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    Silane-Terminated Polyurethanes With High Strength PDF

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    Silane-Terminated Polyurethanes With High Strength PDF

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    Silane-Terminated Polyurethanes With High Strength PDF

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    Gizem D.

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    2) United States Patent (10) Patent No: US 8,394,909 B2 Porsch et al. (45) Date of Patent: Mar. 12, 2013 (S8)_ SILANE-TERMINATED POLYURETHANES 619550 A 122000 Dabise WITH HIGH STRENGTH AND HIGH aoe y oan Hewat ELONGATION chr BL 200 Dore 6250484 BL 72001 Gra ta (75) Inventors: Michal J Porse, Minncpois, MN Sesh BL anol Stat (US). Kelly A. Kula Freudenberg, 6230 BL 82001 Ola Brevi MN (8) 6361322 BL 82001 hl 630 Shon (73) Assignee: Construction Research & Technology cx cca ta Gmbh Tostbee (D2) oaese aa ave (*) Notice: Subject to any disclaimer, the term of this. 6.423.661 ‘McGraw et al. Patent is extended orajvsted under 35 S50 05 Mecha lal US.C. 154(b) by 274 days. 6.440.541 Humphrey et al cians tha ca (21) Appl. Nos 12848.041 oat Wares. (22) Fle) ee. 292008 satin Mint cams Keene @) Prior Publication Data ena we csr Schsticg al US2000027T101 Sep. 10,2008 ae Since Sannet faunal : 5 consis Mata Related US. Applicaton Dats set38i6 Mal (68) Contimaton of application No. 10808.084, fil on 81602 intorgca Mar 24,2004, noe Pat No. 788220 2 rsh oy Ime. Poncho 2828 cite t4as anos) oozinodssy em eal cong 141020080) Smauisit Hang C086 1842 (2006.01) a002 188068 aoe orga conc ess (200601) inno fonlereta 2) US.cL S288, 528/50, 2815; 52838GpouoCTa1 Sujet (58) Field of Classification Search 528/28, pe a mee 528/33, 38, 30 3 nals et ‘See application file for complete search history, MMOOOITSHD AL $2006 Roeser tal FOREIGN PATENT DOCUMENTS (56) References Cited EP 158893 Al 10/1985 & tears BI Inns US. PATENT DOCUMENTS Wo woo tae "Stone eer OTHER PUBLICATIONS A TTIGEE Bode a ane Ace or eee Feng, TeMinan alin Bc Sie thane ome Saat ome Eanes Papi of Connon Sean Adbaes Ags A Sonu A Sete Syme 198 pp 02S A3eno A Sw Ribera: GGMan A DD Board * ited by examiner ‘Soran A Tibet carat Shoes Sass, Primary Examiner —Rabon Sergent QDs Intl (14) orney, don, oF Fim —Curaolo Sit Co, LP 2 Sten Rata rao Salvatore A Sido 5 Boe Racal Joseph. Corsa; Salatre A Sid 2190 Bal 6) ABSTRACT A 11/1991 Higuchi et a. A silane-terminated polyurethane composition is the reaction. Ngo. Hig h 2793 Ka predict of slanteminated poljurhane prepolymer ese Component silne-tenminted monomeric eiseyant, 3 ngs Rear sndopionally at eset one mlifunctna isin ret A Tisoe baal jane component, A method for making’ a composition Sssp6 Enmetingtat includes providing iane-erminat poet pre- $1908 lnk sonpoven Hane ron mare sy. 51998 ‘Shale et al {61008 Mowreret st 21989 Morenet al. {199 Roeser eta 111999 Ashmont 121999 Waldman etal 121999 Shafer al 52000 Clineet 142000 Roeser et (62000 Roeser et 077902 A polymer con ‘nate componeat, and optionally at last one multifunctional trsilane of teraslane component, and (b) combining the prepolymer component, monomeric component, and ‘optional molifunetional silane component to form asilane- ‘eminated polyurethane reaction product with a ensile strength of about 4 MPa or greater and an elongation of about 200% or greater 30 Claims, 4 Drawing Sheets US 8,394,909 B2 Sheet 1 of 4 Mar. 12, 2013 US. Patent L ‘SlaA oles HO/OON puZ ors / 7 ees / o1e4 HO/OON jsb [isd] yyBuadys ajisuay