Patent Application: US-61261700-A

Abstract:
this invention relates to methods for the preparation of hyperbranched siloxane polymers by anionic polymerization of a cyclotrisiloxane having the functional group si — oh , and for the preparation of linear siloxane polymers by cationic or anionic polymerization of a cyclotrisiloxane having a vinylterminated functional group . furthermore , this invention concerns novel cyclotrisiloxanes useful for the preparation of the aforementioned polymers .

Description:
according to a preferred embodiment , each r - substituent in the cyclotrisiloxane of formula ( i ) is the same and is an alkyl of 1 to 4 carbon atoms . most preferably , each r - substituent is methyl . the anionic polymerization of the si — oh functionalized cyclotrisiloxane ( compound ( ii )) can be carried out in the presence of a lithium containing base , for example an alkyl lithium such as n - butyl lithium or triphenylmethyl lithium , or lithium diisopropyl amide . the polymerization can be carried out in bulk or in a suitable solvent . as an example of a suitable solvent can be mentioned thf . alternatively , the anionic polymerization can be carried out by subjecting the si — oh functionalized cyclotrisiloxane to a catalytic amount of superbase such as a phosphazene . a particularly useful superbase is phosphazene base p 4 - t - bu [ 1 - tert - butyl - 4 , 4 , 4 - tris ( dimethylamino )- 2 , 2 - bis [ tris ( dimethylamino )- phosphoranyliden - amino ]- 2λ 5 , 4λ 5 - catenadi ( phosphazene )]. the preparation of linear siloxane polymers can be carried out by cationic polymerization initiated by an acid such as trifluoromethane sulfonic acid ( triflic acid ) or by anionic polymerization initiated by bases such as dilithium diphenylsilanolate or dilithium tetramethylsiloxanediolate . the invention will be described more in detail in the experimental section in the following non - limiting examples . 1 h , 13 c and 29 si nmr spectra were obtained on a bruker amx - 500 mhz spectrometer operating in the ft mode . 1 h nmr spectra were run on 5 % w / v chloroform - d solutions . forty percent w / v solutions in acetone - d 6 were used to obtain 29 si and 13 c nmr spectra . 13 c nmr spectra were obtained with broad band proton decoupling . an inverse gate decoupling pulse sequence with a 60 sec delay was used to acquire 29 si nmr spectra . tetramethylsilane ( tms ) was used as an internal standard for 1 h , 13 c and 29 si nmr spectra . ir spectra of neat films on nacl plates were recorded on a perkin elmer spectrum 2000 ff - ir spectrometer . gpc analysis of the molecular weight distribution of the polymers was performed on a waters system equipped with a refractive index detector . two 7 . 8 mm × 300 mm styragel columns packed with & lt ; 5 μ divinylbenzene cross - linked polystyrene hr4 and hr2 in series were used for the analysis . the eluting solvent was toluene at a flow rate of 0 . 