CA2187233C - Ethylene .alpha.-olefin block copolymers and methods for production thereof - Google Patents
Ethylene .alpha.-olefin block copolymers and methods for production thereof Download PDFInfo
- Publication number
- CA2187233C CA2187233C CA002187233A CA2187233A CA2187233C CA 2187233 C CA2187233 C CA 2187233C CA 002187233 A CA002187233 A CA 002187233A CA 2187233 A CA2187233 A CA 2187233A CA 2187233 C CA2187233 C CA 2187233C
- Authority
- CA
- Canada
- Prior art keywords
- block
- block copolymer
- ethylene
- polymer
- weight percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 100
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000005977 Ethylene Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 155
- -1 polyethylene Polymers 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 150000001993 dienes Chemical class 0.000 claims abstract description 51
- 229920000573 polyethylene Polymers 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 25
- 239000004711 α-olefin Substances 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 230000008878 coupling Effects 0.000 claims abstract description 16
- 238000010168 coupling process Methods 0.000 claims abstract description 16
- 238000005859 coupling reaction Methods 0.000 claims abstract description 16
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 6
- 239000004831 Hot glue Substances 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 61
- 239000003054 catalyst Substances 0.000 claims description 56
- 238000006116 polymerization reaction Methods 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 20
- 239000007822 coupling agent Substances 0.000 claims description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 18
- 239000010687 lubricating oil Substances 0.000 claims description 14
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 150000003682 vanadium compounds Chemical class 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 7
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical group CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 claims description 6
- 239000010426 asphalt Substances 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 claims description 4
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 4
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002879 Lewis base Substances 0.000 claims description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 150000007527 lewis bases Chemical group 0.000 claims description 4
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical group CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 238000007306 functionalization reaction Methods 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 claims description 2
- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- BDEXHIMNEUYKBS-UHFFFAOYSA-N 5-cyclopent-2-en-1-ylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CCCC1C1C(C=C2)CC2C1 BDEXHIMNEUYKBS-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims 4
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims 4
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 claims 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims 1
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 abstract description 34
- 229920002943 EPDM rubber Polymers 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- 239000000306 component Substances 0.000 abstract 2
- 239000002816 fuel additive Substances 0.000 abstract 1
- 239000003879 lubricant additive Substances 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000002156 mixing Methods 0.000 description 18
- 229920001971 elastomer Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 9
- 241000894007 species Species 0.000 description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000006276 transfer reaction Methods 0.000 description 4
- FUDNBFMOXDUIIE-UHFFFAOYSA-N 3,7-dimethylocta-1,6-diene Chemical compound C=CC(C)CCC=C(C)C FUDNBFMOXDUIIE-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000012967 coordination catalyst Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000011953 free-radical catalyst Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KEMUGHMYINTXKW-NQOXHWNZSA-N (1z,5z)-cyclododeca-1,5-diene Chemical compound C1CCC\C=C/CC\C=C/CC1 KEMUGHMYINTXKW-NQOXHWNZSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RJUCIROUEDJQIB-GQCTYLIASA-N (6e)-octa-1,6-diene Chemical compound C\C=C\CCCC=C RJUCIROUEDJQIB-GQCTYLIASA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- IZLXZVWFPZWXMZ-UHFFFAOYSA-N 5-cyclohexylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2=C1CCCCC1 IZLXZVWFPZWXMZ-UHFFFAOYSA-N 0.000 description 1
- VSQLAQKFRFTMNS-UHFFFAOYSA-N 5-methylhexa-1,4-diene Chemical compound CC(C)=CCC=C VSQLAQKFRFTMNS-UHFFFAOYSA-N 0.000 description 1
- CJQNJRMLJAAXOS-UHFFFAOYSA-N 5-prop-1-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=CC)CC1C=C2 CJQNJRMLJAAXOS-UHFFFAOYSA-N 0.000 description 1
- 101100378709 Arabidopsis thaliana AIR3 gene Proteins 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 0 C(CC1CC1)C*=*[C@]1*CCNC1 Chemical compound C(CC1CC1)C*=*[C@]1*CCNC1 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005604 azodicarboxylate group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OQROAIRCEOBYJA-UHFFFAOYSA-N bromodiphenylmethane Chemical compound C=1C=CC=CC=1C(Br)C1=CC=CC=C1 OQROAIRCEOBYJA-UHFFFAOYSA-N 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000011951 cationic catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- KYVVLBCWPRONOU-UHFFFAOYSA-N ethene hexane Chemical compound C=C.CCCCCC KYVVLBCWPRONOU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920006343 melt-processible rubber Polymers 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1666—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing non-conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/02—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/10—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing cycloaliphatic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/14—Synthetic waxes, e.g. polythene waxes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol-fuelled engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Emergency Medicine (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
This invention relates to block polymers containing both crystalline and ela stomeric blocks, the block copolymer having an A block and a B block. The A block is a polyethylene or an ethylene polymer optional ly containing an alpha-olefin and optional a non-conjuga ted diene, and is generally crystalline. The B block is an ethylene, .alpha.-ol efin copolymer. Also disclosed is a process for manufac ture of the block copolymers and methods for coupling the block copolymers. Coupled block cop olymers are useful as thermoplastic elastomers exhibitin g physical properties approaching those of crosslinked EP or EPDM elastomers, but showing thermal processability after coupling. The block copolymers of the present invention may also be used as a lubricant or fuel additive, as a plastics blend component, and as a compon ent in hot melt adhesives.
Description
APPLICATION FOR E&TENT
Tifle: ETHYLENE a-OLEFIN BLOCK COPOLYMERS AND
METHODS FOR PRODUCTION THEREOF
Technical Field This invention relates to block polymers containing both crystalline and elastomeric blocks. The copolymers have blocks of polyethylene optionally containing an a-olefin and a non-conjugated diene and blocks containing ethylene and an a-olefin.
A novel process for producing the block copolymers is also provided.
BACKGROUND
Block copolymers are well known. They have been used commercially as components in adhesives, as melt processable rubbers, in impact resistant thermoplastics, as compatibilizers, as "surfactants" for emulsifying polymer-polymer blends, and as viscosity index improvers in lubricating oils. A block copolymer is created when two or more polymer molecules of different chemical composition are covalently bonded in an end-to-end fashion. While a wide variety of block copolymer architectures are possible, most block copolymers of interest involve the covalent bonding of hard plastic blocks, which are substantially crystalline or glassy, to elastomeric blocks forming thermoplastic elastomers. Other block copolymers, such as rubber-rubber (elastomer-elastomer), glass-glass, and glass-crystalline block copolymers are also possible and may have commercial importance. Two common types of block copolymer structures are the diblock and tri-block forms. However, multi-block copolymers, in which more than three blocks are bonded together, are also desirable. The multi-block copolymers include either linear multi-block or multi-arm star block polymers.
Tri-block and multi-block copolymers containing "hard" and "soft" blocks have the unique ability of behaving as thermoplastic elastomers, combining thermoplasticity with rubber-like behavior. The typical requirement for achieving thermoplastic elastomeric behavior is the ability to develop a two-phase physical network.
Such a system is composed of a portion of hard block, having a glass transition temperature (Tg) or melting temperature (Tm) above the service temperature of a fabricated end use product, and a portion of a soft block, having a Tg below the service temperature. The hard blocks associate to form domains that serve as physical crosslinks and reinforcement sites. The reinforcement sites and physical cross-links are thermally reversible, making it possible to process the polymer as a melt phase material at temperatures above the Tg or Tm of the hard block. Among the advantages of having a physically cross-linked system that is thermally reversible is that while below the Tg or Tm of the hard block such polymers exhibit properties approaching those of fully-cured, i.e. chemically crosslinked elastomers, but unlike such cured elastomers, by heating these polymers above Tg or Tm of the hard block, the physical crosslinks are eliminated and the material can be processed. The advantage of such systems will be well known to those of ordinary skill in the art.
A substantial amount of work has been done in an attempt to synthesize olefinic block copolymers. The ideal catalyst system would produce a"living polymer".
Unlike typical Ziegler-Natta polymerization processes, living polymerization processes involve only initiation and propagation steps and essentially lack chain terminating side reactions.
This permits the synthesis of the predetermined and well-controlled structures desired in a block copolymer. A polymer created in a"living" system can have a narrow or extremely narrow distribution of molecular weight and be essentially monodisperse.
Living catalyst systems are characterized by an initiation rate which is on the order of or exceeds the propagation rate, and the absence of termination or transfer reactions. In addition, these catalyst systems are preferably characterized by the presence of a single type of active site. To produce a high yield of block copolymer product in a polymerization process the catalyst must exhibit living characteristics to. a substantial extent.
Anionic polymerization routes to ideal block copolymers have been studied.
Butadiene-isoprene block copolymers have been synthesized using the sequential monomer addition technique. In sequential addition, a certain amount of one of the monomers is contacted with the catalyst. Once a first such monomer has reacted to substantial extinction forming the first block, a certain amount of the second monomer or monomer species is introduced and allowed to react to form the second block.
The process may be repeated using the same or other anionically polymerizable monomers.
Ethylene and other a-olefins, such as propylene and butene, are not directly block polymerizable by anionic techniques.
U.S. patent 4,804,794 to Ver Strate, et al., discloses segmented'copolymers of ethylene and at least one other alpha-olefin. The copolymers have a narrow MWD
(Mw/Mn) less than 2. The copolymers have one segment that is crystallizable and at least one low crystallinity segment. A vanadium catalyst is utilized with an organoaluminum cocatalyst. The polymerization is carried out in a mix-free reactor.
WO 9112-285-A to Turner, et al., discloses a process for production of block copolymers of ethylene with an alpha-olefin and the polymer produced by the process.
The process includes sequentially contacting ethylene with an alpha-olefin in the presence of an ionic catalyst to produce a block copolymer. The ionic catalyst comprises the reaction product of a first component which is a bis (cyclopentadienyl) derivative of a metal of Group IV-B of the Periodic Table of the Elements which metal is capable of forming a cation formally having a coordination number of 3 and a valence of -4; and at least one second component comprising a cation capable of donating a proton and a compatible non coordinating anion.
While many patents and publications claim the Ziegler-Natta catalyzed synthesis of block copolymers from ethylene and propylene, there is little evidence that these products were obtained in high purity. In Boor, J. Ziegler-Natta Catalysts and Polvmerization. Academic Press, 1979, Boor states that the known kinetic features of heterogeneous Ziegler-Natta catalysts suggest that it is unlikely that block polymers were synthesized in a substantial yield, as compared to the total polymer formed.
In this context, several dithculties arise in the use of known coordination catalysts for the block copolymerization of a-olefins. Among those are the fact that conventional catalysts are typically multi-sited, and a significant fraction of the active sites are unstable. This leads to non-uniform chain initiation and termination which, in turn, lowers the theoretical block copolymer yield. In addition, chain transfer rates during polymerization with known coordination catalysts are high. This is especially true with metallocene catalyst systems where thousands of chains may be produced per active WO 95/27746 21$ 72 3 3 PCT/US95/04250 site.
SUMMARY
The present invention is directed to procedures to make the use of certain coordination catalysts possible for production of alpha-olefin block copolymers of the crystalline-elastomeric type in high purity. These block copolymers and methods of their manufacture by a Ziegler-Natta type catalyst are objects of our invention. We will demonstrate the existence of high yields of true block copolymers. Evidence of the existence of such high yield of true block copolymer, as stated above, has been substantially absent prior to the present invention.
The present invention comprises a novel block polymer having an A block and a B block, and if a diene is present in the A block, a nodular polymer formed by coupling two or more block polymers. The A block is an ethylene polymer optionally containing an alpha-olefin and /or a non-conjugated diene. The diene, if present in the A
block, is present in an amount up to 10 mole percent based on the total moles of the monomers of the block copolymer. The B block has a first polymer segment that is an ethylene and an alpha-olefin copolymer segment, the first polymer segment is contiguous to a junction of the A block and the B block. The B block may have a tip segment, the tip segment is fiirthest from the A B junction, and the tip segment is a polymer of ethylene and an alpha-olefin. The tip segment of the B block may comprise an ethylene, alpha-olefin copolymer with an average ethylene content of at least 60 mole percent based on the total tip segment, the tip segment melts in the range of from 35 C to 130 C
as measured by DSC.
The present invention also comprises a process for producing these block copolymers, which has the steps of 3 0 (a) Forming a catalyst species by premixing a vanadium compound and an organoaluminum compound. The pre-mixing step is carried out for a sufficient period of time to provide an adequate amount of active catalyst species;
(b) Feeding the reaction product of step (a) to a niix free reactor concurrently with a monomer stream made up of ethylene, optionally an alpha-olefin and optionally a non-conjugated diene;
WO 95/27746 2 18 7 2 3 3 pCT/US95/04250 (c) Feeding at least a second monomer blend made up of ethylene, and an alpha-olefin, If a diene is present, the block copolymer may be coupled using the residual olefinic functionality of the diene to produce nodular polymers. Coupling can take place either in the reactor, or post reactor.
The coupled polymer will generally be useful in, among other appGcations, lubricating oils, as viscosity iinprovers or dispersants. A coupling agent may be used to couple two or more block copolymers.
These block copolymers find use as thermoplastic elastomers (TPE), plastics blending components, in fuel lubricating and heating oils, as a bitumen modifier, in roof sheeting compounds, and in hot melt adhesives.
These and other features, aspects and advantages of the present invention will become better understood with reference to the following description, appended claims and accompanying drawings where:
BRIEF DESCR.iMON OF THE DRAWINGS
Figure 1 is a Differential Scanning Calorimeter (DSC) thermogram for polymer 2A described in Example 2.
Figure 2 is a DSC thermogram for polymer 2B described in Example 2.
Figure 3 is a DSC thermogram of a pure polyethylene A block.
Figure 4 is a schematic representation of a process for producing polymer in accordance with our invention.
DESCRIPTION OF THE PREFEMU FMBODIMENTS
The present invention is directed to procedures to make and use certain alpha-olefin block copolymers of the crystalline-elastomeric type in high purity using certain WO 95127746 21 8723 3 PCT/uS95/04250 coordinadon catalysts. These block copolymers and methods of their manufacture by a Ziegler-Natta type catalyst are among the objects of our invention.
The present invention comprises a novel block copolymer having an A block and a B block and when a diene is present in the A block, a nodular polymer formed by coupling two or more block copolymers. The nodular polymer may optiohally contain a coupling agent Y;
(1) "A" denotes a block comprising polyethylene, and optionally an a-olefin comonomer not exceeding 5 mole percent based on the total moles of monomers in the A block, and further optionally containing up to 10 mole percent of a non-conjugated diene. The diene is present at this mole percent based on the total A
B block copolymer.
The A block is present in the block copolymer preferably in the range of from to 90 weight percent based on the total weight of the block copolymer. More preferably in the range of from 10 to 60 weight percent, most preferably in the range of from 20 to 50 weight percent.
(2) "B" denotes a block comprising ethylene and an a-olefin copolymer. The B
block comprises one or more segments. If there is one segment in the B block, it will be an ethylene, a-olefin segment. If there are two or more segments in the B
block, the first segment immediately following the junction of the A and B
blocks will be an ethylene a-olefin copolymer segment. The tip or end segment will be located in the portion of the B block furthest from the A B junction. If there are two segments, the second or tip segment will be an ethylene, a-olefin copolymer with an average ethylene content of at least 60 mole percent based on the total moles of the monomers of the tip segment, and which melts in the range of 3 5 to 130 C, as measured by DSC.
Optionally the B block has an intramolecular composition distribution such that at least two portions of the B block, each portion comprising at least 5 weight percent of the B block, differ in composition by at least 5 weight percent ethylene. The B block is present in the block copolymer in the range of from 10 to 95 weight percent based on the total weight of the block copolymer.
Tifle: ETHYLENE a-OLEFIN BLOCK COPOLYMERS AND
METHODS FOR PRODUCTION THEREOF
Technical Field This invention relates to block polymers containing both crystalline and elastomeric blocks. The copolymers have blocks of polyethylene optionally containing an a-olefin and a non-conjugated diene and blocks containing ethylene and an a-olefin.
A novel process for producing the block copolymers is also provided.
BACKGROUND
Block copolymers are well known. They have been used commercially as components in adhesives, as melt processable rubbers, in impact resistant thermoplastics, as compatibilizers, as "surfactants" for emulsifying polymer-polymer blends, and as viscosity index improvers in lubricating oils. A block copolymer is created when two or more polymer molecules of different chemical composition are covalently bonded in an end-to-end fashion. While a wide variety of block copolymer architectures are possible, most block copolymers of interest involve the covalent bonding of hard plastic blocks, which are substantially crystalline or glassy, to elastomeric blocks forming thermoplastic elastomers. Other block copolymers, such as rubber-rubber (elastomer-elastomer), glass-glass, and glass-crystalline block copolymers are also possible and may have commercial importance. Two common types of block copolymer structures are the diblock and tri-block forms. However, multi-block copolymers, in which more than three blocks are bonded together, are also desirable. The multi-block copolymers include either linear multi-block or multi-arm star block polymers.
