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Patent US5306779 - Hydrogenated diene block copolymer and composition comprising the same - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA hydrogenated diene block copolymer having a polystyrene-reduced number-average molecular weight of 50,000-600,000 which is a hydrogenation product of an (A)-(B) block copolymer in which (A) means an alkenyl aromatic compound polymer block and (B) means a conjugated diene homopolymer block wherein the...http://www.google.com/patents/US5306779?utm_source=gb-gplus-sharePatent US5306779 - Hydrogenated diene block copolymer and composition comprising the sameAdvanced Patent SearchPublication numberUS5306779 APublication typeGrantApplication numberUS 07/937,723Publication dateApr 26, 1994Filing dateSep 1, 1992Priority dateMay 19, 1989Fee statusPaidAlso published asDE69032963D1, DE69032963T2, DE69033210D1, DE69033210T2, EP0398758A2, EP0398758A3, EP0398758B1, EP0709413A1, EP0709413B1, US5191024, US5346964Publication number07937723, 937723, US 5306779 A, US 5306779A, US-A-5306779, US5306779 A, US5306779AInventorsTooru Shibata, Toshio Teramoto, Yoshiharu Hashiguchi, Kunio GoshimaOriginal AssigneeJapan Synthetic Rubber Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (5), Referenced by (32), Classifications (25), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetHydrogenated diene block copolymer and composition comprising the same
[(A)-(B)-(C)]n -X
The composition of the modified hydrogenated diene block copolymer (I) of this invention and the thermoplastic polar resin (III) can be obtained by kneading the two components preferably at a temperature of 200�-350� C. using an extruder, a Banbury mixer, a kneader, rolls or the like.
Molecular weight was obtained as a polystyrene-reduced molecular weight, by gel permeation chromatography at 135� C. using trichlorobenzene as
temperature bath of 40� C. under a load of 30 g/cm2 for 24 hours to allow them to stick to each other and form blocks, and rating the blocks as follows.
Tensile strength (TB) was obtained by measuring a breaking strength (kg�f/cm2) at a drawing speed of 500 m/min using a JIS No. 3 dumbbell.
When the conversion of the monomers added reached approximately 100%, the reaction mixture was cooled to 70� C. Thereto were added 0.6 g of n-butyl-lithium, 0.6 g of 2,6-tert-butyl-p-cresol, 0.28 g of bis(cyclopentadienyl)titanium dichloride and 1.1 g of diethylaluminum chloride. The resulting mixture was subjected to reaction for 1 hour with the reaction pressure being maintained at 10.0 kg/cm2 with hydrogen gas.
TABLE 1__________________________________________________________________________            Example             Comparative Example            1    2    3    4    1    2    3__________________________________________________________________________Hydrogenated diene block            Copoly-                 Copoly-                      Copoly-                           Copoly-                                Copoly-                                     Copoly-                                          Copoly-copolymer        mer  mer  mer  mer  mer  mer  mer            P-1  P-2  P-3  P-4  P-5*1                                     P-6  P-7*2Micro structure1Total bound styrene content (%)            30   15   30   35   30   30   302Proportion of bound styrene            10    5   10   20   --   10   (30)content of Block (A) in totalcopolymer (%)3Vinyl content of butadiene            40   40   20   40   40   40   40portion in Block (B) (%)Properties of copolymer1Hydrogenation degree (%)            98   96   97   98   97   79   982Molecular weight (�10-4)            15   17   15   16   17   15   103Melt flow rate (230� C., 5 Kg)            40   35   33   30   28   37    34Blocking tendency of pellets            &#8858;                 &#9711;                      &#8858;                           &#8858;                                x    &#8858;                                          &#8858;__________________________________________________________________________ Note: *1 Hydrogenation product of styrene1,3-butadiene random copolymer. *2 Hydrogenation product of polystyrenepolybutadiene-polystyrene triblock copolymer.
