so that the molecular weight for the functional polysilicone is in the range of from 400 to 10,000. The present invention further relates to a composition which includes an aminopolysiloxanes hardener component.

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    US 2 «i» United States « Klaassens et al. (51) AMINO-FUNCTIONAL POLYSILOXANES. AND THEIR USE IN COATINGS (79) Inventors: Lars War Klaassens, Haarlem (NL): Jan De Jong, Zaandam (NL); Henk Van Der Poel, Voorhout (NL): Christopher Slingeneijer De Goeswin, Hensies (BE), Sibel Mill, Riemerling (DE) Correspondence Address: KNOBBE MARTENS OLSON & BEAR LLP 2040 MAIN STREET. FOURTEENTH FLOOR IRVINE, CA 92614 (US) (21) Appl. Nos 10812,940 PCT Filed: Apr: 30, 2008 (85) PCT No: PCT/EPURssi3 (0) Foreign Application Peority Data May 3, 2002 (EP) cnaa70791 May 3.2002 (EP). 24470817 Publication Classiicato (1) mew? (2) USC. (CoRG_77/26 ‘528/38 6 ABSTRAC The present invention relates to an aming-funetional polysi= Joxane of formula (1) where each R™ is independently selected from alkyl o aryl radials, each Ris independently 1S 200S0148752A1 Patent Application Publication co) Pub. No.: US 2005/0148752 Al (43) Pub. Date: Jul. 7, 2005, selected from hydrogen, alkyl or aryl radicals, mis selected 0 thatthe molecular weight forthe functional polysiloxane is in the range of from 400 to 10,000 and R° isa bivalent radical or —O—R'—-NH-R° is hydroxy or alkoxy, and R° is selected from hycogen, aminoslky, aminoalkeny, ami- rnoaryl, aminocycloalky| radical, optionally substituted by alkyl, aryl, cycloalkyl, halogen, hydroxy, alkoxy, thioalkl, ‘amino, amino derivatives, amido, amidoxy, ait, cyano, Keto, acyl derivatives, acyloxy derivatives, carboxy, ester, ether, esteroxy, heterocycle, alkenyl or alkyayl and where 0 0 90% of —O—R°—NHR® is hydroxy or alkoxy. The present invention further relates to an epoxy-polysiloxane ‘composition which includes an aminopolysiloxane hardener ‘component of an amino-funetional polysiloxane hardener ‘component of formula (1), having active hydrogens able t0 react with epoxy groups in an epoxy resin to form epoxy polymers, and able to react with a polysloxane to form polysiloxane polymers, whesein the epoxy chain polymers and polysiloxane polymers polymerize 10 fom a cured epoxy-polysiloxane polymer composition Patent Application Publication Jul. 7,2005 Sheet 1 of 3 US 2005/0148752 Al Gloss Retention QUV-B 100 =a ceatnat 95 |—k—Coating It costing 90 85 80 75 70 65 60 55 50 45 H60 Gloss Retention [%] 0 500 1000 1500 2000 2500 3000 Exposure in QUV-B [Hrs] Figure 1 Patent Application Publication Jul. 7,2005 Sheet 2 of 3 US 2005/0148752 AL 109) 90 80 zg” “4 i © 2 ~3 ot 3 7” 4 g 5 30 20 ee ee ee ee) Exposure to OUVre] Figure 2 Patent Application Publication Jul. 7,2005 Sheet 3 of 3 US 2005/0148752 AL Gloss Retention QUV-B to Glos Retention [6] oS 88SSSSESB 0 500 1000 1500 2000 2500 Exposure In QUY-B Hrs) Figure 3 US 2005/0148752 Al AMINO-FUNCTIONAL POLYSILOXANES AND. ‘THEIR USE IN COATINGS FIELD OF THE INVENTION [0001] This invention relates to new amino-funetional polysiloxanes usoful as resins. Ths invention also relates to the use of these amino-functional polysiloxanes in resin- based compositions useful for protective coatings and the like, This invention further relates epoxy-polysiloxane resin based compositions seful for protective coatings and the like having improved gloss retention BACKGROUND [0002]. Polysiloxanes are known to give interesting prop fttes a resins and costings. True advancements in the State-of-the-art for protective coatings require substantial Jmprovemenis in weathering (primarily resistance 0 ulra- violet radiation), beat resistance, chemical resistance and corrosion control. Polysiloxane chemistry offers the poten- tial for providing many of these advancements, Polysiloxane {defined as a polymer consisting of repeating silicon- ‘oxygen atoms in the backbone that imparts several advan- tages over previously used carbon-based polymer binders; ‘one of these advantages being an enhanced chemical and