US. Patent Mar. 12,2013 Sheet 2 of 4 US 8,394,909 B2 2"4 NCO/OH ratio FIG. 2 1.67 so 8 6 ¢s > 2 oS 8 8 8 8 $§ eo 8 N A 18‘ NCO/OH ratio [%] voneBuolg US 8,394,909 B2 Sheet 3 of 4 Mar. 12, 2013 US. Patent [%] uojeGuo|3 € ‘Sls uonebBuojy y}Buag ajisuay auelisiay jusoled 1YBIEM, Oe SL %OL %S ot T OSOL os OOLL ool 7 OSLL ost 7 o0zt 0c + 7 OSZL ose O0eL o0e oOseL ose to 7 meusaresnens OOU "< [isd] yBuays aysuay US. Patent Mar. 12,2013 Sheet 4 of 4 US 8,394,909 B2 [4] uoneBuol3 ° °o °o 2 vt s s 8 8 s : 8 2 8 & 2 ° oO tt Ht x S s = , oF e = la ;2 6 6 2 G oa = SD = x $s oD N c s gc ag 20 =D tt tt Be 2 ° 2 ° ° 2 2 9 S 8 s 32 8 2 3 Rg £ 8 3 Fu [isd] yBueng oysuay US 8,394,909 B2 1 ‘SHLANE-TERMINATED POLYURETHANES WITH HIGH STRENGTH AND HIGH ELONGATION (CROSS REFERENCE TO RELATED APPLICATIONS: ‘This application isa continuation of US. Ser. No. 10/808, (084 filed on Mar. 24, 2004, now U.S. Pat. No 7,482,420. BACKGROUND Polyurethane materials demonstrate unique combination ‘ofperiormance properties inching excellent abrasion esis- ‘ance, Nexibilty, hardness, chemical sistance, solventesis- tance, light stability, and weatheraily “The perlormunee properties of polyurethanes make them suitable for many useful products, including coatings, ahe- sives, sealants, and compositions, Standard polyurethanes, however, ave disadvantages related to the presence of i ‘yates, sochas sensitivity to humid application conditions. Silane-terminated polyurethanes can be formulate to beso ‘cyanate-fee, but have not previously demonstrated the high tensile strength and high elongation properties required for high performance applications ‘What is needed inthe at are polyurethane materials that reno sensitive to huanid application conditions, Whatisalso needed in the ar is a high performance silane-terminated Polyurethane that is isceyanatesfree and has both high seength and high elongation, These properties are met with the rection product ofa silane-terminated polyurethane pre- polymer anda silane-terminated monomeric disocyanate. SUMMARY. A silne-terminated polyurethane composition is pro= Vide, comprising the reaction product of sine-terminated polyurethane prepolymer componea, a silo-terminated ‘monomeric disoeyanate component, and optionally a tsi= lane or ttasilane component In certain embodiments of the silane-terminated polyure- thane composition: 1) the silane-temninated polyurethane prepolymer compo- ‘ent comprises atleast one of i) a prepolymer reaction product of atleast one disoey- ‘aate and at lest one polyol with a mole ratio of isoeyanate groups to hydroxy groups of about 1.13110 about 2:1, ssid prepolymer reaction proit temi- ‘ated with an aminoslane endcapper of the formu ‘ora mereaptosilane endeapper ofthe formu: HS ALSiRIOR. whersin R represents 8, 10 Cyy alkyl group, a group having the formula —A’—Si(R (OR?) oF a group having the formula —CH(COOR*)—CH, (COR); A represents aC, 10 Co linear, branched oreyelie alkylene group; represents CH orCH aroup; R? represents, toC alkyl group; R? repre sents, t0C; alkyl group: RrepesentsaC, t0C alkyl group; and xis 0 oF or ii)a prepolymer reaction product of at lest one dio cyanate and at least one polyol with a mole ratio of ‘soeyanate groupsto hydroxy groups ofaboutO.5:1 10 about 09:1, said prepolymer reaction product termi s Fa 2 nated with an isoeyanatoslane endeapper ofthe for soul wherein A® represents a C, to C, linear or branched alkylene soup: R! represents CH, or Call rou BY represents aC, oC! group; and xis or b) the silae-terminsted monomer disocyanate compo: nent comprises at least one monomeric disoevanate fully reacted with an aminosilaneendeapper ofthe for snl: BONTALSim (OR, ‘ora mereaptosilaneendeapper of the formals: WA SIROR wherein R represents @ Cy 10 Cy alkyl group, 2 group having the formula —A'—Si(R) (OR). ora group having the formula —CH(COOR")—CHL{COOR*). A! representsaC,10C, linear branchedoreyelialkylene soup: R! represents CH orl gn00p;R? represents 4, to, aly group: R? represents a C, toC,, alkyl ‘group: represents aC, 10 alkyl group: and isOor iyand «)the optional trslane ortetrasilane component comprises atleast one ofa polyether tsilane componeat, a poly= ‘eer tetraslane component, or alos molecular weight silane adduct comprising at lest one of « tile adduct ora terasilane adduct A mulicomponent formulation is provide comprising 8) atleast one of i) silane-erminatedpolytretane prepolymer compo- ‘nent comprising a prepolymer reaction product of a least one disoeyanate and at last one polyol with a ple ratio ofisoeyanate groups to hydony groups of about 11:1 to about 2:1, sid prepolymer reaction ‘prodvet terminated with an aminoslane eneapper of the formu: AONIAI- Sim OR. ‘ora mercaptosilane endeapper ofthe formula: TS-A-Si)/OR whetein R represent aC, tC,» ali group, a group having the formula —A'—Si(R)(OR?},. OF & soup having the formula —CH(COOR*) CH, (COOR!); A" represents aC, t Co linear, branched oreyelicaliylene group: Represents aC, orCl soup, R? represents aC; toCgalhy] group: R? repre sentsaC, toC; alkyl group; RrepresentsaC, toCyy alkyl group: and xis Oo 1 0¢ iia siane-terminated polyurethane prepolymer compo- ‘nent comprising a prepolymer reaction product of a least one disoeyanate and atleast one polyol with 2 mole rato ofisoeyanate groups to hydroxy groups of about 0.5: to about 0.91, sid prepolymer reaction proto terminate with an isoeyanatosilane endeap- perof the fom: ex A SiROR a ‘wherein A* represents a C, 10 C, linear oF branched allylene group: R! represents CH, or Cero: I represents; to Cally aroup: and xis or I: b) atleast one monomeric disocyanate Tally reacted with an aminosline endeapper ofthe formu: ROME-ASiR 08, ‘ora mercaptosilane endcapper of the formula: HS—A'SiR/OR US 8,394,909 B2 3 ‘wherein R represents a C, 10 Cyy alkyl group, a group the formula —A'—Sif}) (OR), oF@ group the formula —CH(COOR"} -CH,(COOR*); A! represents aC, oC linear,branched or yeti alkylene group; repesentsaCH,orCH group: represents 4, to Cy alkyl group: RY represents aC to C.s alkyl soup: Represents, to alky group: and xs 00r Tyan «) optionally at least one ofa polyether trsilane compo- rent, a polyether tetraslane component, or a lw ‘molecular weight silane adduet comprising at eat one ofa trsilan addct ora tetrasilane aoc Wherein when components a,b, and optional e are com bins, slane-terminated polyurethane reaction product i formed that has tensile strength of about 4 MPs or erester ‘and an elongation of about 200% or greater. A method for making a silne-terminated polywethane ‘composition is provided compris: ‘) providing a prepolymer component, monomeric com- ‘ponent, andoptonally at east one mltifnetionalom- pone, wherein the prepolymer component comprises silaneterminated polyurethane prepolymer, the mono- ‘meric component comprises aslane-terminated mono- ‘meric «isocyanate, and the optional multifunctional component comprises atleast one ofa trslane or tt ‘silane component and ') combining the prepolymer component, the monomeric ceamponent, and optionally the at east one multfane- tional component to form asilane-erminated