US20160083487A1 - Functional Polyisobutylene-Containing Oligomers and Polymers - Google Patents
Functional Polyisobutylene-Containing Oligomers and Polymers Download PDFInfo
- Publication number
- US20160083487A1 US20160083487A1 US14/934,941 US201514934941A US2016083487A1 US 20160083487 A1 US20160083487 A1 US 20160083487A1 US 201514934941 A US201514934941 A US 201514934941A US 2016083487 A1 US2016083487 A1 US 2016083487A1
- Authority
- US
- United States
- Prior art keywords
- capping
- polymer
- reaction
- pib
- chain
- 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.)
- Abandoned
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 27
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 71
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- -1 heteroalkenyl Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000002318 adhesion promoter Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000006254 rheological additive Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004404 heteroalkyl group Chemical group 0.000 claims 5
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 229920002367 Polyisobutene Polymers 0.000 abstract description 38
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 9
- 238000007345 electrophilic aromatic substitution reaction Methods 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002841 Lewis acid Substances 0.000 abstract description 6
- 150000007517 lewis acids Chemical class 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000010552 living cationic polymerization reaction Methods 0.000 abstract description 2
- 238000010550 living polymerization reaction Methods 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 description 38
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 125000000524 functional group Chemical group 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910003074 TiCl4 Inorganic materials 0.000 description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 150000001345 alkine derivatives Chemical class 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 6
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 5
- RGLHEMZXTOODQW-UHFFFAOYSA-N 4-phenoxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC1=CC=CC=C1 RGLHEMZXTOODQW-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 0 *C(P)C(C)(C)C[1*].C=C(C)C.[1*]CC(C)(C)C Chemical compound *C(P)C(C)(C)C[1*].C=C(C)C.[1*]CC(C)(C)C 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000001805 chlorine compounds Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000000335 thiazolyl group Chemical group 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([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
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000011160 magnesium carbonates Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- SEAZOECJMOZWTD-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethyl)silane Chemical compound CO[Si](OC)(OC)CC1CO1 SEAZOECJMOZWTD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C08F8/00—Chemical modification by after-treatment
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
- C08F110/10—Isobutene
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
- C08F10/10—Isobutene
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
-
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
Definitions
- One aspect relates to methods of making functional polyisobutylene (PIB)-containing oligomers and polymers and the materials made thereby.
- Another aspect relates to compositions made from the functional polyisobutylene (PIB)-containing oligomers and polymers.
- reaction do not proceed to completion.
- Reactants are added in excess of the stoichiometric amount calculated for that reaction to force reactions to proceed to completion.
- One embodiment provides a method of making functional polyisobutylene (PIB)-containing oligomers and polymers.
- PIB polyisobutylene
- the synthesis of functional PIB-containing polymers can be achieved directly under cationic polymerization conditions and does not include any post-polymerization reactions.
- the desired functionality is introduced by direct Electrophilic Aromatic Substitution (EAS) reaction using substituted phenyl ring carrying desirable functionalities that do not react with Lewis acid but have weak association with Lewis acid, which still allow living polymerization and EAS reaction under living cationic polymerization conditions.
- EAS Electrophilic Aromatic Substitution
- polyisobutylene or isobutylene containing oligomers and polymers can be prepared using stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain.
- the resulting quantitative or nearly quantitative product contains very little or no unreacted capping reagent(s) to remove, which makes the work-up easier, faster and provides oligomers with high purity.
- the disclosed compounds include any and all isomers and stereoisomers.
- the disclosed materials and processes may be alternately formulated to comprise, consist of, or consist essentially of, any appropriate components, moieties or steps herein disclosed.
- the disclosed materials and processes may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants, moieties, species and steps used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objective of the present disclosure.
- Alkyl or “alkane” refers to a hydrocarbon chain or group containing only single bonds.
- the alkane can be a straight hydrocarbon chain or a branched hydrocarbon group.
- the alkane can be cyclic.
- the alkane can contain 1 to 20 carbon atoms, advantageously 1 to 10 carbon atoms and more advantageously 1 to 6 carbon atoms. In some embodiments the alkane can be substituted.
- alkanes include methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and decyl.
- alkenyl refers to a hydrocarbon chain or group containing one or more double bonds.
- the alkenyl can be a straight hydrocarbon chain or a branched hydrocarbon group.
- the alkene can be cyclic.
- the alkene can contain 1 to 20 carbon atoms, advantageously 1 to 10 carbon atoms and more advantageously 1 to 6 carbon atoms.
- the alkene can be an allyl group.
- the alkene can contain one or more double bonds that are conjugated. In some embodiments the alkene can be substituted.
- Alkoxy refers to the structure —OR, wherein R is hydrocarbyl.
- Alkyne or “alkynyl” refers to a hydrocarbon chain or group containing one or more triple bonds.
- the alkyne can be a straight hydrocarbon chain or a branched hydrocarbon group.
- the alkyne can be cyclic.
- the alkyne can contain 1 to 20 carbon atoms, advantageously 1 to 10 carbon atoms and more advantageously 1 to 6 carbon atoms.
- the alkyne can contain one or more triple bonds that are conjugated. In some embodiments the alkyne can be substituted.
- Aryl or “Ar” refers to a monocyclic or multicyclic aromatic group.
- the cyclic rings can be linked by a bond or fused.
- the aryl can contain from 6 to about 30 carbon atoms; advantageously 6 to 12 carbon atoms and in some embodiments 6 carbon atoms.
- Exemplary aryls include phenyl, biphenyl and naphthyl. In some embodiments the aryl is substituted.
- “Cationic polymerization” refers to polymerization of a monomer using a carbocationic initiator; a coinitiator such as a Lewis Acid, for example TiCl 4 ; and a cationically polymerizable monomer.
- the reaction is typically performed in a solvent or mixture of solvents at low temperature (for example less than 0° C.) and substantially excluding moisture.
- “Ester” refers to the structure R—C(O)—O—R′ where R and R′ are independently selected hydrocarbyl groups.
- the hydrocarbyl groups can be substituted or unsubstituted.
- Halogen or “halide” refers to an atom selected from fluorine, chlorine, bromine and iodine.
- Hetero refers to one or more heteroatoms in a structure. Exemplary heteroatoms are independently selected from N, O and S.
- Heteroaryl refers to a monocyclic or multicyclic aromatic ring system wherein one or more ring atoms in the structure are heteroatoms. Exemplary heteroatoms are independently selected from N, O and S. The cyclic rings can be linked by a bond or fused. The heteroaryl can contain from 5 to about 30 carbon atoms; advantageously 5 to 12 carbon atoms and in some embodiments 5 to 6 carbon atoms.
- heteroaryls include furyl, imidazolyl, pyrimidinyl, tetrazolyl, thienyl, pyridyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, thiazolyl, quinolinyl and isoquinolinyl.
- the heteroaryl is substituted.
- Hydrocarbyl refers to a group containing carbon and hydrogen atoms.
- the hydrocarbyl can be linear, branched, or cyclic group.
- the hydrocarbyl can be alkyl, alkenyl, alkynyl or aryl. In some embodiments, the hydrocarbyl is substituted.
- Lewis acid refers to a chemical entity that is capable of accepting a pair of electrons.
- (Meth)acrylate refers to acrylate and methacrylate.
- Oligomer refers to a defined, small number of repeating monomer units such as 10-5,000 units, and advantageously 10-1,000 units which have been polymerized to form a molecule. Oligomers are a subset of the term polymer.