Tri-block and multi-block copolymers containing "hard" and "soft" blocks have the unique ability of behaving as thermoplastic elastomers, combining thermoplasticity with rubber-like behavior. The typical requirement for achieving thermoplastic elastomeric behavior is the ability to develop a two-phase physical network.
Such a system is composed of a portion of hard block, having a glass transition temperature (Tg) or melting temperature (Tm) above the service temperature of a fabricated end use product, and a portion of a soft block, having a Tg below the service temperature. The hard blocks associate to form domains that serve as physical crosslinks and reinforcement sites. The reinforcement sites and physical cross-links are thermally reversible, making it possible to process the polymer as a melt phase material at temperatures above the Tg or Tm of the hard block. Among the advantages of having a physically cross-linked system that is thermally reversible is that while below the Tg or Tm of the hard block such polymers exhibit properties approaching those of fully-cured, i.e. chemically crosslinked elastomers, but unlike such cured elastomers, by heating these polymers above Tg or Tm of the hard block, the physical crosslinks are eliminated and the material can be processed. The advantage of such systems will be well known to those of ordinary skill in the art.
A substantial amount of work has been done in an attempt to synthesize olefinic block copolymers. The ideal catalyst system would produce a"living polymer".
Unlike typical Ziegler-Natta polymerization processes, living polymerization processes involve only initiation and propagation steps and essentially lack chain terminating side reactions.
This permits the synthesis of the predetermined and well-controlled structures desired in a block copolymer. A polymer created in a"living" system can have a narrow or extremely narrow distribution of molecular weight and be essentially monodisperse.
Living catalyst systems are characterized by an initiation rate which is on the order of or exceeds the propagation rate, and the absence of termination or transfer reactions. In addition, these catalyst systems are preferably characterized by the presence of a single type of active site. To produce a high yield of block copolymer product in a polymerization process the catalyst must exhibit living characteristics to. a substantial extent.
Anionic polymerization routes to ideal block copolymers have been studied.
Butadiene-isoprene block copolymers have been synthesized using the sequential monomer addition technique. In sequential addition, a certain amount of one of the monomers is contacted with the catalyst. Once a first such monomer has reacted to substantial extinction forming the first block, a certain amount of the second monomer or monomer species is introduced and allowed to react to form the second block.
The process may be repeated using the same or other anionically polymerizable monomers.
Ethylene and other a-olefins, such as propylene and butene, are not directly block polymerizable by anionic techniques.
U.S. patent 4,804,794 to Ver Strate, et al., discloses segmented'copolymers of ethylene and at least one other alpha-olefin. The copolymers have a narrow MWD
(Mw/Mn) less than 2. The copolymers have one segment that is crystallizable and at least one low crystallinity segment. A vanadium catalyst is utilized with an organoaluminum cocatalyst. The polymerization is carried out in a mix-free reactor.
WO 9112-285-A to Turner, et al., discloses a process for production of block copolymers of ethylene with an alpha-olefin and the polymer produced by the process.
The process includes sequentially contacting ethylene with an alpha-olefin in the presence of an ionic catalyst to produce a block copolymer. The ionic catalyst comprises the reaction product of a first component which is a bis (cyclopentadienyl) derivative of a metal of Group IV-B of the Periodic Table of the Elements which metal is capable of forming a cation formally having a coordination number of 3 and a valence of -4; and at least one second component comprising a cation capable of donating a proton and a compatible non coordinating anion.
While many patents and publications claim the Ziegler-Natta catalyzed synthesis of block copolymers from ethylene and propylene, there is little evidence that these products were obtained in high purity. In Boor, J. Ziegler-Natta Catalysts and Polvmerization. Academic Press, 1979, Boor states that the known kinetic features of heterogeneous Ziegler-Natta catalysts suggest that it is unlikely that block polymers were synthesized in a substantial yield, as compared to the total polymer formed.
In this context, several dithculties arise in the use of known coordination catalysts for the block copolymerization of a-olefins. Among those are the fact that conventional catalysts are typically multi-sited, and a significant fraction of the active sites are unstable. This leads to non-uniform chain initiation and termination which, in turn, lowers the theoretical block copolymer yield. In addition, chain transfer rates during polymerization with known coordination catalysts are high. This is especially true with metallocene catalyst systems where thousands of chains may be produced per active WO 95/27746 21$ 72 3 3 PCT/US95/04250 site.
SUMMARY
The present invention is directed to procedures to make the use of certain coordination catalysts possible for production of alpha-olefin block copolymers of the crystalline-elastomeric type in high purity. These block copolymers and methods of their manufacture by a Ziegler-Natta type catalyst are objects of our invention. We will demonstrate the existence of high yields of true block copolymers. Evidence of the existence of such high yield of true block copolymer, as stated above, has been substantially absent prior to the present invention.
The present invention comprises a novel block polymer having an A block and a B block, and if a diene is present in the A block, a nodular polymer formed by coupling two or more block polymers. The A block is an ethylene polymer optionally containing an alpha-olefin and /or a non-conjugated diene. The diene, if present in the A
block, is present in an amount up to 10 mole percent based on the total moles of the monomers of the block copolymer. The B block has a first polymer segment that is an ethylene and an alpha-olefin copolymer segment, the first polymer segment is contiguous to a junction of the A block and the B block. The B block may have a tip segment, the tip segment is fiirthest from the A B junction, and the tip segment is a polymer of ethylene and an alpha-olefin. The tip segment of the B block may comprise an ethylene, alpha-olefin copolymer with an average ethylene content of at least 60 mole percent based on the total tip segment, the tip segment melts in the range of from 35 C to 130 C
as measured by DSC.
The present invention also comprises a process for producing these block copolymers, which has the steps of 3 0 (a) Forming a catalyst species by premixing a vanadium compound and an organoaluminum compound. The pre-mixing step is carried out for a sufficient period of time to provide an adequate amount of active catalyst species;
(b) Feeding the reaction product of step (a) to a niix free reactor concurrently with a monomer stream made up of ethylene, optionally an alpha-olefin and optionally a non-conjugated diene;
WO 95/27746 2 18 7 2 3 3 pCT/US95/04250 (c) Feeding at least a second monomer blend made up of ethylene, and an alpha-olefin, If a diene is present, the block copolymer may be coupled using the residual olefinic functionality of the diene to produce nodular polymers. Coupling can take place either in the reactor, or post reactor.
The coupled polymer will generally be useful in, among other appGcations, lubricating oils, as viscosity iinprovers or dispersants. A coupling agent may be used to couple two or more block copolymers.
These block copolymers find use as thermoplastic elastomers (TPE), plastics blending components, in fuel lubricating and heating oils, as a bitumen modifier, in roof sheeting compounds, and in hot melt adhesives.
These and other features, aspects and advantages of the present invention will become better understood with reference to the following description, appended claims and accompanying drawings where:
BRIEF DESCR.iMON OF THE DRAWINGS
Figure 1 is a Differential Scanning Calorimeter (DSC) thermogram for polymer 2A described in Example 2.
Figure 2 is a DSC thermogram for polymer 2B described in Example 2.
Figure 3 is a DSC thermogram of a pure polyethylene A block.
Figure 4 is a schematic representation of a process for producing polymer in accordance with our invention.
DESCRIPTION OF THE PREFEMU FMBODIMENTS
The present invention is directed to procedures to make and use certain alpha-olefin block copolymers of the crystalline-elastomeric type in high purity using certain WO 95127746 21 8723 3 PCT/uS95/04250 coordinadon catalysts. These block copolymers and methods of their manufacture by a Ziegler-Natta type catalyst are among the objects of our invention.
The present invention comprises a novel block copolymer having an A block and a B block and when a diene is present in the A block, a nodular polymer formed by coupling two or more block copolymers. The nodular polymer may optiohally contain a coupling agent Y;
(1) "A" denotes a block comprising polyethylene, and optionally an a-olefin comonomer not exceeding 5 mole percent based on the total moles of monomers in the A block, and further optionally containing up to 10 mole percent of a non-conjugated diene. The diene is present at this mole percent based on the total A
B block copolymer.
The A block is present in the block copolymer preferably in the range of from to 90 weight percent based on the total weight of the block copolymer. More preferably in the range of from 10 to 60 weight percent, most preferably in the range of from 20 to 50 weight percent.
(2) "B" denotes a block comprising ethylene and an a-olefin copolymer. The B
block comprises one or more segments. If there is one segment in the B block, it will be an ethylene, a-olefin segment. If there are two or more segments in the B
block, the first segment immediately following the junction of the A and B
blocks will be an ethylene a-olefin copolymer segment. The tip or end segment will be located in the portion of the B block furthest from the A B junction. If there are two segments, the second or tip segment will be an ethylene, a-olefin copolymer with an average ethylene content of at least 60 mole percent based on the total moles of the monomers of the tip segment, and which melts in the range of 3 5 to 130 C, as measured by DSC.
Optionally the B block has an intramolecular composition distribution such that at least two portions of the B block, each portion comprising at least 5 weight percent of the B block, differ in composition by at least 5 weight percent ethylene. The B block is present in the block copolymer in the range of from 10 to 95 weight percent based on the total weight of the block copolymer.
The tip of the B block can comprise up to 50 weight percent of the B block, preferably in the range of from 3 to 20 weight percent, more preferably in the range of from 5 to 15 weight percent, all weight percents of the tip based on the total weight of the B block. The tip segment, when present, is typically the segment furthest from the A
B junction.
Y is a coupling agent which has reacted with the residual olefinic functionality in the block polymers and has coupled two or more block polymer molecules.
A is a crystalline block and B has elastomeric segments. B may optionally contain a low level of crystallinity.
COPOLYME ,L~B AICKS
BI,OCK...~
Block A comprises polyethylene which optionaHy may contain up to 10 mole percent of a non-conjugated diene (based on the total moles of the monomers of the A B
copolymer). The A block may optionally contain an a-oleSn comonomer at a level not exceeding 5 mole percent based on the total moles of the monomers of the A
block. If block A contains a non-conjugated diene it will be present in the A block preferably in the range of from 0.01 to 5 mole percent, more preferably in the range of from 0.03 to 2 mole percent, most preferably in the range of from 0.05 to 1 mole percent based on the total moles of the monomers of the A B block copolymer. Block A comprises 5 to 90 weight percent of the entire polymer, preferably 10 to 60 weight percent , most preferably 20 to 50 weight percent of the entire polymer. The A block has a T.
of at least 110 C, preferably at least 105 C, more preferable at least 120 C.
BLOCK B
Block B is an elastomer that comprises an ethylene and an a-olefin copolymer.
Block B optionally has an intramolecular-compositional distribution such that at least two portions of the B block, each of said portions comprising at least 5 weight percent of said B block, differ in composition by at least 5 weight percent ethylene.
Intramolecular-compositional distribution is the compositional variation, in terms of ethylene, along the polymer chain or block. It is expressed as the minimum difference in _$_ average ethylene composition in weight percent of ethylene that exists between two portions of a single block, each portion comprising at least 5 weight percent of the block. Intramolecular-compositional distribution is determined using the, procedures disclosed in U.S. Patent No. 4,959,436, The B block comprises 95 to 10 weight percent of the total weight of the block copolymer, preferably 90 to 40 weight percent; more preferably 80 to 50 weight percent.
The B block comprises one or more segments. If there are two or more segments in the B block, the tip or end segment fiuthest from the junction of the A block and the B block will comprise an ethylene, a-olefin copolymer with an average ethylene content of at least 60 mole percent based on the total moles of the monomers of the tip segment. The tip segment melts in the range of from 35 C to 130 C as measured by DSC
The tip of the B block can comprise up to 50 weight percent of the B block, preferably in the range of from 3 to 20 weight percent, more preferably in the range of from 5 to 15 weight percent, all weight percents of the tip based on the total weight of the B block. The tip segment, when present, is typically the segment furthest from the A
B junction.
The B block can comprise an average ethylene content in the range of from 20 to 90 mole percent, preferably in the range of from 30 to 85 mole percent, and most preferably in the range of from 50 to 80 mole percent based on the total moles of the monomers of the B block.
The block copolymers of the invention are fiarther characterized in that they have a number average molecular weight of between 750 and 20,000,000, and have a molecular weight distribution characterized by a Mq,/Mn ratio of less than 2.5. The block copolymers have an n-hexane soluble portion, at 22 C not exceeding 50 weight percent, preferably not exceeding 40 weight peroent, and more preferably not exceeding 30 weight percent, based on the total weight of the block copolymer. The products of the present invention are further characterized by a relatively small amount of polymer chains in the final product that contain only an A block or only a B block.
The presence of such materials could detract from overall product properties. A typical characteristic WO 95/27746 PCT/Us95/04250 21$723 3-of the preferred product of this invention is that the block copolymer contains at least 50 % (weight) of the desired A B structure as polymerized. Product purification is not necessary to obtain good properties.
Monomers Alpha-olefins particularly useful in the practice of this invention are those having from 3 to 8 carbon atoms, e.g. propylene, butene-l, pentene-I, etc. Alpha-olefins of 3 to 6 carbon atoms are preferred due to economic considerations. The most preferred a-olefin is propylene.
Typical non-limiting examples of non-conjugated dienes useful in the practice of this invention are:
(a) straight chain acyclic dienes such as: 1,4-hexadiene; 1,6-octadiene;
(b) branched chain acyclic dienes such as: 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dirnethyl-1,7-dioctadiene; and the mixed isomers of dihydromyrcene and dihydro-ocinene;
(c) single ring dienes such as: 1,4-cyclohexadiene; 1,5-cyclooctadiene; and 1,5-cyclododecadiene;
(d) multi-ring fixed and fused ring dienes such as: tetrahydroindene;
methyltetra-hydroindene; dicyclopentadiene; bicyclo-(2,2,1)-hepta-2, 5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-propenyl-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, vinyl norbornene, and norbornadiene.
Of the non-conjugated dienes useful in the practice of the invention, dienes containing at least one of the double bonds in a strained ring are preferred.
The most preferred dienes are 5-ethylidene-2-norbornene and vinyl-norbornene.
Conjugated dienes are also contemplated.
-Polymerization The novel polymers of our invention are prepared by polymerization in a mix-fiee reactor similar to that taught in U.S. Patent No. 4,959,436.
Previously, those of skill in the art thought that a solution polymerization process such as that taught in U.S. Patent No. 4,959,436 would not be suitable for producing block copolymers such as the ones described above in which one of the blocks, polyethylene, is insoluble in the solvent. The insolubility could lead to reactor fouling and mass transport problems. In turn, these problems could prevent the fonmation of the desired well-defined polymer structure and significantly reduce catalyst efficiency.
Surprisingly, we have found that the block polymers of our invention can be made in a mix-free reactor when the initial monomer feed consists essentially of ethylene, and optionally such that up to 5 mole percent of the A block is alpha olefin and optionally a diene sufficient to incorporate up to 10 mole percent of a non-conjugated diene (based on the total of the monomers of the block copolymer). This, the A
block, is.
polymerized first. During this part of the reaction, the polyethylene (A) block may be only partially soluble in the reaction diluent and the insoluble polymer block forms a suspension in the diluent.
Once the polymerization of the A block is substantially complete, one or more additional monomer feeds are introduced into the reactor containing ethylene, and an a-olefin. The reaction of the comonomer mixtures forms the B block of the block polymer or the first segment of the B block if there is more than one segment. The B
block is polymerized onto the polyethylene or A block formed earlier. When this second part of the polymerization occurs, there is a noticeable change in the appearance of the reaction medium. As the chains become solubilized through the addition of the B block, the turbidity of the medium decreases appreciably and the quantity of polymer particles in the diluent is markedly reduced. When a tubular reactor is employed, several monomer feeds along the reactor length may be used to control the composition and amount of the B block and form the segments of the B block. The final feeds to the reactor may contain a higher ethyleneJa-olefin ratio to form a semi-crystalline segment at the tip of the B block., giving the B block a melting point in the range of from 35 to 130 C.
QwAn the pOlymets Block polymers of our invention may incorporate a diene. The residual olefinic functionaiity in diene containing block polymers can be reacted with coupling agents to produce novel nodular polymers.
Suitable coupling reagents and coupling techinques are described in U.S.
Patent 4,882,406r Coupling can take place either within the polymerization reactor or in a post-polymerization reaction. With the diene in the A
block, the polyethylene segment containing the diene is in a central polyethylene nodule with EP block extending outwards.
There are various coupling agents that are capable of reacting with the residual unsaturation in the polymer chains to cause coupling of two or more block polymer molecules.
