Source: http://www.google.es/patents/USH1388?dq=flatulence
Timestamp: 2017-10-24 06:08:01
Document Index: 161545827

Matched Legal Cases: ['Application No. 87012609', 'Application No. 88207488', 'Application No. 89024144', 'Application No. 89285093', 'Application No. 87012609', 'Application No. 88207488', 'Application No. 89024144', 'Application No. 89285093']

Patente USH1388 - Polyolefin polymer and method of making same - Google Patentes
A polyolefin composition comprises repeating units of a metathesis polymerizable olefin monomer, a metathesis polymerization procatalyst, a metathesis polymerization procatalyst activator, and at least one member selected from the group consisting of: (i) a Lewis acid catalyst and a Lewis acid cocatalyst,...http://www.google.es/patents/USH1388?utm_source=gb-gplus-sharePatente USH1388 - Polyolefin polymer and method of making same
Número de publicación USH1388 H
Número de solicitud US 07/997,303
Número de publicación 07997303, 997303, US H1388 H, US H1388H, US-H-H1388, USH1388 H, USH1388H
Inventores Albert S. Matlack
Citas de patentes (55), Otras citas (56), Citada por (3), Clasificaciones (4), Eventos legales (1)
Polyolefin polymer and method of making same
US H1388 H
TABLE 1  Metathesis - Cationic Polymerization of Dicyclopentadiene Std. activator  used at 2000 monomer per W, with one dichlorodiphenylmethane per W in the catalyst. Bell means WOCl2 (0-2,6-diisopropylphenyl)2 used at the same level. The order of addition to the monomer was from left to right across the table. 2X means double the usual amount.      Co-Moderator  Catalyst      Glass   Lewis for Lewis  for Lewis Initial  Maximum % Transition Example Metathesis Acid Acid  Acid Temp. Seconds Seconds Temp. Residual Temp. Number Catalyst Weight % Weight % Activator Weight % C.° to Gel to 100°  C. °C. Monomer °C. Notes   1 std. none none std. none 33 3 29 205 -- -- -- (compara- tive) 2 std. none none std. 1 isobutyl 33 1-2 39 204 -- -- -- (compara-     chloride tive) 3 std. none none std. 0.5 32 2 32 200 0.55 134 Activator and isobutyl chloride combined (compara-     isobutyl       before addition. tive)     chloride 4 std. none none std. none 33 3 28 203 1.73 128 No dichlorodiphenylmethane. (compara- tive) 5 std. none none std. none 33 3 28 207 0.46 144 -- (compara- tive) 6 std. none none std. 0.25 tert- 32 3 29 204 0.53 122 No dichlorodiphenylmethane. (compara-     butyl tive)  chloride 7 std. none none std. 0.25 tert- 31 7 33 205 0.19 137 -- (compara-     butyl tive)     chloride 8 std. none none std. none 31 5 30 205 0.41 -- -- (compara- tive) 9 std. none none std. 0.5 32 6-7 30 208 -- -- -- (compara-     isobutyl tive)     chloride 10 Bell none 0.2 tributyltin none 32 instant 17 160 0.83 -- -- (compar-   diglyme hydride ative) 11 std. none none std. none 31 3 29 214 0.52 139 -- (compar- ative) 12 std. none none std. 0.5 tert- 30 3 30 209 0.16 -- -- (compar-    butyl ative)     chloride 13 std. none none std. 0.5 29 1 50 191 0.42 -- A duplicate run contained 0.59 Cp2. (compar-     isobutyl ative)chloride 14 std. none none std. none 31 3 34 194 1.56 -- -- (compar- ative) 15 std. none none std. none 32 3 24 214 0.43 132 -- (compar- ative) 16 Bell none none ethyl- none 32 5 -- 208 0.56 131 After 5 minutes heated to 72° C. to get exotherm. (compar-    aluminum ative)    chloride-n-     propoxide 17 2X Bell none none 2X none 32 6 -- 211 0.20 117 After 5 minutes heated to 70° C. to get exotherm. (compar-    ethyl- ative)    aluminum     chloride-n-     propoxide 18 Bell none none ethyl- 0.5 tert- 32 30  -- 219 0.58 139 After 5 miinutes heated to 72° C. to get exotherm. A (compar-    aluminum butyl    duplicate run gelled in 5 seconds; 0.82% residual Cp2 ; ative)  chloride-n- chloride       Tg 136° C.     propoxide 19 std. none none std. none 31 3 33 213 0.71 133 -- (compar- ative) 20 std. 0.5 none std. 0.25 31 1 30 194 -- -- --   boron   isobutyl   tri-   chloride fluoride   etherate 21 std. 0.5 none std. 0.25 tert- 32 1 30 202 0.10 140 No dichlorodiphenylmethane.   