- One step reaction refers to a chemical reaction to form a functionalized PIB containing oligomer or polymer wherein polymerization of isobutylene or an isobutylene containing monomer mixture and functionalization of the resulting oligomer or polymer is performed in the same reaction vessel and under cationic polymerization reaction conditions.
- Polyaromatic hydrocarbon or “PAr” or “polycyclic aromatic hydrocarbon” refers to a fused, multicyclic aromatic group for example containing 2 to 20 ring moieties.
- the polyaromatic hydrocarbon can contain from 6 to about 120 ring carbon atoms; advantageously 6 to 20 ring carbon atoms.
- the polyaromatic hydrocarbon contains heteroatoms as ring atoms.
- Exemplary polyaromatic hydrocarbons include naphthalene, anthracene, phenanthrene and fluorene.
- the aryl is substituted.
- Polymer refers to any polymerized product greater in chain length and molecular weight than the oligomer. Polymers can have a degree of polymerization of about 50 to about 25000. As used herein polymer includes oligomers and polymers. As used herein polymer includes homopolymers and copolymers.
- “Substituted” refers to the presence of one or more substituents on a molecule in any possible position. Useful substituents are those groups that do not significantly diminish the disclosed reaction schemes. Exemplary substituents include, for example, H, halogen, (meth)acrylate, epoxy, oxetane, urea, urethane, N 3 , NCS, CN, NCO, NO 2 , NX 1 X 2 , OX 1 , C(X 1 ) 3 , C(halogen) 3 , COOX 1 , SX 1 , Si(OX 1 ) i X 2 3-1 , alkyl, alcohol, alkoxy; wherein X 1 and X 2 each independently comprise H, alkyl, alkenyl, alkynyl or aryl and I is an integer from 0 to 3.
- One embodiment is a method of making PIB diacrylate by direct capping living PIB using stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain.
- stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain to provide a quantitative or nearly quantitative product containing very little or no unreacted capping reagent(s).
- Stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain are ratios where functionalization of the product is maximized.
- Ratios (of equivalents) of the capping or functionalization reagent to polymer end-chain can be in the range of 0.7 to 5; advantageously can be in the range of 0.8 to 2. Preferably the ratio is in the range of about 1, such as 0.9 to 1.1.
- Ratio of the capping or functionalization reagent to polymer end-chain equivalents of the capping or functionalization reagent/equivalents of polymer end-chain.
- the capping reagent contains electro-donating groups. Suitable electro-donating groups include three major categories, phenoxy type structure, aryl substituted aromatic structure and alkyl substituted aromatic structure.
- Functional groups can be any group which can undergo reaction and cause crosslinking.
- suitable functional groups include acrylate, methacrylate, isocyanate, acrylic isocyanate, silane, chlorosilane, alkoxysilane etc and the functional groups can be either terminal groups or pendant groups in the oligomers and polymers.
- Initiators with one or more initiation sites can be used for synthesis of functional PIB-containing oligomers and polymers, including bi-functional initiator, which carries one or more functional groups other than initiation site.
- PIB-containing oligomers and polymers with one or more terminal or pendant functionalities can be prepared.
- the direct capping reaction can generate functionality at the oligomers and polymer chain end.
- the functional PIB with same or varied functionalities can be prepared using bi-functional initiator.
- Components in RIB-containing co-oligomers and co-polymers can be any monomer which can be polymerized by cationic polymerization mechanism. Suitable monomers include styrene and isoprene.
- One embodiment includes a method of making functional PIB homo-oligomer or polymer and co-polymers directly under cationic polymerization conditions and not including any post-polymerization reactions (Chart 1).
- the desirable functionality is introduced by a capping reaction under cationic polymerization condition. Since a living PIB center is cation bearer, electrophilic aromatic substitution (EAS) reaction can be utilized as a capping reaction by a careful choice of substitutive aromatic structures. Electro-donating groups will facilitate the EAS reaction; therefore, three major categories (Chart 2) of capping reagent are discussed: aromatics with non-aromatic electro donating groups, polyaromatics and benzoid polycyclic aromatic hydrocarbon.
- EAS electrophilic aromatic substitution
- the method of making functional PIB homo oligomer or polymer and co-polymers directly uses stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain under cationic polymerization conditions.
- the functional polyisobutylene or isobutylene containing oligomers and polymers prepared using stoichiometric or near stoichiometric ratios of the capping or functionalization reagent provide quantitative or nearly quantitative functionality.
- the resulting product contains very little or no unreacted capping reagent(s) to remove, which makes the work-up easier, faster and provides oligomers with high purity.
- acrylate functional polyisobutylene oligomers were prepared using 1.07 stoichiometric ratio of phenoxybutyl acrylate (PBA) to polymer chain-end in 15 minutes at ⁇ 70C starting from polyisobutylene di-(tertiary chloride) with molecular weight of 12000.
- the acrylate functionality of functional PIB is 1.70 compared to a functionality of 1.74 for the PIB di-(tertiary chloride).
- the PBA capping was performed at ⁇ 50C while keeping other conditions unchanged.
- the obtained acrylate functionality of functional PIB is 1.60 after 15 min capping reaction. When the capping reaction was extended to 2.5h, the obtained acrylate functionality was substantially the same (1.57). Both Examples indicate that the PBA capping reaction went very quickly at ⁇ 50C to ⁇ 70C. The lower temperature is beneficial for functionality.
- the functional groups useful in the method are not generally limited and include any functional group that does not interfere the capping reaction.
- Some useful functional groups include acrylate, methacrylate, isocyanate, acrylic isocyanate, silane, alkoxysilane and chlorosilane.
- the functional groups can be either end groups or pendant groups in the oligomers or polymer.
- the introduced functional group can be used for click chemistry.
- the components in PIB-containing oligomers or polymers can be from styrene, isoprene or other monomers which can be polymerized by cationic polymerization mechanism.
- the weight ratio of co-monomer can range from 1% to 30%.
- the functionalized PIB containing polymers and oligomers can be used as one component of a curable composition.
- Other components of the curable composition include one or more of a co-monomer, catalyst, filler, antioxidant, reaction modifier, adhesion promoter, rheology modifier.
- the curable composition can optionally include a co-monomer.
- Useable co-monomers include polymerizable materials other than the PIB functionalized oligomer or polymer.
- the curable composition can include a catalyst to modify speed of the initiated reaction.
- the curable composition can optionally include a filler.
- a filler include, for example, lithopone, zirconium silicate, hydroxides, such as hydroxides of calcium, aluminum, magnesium, iron and the like, diatomaceous earth, carbonates, such as sodium, potassium, calcium, and magnesium carbonates, oxides, such as zinc, magnesium, chromic, cerium, zirconium and aluminum oxides, calcium clay, fumed silicas, treated silicas, precipitated silicas, untreated silicas, graphite, synthetic fibers and mixtures thereof.
- When used filler can be employed in concentrations effective to provide desired physical properties in the uncured composition and cured reaction products and typically in concentrations of about 0.1% to about 70% by weight of composition.
- the curable composition can optionally include an anti-oxidant.
- an anti-oxidant include those available commercially from Ciba Specialty Chemicals under the tradename IRGANOX. When used, the antioxidant should be used in the range of about 0.1 to about 15 weight percent of curable composition, such as about 0.3 to about 1 weight percent of curable composition.
- the curable composition can include a reaction modifier.
- a reaction modifier is a material that will increase or decrease reaction rate of the curable elastomeric sealant composition.