3 ml / min . the retention times were calibrated against known monodisperse polystyrene standards . tga of the polymers was measured on a shimadzu tga - 50 instrument . the temperature program was 4 ° c ./ min from 25 to 850 ° c . t g of the polymer was determined by dsc on a perkin - elmer dsc - 7 . the temperature program for the analysis we begun at − 150 ° c . the temperature was increased at a rate of 10 ° c ./ min . light scattering cps / malls was performed with a wyatt dawn - dsp malls detector , which is inserted between the gpc columns and r410 ri detector . data were analyzed with a wyatt astra system . thf was used as the eluant . all reactions were conducted in flame dried glassware under an atmosphere of argon . 1 , 3 - dihydridotetramethyldisiloxane ( 57 g , 0 . 42 mol ) and methyltrichlorosilane , ( 96 g , 0 . 64 mol ) were placed into 200 ml rb flask equipped with a teflon covered magnetic stirbar and sealed with a rubber septum . the catalyst solution ( 500 μl ) was injected into flask at room temperature ( rt ). no reaction occurred . dry hcl gas was slowly bubbled into solution . excess pressure was relieved through a syringe needle which was attached to a drying tube which was filled with drierite . an exothermic reaction occurred . the contents of the flask warmed to about 35 ° c . in 10 minutes . addition of gaseous hcl gas was continued for 2 h . the reaction mixture was distilled through a 50 cm vacuum jacketed column which was packed with stainless steel saddles . a fraction , 33 . 6 g ( 42 % yield ), bp 116 ° c ., was collected . 1 h nmr δ : 0 . 32 ( d , 6h , j = 3 hz ), 0 . 84 ( s , 3h ), 4 . 77 ( septet , 1h , j = 3 hz ); 13 c nmr δ : − 0 . 17 , 5 . 97 ; 29 si nmr δ : − 17 . 10 ( 1si ), 0 . 94 ( 1si ). ir ν : 2966 , 2151 , 1414 , 1258 , 1088 , 904 , 797 cm − 1 . the compound was prepared by the controlled hydrolysis of dimethyldichlorosilane ( 5 ). 1 , 1 - dichloro - 1 , 3 , 3 - trimethyldisiloxane ( 25 . 0 g , 0 . 13 mol ) in 30 ml et 2 o and tetramethyldisiloxane - 1 , 3 - diol ( 22 . 0 g , 0 . 13 mol ) in 30 ml et 2 o were added dropwise to a solution of et 3 n ( 28 . 0 g , 0 . 28 mol ) and 170 mnl et 2 o over one hour at rt . after stirring for 2 h , the reaction mixture was filtered and washed with water , dilute h 3 po 4 solution and saturated nahco 3 . it was dried over anhydrous mgso 4 , filtered and the volatiles were removed by evaporation under reduced pressure . fractional distillation through a 10 cm vacuum jacketed column gave a fraction , 26 . 9 g ( 72 % yield ), bp 81 ° c . ( 40 mm hg ). 1 h nmr δ : 0 . 09 ( s , 3h ), 0 . 12 ( s , 6h ), 0 . 14 ( s , 6h ), 0 . 20 ( d , 6h , j = 3 hz ), 4 . 75 ( sept ., 1h , j = 3 hz ). 13 c nmr δ : − 3 . 11 , 0 . 52 , 0 . 72 , 0 . 82 . 29 si nmr δ : − 56 . 20 ( 1si ), − 8 . 50 ( 2si ), − 5 . 72 ( 1si ). ir ν : 2966 , 2907 , 2133 , 1406 , 1260 , 1089 , 1020 , 907 , 862 , 810 , 770 , 624 cm − 1 . a homogenous solution was formed from 1 - dimethylsiloxy - 1 , 3 , 3 , 5 , 5 - pentamethylcyclotrisiloxane obtained in example 1 ( 20 . 0 g , 70 inmol ), 250 ml dioxane and 30 ml distilled water . palladium catalyst ( 10 % pd / c , 0 . 5 g ) was added to the solution in three aliquots at rt , and the system was allowed to react for 12 h . no more h 2 evolved when small amount of additional catalyst was added . after filtration and removal of volatiles by evaporation , fractional distillation gave a fraction , 19 . 