Into a 10-liter autoclave were fed 5,000 g of degassed and dehydrated cyclohexane and 40 g of styrene. Thereto were added 200 g of tetrahydrofuran and 0.3 g of n-butyllithium. The resulting mixture was subjected to adiabatic polymerization for 30 minutes starting from 50� C. The reaction mixture was cooled to 10� C. and 600 g of 1,3-butadiene and 170 g of styrene were added. The resulting mixture was subjected to polymerization. 95 g of styrene and 95 g of 1,3-butadiene were further added, and the polymerization was continued. Then, the reaction mixture was subjected to the same hydrogenation reaction a in Example 5.
TABLE 2__________________________________________________________________________            Example            5    6    7    8    9    10   11__________________________________________________________________________Hydrogenated diene block            Copoly-                 Copoly-                      Copoly-                           Copoly-                                Copoly-                                     Copoly-                                          Copoly-copolymer        mer  mer  mer  mer  mer  mer  mer            Q-1  Q-2  Q-3  Q-4  Q-5  Q-6  Q-7Micro structure1Total bound styrene content (%)            5    10   25.8 30.5 22.2 30   302Proportion of total bound            5    4.5  24   13.5 20   25   30styrene content of Block (A)and Tapered Block (C) in totalcopolymer (%)3Vinyl content of butadiene            81   80   77   78   65   77   85portion in Block (B) (%)Properties of copolymer1Hydrogenation degree (%)            98   97   98   99   98   97   992Molecular weight (�10-4)            29.5 31   28.9 29.2 11.5 11.0 11.03Melt flow rate (230� C., 12.5 Kg)            2.0  2.3  1.3  1.2  0.7  1.1  1.14Easiness of pelletization            &#9711;                 &#9711;                      &#9711;                           &#9711;                                &#9711;                                     &#9711;                                          &#9711;5Blocking tendency of pellets            &#9711;                 &#9711;                      &#8858;                           &#8858;                                &#8858;                                     &#8858;                                          &#8858;__________________________________________________________________________
TABLE 3__________________________________________________________________________      Example             Comparative Example      12   13   14   15   4    5    6    7__________________________________________________________________________Compounding recipeCopolymer (I)      Copoly-           Copoly-                Copoly-                     Copoly-                          Copoly-                               Copoly-Type       mer P-1           mer P-2                mer P-3                     mer P-4                          mer P-6                               mer P-8                                    EP*2                                         --Parts      25   25   25     25 25     25   25 --Non-polar resin (II)Type       PP*1           PP*1                PP*1                     PP*1                          PP*1                               PP*1                                    PP*1                                         PP*1Parts      75   75   75     75 75     75   75   100Physical propertiesMelt flow rate      12   11   10      9.7                          12      7.1                                       5.0                                            14(230� C., 2.16 kg)(g/10 min)Izod impact strength      35   30   31     32 27      7.1                                      14    4.1(-40� C.) (kg � cm/cm)Flexural modulus      6,600           6,500                6,500                     6,900                          6,400                               6,300                                    6,200                                         10,300(kg � f/cm2)Surface gloss      66   65   62     70 36     41   25    63(incident angle =60�) (%)__________________________________________________________________________ Note: *1 Polypropylene resin (Polypropylene BC2 manufactured by Mitsubishi Petrochemical Co., Ltd.) *2 Ethylenepropylene copolymer rubber (JSR EP07P manufactured by Japan Synthetic Rubber Co., Ltd.)