. Coupling may be carried out with cationic catalysts such as Lewis acids.
Suitable Lewis acids may be selected from the group consisting of: AIX3, BX3, SnX4, SbXs1 AI1YX3õy where y is 0 to 1.5 and R is a hydrocarbon radical, BX4, TiX4 and mixtures thereof, where X is selected from the group consisting of chlorine, bromine, and iodine.
Chlorine is prefeired. For Lewis acids that do not interfere with the functioning of the catalyst system used to cany out the polymeriaation, the Lewis acid can be added directly to the reactor so that chain coupling oceurs at the same time as the polymerization. Alternately the coupling agent can be added following the polymerization.
According to yet another embodiment the coupling agent may be a free radical catalyst. The free radical catalyst may be a peroxide selected from the group consisting of: dicumyl peroxide, di-tertiarybutylperoxide, t-butylperbenzoate, 1,1-di(t-butylperoxy)-3,3,5-trimethyl cyclohexane, and mixtures thereof Other free radical catalysts include azo-bisisobutylnitrile, azodicarboxylate, and mixtures thereof.
Peroxides can couple non-diene containing portions of the chain and produce a cross-linked network. Care must be taken when they are used as coupling agents.
In yet another embodiment the coupling agent may be selected from the group consisting of sulfur dichloride, disulfenyl halides, borane, dithoalkanes, other sulfur and accelerated sulfur curatives and mixtures thereot such as mercaptobenzothiozole, tetramethyltlnuram disulfide, and butyl zymate. It is apparent that any of the conventional vulcanization systems useful for EPDM may be employed.
Resins and other reagents may also be employed for coupling. For example alkyl phenol fonmaldehyde mixtures will couple olefins in certain cases with catalysts such as ZnClz , N bromosuccinimide or diphenylbromomethane.
Also contemplated as a coupling mechanism is the use of irradiation or electron beams.
For certain non-conjugated dienes, such as norbomadiene, vinyl norbomene, dicyclopentadiene and tetrahydroindene, both double bonds are polymerizable to a greater or lesser extent by the polymerization catalysts of this invention.
With dienes of this type chains can become cheniically coupled to each other during polymerization by reaction of the remaining double bond in an enchained diene monomer with a growing chain. This process will lead to coupling of chains in the reactor even in the absence of a coupling agent Y.
The efficiency of olefin utilization will detenmine what level of coupling agent to use in relation to the amount of diene in the block copolymer. The purpose is to couple the diblocks to an extent which yields good mechanical properties but does not raise viscosity or produce gel to the extent that the coupled product is not processable.
The Reaction Solvent Processes in accordance with the present invention produce copolymers by polymerization; of a reaction mixture comprised of catalyst, ethylene and at least one additional a-olefin monomer and optionally diene. Polymerization in the presence of a diluent which has the capability to dissolve a major portion of the final product is preferred. Suitable solvents are described in U.S. patent number 4,882,406.
Polvmerization Reactor These processes are carried out in a mix-free reactor system, which is one in which substantially no mixing occurs betwean portions of the reaction mixture that contain polymer chains initiated at different times. Suitable reactors are disclosed in U.S. patents 4,959,436 and 4,882,406r Additional reaction considerations are also disclosed in these references.
To obtain the desired A B block polymer, it is necessary to add additional reactants (e.g., at least one of the monomers ethylene, a-olefin or diene) either at some point or points along the length of a tubular reactor, or during the course of polymerization in a batch reactor, or at various points in a train of continuous flow stirred reactors. However, it is also preferred to add essentially all of the catalyst at the inlet of a continuous flow reactor or at the onset of batch reactor operation to meet the requirement that essentiaUy all polymer chains are initiated simultaneously.
To make diene containing block polymers, diene is fed at the reactor inlet to incorporate diene into an A block. IViultiple feeds of ethylene and propylene can be used to control the amount and composition of the segments in the B block.
Since the tubular reactor is the prefenred reactor system for carrying out processes in accordance with the prefened embodiment, the illustrative descriptions and examples that follow are drawn to that system, but will apply to other reactor systems as will readily occur to those of ordinary skill in the art having the benefit of the present disclosure. However, as would readily occur to those of ordinary slcill in the art having the benefit of the present disclosure, more than one reactor could be used, either in parallel, or in series with multiple monomer feeds to vary intramolecular composition.
The Catalvst The composition of the catalyst used to produce ethylene, a-olefin copolymers has a prof embodiment should be such as to yield essentially one active catalyst species in the reaction mixture. More specifically, it should yield one primary active catalyst species which provides for substantially aU of the polymerization reaction. Additional active catalyst species could be present, provided that they do not produce a significant amount of polymer which detracts from the performance of the polymer produced. Such additional active catalyst species may provide as much as 35% by weight of the total copolymer. Preferably, they should account for 10% by weight or less of by the copolymer. Thus, the essentially one active species should provide for at least 65% by weight of the total copolymer produced, preferably for at least 90"/o by weight thereof.
The extent to which a catalyst species contributes to the polymerization can be readily determined using the below-described techniques for characterizing catalyst according to the number of active catalyst species. Techniques for characterizing catalyst according to the number of active catalyst species are within the skill of the art.
These techniques are shown in Cozewith, C. and Ver Strate, G., "Ethylene-Propylene Copolymers.
Reactivity Ratios, Evaluation and Significance", MAmmolecules_ 4, 482 (1971),,~:
The preferred catalyst system in practicing processes in accordance with these embodiments comprises a hydrocarbon-soluble vanadium compound in which the vanadium valence is 3 to 5 and an organo-aluminum compound, with the provision that the catalyst system yields essentially one active catalyst as described above.
At least one of the vanadium compound/organo-aluminum pair selected must also contain a valence-bonded halogen. Vanadium compounds useful in practicing processes in accordance with the present invention could be:
WO 95/27746 21vp 723 3 - PGT/U895104250 O (1) VCIx(OR)3.x;
VC1x(COOR)3-x ; (2) where x 0 to 3 and R = a hydrocarbon radical;
VC14;
ii V(AcAc)z;
V(AcAc)3;
VCIX(AcAc)3.x; (3) where AcAc = acetyl acetonate; and where x=1 or 2; and VC13.nB;
where n = 2 to 3 and B = Lewis base capable of making hydrocarbon-soluble complexes with VC13, such as tetrahydrofuran, 2-methyl-tetrahydrofuran and dimethyl pyridine. In Fonmulas (1) and (2) above, R preferably represents a C, to Cla aliphatic, alicyclic or aromatic hydrocarbon radical such as ethyl (Et), phenyl, isopropyl, butyl, propyl, n-butyl, i-butyl, t-butyl, hexyl, cyclohexyl, octyl, naphthyl, etc.
Non-limiting illustrative examples of formulas (1) and (2) compounds are vanadyl trihalides, alkoxy halides and alkoxides such as VOCl3, VOCIz(OBu) where Bu = butyl, VO(OC2H5)3, and vanadium dichloro hexanoate. The most preferred vanadium compounds are VCl4, VOC13, and VOCIz(OR).
As already noted, the co-catalyst is preferably an organoaluniinum compound.
In terms of chemical formulas, these compounds could be as follows:
AIR3 Al(OR')Rz AIRlX R2AI-O-A1R2 AIRRX
AIRX2 methyl alumoxane where R and R' represent hydrocarbon radicals, the same or different, as desczibed above with respect to the vanadium compound formula and X is a halogen selected from the group consisting of bromine, iodine, and chlorine. Chlorine is preferred. The most preferred organoaluminum compound for use with a vanadium catalyst is an aluminum alkyl sesquichloride such as AL=Et3C13 or A1Z('iBu)3C13. The catalyst and its effects on the polymerization are disclosed in U.S. patent 4,882,406. _ With reference again to processes for making copolymer in accordance with our invention, certain combinations of vanadium and aluminum compounds that can comprise the catalyst system can cause branching and gellation during the polymerization for polymers containing high levels of diene. To prevent this from happening, Lewis bases such as ammonia, tetrahydrofuran, pyridine, tributylamine, tetrahydrothiophene, tetraalkoxysilane, etc., can be added to the polymerization system using techniques well known to those skilled in the art.
Chain transfer reactions during tubular reactor polymerization in accordance with our invention broadens polymer molecular weight distribution and causes the fornation of undesirable blocks such as A-only polymer or B-only polymer rather than the desired A B block copolymers of the present invention. It is desireable to operate at low temperature and in the absence of Hydrogen to avoid transfer reactions. U.S.
patent 4,882,406 discloses chain transfer reactions.' Molecular weight distribution and percent of block polymer in the final product are also affected by catalyst deactivation during the course of the polymerization which leads to termination of growing chains. Early chain tennination will reduce the yield of the desired block copolymers. Deactivation can be reduced by using the shortest residence time and lowest temperature in the reactor that will produce the desired monomer conversions.
Gel Permeation Chromatogaphy (GPC) and several analytical techniques are used to characterize the polymer and its performance in varlous applications.
These techniques have been described in several publications notably U.S. Patent No.
4,989,436.,;
Molecular weight and composition ~ts are described in G. Ver Strate, C.
Cozewith, S. Ju, Macromolecules. 21, 3360 (1988). The variety of other techniques used are soundly based in polymer structure characterization as descn'bed in "Structure Characterization" The Science and Technology of Elastomers, F. Eirich, editor, Academic Press 1978 Chapter 3 by G. Ver Strate. Differential scanning calorimetry (DSC) is used to characterize the block polymers described herein. The standard protocol for these analysis is to load the calorimeter at 20 C with a specimen free of molding strains, to cool the sample to -75 C, scan to 180 C at 10 C/min., cool to -75 C, and re-run the scan. Ti, T. and heat of fusion are evaluated. In some cases, low melting crystallinity will not be seen on the second scan as it may take many hours to develop even at low temperatures.
Catal, -sPreparation Polymerizations in accordance with the preferred embodiments should be conducted in such a manner and under conditions sufficient to initiate propagation of essentially all copolymer chains simultaneously. This can be accomplished by utilizing the process steps and conditions described in U.S. patent 4,959,436. 25 Reaction Tempgrjture The temperature of the reaction mixture should also be kept within certain limits.
The temperature at the reactor inlet should be high enough to provide complete, rapid chain initiation at the start of the polymerization reaction. The length of time the reaction mixture spends at high temperature must be short enough to minimize the amount of undesirable chain transfer and catalyst deactivation reactions. Control of the reaction temperature in light of the fact that the reaction is exothermic, is disclosed in U.S. patent 4,959,436., Residence Time Residence time of the reaction mixture in the mix-free reactor can vary over a wide range. The minimum could be as low as 0.5 seconds. A preferred minimum is seconds. The maximum could be as high as 3600 seconds. A preferred maximum is 900 seconds. The most preferred maximum is 300 seconds.
Process Flow When a tubular reactor is used the rate of flow of the reaction mixture through the reactor should be high enough to provide good mixing of the reactants in the radial direction and minimize mixing in the axial direction. Good radial mixing promotes homogeneous temperature and polymerization rate at all points in a reactor cross section. Radial temperature gradients may tend to broaden the molecular weight distribution of the copolymer since the polymerization rate is faster in the high temperature regions. Those of ordinary skill in the art will recognize that achievement of these objectives is difficult in the case of highly viscous solutions. This problem can be overcome to some extent through the use of radial mixing devices such as static mixers (e.g., those produced by the Kenics Corporation).
For purposes of illustration, we assume that a block copolymer of polyethylene and of ethylene and propylene (EP) copolymer is to be produced using as catalyst components vanadium tetrachloride and ethyl aluminum sesquichloride. The polymerization is adiabatic, using hexane diluent for both the catalyst system and the reaction mixture.
In a preferred embodiment, with reference to the process flow diagam in Figure 4, the premixing device 1 comprises a temperature control bath 2, a fluid flow conduit 3 and mixing device 4 (e.g., a mixing tee). To mixing device 4, are fed hexane solvent, vanadium tetrachloride and ethyl aluminum sesquichloride through feed conduits 5, 6 and 7, respectively. Upon being mixed in mixing device 4, the resulting catalyst mixture is caused to flow within conduit 3, optionally in the form of a coiled tube, for a time long enough to produce the active catalyst at the temperature set by the temperature bath.
The temperature of the bath is set to give the desired temperature in conduit 3, at the outlet of the bath. Upon leaving the premixing device, the, catalyst solution flows --- ---- ------------- -"n'nxc.wrroisz 2 .~ 8 7 2 3 3 through conduit 8 into mixing zone 9, where it is intinzately mixed with a stream contaicting hexane diluent and the monomer to be incarporated into the A
block, in this case ethyleno; and which is fed through conduit 10. Any sultable mixing device can be used such as mechanical mixer, orifice mixer or mixang tee. For economic reasons, the miocing tee is preferred. The residence time of the reactiion mixture in cnixing zone 9, is kept short enough to prevent significant potymer formation therein before being fed through conduit 11 to tubular reactor 12. A}terna#ively, streams 8 and 10 can be fed directly to the inlet of reactor 12, if the flow ratea are high enough to sccomplish the desired level of intimate mixing. Stream 10, the heatane with dissolved monomers, may be cooled upstream of mixing zone 9 to provide the desired feed temperature at the reactor inlet.
Tubular, reactor 12 is "wn with intecrnedi,ate feed points 13, 14, and 14a where additional monomers (e.g., ethylene and propylene) and/or hexane can be fed to the ls reactor for example, feeding at least a second monomer blend comprising an ethylene and an a-olefin, at a time of at least 0.1 seconds affter the above step. The additional feeds are used to control the composition of the block copolymer. The number of side feeds required and the spacing along the reactor length depends on final poiymer structure desired VVhile the rea.ctor can be operated adiabatically, external cooling means such as a cooling jacket surrounding at least a portion of the reaetor system 12, can be provided to maintain reaction mixture temperature vwithin desired limits.
Having thus described the above illustrotive rcactor system, it will readily occur to thase of ordinary skill in the art that many variaakiona can be made within the scope of the present inverrtion. For example, the placement and number of multiple feed sites, the choice of temperature profile during polymerization and the concentrations of reactants, can be varied to suit the end-use application.
Fynctjg iza ' n of the Bl k Cooolvmers The. polynacrs produced in accordance with the present invention can be functionalized, i.e., chemically modified, to have at least one functional group present within its structure, which funetional group is capable of: (1) undergoing further chemical reaction (e,g, daivatization) with other m,ateaiallor (2) imparting desirable properties not otherwise possessed by the polymer alone, absent chernical nwdiScation.
The fuwtional group can be incoTporated into tha hackbone of the polymer or can be attached as a pendant group from the polymer backbone. The functional group typicaUy AMENDED SHEET
will be polar and contain hetero atoms such as P, 0, S, N, halogen and/or boron. It can be attached to the saturated hydrocarbon part of the polymer via substitution reactions or to an olefinic portion via addition or cycloaddition reactions.
Alternatively, the functional group can be incorporated into the polymer by oxidation or cleavage of a small portion of the diene containing portion of the polymer (e.g., as in ozonolysis).
Useful functionalization reactions include: maleation, halogenation, "ene"
reactions, reactions with a phenol group, reaction at the point of unsaturation with carbon monoxide, reaction by free radical addition or abstraction and reaction by epoxidation or chloroamination.
As indicated, a functionalized polymer is one which is chemically modified primarily to enhance its ability to participate in a wider variety of chemical reactions than would otherwise be possible with the unfunctionalized polymer. In contrast, a derivatized polymer is one which has been chemically modified to perform one or more functions in a significantly improved way relative to the unfunctionalized polymer and/or the functionalized polymer. Representative of such functions are dispersancy and/or viscosity modification in lubricating oil compositions. The derivatized polymers can include the reaction product of the above recited functionalized polymer with a nucleophilic reactant, which includes amines; alcohols, amino-alcohols and mixtures thereof, to form oil soluble salts, amides, imides, oxazolines, reactive metal compounds and esters of mono- and dicarboxylic acids, and anhydrides. Suitable properties sought to be imparted to the derivatized polymer include especially dispersancyõ but also multifunctional viscosity modification, antioxidancy, friction modification, antiwear, antirust, anti-seal swell, and the like.
Ash-producing detergents can be made using the functionalized polymers of the present invention as exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with alkyl phenols, alkyl sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared from the functionalized olefin polymer of the present invention with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, and sulfur, white phosphorus and a sulfur halide, or phosphorothiotic chloride. Preferred ash-producing detergents which can be derived from the functionalized polymers of the present invention include the metal salts of alkyl sulfonic acids, alkyl phenols, sulfurized alkyl salicylates, alkyl naphthenates and other oil soluble mono- and dicarboxylic acids.
WO 95/27746 2 1 8 7 23' J PGT/[JS95/04250 ~...