- quinones such as hydroquinone, monomethyl ether hydroquinone (MEHQ), napthoquinone and anthraquinone, may also be included to scavenge free radicals in the curable elastomeric sealant composition and thereby slow reaction of that composition and extend shelf life.
- the reaction modifier can be used in the range of about 0.1 to about 15 weight percent of curable composition.
- the curable composition can include one or more adhesion promoters that are compatible and known in the art.
- adhesion promoters include octyl trimethoxysilane (commercially available from Chemtura under the trade designation A-137), glycidyl trimethoxysilane (commercially available from Chemtura under the trade designation A-187), methacryloxypropyl trimethoxysilane (commercially available from Chemtura under the trade designation of A-174), vinyl trimethoxysilane, tetraethoxysilane and its partial condensation products, and combinations thereof.
- the adhesion promoter can be used in the range of about 0.1 to about 15 weight percent of curable composition.
- the curable composition can optionally include a thixotropic agent to modify rheological properties of the uncured composition.
- a thixotropic agent to modify rheological properties of the uncured composition.
- Some useful thixotropic agents include, for example, silicas, such as fused or fumed silicas, that may be untreated or treated so as to alter the chemical nature of their surface. Virtually any reinforcing fused, precipitated or fumed silica may be used.
- treated fumed silicas include polydimethylsiloxane-treated silicas and hexamethyldisilazane-treated silicas.
- Such treated silicas are commercially available, such as from Cabot Corporation under the tradename CAB-O-SIL ND-TS and Degussa Corporation under the tradename AEROSIL, such as AEROSIL R805.
- untreated silicas examples include commercially available amorphous silicas such as AEROSIL 300, AEROSIL 200 and AEROSIL 130.
- commercially available hydrous silicas include NIPSIL E150 and NIPSIL E200A manufactured by Japan Silica Kogya Inc.
- rheology modifier When used rheology modifier can be employed in concentrations effective to provide desired physical properties in the uncured composition and cured reaction products and typically in concentrations of about 0.1% to about 70% by weight of composition.
- the curable elastomeric composition can optionally include other conventional additives at known concentrations effective to provide expected properties so long as they do not inhibit the desirable properties such as curing mechanism, elongation, low temperature sealing force, tensile strength, chemical resistance.
- optional additives include, for example, reinforcing materials such as fibers, diluents, reactive diluents, coloring agents and pigments, moisture scavengers such as methyltrimethoxysilane and vinyltrimethyloxysilane and the like may be included.
- a curable composition can typically comprise:
- uncured composition viscosity can be formulated for application method and desired cycle time.
- the curable composition can be used as an adhesive to bond substrates together.
- the curable composition is believed to be useful in bonding components for films, laminations, composite structures and electronic or electrical devices.
- the curable composition can be used as a sealant.
- Components to be sealed by the disclosed curable compositions have a first predetermined sealing surface that is aligned with a second predetermined sealing surface.
- the aligned sealing surfaces are in a fixed relationship and move very little relative to each other.
- the aligned sealing surfaces are generally in fluid communication with a chamber. The seal formed between the aligned sealing surfaces prevents movement of materials between the surfaces and into, or out of, the chamber.
- the predetermined sealing surfaces are designed to allow a curable composition to be disposed on one or both surfaces during initial assembly of the component to form a seal therebetween. Design of the predetermined sealing surfaces enhances parameters such as alignment of the surfaces, contact area of the surfaces, surface finish of the surfaces, “fit” of the surfaces and separation of the surfaces to achieve a predetermined sealing effect.
- a predetermined sealing surface does not encompass surfaces that were not identified or designed prior to initial assembly to accommodate a seal or gasket, for example the outside surface of a component over which a repair material is molded or applied to lessen leaking. Sealing surfaces on an engine block and oil pan or engine intake manifold are examples of sealing surfaces in fixed relationship.
- the disclosed curable compositions can be in a flowable state for disposition onto at least a portion of one sealing surface to form a seal between the surfaces when they are aligned.
- the curable composition can be applied as a film over the sealing surface.
- the curable composition can also be applied as a bead in precise patterns by tracing, screen printing, robotic application and the like.
- the disclosed compositions are typically dispensed as a liquid or semi-solid under pressure through a nozzle and onto the component sealing surface.
- the nozzle size is chosen to provide a line or bead of composition having a desired width, height, shape and volume.
- the curable composition can be contained in a small tube and dispensed by squeezing the tube; contained in a cartridge and dispensed by longitudinal movement of a cartridge sealing member; or contained in a larger container such as a 5 gallon pail or 55 gallon drum and dispensed at the point of use by conventional automated dispensing equipment.
- Container size can be chosen to suit the end use application.
- the curable composition can be used to form a formed in place gasket (FIPG).
- FIPG formed in place gasket
- the composition is dispensed onto a first predetermined sealing surface.
- the first predetermined sealing surface and dispensed composition is aligned and sealingly engaged with a second predetermined sealing surface before the composition has fully cured.
- the composition will adhere to both sealing surfaces as it cures.
- the curable composition can be used to form a cured in place gasket (CIPG).
- CIPG cured in place gasket
- the composition is dispensed onto a first predetermined sealing surface and allowed to substantially cure before contact with a second predetermined sealing surface.
- the first sealing surface and cured composition is sealingly engaged with the second sealing surface thereby compressing the cured composition to provide a seal between the sealing surfaces.
- the composition will adhere to only the first sealing surface.
- the curable composition can be used to form a mold in place gasket (MIPG).
- MIPG mold in place gasket
- the part comprising the first predetermined sealing surface is placed in a mold.
- the composition is dispensed into the mold where it contacts the first sealing surface.
- the composition is typically allowed to cure before removal from the mold.
- the first sealing surface and molded composition is sealingly engaged with a second predetermined sealing surface thereby compressing the cured composition to provide a seal between the sealing surfaces.
- the composition will adhere to only the first sealing surface.
- the curable composition can be used in liquid injection molding (LIM).
- LIM liquid injection molding
- uncured composition is dispensed into a mold without any predetermined sealing surface under controlled pressure and temperature.
- the composition is typically allowed to cure before removal from the mold. After removal the molded part will retain its shape.
- the molded gasket is disposed between two predetermined sealing surfaces and compressed to provide a seal between the sealing surfaces.
- PIB di-tert-CI 41.00 g was dissolved in anhydrous n-butyl chloride (109.85 g) in a moisture-free environment. The mixture was then chilled down in a ⁇ 70 C cool bath with stir (210 rpm). n-Hexane (10.15 g), lutidine (0.10 g) and phenoxybutyl acrylate (1.60 g) were added to above reaction mixture in order. The reaction temperature was continuously monitored until ⁇ 70C was reached. TiCl4 (10.34 g) was then added at this temperature in one portion. The mixture was allowed to react at this condition for 15 min.
- PIB di-tent-CI 41.00 g was dissolved in anhydrous n-butyl chloride (109.85 g) in a moisture-free environment. The mixture was then chilled down in a ⁇ 70 C cool bath with stir (210 rpm). n-Hexane (10.15 g), lutidine (0.10 g) and phenoxybutyl acrylate (1.60 g) were added to above reaction mixture in order. The reaction temperature was continuously monitored until ⁇ 55 C was reached. TiCl4 (10.34 g) was then added at this temperature in one portion. The mixture was allowed to react at this condition for 15 min.