potyure- ‘thane reaction product; Wherein the silane terminated polyurethane rection product has a tensile strength of about 4 MPa or greater and an elon- sation of about 200% or ereatr [BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 isa three dimensional representation of tensile strength of ceria silane-terninated polyurethane reaction products synthesized fom isoeyanate terminated prepoly- mers of diseyanate and polyol wing a ratio of isocyanate groups to hydroxy groups less than 2:1, blended with mono meric dsoeyanates to increase the rato above 21 FIG. 2 a tree dimensional representation of elongation percentage of censin silane-temminated polyurethane reac- tion products synthesized from isocyanate terminated pre- polymers of disoeyanate and polyol having a rato af socy- nate groups to hydroxy groups les than 2:1, blended with rmonomeri diseyanates to increase the rato above 2:1 FIG. 3is a graph showing the tnsile strength and elonga- tion percentage fora silane-terminated polyurethane reaction product according to ceriin embodimentsasa fusetion ofthe ‘weight percentage of polyether trsilane component. FIG. 4s a graph showing the tensile strength ad elonga- tion percentage fora silane-terminated polyurethane reaction productaceording to ceriain embadimentsasa function ofthe ‘weight percentage of low molecular Weight tisilane compo- nent DETAILED DESCRIPTION A silane-lenminated polyurethane composition comprises the rection product of silane-terminated polyurethane pre= s 4 polymer component, asilane-ermnated monomeric disoey- nate component, and optionally a tsilane or tetrasiane component ‘Thesilaneterminated polyurethane composition may also comprise the reaction product ofa ilne-trminate polyure- thane prepolymer component, atleast one mnomeriediso- cyanate filly rected with an aminosilane endeapper or & mereaposilane endcappe, and optionally atleast one multi- fanctional component selected from the group consisting of a polyether tsilane component, a polyether tetrasilane com ponent oF alow molecular weight silane adit comprising atleast one ofa tsilan adduet or a tetasilane adet. In certain emiboxtments, the silane-teminated polyure- thane prepolymer component comprises a prepolymer reac- tion product of atleast one disoeyanate and atleast one polyol with a mole ratio of isoeyanate groups 10 hydroxy ups of about 11:1 to about 2:1, wherein the prepolymer reaction products terminated wit an aminoslaneendcapper ofthe formula: RNH—A'—Si(R') (OR?),,.oramercap- tosilne endcapper of the formula: HS—A'—Si(R), (OR?) wherein R represents a C, 10 Cy alkyl group. srouphaving the formula —A'—Si(")OR’)s.ora soup having the formula —CH{COOR?}—CH(COOR*}:A'rep- resents. aC, 10€, linear, branched or eyelc alkylene group: Ri represents CH oF Calls group: R? represents aC, 10C, alkyl group; R? represents 3, to Cy alkyl group; R* repre= sents aC, to Cally grou and x sO nother embodiments the silane-teminates polyurethane prepolymer component comprises & prepolymer reaction product of at last one diisocyanate and atleast one polyol With a mole ratio of soeyanate groups to hydroxy proups of shout 05:1 to about 0:1, wherein the prepolymer reaction put is terminated with an fsoeyanatosianeendeapper of the formula: OCN—A?