TABLE 4__________________________________________________________________________                               Comparative      Example                  Example      16   17   18   19   20   8__________________________________________________________________________Compounding recipeCopolymer (I)      Copoly-           Copoly-                Copoly-                     Copoly-                          Copoly-                               CopolymerType       mer Q-1           mer Q-2                mer Q-3                     mer Q-4                          mer Q-5                               P-5Parts        25   25   25   25   25   25Non-polar resin (II)Type       PP   PP   PP   PP   PP   PPParts        75   75   75   75   75   75Physical propertiesMelt flow rate        11.5             13.0                  15.0                       12.0                            10.5                                  6.3(230� C., 2.16 kg)(g/10 min)Izod impact strength(kg � cm/cm)-20� C.        13.6             12.0                  13.2                       14.5                            12.3                                 10.5-40� C.        11.2             10.1                  11.1                       12.6                            10.1                                  8.8Flexural modulus      2,370           2,500                2,800                     2,400                          2,600                               5,050(kg � f/cm2)Surface gloss        64   45   47   50   52   23(incident angle =60�) (%)Peeling strength of         1.5              1.4                   1.4                        1.7                             1.6                                  1.1film (g/cm)__________________________________________________________________________
TABLE 5__________________________________________________________________________                       Comparative            Comparative      Example          Example                              Example         Example      21    22    23   9      24   25    26   10     11__________________________________________________________________________Compounding receipeCopolymer (I)      Copoly-            Copoly-                  Copoly-                       Copolymer                              Copoly-                                   Copoly-                                         Copoly-                                              CopolymerType       mer P-1            mer P-2                  mer P-1                       P-7    mer P-1                                   mer P-1                                         mer P-1                                              P-7    --Parts      20    20    20   20     20   20    20   20     --Polar resin (III)Type       Nylon 6            Nylon 6                  Nylon 6                       Nylon 6                              PBT*3                                   PBT*3                                         PBT*3                                              PBT*3                                                     PBT*3Parts      80    80    80   80     80   80    80   80     100Maleic anhydride      0.4   0.4   0.4  0.4    --   --    --   --     --PartsPeroxide*1      0.1   0.1   0.1  01     --   --    --   --     --PartsCompatibilizing agent*2      --    --    --   --     --    5     5    5     --PartsPhysical propertiesIzod impact strength      68    81    85   45     39   83    85   32      5(23� C.) (kg � cm/cm)Appearance of molded      &#9711;            &#9711;                  &#9711;                       X      &#9711;                                   &#9711;                                         &#9711;                                              X      &#9711;article__________________________________________________________________________ Note: *1 2,5di(tert-butylperoxy)hexane *2 Ethyleneglycidyl methacrylate copolymergrafted polymethyl methacrylate (Modiper 4200 manufactured by Nippon Oil &amp; Fats Co., Ltd.) *3 Polybutylene terephthalate *4 Polyethylene terephthalate
An epoxy resin composition was obtained in the same manner as in Example 27, except that Copolymer P-9 was changed to 10 parts of a liquid carboxy NBR (Hycar CTBN 1300 �8 manufactured by BF Goodrich Co.) widely used for modification of epoxy resin.
TABLE 6__________________________________________________________________________                     Comparative     Comparative      Example        Example    Example                                     Example      27   28   29   12    13   30   14    15__________________________________________________________________________Compounding recipeCopolymer (I)      Copoly-           Copoly-                Copoly-         Copoly-Type       mer P-9           mer P-9                mer P-9                     Liq. NBR                           --   mer P-9                                     Liq. NBR                                           --Parts      10   2    30   10    --   10   10    --Polar resin (III)1Type      CNER*1           CNER*1                CNER*1                     CNER*1                           CNER*1                                --   --    --Parts      100  100  100  100   100  --   --    --2Type      PR*2           PR*2                PR*2                     PR*2                           PR*2                                PR*2                                     PR*2                                           PR*2Parts      50   50   50   50    50   100  100   100Curing agent1Type      MI*3           MI*3                MI*3                     MI*3                            MI*3                                --   --    --Parts      5    5    5    5     5    --   --    --2Type      --   --   --   --    --   HMTM*4                                     HMTM*4                                           HMTM*4Parts      --   --   --   --    --   10   10    10Physical propertiesIzod impact strength      6.3  4.3  8.2  3.5   3.2  3.3  1.0   1.2(23� C.) (kg � cm/cm)Flexural modulus      5.5  4.8  8.2  4.6   4.2  3.6  2.4   2.2(kg � f/cm2)Volume resistivity      1.6 � 1016           1.5 � 1016                1.1 � 1016                     8.9 � 1014                           1.5 � 1016                                1.1 � 1014                                     1.7 � 1013                                           1.1 � 1014__________________________________________________________________________ Note: *1 Cresolnovolac type epoxy resin *2 Phenol resin (novolac type) *3 2Methylimidazole *4 Hexamethylenetetramine