- PIB di-tert-Cl 39.65 g was dissolved in anhydrous n-butyl chloride (158 g) in a moisture-free environment. The mixture was then chilled down in a ⁇ 73 C cool bath with stir (140 rpm). Lutidine (0.10 g) and phenoxyethyl acrylate (3.56 g) were added to above reaction mixture in order. The reaction temperature was continuously monitored until ⁇ 73 C was reached. TiCl4 (14.27 g) was then added at this temperature in one portion. The mixture was allowed to react at this condition for 3 hours. 1H NMR sample aliquot was taken and quenched with pre-chilled MeOH, a functionality of 1.35 was achieved by peak area integration calculation. Additional reaction time did not provide a better functionality.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
Description
- One aspect relates to methods of making functional polyisobutylene (PIB)-containing oligomers and polymers and the materials made thereby. Another aspect relates to compositions made from the functional polyisobutylene (PIB)-containing oligomers and polymers.
- Typically, reactions do not proceed to completion. Reactants are added in excess of the stoichiometric amount calculated for that reaction to force reactions to proceed to completion.
- One embodiment provides a method of making functional polyisobutylene (PIB)-containing oligomers and polymers. By the disclosed method, the synthesis of functional PIB-containing polymers can be achieved directly under cationic polymerization conditions and does not include any post-polymerization reactions. The desired functionality is introduced by direct Electrophilic Aromatic Substitution (EAS) reaction using substituted phenyl ring carrying desirable functionalities that do not react with Lewis acid but have weak association with Lewis acid, which still allow living polymerization and EAS reaction under living cationic polymerization conditions. In the disclosed method functional polyisobutylene or isobutylene containing oligomers and polymers can be prepared using stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain.
- Experience would suggest that use of stoichiometric ratios would lead to incomplete reaction and lower functionalization of the end product. Typically, non-stoichiometric ratios are used to force the reaction to completion.
- Surprisingly, and contrary to common experience, using the disclosed method with a capping or functionalization reaction that is stoichiometrically quantitative or nearly quantitative provides highly functional polyisobutylene or isobutylene containing oligomers and polymers. Use of lower than stoichiometric ratios in the capping reaction lead to incomplete reaction and lower functionalization of the end product. Use of higher than stoichiometric ratios in the capping reaction lead to incomplete reaction and lower functionalization of the end product. Thus too little or too much capping reagent leads to incomplete reaction and lower functionalization of the end product.
- Further, by using stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain the resulting quantitative or nearly quantitative product contains very little or no unreacted capping reagent(s) to remove, which makes the work-up easier, faster and provides oligomers with high purity.
- The disclosed compounds include any and all isomers and stereoisomers. In general, unless otherwise explicitly stated the disclosed materials and processes may be alternately formulated to comprise, consist of, or consist essentially of, any appropriate components, moieties or steps herein disclosed. The disclosed materials and processes may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants, moieties, species and steps used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objective of the present disclosure.
- When the word “about” is used herein it is meant that the amount or condition it modifies can vary some beyond the stated amount so long as the function and/or objective of the disclosure are realized. The skilled artisan understands that there is seldom time to fully explore the extent of any area and expects that the disclosed result might extend, at least somewhat, beyond one or more of the disclosed limits. Later, having the benefit of this disclosure and understanding the concept and embodiments disclosed herein, a person of ordinary skill can, without inventive effort, explore beyond the disclosed limits and, when embodiments are found to be without any unexpected characteristics, those embodiments are within the meaning of the term about as used herein.
- Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art. As used herein for each of the various embodiments, the following definitions apply.
- “Alkyl” or “alkane” refers to a hydrocarbon chain or group containing only single bonds. The alkane can be a straight hydrocarbon chain or a branched hydrocarbon group. The alkane can be cyclic. The alkane can contain 1 to 20 carbon atoms, advantageously 1 to 10 carbon atoms and more advantageously 1 to 6 carbon atoms. In some embodiments the alkane can be substituted. Exemplary alkanes include methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and decyl.
- “Alkenyl” or “alkene” refers to a hydrocarbon chain or group containing one or more double bonds. The alkenyl can be a straight hydrocarbon chain or a branched hydrocarbon group. The alkene can be cyclic. The alkene can contain 1 to 20 carbon atoms, advantageously 1 to 10 carbon atoms and more advantageously 1 to 6 carbon atoms. The alkene can be an allyl group. The alkene can contain one or more double bonds that are conjugated. In some embodiments the alkene can be substituted.
- “Alkoxy” refers to the structure —OR, wherein R is hydrocarbyl.
- “Alkyne” or “alkynyl” refers to a hydrocarbon chain or group containing one or more triple bonds. The alkyne can be a straight hydrocarbon chain or a branched hydrocarbon group. The alkyne can be cyclic. The alkyne can contain 1 to 20 carbon atoms, advantageously 1 to 10 carbon atoms and more advantageously 1 to 6 carbon atoms. The alkyne can contain one or more triple bonds that are conjugated. In some embodiments the alkyne can be substituted.
- “Aryl” or “Ar” refers to a monocyclic or multicyclic aromatic group. The cyclic rings can be linked by a bond or fused. The aryl can contain from 6 to about 30 carbon atoms; advantageously 6 to 12 carbon atoms and in some embodiments 6 carbon atoms. Exemplary aryls include phenyl, biphenyl and naphthyl. In some embodiments the aryl is substituted.
- “Cationic polymerization” refers to polymerization of a monomer using a carbocationic initiator; a coinitiator such as a Lewis Acid, for example TiCl4; and a cationically polymerizable monomer. The reaction is typically performed in a solvent or mixture of solvents at low temperature (for example less than 0° C.) and substantially excluding moisture.
- “Ester” refers to the structure R—C(O)—O—R′ where R and R′ are independently selected hydrocarbyl groups. The hydrocarbyl groups can be substituted or unsubstituted.
- “Halogen” or “halide” refers to an atom selected from fluorine, chlorine, bromine and iodine.
- “Hetero” refers to one or more heteroatoms in a structure. Exemplary heteroatoms are independently selected from N, O and S.
- “Heteroaryl” refers to a monocyclic or multicyclic aromatic ring system wherein one or more ring atoms in the structure are heteroatoms. Exemplary heteroatoms are independently selected from N, O and S. The cyclic rings can be linked by a bond or fused. The heteroaryl can contain from 5 to about 30 carbon atoms; advantageously 5 to 12 carbon atoms and in some embodiments 5 to 6 carbon atoms. Exemplary heteroaryls include furyl, imidazolyl, pyrimidinyl, tetrazolyl, thienyl, pyridyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, thiazolyl, quinolinyl and isoquinolinyl. In some embodiments the heteroaryl is substituted.
- “Hydrocarbyl” refers to a group containing carbon and hydrogen atoms. The hydrocarbyl can be linear, branched, or cyclic group. The hydrocarbyl can be alkyl, alkenyl, alkynyl or aryl. In some embodiments, the hydrocarbyl is substituted.
- “Lewis acid” refers to a chemical entity that is capable of accepting a pair of electrons.
- “(Meth)acrylate” refers to acrylate and methacrylate.
- “Oligomer” refers to a defined, small number of repeating monomer units such as 10-5,000 units, and advantageously 10-1,000 units which have been polymerized to form a molecule. Oligomers are a subset of the term polymer.
- “One step reaction” refers to a chemical reaction to form a functionalized PIB containing oligomer or polymer wherein polymerization of isobutylene or an isobutylene containing monomer mixture and functionalization of the resulting oligomer or polymer is performed in the same reaction vessel and under cationic polymerization reaction conditions.