boron   butyl   tri-   chloride fluoride   etherate 22 std. 0.5 none std. 0.25 tert- 32 1 23 200 0.15 141 --   boron   butyl   tri-   chloride   fluoride   etherate 23 std. 0.5 none std. none 31 2-3 21 204 0.12 139 No dichlorodiphenylmethane. (compar-  boron ative)  tri-   fluoride   etherate 24 std. 0.5 none std. none 31 2-3 20 207 0.21 139 -- (compar-  boron ative)  tri-   fluoride etherate 25 Bell 1.0 0.1 tributyltin 0.25 32 6 -- 184 -- -- Tert-butyl chloride mixed with tributyltin hydride   boron trimethyl hydride tert-butyl       before addition. Polymer foam 2.5 times usual size. tri- phosphite  chloride   fluoride   etherate 26 Bell none none ethyl- none 32 instant 14 -- 1.24 127 -- (compar-    aluminum ative) dichloride 27 Bell none 0.2 0.5 ethyl- none 32 3 106  189 2.61  93 -- (compar-   trimethyl aluminum ative)   phosphite dichloride 28 Bell 0.5 0.2 tributyltin 0.25 benzyl 31 10  32 205 0.10 153 Foamed plug twice normal size.   boron tributyl hydride chloride   tri- phosphite fluoride   etherate 29 2X std. 0.5 none 2X std. 0.33 tert- 31 <1  27 200 0.15 121 --   boron   butyl   tri-   chloride   fluoride-   N,N- diethyl-   aniline 30 2X std. 0.5 none 2X std. 0.33 tert- 31 3 75 200 0.12 123 --   boron   butyl   tri-   chloride   fluoride   tetra- hydro-   furan 31 2X std. 1.0 none 2X std. 0.66 tert- 31 <1  26 205 0.18 121 --   boron   butyl   tri-   chloride   fluoride-   N,N-di-   ethyl-  aniline 32 std. 0.5 0.25 N,N- std. 0.25 tert- 31 2-3 63 207 0.15 137 --   boron diethyl-  butyl   tri- aniline  chloride   fluoride   etherate 33 std. 0.5 none std. 0.5 31 4 49 199 0.12 -- --   boron   isobutyl tri-   chloride   fluoride   etherate 34 std. 0.5 none std. 0.25 31 <1 -- 202 0.11 -- --   boron   isobutyl   tri-   chloride   fluoride etherate 35 std. 0.5 none std. 0.5 tert- 31 <1  36 199 0.10 -- Duplicate runs 0.08 & 0.12% residual Cp2.   boron   butyl   tri-   chloride fluoride   etherate 36 std. 0.5 0.3 std. 0.5 31 5-6 39 205 0.60 -- -- boron pyridine  isobutyl   tri-   chloride   fluoride   etherate 37 std. 0.5 1.6 qui- std. 0.5 31 5 42 207 0.13 -- --   boron nuclidine  isobutyl   tri-   chloride   fluoride   etherate 38 Bell none 0.6 ethyl- 0.5 tert- 31 -- -- 214 0.13 -- No reaction in five miutes at 31° C. Heating to 60° C. gave (compar-   diglyme aluminum butyl the exotherm. ative)    dichloride chloride 39 std. 0.5 1.0 N,N- std. 0.25 tert- 32 7-8 34 199 0.12 -- --   boron diethyl-  butyl   tri- aniline  chloride   fluoride   etherate 40 std. 0.5 0.6 std. 0.25 tert- 32 7 36 205 0.10 -- --   boron diglyme  butyl   tri-   chloride fluoride   etherate 41 std. 0.5 0.25 std. 0.5 tert- 32 instant 19 205 0.14 -- --   boron maleic  butyl   tri- anhydride  chloride   fluoride etherate 42 Bell 0.5 0.25 tri- 0.25 benzyl 31 7 44 201 1.47 140 -- boron maleic butyltin chloride   tri- anhydride hydride   fluoride 0.2 etherate tributyl    phosphite 43 Bell none 0.6 0.50 ethyl- 0.5 tert- 31 120-140 -- 209 0.10 -- No reaction in 5 minutes. Heating to 47° C. gave (compar-   butyl- aluminum butyl       exotherm. Monomer mixture slightly hazy. ative)   diglyme dichloride chloride 44 Bell 0.5 0.2 tributyltin 0.5 tert- 32 instant 10 169 0.07 -- --   boron diglyme hydride butyl   tri-   chloride   fluoride   etherate 45 Bell none 0.6 ethyl- 0.5 tert- 75 1- 2 44 225 0.43 -- -- (compar-   diglyme aluminum butyl ative)    dichloride chloride 46 std. 0.5 0.6 std. 0.5 tert- 31 7 128  197 0.07 -- --   boron diglyme  butyl  tri- 0.25  chloride fluoride maleic   etherate anhydride 47 std. 0.5 none std. 0.5 tert- 31 1 15 207 0.28 -- 91% gel, 177% swell. A duplicate run gave 0.07%   boron   butyl       residual dicyclopentadiene.   tri-   chloride   fluoride etherate 48 std. 0.5 0.6 std. 0.25 tert- 32 6 43 206 0.11 -- Duplicate runs behaved similarly.   boron diglyme  butyl   tri-   chloride fluoride   etherate 49 std. 1.0 0.6 std. 0.5 tert- 32 4 53 205 0.05 -- --   boron diglyme  butyl   tri-   chloride   fluoride   etherate 50 std. 0.5 0.6 std. 0.5 31 12 300  189 0.06 129 0.09% vinylbenzyl chloride remained.   boron diglyme  vinylbenzyl   tri-   chloride   fluoride etherate 51 std. 1.0 0.6 std. 0.5 tert- 31 8 115  203 0.09 127 -- boron diglyme  butyl   tri-   chloride   fluoride   etherate 52 std. 0.5 0.6 std. 0.5 benzyl 31 5 21 204 0.08 126 --   boron diglyme  chloride tri-   fluoride   etherate 53 std. 0.5 0.6 std. 0.7 1- 31 9 20 202 0.09 125 --   boron diglyme  bromo-   tri-   decane   fluoride   etherate 54 std. 0.5 0.6 std. 0.5 2- 30 9 24 200 0.08 125 --   boron diglyme ethylhexyl   tri-   bromide   fluoride   etherate 55 std. 0.5 0.6 std. 0.5 2- 30 10  26 202 0.22 126 --   boron diglyme  ethylhexyl   tri- chloride   fluoride   etherate 56 std. 0.5 0.6 std. 0.25 30 7 26 205 0.34 127 --   boron diglyme  tert-butyl   tri-   acetate   fluoride etherate 57 std. 0.5 0.6 std. none 32 7 21 201 0.11 132 -- (compar- boron diglyme ative)  tri-   fluoride   etherate 58 2X std. 1.0 tin none 2X std. 0.5 tert- 32 instant -- 207 0.07 107 Temperature climbed from 32 to 40°  C. in 5 minutes.   (IV)   butyl       Heating to 50° C. gave the exotherm.   