6 g ( 66 mmol , 93 % yield ), bp 52 ° c . ( 0 . 1 mm hg ). 1 h nmr δ : 0 . 10 ( 6h ), 0 . 11 ( 3h ), 0 . 12 ( 6h ), 0 . 15 ( 6h ), 5 . 15 ( 1h ). 13 c nmr δ : − 2 . 81 , 0 . 85 . 29 si nmr δ : − 57 . 63 ( 1si ), − 12 . 45 ( 1si ), − 8 . 32 ( 2si ). ir ν : 3339 ( br ), 2966 , 2907 , 1411 , 1262 , 1092 , 1023 , 880 , 867 , 809 , 764 , 624 cm − 1 . the preparation was carried out according to the procedure described in example 1 from 1 - phenyl - 1 , 1 - dichloro - 3 , 3 - dimethyldisiloxane ( 22 . 0 g , 88 mmol ), tetramethyldisiloxane - 1 , 3 - diol ( 14 . 56 g , 88 mmol ), and et 3 n ( 18 . 6 g , 184 mmol ) in 210 ml diethyl ether . 13 . 02 g ( yield 43 %), bp . 86 ° c . ( 1 mm hg ). 1 h nmr δ : 0 . 17 ( s , 6h ), 0 . 24 ( s , 6h ), 0 . 26 ( d , 6h , j = 2 . 5 hz ), 4 . 82 ( sept . 1h , j = 2 . 5 hz ), 7 . 42 ( m , 3h ), 7 . 65 ( m , 2h ). 13 c nmr δ : 0 . 80 , 0 . 98 , 1 . 23 , 128 . 42 , 130 . 86 , 133 . 73 , 134 . 30 . 19 f nmr δ : 29 si nmr δ : − 70 . 00 ( 1si ), − 7 . 27 ( 2si ), − 3 . 90 ( 1 si ). ir ν : 2964 , 2133 , 1431 , 1261 , 1133 , 1084 , 1021 , 998 , 902 , 851 , 808 , 771 , 699 , 641 cm − 1 . the preparation was carried out according to the procedure described in example 2 from 1 - dimethylsiloxy - 1 - phenyl - 3 , 3 , 5 , 5 - tetramethylcyclotrisiloxane from example 2 ( 8 . 34 g , 24 mmol ), distilled water ( 10 ml ), catalyzed by 0 . 4 g 10 % pd / c . 6 . 18 g ( yield 71 %), bp . 94 ° c . ( 0 . 2 mm hg ). 1 h nmr δ : 0 . 13 ( s , 6h ), 0 . 16 ( s , 6h ), 0 . 23 ( s , 6h ), 5 . 37 ( s , 1h ), 7 . 41 ( m , 3h ), 7 . 67 ( m , 2h ). 13 c nmr δ : 0 . 62 , 0 . 90 , 1 . 10 , 128 . 31 , 130 . 72 , 134 . 38 . 29 si nmr δ : − 71 . 73 ( 1si ), − 11 . 97 ( 1si ), − 7 . 35 ( 2si ). ir ν : 3392 , 2964 , 1595 , 1431 , 1262 , 1133 , 1189 , 1020 , 998 , 879 , 852 , 808 , 745 , 717 , 699 , 641 , 593 cm − 1 . vinyldimethylchlorosilane ( 4 . 0 g , 33 mmol ) in 10 ml et 2 o was added dropwise to a solution of 1 - dimethylhydroxysiloxyl - 1 , 3 , 3 , 5 , 5 - pentamethylcyclotrisiloxane prepared in example 2 ( 4 . 85 g , 16 mmol ), 60 ml et 2 o and et 3 n ( 4 . 0 g , 40 mmol ) at rt during 20 min . after 5 h , the reaction was filtered . the filtrate was washed with water , dilute aqueous h 3 po 4 and saturated nahco 3 , to remove the triethylammonium chloride , dried over anhydrous mgso 4 and filtered . final product was obtained in 4 . 91 g ( 0 . 13 mol , yield 79 %) by fractional distillation at 50 ° c . /( 0 . 15 mm hg ). 1 h nmr δ : 0 . 09 ( s , 6h ), 0 . 11 ( s , 3h ), 0 . 13 ( s , 6h ), 0 . 15 ( d , 6h , j = 0 . 5 hz ), 0 . 17 ( s , 6h ), 5 . 76 ( dd , 1h , j = 21 and 4 hz ), 5 . 93 ( dd , 1h , j = 15 and 4 hz ), 6 . 14 ( dd , 1h , j = 21 and 15 hz ). 13 c nmr δ : − 2 . 73 , 0 . 36 , 0 . 77 , 0 . 93 , 1 . 07 , 132 . 08 , 139 . 69 . 29 si nmr δ : − 58 . 11 ( 1si ), − 20 . 30 ( 1si ), − 8 . 40 ( 2si ), − 3 . 53 ( 1si ). ir ν : 3052 , 2965 , 2906 , 1596 , 1408 , 1261 , 1068 , 1021 , 862 , 839 , 808 , 763 , 710 , 625 cm − 1 . 3 ′- vinyl - 1 ′, 1 ′, 3 ′, 3 ′- tetramethyldisiloxyl - 1 , 3 , 3 , 5 , 5 - pentamethylcyclotrisiloxane from example 5 ( 1 . 0 g , 2 . 