—Si(R') (OR?) , wherein A? epre= sents aC, oC linear or branched alkylene group: repre= sents @ CH oF CH, group; R* represents @ C10 Cy alkyl s1oup; and x is 0 or 1. The silane-trminated polyurethane prepolymer component may'also comprise the above pre- polymer reaction products teminated with a combination of minosilane, mereaptoslane, and isoeyanatosilane endeap- pers Generally, isceyaatoslanes are wed to endeap hydroxy terminated prepolymers (i.e, having a mole rato of soevan- ate groups tohydroxy groups (NCOVOH ratios) les than 1.0), and aminosilanes or mercaptoslanes are used to endcap NCO-teminated prepolymers (ie, NCOCOH ratios greater than 1.0) and the diboeyanates “The silane-terminstd polyurethane composition may f= ther comprise the wation product of the silane-terminated polyurethane prepolymer component and at eat one mono= merc disoeyanate fly reacted with an aninosilane endeap- per ofthe formula: R—NE—A'—Si(R)OR?)s. oramer- ceposilane endcepper of the formula: HS—A'—Si(R!), (OR?),.. wherein R represents a C, to Cy alkyl group, 3 roup having the formula —A'—Si(R)OR?)s,0ra group having the formula —CH(COOR?}—CHCOOR’} A! rep- resents C10 linear, branched or yelc alkylene group: R' represents CH, oF C,H group; R? represents aC, 10C, allyl group; R? represents aC, to Cs alkyl group; R* repre= sents aC; to Cs alkyl group and xis or I US 8,394,909 B2 5 In certain embodiments, the silane-terminated polyure- thane composition comprises the reaction product of batt 70 to about 9S percent by Weight silane-terminated polyurethane prepolymer and about to about 30 percent by weight silane- terminated monomeric disoeyanae, optionally including up to about 30 percent by weight trisilane oF etrasilane compo nent, discussed in more desl below. “The performance capabilites of the composition can be ‘expressed in terms of measured physical properties such a8 yo tensile strength and elongation pereentage measured by’ a standard test method suchas ASTMD412, Tensilestengthis the force needed to totcha material until it breaks, Elonga- tion percentage or elongation at break show much the mate- rial suetches before it breaks, asa percentage of it original slimensions. “The polyol of the silane-ermiatod polyurethane prepay’ ‘mer component may comprise a diol or higher funetionslity polyol, and may be selected from the group consisting of 3, polyether polyols, polyester polyols, and combinations thereof For ilustation purposes but not by way of limitation, the polyol may be selected from the group consisting of polypro- pylene glycols, polytetramethylene glycols polyoxyalkylene diols and tiols, polycaprolactone diols and trols, and com- binations thereof. Polyoxyaldylene polyols include polyethers prepared by the copolymerization of eyeic ethers selected fom the group ‘consisting of ethylene oxide, propylene oxide, trimethylene ‘oxide, teeahydrofuran, and mixtures ofthese eyelic eters ‘with aliphatic polyols selected from the group consisting of| celhylene glycol, 1 3-butanedio, diethylene glyco, dipeopy- lene glyco, 1.2-propylene glyco, 13-propylene glycol, 1 4- butylene glycol, and mixtures ofthese aliphatic polyols. Rep- resentative polyoxyalkylene polyols include the described polyethers, polyethylene glycols, polypropylene glycols, polytevamethylene glycols and mixtures there, Representative examples of polyols include Voranol™ 220-028 and Voranol™ 220-056N (available from Dow ‘Chemical Company. Midland, Mich) as well as Aeclaim™ 4200, Acclaim™ 6300, Acclaim™ $200 and Acclaim™ 12200 (avilable from Bayer Corporation, Pittsburgh, Pa). In certain embodiments, the polyol ofthe silane-temni- nated polyurethane prepolymer component has a molecular ‘weight in the range of about $00 to about 20000, In ater ‘embodiments, the polyol asa molecular weight in the range ‘of about 4000 to