bromide   chloride 59 std. 1.1 tin 0.3 std. 1.0 32 <1  -- 224 0.36 117 After 5 minutes, heated to 82° C. to get exotherm. (IV) diglyme  isobutyl   chloride 0.25  chloride    maleic    anhydride 60 std. 0.5 0.67 std. 0.5 tert- 31 10  105  105 0.63 -- 3 ml run with 0.8 × 10 cm steel rod in test tube.   boron diglyme  butyl   tri-  chloride   fluoride   etherate 61 std. 0.5 0.67 std. 0.5 tert- 32 6 184   184 0.16 -- --   boron diglyme  butyl   tri-   chloride   fluoride etherate 62 Bell none 0.85 n- 0.5 ethyl- 0.5 32 26  -- 117 1.75 -- Contained rod as in Ex. No. 24. Heated to 65° C. to get (compara-   hexyl aluminum isobutyl       exotherm. tive)   ether dichloride chloride 63 2X std. 0.5 0.67 2X std. 0.5 29 3 --  93 0.20 -- Contained rod as in Ex. No. 24. Maximum temperature   boron diglyme  isobuty reached in 47 seconds.   tri-   chloride   fluoride   etherate 64 std. 1.0 0.67 std. 0.5 29 1-2 35 121 0.76 -- Contained rod as in Ex. No. 24.  boron diglyme  isobutyl   tri-   chloride   fluoride   etherate 65 Bell none 0.67 0.5 ethyl- 0.5 -- -- -- 124 2.86 -- Contained rod as in Ex. No. 24. Heated to 80° C. to get (compara-   diglyme aluminum isobutyl       exotherm. tive)    dichloride chloride 66 2X std. 1.0 1.3 2X std. 1.0 59 --    3.35   117.5 0.20 -- Contained 3.75% EPDM rubber. Run on mini RIM   boron diglyme  isobutyl       machine. 100% swell; very little odor, possibly trace   tri-   chloride       of odor of ethyl ether, 647 kg/cm2 flexural strength,   fluoride          5.0% flexural strain, 18900 kg/cm2 flexural modulus,   etherate 6.8-6.9 mm deflection (9.2 kpsi flexural strength, 269             kpsi flexural modulus), 9.11 ft lb/inch width in notched             Izod impact test at 23° C., 83° C. deflection temperature under 264 psi load. 67 2X std. 1.0 0.67 2X std. 1.0 32 7 88 -- 2.38 -- Contained rod as in Ex. No. 24.   boron diglyme  isobutyl tri-   chloride   fluoride   etherate
TABLE 2  Metathesis - Cationic Copolymerization or Alkylation Conventions as in Table 1. Cp2 & Cp3 inidcate di- and tricyclopentadiene. 2X means two times.   Other   Moderator         Glass    Monomer or  Lewis for  Cocatalyst Initial   Max. % % Residual Trans. Ex.  Compound to Metathesis Acid Lewis Acid  for Lewis Temp. Seconds Seconds Temp. ResidualOther Temp. Number Cp2 & Cp3 be Alkylated Catalyst Weight % Weight % Activator Acid °C. to Gel to 100° C. °C. Cp2 Compound °C. Notes   68 80 Cp2 20 m- std. 1 BF3 none std. 0.5 isobutyl 31 <1  54 192 -- -- -- Activator and isobutyl   diisopro-  etherate   chloride    chloride combined before   penylbenzene             addition. 69 80 Cp2 20 m- std. 1 BF3 none Std. 0.5 isobutyl  4 30-50 306  189 0.01 -- -- Put in 33° C. block after   diisopro-  etherate chloride        60 sec. Post-cured 90° C./   penylbenzene1 hr. 70 80 Cp2 20 m- std. 1 BF3 none std. 0.5 chloro- 31 2-3 -- 203 -- -- -- Ten minutes to 46° C.,   diisopro-  etherate  di-phenyl-        then heated to 55° C. to   penylbenzene methane        get the strong exotherm. 71 80 Cp2 20 m- std. 0.5 BF3 none std. 0.5 isobutyl 32  1 47 179 0.00- 1.30 m- 107 Activator and isobutyl   diisopro-  etherate   chloride     0.02 diiso-  chloride combined before   penylbenzene           propenyl-  addition. 6.9% higher GC              benzene  peaks present. 72 80 Cp2 20 m- std. 0.5 BF3 none std. 0.25 isobutyl 32 2-3 50 181 0.01- 1.24 m- -- -- diisopro-  etherate   chloride     0.02 diiso-   penylbenzene propenyl-              benzene 73 (com- 60 Cp2 none std. none none std. none  3 -- -- 191 0.57 -- 182 Exotherm after placing parative) 40 Cp3              in 33° C. block. 74 60 Cp2 none std. 1 BF3 none std. 0.5 isobutyl  3 2-3 -- 186 0.02 -- none Exotherm after placing  40 Cp3   etherate   chloride       ob- in 33° C. block.               served Activator and isobutyl chloride combined before                addition. 75 80 Cp2 20 α-methyl- std. 1 BF3 none std. 0.5 isobutyl  3  1 175  170 0.02- 0.42 α- 69.5 Exotherm after placing   styrene  etherate chloride     0.03 methyl-  in 33° C. block,              styrene 14.7% of α-methyl-styrene                dimer present. 76 80 Cp2 20 5- std. 1 BF3 none std. 0.5 isobutyl  2 -- -- 186 0.04- 0 5- none Placed in 33° C. block   ethylidene-2-  etherate chloride     0.06 ethylidene- ob- after four minutes.   norbornene2-nor- served              bornene 77 80 Cp2 15 α-methyl- std. 0.5 BF3 none std. 0.25 isobutyl  0 300  415 158 0.01- 0.26 α- none Put in 32° C. block after   styrene  etherate chloride     0.02 methyl- ob- five minutes. Post cured   5 m-diisopro-    styrene, served 90° C./1 hr. 8.1% α-   penylbenzene      0.10 m-  methylstyrene dimer              diiso-  present.     propenyl-              benzene 78 80 Cp2 13 m- std. 0.5 BF3 none std. 0.25 isobutyl 32 2-3 -- 176 0.00- 0.43 m- 72.5 -- diisopro-  etherate   chloride     0.01 diiso-   penylbenzene propenyl-   7 naphthalene           benzene              0.62   naphtha-              lene 79 80 Cp2 15 β-pinene std. 0.5 BF3 none std. 0.25 31  1 57 183 0.16 0 β-pinene 80 2.0% unknown GC peaks   5 m-  etherate   isobutyl      0.22 m-  between β-pinene and m-   diisopropenyl-     chloride      diiso-  diisoprop enylbenzene,   benzene           propenyl-  5.8% higher than m-benzene  diisopropenylbenzene. 