The derivatized polymer compositions of the present invention, can be used as ashless dispersants in lubricant and fuel compositions. Various types of ashless dispersants can be made by derivatizing the polymer of the present invention and are suitable for use in the lubricant compositions. The following are illustrative:
1. Reaction products of functionaliaed polymer of the present invention derivatized with nucleophitic reagents such as amine compounds, e.g. nitrogen containing compounds, organic hydroxy compounds such as phenols and alcohols.
2. Reaction products of the polymer of the present invention functionalized with an aromatic hydroxy group and derivatized with aldehydes (especially formaldehyde) and amines especially polyalkylene polyamines, through the Mannich reaction, which may be characterized as "Mannich dispersants".
3. Reaction products of the polymer of the present invention which have been functionalized by reaction with halogen and then derivatized by reaction with amines (e.g. direct amination), preferably polyalkylene polyamines.
The functionalized polymers, particulariy acid functionalized polymers, of the present invention can be reacted with alcohols, e.g., to form esters.
Procedures are well known for reacting high molecular weight carboxylic acids with alcohols to produce acidic esters and neutral esters. These same techniques are applicable to preparing esters from the functaonalized polymer of this invention and the alcohols described above. The hydroxy aroniatic functionalized polymer aldehyde/amino condensates useful as ashless dispersants in the compositions of this invention include those generally referred to as Mannich condensates. A useful group of Mannich Base ashless dispersants are those formed by condensing phenol fimctionalized polymer with fonmaldehyde and polyethylene amines, e.g., tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxpropylene amines, e.g., polyoxyproylene diamine and combinations thereof.
A useful class of nitrogen containing condensation products for use in the present invention are those made by a "2-step process" as disclosed in U.S. Patent No.
4,273,891. Condensates made from sulfur-containing condensates are described in U.S.
Patent Nos. 3,368,972; 3,649,229; 3,600,372; 3,649,659; and 3,741,896 These patents also disclose sulfur-containing Mannich condensates. Useful reactive metals or reactive metal compounds are those which will form metal salts or metal-containing complexes with the functionalized polymer.
The polymer of the present invention may be used as a component of a synthetic base oil. The functionalized polymer, in addition to acting as intermediates for dispersant can be used as a molding release agent, molding agent, metal working lubricant, thickeners and the like. The additives of the present invention are primarily useful in lubrication oil compositions which employ a base oil in which the additives are dissolved or dispersed therein. Such base oils may be natural or synthetic.
Base oils suitable for use in preparing the lubrication oil composition of the present invention include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-ignited intemal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like.
Lubricating oil formulations containing the additives of the present invention conventionally contain other types of additives that contribute other characteristics that are required in the formulation. Typical of such other additives are detergent/'inhibitors, viscosity modifiers, wear inhibitors, oxidation inhibitors, corrosion inhibitors, friction modifiers, foam inhibitors, rust inhibitors, demulsifiers, lube oil flow improvers, and seal swell control agents, etc.
APPLICATIONS
Use in Lubricatinst Oils The novel block copolymers of the invention may be used as viscosity modifiers or with suitable functionalization and/or derivatization, as multifunctional viscosity modifiers, and as dispersants, for lubricating oils. This is especially true for block polymers where there is a diene in the A block, and the polymers are in turn coupled to form a nodular polymer. From studies of hydrogenated block polymers of polyisoprene and polybutadiene, those of ordinary skill in the art are aware that such structures lead to good viscosity-temperature behavior (Ver Strate, G., Struglinski, M., "Polymers as Rheology Modifiers," Schulz, D. & Glass, J., ed. ACS Symp. 462, p. 257, 1991).
Use of block copolymers are disclosed in. U.S. patent 4,959,436, -With further modification such block copolymers are usefuI as multifunctional viscosity modifiers as disclosed in U.S. Patent No. 5,210,146.;
Copolymer products made in accordance with the present invention when dissolved in oil have excellent low temperature properties which makes them suitable for lube oil applications. Accordingly, lube oil compositions made in accordance with the present invention preferably have a IVyni Rotary Viscosity (MRV) measurement in centipoise (cps) at -25 C according to ASTM D 3829 of less than 30,000. A more prefened MRV is less than 20,000, with less than 10,000 being most preferred.
Other Uses of Block Co~olMers Plastics Blendinst Impact modification of thermoplastics is commonly achieved by forming a rubber/plastic blend composition. For this application, it is desirable to have rubber that is in pellet form. This is accomplished in the case of ethylene/propylene rubbers by adjusting the polymer composition so that it is rich enough in ethylene content to be semicrystalline. At that composition (- 70 weight percent ethylene) the glass transition temperature of the polymer is raised by some 10 C above its value of -55 C at 45 weight percent ethylene. Because of this elevated Tg and raised modulus due to crystallinity, the blend of polypropylene and EP does not have its optimum lowest ductile-brittle transition. By preparing the polymer of this invention, it is possible to render the polymer pelletizeable via the PE blocks with the elastomeric B block having low T.
which gives optimum low temperature properties. In impact modified blends of high density polyethylene or of polypropylene which can be used in film or other finished goods, it is advantageous to have an agent which stabilizes the morphology of the thermoplastic/rubber blend. Polymers of this invention exhibit compatibilizer activity in such blends. A given small particle size can be obtained with reduced mixing energy and with their morphology stabilized against ripening or coarsening.
Fuel and Heating Oils Fuel and heating oils contain wax which plugs pipes and filters if the wax crystallizes into anisotropic needles or platelets. The polymers of this invention with an oil soluble B block and a PE A block which nucleates wax crystallization cause granular crystals to form when added to waxy fuels or heating oil , which crystals do not plug the delivery system.
Hot Melt Adhesives Block polymers are employed in hot melt adhesives. Heretofore, it has not been possible to obtain polyethylene/propylene polymers with softening points above which also maintains a low Tg. PE/EP block polymers of this invention can provide such perfonmance.
Bitumen Modification The bitumen employed in asphalt paving flows during service leading to "rutting"
on highways. This problem can be eliminated by incorporating polymers to provide resilience. The polymers of the present invention are useful in this application as they can be supplied as pellets or crumbs. Once in the asphalt, the PE blocks provide reinforcement and physical crosslinks to give the binder an elastic network-like response.
The preferred embodiment of the present invention and the preferred methods of maldng and using it have been detailed above. Those reading the embodiments should understand that the above description is illustrative, and that other embodiments of the invention can be employed without departing from the full scope of the invention as set forth in the claims that follow.
The invention is further described by the following examples:
Prgparation of Uncoupled Block Polymers x 1 1 Polymerization was carried out in a 0.793 cm diameter tubular reactor with hexane as the reaction diluent. The reactor contained a series of feed inlets along its length. In this example, A B block polymers are formed. The A block is polyethylene (PE) and in runs 1A and 1B the B block is an ethylene/propylene copolymer (EP). These polymers were produced using VC 14 catalyst and A12Et3C 13 (EASC) co-catalyst.
The catalyst and co-catalyst were fed into a mixing tee as dilute solutions in hexane at a temperature of 10 C. After mixing, the combined catalyst components flowed through a tube with a residence time of 10 seconds at 10 C before entering the reactor. The monomer feed to the reactor inlet was a solution of ethylene in hexane at 20 C
which was mixed with the catalyst stneam to start the polymerization. The reactor was operated adiabatically so that temperature increased along its length.
After a residence time of 0.024 minutes, during which the block A
(polyethylene) was formed, a feed of ethylene and propylene dissolved in hexane was added via a sidestream injection point to begin polymerization of the B block. Two more ethylene-propylene side feeds were added at residence times of 0.064 and 0.1 minutes to increase the length of the B block. The polymerization was quenched with isopropanol at the end of the reactor. The final reaction temperature was 22 C.
In Examples lA and 1B no diene was used and the polymerization was quenched at 0.14 niin. The reaction conditions of polymerizations 1A and 1B are shown in Table 1.
Runs IA and 1B
A number of polymerization experiments were carried out at the conditions used in runs 1A and 1B, but with a polymerization quench injected into the reactor at a residence time of 0.024 min. so that only polyethylene was produced. From the amount of polymer collected in a known period of time, it was deterniined that close to 100% of the ethylene fed to the reactor in the main flow had reacted to form polyethylene. Thus in Examples 1A and 1B, the rate at which the polyethylene A block is produced is equal to the feed rate of ethylene in the main flow. The rate at which the elastomeric B block is produced can be found by subtracting the A block production rate from the measured total polymerization rate. The percentages of A and B block in the polymer are then calculated by dividing the respective polymerization rates of these blocks by the total polymerization rate. The average ethylene content of the polymer is equal to the ethylene content of the A block, which is 100%, times the fraction of the A
block in the polymer, plus the ethylene content of the B block times the fraction of B
block in the polymer. Thus the ethylene content of the B block can be calculated from the measured average ethylene content of the whole polymer and the polymerization rates from the equation:
Ethylene content of B block, weight percent = (average polymer %
ethylene content - 100 x weight fraction of A block in the total polymer)/weight fraction of B block in the total polymer (all terms are in weight units) The ethylene content of the entire polymer was determined by infrared spectroscopy using the calibration described in I. J. Gardner, C. Cozewith, and G.
Ver Strate, Rubber Chemistrv and Technoloav, vol. 44, 1015, 1971.
The calculated polymer composition is shown in Table 2 along with other measurements of the polymer structure (GPC and DSC). Of particular note is the narrow MWD of the polymers.
Tensile properties of the polymers produced were determined in the following manner. A sheet of polymer 15x 15x0.2 cm was prepared by compression molding for 15 minutes at 150 C. An aluminum mold was used with Teflon coated aluminum foil used as a release agent. Dumbbell-type specimens were die cut from the sheet.
These specimens in tura were strained in tension at a crosshead speed of 12.5 cm/min. Initial jaw separation was 5 cm. with 3.3 cm of the specimen undergoing most of the deformation between the fiducial marks. Data were collected at 20 C.
Engineering modulii were calculated as force at a given percent elongation divided by the original unstrained specimen cross-sectional area.
Table 3 shows the modulii and tensile strength of the polymer for runs IA and lB.
The mechanical properties are a function of molecular weight and the polyethylene block content. The modulus of the polymer containing the larger amount of PE block (lA) are slightly higher than that with a somewhat lower polyethylene block content (1B).
ExMIe 2 A second series of polymerization runs were conducted following the procedures outlined in Example 1. The initial monomer feed to the reactor contained only ethylene to produce the polyethylene A block, two side stream feeds were then added to make the B block. A final feed was introduced with a high ethylene content to produce a semi-3 5 crystalline EP segment at the end or tip of the B block. Reaction conditions for runs 2A
and 2B are shown in Table 1. In example 2A, a higher initial ethylene feed rate was used than in Example 2B to give the polymer a higher molecular weight and a greater percentage of A block.
These polymers were characterized in a manner similar to the polymers produced in Example 1. The results of these analyses are listed in Table 2. The semicrystalline end segment of the B block of Example 2A averaged 72.2 weight percent ethylene, while the semicrystalline end segment of the B block of Example 2B averaged 70 weight percent ethylene. DSC analysis of the polymers, as shown in Figures 1 and 2, show that the polymers contain a semi-crystalline firaction melting at 42 C in addition to a polyethylene fraction which melts at 122 to 124 C. The modulii and tensile strength of the polymers for runs 2A and 2B are shown in Table 3.
EmMle 3 A polymerization was carried out by the procedure in Example 1 using the reaction conditions as shown in Table 4(samples 3A and 3B). The diene, ENB, was added to the main reactor feed to produce a polymer containing ENB in the PE
block.
Ethylene and propylene feeds were added to the reactor at residence times of 0.024 and 0.066 min. ENB feed rates were 2.8 and 1.7 g/hr. and the corresponding polymers contained 0.333 and 0.14 weight percent ENB. These polymers when coupled are useful as lubricating oil viscosity modifiers.
EaMle 4 In this example, a number of A B block polymers made by the procedure in Example 1 but over a broad range of reaction conditions, are tested for solubility in hexane at 22 C. The purpose of this testing is to determine how much B block is unconnected to an A block. The composition and molecular weight of the polymers vary widely. Solubility is determined by pressing 2.0 g of the block polymer onto a 20 mesh screen and immersing the polymer and screen in 200 cc of n-hexane. Wide-mouthed bottles were used and were occasionally swirled over a period of 3 to 5 days.
The screen is removed and dried to constant weight in a vacuum oven to determine the amount of insoluble polymer. The hexane supernatant liquid is evaporated to dryness and the residue is weighed to measure the amount of soluble polymer. The sum of the two fractions showed 100% of the starting polymer is accounted for.
_ 28 _ A control sample of a high density polyethylene which was melt blended with EPDM in a BrabenderImixing head at 180 C was also extracted in the same manner.
These results are presented in Table 5. In the control blend, all 40% of the EPDM was extractable, showing that the rubber is soluble, even at high PE block content, if it is not attached to a PE block. An infrared analysis showed the soluble material to be over 98%
EPDM. PE is not extracted. All of the block polymers of Table 5 show soluble rubber of less than 25%.
Examnle 5 rophetic Example) In this example analyses for PE block content and yield of A B block polymer as a percentage of the total product is described. Three A B block copolymers with a diene containing segment in the A block, are produced by the procedure described in Example 1. Nearly 100% of the ethylene has reacted by the time that the first ethylene/propylene side stream feed is added to make the elastomeric B block. Thus, the weight percent of A block in a polymer can be estimated by dividing the ethylene feed rate in the main flow to the reactor inlet by the total polymerization rate. We can also estimate the amount of A block by dividing the heat of fusion measured by DSC over the melting range of 80 C
to 135 C, by the heat of fusion measured by DSC for a pure polyethylene A
block of approximately the same molecular weight, as shown in Figure 3, made by adding only an ethylene feed to the reactor. A value of 181 J/g. is used for the heat of fusion of polyethylene based on averaging the results from a number of samples.
The polymer samples are fractionated in a Kumagawa apparatus. In this apparatus an individual sample is sequentially extracted with a series of solvents of increasing boiling point. For each solvent continuous extraction is carried out until all soluble polymer is dissolved. The solvents used and their boiling points (bp) were: n-hexane (bp=69 C), cyclohexane (bp=81 C), n-heptane (bp= 98 C), and toluene (bp=
111 C). The polymer soluble in each solvent is recovered, weighed, and analyzed by DSC. By determining the amount of polymer soluble in each solvent and the amount and percentage of PE block in that soluble portion, the percentage of the portion that was non-crystalline EP block can be calculated.
Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the 2l~ ~2 preferred versions contained herein.
MAIN FLOW g/h hexane 53803 53803 5380:3 53803 :L O propylene 0 0 0 0 ethylene 151 124 151 73 VC14 1.8 1.5 2.4 2.4 Al/V mol/mol 8 8 8 8 1.5 SIDE STREAM 1, g/h hexane 8910 8910 8910 8910 propylene 1228 1354 1125 1125 ethylene 110 148 122 122 SIDE STREAM 2, g/h 2 0 hexane 6138 6138 5910 5910 propylene 358 509 413 413 ethylene 85 110 130 130 SIDE STREAM 3, g/hr hexane 6217 6217 7920 7920 2 5 propylene 347 405 510 510 ethylene 80 108 255 255 TEMPERATURE, C
feed 20 20 19 19 reactor outlet 22 22 25 24 30 RESIDENCE 'ITME, min.
to side stm,am 1 0.024 0.024 0.024 0.024 to side stream 2 0.064 0.064 0.109 0.109 to side streem 3 0.10 0.10 0.147 0.147 to side stream 4 35 Total 0.139 0.139 0.183 0.183 PROCESS RESULTS
wt % C2 in polymer 71.6 70.8 72.2 70.1 wt % ENB in polymer 0 0 0 0 Mooney(1+4, 150 C) 109 91.1 114 131 40 Mw x 10-3 189 246 222 209 Mn x 10-3 108 149 115 106 Mw/Mn 1.67 1.7 1.91 1.99 Poly Rate, g/h 387 368 689 597 C2=conv % 65 54.8 75.6 72.2 45 C3=conv =, % 5.7 4.4 9.4 8.7 Cat efl;g poly/g VC14 215 245.3 297 249 ' conv = conversion . .;:: ::. ,: .::::. .=.:
. .... . . = . .., ..::.,=..,~,=: =.,:::; ::.>F<::.:~., ., .. . . . :;.,.. .
~~
; ' ~;=< ~.. :. .,= = :<c =:. .. : ::<.