6 miol ) in 250 μl of 1 , 1 , 2 - trichlorotrifluoroethane was cooled to − 78 ° c . and 5 μl trifluoromethane sulfonic acid ( triflic acid ) was injected into solution . additional 1 , 1 , 2 - trichlorotrifluoroethane ( 3 × 250 μl ) was added when the system became too viscous to permit stirring . the reaction was quenched after 0 . 5 h by addition of 20 mg , 0 . 12 mmol hexamethyldisilazane . polymer was precipitated three times from a mixture of et 2 o / meoh , and dried under vacuum for 12 h . in this way , 0 . 48 g ( 48 % yield ) of polymer was obtained . m n / m w = 83 , 900 / 28 , 300 . 1 h nmr δ : 0 . 08 - 0 . 18 ( m , 27h ), 5 . 75 ( dd , 1h , j = 20 . 5 and 4 hz ), 5 . 92 ( dd , 1h , j = 15 and 4 hz ), 6 . 13 ( dd , 1ih , j = 20 . 5 and 15 hz ). 13 c nmr δ : − 2 . 04 , − 2 . 02 , − 0 . 39 , 1 . 11 1 . 15 , 1 . 18 , 1 . 20 , 1 . 23 , 1 . 28 , 131 . 96 , 139 . 57 . 29 si nmr δ : − 67 . 17 , − 67 . 11 , − 21 . 93 , 21 . 92 , − 21 . 84 , − 21 . 76 , − 21 . 75 , − 21 . 68 , − 21 . 04 , − 3 . 95 , − 3 . 94 . ir ν : 3053 , 2964 , 2906 , 1596 , 1408 , 1261 , 1094 , 1030 , 956 , 839 , 799 , 756 , 707 , 518 cm − 1 . dilithium diphenylsilanolate was prepared by treatment of diphenylsilanediol with n - butyl lithium in thf . styrene was used as an indicator ( 8 ). initiator ( 22 μl , 10 μmol ) was injected to a solution of 3 ′- vinyl - 1 ′, 1 ′, 3 ′, 3 ′- tetramethyldisiloxyl - 1 , 3 , 3 , 5 , 5 - pentamethylcyclotrisiloxane from example 5 ( 1 . 0 g , 2 . 6 mmol ) in 250 μl thf at rt . polymerization was carried out for 24 h , after which it was quenched with vinyldimethylchlorosilane ( 0 . 1 g , 0 . 8 mmol ). the polymer was precipitated three times with et 2 o / meoh and dried in vacuum for 10 h , yielding 0 . 92 g ( 92 %) of product . m w / m n = 29 , 100 / 12 , 400 . tga : decomposition begins at 425 ° c . at 530 ° c ., 90 % of material is left . at 655 ° c ., half of the total weight is lost . forty five percent residue is left at 850 ° c . preparation of a linear siloxane polymer by anionic polymerization using a superbase the superbase ( phosphazene base p 4 - t - bu ( 1m in n - hexane ) ( 2 μl , 2 μmol ) was injected into solution of 3 ′- vinyl - 1 ′, 1 ′, 3 ′, 3 ′- tetramethyldisiloxyl - 1 , 3 , 3 , 5 , 5 - pentamethylcyclotrisiloxane ( 1 . 0 g , 2 . 6 mmol ) in 250 pl tbf at rt . after 0 . 5 h , reaction was quenched with dimethylvinylchlorosilane ( 0 . 1 g , 0 . 8 mmol ). volatiles were removed by vacuum . reaction product was low viscous liquid , m w / m n = 8700 / 2100 . the monomer ( 1 - dimethylhydroxysiloxyl - 1 , 3 , 3 , 5 , 5 - pentamethylcyclotrisiloxane ), 2 . 0 g , 6 . 7 mmol and thf 1 . 0 ml were cooled to − 9 ° c . and the base ( p 4 - t - bu ) ( 8 μl , 8 μmol ) was injected . after 4 h , 1 ml thf , et 3 n ( 2 ml , 7 . 3 mmol ) and 1 ml vinyldimethylchlorosilane was added , and stirring was continued for 12 h . polymer was extracted into hexamethyldisiloxane , washed with aq . nacl and precipitated three times from tbf / meoh . yield 2 . 47 g ( 96 %), m w / m n = 15400 / 5900 . 1 h nmr δ : 0 . 05 - 0 . 20 ( m , 27h ), 5 . 74 ( dd , 0 . 65h , j = 20 . 5 and 4 . 5 hz ), 5 . 76 ( dd , 0 . 35h , j = 20 . 5 and 4 . 5 hz ), 5 . 91 ( dd , 0 . 65h , j = 14 and 4 . 