80 95 Cp2 5 2,6-di- std. 0.5 BF3 none std. 0.25 isobutyl 31  1 42 198 0.04- 5.6 2,6- 111 -- tert-  etherate   chloride     0.06 di-tert-   butylphenol butyl-              phenol 81 90 Cp2 10 std. 0.5 BF3 none std. 0.25 isobutyl 31  1 27 185 0.16- 12.9 70 Plug slightly foamed. naphthalene  etherate   chloride     0.23 naphtha-              lene 82 80 Cp2 20 std. 0.5 BF3 none std. 0.25 isobutyl 31  5 66 182 0.06 -- 110 Rubber, catalyst and   polyisoprene  etherate   chloride    Lewis acid in half the Cp2 ;                rubber activator and co-                catalyst in the other half. 83 95 Cp2 5 Bell -- none 0.5 ethyl- 0.25 tert- 31  1 57 179 0.06- 3.87 101 Poorly mixed. diphenylamine    aluminum butyl     0.29 diphenyl-       di-chloride chloride      amine 84 48 Cp2 20 std. 0.5 none std. 0.25 tert- 31 3 -- 192 0.98 -- none 10 ml run. Rubber,  32 Cp3 polyisoprene boron   butyl       ob- catalyst and Lewis acid in     tri-   chlorideserved half the monomer;     fluoride           activator and cocatalyst in     etherate           the other. After 5 minutes  the temperature was 39° C.                Heating to 65° C. gave the                exotherm. Post-cured at90° C./1 hour. 85 80 Cp2 20 m- std. 0.5 none std. 0.25 tert- 30 8-9 94 173 0.11 -- -- --   diisopro-  boron   butyl   penylbenze ne  tri-   chloride     fluoride-     N,N-di-     ethyl-     aniline 86 80 Cp2 20 m- std. 0.5 none std. 0.25 tert- 31  8 -- 194 -- -- -- After five minutes at   diisopro-  boron   butyl        31° C., heated to 60° C. to   penylbenzene  tri-   chloride        get exotherm.     fluoride     tetra-     hydro-     furan 87 80 Cp2 20 5- std. 0.5 none std. 0.5 isobutyl  0 <1  -- 199 0.09 -- --  Placed in block at 31° C.   ethylidene-2-  boron   chloride        after 5 minutes.   norbornene  tri-     fluoride     etherate 88 60 Cp2 none std. 1.0 none std. 0.5 tert-  3  3 -- 166 0.22 -- -- Put in 32° C. block after  40 Cp3   boron   butyl        5 minutes.tri-   chloride     fluoride     etherate89 60 Cp2 none std. 0.5 none std. 0.25 tert- 3 4 -- 171 0.44 -- -- Put in 32° C. block after  40 Cp3   boron   butyl        5 minutes.    tri- chloride     fluoride     etherate 90 (com- 60 Cp2 none std. none none std. none  3 300  -- 160 1.40 -- -- Put in 32° C. block after parative) 40 Cp3              5 minutes. 91 60 Cp2 none std. 0.5 none std. 0.25 32  1 30 201 0.22 -- -- --  40 Cp3   boron  tert-butyl     tri-   chloride     fluoride     etherate 92 42 Cp2 15 5- Bell none 0.6 ethyl- 1.0 2- 32 -- -- 202 0.75 -- -- No reaction in 5 minutes.  28 Cp3 ethylidene-   diglyme aluminum ethylhexyl Heating to 70° C. pro-   2-norbornene    dichloride bromide  duced the exotherm. A   15             duplicate run had no   polyisopre ne             residual Cp2, Cp3, or 5- ethylidene-2-norbornene                and had Tg 154° C. 93 75 Cp2 20 5- Bell none 0.6 ethyl- 0.5 tert- 32 -- -- 218 none no 5-ethyl -- No reaction in 5 minutes.   ethylidene-   diglyme aluminum butyl      idene-2-  Heating to 60° C. induced   2-norbornene dichloride chloride      nor-  the exotherm.   5           bornene diphenylamine           2.79%              diphenyl-              amine 94 75 Cp2 20 5- Bell none 0.6 ethyl- 0.5 32 -- -- 205 none no 5- -- No reaction in 5 minutes.   ethylidene-2-   diglyme aluminum tert-butylethylidene-  Heating to 70°  C. gave   norbornene    dichloride chloride      2-nor-  the exotherm.  5 2,6-di-           bornene   tert-           2.71% 2,6-   butylphenol    di-tert-               butyl-                phenol 95 42 Cp2 15 5- Bell none 0.6 ethyl- 1.0 2-ethyl- 31 -- -- -- none no Cp3 154 No reaction in 5 minutes.  28 Cp3 ethylidene- diglyme aluminum hexyl      no 5-  Heated 90° C./1 hour. 2-norbornene    dichloride bromide      ethylidene-  Extraction of a duplicate   15           2-nor-  run with methylene   polyisoprenebornene  chloride removed 8.4%,                compared to 0.5% for a                control run with                monomer ratios, 51:34:15:0. 96 95 Cp2 5 p-diisopro- Bell none 0.6 ethyl- 0.5 31 -- --  170 0.16 0.49 p- 100 Mixed at 31° C., then   penylbenzene diglyme aluminum tert-butyl      diiso-  heated immediately to dichloride chloride      propenyl-  73° C.              benzene 97 90 CP2 10 p- Bell none 0.6 ethyl-. 