TABLE 7__________________________________________________________________________              Example              31    32    33    34    35__________________________________________________________________________Modified hydrogenated diene block              Copolymer                    Copolymer                          Copolymer                                Copolymer                                      Copolymercopolymer          Q-12  Q-13  Q-14  Q-15  Q-16Compounding recipe (parts)Hydrogenated diene block copolymer              Copolymer                    Copolymer                          Copolymer                                Copolymer                                      Copolymer              Q-1   Q-1   Q-2   Q-3   Q-4Maleic anhydride   2.5   6.0   --    --    2.5Glycidyl methacrylate              --    --    2.5   --    --Diethylaminoethyl methacrylate              --    --    --    4.0   --Perhexa 25B        0.15  0.30  0.15  0.15  0.15Analysis of grafted product (amount ofmonomer grafted, parts)Maleic anhydride   0.70  2.0   --    --    0.62Glycidyl methacrylate              --    --    0.39  --    --Diethylaminoethyl methacrylate              --    --    --    1.2   --Modified hydrogenated diene blockcopolymerHydrogenation degree (%)              99 or more                    99 or more                          99 or more                                99 or more                                      99 or moreMolecular weight (�10-4)              30    30    32    29    30Easiness of pelletization              &#9711;                    &#9711;                          &#9711;                                &#9711;                                      &#9711;Blocking tendency of pellets              &#9711;                    &#9711;                          &#9711;                                &#8858;                                      &#8858;__________________________________________________________________________
TABLE 8__________________________________________________________________________      Example                     Compartive Example      36    37   38    39   40    16     17    18   19__________________________________________________________________________Compounding recipeCopolymer blendedType       Copoly-            Copoly-                 Copoly-                       Copoly-                            Copoly-                                  Unhydro-                                         CTBN  JSR  --      mer Q-12            mer Q-13                 mer Q-14                       mer Q-15                            mer Q-16                                  genated Q-1  N220Sparts      10    10   10    10   10    10     10    10   --Physical propertiesFlexural modulus      2.3   2.6  2.1   2.8  2.1   3.4    4.6   5.1  4.2(kg � f/cm2)Izod impact      5.6   6.1  5.2   5.5  5.6   3.7    3.2   5.5  3.5strength (23� C.)(kg � cm/cm)Izod impact      5.2   6.0  5.1   5.3  5.1   3.5    2.9   3.9  3.6strength afterthermal ageing*1(23� C.) (kg � cm/cm)Flow property      4.5   4.0  3.5   3.0  3.2   2.9    3.4   3.0  6.3(cc/sec, � 10-2)__________________________________________________________________________ Note: *1 150� C. � 120 hours
TABLE 9__________________________________________________________________________      Example                  Compartive Example      41   42   43   44   45   20     21   22__________________________________________________________________________Compounding recipeCopolymer blendedType       Copoly-           Copoly-                Copoly-                     Copoly-                          Copoly-                               Unhydro-                                      CTBN JSR      mer Q-12           mer Q-13                mer Q-14                     mer Q-15                          mer Q-16                               genated Q-1 N220Sparts      10   10   10   10   10   10     10   10Physical propertiesFlexural modulus      2.1  2.2  1.8  2.0  1.9  2.7    2.2  2.2(kg � f/cm2)Izod impact      2.6  2.9  2.5  2.7  2.9  2.4    1.2  1.2strength (23� C.)(kg � cm/cm)Izod impact      2.0  2.4  2.2  2.2  2.3  0.9    1.0  1.0strength afterthermal ageing*1(23� C.) (kg � cm/cm)__________________________________________________________________________ Note: *1 150� C. � 120 hours
TABLE 10__________________________________________________________________________                Compartive      Comparative      Example   Example                      Example   Example                                       Example      46   47   23    48   49   24     50__________________________________________________________________________Compounding recipeCopolymer (I)Type       Copoly-           Copoly-                Copolymer                      Copoly-                           Copoly-                                Copolymer                                       Copoly-      mer Q-12           mer Q-13                Q-8   mer Q-14                           mer Q-15                                Q-8    mer Q-16Parts      20   20   20    20   20   20     20Polar resin (III)Type       N-66*1           N-66*1                N-66*1                      PBT*2                           PAc*3                                PAc*3                                       PC*4Parts      80   80   80    80   80   80     80Physical propertiesIzod impact      80   85    5    NB   20    5     50strength(23� C.) (kg � cm/cm)Appearance of      &#9711;           &#9711;                X     &#9711;                           &#9711;                                &#9711;                                       &#9711;molded article__________________________________________________________________________ Note: *1 Nylon 6,6 (Amilan CM3006 manufactured by TORAY INDUSTRIES, LTD.) *2 Polybutylene terephthalate (Duranex XD 499 manufactured by Polyplastic K.K.) *3 Polyacetal (Duracon M90 manufactured by Polyplastic K.K.) *4 Polycarbonate (Iupilon S100 manufactured by MITSUBISHI GAS CHEMICAL CO., LTD.)