,:.,=: =:.,, ,. r:." , ;.,,:,.;.',+.: ii;.=,'''~.,i,.i,d:<'' ;%:=::
Poly rate A block, g/hr 151 124 151 73 Poly rate B block, glhr 236 244 319 355 Poly rate C block, g/hr 0 0 259 265 A block, wt % 39.0 33.7 20.7 10.5 B block, wt % 61.0 66.3 43.7 51.2 C block, wt % 0 0 35.5 38.2 wt % C2= in whole 1 er 71.6 72.9 72.2 70.1 wt % C2= in B block before final 53.4 59.1 59.0 63.9 feed wt % C2= in B block after fuwi feed 72.2 70.1 wt % ENB whole polymer wt % ENB in EPDM ent ~"~rPC::><? :::' :
Mw x 10-3 189 246 221 209 Mn x 10-3 108 149 115 106 Mw/Mn 1.67 : .7 1.91 1.99 A block, J/g 48 33 29.2 21.3 B block, J/ 0.82 3.59 4.14 Wt. % soluble in n-hexane 2.3 2.6 :; .:...:....:::::::::.::.., :.; . ,.,, . .,:=::<..::.::>L.::~::.:~:.:<:
:................ .
,:.. . :. :::::.......... .y:
. . , : ::::. = .
=: ,.,.~.:..; =tS.::.',.i5;.'= ': i~f ..=~. ~ ~=7,.:~: ...::=::=::.; =: ~';:::~:~:::;<::; :
..:~7~~i?+:::: ;?f:.'=:~:[ki~'i;;ii '?~~:~a7i:':'i'ii 100% MODULUS, MPa 2.4 2.3 2.7 2.2 TENSII.E STRENGTH AT BREAK, 3.5 9.7 15.4 5.4 MPA
EXTENSION AT BREAK, % 780 1220 1090 740 WO 95/27746 2 8 7 23~ PCT/US95/04250 ~.
TABLE 4 (Example 3) . . : . . .. :.....:::... . . .: .:.: ,. ..; .. . .
' ~~ . '~
=.~
.... ......:..~...:=::....{i::: ' . .. : ::: . ..~ .: :..::::... ..
:'' . =. :.:. ~ a ......;.:...
N<=:
v . .. .:. ...... . . .: . ...::................... ......................
.............
hexane 53605 53526 propylene 0 0 ethylene 253 253 diene 2.8 1.71 catalyst 3.36 3.36 AIN, mol/mol 7 ........
~14~~"~'REJRIM:.~ . ;::,:.:.<.;::<.:::>:.:= .:.:..::.::.::<:>::;>:;:;: ::>::;
hexane 6692 6692 propylene 1234 1234 ethylene hexane 9900 9900 propylene 468 471 ethylene 112 112 hexane propylene ethylene ENB
,.......
E~l: ::. S :;::>:
..... .................... ..
Reactor feed, C 20 20 Reactor outlet, C 31 31 a~3~kEt~CE TtM mEn to side stream 1 0.024 0.024 to side stream 2 0.066 0.066 to side stream 3 Total 0.142 0.142 _ ...:..
PR~JC0S REgULTS
..::.. .
Wt. % C2=in polymer 73.2 71.5 Wt. % ENB in polymer 0.33 0.14 Mooney 1+ 4, 150 C 51 49.8 A Block, % of polymer Poly Rate, g/h 592.5 604 C2= aonv, % * 90.8 90.6 C3= conv, % * 9.3 10.1 ENB conv, % * 69.8 49.5 Cat eff, I/ VCI 176.4 179.8 *conv = conversion 32 _, Run Wt. % C2= Mn x 10-3 Mw x 10-3 Hexane soluble, in Pol . %
317a 68 75 139 12.1 317b 68 ~ 97 193 13.0 317c 71 118 228 4.9 317d 69 92 189 12.5 318a 63 69 118 22.1 318b 62 62 118 23.5 318c 64 88 208 16.6 318d 66 92 179 16.9 319a 66 108 160 13.2 319c 68 108 230 7.8 320a 71 108 206 4.1 320c 70 128 237 3.3 323a 72 137 289 2.9 323b "71~y_~_ 152 307 2.2 332a 68 149 258 11.3 333a 68~~~ 104 212 7.7 334a 69 126 :195 4.9 334b 67117 178 8.0 335a 66 M~ 94 343 10.1 335b 70 - 6.5 336a 69 15.2 336d 6f, ~ 19.0 336e 69 74 147 3.7 338b - - 6.0 60% HDPE/ 39.6 40% EPDM
40 !o HDPE/ 610 60% EPDM
B junction.
Y is a coupling agent which has reacted with the residual olefinic functionality in the block polymers and has coupled two or more block polymer molecules.
A is a crystalline block and B has elastomeric segments. B may optionally contain a low level of crystallinity.
COPOLYME ,L~B AICKS
BI,OCK...~
Block A comprises polyethylene which optionaHy may contain up to 10 mole percent of a non-conjugated diene (based on the total moles of the monomers of the A B
copolymer). The A block may optionally contain an a-oleSn comonomer at a level not exceeding 5 mole percent based on the total moles of the monomers of the A
block. If block A contains a non-conjugated diene it will be present in the A block preferably in the range of from 0.01 to 5 mole percent, more preferably in the range of from 0.03 to 2 mole percent, most preferably in the range of from 0.05 to 1 mole percent based on the total moles of the monomers of the A B block copolymer. Block A comprises 5 to 90 weight percent of the entire polymer, preferably 10 to 60 weight percent , most preferably 20 to 50 weight percent of the entire polymer. The A block has a T.
of at least 110 C, preferably at least 105 C, more preferable at least 120 C.
BLOCK B
Block B is an elastomer that comprises an ethylene and an a-olefin copolymer.
Block B optionally has an intramolecular-compositional distribution such that at least two portions of the B block, each of said portions comprising at least 5 weight percent of said B block, differ in composition by at least 5 weight percent ethylene.
Intramolecular-compositional distribution is the compositional variation, in terms of ethylene, along the polymer chain or block. It is expressed as the minimum difference in _$_ average ethylene composition in weight percent of ethylene that exists between two portions of a single block, each portion comprising at least 5 weight percent of the block. Intramolecular-compositional distribution is determined using the, procedures disclosed in U.S. Patent No. 4,959,436, The B block comprises 95 to 10 weight percent of the total weight of the block copolymer, preferably 90 to 40 weight percent; more preferably 80 to 50 weight percent.
The B block comprises one or more segments. If there are two or more segments in the B block, the tip or end segment fiuthest from the junction of the A block and the B block will comprise an ethylene, a-olefin copolymer with an average ethylene content of at least 60 mole percent based on the total moles of the monomers of the tip segment. The tip segment melts in the range of from 35 C to 130 C as measured by DSC
The tip of the B block can comprise up to 50 weight percent of the B block, preferably in the range of from 3 to 20 weight percent, more preferably in the range of from 5 to 15 weight percent, all weight percents of the tip based on the total weight of the B block. The tip segment, when present, is typically the segment furthest from the A
B junction.
The B block can comprise an average ethylene content in the range of from 20 to 90 mole percent, preferably in the range of from 30 to 85 mole percent, and most preferably in the range of from 50 to 80 mole percent based on the total moles of the monomers of the B block.
The block copolymers of the invention are fiarther characterized in that they have a number average molecular weight of between 750 and 20,000,000, and have a molecular weight distribution characterized by a Mq,/Mn ratio of less than 2.5. The block copolymers have an n-hexane soluble portion, at 22 C not exceeding 50 weight percent, preferably not exceeding 40 weight peroent, and more preferably not exceeding 30 weight percent, based on the total weight of the block copolymer. The products of the present invention are further characterized by a relatively small amount of polymer chains in the final product that contain only an A block or only a B block.
The presence of such materials could detract from overall product properties. A typical characteristic WO 95/27746 PCT/Us95/04250 21$723 3-of the preferred product of this invention is that the block copolymer contains at least 50 % (weight) of the desired A B structure as polymerized. Product purification is not necessary to obtain good properties.
Monomers Alpha-olefins particularly useful in the practice of this invention are those having from 3 to 8 carbon atoms, e.g. propylene, butene-l, pentene-I, etc. Alpha-olefins of 3 to 6 carbon atoms are preferred due to economic considerations. The most preferred a-olefin is propylene.
Typical non-limiting examples of non-conjugated dienes useful in the practice of this invention are:
(a) straight chain acyclic dienes such as: 1,4-hexadiene; 1,6-octadiene;
(b) branched chain acyclic dienes such as: 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dirnethyl-1,7-dioctadiene; and the mixed isomers of dihydromyrcene and dihydro-ocinene;
(c) single ring dienes such as: 1,4-cyclohexadiene; 1,5-cyclooctadiene; and 1,5-cyclododecadiene;
(d) multi-ring fixed and fused ring dienes such as: tetrahydroindene;
methyltetra-hydroindene; dicyclopentadiene; bicyclo-(2,2,1)-hepta-2, 5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-propenyl-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, vinyl norbornene, and norbornadiene.
Of the non-conjugated dienes useful in the practice of the invention, dienes containing at least one of the double bonds in a strained ring are preferred.
The most preferred dienes are 5-ethylidene-2-norbornene and vinyl-norbornene.
Conjugated dienes are also contemplated.
-Polymerization The novel polymers of our invention are prepared by polymerization in a mix-fiee reactor similar to that taught in U.S. Patent No. 4,959,436.
Previously, those of skill in the art thought that a solution polymerization process such as that taught in U.S. Patent No. 4,959,436 would not be suitable for producing block copolymers such as the ones described above in which one of the blocks, polyethylene, is insoluble in the solvent. The insolubility could lead to reactor fouling and mass transport problems. In turn, these problems could prevent the fonmation of the desired well-defined polymer structure and significantly reduce catalyst efficiency.
Surprisingly, we have found that the block polymers of our invention can be made in a mix-free reactor when the initial monomer feed consists essentially of ethylene, and optionally such that up to 5 mole percent of the A block is alpha olefin and optionally a diene sufficient to incorporate up to 10 mole percent of a non-conjugated diene (based on the total of the monomers of the block copolymer). This, the A
block, is.
polymerized first. During this part of the reaction, the polyethylene (A) block may be only partially soluble in the reaction diluent and the insoluble polymer block forms a suspension in the diluent.
Once the polymerization of the A block is substantially complete, one or more additional monomer feeds are introduced into the reactor containing ethylene, and an a-olefin. The reaction of the comonomer mixtures forms the B block of the block polymer or the first segment of the B block if there is more than one segment. The B
block is polymerized onto the polyethylene or A block formed earlier. When this second part of the polymerization occurs, there is a noticeable change in the appearance of the reaction medium. As the chains become solubilized through the addition of the B block, the turbidity of the medium decreases appreciably and the quantity of polymer particles in the diluent is markedly reduced. When a tubular reactor is employed, several monomer feeds along the reactor length may be used to control the composition and amount of the B block and form the segments of the B block. The final feeds to the reactor may contain a higher ethyleneJa-olefin ratio to form a semi-crystalline segment at the tip of the B block., giving the B block a melting point in the range of from 35 to 130 C.
QwAn the pOlymets Block polymers of our invention may incorporate a diene. The residual olefinic functionaiity in diene containing block polymers can be reacted with coupling agents to produce novel nodular polymers.
Suitable coupling reagents and coupling techinques are described in U.S.
Patent 4,882,406r Coupling can take place either within the polymerization reactor or in a post-polymerization reaction. With the diene in the A
block, the polyethylene segment containing the diene is in a central polyethylene nodule with EP block extending outwards.
There are various coupling agents that are capable of reacting with the residual unsaturation in the polymer chains to cause coupling of two or more block polymer molecules.
. Coupling may be carried out with cationic catalysts such as Lewis acids.
Suitable Lewis acids may be selected from the group consisting of: AIX3, BX3, SnX4, SbXs1 AI1YX3õy where y is 0 to 1.5 and R is a hydrocarbon radical, BX4, TiX4 and mixtures thereof, where X is selected from the group consisting of chlorine, bromine, and iodine.
Chlorine is prefeired. For Lewis acids that do not interfere with the functioning of the catalyst system used to cany out the polymeriaation, the Lewis acid can be added directly to the reactor so that chain coupling oceurs at the same time as the polymerization. Alternately the coupling agent can be added following the polymerization.
According to yet another embodiment the coupling agent may be a free radical catalyst. The free radical catalyst may be a peroxide selected from the group consisting of: dicumyl peroxide, di-tertiarybutylperoxide, t-butylperbenzoate, 1,1-di(t-butylperoxy)-3,3,5-trimethyl cyclohexane, and mixtures thereof Other free radical catalysts include azo-bisisobutylnitrile, azodicarboxylate, and mixtures thereof.
Peroxides can couple non-diene containing portions of the chain and produce a cross-linked network. Care must be taken when they are used as coupling agents.
In yet another embodiment the coupling agent may be selected from the group consisting of sulfur dichloride, disulfenyl halides, borane, dithoalkanes, other sulfur and accelerated sulfur curatives and mixtures thereot such as mercaptobenzothiozole, tetramethyltlnuram disulfide, and butyl zymate. It is apparent that any of the conventional vulcanization systems useful for EPDM may be employed.
Resins and other reagents may also be employed for coupling. For example alkyl phenol fonmaldehyde mixtures will couple olefins in certain cases with catalysts such as ZnClz , N bromosuccinimide or diphenylbromomethane.
Also contemplated as a coupling mechanism is the use of irradiation or electron beams.
For certain non-conjugated dienes, such as norbomadiene, vinyl norbomene, dicyclopentadiene and tetrahydroindene, both double bonds are polymerizable to a greater or lesser extent by the polymerization catalysts of this invention.
With dienes of this type chains can become cheniically coupled to each other during polymerization by reaction of the remaining double bond in an enchained diene monomer with a growing chain. This process will lead to coupling of chains in the reactor even in the absence of a coupling agent Y.
The efficiency of olefin utilization will detenmine what level of coupling agent to use in relation to the amount of diene in the block copolymer. The purpose is to couple the diblocks to an extent which yields good mechanical properties but does not raise viscosity or produce gel to the extent that the coupled product is not processable.
The Reaction Solvent Processes in accordance with the present invention produce copolymers by polymerization; of a reaction mixture comprised of catalyst, ethylene and at least one additional a-olefin monomer and optionally diene. Polymerization in the presence of a diluent which has the capability to dissolve a major portion of the final product is preferred. Suitable solvents are described in U.S. patent number 4,882,406.
Polvmerization Reactor These processes are carried out in a mix-free reactor system, which is one in which substantially no mixing occurs betwean portions of the reaction mixture that contain polymer chains initiated at different times. Suitable reactors are disclosed in U.S. patents 4,959,436 and 4,882,406r Additional reaction considerations are also disclosed in these references.
To obtain the desired A B block polymer, it is necessary to add additional reactants (e.g., at least one of the monomers ethylene, a-olefin or diene) either at some point or points along the length of a tubular reactor, or during the course of polymerization in a batch reactor, or at various points in a train of continuous flow stirred reactors. However, it is also preferred to add essentially all of the catalyst at the inlet of a continuous flow reactor or at the onset of batch reactor operation to meet the requirement that essentiaUy all polymer chains are initiated simultaneously.
To make diene containing block polymers, diene is fed at the reactor inlet to incorporate diene into an A block. IViultiple feeds of ethylene and propylene can be used to control the amount and composition of the segments in the B block.
Since the tubular reactor is the prefenred reactor system for carrying out processes in accordance with the prefened embodiment, the illustrative descriptions and examples that follow are drawn to that system, but will apply to other reactor systems as will readily occur to those of ordinary skill in the art having the benefit of the present disclosure. However, as would readily occur to those of ordinary slcill in the art having the benefit of the present disclosure, more than one reactor could be used, either in parallel, or in series with multiple monomer feeds to vary intramolecular composition.
The Catalvst The composition of the catalyst used to produce ethylene, a-olefin copolymers has a prof embodiment should be such as to yield essentially one active catalyst species in the reaction mixture. More specifically, it should yield one primary active catalyst species which provides for substantially aU of the polymerization reaction. Additional active catalyst species could be present, provided that they do not produce a significant amount of polymer which detracts from the performance of the polymer produced. Such additional active catalyst species may provide as much as 35% by weight of the total copolymer. Preferably, they should account for 10% by weight or less of by the copolymer. Thus, the essentially one active species should provide for at least 65% by weight of the total copolymer produced, preferably for at least 90"/o by weight thereof.
The extent to which a catalyst species contributes to the polymerization can be readily determined using the below-described techniques for characterizing catalyst according to the number of active catalyst species. Techniques for characterizing catalyst according to the number of active catalyst species are within the skill of the art.
These techniques are shown in Cozewith, C. and Ver Strate, G., "Ethylene-Propylene Copolymers.
Reactivity Ratios, Evaluation and Significance", MAmmolecules_ 4, 482 (1971),,~:
The preferred catalyst system in practicing processes in accordance with these embodiments comprises a hydrocarbon-soluble vanadium compound in which the vanadium valence is 3 to 5 and an organo-aluminum compound, with the provision that the catalyst system yields essentially one active catalyst as described above.