0.5 32 -- -- -- 0.10 0.54 p- 94 Mixed at 31°  C., then   diisopro-   diglyme aluminum tert-butyl      diiso-  heated immediately to   penylbenzene    dichloride chloride      propenyl- 73° C.              benzene 98 54 Cp2 5 naphthalene std. 1.0 0.6 std. 0.5 tert- 31  4 84 179 0.17 4.58 125 --  36 Cp3 5 diiso- boron diglyme  butyl      naphtha-   butylene  tri-   chloride      lenefluoride         3.15     etherate         diiso- butylene 99 80 Cp2 20 polyindane std. 0.5 0.6 std. 0.5 31 12 148 169 0.12 -- 126 Polyindane made by treat-     boron diglyme  tert-butyl  ment of m-diisopropenyl-     trifluor   chloride        benzene with acid.     ide     etherate 100 95 Cp2 5 poly std. 0.5 0.6 std. 0.5 tert- 32  2 45 181 0.20 -- 135 --   (vinylbenzyl  boron diglyme butyl   chloride)  trifluo-   chloride     ride     etherate 101 (com- 80 Cp2 20 acenaph- std. none 0.6 std. 0.25 31 12 -- 200 0.14 6.1 109 After 5 minutes at 31° C., parative)  thylene   diglyme tert-butyl      acenaph-  heated to 55° C. to        chloride  thylene  get exotherm. 102 (com- 90 Cp2 10 5,5'- std. none 0.6 std. 0.25 31 200   -- 203 0.95 0.36 5,5'- 164 After 5 minutes at 31° C., parative)  sulfonyl-   diglyme  tert-butyl      sulfonyl-  heated to 63° C. to   bis(2-     chloride      bis(2-  get exotherm.   norbornene)    norbor-              nene) 103 (com- 90 Cp2 10 5,5'- std. none none std. none 31 14 40 199 0.90 -- 142 -- parative)  sulfonyl-   bis(2-   norbornene) 104 (com- 48 Cp2 10 Bell none 0.6 ethyl- 0.5 31 -- -- 200 0.62 0.08 Cp3 178 Heated to 73° C. to get parative) 32 Cp3 polyisoprene   diglyme aluminum tert-butyl      0.12 -- exotherm.   10    dichloride chloride      diester   hexamethy- lene-bis(5-   norbornene-2-   carboxylate) 105 (com- same same 2X std. none none 2X std. none 31 26 56 169 0.30 -- 158 -- parative) 106 90 Cp2 10 1,4,5,8- std. 0.5 0.6 std. 0.25 31  6 22 205 0.08 0 di- 177 --   dimethano-  boron diglyme  tert-butyl      methanohex   1,4,4a,5,8,8 a-  tri-   chloride      ahydro-   hexahydro-  fluoride         naphtha-   naphthalene           lene 107 (com- 90 Cp2 10 1,4,5,8- std. none none std. none 32  2 27 212 0.97 -- 168 -- parative)  dimethano- 1,4,4a,5,8,8a-   hexahydro-   naphthalene 108 (com- 73 Cp2 18 Bell none 0.6 ethyl- 0.5 tert- -- -- -- 179 0.06 9.1  96 The exotherm occurred on parative)  polyisoprene   diglyme aluminum butyl diamine  heating to 100°  C.   9 N,N'-    dichloride chloride diphenyl-p-   phenylene-   diamine 109 80 Cp2 13 5- Bell none 0.6 ethyl- 0.5 -- -- -- 197 0.14 0 5-  76 Heated to 63° C. to get ethylidene-2-   diglyme aluminum tert-butyl      ethylidene-  exotherm.  norbornene    dichloride chloride      2-norbor-   7 naphthalene    nene 6.4              naphtha-              lene 110 70 Cp2 20 5- std. 1.0 0.6 std. 0.5 31  9 38 201 0 0 5-  92 --   ethylidene-2- boron diglyme  tert-butyl      ethylidene-   norbornene  tri-   chloride 2-norbor-   10 1,5-  fluoride         nene   cycloocta- 5.3 1,5-   diene           cycloocta-              diene 111 70 Cp2 20 5- std. 1.0 0.6 std. 0.5 31  9 37 197 0 0 5-  97 --   ethylidene-2- boron diglyme  tert-butyl      ethylidene-   norbornene  trifluor chloride      2-norbor-   10 1,5,9-  ide         nene   cyclododeca-  7.4 1,5,9-   triene           cyclodo-              decatriene 112 80 Cp2 13 poly- Bell none 0.6 ethyl- 0.5 -- -- -- 181 -- -- 102 Heated to 75° C. to get   isoprene   diglyme aluminum tert-butyl  exotherm. Some foaming.   7 naphthalene    dichloride chloride 113 54 Cp2 10 std. 0.5 0.6 std. 0.5 31 instant -- 134 5.95 2.46 Cp3  82 Activator, tert-butyl  36 Cp3 hexamethyl-  boron diglyme  tert-butyl      1.94  chloride and diglyme   cyclo-  tri- chloride      hexamethyl  mixed with monomers   trisiloxane  fluoride cyclotri-  before adding catalyst and     etherate         siloxane  boron trifluoride etherate.                Poor mixing. 114 42 Cp2 15 5- 2X Bell 1.0 0.6 2X ethyl- 0.5 isobutyl -- -- -- 184 -- -- 146 Heated to 75° C. to get the  28 Cp3 ethylidene-2-  boron diglyme aluminum chloride        exotherm.   norbornene  trifluor di-chloride   15  ide   polyisoprene  etherate 115 42 Cp2 15 5- 2X std. 1.0 none 2X std. 0.5 isobutyl 31 10 56 169 -- -- 150 See Ex. No. 136 for  28 Cp3 ethylidiene-  boron   chloride        extraction of the rubber.   2-norbornene  trifluor   15  ide   polyisoprene 116 95 Cp2 5 p-diisopro- 2X std. 1.0 Tin none 2X std. 0.5 isobutyl -- -- -- 207 -- --  79 Heated to 63° C. to get   penylbenzene  (IV) chloride        exotherm.     bromide 117 90 Cp2 10 m- 2X std. 1.0 Tin none 2X std. 0.5 isobutyl -- -- -- 187 -- --  54 Heated to 63° C. to get   diisopro-  (IV)   chloride exotherm.   penylbenzene  bromide 118 90 Cp2 10 2X std. 0.7 Tin none 2X std. 0.5 isobutyl -- -- -- 203 0.13 -- 132 Heated to 57° C. to get   polyisoprene  (IV)   chloride        exotherm.     