When the conversion of the monomers added reached approximately 100%, the reaction mixture was cooled to 70� C. Thereto were added 0.6 g of n-butyl-lithium, 0.6 g of 2,6-tert-butylcresol, 0.28 g of bis(cyclopentadienyl)titanium dichloride and 1.1 g of diethylaluminum chloride. The resulting mixture was subjected to reaction for 1 hour with the reaction mixture being maintained at 10.0 kg/cm2 with hydrogen gas.
TABLE 11__________________________________________________________________________             Example             Comparative Example             51   52   53   54   1    25   26             Co-  Co-  Co-  Co-  Co-  Co-  Co-Hydrogenated diene block             polymer                  polymer                       polymer                            polymer                                 polymer                                      polymer                                           polymercopolymer         G-1  G-2  G-3  G-4  P-5*1                                      G-5  G-6*2__________________________________________________________________________  Micro structure1 Total bound styrene content (%)             30   15   30   35   30   30   302 Proportion of total bound             15    7   15   20   --   15   30  styrene content of Block (A)  and Tapered Block (C) in total  copolymer (%)3 Proportion of bound styrene              5    4    5   10   --    5   15  content of Block (A) in total  copolymer (%)4 Vinyl content of butadiene             40   40   20   35   40   40   40  portion in Block (B) (%)  Properties of copolymer1 Hydrogenation degree (%)             98   97   96   98   97   79   972 Molecular weight (� 10-4)             16   17   18   18   17   18   103 Melt flow rate (230� C., 5 Kg)             35   30   32   28   28   41    35 Blocking tendency of pellets             &#8858;                  &#9711;                       &#8858;                            &#8858;                                 X    &#9711;                                           &#8858;__________________________________________________________________________ Note: *1 : Hydrogenation product of random copolymer of styrene and 1,3butadiene. *2 : Hydrogenation product of polystyrenepolybutadiene-polystyrene triblock copolymer.
TABLE 12__________________________________________________________________________       Example             Comparative Example       55   56   57   58   27   28   29  7__________________________________________________________________________Compounding recipeCopolymer (I)Type        Copoly-            Copoly-                 Copoly-                      Copoly-                           Copoly-                                Copoly-                                     EP*2                                         --       mer G-1            mer G-2                 mer G-3                      mer G-4                           mer G-5                                mer G-6Parts       25   25   25   25   25   25   25  --Non-polar resin (II)Type        PP*1            PP*1                 PP*1                      PP*1                           PP*1                                PP*1                                     PP*1                                         PP*1Parts       75   75   75   75   75   75   75  100Physical propertiesMelt flow rate       10   10   11   9.0  12   5.0  5.0 14(230�C., 2.16 kg)(g/10 min)Izod impact strength       29   25   26   22   27   7.1  14  4.1(-40� C.) (kg � cm/cm)Flexural modulus       6,800            6,600                 6,900                      7,000                           6,800                                6,300                                     6,200                                         10,300(kg � f/cm2)Surface gloss       70   69   64   72   50   41   25  63(incident angle =60�) (%)__________________________________________________________________________ Note: *1 Polypropylene resin (Polypropylene BC2 manufactured by Mitsubishi Petrochemical Co., Ltd.) *2 Ethylenepropylene copolymer rubber (JSR EP07P manufactured by Japan Synthetic Rubber Co., Ltd.)