thermal resistance due t the silicon-oxygen bond. Polysi- Joxane’s polymer linkage is also transparent to ultraviolet light making it resistant to degradation by ultaviolet ra tion, Finally, polysiloxane is not combustible and is resistant toa wide range of chemicals and solvents, including acids [0003] | Amino-functional siloxanes have been described, US. Pat. No. 4,413,108 to Wacker describes a process for preparing amino-functional polysiloxanes and copolymers thereof, ‘These amino-funetional polysiloxanes possess. & SiC bond between the polymere polysiloxane backbone ‘nd the functional linking arm, Furthermore, DE 125 171 to Schering describes a process for preparing amino-fune- tional siloxanes. [0004] Epoxy-hased protective coating materials are well, Known and have gained commercial acceptance as protec- tive and decorative coatings fr steel, aluminum, galvanized steel and concrete in maintenance, marine, construction, architectural, arerafl and product finishing’ markets. The basic aw materials used to prepare these coatings generally ‘comprise as essential components (a) an epoxy resi, (b) 2 hardener and (c) a piement or filler component [0005] Epoxy-hased protective coatings possess many’ properties Which make them desirable as coating materials. ‘They are realy available and ate easly applied by avarety ‘of methods including spraying, colling and brushing. They adhere well o steel, concrete and other substrates, have low ‘moisture vapor transmission rates and act as baeiees 10 ‘water, chloride and sulfate ion ingress, provide excelent ‘conosion protection under a variety of atmospheric expo- ‘ire conliions and have good resistance to many chemicals and solvents. Epoxy-based coatings generally show excel- leat protective properties, but have a considerable drawback hiel isthe limited gloss and color eetention when atmo- spherically exposed, [0006] _Epoxy-polysifoxane based compounds are known, from U.S, Pat, No, 5,618,860, Although epoxy-polysiloxane based coating materials generally do have resistance 10 ‘weathering in sunlight, some of them still have poor gloss retention, Jul. 7, 2005 [0007] Thus, while epoxy-polysitoxane based coating materials have gined commercial acceptance, the need rnevercless remo for epoxy-polysiloxane based materi als with improved properties. Coating materials. with ‘improved gloss retention are needed for both primary and secondary chemical containment structures, for protecting steel and concrete in chemical, power generation, ral car, sewage and waste water tealment, and paper and pulp processing industries. [0008] 11 is an object of the present invention to provide ‘ew amino-Iunetional polysiloxanes with great variety in amine structures, whieh can be prepared with a simple ‘method. I is another object to inttoduee amino-funetional groups on a polysiloxane backbone, which are reactive, eg. ‘with epoxy radicals I is yet another object of the present wention 1 provide new polymer compositions comprising sid amino-functional polysiloxane, with improved hardness evelopment. It is another object to provice new polymer ‘compositions comprising said amino-functional polysilox- ane having improved gloss retention, and weathering resis- tance. A further object of the present invention is therefore {o provide an cpoxy-polysiloxane based coating composi- ‘ion having improved gloss reteation while other properties like curing, hardness development, and chemical resistance ave preserved SUMMARY OP THE INVENTION [0009] In s frst aspect of the present invention, novel amino-funetionalpolysiloxanes. of formula (1) are escribed, wherein each R’ is independently selected from the group comprising alkyl and aryl, each R® is indepen- ently selected from the group comprising hydrogen, alkyl and aryl radicals, nis selected so tit the molecular weight forthe functional polysiloxane is inthe range of from 40) 10 10,008 and R? isa bivalent radial or -O—R*—-NH—R?