bromide 119 48 Cp2 10 Bell none 0.85 n- 0.5 ethyl- 0.5 -- -- -- 211 0.21 0.01 Cp3 none Heated to 80°  C. to get  32 Cp3 polyisoprene   hexyl aluminum tert-butyl <0.11 ob- exotherm.   10   ether di-chloride chloride      diester served   hexamethylene-   bis(2-nor-   bornene-5   carboxylate) 120 48 Cp2 10 Bell none 0.6 butyl diethyl- 0.5 -- -- -- 182 0.59 0.34 Cp3 153 Heated to 75° C. to get  32 Cp3 polyisoprene diglyme aluminum tert-butyl      <0.11  exotherm.   10    chloride 6 chloride      diester   hexamethylene    Al/W   bis(2-   norborene-5- carboxylate) 121 80 Cp2 20 5- std. 0.5 0.67 std. 0.5 isobutyl --  1 -- -- 0.47 -- -- 3 ml. run with 0.8 ×  10   ethylidiene-  boron diglyme  chloride        cm steel rod in test tube.   2-norbornene  tri-fluoride     etherate 122 80 Cp2 20 5- 2X std. 1.0 1.3 2X std. 1.0 isobutyl 32  5 13 -- 0.11 -- -- Contained steel rod as in   ethylidene-2-  boron diglyme  chloride        Ex. No. 121   norbornene  tri-     fluoride etherate 123 80 Cp2 20 5- 2X std. 1.0 1.3 2X std. 1.0 isobutyl 51 -- instant 98.5 0.40 -- -- Contained EPDM rubber.   ethylidene-2-  boron diglyme  chloride        Odor not of dicylco-   norbornene  tri-   pentadiene, possibly of 5-     fluoride           ethylidene-2-norborne ne;     etherate           280% swell; 624 kg/cm.sup. 2 (8.9 kpsi) flexural strength,                5.00% flexural strain,      18500 kg/cm2 (263 kpsi)                flexural modulus, 6.77-6.90                mm deflection; 7.28 ft lb/                inch width in notched Izod                impact test at 23° C.;     79° C. deflection tempera-                ture under 264 psi load. 124 80 Cp2 20 5- Bell none none ethyl- 0.5 32 2-3 -- 224 0.06 -- 124 After 5 minutes heated to   ethylidene-2-    aluminum tert-butyl        72° C. to get exotherm.   norbornene chloride-n- chloride       propoxide 125 80 Cp2 20 4- Bell none none ethyl- 0.5 tert- 32 400 -- 184 0.53 --  48 After 5 minutes heated to   methylstyrene    aluminum butyl        72° C. to get exotherm.       chloride-n- chloride       propoxide 126 75 Cp2 15 5- std. 0.5 0.6 std. 0.25 isobutyl 30  5 23 226 0.07 -- 175 -- ethylidene-2-  boron diglyme  chloride   norbornene  tri-   10 dimethano-   fluoride   hexahydro-  etherate   naphthalene 127 same same 2X std. 1.0 1.25 2X std. 1.0 isobutyl 31 -- -- -- 0.26 -- none Contained steel rod as     boron diglyme  chloride       ob- in Ex. No. 121     tri- served     fluoride     etherate 128 45 Cp2 same std. 0.5 0.6 std. 0.25 isobutyl 31  5 21 229 0.08 -- none  30 Cp3   boron diglyme  chloride       ob-     tri-          served     fluoride etherate 129 same same 2X std. 1.0 1.25 2X std. 1.0 isobutyl  3 -- -- -- 0.21 -- none Contained steel rod as in     boron diglyme  chloride ob- Ex. No. 121     tri-          served     fluoride     etherate 130 70 Cp2 15 5- 2X std. 1.0 1.3 2X std. 1.0 isobutyl 31  7 21 178 0.09 -- 114 Extraction overnight twice   ethylidene-2-  boron diglyme chloride        with methylene chloride   norbornene  tri- removed 20.5%.   15 polyindane  fluoride     etherate 131 (com- 42 Cp2 15 5- std. none none std. none 31  3 -- 207 0.64 -- 166 After 5 minutes heated to parative) 28 Cp3 ethylidene-2- 90° C. to get exotherm.   norbornene   15   polyisoprene 132 (com- same same 2X std. none none 2X std. none 31  3 79 158 0.54 -- 145 parative) 133 70 Cp2 15 5- 2X std. 1.0 1.3 2X std. 1.0 isobutyl 28 1-2 17 165 0.06 -- 127 Polydicyclopentadiene made   ethylidene-2-  boron diglyme  chloride        with aluminum chloride.   norbornene  tri- Extraction with methylene   15 poly-  fluoride           chloride overnight twice   (dicyclo-  etherate           removed 11.7%   pentadien e) 134 54 Cp2 10 std. 0.5 0.6 std. 0.5 isobutyl 31  5 -- 197 0.02- 0.05 Cp3, 159 Went from 31° C. to 40° C.  36 Cp3 hexamethyl-  boron diglyme  chloride     0.04 3.3  in 5 minutes. Heated to   cyclotri-  tri-         siloxane  47° C. to get exotherm. siloxane  fluoride     etherate 135 54 Cp2 10 std. none none std. 0.5 isobutyl 32  3 26 208 -- -- -- --  36 Cp3 hexamethyl- chloride   cyclotri-   siloxane 136 42 Cp2 15 5- 2X std. 1.0 none 2X std. 0.5 isobutyl 31  8 76 174 -- -- -- A duplicate of Ex. No.  28 Cp3 ethylidene-2-  boron   chloride        115. Extraction overnight    norbornene  tri-           twice with methylene   15 fluoride   chloride removed 12%.   polyisoprene  etherate 137 95 Cp2 5-p-diisopro- 2X std. 1.0 tin none 2X std. 0.5 isobutyl 31 30 -- 195 -- -- -- A duplicate of Ex. No.   penylbenzene  (IV)   chloride        116. Went from 31° C. to     bromide           34° C. in 5 minutes.                Heated to 63° C. to get the  exotherm. Two overnight                extractions with methylene     chloride removed 13%.