TABLE 13__________________________________________________________________________                      Comparative           Comparative       Example        Example                             Example        Example       59   60   61   30     62   63   64   31   32__________________________________________________________________________Compounding recipeCopolymer (I)Type        Copoly-            Copoly-                 Copoly-                      Copolymer                             Copoly-                                  Copoly-                                       Copoly-                                            Copoly-                                                 --       mer G-1            mer G-2                 mer G-1                      G-6    mer G-1                                  mer G-1                                       mer G-1                                            mer G-6Parts       20   20   20   20     20   20   20   20   --Polar resin (II)Type        N-6*3            N-6*3                 N-66*4                      N-6*3                             PBT*5                                  PBT*5                                       PET*6                                            PBT*5                                                 PBT*5parts       80   80   80   80     80   80   80   80   100Moleic anhydride       0.4  0.4  0.4  0.4    --   --   --   --   --PartsPeroxide*1       0.1  0.1  0.1  0.1    --   --   --   --   --PartsCompatibilizing agent*2       --   --   --   --     --    5    5    5   --PartsPhysical propertiesIzod impact strength       65   80   85   45     37   79   80   32    5(23�C.) (kg � cm/cm)Appearance of molded       &#9711;            &#9711;                 &#9711;                      X      &#9711;                                  &#9711;                                       &#9711;                                            X    &#9711;article__________________________________________________________________________ Note: *1 : 2,5Di(tert-butylperoxy)hexane *2 : Ethyleneglycidyl methacrylate copolymergrafted polymethyl methacrylate (Modiper 4200 manufactured by Nippon Oil &amp; Fats Co., Ltd.) *3 : Nylon6 *4 : Nylon6,6 *5 : Polybutylene terephthalate *6 : Polyethylene terephthalate
TABLE 14__________________________________________________________________________                         Comparative         Comparative      Example            Example      Example                                             Example      65    66     67    33     13    68     14    15__________________________________________________________________________Compounding recipeCopolymer (I)Type       Copoly-            Copoly-                   Copoly-                         Liq. NBR                                --    Copoly-                                             Liq. NBR                                                   --      mer G-8            mer G-8                   mer G-8            mer G-8Parts      10     2     30    10     --    10     10    --Polar resin (III)1 Type     CNER*1            CNER*1                   CNER*1                         CNER*1                                CNER*1                                      --     --    --  Parts    100   100    100   100    100   --     --    --2 Type     PR*2            PR*2                   PR*2                         PR*2                                PR*2                                      PR*2                                             PR*2                                                   PR*2  Parts    50    50     50    50     50    100    100   100Curing Agent1 Type     MI*3            MI*3                   MI*3                         MI*3                                 MI*3                                      --     --    --  Parts    5     5      5     5      5     --     --    --2 Type     --    --     --    --     --    HMTM*4                                             HMTM*4                                                   HMTM*4  Parts    --    --     --    --     --    10     10    10Physical propertiesIzod impact strength      6.3   4.5    8.3   3.5    3.2   3.2    1.0   1.2(23�C.) (kg � cm/cm)Flexural modulus      5.4   4.7    8.0   4.6    4.2   3.6    2.4   2.2(kg � f/cm2)Volume resistivity      1.7 � 1016            1.5 � 1016                   1.2 � 1016                         8.9 � 1014                                1.5 � 1016                                      1.2 � 1014                                             1.7 � 1013                                                   1.1 �                                                   1014__________________________________________________________________________ Note: *1 : Cresolnovolac type epoxy resin *2 : Phenol resin (novolac type) *3 : 2Methylimidazole *4 : Hexamethylenetetramine
TABLE 15__________________________________________________________________________Hydrogenated diene      Copoly-           Copoly-                Copoly-                     Copoly-                          Copoly-                               Copoly-                                    Copoly-                                         Copoly-                                              Copoly-block copolymer      mer Q-17           mer Q-18                mer Q-19                     mer Q-20                          mer Q-21                               mer Q-22                                    mer Q-23                                         mer Q-24                                              mer Q-25__________________________________________________________________________Block copolymerbefore hydrogenationBound styrene      30   30   30   20   40   30   30   30   30content of Block(A) (%)Vinyl content of      80   70   90   