5 hz ), 5 . 92 ( dd , 0 . 35h , j = 14 and 4 . 5 hz ), 6 . 13 ( dd , 0 . 65h , j = 20 . 5 and 14 . 5 hz ), 6 . 13 ( dd , 0 . 35h , 20 . 5 and 14 . 5 hz ). 13 c nmr δ : − 2 . 79 , − 2 . 11 , 0 . 25 , 0 . 36 , 0 . 75 - 1 . 23 ( m ), 131 . 84 , 131 . 97 , 139 . 27 , 139 . 49 . 29 si nmr δ : − 67 . 27 , 067 . 20 , − 67 . 14 , − 67 . 06 , − 66 . 20 , − 66 . 14 , − 66 . 06 , − 22 . 05 , − 21 . 97 , − 21 . 89 , − 21 . 82 , − 21 . 80 , − 21 . 76 , − 21 . 74 , − 21 . 11 , − 8 . 55 , − 4 . 00 , − 3 . 66 , − 3 . 64 . ir ν : 3053 , 2964 , 2906 , 1596 , 1408 , 1261 , 1093 , 1028 , 956 , 839 , 799 , 756 , 707 , 519 cm − 1 . thf ( 0 . 3 ml ) and phosphazene base p 4 - t - bu solution ( 10 μl , fluka chemie ag ) were placed into a test tube equipped with a teflon covered magnetic stirbar and sealed with a rubber septum . it was cooled down to − 15 ° c . and pentamethyl - cyclotrisiloxane - 1 - ol ( 1 . 70 g , 7 . 57 mmol ) was added slowly over a 30 min period . the system was allowed to react at − 15 ° c . for 5 hours followed by 4 days at rt after which et 3 n ( 1 . 5 ml , 10 . 8 mmol ), phenyldimethylchlorosilane ( 1 . 5 ml , 9 . 07 mmol ), and 3 ml thf were added to end cap the polymer . after 24 hours , the solution was filtered and the ammonium salt discarded . the volatiles were evaporated under vacuum and the polymer was precipitated three times from et 2 o / meoh . yield 1 . 72 g , ( 63 . 3 %). m w / m n = 32 , 020 / 11 , 320 ( gpc ), m w / m n = 62 , 980 / 13 , 240 ( light scattering ). tg =− 98 ° c ., t m =− 56 ° c . 1 h nmr δ : 0 . 13 ( m , 15 . 8h ), 0 . 37 ( m , 5 . 2h ), 7 . 29 ( s , 2 . 6h ), 7 . 56 ( s , 0 . 9h ), 7 . 59 ( s , 0 . 8h ). 13 c nmr δ : − 2 . 01 ( m ), 0 . 80 ( m ), 1 . 20 ( m ), 127 . 97 , 129 . 57 , 129 . 60 , 133 . 21 , 133 . 27 , 133 . 29 , 139 . 41 , 139 . 44 , 139 . 64 , 139 . 68 . 29 si nmr δ : − 67 . 78 , − 67 . 34 , − 67 . 25 , − 66 . 29 , − 65 . 86 , − 65 . 79 , − 21 . 73 , − 21 . 58 , − 21 . 53 , − 21 . 37 , − 21 . 34 , − 20 . 53 , − 8 . 29 , − 8 . 15 , − 2 . 25 , − 2 . 12 , − 1 . 76 , − 1 . 62 , ir ν : 3091 , 3072 , 3053 , 3025 , 3012 , 2963 , 2905 , 1592 , 1488 , 1429 , 1412 , 1261 , 1120 , 1090 , 1027 , 999 , 857 , 831 , 800 , 755 , 726 , 699 , 668 cm − 1 . tga : 95 % left at 437 ° c . 50 % left at 576 ° c . after 600 ° c ., 25 % residue remains . it will be appreciated that the methods of the present invention can be incorporated in the form of a variety of embodiments , only a few of which are disclosed herein . it will be apparent for the specialist in the field that other embodiments exist and do not depart from the spirit of the invention . thus , the described embodiments are illustrative and should not be construed as restrictive . 1 . rebrov , e . a ; vasilenko , n . g ; muzafarov , a . m ; et al ; polym . preprints , ( 1998 ) 39 ( 1 ), 479 , 481 , 581 . 2 . kazakova , v ; myakushev , v ; strelkova , t ; muzafarov , a ;. preprints , ( 1998 ) 39 ( 1 ), 483 . 3 . herzig , c ; deubzer , b ; polym preprints , ( 1998 ) 39 ( 1 ), 477 . 4 . uchida , h ; kabe , y ; yoshino , k ; kawamata , a ; tsumuraya , t ; masamune , s ; j . am . chem . soc . 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