TABLE 3__________________________________________________________________________Metathesis - Anionic Polymerization of Dicyclopentadiene__________________________________________________________________________                         ProcatalystExample    Other  Metathesis  Activator/                                Initial                                     Seconds                                          SecondsNumberCp2 & Cp3      Monomer             Catalyst                   Moderator                         Anionic                                Temp °C.                                     to Gel                                          to 100° C.__________________________________________________________________________138  100 Cp2      none   Bell  none  n-     31   1    194                         butyllithium139  100 Cp2      none   Bell  none  dibutylzine                                32   3    36140  48 Cp2      20     Bell  none  dibutylzinc                                31   1132 Cp3      caprolactone141  same  same   2X std.                   none  2X std.                                31   --   --142  60 Cp2      none   2X std.                   none  2X std.                                31   3    2440 Cp3143  48 Cp2      20     std.  none  dibutylzinc                                31   --   --32 Cp3      caprolactone144  54 Cp2      10     Bell  none  dibutylzinc                                30   5    3836 Cp3      hexamethyl-      cyclotri-      siloxane__________________________________________________________________________                     % Residual                           Glass    Example         Maximum               % Residual                     Other Trans.    Number         Temp °C.               Cp2                     Monomer                           Temp °C.                                Notes__________________________________________________________________________    138  139   --    --    113  Poor mixing. Post-cured 90°                                C./1                                hour.    139  195   3.58  --    152  Temperature rose to 40° C. in                                5                                minutes.    140  181   1.12-1.25                     0.71 Cp3 -                           --   Heating to 72° C. gave the                                strong                     caprolacton                                exotherm. 10% weight loss by                                370° C. (under nitrogen, at                                20° C./minute).    141  --    0.54        151  Exotherm sometime after 5                                minutes. 7% weight loss by                                370° C.    142  203   --    --    --   Control for Ex. No. 141. 3.5%                                weight loss by 370° C.    143  164   3.12  --    135  Went from 31° C. to                                61° C. in 5                                minutes.                                Heating to 75° C. gave the                                exotherm.    144  187   0.38  --    147  --__________________________________________________________________________
TABLE 4__________________________________________________________________________Metathesis - Free Radical CopolymerizationConventions as in Tables 1, 2 and 3. Azobis means 2,2'-azobis(2-methylpropionitrile). Solids were put in the tube first.The free radical sources were dissolved in the monomers__________________________________________________________________________first.Ex.                  Metathesis                      Methasis                           Free Radical Source,                                      Initial                                            SecondsNumberCp2 & Cp3      Other Monomer                Catalyst                      Activator                           Weight %   Temp. °C.                                            to Gel__________________________________________________________________________145  100 Cp2      none      std. + 1                      std. 0.5 azobis 31    3                diglyme/W  0.5 dicumyl peroxide146  100 Cp2      none      std. + 1                      std. 0.5 azobis 32    2-3                diglyme/W  0.5 2,5-dimethyl-2,5-                           di-tert-butylperoxy                           hexane147  100 Cp2      none      std. + 1                      std. 0.5 2,2'-azobis(2-                                      32    2-3                diglyme/W  methylbutyronitrile)                           0.5 dicumyl peroxide148  100 Cp2      none      2X std.                      2X std.                           0.5 tert-  32    10                           butylperoxyoctoate                           0.5 dicumyl peroxide149  100 Cp2      none      std.  std. 0.5 1,1'-azobis                                      32    6                           (cyclohexanecarbo-                           nitrile)                           0.5 dicumyl peroxide150  100 Cp2      none      std. + 1                      std. 0.5 2,2'-azobis(2-                                      31    4                diglyme/W  methylbutyronitrile)                           0.5 tert-butyl-peroxide151  100 Cp2      none      std.  std. 1.25 1,1-bis(tert-                                      30    5                           butylperoxy)-                           3,3,5-                           trimethylcyclohexane                           (40% on CaCO3)                           1.0 dicumyl peroxide152  100 Cp2      none      2X std.                      2X std.                           0.5 tert-butyl                                      32    5                           peroctoate                           0.5 2,5-dimethyl-2,5-                           di-tert-                           butylperoxyhexane153  100 Cp2      none      std.  std. 0.5 2,2'-azobis(2-                                      27    3                           methylbutyronitrile)                           0.5 azo-tert-butane154  90 Cp2      7.5 isobornyl                2X std.                      2X std.                           0.5 2,2'-azobis(2-                                      32    5      methacrylate         methyl-butyronitrile)      2.5                  0.5 dicumyl peroxide      trimethylolpropane-      trimethacrylate155  same  same      2X std.                      2X std.                           0.5 tert-butyl                                      32    6                           peroctoate                           0.5 dicumyl peroxide156  80 Cp2      15 4-methylstyrene                2X std.                      2X std.                           same       32    12      5 divinylbenzene157  80 Cp2      15 isobornyl                2X std.                      2X std.                           0.5 dicumyl peroxide                                      32    7      methacrylate      5      trimethylolpropane-      trimethacrylate158  80 Cp2      15 4-methylstyrene                2X std.                      2X std.                           0.5 dicumyl peroxide                                      32    12      divinylbenzene159  90 Cp2      10 dimethanohexa-                std.  std. 0.5 tert-butyl                                      31    9      hydronaphthalene     peroctoate                           0.5 dicumyl peroxide160  80 Cp2      10 dimethanohexa-                std.  std. same       31    17      hydronaphthalene      10 divinylbenzene161  90 Cp2      10        std.  std. same       31    7      trimethylolpropane-      trimethacrylate162  90 Cp2      7 4-methylstyrene                2X std.                      2X std.                           0.5 tert-butyl                                      31    26      3 divinylbenzene     peroctoate                           0.5 dicumyl peroxide                           0.5 N,N-diethylaniline163  80 Cp2      15 4-methylstyrene                2X std.                      2X std.                           0.5 tert-butyl                                      30    60      5 divinylbenzene     peroctoate                           0.5 dicumyl peroxide164  same  same      Bell  tributyl-                           0.5 2,2'-azobis(2-                                      30    6                      tin  methyl-butyronitrile)                      hydride                           0.5 dicumyl peroxide165  100 Cp2      none      Bell  tributyl-                           same       28    1-2                      tin                      hydride166  90 Cp2      10 dimethanohexa-                Bell  tributyl-                           same       28    1-2      hydronaphthalene                      tin                      hydride167  90 Cp2      10 isobornyl                Bell  tributyl-                           same       26    1-2      methacrylate    tin                      hydride168  90 Cp2      7.5 4-    std.  std. 0.5 2,2'-azobis(2-                                      29    3      methylstyrene        methyl-butyronitrile)      2.5 divinylbenzene   0.5 azo-tert-butane169  87.6 Cp2      10 isobornyl                2X std.                      2X std.                           0.6 dicumyl peroxide                                      1.4   10      methacrylate         0.6 2,2'-azobis(2-      2.4                  methyl-butyronitrile)      trimethylolpropane-      trimethacrylate__________________________________________________________________________                        %                  %     Residual                              Glass  Ex.  