80   80   80   80   80   80butadiene portionin Block (B) (%)Coupling   Not  Not  Not  Not  Not  Not  Not  Made Not      made made made made made made made      madePolystyrene-      12.1 12.1 12.1 12.1 12.1 7.0  18.5 26.0 12.1reduced number-average molecularweight (� 10-4)General formula      A-B-A           A-B-A                A-B-A                     A-B-A                          A-B-A                               A-B-A                                    A-B-A                                         [A-B-                                              A-B-A                                         A]4 SiHydrogenated dieneblock copolymerHydrogenation      99 or           99 or                99 or                     99 or                          99 or                               99 or                                    99 or                                         99 or                                              51degree of butadiene      more more more more more more more moreportion (%)Hydrogenation      1 or less           1 or less                1 or less                     1 or less                          1 or less                               1 or less                                    1 or less                                         1 or less                                              1 or lessdegree of styreneportion (%)__________________________________________________________________________
TABLE 16__________________________________________________________________________          Example          68    69    70    71    72    73    74    75__________________________________________________________________________Compounding recipe (parts)Polyolefin     Type A-1   A-1   A-2   A-1   A-1   A-1   A-1   A-1     Amount          40    25    25    25    25    25    25    25Hydrogenated diene     Type Copolymer                Copolymer                      Copolymer                            Copolymer                                  Copolymer                                        Copolymer                                              Copolymer                                                    Copolymerblock copolymer          Q-17  Q-17  Q-17  Q-17  Q-18  Q-19  Q-20  Q-21     Amount          60    75    75    75    75    75    75    75Oil       Type --    --    --    Paraffinic                                  Paraffinic                                        Paraffinic                                              Paraffinic                                                    Paraffinic     Amount          --    --    --    60    60    60    60    60Crosslinking agent/          --    --    --    --    --    --    --    --crosslinking acidEvaluation resultsMechanical propertiesTB (kg � f/cm2)          250   210   210   50    45    50    50    50EB (%)    600   525   630   345   345   375   375   375Thermal ageing resistanceTB (kg � f/cm2)          250   210   210   50    45    50    50    50EB (%)    600   525   630   375   345   375   375   375Hardness (JIS A)          96    88    88    50    53    47    49    51Tension set (%)          12     7     6     4     5     6     5     5Transparency   &#9711;                &#9711;                      &#9711;                            &#9711;                                  &#9711;                                        &#9711;                                              &#9711;                                                    &#9711;__________________________________________________________________________                                              Comparative          Example                             Example          76    77    78    79    80    81    34    35__________________________________________________________________________Compounding recipe (parts)Polyolefin     Type A-1   A-1   A-2   A-1   A-1   A-1   A-1   A-1     Amount          25    25    25    25    25    25    25    25Hydrogenated diene     Type Copolymer                Copolymer                      Copolymer                            Copolymer                                  Copolymer                                        Copolymer                                              Copolymer                                                    EPDM*block copolymer          Q-22  Q-23  Q-24  Q-17  Q-17  Q-17  Q-25     Amount          75    75    75    75    75    75    75    75Oil       Type Paraffinic                Paraffinic                      Paraffinic                            Paraffinic                                  Paraffinic                                        Paraffinic                                              Paraffinic                                                    Paraffinic     Amount          60    60    60    70    60    60    60    60Crosslinking agent/          --    --    --    --    0.1/0.5                                        --    --    --crosslinking acidEvaluation resultsMechanical propertiesTB (kg � f/cm2)          42    45    54    45    55    52    35    48EB (%)    315   375   345   600   465   435   285   330Thermal ageing resistanceTB (kg � f/cm2)          42    52    54    45    53    52     5    48EB (%)    315   375   345   600   455   435   100   330Hardness (JIS A)          39    50    50    37    55    48    40    60Tension set (%)           4     4     4     2     2     3     8     9Transparency   &#9711;                &#9711;                      &#9711;                            &#9711;                                  &#9711;                                        &#9711;                                              &#916;                                                    &#916;__________________________________________________________________________ Note: *Ethylenepropylene-ethylidenenorbornene copolymer.