- “Polyaromatic hydrocarbon” or “PAr” or “polycyclic aromatic hydrocarbon” refers to a fused, multicyclic aromatic group for example containing 2 to 20 ring moieties. The polyaromatic hydrocarbon can contain from 6 to about 120 ring carbon atoms; advantageously 6 to 20 ring carbon atoms. In some embodiments the polyaromatic hydrocarbon contains heteroatoms as ring atoms. Exemplary polyaromatic hydrocarbons include naphthalene, anthracene, phenanthrene and fluorene. In some embodiments the aryl is substituted.
- “Polymer” refers to any polymerized product greater in chain length and molecular weight than the oligomer. Polymers can have a degree of polymerization of about 50 to about 25000. As used herein polymer includes oligomers and polymers. As used herein polymer includes homopolymers and copolymers.
- “Substituted” refers to the presence of one or more substituents on a molecule in any possible position. Useful substituents are those groups that do not significantly diminish the disclosed reaction schemes. Exemplary substituents include, for example, H, halogen, (meth)acrylate, epoxy, oxetane, urea, urethane, N3, NCS, CN, NCO, NO2, NX1X2, OX1, C(X1)3, C(halogen)3, COOX1, SX1, Si(OX1)iX2 3-1 , alkyl, alcohol, alkoxy; wherein X 1 and X2 each independently comprise H, alkyl, alkenyl, alkynyl or aryl and I is an integer from 0 to 3.
- One embodiment is a method of making PIB diacrylate by direct capping living PIB using stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain. By using stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain to provide a quantitative or nearly quantitative product containing very little or no unreacted capping reagent(s). Stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain are ratios where functionalization of the product is maximized. Ratios (of equivalents) of the capping or functionalization reagent to polymer end-chain can be in the range of 0.7 to 5; advantageously can be in the range of 0.8 to 2. Preferably the ratio is in the range of about 1, such as 0.9 to 1.1. Ratio of the capping or functionalization reagent to polymer end-chain =equivalents of the capping or functionalization reagent/equivalents of polymer end-chain.
- The capping reagent contains electro-donating groups. Suitable electro-donating groups include three major categories, phenoxy type structure, aryl substituted aromatic structure and alkyl substituted aromatic structure.
- Functional groups can be any group which can undergo reaction and cause crosslinking. Some suitable functional groups include acrylate, methacrylate, isocyanate, acrylic isocyanate, silane, chlorosilane, alkoxysilane etc and the functional groups can be either terminal groups or pendant groups in the oligomers and polymers.
- Initiators with one or more initiation sites can be used for synthesis of functional PIB-containing oligomers and polymers, including bi-functional initiator, which carries one or more functional groups other than initiation site. In some embodiments PIB-containing oligomers and polymers with one or more terminal or pendant functionalities can be prepared. With the bi-functional initiator, the direct capping reaction can generate functionality at the oligomers and polymer chain end. The functional PIB with same or varied functionalities can be prepared using bi-functional initiator.
- Components in RIB-containing co-oligomers and co-polymers can be any monomer which can be polymerized by cationic polymerization mechanism. Suitable monomers include styrene and isoprene.
- One embodiment includes a method of making functional PIB homo-oligomer or polymer and co-polymers directly under cationic polymerization conditions and not including any post-polymerization reactions (Chart 1). The desirable functionality is introduced by a capping reaction under cationic polymerization condition. Since a living PIB center is cation bearer, electrophilic aromatic substitution (EAS) reaction can be utilized as a capping reaction by a careful choice of substitutive aromatic structures. Electro-donating groups will facilitate the EAS reaction; therefore, three major categories (Chart 2) of capping reagent are discussed: aromatics with non-aromatic electro donating groups, polyaromatics and benzoid polycyclic aromatic hydrocarbon.
- The method of making functional PIB homo oligomer or polymer and co-polymers directly uses stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain under cationic polymerization conditions. The functional polyisobutylene or isobutylene containing oligomers and polymers prepared using stoichiometric or near stoichiometric ratios of the capping or functionalization reagent, provide quantitative or nearly quantitative functionality. Also, by using stoichiometric or near stoichiometric ratios of the capping or functionalization reagents, the resulting product contains very little or no unreacted capping reagent(s) to remove, which makes the work-up easier, faster and provides oligomers with high purity.
- As shown in Example 2, acrylate functional polyisobutylene oligomers were prepared using 1.07 stoichiometric ratio of phenoxybutyl acrylate (PBA) to polymer chain-end in 15 minutes at −70C starting from polyisobutylene di-(tertiary chloride) with molecular weight of 12000. The acrylate functionality of functional PIB is 1.70 compared to a functionality of 1.74 for the PIB di-(tertiary chloride). As shown in Example 3, the PBA capping was performed at −50C while keeping other conditions unchanged. The obtained acrylate functionality of functional PIB is 1.60 after 15 min capping reaction. When the capping reaction was extended to 2.5h, the obtained acrylate functionality was substantially the same (1.57). Both Examples indicate that the PBA capping reaction went very quickly at −50C to −70C. The lower temperature is beneficial for functionality.
- When phenoxyethyl acrylate (PEA) was used as capping agent with the ratio of PEA/polymer chain=2 (See Example 4), the obtained acrylate functionality after a 3 hour capping reaction is 1.35, which is substantially lower than the 1.74 functionality of polyisobutylene di-(tertiary chloride). This is contrary to expectations as it is expected that an increase in capping or functionalization equivalents would increase the acrylate functionality and decrease the reaction time.
- The functional groups useful in the method are not generally limited and include any functional group that does not interfere the capping reaction. Some useful functional groups include acrylate, methacrylate, isocyanate, acrylic isocyanate, silane, alkoxysilane and chlorosilane. The functional groups can be either end groups or pendant groups in the oligomers or polymer. The introduced functional group can be used for click chemistry.
- The components in PIB-containing oligomers or polymers can be from styrene, isoprene or other monomers which can be polymerized by cationic polymerization mechanism. The weight ratio of co-monomer can range from 1% to 30%.
- Below is Chart 1: Direct capping reaction scheme
- Below is Chart 2: Capping agent: three categories
- The functionalized PIB containing polymers and oligomers can be used as one component of a curable composition. Other components of the curable composition include one or more of a co-monomer, catalyst, filler, antioxidant, reaction modifier, adhesion promoter, rheology modifier.
- Co-monomer
- The curable composition can optionally include a co-monomer. Useable co-monomers include polymerizable materials other than the PIB functionalized oligomer or polymer.
- Catalyst
- The curable composition can include a catalyst to modify speed of the initiated reaction.
- Filler
- The curable composition can optionally include a filler. Some useful fillers include, for example, lithopone, zirconium silicate, hydroxides, such as hydroxides of calcium, aluminum, magnesium, iron and the like, diatomaceous earth, carbonates, such as sodium, potassium, calcium, and magnesium carbonates, oxides, such as zinc, magnesium, chromic, cerium, zirconium and aluminum oxides, calcium clay, fumed silicas, treated silicas, precipitated silicas, untreated silicas, graphite, synthetic fibers and mixtures thereof. When used filler can be employed in concentrations effective to provide desired physical properties in the uncured composition and cured reaction products and typically in concentrations of about 0.1% to about 70% by weight of composition.
- Antioxidant
- The curable composition can optionally include an anti-oxidant. Some useful antioxidants include those available commercially from Ciba Specialty Chemicals under the tradename IRGANOX. When used, the antioxidant should be used in the range of about 0.1 to about 15 weight percent of curable composition, such as about 0.3 to about 1 weight percent of curable composition.