At least one of the vanadium compound/organo-aluminum pair selected must also contain a valence-bonded halogen. Vanadium compounds useful in practicing processes in accordance with the present invention could be:
WO 95/27746 21vp 723 3 - PGT/U895104250 O (1) VCIx(OR)3.x;
VC1x(COOR)3-x ; (2) where x 0 to 3 and R = a hydrocarbon radical;
VC14;
ii V(AcAc)z;
V(AcAc)3;
VCIX(AcAc)3.x; (3) where AcAc = acetyl acetonate; and where x=1 or 2; and VC13.nB;
where n = 2 to 3 and B = Lewis base capable of making hydrocarbon-soluble complexes with VC13, such as tetrahydrofuran, 2-methyl-tetrahydrofuran and dimethyl pyridine. In Fonmulas (1) and (2) above, R preferably represents a C, to Cla aliphatic, alicyclic or aromatic hydrocarbon radical such as ethyl (Et), phenyl, isopropyl, butyl, propyl, n-butyl, i-butyl, t-butyl, hexyl, cyclohexyl, octyl, naphthyl, etc.
Non-limiting illustrative examples of formulas (1) and (2) compounds are vanadyl trihalides, alkoxy halides and alkoxides such as VOCl3, VOCIz(OBu) where Bu = butyl, VO(OC2H5)3, and vanadium dichloro hexanoate. The most preferred vanadium compounds are VCl4, VOC13, and VOCIz(OR).
As already noted, the co-catalyst is preferably an organoaluniinum compound.
In terms of chemical formulas, these compounds could be as follows:
AIR3 Al(OR')Rz AIRlX R2AI-O-A1R2 AIRRX
AIRX2 methyl alumoxane where R and R' represent hydrocarbon radicals, the same or different, as desczibed above with respect to the vanadium compound formula and X is a halogen selected from the group consisting of bromine, iodine, and chlorine. Chlorine is preferred. The most preferred organoaluminum compound for use with a vanadium catalyst is an aluminum alkyl sesquichloride such as AL=Et3C13 or A1Z('iBu)3C13. The catalyst and its effects on the polymerization are disclosed in U.S. patent 4,882,406. _ With reference again to processes for making copolymer in accordance with our invention, certain combinations of vanadium and aluminum compounds that can comprise the catalyst system can cause branching and gellation during the polymerization for polymers containing high levels of diene. To prevent this from happening, Lewis bases such as ammonia, tetrahydrofuran, pyridine, tributylamine, tetrahydrothiophene, tetraalkoxysilane, etc., can be added to the polymerization system using techniques well known to those skilled in the art.
Chain transfer reactions during tubular reactor polymerization in accordance with our invention broadens polymer molecular weight distribution and causes the fornation of undesirable blocks such as A-only polymer or B-only polymer rather than the desired A B block copolymers of the present invention. It is desireable to operate at low temperature and in the absence of Hydrogen to avoid transfer reactions. U.S.
patent 4,882,406 discloses chain transfer reactions.' Molecular weight distribution and percent of block polymer in the final product are also affected by catalyst deactivation during the course of the polymerization which leads to termination of growing chains. Early chain tennination will reduce the yield of the desired block copolymers. Deactivation can be reduced by using the shortest residence time and lowest temperature in the reactor that will produce the desired monomer conversions.
Gel Permeation Chromatogaphy (GPC) and several analytical techniques are used to characterize the polymer and its performance in varlous applications.
These techniques have been described in several publications notably U.S. Patent No.
4,989,436.,;
Molecular weight and composition ~ts are described in G. Ver Strate, C.
Cozewith, S. Ju, Macromolecules. 21, 3360 (1988). The variety of other techniques used are soundly based in polymer structure characterization as descn'bed in "Structure Characterization" The Science and Technology of Elastomers, F. Eirich, editor, Academic Press 1978 Chapter 3 by G. Ver Strate. Differential scanning calorimetry (DSC) is used to characterize the block polymers described herein. The standard protocol for these analysis is to load the calorimeter at 20 C with a specimen free of molding strains, to cool the sample to -75 C, scan to 180 C at 10 C/min., cool to -75 C, and re-run the scan. Ti, T. and heat of fusion are evaluated. In some cases, low melting crystallinity will not be seen on the second scan as it may take many hours to develop even at low temperatures.
Catal, -sPreparation Polymerizations in accordance with the preferred embodiments should be conducted in such a manner and under conditions sufficient to initiate propagation of essentially all copolymer chains simultaneously. This can be accomplished by utilizing the process steps and conditions described in U.S. patent 4,959,436. 25 Reaction Tempgrjture The temperature of the reaction mixture should also be kept within certain limits.
The temperature at the reactor inlet should be high enough to provide complete, rapid chain initiation at the start of the polymerization reaction. The length of time the reaction mixture spends at high temperature must be short enough to minimize the amount of undesirable chain transfer and catalyst deactivation reactions. Control of the reaction temperature in light of the fact that the reaction is exothermic, is disclosed in U.S. patent 4,959,436., Residence Time Residence time of the reaction mixture in the mix-free reactor can vary over a wide range. The minimum could be as low as 0.5 seconds. A preferred minimum is seconds. The maximum could be as high as 3600 seconds. A preferred maximum is 900 seconds. The most preferred maximum is 300 seconds.
Process Flow When a tubular reactor is used the rate of flow of the reaction mixture through the reactor should be high enough to provide good mixing of the reactants in the radial direction and minimize mixing in the axial direction. Good radial mixing promotes homogeneous temperature and polymerization rate at all points in a reactor cross section. Radial temperature gradients may tend to broaden the molecular weight distribution of the copolymer since the polymerization rate is faster in the high temperature regions. Those of ordinary skill in the art will recognize that achievement of these objectives is difficult in the case of highly viscous solutions. This problem can be overcome to some extent through the use of radial mixing devices such as static mixers (e.g., those produced by the Kenics Corporation).
For purposes of illustration, we assume that a block copolymer of polyethylene and of ethylene and propylene (EP) copolymer is to be produced using as catalyst components vanadium tetrachloride and ethyl aluminum sesquichloride. The polymerization is adiabatic, using hexane diluent for both the catalyst system and the reaction mixture.
In a preferred embodiment, with reference to the process flow diagam in Figure 4, the premixing device 1 comprises a temperature control bath 2, a fluid flow conduit 3 and mixing device 4 (e.g., a mixing tee). To mixing device 4, are fed hexane solvent, vanadium tetrachloride and ethyl aluminum sesquichloride through feed conduits 5, 6 and 7, respectively. Upon being mixed in mixing device 4, the resulting catalyst mixture is caused to flow within conduit 3, optionally in the form of a coiled tube, for a time long enough to produce the active catalyst at the temperature set by the temperature bath.
The temperature of the bath is set to give the desired temperature in conduit 3, at the outlet of the bath. Upon leaving the premixing device, the, catalyst solution flows --- ---- ------------- -"n'nxc.wrroisz 2 .~ 8 7 2 3 3 through conduit 8 into mixing zone 9, where it is intinzately mixed with a stream contaicting hexane diluent and the monomer to be incarporated into the A
block, in this case ethyleno; and which is fed through conduit 10. Any sultable mixing device can be used such as mechanical mixer, orifice mixer or mixang tee. For economic reasons, the miocing tee is preferred. The residence time of the reactiion mixture in cnixing zone 9, is kept short enough to prevent significant potymer formation therein before being fed through conduit 11 to tubular reactor 12. A}terna#ively, streams 8 and 10 can be fed directly to the inlet of reactor 12, if the flow ratea are high enough to sccomplish the desired level of intimate mixing. Stream 10, the heatane with dissolved monomers, may be cooled upstream of mixing zone 9 to provide the desired feed temperature at the reactor inlet.
Tubular, reactor 12 is "wn with intecrnedi,ate feed points 13, 14, and 14a where additional monomers (e.g., ethylene and propylene) and/or hexane can be fed to the ls reactor for example, feeding at least a second monomer blend comprising an ethylene and an a-olefin, at a time of at least 0.1 seconds affter the above step. The additional feeds are used to control the composition of the block copolymer. The number of side feeds required and the spacing along the reactor length depends on final poiymer structure desired VVhile the rea.ctor can be operated adiabatically, external cooling means such as a cooling jacket surrounding at least a portion of the reaetor system 12, can be provided to maintain reaction mixture temperature vwithin desired limits.
Having thus described the above illustrotive rcactor system, it will readily occur to thase of ordinary skill in the art that many variaakiona can be made within the scope of the present inverrtion. For example, the placement and number of multiple feed sites, the choice of temperature profile during polymerization and the concentrations of reactants, can be varied to suit the end-use application.
Fynctjg iza ' n of the Bl k Cooolvmers The. polynacrs produced in accordance with the present invention can be functionalized, i.e., chemically modified, to have at least one functional group present within its structure, which funetional group is capable of: (1) undergoing further chemical reaction (e,g, daivatization) with other m,ateaiallor (2) imparting desirable properties not otherwise possessed by the polymer alone, absent chernical nwdiScation.
The fuwtional group can be incoTporated into tha hackbone of the polymer or can be attached as a pendant group from the polymer backbone. The functional group typicaUy AMENDED SHEET
will be polar and contain hetero atoms such as P, 0, S, N, halogen and/or boron. It can be attached to the saturated hydrocarbon part of the polymer via substitution reactions or to an olefinic portion via addition or cycloaddition reactions.
Alternatively, the functional group can be incorporated into the polymer by oxidation or cleavage of a small portion of the diene containing portion of the polymer (e.g., as in ozonolysis).
Useful functionalization reactions include: maleation, halogenation, "ene"
reactions, reactions with a phenol group, reaction at the point of unsaturation with carbon monoxide, reaction by free radical addition or abstraction and reaction by epoxidation or chloroamination.
As indicated, a functionalized polymer is one which is chemically modified primarily to enhance its ability to participate in a wider variety of chemical reactions than would otherwise be possible with the unfunctionalized polymer. In contrast, a derivatized polymer is one which has been chemically modified to perform one or more functions in a significantly improved way relative to the unfunctionalized polymer and/or the functionalized polymer. Representative of such functions are dispersancy and/or viscosity modification in lubricating oil compositions. The derivatized polymers can include the reaction product of the above recited functionalized polymer with a nucleophilic reactant, which includes amines; alcohols, amino-alcohols and mixtures thereof, to form oil soluble salts, amides, imides, oxazolines, reactive metal compounds and esters of mono- and dicarboxylic acids, and anhydrides. Suitable properties sought to be imparted to the derivatized polymer include especially dispersancyõ but also multifunctional viscosity modification, antioxidancy, friction modification, antiwear, antirust, anti-seal swell, and the like.
Ash-producing detergents can be made using the functionalized polymers of the present invention as exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with alkyl phenols, alkyl sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared from the functionalized olefin polymer of the present invention with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, and sulfur, white phosphorus and a sulfur halide, or phosphorothiotic chloride. Preferred ash-producing detergents which can be derived from the functionalized polymers of the present invention include the metal salts of alkyl sulfonic acids, alkyl phenols, sulfurized alkyl salicylates, alkyl naphthenates and other oil soluble mono- and dicarboxylic acids.
WO 95/27746 2 1 8 7 23' J PGT/[JS95/04250 ~...
The derivatized polymer compositions of the present invention, can be used as ashless dispersants in lubricant and fuel compositions. Various types of ashless dispersants can be made by derivatizing the polymer of the present invention and are suitable for use in the lubricant compositions. The following are illustrative:
1. Reaction products of functionaliaed polymer of the present invention derivatized with nucleophitic reagents such as amine compounds, e.g. nitrogen containing compounds, organic hydroxy compounds such as phenols and alcohols.
2. Reaction products of the polymer of the present invention functionalized with an aromatic hydroxy group and derivatized with aldehydes (especially formaldehyde) and amines especially polyalkylene polyamines, through the Mannich reaction, which may be characterized as "Mannich dispersants".
3. Reaction products of the polymer of the present invention which have been functionalized by reaction with halogen and then derivatized by reaction with amines (e.g. direct amination), preferably polyalkylene polyamines.
The functionalized polymers, particulariy acid functionalized polymers, of the present invention can be reacted with alcohols, e.g., to form esters.
Procedures are well known for reacting high molecular weight carboxylic acids with alcohols to produce acidic esters and neutral esters. These same techniques are applicable to preparing esters from the functaonalized polymer of this invention and the alcohols described above. The hydroxy aroniatic functionalized polymer aldehyde/amino condensates useful as ashless dispersants in the compositions of this invention include those generally referred to as Mannich condensates. A useful group of Mannich Base ashless dispersants are those formed by condensing phenol fimctionalized polymer with fonmaldehyde and polyethylene amines, e.g., tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxpropylene amines, e.g., polyoxyproylene diamine and combinations thereof.
A useful class of nitrogen containing condensation products for use in the present invention are those made by a "2-step process" as disclosed in U.S. Patent No.
4,273,891. Condensates made from sulfur-containing condensates are described in U.S.
Patent Nos. 3,368,972; 3,649,229; 3,600,372; 3,649,659; and 3,741,896 These patents also disclose sulfur-containing Mannich condensates. Useful reactive metals or reactive metal compounds are those which will form metal salts or metal-containing complexes with the functionalized polymer.
The polymer of the present invention may be used as a component of a synthetic base oil. The functionalized polymer, in addition to acting as intermediates for dispersant can be used as a molding release agent, molding agent, metal working lubricant, thickeners and the like. The additives of the present invention are primarily useful in lubrication oil compositions which employ a base oil in which the additives are dissolved or dispersed therein. Such base oils may be natural or synthetic.
Base oils suitable for use in preparing the lubrication oil composition of the present invention include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-ignited intemal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like.
Lubricating oil formulations containing the additives of the present invention conventionally contain other types of additives that contribute other characteristics that are required in the formulation. Typical of such other additives are detergent/'inhibitors, viscosity modifiers, wear inhibitors, oxidation inhibitors, corrosion inhibitors, friction modifiers, foam inhibitors, rust inhibitors, demulsifiers, lube oil flow improvers, and seal swell control agents, etc.
APPLICATIONS
Use in Lubricatinst Oils The novel block copolymers of the invention may be used as viscosity modifiers or with suitable functionalization and/or derivatization, as multifunctional viscosity modifiers, and as dispersants, for lubricating oils. This is especially true for block polymers where there is a diene in the A block, and the polymers are in turn coupled to form a nodular polymer. From studies of hydrogenated block polymers of polyisoprene and polybutadiene, those of ordinary skill in the art are aware that such structures lead to good viscosity-temperature behavior (Ver Strate, G., Struglinski, M., "Polymers as Rheology Modifiers," Schulz, D. & Glass, J., ed. ACS Symp. 462, p. 257, 1991).
Use of block copolymers are disclosed in. U.S. patent 4,959,436, -With further modification such block copolymers are usefuI as multifunctional viscosity modifiers as disclosed in U.S. Patent No. 5,210,146.;
Copolymer products made in accordance with the present invention when dissolved in oil have excellent low temperature properties which makes them suitable for lube oil applications. Accordingly, lube oil compositions made in accordance with the present invention preferably have a IVyni Rotary Viscosity (MRV) measurement in centipoise (cps) at -25 C according to ASTM D 3829 of less than 30,000. A more prefened MRV is less than 20,000, with less than 10,000 being most preferred.
Other Uses of Block Co~olMers Plastics Blendinst Impact modification of thermoplastics is commonly achieved by forming a rubber/plastic blend composition. For this application, it is desirable to have rubber that is in pellet form. This is accomplished in the case of ethylene/propylene rubbers by adjusting the polymer composition so that it is rich enough in ethylene content to be semicrystalline. At that composition (- 70 weight percent ethylene) the glass transition temperature of the polymer is raised by some 10 C above its value of -55 C at 45 weight percent ethylene. Because of this elevated Tg and raised modulus due to crystallinity, the blend of polypropylene and EP does not have its optimum lowest ductile-brittle transition. By preparing the polymer of this invention, it is possible to render the polymer pelletizeable via the PE blocks with the elastomeric B block having low T.
which gives optimum low temperature properties. In impact modified blends of high density polyethylene or of polypropylene which can be used in film or other finished goods, it is advantageous to have an agent which stabilizes the morphology of the thermoplastic/rubber blend. Polymers of this invention exhibit compatibilizer activity in such blends. A given small particle size can be obtained with reduced mixing energy and with their morphology stabilized against ripening or coarsening.
Fuel and Heating Oils Fuel and heating oils contain wax which plugs pipes and filters if the wax crystallizes into anisotropic needles or platelets. The polymers of this invention with an oil soluble B block and a PE A block which nucleates wax crystallization cause granular crystals to form when added to waxy fuels or heating oil , which crystals do not plug the delivery system.