about 12000. In another embodiment, the polyol comprises polypropylene glycol witha mumberaver- age molecular weight inthe range of about 4000 to about 12000, and the polypropylene glycol has a degree of unsat- uration of fess than about 0.04 meq/g. The molecular weight is either a calculated molecular weight, ic. the sum of the ‘atomic weights of the atoms making up the material o the molecular weight is 8 number average molecular weight determined based on ead group analysis or measurement of colligative properties by ebulliometry, eryoscopy, or meni- brane osmomeny For illustration purposes but not by way of imitation, each lisoeyanate reactant may be selected from the group consist- ing of hexamethylene disocyanate (HDI), 44liphenyl- metne isocyanate (MDI), 24-diphenylmethane disoey- nate, blends of 44-diphenylmethane diisoeyanste (MDI) 6 Wwith2.4-iphenylmethane disoeyanate,24-oluene disoey- nate (TDD, 2,toluene disoeyanste, blends of 2.4-toluene diisoeyaate (TDI) with 2,olene disoeyanate, 1-s0ey- anato-3,3rimety-5.soeyanatomethyleylohexane (PDD, cieyclohexyimethane-4.4-isocyanate, and combi- nations thereof. In one embodiment, the disoeyanate com prises a blend of 4,4-Si(R'}) (OR"),,5 ‘atleast one of i) RX (NHR), oF (870), (R),Si—A' ANH, and i) at east one ot SiR OR hs, 5 BOR?) K i) (0), (RY,Si—A NH and ipa disocyanate; .0)3) polyeber tami andi) at hast one of eee fat least one of: i dietiylenetiamine or tretiylenetetramine, and i) at least one of wom, «fc. wherein A? represents a C, 10 Cy linear, or branched alkylene group: A® represents'2 C, 10 Cy Hiear, branched or eylic alkylene sroup optionally iter- ‘ped with one or more ether oxygen atoms; R? ep- resents a branched aliphatic hydrocarbon residue, a branched aiphiic ether reside, or an alky-substi- tuted isocyanurate residue; R® represents Hora CH, 1s Fa » M group: R7 repesenis Ha C, 10 Cy allyl group, a group having the formula —A'—Si(R) (OR), oF 4 group having the formula —CH(COOR") Ci, (COR); A represents aC, 1 Co linear, branched oreyelicaliylene group; RrepresentsaC,orCH, aroup: R? represents aC, to alkyl group: R?repre= sentsaC,t0C; alkyl group; RrepresentsaC, toy alkyl group; xis Oor Isandy is 3 or 4 18. The multicomponent formulation of claim 14, wherein thea east one polyol isselete from the group consisting of polyether polyols, polyester polyols, and combinations there, 19. The mullcomponen formulation of sim 14, wherein teat est one polyols selected from he proup consistingof polypropylene alycols, polytetrametbylene glycols polyoxy- alkylene diols and trols, polyeaprlactone diols and trols, and combinations there: 20. Te multicomponent formulation of claim 14, wherein 2 theat least one polyol is selected rom the group consisting of| polyethylene glycols, polypropylene glycols, poyterameth- lene alyeos, polyethers prepared hy the copolymediztion ofeycic ethers selected fom he group consisting of ethylene oxide, propylene oxide, rimethylene oxide tay ofan, and mixtues of these eyelc ethers, with aliphatic pools select from the group consisting ofeylene glycol, 13- butanediol diethylene gol, dipopylene glycol 1,2-propy~ Jone glyol, 13-prpylene geo, 1 4-buylene aljeo, and mixtures ofthese polyols, ad combinations selected fem this group of alyeos and polyester. 21. The mltcomponen formulation of sim 14, wherein cach isocyanate is selected fom the group consisting of hexametbylene disocyanste (HDI), 44iphenylmethane isocyanate (MD), 2,4-dphenslnethane disoeyanate Blends of 44

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