- Reaction Modifier
- The curable composition can include a reaction modifier. A reaction modifier is a material that will increase or decrease reaction rate of the curable elastomeric sealant composition. For example, quinones, such as hydroquinone, monomethyl ether hydroquinone (MEHQ), napthoquinone and anthraquinone, may also be included to scavenge free radicals in the curable elastomeric sealant composition and thereby slow reaction of that composition and extend shelf life. When used, the reaction modifier can be used in the range of about 0.1 to about 15 weight percent of curable composition.
- Adhesion Promoter
- The curable composition can include one or more adhesion promoters that are compatible and known in the art. Examples of useful commercially available adhesion promoters include octyl trimethoxysilane (commercially available from Chemtura under the trade designation A-137), glycidyl trimethoxysilane (commercially available from Chemtura under the trade designation A-187), methacryloxypropyl trimethoxysilane (commercially available from Chemtura under the trade designation of A-174), vinyl trimethoxysilane, tetraethoxysilane and its partial condensation products, and combinations thereof. When used, the adhesion promoter can be used in the range of about 0.1 to about 15 weight percent of curable composition.
- Rheology Modifiers
- The curable composition can optionally include a thixotropic agent to modify rheological properties of the uncured composition. Some useful thixotropic agents include, for example, silicas, such as fused or fumed silicas, that may be untreated or treated so as to alter the chemical nature of their surface. Virtually any reinforcing fused, precipitated or fumed silica may be used.
- Examples of treated fumed silicas include polydimethylsiloxane-treated silicas and hexamethyldisilazane-treated silicas. Such treated silicas are commercially available, such as from Cabot Corporation under the tradename CAB-O-SIL ND-TS and Degussa Corporation under the tradename AEROSIL, such as AEROSIL R805.
- Examples of untreated silicas include commercially available amorphous silicas such as AEROSIL 300, AEROSIL 200 and AEROSIL 130. Commercially available hydrous silicas include NIPSIL E150 and NIPSIL E200A manufactured by Japan Silica Kogya Inc.
- When used rheology modifier can be employed in concentrations effective to provide desired physical properties in the uncured composition and cured reaction products and typically in concentrations of about 0.1% to about 70% by weight of composition.
- The curable elastomeric composition can optionally include other conventional additives at known concentrations effective to provide expected properties so long as they do not inhibit the desirable properties such as curing mechanism, elongation, low temperature sealing force, tensile strength, chemical resistance. Example of such optional additives include, for example, reinforcing materials such as fibers, diluents, reactive diluents, coloring agents and pigments, moisture scavengers such as methyltrimethoxysilane and vinyltrimethyloxysilane and the like may be included.
- A curable composition can typically comprise:
-
- about 10 to 95 wt % of a functional group containing PIB oligomer or polymer;
- about 0 to 80 wt % co-monomer;
- about 0 to 20 wt % cross-linking agent;
- about 0 to 20 wt % of a catalyst;
- about 0 to 70 wt % of a filler;
- about 0 to 15 wt % of a antioxidant;
- about 0 to 15 wt % of a reaction modifier;
- about 0 to 15 wt% of adhesion promoter;
- about 0 to 70 wt % of rheology modifier;
- about 0 to 10 wt % of other conventional additives.
- Specific physical properties required for the uncured, composition will depend on application. For example, uncured composition viscosity can be formulated for application method and desired cycle time.
- Specific physical properties required for cured reaction products of the composition will depend on application, minimum and maximum operating temperatures within the application, desired tensile strength at high temperatures and desired sealing force at low temperatures.
- In one embodiment the curable composition can be used as an adhesive to bond substrates together. The curable composition is believed to be useful in bonding components for films, laminations, composite structures and electronic or electrical devices.
- In one embodiment the curable composition can be used as a sealant. Components to be sealed by the disclosed curable compositions have a first predetermined sealing surface that is aligned with a second predetermined sealing surface. Typically, the aligned sealing surfaces are in a fixed relationship and move very little relative to each other. The aligned sealing surfaces are generally in fluid communication with a chamber. The seal formed between the aligned sealing surfaces prevents movement of materials between the surfaces and into, or out of, the chamber.
- One or both of the sealing surfaces can be machined or formed. The predetermined sealing surfaces are designed to allow a curable composition to be disposed on one or both surfaces during initial assembly of the component to form a seal therebetween. Design of the predetermined sealing surfaces enhances parameters such as alignment of the surfaces, contact area of the surfaces, surface finish of the surfaces, “fit” of the surfaces and separation of the surfaces to achieve a predetermined sealing effect. A predetermined sealing surface does not encompass surfaces that were not identified or designed prior to initial assembly to accommodate a seal or gasket, for example the outside surface of a component over which a repair material is molded or applied to lessen leaking. Sealing surfaces on an engine block and oil pan or engine intake manifold are examples of sealing surfaces in fixed relationship.
- In one embodiment the disclosed curable compositions can be in a flowable state for disposition onto at least a portion of one sealing surface to form a seal between the surfaces when they are aligned. The curable composition can be applied as a film over the sealing surface. The curable composition can also be applied as a bead in precise patterns by tracing, screen printing, robotic application and the like. In bead applications the disclosed compositions are typically dispensed as a liquid or semi-solid under pressure through a nozzle and onto the component sealing surface. The nozzle size is chosen to provide a line or bead of composition having a desired width, height, shape and volume. The curable composition can be contained in a small tube and dispensed by squeezing the tube; contained in a cartridge and dispensed by longitudinal movement of a cartridge sealing member; or contained in a larger container such as a 5 gallon pail or 55 gallon drum and dispensed at the point of use by conventional automated dispensing equipment. Container size can be chosen to suit the end use application.
- In one embodiment the curable composition can be used to form a formed in place gasket (FIPG). In this application the composition is dispensed onto a first predetermined sealing surface. The first predetermined sealing surface and dispensed composition is aligned and sealingly engaged with a second predetermined sealing surface before the composition has fully cured. The composition will adhere to both sealing surfaces as it cures.
- In one embodiment the curable composition can be used to form a cured in place gasket (CIPG). In this application the composition is dispensed onto a first predetermined sealing surface and allowed to substantially cure before contact with a second predetermined sealing surface. The first sealing surface and cured composition is sealingly engaged with the second sealing surface thereby compressing the cured composition to provide a seal between the sealing surfaces. The composition will adhere to only the first sealing surface.
- In one embodiment the curable composition can be used to form a mold in place gasket (MIPG). In this application the part comprising the first predetermined sealing surface is placed in a mold. The composition is dispensed into the mold where it contacts the first sealing surface. The composition is typically allowed to cure before removal from the mold. After molding, the first sealing surface and molded composition is sealingly engaged with a second predetermined sealing surface thereby compressing the cured composition to provide a seal between the sealing surfaces. The composition will adhere to only the first sealing surface.
- In one embodiment the curable composition can be used in liquid injection molding (LIM). In this application uncured composition is dispensed into a mold without any predetermined sealing surface under controlled pressure and temperature. The composition is typically allowed to cure before removal from the mold. After removal the molded part will retain its shape. In sealing applications the molded gasket is disposed between two predetermined sealing surfaces and compressed to provide a seal between the sealing surfaces.
- The following examples are included for purposes of illustration so that the disclosure may be more readily understood and are in no way intended to limit the scope of the disclosure unless otherwise specifically indicated.