Hot Melt Adhesives Block polymers are employed in hot melt adhesives. Heretofore, it has not been possible to obtain polyethylene/propylene polymers with softening points above which also maintains a low Tg. PE/EP block polymers of this invention can provide such perfonmance.
Bitumen Modification The bitumen employed in asphalt paving flows during service leading to "rutting"
on highways. This problem can be eliminated by incorporating polymers to provide resilience. The polymers of the present invention are useful in this application as they can be supplied as pellets or crumbs. Once in the asphalt, the PE blocks provide reinforcement and physical crosslinks to give the binder an elastic network-like response.
The preferred embodiment of the present invention and the preferred methods of maldng and using it have been detailed above. Those reading the embodiments should understand that the above description is illustrative, and that other embodiments of the invention can be employed without departing from the full scope of the invention as set forth in the claims that follow.
The invention is further described by the following examples:
Prgparation of Uncoupled Block Polymers x 1 1 Polymerization was carried out in a 0.793 cm diameter tubular reactor with hexane as the reaction diluent. The reactor contained a series of feed inlets along its length. In this example, A B block polymers are formed. The A block is polyethylene (PE) and in runs 1A and 1B the B block is an ethylene/propylene copolymer (EP). These polymers were produced using VC 14 catalyst and A12Et3C 13 (EASC) co-catalyst.
The catalyst and co-catalyst were fed into a mixing tee as dilute solutions in hexane at a temperature of 10 C. After mixing, the combined catalyst components flowed through a tube with a residence time of 10 seconds at 10 C before entering the reactor. The monomer feed to the reactor inlet was a solution of ethylene in hexane at 20 C
which was mixed with the catalyst stneam to start the polymerization. The reactor was operated adiabatically so that temperature increased along its length.
After a residence time of 0.024 minutes, during which the block A
(polyethylene) was formed, a feed of ethylene and propylene dissolved in hexane was added via a sidestream injection point to begin polymerization of the B block. Two more ethylene-propylene side feeds were added at residence times of 0.064 and 0.1 minutes to increase the length of the B block. The polymerization was quenched with isopropanol at the end of the reactor. The final reaction temperature was 22 C.
In Examples lA and 1B no diene was used and the polymerization was quenched at 0.14 niin. The reaction conditions of polymerizations 1A and 1B are shown in Table 1.
Runs IA and 1B
A number of polymerization experiments were carried out at the conditions used in runs 1A and 1B, but with a polymerization quench injected into the reactor at a residence time of 0.024 min. so that only polyethylene was produced. From the amount of polymer collected in a known period of time, it was deterniined that close to 100% of the ethylene fed to the reactor in the main flow had reacted to form polyethylene. Thus in Examples 1A and 1B, the rate at which the polyethylene A block is produced is equal to the feed rate of ethylene in the main flow. The rate at which the elastomeric B block is produced can be found by subtracting the A block production rate from the measured total polymerization rate. The percentages of A and B block in the polymer are then calculated by dividing the respective polymerization rates of these blocks by the total polymerization rate. The average ethylene content of the polymer is equal to the ethylene content of the A block, which is 100%, times the fraction of the A
block in the polymer, plus the ethylene content of the B block times the fraction of B
block in the polymer. Thus the ethylene content of the B block can be calculated from the measured average ethylene content of the whole polymer and the polymerization rates from the equation:
Ethylene content of B block, weight percent = (average polymer %
ethylene content - 100 x weight fraction of A block in the total polymer)/weight fraction of B block in the total polymer (all terms are in weight units) The ethylene content of the entire polymer was determined by infrared spectroscopy using the calibration described in I. J. Gardner, C. Cozewith, and G.
Ver Strate, Rubber Chemistrv and Technoloav, vol. 44, 1015, 1971.
The calculated polymer composition is shown in Table 2 along with other measurements of the polymer structure (GPC and DSC). Of particular note is the narrow MWD of the polymers.
Tensile properties of the polymers produced were determined in the following manner. A sheet of polymer 15x 15x0.2 cm was prepared by compression molding for 15 minutes at 150 C. An aluminum mold was used with Teflon coated aluminum foil used as a release agent. Dumbbell-type specimens were die cut from the sheet.
These specimens in tura were strained in tension at a crosshead speed of 12.5 cm/min. Initial jaw separation was 5 cm. with 3.3 cm of the specimen undergoing most of the deformation between the fiducial marks. Data were collected at 20 C.
Engineering modulii were calculated as force at a given percent elongation divided by the original unstrained specimen cross-sectional area.
Table 3 shows the modulii and tensile strength of the polymer for runs IA and lB.
The mechanical properties are a function of molecular weight and the polyethylene block content. The modulus of the polymer containing the larger amount of PE block (lA) are slightly higher than that with a somewhat lower polyethylene block content (1B).
ExMIe 2 A second series of polymerization runs were conducted following the procedures outlined in Example 1. The initial monomer feed to the reactor contained only ethylene to produce the polyethylene A block, two side stream feeds were then added to make the B block. A final feed was introduced with a high ethylene content to produce a semi-3 5 crystalline EP segment at the end or tip of the B block. Reaction conditions for runs 2A
and 2B are shown in Table 1. In example 2A, a higher initial ethylene feed rate was used than in Example 2B to give the polymer a higher molecular weight and a greater percentage of A block.
These polymers were characterized in a manner similar to the polymers produced in Example 1. The results of these analyses are listed in Table 2. The semicrystalline end segment of the B block of Example 2A averaged 72.2 weight percent ethylene, while the semicrystalline end segment of the B block of Example 2B averaged 70 weight percent ethylene. DSC analysis of the polymers, as shown in Figures 1 and 2, show that the polymers contain a semi-crystalline firaction melting at 42 C in addition to a polyethylene fraction which melts at 122 to 124 C. The modulii and tensile strength of the polymers for runs 2A and 2B are shown in Table 3.
EmMle 3 A polymerization was carried out by the procedure in Example 1 using the reaction conditions as shown in Table 4(samples 3A and 3B). The diene, ENB, was added to the main reactor feed to produce a polymer containing ENB in the PE
block.
Ethylene and propylene feeds were added to the reactor at residence times of 0.024 and 0.066 min. ENB feed rates were 2.8 and 1.7 g/hr. and the corresponding polymers contained 0.333 and 0.14 weight percent ENB. These polymers when coupled are useful as lubricating oil viscosity modifiers.
EaMle 4 In this example, a number of A B block polymers made by the procedure in Example 1 but over a broad range of reaction conditions, are tested for solubility in hexane at 22 C. The purpose of this testing is to determine how much B block is unconnected to an A block. The composition and molecular weight of the polymers vary widely. Solubility is determined by pressing 2.0 g of the block polymer onto a 20 mesh screen and immersing the polymer and screen in 200 cc of n-hexane. Wide-mouthed bottles were used and were occasionally swirled over a period of 3 to 5 days.
The screen is removed and dried to constant weight in a vacuum oven to determine the amount of insoluble polymer. The hexane supernatant liquid is evaporated to dryness and the residue is weighed to measure the amount of soluble polymer. The sum of the two fractions showed 100% of the starting polymer is accounted for.
_ 28 _ A control sample of a high density polyethylene which was melt blended with EPDM in a BrabenderImixing head at 180 C was also extracted in the same manner.
These results are presented in Table 5. In the control blend, all 40% of the EPDM was extractable, showing that the rubber is soluble, even at high PE block content, if it is not attached to a PE block. An infrared analysis showed the soluble material to be over 98%
EPDM. PE is not extracted. All of the block polymers of Table 5 show soluble rubber of less than 25%.
Examnle 5 rophetic Example) In this example analyses for PE block content and yield of A B block polymer as a percentage of the total product is described. Three A B block copolymers with a diene containing segment in the A block, are produced by the procedure described in Example 1. Nearly 100% of the ethylene has reacted by the time that the first ethylene/propylene side stream feed is added to make the elastomeric B block. Thus, the weight percent of A block in a polymer can be estimated by dividing the ethylene feed rate in the main flow to the reactor inlet by the total polymerization rate. We can also estimate the amount of A block by dividing the heat of fusion measured by DSC over the melting range of 80 C
to 135 C, by the heat of fusion measured by DSC for a pure polyethylene A
block of approximately the same molecular weight, as shown in Figure 3, made by adding only an ethylene feed to the reactor. A value of 181 J/g. is used for the heat of fusion of polyethylene based on averaging the results from a number of samples.
The polymer samples are fractionated in a Kumagawa apparatus. In this apparatus an individual sample is sequentially extracted with a series of solvents of increasing boiling point. For each solvent continuous extraction is carried out until all soluble polymer is dissolved. The solvents used and their boiling points (bp) were: n-hexane (bp=69 C), cyclohexane (bp=81 C), n-heptane (bp= 98 C), and toluene (bp=
111 C). The polymer soluble in each solvent is recovered, weighed, and analyzed by DSC. By determining the amount of polymer soluble in each solvent and the amount and percentage of PE block in that soluble portion, the percentage of the portion that was non-crystalline EP block can be calculated.
Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the 2l~ ~2 preferred versions contained herein.
MAIN FLOW g/h hexane 53803 53803 5380:3 53803 :L O propylene 0 0 0 0 ethylene 151 124 151 73 VC14 1.8 1.5 2.4 2.4 Al/V mol/mol 8 8 8 8 1.5 SIDE STREAM 1, g/h hexane 8910 8910 8910 8910 propylene 1228 1354 1125 1125 ethylene 110 148 122 122 SIDE STREAM 2, g/h 2 0 hexane 6138 6138 5910 5910 propylene 358 509 413 413 ethylene 85 110 130 130 SIDE STREAM 3, g/hr hexane 6217 6217 7920 7920 2 5 propylene 347 405 510 510 ethylene 80 108 255 255 TEMPERATURE, C
feed 20 20 19 19 reactor outlet 22 22 25 24 30 RESIDENCE 'ITME, min.
to side stm,am 1 0.024 0.024 0.024 0.024 to side stream 2 0.064 0.064 0.109 0.109 to side streem 3 0.10 0.10 0.147 0.147 to side stream 4 35 Total 0.139 0.139 0.183 0.183 PROCESS RESULTS
wt % C2 in polymer 71.6 70.8 72.2 70.1 wt % ENB in polymer 0 0 0 0 Mooney(1+4, 150 C) 109 91.1 114 131 40 Mw x 10-3 189 246 222 209 Mn x 10-3 108 149 115 106 Mw/Mn 1.67 1.7 1.91 1.99 Poly Rate, g/h 387 368 689 597 C2=conv % 65 54.8 75.6 72.2 45 C3=conv =, % 5.7 4.4 9.4 8.7 Cat efl;g poly/g VC14 215 245.3 297 249 ' conv = conversion . .;:: ::. ,: .::::. .=.:
. .... . . = . .., ..::.,=..,~,=: =.,:::; ::.>F<::.:~., ., .. . . . :;.,.. .
~~
; ' ~;=< ~.. :. .,= = :<c =:. .. : ::<.
,:.,=: =:.,, ,. r:." , ;.,,:,.;.',+.: ii;.=,'''~.,i,.i,d:<'' ;%:=::
Poly rate A block, g/hr 151 124 151 73 Poly rate B block, glhr 236 244 319 355 Poly rate C block, g/hr 0 0 259 265 A block, wt % 39.0 33.7 20.7 10.5 B block, wt % 61.0 66.3 43.7 51.2 C block, wt % 0 0 35.5 38.2 wt % C2= in whole 1 er 71.6 72.9 72.2 70.1 wt % C2= in B block before final 53.4 59.1 59.0 63.9 feed wt % C2= in B block after fuwi feed 72.2 70.1 wt % ENB whole polymer wt % ENB in EPDM ent ~"~rPC::><? :::' :
Mw x 10-3 189 246 221 209 Mn x 10-3 108 149 115 106 Mw/Mn 1.67 : .7 1.91 1.99 A block, J/g 48 33 29.2 21.3 B block, J/ 0.82 3.59 4.14 Wt. % soluble in n-hexane 2.3 2.6 :; .:...:....:::::::::.::.., :.; . ,.,, . .,:=::<..::.::>L.::~::.:~:.:<:
:................ .
,:.. . :. :::::.......... .y:
. . , : ::::. = .
=: ,.,.~.:..; =tS.::.',.i5;.'= ': i~f ..=~. ~ ~=7,.:~: ...::=::=::.; =: ~';:::~:~:::;<::; :
..:~7~~i?+:::: ;?f:.'=:~:[ki~'i;;ii '?~~:~a7i:':'i'ii 100% MODULUS, MPa 2.4 2.3 2.7 2.2 TENSII.E STRENGTH AT BREAK, 3.5 9.7 15.4 5.4 MPA
EXTENSION AT BREAK, % 780 1220 1090 740 WO 95/27746 2 8 7 23~ PCT/US95/04250 ~.
TABLE 4 (Example 3) . . : . . .. :.....:::... . . .: .:.: ,. ..; .. . .
' ~~ . '~
=.~
.... ......:..~...:=::....{i::: ' . .. : ::: . ..~ .: :..::::... ..
:'' . =. :.:. ~ a ......;.:...
N<=:
v . .. .:. ...... . . .: . ...::................... ......................
.............
hexane 53605 53526 propylene 0 0 ethylene 253 253 diene 2.8 1.71 catalyst 3.36 3.36 AIN, mol/mol 7 ........
~14~~"~'REJRIM:.~ . ;::,:.:.<.;::<.:::>:.:= .:.:..::.::.::<:>::;>:;:;: ::>::;
hexane 6692 6692 propylene 1234 1234 ethylene hexane 9900 9900 propylene 468 471 ethylene 112 112 hexane propylene ethylene ENB
,.......
E~l: ::. S :;::>:
..... .................... ..
Reactor feed, C 20 20 Reactor outlet, C 31 31 a~3~kEt~CE TtM mEn to side stream 1 0.024 0.024 to side stream 2 0.066 0.066 to side stream 3 Total 0.142 0.142 _ ...:..
PR~JC0S REgULTS
..::.. .
Wt. % C2=in polymer 73.2 71.5 Wt. % ENB in polymer 0.33 0.14 Mooney 1+ 4, 150 C 51 49.8 A Block, % of polymer Poly Rate, g/h 592.5 604 C2= aonv, % * 90.8 90.6 C3= conv, % * 9.3 10.1 ENB conv, % * 69.8 49.5 Cat eff, I/ VCI 176.4 179.8 *conv = conversion 32 _, Run Wt. % C2= Mn x 10-3 Mw x 10-3 Hexane soluble, in Pol . %
317a 68 75 139 12.1 317b 68 ~ 97 193 13.0 317c 71 118 228 4.9 317d 69 92 189 12.5 318a 63 69 118 22.1 318b 62 62 118 23.5 318c 64 88 208 16.6 318d 66 92 179 16.9 319a 66 108 160 13.2 319c 68 108 230 7.8 320a 71 108 206 4.1 320c 70 128 237 3.3 323a 72 137 289 2.9 323b "71~y_~_ 152 307 2.2 332a 68 149 258 11.3 333a 68~~~ 104 212 7.7 334a 69 126 :195 4.9 334b 67117 178 8.0 335a 66 M~ 94 343 10.1 335b 70 - 6.5 336a 69 15.2 336d 6f, ~ 19.0 336e 69 74 147 3.7 338b - - 6.0 60% HDPE/ 39.6 40% EPDM
40 !o HDPE/ 610 60% EPDM
Claims (23)
1. A block copolymer comprising an A and a B block wherein:
said A block consists essentially of an ethylene polymer;
said B block comprising a first polymer segment contiguous to a junction of said A
block and said B block, said first segment comprising ethylene and an alpha-olefin;
said B block having an intramolecular composition distribution such that at least two portions of the B block, each portion comprising at least 5 weight percent of the B
block, differ in composition by at least 5 weight percent ethylene;
said B block having a tip segment, said tip segment being further from said junction, said tip segment being a polymer of ethylene, and an alpha-olefin, and wherein said tip segment has an ethylene content of at least 60 mole percent based on the total moles of the monomers of said tip segment, and wherein said B block melts in the range of from 35 to 130°C; and wherein the A block is present in the copolymer in the range of 5 to 90 weight percent and the B block is present in the range of 10 to 95 weight percent, both based on the total weight of block copolymer.
said A block consists essentially of an ethylene polymer;
said B block comprising a first polymer segment contiguous to a junction of said A
block and said B block, said first segment comprising ethylene and an alpha-olefin;
said B block having an intramolecular composition distribution such that at least two portions of the B block, each portion comprising at least 5 weight percent of the B
block, differ in composition by at least 5 weight percent ethylene;
said B block having a tip segment, said tip segment being further from said junction, said tip segment being a polymer of ethylene, and an alpha-olefin, and wherein said tip segment has an ethylene content of at least 60 mole percent based on the total moles of the monomers of said tip segment, and wherein said B block melts in the range of from 35 to 130°C; and wherein the A block is present in the copolymer in the range of 5 to 90 weight percent and the B block is present in the range of 10 to 95 weight percent, both based on the total weight of block copolymer.