Seconds             Maximum                  Residual                        Other Transition  Number       to 100° C.             Temp. ° C.                  Cp2                        Monomer                              Temp. °C.                                    Notes__________________________________________________________________________  145  26    207  2.51  --    108   --  146  27    210  2.98  --    104   --  147  28    214  2.28  --    113   --  148  34    210  0.46  --    115   --  149  24    213  1.84  --    123   --  150  22    205  2.56  --    114   --  151  33    202  6.87  --    --    duplicate run had Tg                                    85° C.  152  27    214  0.43  --    112   --  153  23    214  0.62  --    130   --  154  32    184  7.40  --    73    --  155  97    184  4.48  --    76    --  156  30    207  0.63  --    46    --  157  140   159  9.97  --    53    --  158  28    220  1.08  --    51    --  159  50    225  0.99  --    138   --  160  66    228  1.32  --    108   --  161  --    185  8.91  --    73    Temperature to 37° C. in                                    5                                    minutes, then heated to                                    72°  C. to get exotherm.  162  127   202  1.50  2.37 4-                              59    Metathesis activator and                        methyl-     N,N-diethylaniline                        styrene     combined before addition.  163  274   179  2.66  0.66  none ob-                                    --                        divinyl-                              served                        benzene  164  63    164  0.20  --    90.7  25% larger than original                                    volume.  165  62    200  0.86  --    137   --  166  65    217  0.75  --    177   --  167  113   178  1.72  --    136   --  168  24    189  0.42  --    91    --  169  110   149  2.64  0,52  --    --                        isobornyl                        methacry-                        late 0.07                        trimethyl                        propane                        tri-                        acrylate__________________________________________________________________________
TABLE 5__________________________________________________________________________Metathesis - HydrosilationThe catalyst for a 5 ml polymerization was 0.06 ml containing 0.045 mlstandard catalyst (0.02 mmole W), containing onediphenyldichloromethane per W and 0.0165 ml platinum/siloxane complex insilicon fluid (3% Pt).Other convention as in Tables 1 & 2.__________________________________________________________________________               Metathesis +Example             Hydrosil.          Initial                                       Seconds                                            SecondsNumberCp2 & Cp3      Other Monomer               Catalyst                      Moderator                             Activator                                  Temp °C.                                       to Gel                                            to 100° C.__________________________________________________________________________170  90 Cp2      10       std. + Pt                      0.25%  std. 31   20   --      methylhydrocy   maleic      cio-siloxanes   anhydride171  90 Cp2      10 methyl-               2X (std. +                      0.25%  2X std.                                  31   12   --      hydrocyclo-               Pt)    maleic      siloxanes       anhydride172  80 Cp2      20 methyl-               std. + Pt.                      0.25%  std. 32   19   --      hydrocyclo-     maleic      siloxanes       anhydride173  80 Cp2      20 methyl-               2X (std. +                      0.25%  2X std.                                  31   15   315      hydrocyclo-               Pt.)   maleic      siloxanes       anhydride174  90 Cp2      10(15-   std. + Pt.                      1.0% maleic                             std. 32    9   70      18%)methyl-     anhydride      hydro(82-      85%)di-      methyl-      siloxane      copolymer175  90 Cp2      10(3-    std. + Pt.                      1.0% maleic                             std. 32   8-9  99      4%)methyl-      anhydride      hydro-(96-      97%)dimethyl-      siloxane      copolymer176  100 Cp2      none     std. + Pt                      1.0% maleic                             std. 32    8   --                      anhydride177  100 Cp2      none     std. + Pt                      none   std. 32    3   81__________________________________________________________________________                      % Residual                            Glass    Example          Maximum                % Residual                      Other Trans.    Number          Temp °C.                Cp2                      Monomer                            Temp °C.                                 Notes__________________________________________________________________________    170   214   0.20  --    86   After 5 minutes, heated to                                 45° C.                                 to get exotherm. Hydrosilation                                 33% complete by solid state 29                                 Si                                 NMR.    171   221   0.05-0.07                      0.30 silane                            85   37°  C. after 5 minutes,                                 then                                 heated to 40° C. to get                                 exotherm.                                 Hydrosilation 45% complete by                                 solid state 29 Si NMR.    172   214   0.29  --    76   Heated to 50° C. after 5                                 minutes                                 to get exotherm. Hydrosilation                                 36% complete by solid state 29                                 Si                                 NMR.    173   189   0.15  --    82   Hydrosilation 42% complete by                                 solid state 29 Si NMR.    174   190   0.20  --    144  Two extractions overnight with                                 methylene chloride removed 9.5%.    175   187   0.34  --    152  Two extractions overnight with                                 methylene chloride removed                                 10.8%.    176   205   0.23  --    141  Went from 32° C. to                                 41° C. in 5                                 minutes.                                 Heating to 50° C. gave the                                 exotherm.                                 Two extractions overnight with                                 methylene chloride removed 1.2%.    177   207   0.33  --    136__________________________________________________________________________
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US20020188047 * 1 Feb 2002 12 Dic 2002 Imperial Chemical Industries Plc Organometallic compositions and polyisocyanate compositions containing them
US20100324247 * 19 Oct 2007 23 Dic 2010 Zeon Corporation Polymerizable composition, crosslinkable resin, and production methods and applications thereof
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