TABLE 17______________________________________           Example           82     83       84______________________________________Com-  (M) Component   20       40     60pound- Polyolefin resin PPing   (N) Component   80       60     40recipe Hydrogenated end-(part) blocked randam SBR Crosslinking agent                   2.0      2.0    2.0 Peroxide master batch Co-crosslinking agent                    0.20     0.30                                    0.24 Divinylbenzene Extender oil (paraffinic                 30       --     -- oil)Physi- 100% Tensile stress                 22       74     126cal   (kg/cm2)proper- 300% Tensile stress                 61       92     130ties at (kg/cm2)ordin- Tensile strength                 65       133    175ary   (kg/cm2)state Elongation at break (%)                 350      550    500 Hardness (Shore D)                 60       45     60                 (JIS A) Fatigue resistance                  6       14     12 (Length of cracks which grow when flexed 104 times) Appearance of molded                 &#9711;                          &#9711;                                 &#9711; article______________________________________
PREPARATION OF COMPONENT (A) (SYNTHESIS OF POLYMERS R-1 TO R-4)
Then, the reaction mixture was adjusted to 70� C., and thereto were added 1.5 g of n-butyllithium, 1.5 g of 2,6-di-tert-butyl-p-cresol, 0.5 g of bis(cyclopentadienyl)titanium dichloride and 2 g of diethyl-aluminum chloride. Hydrogenation was effected at a hydrogen pressure of 10 kg/cm2. The reaction mixture was returned to an atmosphere of room temperature and atmospheric pressure, taken out of the autoclave, poured into water, and subjected to steam distillation to remove the solvent, to obtain a hydrogenated diene block copolymer (hereinafter referred to Copolymer R-1).
TABLE 19__________________________________________________________________________  (a) Component          (b') Component                  (c) Component                          Evaluation results  Type and          Type and                  Type and                          Izod impact                                 Appearance of  amount  amount  amount  strength                                 molded  (parts) (parts) (parts) (kg � cm/cm)                                 article__________________________________________________________________________Example 89  R-2 10  b'-1 50 c-1/c-4 25/5                          75     &#9711;Example 90  R-2 10  b'-2 20  c-1/c-4 25/35                          63     &#9711;Example 91  R-2 10  b'-1/b'-2 30/20                  c-1/c-4 25/5                          78     &#9711;Comparative  R-4 10  b'-1 50 c-1/c-4 25/5                          12     XExample 37__________________________________________________________________________
TABLE 20__________________________________________________________________________  (a)   (b')  (c)  Component        Component              Component                    Evaluation results  Type and        Type and              Type and                    Izod impact                           Heat deformation                                    Appearance of  amount        amount              amount                    strength                           temperature                                    molded  (parts)        (parts)              (parts)                    (kg � cm/cm)                           (264 psi) (�C.)                                    article__________________________________________________________________________Example 92  R-2 15        b"-1 42.5              c-5 42.5                    54     92       &#9711;Comparative  R-4 15        b'-1 42.5              c-5 42.5                     4     70       XExample 38__________________________________________________________________________
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2010Kuraray Co., Ltd.Thermoplastic polymer composition and shaped article composed of the sameUS20140102930 *Dec 27, 2013Apr 17, 2014Kuraray Co., Ltd.Thermoplastic elastomer composition, molded article, and sealing material for medical useWO2011059225A2 *Nov 10, 2010May 19, 2011(주) 엘지화학Preparation method of vinyl aromatic hydrocarbon-conjugated diene block copolymer using coupling reaction with improved ion stabilityWO2012050740A1Sep 19, 2011Apr 19, 2012Kraton Polymers U.S. LlcElastic, moisture-vapor permeable films, their preparation and their use* Cited by examinerClassifications U.S. Classification525/314, 525/282, 525/940, 525/293, 525/279, 525/286, 525/303, 525/98, 525/312, 525/285, 525/105, 525/301International ClassificationC08F8/04, C08F297/04, C08L53/02, C08L51/00Cooperative ClassificationY10S525/94, C08F297/04, C08L53/025, C08L51/006, C08F8/04European ClassificationC08F8/04, C08L51/00C, C08L53/02B, C08F297/04Legal EventsDateCodeEventDescriptionSep 22, 1997FPAYFee paymentYear 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