2. A block copolymer according to claim 1 wherein:
said A block consists essentially of an ethylene, non-conjugated diene polymer;
wherein said non-conjugated diene is present m said block copolymer in the range of from 0.03 to 2 mole percent based on the total moles in said block copolymer; and wherein said non-conjugated diene is 5-ethylidene-2-norbornene, vinylnorbornene, tetrahydroindene, 5-methylene-2-norbornene, dicyclopentadiene, methyltetra-hydroindene, bicyclo-(2,2,1)-hepta-2,5-diene, 5-propenyl-2-norbomene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyctohexylidene-2-norbornene or norbornadiene.
said A block consists essentially of an ethylene, non-conjugated diene polymer;
wherein said non-conjugated diene is present m said block copolymer in the range of from 0.03 to 2 mole percent based on the total moles in said block copolymer; and wherein said non-conjugated diene is 5-ethylidene-2-norbornene, vinylnorbornene, tetrahydroindene, 5-methylene-2-norbornene, dicyclopentadiene, methyltetra-hydroindene, bicyclo-(2,2,1)-hepta-2,5-diene, 5-propenyl-2-norbomene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyctohexylidene-2-norbornene or norbornadiene.
3. A block copolymer according to claim 1 or 2 wherein:
said A block consists of an ethylene polymer, wherein said A block further contains a non-conjugated diene up to 10 mole percent, and wherein said A
block has a T m of at least 110°C.
said A block consists of an ethylene polymer, wherein said A block further contains a non-conjugated diene up to 10 mole percent, and wherein said A
block has a T m of at least 110°C.
4. A block copolymer according to any one of claims 1 to 3, said B block having 2 or more segments, wherein:
the A block is an ethylene polymer optionally comprising an alpha-olefin and a non-conjugated diene wherein said non-conjugated diene is present in said block copolymer in the range of from 0.03 to 2 mole percent based on the total moles in said block copolymer, said alpha-olefin if present in said A block is present at less than 5 mole percent, and said B block having a tip segment of ethylene and an a-olefin;
said tip segment being at the end of said B block, said tip segment being furthest of said segments from an AB junction;
said B block having an intramolecular composition distribution such that at least two portions of the B block, each portion comprising at least 5 weight percent of the B
block, differ in composition by at least 5 weight percent ethylene;
said block copolymer having an n-hexane soluble portion, not exceeding 30 weight percent based on the total weight of the block copolymer;
wherein said block copolymer is made by a process utilizing a vanadium catalyst system, wherein said vanadium catalyst system includes a vanadium compound premixed with an organoaluminum compound, said premixing being for a sufficient time to produce an adequate quantity of active catalyst;
wherein said vanadium compound is represented by the general formula:
or VCl x(COOR)3-x; (2) where x = 0 to 3 and R = a hydrocarbon radical;
or VCl4;
or where AcAc = acetyl acetonate;
or V(AcAc)3;
or where x = 1 or 2;
or VCl3.cndot.nB;
where n = 2 to 3 and B = Lewis base for making hydrocarbon-soluble complexes with VCl3, where B is tetrahydrofuran, 2-methyl-tetrahydrofuran or dimethyl pyridine;
wherein the organoaluminum compound is represented by the formula AlR3, Al(OR')R2; AlR2X; R2Al-O-AlR2; AlR'RX; Al2R3X3 or AlRX2, where R and R' represent hydrocarbon radicals, said R and R' being the same or different and wherein X
is bromine, chlorine or iodine;
wherein said B block has an intra-molecular-composition distribution, wherein at least 2 portions of said B block each portion comprising at least 5 weight percent of said B
block, said 2 portions differing in ethylene content by at least 5 weight percent;
wherein said alpha-olefin in said B block and said A block is propylene;
wherein said B block is present in the range of 40 - 90 weight percent based on the total weight of polymer, as polymerized;
wherein said A B block copolymer has a Mw/Mn of less than 2.5; and wherein said A block is present in said block copolymer in the range of from 10 to 60 weight percent.
the A block is an ethylene polymer optionally comprising an alpha-olefin and a non-conjugated diene wherein said non-conjugated diene is present in said block copolymer in the range of from 0.03 to 2 mole percent based on the total moles in said block copolymer, said alpha-olefin if present in said A block is present at less than 5 mole percent, and said B block having a tip segment of ethylene and an a-olefin;
said tip segment being at the end of said B block, said tip segment being furthest of said segments from an AB junction;
said B block having an intramolecular composition distribution such that at least two portions of the B block, each portion comprising at least 5 weight percent of the B
block, differ in composition by at least 5 weight percent ethylene;
said block copolymer having an n-hexane soluble portion, not exceeding 30 weight percent based on the total weight of the block copolymer;
wherein said block copolymer is made by a process utilizing a vanadium catalyst system, wherein said vanadium catalyst system includes a vanadium compound premixed with an organoaluminum compound, said premixing being for a sufficient time to produce an adequate quantity of active catalyst;
wherein said vanadium compound is represented by the general formula:
or VCl x(COOR)3-x; (2) where x = 0 to 3 and R = a hydrocarbon radical;
or VCl4;
or where AcAc = acetyl acetonate;
or V(AcAc)3;
or where x = 1 or 2;
or VCl3.cndot.nB;
where n = 2 to 3 and B = Lewis base for making hydrocarbon-soluble complexes with VCl3, where B is tetrahydrofuran, 2-methyl-tetrahydrofuran or dimethyl pyridine;
wherein the organoaluminum compound is represented by the formula AlR3, Al(OR')R2; AlR2X; R2Al-O-AlR2; AlR'RX; Al2R3X3 or AlRX2, where R and R' represent hydrocarbon radicals, said R and R' being the same or different and wherein X
is bromine, chlorine or iodine;
wherein said B block has an intra-molecular-composition distribution, wherein at least 2 portions of said B block each portion comprising at least 5 weight percent of said B
block, said 2 portions differing in ethylene content by at least 5 weight percent;
wherein said alpha-olefin in said B block and said A block is propylene;
wherein said B block is present in the range of 40 - 90 weight percent based on the total weight of polymer, as polymerized;
wherein said A B block copolymer has a Mw/Mn of less than 2.5; and wherein said A block is present in said block copolymer in the range of from 10 to 60 weight percent.
5. The block polymer of claim 4 wherein R represents a C1 to C10 aliphatic, alicyclic, or aromatic hydrocarbon radical.
6. The block copolymer of any one of claims 1-4 wherein said block copolymer is present at greater than 50 weight percent based on the total weight of polymer as polymerized.
7. The block copolymer of any one of claims 1-4, wherein said B block has an average ethylene content in the range of from 20 to 90 mole percent based on the total moles of the monomers of the B block.
8. The block copolymer of any one of claims 1-4 wherein said alpha-olefin, if present in one or both of said A block and or said B block, is propylene.
9. The block copolymer of claim 4 wherein said tip segment is present in said B
block at a level up to 50 weight percent based on the total weight of said B
block.
block at a level up to 50 weight percent based on the total weight of said B
block.
10. The block copolymer of any one of claims 1-4, wherein said block copolymer has a Mw/Mn of less than 2.5.
11. The block copolymer of any one of claims 1-4, wherein said A block comprises in the range of from 10 to 60 weight percent of said block copolymer.
12. The block copolymer of any one of the claims 1-4, wherein said block copolymer has a number average molecular weight in the range of from 750 to 20,000,000.
13. An oil composition comprising the block copolymer of any one of claims 1-4, and a fuel oil, heating oil or lubricating oil.
14. A lubricating oil comprising a viscosity modifier or a dispersant, said viscosity modifier being one of the block copolymer of any one of claims 1-4 or a functionalized derivative of the block copolymer of any one of claims 1-4, said dispersant being a functionalized derivative of the block copolymer of any one of claims 1-4.
15. A functionalization reaction product comprising the block copolymer of any one of claims 1-4.
16. A lubricating oil concentrate or lubricating oil comprising the block copolymer of any one of claims 1-4.
17. Use of the block copolymer of any one of claims 1-4 as a constituent in a thermoplastic elastomer, a thermoplastic blend, a hot melt adhesive, a bitumen blend or a roof sheeting compound.
18. The block copolymer of any one of claims 1-4, wherein:
said block copolymer is coupled with at least another of said block copolymers and wherein said coupling takes place in the presence of a coupling agent, said coupling agent being AlX3, BX3, SnX4, SbX5, AlR y X3-y, where y is 0 to 1.5 and R is a hydrocarbon radical, BX4, TiX4, or a mixture thereof, where X is selected from the group consisting of chlorine, bromine, and iodine; or said coupling agent being a free radical coupling agent being dicumyl peroxide, d-tertiarybutylperoxide, t-butylperbenzoate, 1,1-di(t-butylperoxy)-3,3,5-trimethyl cyclohexane, azo-bisisobutyronitrile azodicarboxylate or a mixture thereof; or said coupling agent being a free radical coupling agent being sulfur dichloride, disulfonyl halides, borane, dithioalkanes or a mixture thereof; or said coupling agent being an alkyl phenol formaldehyde mixture catalyzed with a catalyst being ZnCl2, N-bromosuccinimide or diphenylbrontomethane; or said coupling agent being sulfur and a sulfur accelerator; and wherein said coupling takes place in a polymerization reactor or post reactor.
said block copolymer is coupled with at least another of said block copolymers and wherein said coupling takes place in the presence of a coupling agent, said coupling agent being AlX3, BX3, SnX4, SbX5, AlR y X3-y, where y is 0 to 1.5 and R is a hydrocarbon radical, BX4, TiX4, or a mixture thereof, where X is selected from the group consisting of chlorine, bromine, and iodine; or said coupling agent being a free radical coupling agent being dicumyl peroxide, d-tertiarybutylperoxide, t-butylperbenzoate, 1,1-di(t-butylperoxy)-3,3,5-trimethyl cyclohexane, azo-bisisobutyronitrile azodicarboxylate or a mixture thereof; or said coupling agent being a free radical coupling agent being sulfur dichloride, disulfonyl halides, borane, dithioalkanes or a mixture thereof; or said coupling agent being an alkyl phenol formaldehyde mixture catalyzed with a catalyst being ZnCl2, N-bromosuccinimide or diphenylbrontomethane; or said coupling agent being sulfur and a sulfur accelerator; and wherein said coupling takes place in a polymerization reactor or post reactor.
19. The block copolymer of any one of claims 1-4, wherein said A block contains in the range of from 0.05 to 1 mole percent of said non-conjugated diene based on the total moles of the monomers of the block copolymer.
20. A process for preparing an olefin block copolymer, comprising the steps of:
(a) forming a catalyst by premixing the reaction product of a vanadium compound represented by the formula:
or VCl x(COOR)3-x; (2) where x = 0 to 3 and R = a hydrocarbon radical;
or VCl4;
or where AcAc = acetyl acetonate;
or V(AcAc)3;
or where x = 1 or 2;
or VCl3.cndot.nB;
where n = 2 to 3 and B = Lewis base for making hydrocarbon-soluble complexes with VCl3, where B is tetrahydrofuran, 2-methyl-tetrahydrofuran or dimethyl pyridine;
an organoaluminum compound represented by the formula AlR3, Al(OR')R2;
AlR2X; R2Al-O-AlR2, AlR'RX; Al2R3X3 or AlRX2, where R and R' represent hydrocarbon radicals, said R and R' being the same or different and wherein X
is bromine, chlorine or iodine; and where R and R' represent hydrocarbon radicals, said R and R' being the same or different, wherein X is bromine, chlorine or iodine;
said premixing being for a sufficient period of time to produce an adequate quantity of active catalyst;
(b) feeding the reaction product of step (a) to a reactor concurrently with a monomer stream comprising ethylene, optionally an .alpha.-olefin, and optionally a non-conjugated diene; and (c) feeding at least a second monomer blend comprising an ethylene and an .alpha.-olefin, at a time of at least 0.1 seconds after step (b).
(a) forming a catalyst by premixing the reaction product of a vanadium compound represented by the formula:
or VCl x(COOR)3-x; (2) where x = 0 to 3 and R = a hydrocarbon radical;
or VCl4;
or where AcAc = acetyl acetonate;
or V(AcAc)3;
or where x = 1 or 2;
or VCl3.cndot.nB;
where n = 2 to 3 and B = Lewis base for making hydrocarbon-soluble complexes with VCl3, where B is tetrahydrofuran, 2-methyl-tetrahydrofuran or dimethyl pyridine;
an organoaluminum compound represented by the formula AlR3, Al(OR')R2;
AlR2X; R2Al-O-AlR2, AlR'RX; Al2R3X3 or AlRX2, where R and R' represent hydrocarbon radicals, said R and R' being the same or different and wherein X
is bromine, chlorine or iodine; and where R and R' represent hydrocarbon radicals, said R and R' being the same or different, wherein X is bromine, chlorine or iodine;
said premixing being for a sufficient period of time to produce an adequate quantity of active catalyst;
(b) feeding the reaction product of step (a) to a reactor concurrently with a monomer stream comprising ethylene, optionally an .alpha.-olefin, and optionally a non-conjugated diene; and (c) feeding at least a second monomer blend comprising an ethylene and an .alpha.-olefin, at a time of at least 0.1 seconds after step (b).
21. The process of claim 20, wherein said catalyst is comprised of VCl4 as said vanadium compound and Al2R3Cl3 as said organoaluminum compound, where R is an ethyl group.
22. The process of claim 20 wherein said non-conjugated diene, if present, is ethylidene-2-norbornene, vinylnorbornene, 5-methylene-2-norbornene, dicyclopentadiene or tetrahydroindene.
23. The process of claim 20 wherein R represents a C1 to C10 aliphatic, acylic, or aromatic hydrocarbon radical.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US22391294A | 1994-04-06 | 1994-04-06 | |
US08/223,912 | 1994-04-06 | ||
PCT/US1995/004250 WO1995027746A1 (en) | 1994-04-06 | 1995-04-06 | ETHYLENE α-OLEFIN BLOCK COPOLYMERS AND METHODS FOR PRODUCTION THEREOF |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2187233A1 CA2187233A1 (en) | 1995-10-19 |
CA2187233C true CA2187233C (en) | 2007-06-26 |
Family
ID=38278954
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002187233A Expired - Lifetime CA2187233C (en) | 1994-04-06 | 1995-04-06 | Ethylene .alpha.-olefin block copolymers and methods for production thereof |
Country Status (1)
Country | Link |
---|---|
CA (1) | CA2187233C (en) |
-
1995
- 1995-04-06 CA CA002187233A patent/CA2187233C/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CA2187233A1 (en) | 1995-10-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0758348B1 (en) | Ethylene alpha-olefin block copolymers and methods for production thereof | |
EP0760827B1 (en) | ETHYLENE $g(a)-OLEFIN BLOCK COPOLYMERS AND METHODS FOR PRODUCTION THEREOF | |
JP2684001B2 (en) | Olefin copolymer having narrow MWD and method for producing the same | |
AU595466B2 (en) | Lubricating oil compositions containing ethylene-alpha olefin polymers of controlled sequence distribution and molecular homogeneity | |
RU96121912A (en) | ETHYLENE α-OLEFIN BLOCK OF COPOLYMERS AND METHOD FOR ITS PREPARATION | |
US4959436A (en) | Narrow MWD alpha-olefin copolymers | |
JPH01207309A (en) | Improved viscosity controller polymer | |
US20030013623A1 (en) | Olefin copolymer viscocity index improvers | |
AU593881B2 (en) | Copolymer compositions containing a narrow mwd component and process of making same | |
CA2187233C (en) | Ethylene .alpha.-olefin block copolymers and methods for production thereof | |
CA2027403A1 (en) | Multifunctional viscosity index improver derived from polyamine containing one primary amine group and at least one secondary amine group and degraded ethylene copolymer | |
AU615865B2 (en) | Oil additive compositions exhibiting reduced haze containing polymeric viscosity index improver | |
MXPA96004603A (en) | Copolymers in block of alpha-olefine of ethylene and methods for your production | |
EP0204842A1 (en) | Nodular copolymers formed of alpha-olefin copolymers coupled by non-conjugated dienes. | |
MXPA96004604A (en) | Copolymers in block of alpha-olefine of ethylene and methods for your production | |
JPS63502191A (en) | Copolymer composition containing narrow width MWD component and method for producing the same | |
NO884632L (en) | LUBRICATION OIL COMPOSITION CONTAINING ETHYLENE-ALFA-OLEFIN COPOLYMES WITH CONTROLLED SEQUENCE DISTRIBUTION AND MOLECULES HETEROGENITY. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKEX | Expiry |
Effective date: 20150407 |