-
- IB is isobutylene
- m-DCC is meta dicumyl chloride
- (PIB di-tert-CI preparation): IB polymerization is carried out at −80 ° C. under a dry nitrogen atmosphere in a glove box using [IB]=5.1 M, [m-DCC]=33 mM and [Lutidine]=10 mM using methylchloride/hexane (38/62 wt/wt) mixture. TiCl4 (=15 mM) is added to start polymerization. After 30 min polymerization, another portion TiCl4 (=15 mM) is added and the reaction is allowed to proceed for 3 hours (conversion of IB is monitored in-situ to ensure complete conversion). After full conversion of IB, 0.33 eq of MeOH to the total amount to TiCl4 was added to the reactor to quench the cationic reaction.
- Work-Up: The reaction mixture is stripped to remove methylchloride and then quenched with 5% wt aqueous NaOH solution. The organic layer is washed with water twice and with methanol twice. The polymer solution is stripped to remove hexane. PIB di-tert-CI was obtained as a viscous liquid with a functionality of 1.74.
- (phenoxybutyl acrylate end capping): PIB di-tert-CI (41.00 g) was dissolved in anhydrous n-butyl chloride (109.85 g) in a moisture-free environment. The mixture was then chilled down in a −70 C cool bath with stir (210 rpm). n-Hexane (10.15 g), lutidine (0.10 g) and phenoxybutyl acrylate (1.60 g) were added to above reaction mixture in order. The reaction temperature was continuously monitored until −70C was reached. TiCl4 (10.34 g) was then added at this temperature in one portion. The mixture was allowed to react at this condition for 15 min. 1H NMR sample aliquot was taken and quenched with pre-chilled MeOH, a functionality of 1.77 was achieved by peak area integration calculation. This near stoichiometric (1.07 eq) chain end capping reaction was achieved quantitatively in a short period of time, and maintained the original functionality (1.74) without side reactions.
- (phenoxybutyl acrylate end capping): PIB di-tent-CI (41.00 g) was dissolved in anhydrous n-butyl chloride (109.85 g) in a moisture-free environment. The mixture was then chilled down in a −70 C cool bath with stir (210 rpm). n-Hexane (10.15 g), lutidine (0.10 g) and phenoxybutyl acrylate (1.60 g) were added to above reaction mixture in order. The reaction temperature was continuously monitored until −55 C was reached. TiCl4 (10.34 g) was then added at this temperature in one portion. The mixture was allowed to react at this condition for 15 min. 1H NMR sample aliquot was taken and quenched with pre-chilled MeOH, a functionality of 1.60 was achieved by peak area integration calculation. Additional reaction time did not provide a better functionality: F=1.57 at 2.5 hr. Slight variation of functionality might be due to the NMR system error in integration.
- (phenoxyethyl acrylate end capping): PIB di-tert-Cl (39.65 g) was dissolved in anhydrous n-butyl chloride (158 g) in a moisture-free environment. The mixture was then chilled down in a −73 C cool bath with stir (140 rpm). Lutidine (0.10 g) and phenoxyethyl acrylate (3.56 g) were added to above reaction mixture in order. The reaction temperature was continuously monitored until −73 C was reached. TiCl4 (14.27 g) was then added at this temperature in one portion. The mixture was allowed to react at this condition for 3 hours. 1H NMR sample aliquot was taken and quenched with pre-chilled MeOH, a functionality of 1.35 was achieved by peak area integration calculation. Additional reaction time did not provide a better functionality.
- While preferred embodiments have been set forth for purposes of illustration, the foregoing description should not be deemed a limitation of the disclosure herein. Accordingly, various modifications, adaptations and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present disclosure.
Claims (9)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/934,941 US20160083487A1 (en) | 2013-05-10 | 2015-11-06 | Functional Polyisobutylene-Containing Oligomers and Polymers |
US16/746,123 US11142595B2 (en) | 2013-05-10 | 2020-01-17 | Functional polyisobutylene-containing oligomers and polymers |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361822037P | 2013-05-10 | 2013-05-10 | |
PCT/US2014/037476 WO2014183021A1 (en) | 2013-05-10 | 2014-05-09 | Functional polyisobutylene-containing oligomers and polymers |
US14/934,941 US20160083487A1 (en) | 2013-05-10 | 2015-11-06 | Functional Polyisobutylene-Containing Oligomers and Polymers |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2014/037476 Continuation WO2014183021A1 (en) | 2013-05-10 | 2014-05-09 | Functional polyisobutylene-containing oligomers and polymers |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/746,123 Division US11142595B2 (en) | 2013-05-10 | 2020-01-17 | Functional polyisobutylene-containing oligomers and polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
US20160083487A1 true US20160083487A1 (en) | 2016-03-24 |
Family
ID=51867767
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/934,941 Abandoned US20160083487A1 (en) | 2013-05-10 | 2015-11-06 | Functional Polyisobutylene-Containing Oligomers and Polymers |
US16/746,123 Active US11142595B2 (en) | 2013-05-10 | 2020-01-17 | Functional polyisobutylene-containing oligomers and polymers |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/746,123 Active US11142595B2 (en) | 2013-05-10 | 2020-01-17 | Functional polyisobutylene-containing oligomers and polymers |
Country Status (7)
Country | Link |
---|---|
US (2) | US20160083487A1 (en) |
EP (1) | EP2994492B1 (en) |
JP (3) | JP6529961B2 (en) |
KR (2) | KR102306253B1 (en) |
CN (1) | CN105764937B (en) |
TW (1) | TWI643874B (en) |
WO (1) | WO2014183021A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180362676A1 (en) * | 2015-12-11 | 2018-12-20 | Kaneka Corporation | Method of producing (meth)acryloyl-terminated polyisobutylene polymer |
US10840518B2 (en) | 2015-07-30 | 2020-11-17 | Threebond Co., Ltd. | Photocurable resin composition, fuel cell, and sealing method |
US11548974B2 (en) | 2018-03-26 | 2023-01-10 | Medtronic, Inc. | Modified polyisobutylene-based polymers, methods of making, and medical devices |
US12221458B2 (en) | 2019-08-19 | 2025-02-11 | Lg Chem, Ltd. | Organic borate-based catalyst, method for preparing isobutene oligomer using the same and isobutene oligomer prepared thereby |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108752992A (en) * | 2018-05-21 | 2018-11-06 | 朱红艳 | Aqueous peelable resin emulsion of one kind and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04183702A (en) * | 1990-11-17 | 1992-06-30 | Kanegafuchi Chem Ind Co Ltd | Production of isobutylene polymer having functional end |
US20060264577A1 (en) * | 2005-04-08 | 2006-11-23 | Rudolf Faust | Capping reactions in cationic polymerization; kinetic and synthetic utility |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4429099A (en) | 1982-11-22 | 1984-01-31 | The University Of Akron | Phenol terminated polymers and epoxies therefrom |
US4486572A (en) | 1983-07-06 | 1984-12-04 | University Of Akron | Synthesis of amphiphilic block copolymers and networks |