™ is hydroxy or alkoxy, and R° is selected from the group comprising hydrogen, or aminoalkyl, amioalkeayl, ami oaryl, aminocyeloalkyl radical, optionally substituted by alkyl, aryl, cycloalkyl, halogen, hydroxy, alkoxy, thioalkyl, ‘amino, amino derivatives, amido, amidoxy, nitro, e¥ano, eto, acyl derivatives, acyloxy derivatives, carboxy, ester, ther, esteroxy, heteroeyce, alten or alkynyl and wherein (0 40 9076 of —O—R°—NII—R? is hydroxy or alkoxy. ® [0010] According to an embodiment, the amino-fusetional polysiloxane of formula (1) has preferably the following Stoichiometric formula US 2005/0148752 Al WOO. [0011] wherein each R? is independently selected from hydrogen, alkyl, or —R—NH—R’, and R, RE, have the ‘ame meaning a that defined above, and b ar each areal ‘number from 0.0 to 2.0, more in paticula from 0.1 0 2.0, ‘isa real nimber from 0.110 1.0, b is ranging from 0.220, tnd asbge is lower than 4, and wherein 0 10 90% of —O=R’is hydroxy or alkoxy. In the above stoichiometric formula, ai preferably fom 1-410 Obs preferably from (05 10 15 ana is preferably from 0.1 1 0 [0012] Ssid) amino-functional polysiloxane possesses Si-O—C bond between the polymeric backbone and the funetional group. [0013] These novel compounds contain atleast one basic ritrgen which is bonded to silicon via an oxygen tnd which has atleast one hydrogen atom directly bonded to i [0014] In. second aspect, the present invention relates to ‘8 method forthe preparation of tmino-functional polysilox- ane of formula (1). The method of the present invention provides the advantage of being a simple one sep synthesis ‘of said amino-functional polysiloxane from available pols ysiloxane. [0015] The present invention further relates to the use of Said amino-Rinctional polysiloxane as hardener and in coating [0016] The present invention further provides new poly ‘mer compositions comprising sid amino-functional pols Joxane of formula (1) an toa method of preparation thereof. Said polymers show improved hardness development and Improved gloss retention and weathering resistance [0017] In a thint aspect, an epoxy-polysiloxane composi- tion s prepared, according to priniples ofthis invention, by ‘combining the following ingredients [0018] _ potysiloxane of formula (4), wherein each RR is independently selected from the group com= prising hydroxy, alkyl aryl and alkoxy radicals hav- ing up to six carbon atoms, each R"is independently selected Irom the group comprising hydrogen, alkyl land aryl radicals having up to six cacbon aloms and, ‘wherein nis selected so thatthe molecular weight for ‘the polysiloxane i in the range of from about 400 10 10,000, @ [0019] an epoxy resin having more than one 1.2- {epoxy gxoups per molecule with an epoxy equivalent ‘weight in the range of from 100 0 about 5,000, and [0020] aminopotysitoxane hardener component, of ‘an amino-funetional polysiloxane hardener compo- Jul. 7, 2005 nent of formula (1) as described herein having ative hhydrogens able to react with the epoxy groups inthe ‘epoxy resin 10 form epoxy polymers, and able 10 react with the polysiloxane to form’ polysiloxane polymers, wherein the epoxy chain polymers and polysiloxane polymers polymerize to form a cured ‘epoxy-polysiloxane polymer composition. [0021] The aminopolysiloxane hasdener may be any ‘mine-functional polysloxane. Amino-functional polysi loxanes are known from U.S, Pat, No. 3,890,269, EP 02 $30 (09, US. Pat, No, 4,413,104, US, Pa, Nos. 4,972,029 and 4857, 608, EP 0887 366 and US. Pat. No. 3,941,856 hereby Incorporated by elerence, U.S, Pat, No, 3,890,209 relates 10 4 process forthe preparation of amino-functional polysilox- ane polymers by equlibrating a mixture containing a eyetie ‘organo-palysiloxane with an ami functional silicon com- pouind in the presence of «catalyst. [0022] US. Pat. No. 4,857,608 relates to a process for preparing 4 coating by modifying epoxy resins with exga- fosilicon compounds containing 2 basic nitrogen which is bonded to silicon via a carbon andl which bas atleast one hydrogen atom diretly bonded to it. Preferred examples are illustrated in columa 2 from Tine 5 up to column 3 Tine 49 ‘These known aminopolyriloxanes are suitable as a hardener {or the present invention. [0023] ‘The epoxy-polysiloxane composition is prepared by using i the range of from about 10 to 80% by weight polysiloxane, 10 to 50% by weight of the epoxy resin ingredient, 510 40% by weight of the aminopolysiloxane hardener, and optionally upto about 5% by weight catalyst. [0028] It is assumed that the shove- identified ingredients eaet to form a network composition that comprises.» ‘continuous phase epoxy-polysiloxane copolymer. Epoxy polysiloxane compositions of this invention display Improved resistanee 10 ullaviolt light and weathering ia suolight without impairing chemical and corrosion resis- lance when compared to conventional epoxy resin based ‘coatings, Additionally, epoxy-polysloxane compositions of this invention display improved color and gloss retention that reaches a level exhibited by topclass aliphatic polyure- thanes and may obviate the need for top coating DETAILED DESCRIPTION [0025] In a first aspect, the present invention relates 10 ‘mino-functional polysiloxane of formula (1) as described above, Iti to be Understood that formula (1) i llstative ‘nly, and thatthe amino-functional polysloxane according {0 the invention may contain from 0 10 90% of alkoxy or bydeoxy radicals, [0026] As used herein, the term “independently select indicates that the each radical R so described, can be identical or different. For example, each R* in polysiloxane of formula (1) may be different for each value of n, and ‘within each unit of said polysloxane [0027] As used herein “a eal number” refers to a number Which is positive and includes integers and Tractions of| integers of any rational or ierationsl number. For example 2 isa real number from 00 to 2.0 means thal a may assume any value within the range from 0.0 10 2.0. [0028] As uscd herein, the term “alkyl”, alone or in ‘combination, means sraight and branebed chained saturated US 2005/0148752 Al hydrocarbon radicals containing from 1 to 10 carbon atoms, preferably from 1 to 8 carbon atoms, more preferably 1-6 ‘carbon atoms. Examples of such radicals include methyl, ethyl, w-propy], isopropyl, n-butyl, isobutyl, sec-butyl, butyl, 2-methylbutyl, pentyl, iso-amy, hexyl, methyipen- ‘yl, octyl, 2ethylbexy] and tbe like [0029] As used herein, the term “alkenyl”, alone oe in ‘combination, defines stright andl branched chained hylo= ‘carbon radicals containing from 2to about 18 carbon atoms, preferably from 2 to 8 carbon atoms, more preferably 2 ‘carbon atoms containing at least ope double bond such as, for example, ethenyl, propenyl, butenyl, penteny, hexenyl and the ike [0030] The term “atkenylene”, alone o¢ in combination, ‘defines bivalent straight and branched chained hydrocarboo radicals containing from 2 to about 18 carbon atoms, pret ‘erably fom 2 to 8 earboa atoms, more preferably 2-6 carbo atoms containing at least one double bond such as, for ‘eximple, ethenylene, propenylene, butenylene,pentenylene, hrexenylene and the lke [0031] The term “alkoxy” or “alkyloxy", alone or in ‘combination, means alkyl ether radical wherein the term alkyl is as defined above. Examples of suitable allyl cther fadicals include methoxy, elboxy, n-propoxy, isopropoxy, s-bulo, so-bulony, see-buloxy, fer-hutony, bexanoxy and the lke. [0032] The term “alkylene”, alone or in_ combination, defines bivalent straight and branched chaioed saturated hydrocarbon radicals containing from | to 10 carbon atoms, preferably ftom 1 t0 8 carbon atoms, more preferably 1-6 ‘carbon atoms such as, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene and the ike [0033] The term “alkynyl”, alone oF in combination, ‘defines straight and branched chained hydrocarbon radials, having from 2 10 10 carbon atoms containing at feast one triple bond, more preferably from 2 to about 6 carboa atoms. Examples of alkynyl radials include ethynyly propynyl, (propargyD, butyyl, pentynyl, bexynyl and the like. [0034] The term “aminoatkylene” means 4 bivalent alky~ Jee amine rial, wherein the term “alkylene” is defined as above. Examples of aminoalkylene radicals include ami- nomelbylene(—CH.NH—), aminoethylene (—cH.ch aminopropylene, aminoisapropylene, aminobutylene, aminoisobulylene, aminobexylene and the Tike, [0035] The term “aralkyl” alone or in combination, means alkyl as defined herein, wherein an alkyl hydrogen atom 's eplaced by an aryl as defined herein. Examples of aralkyl radicals include benzyl, phenethyl, dibenzylmethyl, meth- sylpbenylmethy, 342-naphthyl-buty, and the like. [0036] The term “aratkylene” as used herein, relates to a s10up of the formula alkylene-arylene in which alkylene is 48 defined ahove. Examples of srakylene radicals include benzylene, phenethylene and the like [0037] The term “aryl” alone or in combination, is meant to include phenyl and nsphiyl which both may be optionally substituted with one or more substituents independently ‘selected from alkyl, alkoxy, halogen, hydroxy, amino nit, ‘eyano, haloalkyl, cizboxy, alkoxycarbonyl, cycloalkyl, el ‘erocycle, amido, optionally mono- or disubstituted a Jul. 7, 2005 carbonyl, methylthio, methylsulfonyl, and phenyl option- ally substituted with one or more substituents selected from alkyl. alkyloxy, halogen, byclroxy, optionally mono- or dis- ubstiuted amino, nfo, eyano, haloalkyl, carboxyl, alkoxy carbonyl, eyeloalky, heterocycle, optionally mono~ or dis- Uubstituled sminocirbonyl, methylio and methylsulfonyl; ‘wherehy the optional substitventson any amino function are independently selected from aly, alkyloxy, beterocyele, bpeteracyeloaikyl,heterocyclooxy, heteroeyelooxyakyl, phe- yl, phenyloxy, pheayloxyalkyl, phenylalkyl, alkyloxye bonylamino, amino, and aminoalkyl whereby each of the amino groups may optionally be moao- or where possible i-substitated with alkyl. Examples of aryl inchudes phen pols, 4-methoxyphenyl, 4(tert-butoxs)phenyl, methyl. ‘emethoxyphenyl, 4-ocophenyl, 4-chlorophenyl, -nieo- phenyl, 3-aminophenyl, S.acetamidophenyl, 4-acctami Sophenyl, 2-methyl-3-acetamidopheayl,2-methyl- Aaminophenyl,— 3methyl-aminophenyl,,—2-amino= imethylphenyl, hydin or epibromobydia) with « polyphenol ia the pre ‘ence of a alkali. Sutale polyphenols inclu resorcinol, ‘alco, lydroguinone bis4-bydroxyphenyl)-22-propane, ie bisphenol A, bis(-hydroxypheny?Ie-bohatane, Ale Aihydroxybenzophenone, bist-hydroxypheny|-1.1-pro- pane. A cetiled lis of suitable epoxide for said reaction ean te foun ia the handbooks A.M, Paquin, "Eponddverbia- dongen und Haze" (Epoxide Compounds and. Resins), Springer Vera, Belin 1958, Chapter IV and H. Lee and K Neville, “Handbook of Epoxy Resins” MC Grat Hill Book Company, New York 1982 Reiss, as well 38.C. A. May, “Epoxy Resine-Chemisity and Technology”, Marcel Dek er, Tne, New York and Basle, 1988 [0064] Suitable epoxy for said reaction may ako be ‘select from the glycidyl ester of branched carboxylic acids © Jul. 7, 2005 ono ey aa Lf o Aa such as the glyidy ester of pivalie or versatic acid con- taining 5 or 10 carbon atoms inthe acid moiety, such as for ceximple Cardura ES or Cardura E10 from Resolution; ‘ielyeidyl ethers of eyclohexane dimethancl, bisptenol A dighyeidyl ether such as Epikote 828, hydoge- ated bisphenol A diglycidyl ether (DGEBA) Spe epoxy resins, such as Eponex 1510; aliphatic epoxy resins such as ‘Analdite DY-C, DY-T and D¥.0397 from Vantin; and bisphenol F diglycidy! ether type epoxy resin such a Epikate 862. from Resolution Performance Products and hydrogenated bisphenol F dighycyl ether type epoxy eesin stich as Ritapox VEA261/R from Rutgers Bakelite, [0065] Suitable polyamine include 1,2iaminoethane, 1.2liaminopropane, 1.3iaminopropane, 1-diaminobu- tie ad higher bomologes aswel 2mety iam xpi, 18 damien, 9.2m 1a rohexane and 2,4;4timethyl-l,-diaminohexane as well as industrial mixtures tery {-amino-3-aminomethyl-35,5- trimethyleyclohexane, » 22-dimethyl--ciaminopropanc, 1 3-biaminomethyl)cyelohexane, 1,2-diamino-cyelobex- ane, 13-bis{aminomethyDbenzene, bi{-aminoeyclohexy methine, bis(4-amnino-3-methyleyclobexylpmethane, 3-423- pentane-1,S

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