US5247021A (en) | 1989-06-06 | 1993-09-21 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Process for preparation of a polymer having reactive terminal group |
WO1995010544A1 (en) * | 1993-10-15 | 1995-04-20 | University Of Massachusetts At Lowell | Capping of living polymers |
US5741859A (en) * | 1997-02-03 | 1998-04-21 | Dow Corning Corporation | Block copolymers of polyisobutylene and polydimethylsiloxane |
US6469115B1 (en) | 2000-05-16 | 2002-10-22 | Dow Corning Corporation | Virtually telechelic silyl-functional polyisobutylene |
DE10207963A1 (en) * | 2002-02-25 | 2003-09-04 | Basf Ag | Production of aromatics substituted with alpha-chloroisopropyl |
DE10317863A1 (en) | 2003-04-16 | 2004-11-04 | Basf Ag | Process for the preparation of polyisobutenyl (meth) acrylates |
DE10322164A1 (en) * | 2003-05-16 | 2004-12-02 | Basf Ag | Process for the preparation of garboxyl-terminated polyisobutenes |
EP2284203B1 (en) * | 2004-08-20 | 2015-03-04 | Chevron Oronite Company LLC | Method for preparation of polyolefins containing exo-olefin chain ends |
CA2691087C (en) | 2007-06-19 | 2016-04-05 | The University Of Akron | Singly-terminated polyisobutylenes and process for making same |
US8513361B2 (en) * | 2007-12-28 | 2013-08-20 | Bridgestone Corporation | Interpolymers containing isobutylene and diene mer units |
EP2274343A1 (en) | 2008-05-02 | 2011-01-19 | Basf Se | Process and apparatus for continuously polymerizing cationically polymerizable monomers |
US8344073B2 (en) | 2009-01-16 | 2013-01-01 | The University Of Southern Mississippi | Functionalization of polyolefins with phenoxy derivatives |
US20120077934A1 (en) * | 2009-03-23 | 2012-03-29 | University Of Massachusetts | Functional Polyisobutylene Based Macromonomers And Methods For Making And Using The Same |
US8592527B2 (en) | 2010-06-14 | 2013-11-26 | University Of Southern Mississippi | Vinyl ether end-functionalized polyolefins |
US20120208013A1 (en) * | 2011-02-15 | 2012-08-16 | 3M Innovative Properties Company | Isobutylene copolymer with grafted polymer groups |
CN103827158B (en) * | 2011-09-27 | 2017-02-15 | 株式会社钟化 | (meth)acryloyl-terminated polyisobutylene polymer, method for producing same, and active energy ray-curable composition |
EP2948482A4 (en) | 2013-01-28 | 2017-02-22 | Henkel IP & Holding GmbH | Synthesis of functional polyisobutylene-containing oligomers and polymers |
-
2014
- 2014-05-09 WO PCT/US2014/037476 patent/WO2014183021A1/en active Application Filing
- 2014-05-09 KR KR1020217014427A patent/KR102306253B1/en active Active
- 2014-05-09 KR KR1020157032905A patent/KR102253845B1/en active Active
- 2014-05-09 EP EP14793981.3A patent/EP2994492B1/en active Active
- 2014-05-09 CN CN201480026693.XA patent/CN105764937B/en active Active
- 2014-05-09 JP JP2016513115A patent/JP6529961B2/en active Active
- 2014-05-09 TW TW103116613A patent/TWI643874B/en active
-
2015
- 2015-11-06 US US14/934,941 patent/US20160083487A1/en not_active Abandoned
-
2018
- 2018-12-12 JP JP2018232748A patent/JP2019065298A/en active Pending
-
2020
- 2020-01-17 US US16/746,123 patent/US11142595B2/en active Active
-
2021
- 2021-04-01 JP JP2021063124A patent/JP2021105181A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04183702A (en) * | 1990-11-17 | 1992-06-30 | Kanegafuchi Chem Ind Co Ltd | Production of isobutylene polymer having functional end |
US20060264577A1 (en) * | 2005-04-08 | 2006-11-23 | Rudolf Faust | Capping reactions in cationic polymerization; kinetic and synthetic utility |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10840518B2 (en) | 2015-07-30 | 2020-11-17 | Threebond Co., Ltd. | Photocurable resin composition, fuel cell, and sealing method |
US20180362676A1 (en) * | 2015-12-11 | 2018-12-20 | Kaneka Corporation | Method of producing (meth)acryloyl-terminated polyisobutylene polymer |
US10604598B2 (en) * | 2015-12-11 | 2020-03-31 | Kaneka Corporation | Method of producing (meth)acryloyl-terminated polyisobutylene polymer |
US11548974B2 (en) | 2018-03-26 | 2023-01-10 | Medtronic, Inc. | Modified polyisobutylene-based polymers, methods of making, and medical devices |
US12221458B2 (en) | 2019-08-19 | 2025-02-11 | Lg Chem, Ltd. | Organic borate-based catalyst, method for preparing isobutene oligomer using the same and isobutene oligomer prepared thereby |
Also Published As
Publication number | Publication date |
---|---|
WO2014183021A1 (en) | 2014-11-13 |
KR102253845B1 (en) | 2021-05-21 |
CN105764937B (en) | 2017-10-31 |
TW201504261A (en) | 2015-02-01 |
JP2021105181A (en) | 2021-07-26 |
JP2019065298A (en) | 2019-04-25 |
JP6529961B2 (en) | 2019-06-12 |
TWI643874B (en) | 2018-12-11 |
KR20210059012A (en) | 2021-05-24 |
EP2994492B1 (en) | 2021-03-17 |
KR20160006706A (en) | 2016-01-19 |
JP2016518499A (en) | 2016-06-23 |
EP2994492A1 (en) | 2016-03-16 |
US11142595B2 (en) | 2021-10-12 |
US20200148798A1 (en) | 2020-05-14 |
KR102306253B1 (en) | 2021-09-29 |
CN105764937A (en) | 2016-07-13 |
EP2994492A4 (en) | 2017-01-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11142595B2 (en) | Functional polyisobutylene-containing oligomers and polymers | |
JP5552419B2 (en) | Curable composition | |
TW201302996A (en) | Curable elastomer compositions with low temperature sealing capability | |
CN104910344A (en) | Preparation method of rapid UV-cured fluorine-containing hydrophobic polyurethane elastic coating layer | |
JP2012102243A (en) | Curable composition and cured product | |
US9828454B2 (en) | Synthesis of functional polyisobutylene-containing oligomers and polymers | |
JP2013148785A (en) | Image display device and manufacturing method of the same | |
CN108084436A (en) | A kind of epoxy curing agent, its preparation method and application | |
CN109135630A (en) | A kind of moisture-curable silicone-containing based polyacrylic acid ester sealant and preparation method thereof | |
US20060111536A1 (en) | Organic polymer having epoxy-group-containing silicon group at end and process for producing the same | |
JP6928732B1 (en) | Curable composition and cured product using it | |
CN110770263A (en) | Polar functionalized hydrocarbon resins post-modified via reactor | |
EP4551613A1 (en) | Polymers containing catechol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: HENKEL CORPORATION, CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BURDZY, MATTHEW P.;FENG, DINGSONG;ZHANG, TIANZHI;AND OTHERS;SIGNING DATES FROM 20131021 TO 20140318;REEL/FRAME:039343/0132 |
|
AS | Assignment |
Owner name: HENKEL IP & HOLDING GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HENKEL CORPORATION;REEL/FRAME:043005/0891 Effective date: 20170714 |
|
AS | Assignment |
Owner name: HENKEL (CHINA) COMPANY LIMITED, CHINA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HENKEL CORPORATION;REEL/FRAME:043629/0336 Effective date: 20170614 Owner name: HENKEL AG & CO. KGAA, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HENKEL (CHINA) COMPANY LIMITED;REEL/FRAME:043629/0765 Effective date: 20170629 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |