AU4180396A - New silicon compounds with sterically hindered linear amine functions, useful for the heat and light stabilization of polymers - Google Patents
New silicon compounds with sterically hindered linear amine functions, useful for the heat and light stabilization of polymers Download PDFInfo
- Publication number
- AU4180396A AU4180396A AU41803/96A AU4180396A AU4180396A AU 4180396 A AU4180396 A AU 4180396A AU 41803/96 A AU41803/96 A AU 41803/96A AU 4180396 A AU4180396 A AU 4180396A AU 4180396 A AU4180396 A AU 4180396A
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- 229920000642 polymer Polymers 0.000 title claims description 45
- 125000003277 amino group Chemical group 0.000 title claims description 29
- 230000006641 stabilisation Effects 0.000 title description 2
- 238000011105 stabilization Methods 0.000 title description 2
- 150000003377 silicon compounds Chemical class 0.000 title 1
- 150000003254 radicals Chemical class 0.000 claims description 67
- -1 hydrocarbon radical Chemical class 0.000 claims description 65
- 125000000524 functional group Chemical group 0.000 claims description 53
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- 150000001412 amines Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 16
- 230000005494 condensation Effects 0.000 claims description 15
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 14
- 150000002894 organic compounds Chemical class 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- 229920001577 copolymer Chemical class 0.000 claims description 10
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920000620 organic polymer Polymers 0.000 claims description 9
- 150000002923 oximes Chemical class 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 229910014033 C-OH Inorganic materials 0.000 claims description 8
- 229910014570 C—OH Inorganic materials 0.000 claims description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 229910018557 Si O Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- 229910008326 Si-Y Inorganic materials 0.000 claims description 3
- 229910006773 Si—Y Inorganic materials 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006237 Beckmann rearrangement reaction Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 102100039246 Elongator complex protein 1 Human genes 0.000 claims description 2
- 101710167754 Elongator complex protein 1 Proteins 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical group 0.000 claims description 2
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical class CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000003921 oil Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000007792 addition Methods 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229910018540 Si C Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SXGXCSASZBCDRM-UHFFFAOYSA-N n-tert-butyl-2-methylbut-3-en-2-amine Chemical compound CC(C)(C)NC(C)(C)C=C SXGXCSASZBCDRM-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 125000005936 piperidyl group Chemical group 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- OSNVTFATVNTMGM-UHFFFAOYSA-N 2-(3,5-dicyclohexyl-4-hydroxyphenyl)propanoic acid Chemical compound OC=1C(C2CCCCC2)=CC(C(C(O)=O)C)=CC=1C1CCCCC1 OSNVTFATVNTMGM-UHFFFAOYSA-N 0.000 description 1
- 102100034241 Elongator complex protein 2 Human genes 0.000 description 1
- 101710167764 Elongator complex protein 2 Proteins 0.000 description 1
- FXNFFCMITPHEIT-UHFFFAOYSA-N Ethyl 10-undecenoate Chemical compound CCOC(=O)CCCCCCCCC=C FXNFFCMITPHEIT-UHFFFAOYSA-N 0.000 description 1
- 241001484259 Lacuna Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical class C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- DQEUYIQDSMINEY-UHFFFAOYSA-M magnesium;prop-1-ene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C=C DQEUYIQDSMINEY-UHFFFAOYSA-M 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- YXIAJHJGVGZXCG-UHFFFAOYSA-N n-tert-butyl-2-methylbut-3-yn-2-amine Chemical compound CC(C)(C)NC(C)(C)C#C YXIAJHJGVGZXCG-UHFFFAOYSA-N 0.000 description 1
- 101150009274 nhr-1 gene Proteins 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Description
WO 96/16127 1 PCT/FR95/01502 NEW SILICONE COMPOUNDS CONTAINING STERICALLY HINDERED LINEAR AMINE FUNCTIONAL GROUPS WHICH ARE USEFUL FOR THE LIGHT AND THERMAL STABILIZATION OF POLYMERS 5 The present invention relates, in its first subject, to new silicone compounds comprising, per molecule, at least one sterically hindered linear amine functional group bonded via an Si-O-C or Si-C bond to the silicon atom; it also relates, in its first 10 subject, to silicone compounds comprising, per molecule, at least one sterically hindered linear amine functional group bonded to the silicon atom via an Si-O-C or Si-C bond and at least one other compatibilizing functional group bonded to the silicon 15 via an Si-C bond. It also relates, in a second subject, to processes for the preparation of the said silicone compounds. It further relates, in a third subject, to the use of the same compounds in polymers for improving their resistance to degradation under the effect of 20 ultraviolet (UV) radiation, of atmospheric oxygen and of heat. Indeed, organic polymers, and more particularly polyolefins and polyalkadienes, degrade when they are subjected to external agents and in 25 particular to the combined effect of air and of solar ultraviolet radiation. This degradation is generally limited by the 2 introduction into the polymer of small amounts of stabilizing agents. Among these anti-UV stabilizers, sterically hindered amines, in particular 2,2,6,6-tetramethyl 5 piperidines, are currently among the most effective. However, in practice, one of the major problems relating to the use of these anti-UV stabilizers is to obtain a good compromise between their effectiveness, which involves their mobility 10 within the polymer, and the permanence of their effect, which involves the use of molecules with a high molecular mass having excellent compatibility with the polymers to be stabilized. It has been proposed in the prior state of 15 the art to resort advantageously to polyorganosiloxanes carrying sterically hindered piperidyl functional groups. Mention may be made, as documents illustrating this prior art, of, for example, the documents Patents JP-A-01/096259, EP-A-0,338,393, EP-A-0,343,717, 20 EP-A-0,358,190, EP-A-0,388,321 and EP-A-0,491,659. However, to the knowledge of the Applicant Company, no document of the prior art describes polyorganosiloxanes which, on the one hand, have a structure in which each sterically hindered amine 25 functional group has a linear structure and, on the other hand, are endowed with properties which are useful for improving the resistance of the polymers to degradation under the effect of UV radiation, of 3 atmospheric oxygen and of heat. More precisely, the present invention relates, in its first subject, to a polyorganosiloxane comprising, per molecule, at least 3 siloxy units, 5 including at least one siloxy functional unit of formula: (1b) XSi(0) 3-) 2 in which: - the symbols Ri are identical or different and represent a monovalent hydrocarbon radical chosen 10 from the linear or branched alkyl radicals having from 1 to 4 carbon atoms and the phenyl radical; - the symbol X represents a monovalent group of formula -A-Z where: A is a single valency bond or an oxygen atom; 15 the symbol Z represents a monovalent group, the free valency of which is carried by a carbon atom, containing a secondary or tertiary amine functional group in a linear hydrocarbon chain containing from 9 to 40 20 carbon atoms, in which the two carbon atoms of the chain situated in the a and a' positions- with respect to the nitrogen atom do not contain a hydrogen atom; a is a number chosen from 0, 1 and 2. 25 The polyorganosiloxane can additionally have 4 at least one other functional unit of formula: (Rpl)bWSi(0)3 2 in which: the symbols R 1 have the same meanings as those given above with respect to the formula (I); 5 the symbol W represents a monovalent group containing a compatibilizing functional group chosen from: a linear or branched alkyl radical having more than 4 carbon atoms; a radical of formula -R 2
-COO-R
3 in which R 2 represents a linear 10 or branched alkylene radical having from 5 to 20 carbon atoms and R 3 represents a linear or branched alkyl radical having from 1 to 12 carbon atoms; a radical of formula -R 4
-O-(R
5 -O)c-R 6 in which R 4 represents a linear or branched alkylene 15 radical having from 3 to 15 carbon atoms, R 5 represents a linear or branched alkylene radical having from 1 to 3 carbon atoms, c is a number from 0 to 10 and R 6 represents a hydrogen atom, a linear or branched alkyl radical having from 1 to 20 12 carbon atoms or an acyl radical -CO-R 7 where R 7 represents a linear or branched alkyl radical having from 1 to 11 carbon atoms; b is a number chosen from 0, 1 and 2. The other possible siloxy unit(s) of the 25 polyorganosiloxane correspond(s) to the formula: 5 (R)d (H)e Si(0) 4 -(d + e) 2 in which - the symbols R 1 have the same meanings as those given above with respect to the formula (I); - d is a number chosen from 0, 1, 2 and 3; 5 e is a number chosen from 0 and 1; - the sum d + e is not greater than 3. The siloxy units of formula (I), when there are more than two of them, can be identical to or different from one another; the same comment also 10 applies to the siloxy units of formulae (II) and (III). In the present statement, the following definitions will be understood to apply: - "linear amine functional groups": monovalent Z groups which do not have the linking unit A via 15 which they are bonded to the silicon atoms; - "compatibilizing functional groups": optional monovalent W groups which are directly bonded to the silicon atoms (in this case, Si-C bonds are then formed); 20 - "mixed organopolysiloxanes (or polymers)": polymers which have both amine functional group(s) and compatibilizing functional group(s); - "organopolysiloxanes without linking units": optionally mixed polymers according to the 25 invention in the structure of which the linear 6 amine functional groups are bonded to the silicon atoms via the linking unit A = valency bond (in this case, Si-C bonds have then been formed); - "organopolysiloxanes containing oxygen linking 5 units": optionally mixed polymers according to the invention in the structure of which the linear amine functional groups are bonded to the silicon atoms via the linking unit A = -0- (in this case, Si-O-C bonds have then been formed). 10 Taking into account the values which the symbols a, b, d and e can take, it should further be understood that the polyorganosiloxanes according to the invention can thus have a linear, cyclic or branched (resin) structure or a mixture of these 15 structures. When it concerns linear polymers, the latter can optionally have up to 50 mol% of branching [units of "T" (RSi03/ 2 ) and/or "Q" (SiO 4
/
2 ) types] . When it concerns polyorganosiloxane resins, the latter are composed of at least two types of 20 different siloxy units, namely "M" (R 3 SiOi/ 2 ) and/or "T" units and optionally "D" (R 2 SiO 2
/
2 )] units; the number of "M" units/number of "Q" and/or "T" units ratio is generally between 4/1 and 0.5/1 and the number of "D" units/number of "Q" and/or "T" units ratio is generally 25 between 0 to 100/1. The numbers of the units of formulae (I), and optionally (II) and (III), are advantageously such that the polyorganosiloxanes according to the invention 7 contain: - at least 0.5 mol%, preferably from 10 to 90 mol%, of linear amine functional groups, and optionally - at least 0.5 mol%, preferably from 10 to 90 5 mol%, of compatibilizing functional groups. The mol% values indicated express the number of moles of functional groups per 100 silicon atoms. The preferred Ri radicals are: methyl, ethyl, n-propyl, isopropyl or n-butyl; more preferentially, at 10 least 80 mol% of the Ri radicals are methyl. The preferred Z amine functional groups are chosen: (i) when A = valency bond: from the monovalent radicals of formula: R9 -R8-C-N-I-R12 V 10 15 in which:
R
8 represents a divalent organic radical of formula: - B 1
-(B
2 )f where: B 1 is a divalent residue chosen from
-CH
2
-CHR
13 - and -CH=CH-, with R 1 3 being a hydrogen 20 atom or a linear or branched alkyl radical having from 1 to 3 carbon atoms; B 2 is a linear or branched alkylene residue having from 1 to 10 8 carbon atoms, with f being a number equal to 0 or 1; - the R 9 and Rio radicals, which are identical or different, are chosen from linear or branched 5 alkyl radicals having from 1 to 4 carbon atoms, the phenyl radical and the benzyl radical; - R 1 , which can be identical to R 9 and/or R 10 , is chosen from a hydrogen atom, linear or branched alkyl radicals having from 1 to 3 carbon atoms and 10 a 0- radical; - R 12 represents a -CR 1 4 RisR 1 6 radical where the R 1 4 ,
R
1 5 and R 1 6 residues, which are identical to or different from one another, and which moreover can be identical to R 9 and/or R 10 , each represent one 15 of the radicals represented by R 9 and Rio; (2i) when A = -0-; from the radicals of formula:
R
1 8 17 1I 2 -RM R-C--RI21 (V 19 in which: - R 17 represents a divalent radical of formula: CH3
-C--(B
I g 22 a 20 where: R22 is chosen f rom a hydrogen atom or the 9 radicals represented by R 9 and R 10 in the formula (IV); B3 is a divalent residue chosen from linear or branched alkylene radicals having from 1 to 10 carbon atoms and linear or branched alkenylene 5 radicals having from 2 to 10 carbon atoms and containing one or a number of ethylenic unsaturation(s) in the chain, with g being a number equal to 0 or 1; - the R 18 and R 19 radicals, which are identical or 10 different, are chosen from the radicals represented by R 9 and R 10 in the formula (IV); - R 20 , which can be identical to Ris and/or R 19 , is chosen from a hydrogen atom and the radicals represented by R 11 in the formula (IV); 15 R 21 represents a -CR 24
R
25
R
26 radical where the R 24
R
25 and R 26 residues, which are identical to or different from one another, and which moreover can be identical to R 22 , R 1 i and/or R 19 , each represent one of the radicals represented by R 9 and R 1 0 in 20 the formula (IV). The amine functional groups Z are more preferentially chosen: (i) when A = valency bond: from those of formula (IV) in which: 25 R 8 is chosen from the divalent radicals of formulae -CH 2
-CH
2 - (in this case, R 1 3 = H and f = 0) and -CH 2
-CH
2
-(B
2 )f- (in this case, R 1 3 = H) where B 2 is a -(CH 2 -)h residue with h being a 10 number from 1 to 6; - R 9 and R 14 , Ris and R 1 6 (constituents of R 1 2 ) are methyl groups; - R 10 is chosen from linear alkyl radicals having 5 from 1 to 3 carbon atoms; and - R 11 represents a hydrogen atom; (2i) when A = -0-: from those of formula (V) in which: - R 17 is chosen from the divalent radicals of 10 formulae: -CCH 3
R
2 2
-(B
3 ) Y where R 2 2 is a hydrogen atom and B 3 is a divalent residue of formula - (CH 2 ) i- with i being a number from 1 to 6; - R 18 , R 19 and R 2 4 , R 2 5 and R 2 6 (constituents of R 2 1 ) are methyl groups; and 15 R 20 represents a hydrogen atom. In the definitions given above with respect to the formulae (IV) and (V), the free valencies appearing with a fatty nature are those which are bonded to the silicon atoms either directly (when A = 20 valency bond) or via an oxygen atom (when A = -0-). The preferred optional compatibilizing functional groups W are chosen: from a linear or branched alkyl radical having from 5 to 18 carbon atoms; a radical of formula -R 2
-COO-R
3 in which R 2 25 represents a linear or branched alkylene radical having from 8 to 12 carbon atoms and R 4 represents a linear or branched alkyl radical having from 1 to 6 carbon atoms; or a radical of formula -R 4 -0-(R 5 -0)c-R 6 in which R 4 11 represents a linear or branched alkylene radical having from 3 to 6 carbon atoms, R 5 represents a linear or branched alkylene radical having from 2 to 3 carbon atoms, c is a number from 0 to 6 and R 6 represents a 5 hydrogen atom, a linear or branched alkyl radical having from 1 to 6 carbon atoms or an acyl radical
-CO-R
7 where R 7 represents a linear or branched alkyl radical having from 1 to 5 carbon atoms. The compatibilizing functional groups W are 10 more preferentially chosen from the n-octyl, n-undecyl, n-dodecyl, n-tridecyl or methyl or ethyl decamethylenecarboxylate radicals. The present invention, taken in its first subject, is more precisely still targeted at: 15 - statistical, sequenced or block, linear, optionally mixed polydiorganosiloxane copolymers of average formula: 1 I R 1 R I 1 RI Y-Si-0 S i-O- Si-O Si-O- -i-O- Si-Y (V) I I RF X W R1 R1 in which: - the symbols R 1 , X and W have the general meanings 20 given above with respect to the formulae (I) and (II); - the symbols Y represents a monovalent radical chosen from R , X, W and a hydrogen atom; 12 - m is a whole or fractional number ranging from 0 to 180; - n is a whole or fractional number ranging from 0 to 180; 5 p is a whole or fractional number ranging from 0 to 10; - q is a whole or fractional number ranging from 0 to 100; - with the conditions according to which: 10 - if m is other than 0 and optionally if n is other than 0: the sum m + n + p + q lies in the range from 5 to 200; the ratio 100m / m + n + p + q + 2 a 0.5; and the ratio 100n / m + n + p + q + 2 2 0.5, this ratio being identical to or 15 different from the preceding ratio; - if m = 0 and optionally if n is other than 0: at least one of the Y substituents represents the X radical; the sum m + n + p + q lies in the range from 5 to 100; and the ratio 100n / m + n + p + q 20 + 2 a 0.5, - if m is other than 0 and n = 0: the sum m + n + p + q lies in the range from 5 to 100; the ratio 100m / m + n + p + q + 2 a 0.5; and optionally at least one of the Y substituents represents the W 25 radical; - if m = 0 and n = 0: the sum p + q lies in the range from 5 to 100; one of the Y substituents being the X radical; and optionally the other Y 13 substituent being the W radical; and those of average formula: RI R1 R1 Ri IHH I 3 1V0 Si-o - -Si- -S-o - Si-(V XW H RI in which: - the symbols R 1 , X and W have the general meanings 5 given above with respect to the formulae (I) and (II); - r is a whole or fractional number ranging from 1 to 9; - s is a whole or fractional number ranging from 0 10 to 9; - t is a whole or fractional number ranging from 0 to 0.5; - u is a whole or fractional number ranging from 0 to 5; 15 the sum r + s + t + u lies in the range from 3 to 10. The polymers of formula (V) which are preferred (so-called LPl polymers) or highly preferred (so-called LP2 polymers) are those in which: 20 the symbols Y represent Ri; - m is a whole or fractional number ranging from 1 to 90; n is a whole or fractional number ranging from 0 14 to 90; - p is a whole or fractional number ranging from 0 to 5; - q is a whole or fractional number ranging from 0 5 to 50; - the sum m + n + p + q is a whole or fractional number ranging from 10 to 100; - the ratio 100m / m + n + p + q + 2 lies in the range from 10 to 90; 10 with the condition according to which if n is other than 0, the ratio 100n / m + n + p + q + 2 lies in the range from 10 to 90, it being possible for this ratio to be identical to or different from the preceding ratio; 15 - the R 1 , X and W radicals simultaneously have the preferential definitions (in the case of LP1 polymers) or more preferential definitions (in the case of LP2 polymers) given above with respect to each of them. 20 The polymers of formula (VI) which are preferred (so-called CP1 polymers) or very preferred (so-called CP2 polymers) are those in which: - r is a whole or fractional number ranging from 1 to 4.5; 25 s is a whole or fractional number ranging from 0 to 4.5; t is a whole or fractional number ranging from 0 to 0.25; 15 - u is a whole or fractional number ranging from 0 to 2.5; - the sum r + s + t + u is a whole or fractional number ranging from 3 to 5; 5 the R , X and W radicals simultaneously have the preferential definitions (in the case of the CPl polymers) or more preferential definitions (in the case of the CP2 polymers) given above with respect to each of them. 10 The polymers of formula (V), which are especially well suited (so-called ELP1 polymers) or very especially well suited (so-called ELP2 polymers) are the LP1 or LP2 polymers defined above in which the symbol n is a number ranging from 1 to 90. 15 The polymers of formula (VI), which are especially well suited (so-called ECP1 polymers) or very especially well suited (so-called ECP2 polymers) are the CP1 or CP2 polymers defined above in which the symbol s is a number ranging from 1 to 4.5. 20 The optionally mixed organopolysiloxanes of the invention without linking units can advantageously be obtained from, and this constitutes a first form of the second subject of the invention: corresponding organohydropolysiloxanes (H), which 25 are free of amine functional group(s) Z and of compatibilizing functional group(s) W, the organic compound(s) which is (are) ethylenically unsaturated at the chain end (W) , 16 from which the amine functional group(s) Z derive(s), - and optionally the compound(s) which is (are) ethylenically unsaturated at the chain end (Z), 5 from which the W functional group(s) derive(s). Thus, the optionally mixed polyorganosiloxanes of the invention without linking units can be obtained by carrying out: - in the case of polymers containing solely amine 10 functional group(s): an addition (hydrosilylation) reaction, or - in the case of mixed polymers containing amine functional group(s) and containing compatibilizing functional group(s): two simultaneous or 15 successive addition (hydrosilylation) reactions, starting with: corresponding organohydropolysiloxanes (H) free of the Z and W functional groups, the organic compound(s) which is(are) ethylenically unsaturated at the chain end (M), from which the Z functional group(s) 20 derive(s), and optionally the compound(s) which is(are) ethylenically unsaturated at the chain end (.), from which the W functional group(s) derive(s). These hydrosilylation reactions can be carried out at a temperature of the order of 20 to 25 200 0 C, preferably of the order of 60 to 120 0 C, in the presence of a catalyst based on a metal of the platinum group; mentioned may in particular be made of the platinum derivatives and complex described in US-A- 17 3,715,334, US-A-3,814,730, US-A-3,159,601 or US-A 3,159,662. The amounts of catalysts used are of the order of 1 to 300 parts per million, expressed as metal 5 with respect to the reaction mixture. In the definition of the "mol of (M)", the olefinic unsaturation capable of reacting with (H) by hydrosilylation will be regarded as the unit entity. Likewise, in the definition of the "mol of ()", the 10 olefinic unsaturation capable of reacting with (H) by hydrosilylation will be regarded as the unit entity. The amounts of reactants which can be used generally correspond to a [() + optionally (E)}/SiH [of (H)] molar ratio which is of the order of 1 to 5 15 and preferably of the order of 1 to 2. The hydrosilylation reactions can take place in bulk or, preferably, in a volatile organic solvent such as toluene, xylene, methylcyclohexane, tetrahydrofuran, heptane, octane or isopropanol; the 20 reaction mixture can additionally contain a buffer agent consisting in particular of an alkali metal salt of a monocarboxylic acid, such as, for example, sodium acetate. At the end of the reactions, the crude 25 optionally mixed polyorganosiloxanes which are obtained can be purified, in particular by passing through a column filled with an ion exchange resin and/or by simple evaporation of the reactants introduced in 18 excess and optionally of the solvent used by heating between 100 and 180*C under reduced pressure. The organohydropolysiloxanes (H) which are used, for example, for the preparation of the linear 5 mixed polydiorganosiloxanes of formula (V) are those of formula: RI RI R1 R I I I I Y'-Si-0- -Si-- -S---Si-Y' (VII) I q H q in which: - the symbols Ri and q have the general or preferential meanings given above with respect to 10 the formula (V); - the symbols Y' represent R 1 or a hydrogen atom; - v is a whole or fractional number equal to m + n + p; - with the condition according to which, if v = 0, q 15 is a number lying in the range from 5 to 100 and then at least one of the Y' radicals represent a hydrogen atom. The organohydropolysiloxanes (H) which are used, for example, for the preparation of the cyclic 20 mixed polydiorganosiloxanes of formula (VI) are those of formula: 19 R1 R1 -- Si- - Si-O- (Vm) i H in which: - the symbols Ri and u have the general or preferential meanings given above with respect to the formula (VI); 5 w is a whole or fractional number equal to r + s + t; - the sum u + w is lies in the range from 3 to 10. Such organohydropolysiloxanes (H) of formulae (VII) and (VIII) are known in the literature and some 10 are commercially available. The unsaturated organic compounds (M), from which the Z functional groups derive, are preferably those of formula: R9 -C-NR RX) in which: 15 the symbols R 2 6 is chosen from the radicals of formula: CH 2
=CR
1 3
-(B
2 )f- and CHmC-(B 2 )f-; the symbols R 13 , B 2 , f, R , R 10
R
11 and R 12 have the general or preferential meanings given above with respect to the formula (IV). 20 As compounds (4), mention may be made, by way 20 of examples, of: N-tert-butyl-1-methyl-l-ethyl-3 butenylamine, N-tert-butyl-1, 1-dimethyl-2-propynylamine or N-tert-butyl-1,1-dimethyl-2-propenylamine. The unsaturated amines (*) are known 5 compounds which are described in particular in US-A-3,067,101. They can be prepared according to a first process, which is described in this prior art, consisting of the following: First process: 10 It is carried out in 2 or 3 stages: (1) chlorination with HC1 of the alcohol of formula
R
2 6
R
9
R
10 C-OH, then (2) condensation of the chlorinated compound obtained with the amine R 12
-NHR
11 in order to result in the desired unsaturated amine, the following 15 synthetic scheme being applied: R9 R2-C-OH + HC1 -+ ItC-C1 + H 2 0 Iko Wj~o 1 Reaction with NHR1 R9 RLC-jR12 + HC1 f 0 (IX) In the case where R 2 6 has the formula CHmC-(B 2 )f- and where it is desired to obtain an amine 21 having an ethylenic unsaturation at the chain end, an additional stage (3), consisting in subjecting the amine (IX) formed above containing acetylenic unsaturation to a catalytic semi-hydrogenation, can 5 then be carried out in order to result in the amine of formula (IX) with R 2 6 being the CH 2 =CH- (B 2 ) f- radical. Other processes which can advantageously be used, and which to the knowledge of the Applicant Company are novel processes, are the second and third 10 processes defined below: Second process: Preparation of the compounds of formula (IX) in which Ri=H, and R 2 6 , R 9 , Rio and R 12 have the meanings indicated above. 15 This second process is carried out in 4 stages: (1) condensation of hydroxylamine (in the hydrochloride form) with the ketone R 1 2
-CO-R
9 , then (2) addition of CH 3
SO
2 C1 to the oxime obtained in order to result in the mesylate 3 of the oxime, then (3) 20 carrying out a Beckmann rearrangement of the mesylate 3 by reaction with the organomagnesium halide R 1 0 MgX, then (4) nucleophilic addition to the imine 4 obtained of the organomagnesium halide R 2 6 MgX, followed by an acid hydrolysis, the following synthetic scheme being 25 applied: 22
R
12 NHi-OH + i CO-R 9
-
C=N-OH + H 2 0 I Reaction with CH 3
SO
2 C1 J2 >2 =N-O-SOCH 3 R9/ + HCI Reaction with 1 0 MgX R9CN R9--C-NH-R12 =- -N - R1 2
R
1 Reaction R10 12 6 MgX + acid hydrolysis - + MgX(SO 3 CH) As regards the practical implementation of the stages (1) to (4), reference will be made, for more details, to the contents of the following documents, which describe, starting with other reactants, 5 operational methods which can be applied in carrying out the various stages of the process under consideration: cf. M. E. Garst et al., J. Org. Chem., 40 (8), p. 1169 (1975) for stage (1); cf. K. Marvoka, S. Nakai and H. Yamamoto, Organic Synthesis, 6, 185 10 (1988) for stage (2); cf. K. Hattori, K. Marvoka and H. Yamamoto, Tetrahedron Letters, 23 (33), 3395-3396 (1982) for stage (3) and cf. H. Yamamoto et al., J. Am. Chem. Soc., 1983, 105, 2831-2843 for stage (4).
23 Third Process: Preparation of the compounds of formula IX in which Ri=H, and R 2 6 , R 9 , Rio and R 12 have the meanings indicated above. 5 This third process is carried out in 2 stages: (1) condensation of the amine R 12 -NH2 and of the ketone R 9
-CO-R
1 o in order to result in the imine 5, then (2) nucleophilic addition to the imine 5 of the organomagnesium halide R 26 MgX, followed by an acid 10 hydrolysis, the following synthetic scheme being applied: R9 R9-CO-R 1 0 + R--NH - C=N-R12 + H 2 0 Reaction with R 2 6MgX + acid hydrolysis R _C-NH-R 1 2 R (IX) As regards the practical implementation of stages (1) and (2), reference will be made, for more details, to the contents of the following documents, 15 which describe, starting with other reactants, operational methods which can be applied in carrying out the various stages of the process under consideration: cf. D. A. Evans and L. A. Domeier, Org.
24 Synth., _54, p. 93 (1974) for stage (1) and cf. H. Yamamoto et al., J. Am. Chem. Soc., 1983, 105, 2831 2843 for stage (2). The unsaturated compounds (W), from which the 5 W functional groups derive, are compounds having an ethylenic unsaturation, situated at the chain end, capable of reacting in a hydrosilylation reaction in the presence of a catalyst based on a metal from the platinum group. 10 As compounds (9), mention may be made, as examples, of 1-octene, 1-undecene, 1-dodecene, 1 tridecene, or methyl or ethyl undecenoate. The optionally mixed organopolysiloxanes of the invention containing oxygen linking units can 15 advantageously be obtained from, and this contributes to a second form of the second subject of the invention: - corresponding organohydropolysilanes (H) which are free of amine functional group(s) Z having the 20 oxygen linking unit and of compatibilizing functional group(s) W, - the hydroxylated organic compound(s) (*I), from which the amine functional group(s) Z having the oxygen linking unit derive (s), 25 and optionally the compound(s) which is(are) ethylenically unsaturated at the chain end (s), from which the W functional group(s) derive(s). The optionally mixed polyorganosiloxanes of 25 the invention containing oxygen linking units can thus be obtained by carrying out: - in the case of polymers containing only amine functional group (s): a dehydrogenation/ 5 condensation reaction, or - in the case of mixed polymers containing amine functional group(s) and containing compatibilizing functional group(s): simultaneous dehydrogenation/condensation and addition 10 (hydrosilylation) reactions or, preferably, successive dehydrogenation/condensation and then addition (hydrosilylation) reactions, starting with: corresponding organohydropolysilanes (H) which are free of Z, having the oxygen linking unit, 15 and W functional groups, the hydroxylated organic compound(s) (4'), from which the Z functional group(s) having the oxygen linking unit derive(s), and the compound(s) which is(are) ethylenically unsaturated at the chain end (W), from which the W functional group(s) 20 derive(s). The said dehydrogenation/condensation and hydrosilylation reactions can be carried out under the same operating conditions (in particular: nature and amount of catalyst; reaction temperature; nature of the 25 optional solvents) as those described above in the context of the addition (hydrosilylation) reactions prevailing in the preparation of the polyorganosiloxanes without linking units.
26 In the definition of the "mol of (*')", the OH functional group which is capable of reacting with (H) by dehydrogenation/condensation will be regarded here as the unit entity; the [('") + optionally 5 (:})]/SiH [of (H))] molar ratio there also varies between 1 and 5 and, preferably, between 1 and 2. The hydroxylated organic compounds (') from which the Z functional groups having the oxygen linking unit derive (alternatively: from which the monovalent 10 groups X derive) are preferably those of formula: 28 -C- R M I9 in which: the symbol R 27 is a hydroxylated radical of formula: CH3 1 3
HO-C--)
?2 the symbols R 2 2 , B 3 , g, Ris, R 19 , R 2 0 and R 2 1 have 15 the general or preferential meanings given above with respect to the formula (V). As compounds (W'), mention may be made, by way of examples, of the species of formulae: 27
CH
3 CH CH I | |
HO-CH--C-NH-C-CH
3 I I
CH
3 CH HO-H-CH NH H , with i = 1 - 6.
CH
3 CH 3 The hydroxylated amines (') are compounds which, to the knowledge of the Applicant Company, are novel products. The same hydroxylated amines (*') can 5 be easily synthesized by carrying out the following processes: Fourth process: Preparation of the compounds of formula (X) in which R 2 7 is the radical
CH
3 HO-C-(B
-
j22 g 10 with g being a number other than zero, and R 22 , B 3 , R 18 ,
R
19 , R 2 0 and R 21 have the meanings indicated above. This fourth process is carried out in 3 stages: (1) chlorination with HCl of the alcohol of formula: 28 R1 8 CH,=C --C-OH then (2) condensation of the chlorinated compound obtained 6 with the amine R 21
-NHR
20 in order to result in the ethylenically unsaturated amine 7, then (3) hydration in sulphuric acid medium of the double bond 5 of the amine 2, the following synthetic scheme being applied: R1
-
Rj8 CH2C I-(4-C-OH + HCI -+ CH==C2(E+-C-CI R19 6 199
+H
2 0 Reaction with R2JNHR2O H20 /H2SO 8R CH2=CR -B 3 -N20 H 8 S 19 HO-C-(B -C-NR-CR (B 122 19 As regards the practical implementation of stages (1) to (3), reference will be made, for more details, to the contents of the following documents 10 which describe, if appropriate starting with other reactants, operating methods which can be applied in carrying out the various stages of the process under 29 consideration: cf. US-A-3,067,101 for stages (1) and (2); cf. cf. J. Meinwald, J. Am. Chem. Soc., 77, p 1617 (1955) for stage (3). Fifth process: 5 Preparation of the compounds of formula (X) in which R 2 7 is the radical CH
HO-CH
(in this case, R 22 = H and g = 0) , and R 18 , R 19 , R 2 0 and
R
21 have the meanings indicated above. This fifth process is carried out in 4 10 stages: (1) chlorination with HC1 of the alcohol of formula: R18 CH=!C-C-OH R1 9 then (2) condensation of the chlorinated compound obtained 8 with the amine R 2 1
-NHR
2 0 in order to result in the acetylenically unsaturated amine 9t, then (3) 15 hydration in sulphuric acid medium of the triple bond of the amine 9, then (4) reduction of the ketone 10 formed to an alcohol in the presence of a suitable metallic reducing agent, the following synthetic scheme being applied: 30 RI 8 CH=C-C-OH HC1 -+ CHEC-C-CI + H 2 O
R
19
R
19 Reaction with R?,1-NHR20 I 0 21 H20/ H 2
SO
4 I R2 CH-CO-C-N .- R C- 0911 R Reduction 2
CH
3 R18 HO-CH-C-NM-R21 RI 9 (X) As regards the practical implementation of stages (1) to (4), reference will be made, for more details, to the contents of the following documents which describe, if appropriate starting with other 5 reactants, operating methods which can be applied in carrying out the various stages of the process under consideration: cf. US-A-3,067,101 for stages (1) and (2); cf. FR-A-2,476,104 for stage (3); cf. Rylander "Catalytic Hydrogenation over Platinium Metals", p. 238 10 to 290, Academic Press, N. Y. (1967) for stage (4). The optionally mixed polyorganosiloxanes according to the invention can be used as stabilizers 31 in combating light, oxidative and thermal degradation of organic polymers, and this constitutes the third subject of the invention. Mention may be made, as examples of such 5 organic polymers, of polyolefins, polyurethanes, polyamides, polyester, polycarbonates, polysulphones, polyethersulphones, polyetherketones, acrylic polymers, their copolymers and their mixtures. Among these polymers, the compounds of the 10 invention have a more particularly effective action with polyolefins and polyalkadienes, such as polypropylene, high density polyethylene, linear low density polyethylene, low density polyethylene, polybutadiene, their copolymers and their mixtures. 15 Taking into account the wide possibilities of variations in the relative numbers of the various siloxy units present in the siloxane chain of the mixed compounds of the invention, these said compounds can be easily adaptable to the various problems to be solved. 20 Yet another subject of the present invention therefore consists in the compositions containing organic polymer stabilized against the harmful effects of heat and of UV by an effective amount of at least one optionally mixed polyorganosiloxane compound. 25 These compositions generally contain from 0.04 to 20 milliequivalents of sterically hindered amine functional group(s) per 100 g of polymer to be stabilized.
32 The polymeric compositions stabilized according to the invention preferably contain from 0.20 to 4 milliequivalents of sterically hindered amine functional group(s) per 100 g of polymer. 5 By way of indication, the stabilized polymeric compositions generally contain from 0.01% to 5% by weight of optionally mixed polyorganosiloxane compound with respect to the polymer. The addition of the optionally mixed 10 polyorganosiloxane compounds can be carried out during or after the preparation of the polymers. These compositions can additionally contain all the additives and stabilizers generally used with the polymers which they contain. Thus, it is possible 15 to use the following stabilizers and additives: antioxidants, such as alkylated monophenols, alkylated hydroquinones, hydroxylated diphenyl sulphides, alkylidenebisphenols, benzyl compounds, acylaminophenols, esters or amides of 3-(3,5-di-tert 20 butyl-4-hydroxylphenyl)propionic acid or esters of 3 (3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid; light stabilizers, such as optionally substituted benzoic acid esters, acrylic esters, nickel compounds or oxalamides; phosphites and phosphonites; metal 25 deactivators; compounds which destroy peroxides; polyamide stabilizers; nucleation agents; fillers and reinforcing agents; or other additives, such as, for example, plasticizers, pigments, optical brighteners or 33 flame retardants. The polymer compositions thus stabilized can be applied in the most varied forms, for example in the form of moulded items, sheets, fibres, cellular 5 materials (foam), sections or coating products, or as film-forming agents (binders) for paints, varnishes, adhesives or cements. The following examples illustrate the present invention. 10 In these examples, theoretical concentration of amine functional groups Z, expressed in milliequivalents (meq) per 100 g of silicone oil, is understood to mean the concentration which the silicone oil would have if all the amine functional groups 15 involved were grafted. Example 1 Example of the preparation of a mixed organopolysiloxane without linking units 1) Preparation (by the technique in accordance with 20 the first process) of N-tert-butyl-1-methyl-l-ethyl-3 butenylamine: 24 g (0.24 mol) of pinacolone
CH
3
-CO-C(CH
3
)
3 ' 24 g (0.348 mol) of hydroxylamine hydrochloride, 27.5 g (0.348 mol) of pyridine and 240 cm 3 of ethanol are 25 introduced into a 500 cm 3 reactor. The mixture is brought to its boiling temperature and thus maintained at reflux for 1 hour. At the end of this time, the 34 reaction mixture is allowed to cool to room temperature (23*C) and, after addition of 240 cm 3 of water, the oxime of pinacolone is isolated by filtration and is dried at room temperature under a reduced pressure of 5 1.33 x 102 Pa; 22 g (0.192 mol) of the said oxime are thus recovered. The molar yield of recovered product is 80%. 22 g of the above oxime, 253 cm 3 of dichloromethane and 40 cm 3 of triethylamine are charged 10 to a second, 1,000 cm 3 .reactor. The mixture is cooled to -20 0 C and 29.7 g (0.20 mol) of methanesulphonic acid chloride CH 3
-SO
2 -Cl are added gradually over a period of 30 minutes. After treatment of the reaction mass, which consists in adding 250 cm 3 of ice-cold water and then 15 150 cm 3 of diethyl ether, in then separating by settling, in then drying the organic phase over Na 2
SO
4 and in concentrating the organic phase on a rotary evaporator, 29.7 g (0.152 mol) of the methanesulphonate of the oxime of pinacolone are obtained. The molar 20 yield of isolated product is 79%. 660'g of toluene and 29.7 g of the methanesulphonate of the oxime of pinacolone are charged to a third, 2,000 cm 3 reactor which has been cooled to -70 0 C. 126 cm 3 (0.456 mol) of a solution of 25 ethylmagnesium bromide in diethyl ether (solution containing 2 mol per litre of organomagnesium compound) are then run in gradually over a period of 50 minutes. After the ethylmagnesium bromide solution has 35 been run in, the temperature of the reaction mixture is allowed to rise to 0*C and then, again gradually over a period of 60 minutes, 89 cm 3 of a solution of allylmagnesium bromide in diethyl ether (solution 5 containing 2 mol per litre) are run in. on completion of the addition, the reaction mixture is hydrolysed by addition of 700 cm 3 of water and of 50 cm 3 of concentrated HC1. After settling and separation, the organic phase is concentrated in a way known per se in 10 order to remove the toluene and the diethyl ether. There are thus recovered 14.6 g of the product of formula:
CH
3 CH 3 CH,=CHCHI C-NH-C-CH
C
2 H
CH
3 Analyses carried out by infrared spectrometry, proton nuclear magnetic resonance and 15 mass spectrometry confirm the structure of this amine. 2) Preparation of the mixed organopolysiloxane: 13 cm 3 of dry toluene, 3.3 g (0.02 mol) of 95% by weight 1-dodecene, 9.76 g (0.056 mol) of N-tert butyl-1-methyl-1-ethyl-3-butenylamine and 0.016 g of 20 sodium acetate are introduced into a 250 cm 3 reactor equipped with a stirrer system and maintained internally under a dry nitrogen atmosphere. Stirring is carried out and the temperature of the reaction mixture 36 is brought to 110*C. The introduction is then carried out of 7 nm 3 (7 Al) of a solution in divinyltetramethyldisiloxane of a platinum complex containing 11.9% by weight of platinum attached to 5 divinyltetramethyldisiloxane as ligand (Karstedt catalyst). 3.78 g of a polymethylhydrosiloxane oil are then gradually run in over a period of 80 minutes, the characteristics of this oil being as follows: 10 Mn = 3160 g, - 1580 meq H/100 g, - average structure: CH 1
(CH
3 )SiO Si-O S(CH 3
)
3 50 After having run in the oil containing hydrosilyl functional groups, the reaction mixture is 15 left to react at 110*C for 45 hours. At the end of this time, the degree of conversion of the hydrosilyl functional groups is 93% (in moles). The excess reactants and the solvent are then removed by evaporation carried out for 2 hours at 140*C 20 under a reduced pressure of 1.33 x 102 Pa. 14.76 g of a clear oil are thus recovered, the characteristics of this oil being as follows: S Mn = 10900 g; 245.9 meq of amine functional groups Z/100 g, the 37 theoretical value being 405 meq/100 g (this basicity value is measured by titrating the oil obtained using a 0.02N perchloric acid solution); average structure of the oil: CH3 -CH3 CH3 (CH)Si SiS-O Si-O -Si(CH3)3 -1 26.6 C ZH, 19.5 H 3.
(CH,)
3
CHTC-C
2
H
5 NH
CHC-CH
3
CH
3 5 proportion of Z functional groups: 51.2% (in moles of functional groups per 100 silicon atoms); proportion of W functional groups: 37.5%. Example 2 Photostabilization of polypropylene 10 The following 2 compositions a and b are prepared in a slow mixer: 38 a b Polypropylene, Eltexe P HV001P (grade 100 g lOOg 10) Stabilizer Si according to Example 1, 0.2 g Part 2), containing 245.9 meq of 5 amine functional groups per 100 g of stabilizer Commercial stabilizer S2: Chimasorb 944 (cf. formula below), containing - 0.2 g 341 meq of piperidyl functional 10 groups per 100 g of stabilizer -N-(CH2)6-NN N N NH N N C I I H1 HH n>1 The abovementioned compositions are converted, under identical operating conditions, in order to result in films with a thickness of 200 pm. The film based on polypropylene stabilized 15 with 51 resulting from the composition [lacuna] (Example 2) and the film based on polypropylene stabilized with S2 resulting from the composition b 39 (Test b) are exposed to the same UV radiation. The aging of the films is monitored by infrared spectrometry. In each test, a measurement is made of the exposure time T to the UV rays necessary for the 5 absorbance by infrared spectrometry of the carbonyl band (at 1720 cm- 1 ) resulting from oxidation to be equal to the absorbance of a reference infrared band (CH 2 band at 2722 cm- 1 ); in other words, a measurement is made of the time T necessary in order to have, in each 10 case, a degree of photooxidation such that: absorbance of the C = 0 band at 1720 cm-1 = 1 absorbance of the CH 2 band at 2722 cm-2 It should be noted that the longer the time measured, the better is the protection conferred by the stabilizer (the C = 0 groups appear more slowly). The results obtained are combined in the 15 following table: Stabilized film Nonstabilized film Example 2 Test b Control Exposure time T 75 70 20 to UV in hours T/number of 0.31 0.21 meq/100 g 40 Example 3 Preparation of an organopolysiloxane without linking units 262.4 g (1.786 mol) of 96% pure (by mass) 5 N-tert-butyl-1, 1-dimethyl-2-propenylamine are introduced into a 1,000 cm 3 four-necked reactor equipped with a central mechanical stirrer, a thermometer and a bulb condenser. The contents of the reactor are brought to 10 85 0 C and the head space of the reactor is rendered inert with nitrogen. The following are then run in using two separate dropping funnels (the additions are begun simultaneously): on the one hand, over 5 hours: 15 - 0.762 ml of the Karstedt catalyst solution described in Example 1 (Part 2) and - 30 g of dry toluene, * and, on the other hand, over 30 minutes: - 420 g (1.692 mol of Si-H functional groups) of a 20 polymethylhydrosiloxane oil with the structure:
(CH
1
)
3 SiO - -Si-O Si-O I Si(CH 3
)
3 I I H - 16 -CH3 39 containing 0.403 equivalent Si-H per 100 g of oil. On two occasions during the reaction (7 hours and then 22 hours after the beginning of the reaction), 0.275 ml of the Karstedt catalyst solution described in 25 Example 1 (Part 2) is again added.
41 69 hours after the beginning of the reaction, the degree of conversion of the hydrosilyl functional groups is 98.8% (in moles). The product obtained is then evaporated for 5 4 hours at 80*C under a reduced pressure of 3.32 x 102 Pa. 588 g of a clear yellow oil are recovered, the characteristics of which oil are as follows: - viscosity: 1000 mPas at 24*C; - Mn = 6265 g; 10 244.6 meg of amine functional groups Z per 100 g of oil; - average structure: CH3CH31 ( SSi-O -Si(CH),
ICH
3
)
3 - Si-Olf0}{i3 -i -16 F 3 -39
(CH)
2
CH;-C-CH
3 NH
CH-C-CH
3 CH, - nuclear magnetic resonance furthermore reveals the presence of 0.8 mol% of T units; 15 proportions of Z functional groups: 28.1% (in moles of functional groups per 100 atoms of Si). Example 4 Preparation of a mixed organopolvsiloxane without linking units 20 70 g of dry toluene are introduced into a 42 1,000 cm 3 four-necked reactor equipped with a central mechanical stirrer, a thermometer and a bulb condenser. The contents of the reactor are brought to 90 0 C, the head space of the reactor is rendered inert 5 with nitrogen and 0.042 ml of the Karstedt catalyst solution described in Example 1 (Part 2) is introduced. The following are then run in simultaneously using two separate dropping funnels: on the one hand: 10 - 201.78 g (1.78 mol) of 99% pure by mass 1-octene, * and, on the other hand: - 230 g (3.392 mol of Si-H functional groups) of a polymethylhydrosiloxane oil with the structure: CH
(CH
3 )3SiO - -Si-O Si(CH 3
)
3 .H -26 containing 1.475 equivalents Si-H per 100 g of oil. 15 4 hours after the beginning of the reaction, the degree of conversion of the hydrosilyl functional groups (in moles) is 50.8% (i.e. a degree of conversion of the octene functional groups of 97%). The following are then run in using two separate dropping funnels 20 (the beginning of the additions being simultaneous): on the one hand, over 1 hour 15 minutes: - 294.2 g (2.003 mol) of 96% pure by mass N-tert-butyl 1,1-dimethyl-2-propenylamine * and, on the other hand: 43 - 20 g of dry toluene and - 627 mg of the Karstedt catalyst solution described in Example 1 (Part 2). 18 hours after the beginning of these two 5 injections, the degree of conversion of the hydrosilyl functional groups is 98.3% (in moles). The product obtained is then evaporated for 4 hours at 90 0 C under a reduced pressure of 3.32 x 102 Pa. 623 g of a clear oil are recovered, the 10 characteristics of which oil are as follows: - viscosity: 1580 mPas at 24*C; - Mn = 4980 g; - 241.3 meq of amine functional groups Z per 100 g of oil; 15 average structure: {H 0CH S (CH,),SiO SibU-O-Si-O -Si(CH3)3 1 12 , 1C 4 (CH2)2 CHi-C-CH NH
CHT-C-CH
3
CH
3 - nuclear magnetic resonance furthermore reveals the presence of 1.6 mol% of T units; - proportions of Z functional groups: 42.9% (in moles of functional groups per 100 atoms of Si); 20 proportions of W functional groups: 49.9%.
Claims (17)
1. Polyorganosiloxane, characterized in that it comprises, per molecule, at least 3 siloxy units, including at least one siloxy functional unit of 5 formula: (4)a XSi(0) (I) 2 in which: - the symbols Ri are identical or different and represent a monovalent hydrocarbon radical chosen from the linear or branched alkyl radicals having 10 from 1 to 4 carbon atoms and the phenyl radical; - the symbol X represents a monovalent group of formula -A-Z where: - A is a single valency bond or an oxygen atom; - the symbol Z represents a monovalent group, 15 the free valency of which is carried by a carbon atom, containing a secondary or tertiary amine functional group in a linear hydrocarbon chain containing from 9 to 40 carbon atoms, in which the two carbon atoms 20 of the chain situated in the a and a' positions with respect to the nitrogen atom do not contain a hydrogen atom; - a is a number chosen from 0, 1 and 2.
2. Polyorganosiloxane according to claim 1, 25 characterized in that the Ri radicals are: methyl, 45 ethyl, n-propyl, isopropyl or n-butyl.
3. Polyorganosiloxane according to claim 1 or 2, characterized in that the amine functional groups Z are chosen: 5 (i) when A = valency bond: from the monovalent radicals of formula: R9 -R -CNR- -R12 (g in which: R 8 represents a divalent organic radical of formula: - B 1 -(B 2 )f 10 where: B 1 is a divalent residue chosen from -CH 2 -CHR 1 3 - and -CH=CH-, with R 1 3 being a hydrogen atom or a linear or branched alkyl radical having from 1 to 3 carbon atoms; B2 is a linear or branched alkylene residue having from 1 to 10 15 carbon atoms, with f being a number equal to 0 or 1; - the R 9 and Rio radicals, which are identical or different, are chosen from linear or branched alkyl radicals having from 1 to 4 carbon atoms, 20 the phenyl radical and the benzyl radical; - R 1 , which can be identical to R 9 and/or R 1 0 , is chosen from a hydrogen atom, linear or branched 46 alkyl radicals having from 1 to 3 carbon atoms and a 0- radical; R represents a -CR 4 R 15 R 16 radical where the R14 R 15 and R 1 6 residues, which are identical to or 5 different from one another, and which moreover can be identical to R 9 and/or R 10 , each represent one of the radicals represented by R 9 and Rio; (2i) when A = -0-; from the radicals of formula: p18 -R1 -C-NAS-2 (V 10 in which: R 1 7 represents a divalent radical of formula: CH, -C- (B 3 4 I g f2 where: R 22 is chosen from a hydrogen atom or the radicals represented by R 9 and Rio in the formula (IV); B 3 is a divalent residue chosen from linear 15 or branched alkylene radicals having from 1 to 10 carbon atoms and linear or branched alkenylene radicals having from 2 to 10 carbon atoms and containing one or a number of ethylenic unsaturation(s) in the chain, with g being a 20 number equal to 0 or 1; 47 - the R 18 and R 19 radicals, which are identical or different, are chosen from the radicals represented by R 9 and R 10 in the formula (IV); - R 20 , which can be identical to R 18 and/or R 19 , is 5 chosen from a hydrogen atom and the radicals represented by R 11 in the formula (IV) ; - R 21 represents a -CR 24 R 25 R 26 radical where the R 24 , R 2 5 and R 26 residues, which are identical to or different from one another, and which moreover can 10 be identical to R 22 , R 18 and/or R 19 , each represent one of the radicals represented by R 9 and R 10 in the formula (IV).
4. Polyorganosiloxane according to any one of claims 1 to 3, characterized in that it additionally 15 comprises at least one other functional unit of formula: (OR)bWSi(0) G 2 in which: - the symbols R 1 have the same meanings as those given above with respect to the formula (I); 20 the symbol W represents a monovalent group containing a compatibilizing functional group chosen from: a linear or branched alkyl radical having more than 4 carbon atoms; a radical of formula -R 2 -COO-R 3 in which R 2 represents a linear 25 or branched alkylene radical having from 5 to 20 48 carbon atoms and R 3 represents a linear or branched alkyl radical having from 1 to 12 carbon atoms; a radical of formula -R4-0-(Rs-O)c-R 6 in which R 4 represents a linear or branched alkylene 5 radical having from 3 to 15 carbon atoms, R 5 represents a linear or branched alkylene radical having from 1 to 3 carbon atoms, c is a number from 0 to 10 and R 6 represents a hydrogen atom, a linear or branched alkyl radical having from 1 to 10 12 carbon atoms or an acyl radical -CO-R 7 where R 7 represents a linear or branched alkyl radical having from 1 to 11 carbon atoms; b is a number chosen from 0, 1 and 2.
5. Polyorganosiloxane according to claim 4, 15 characterized in that the compatibilizing functional groups W are chosen: from a linear or branched alkyl radical having from 5 to 18 carbon atoms; a radical of formula -R 2 -COO-R 3 in which R 2 represents a linear or branched alkylene radical having from 8 to 12 carbon 20 atoms and R 4 represents a linear or branched alkyl radical having from 1 to 6 carbon atoms; or a radical of formula -R 4 -O- (R 5 -O)e-R 6 in which R 4 represents a linear or branched alkylene radical having from 3 to 6 carbon atoms, R 5 represents a linear or branched 25 alkylene radical having from 2 to 3 carbon atoms, c is a number from 0 to 6 and R 6 represents a hydrogen atom, a linear or branched alkyl radical having from 1 to 6 carbon atoms or an acyl radical -CO-R 7 where R 7 49 represents a linear or branched alkyl radical having from 1 to 5 carbon atoms.
6. Polyorganosiloxane according to any one of claims 1 to 5, characterized in that it additionally 5 comprises other siloxy unit(s) of formula: (R)~ (H)eS(O)____ d ei(4-(d +e) 2 in which: - the symbols R 1 have the same meanings as those given above with respect to the formula (I); - d is a number chosen from 0, 1, 2 and 3; 10 e is a number chosen from 0 and 1; - the sum d + e is not greater than 3.
7. Polyorganosiloxane according to any one of claims 1 to 6, characterized in that it is chosen from: - statistical, sequenced or block, linear, optionally 15 mixed polydiorganosiloxane copolymers of average formula: RI R 1 R1 RI 1 RI YS- Si-O -- Si-0-1-- -Si-0 --Si-Y (V) RX W H I m - n ~p~ ~q in which: - the symbols R 1 , X and W have the general meanings given above with respect to the formulae (I) and 20 (II); - the symbols Y represents a monovalent radical 50 chosen from R 1 , X, W and a hydrogen atom; - m is a whole or fractional number ranging from 0 to 180; - n is a whole or fractional number ranging from 0 5 to 180; - p is a whole or fractional number ranging from 0 to 10; - q is a whole or fractional number ranging from 0 to 100; 10 with the conditions according to which: - if m is other than 0 and optionally if n is other than 0: the sum m + n + p + q lies in the range from 5 to 200; the ratio 100m / m + n + p + q + 2 a 0.5; and the ratio 100n / m + n + p + q + 15 2 a 0.5, this ratio being identical to or different from the preceding ratio; - if m = 0 and optionally if n is other than 0: at least one of the Y substituents represents the X radical; the sum m + n + p + q lies in the range 20 from 5 to 100; and the ratio 100n / m + n + p + q + 2 a 0.5, - if m is other than 0 and n = 0: the sum m + n + p + q lies in the range from 5 to 100; the ratio 100m / m + n + p + q + 2 a 0.5; and optionally at 25 least one of the Y substituents represents the W radical; - if m = 0 and n = 0: the sum p + q lies in the range from 5 to 100; one of the Y substituents 51 being the X radical; and optionally the other Y substituent being the W radical; and those of average formula: RI R1 RI RI Si-0----S--Si-0- Si-o3 (V -X W H R1 in which: 5 the symbols R 1 , X and W have the general meanings given above with respect to the formulae (I) and (II) ; - r is a whole or fractional number ranging from 1 to 9; 10 s is a whole or fractional number ranging from 0 to 9; - t is a whole or fractional number ranging from 0 to 0.5; - u is a whole or fractional number ranging from 0 15 to 5; - the sum r + s + t + u lies in the range from 3 to
10. 8. Mixed linear ELP1 polyorganosiloxane according to claim 7, characterized in that: 20 the symbols Y represent Ri; - m is a whole or fractional number ranging from 1 to 90; n is a whole or fractional number ranging from 1 52 to 90; - p is a whole or fractional number ranging from 0 to 5; - q is a whole or fractional number ranging from 0 5 to 50; - the sum m + n + p + q is a whole or fractional number ranging from 10 to 100; - the ratio 100m / m + n + p + q + 2 lies in the range from 10 to 90; 10 the ratio 100n / m + n + p + q + 2 lies in the range from 10 to 90, it being possible for this ratio to be identical to or different from the preceding ratio; - the R 1 , X and W radicals simultaneously have the 15 definitions given above with respect to each of them in the abovementioned claims 2, 3 and 5. 9. Mixed cyclic ECP1 polyorganosiloxane according to claim 7, characterized in that: - r is a whole or fractional number ranging from 1 20 to 4.5; - s is a whole or fractional number ranging from 1 to 4.5; - t is a whole or fractional number ranging from 0 to 0.25; 25 u is a whole or fractional number ranging from 0 to 2.5; the sum r + s + t + u is a whole or fractional number ranging from 3 to 5; 53 the R 1 , X and W radicals simultaneously have the definitions given above with respect to each of them in the abovementioned claims 2, 3 and 5. 10. Process for the preparation of an optionally 5 mixed polyorganosiloxane without linking units, according to any one of claims 1 to 9, characterized in that it consists in carrying out: - in the case of polymers containing solely amine functional group(s): an addition (hydrosilylation) 10 reaction, or - in the case of mixed polymers containing amine functional group(s) and containing compatibilizing functional group(s): two simultaneous or successive addition (hydrosilylation) reactions, 15 starting with: corresponding organohydropolysiloxanes (H) free of the Z and W functional groups, the organic compound(s) which is(are) ethylenically unsaturated at the chain end (M), from which the Z functional group(s) derive(s), and optionally the compound(s) which is(are) 20 ethylenically unsaturated at the chain end (M), from which the W functional group(s) derive(s), and in that the amounts of the reactants involved correspond to a [(T) + optionally (M)]/SiH [of (H)] molar ratio which is of the order of 1 to 5. 25 11. Process according to claim 10, characterized in that the unsaturated organic compounds (M), from which the Z functional groups derive, are preferably those of formula: 54 R9 R 2 6C-NR iR12 (IX) I in which: - the symbol R 26 is chosen from the radicals of formula: CH 2 =CR 13 -(B 2 )f- and CH.C-(B 2 )f_; - the symbols R 1 3 , B 2 , f, R 9 , Rio R 11 and R 12 have the 5 meanings given above with respect to the formula (IV).
12. Process according to claim 11, characterized in that the unsaturated organic compounds (T) of formula (IX) in which R 11 = H and R 2 6 , R 9 , Rio and R 12 10 have the meanings given are prepared by linking together the 4 following stages: (1) condensation of hydroxylamine with the ketone R 12 -CO-R 9 , then (2) addition of CH 3 SO 2 Cl to the oxime obtained in order to result in the mesylate of the oxime, then (3) carrying 15 out a Beckmann rearrangement of the mesylate by reaction with the organomagnesium halide R 1 0 MgX, then (4) nucleophilic addition to the imine obtained of the organomagnesium halide R 26 MgX, followed by an acid hydrolysis. 20 13. Process according to claim 11, characterized in that the unsaturated organic compounds (*) of formula (IX) in which R 11 = H and R 2 6 , R 9 , Rio and R 12 have the meanings given are prepared by linking together the following 2 stages: (1) condensation of 55 the amine R12-NH 2 and of the ketone R 9 -CO-R10 in order to result in an imine, then (2) nucleophilic addition to the imine obtained of the organomagnesium halide R 26 MgX, followed by an acid hydrolysis. 5 14. Process for the preparation of an optionally mixed polyorganosiloxane containing oxygen linking units according to any one of claims 1 to 9, characterized in that it consists in carrying out: - in the case of polymers containing only amine 10 functional group(s): a dehydrogenation/ condensation reaction, or - in the case of mixed polymers containing amine functional group(s) and containing compatibilizing functional group(s): simultaneous 15 dehydrogenation/condensation and addition (hydrosilylation) reactions or successive dehydrogenation/condensation and then addition (hydrosilylation) reactions, starting with: corresponding organohydropolysilanes (H) 20 which are free of Z, having the oxygen linking unit, and W functional groups, the hydroxylated organic compound(s) (W"), from which the Z functional group(s) having the oxygen linking unit derive (s), and the compound(s) which is(are) ethylenically unsaturated at 25 the chain end (Z), from which the W functional group(s) derive(s), and in that the amounts of the reactants involved correspond to a [(*') + optionally (Z )]/SiH [of (H)] molar ratio which is of the order of 1 to 5. 56
15. Process according to claim 14, characterized in that the hydroxylated organic compounds (*') from which the Z functional groups having the oxygen linking unit derive (alternatively: from which the monovalent 5 groups X derive) are those of formula: j18 1- -7'20 21 F-CN- R (X) 9 'p in which: the symbol R 27 is a hydroxylated radical of formula: CH HO-C-pBj 2 the symbols R 2 2 , B 3 , g, R 18 , R 19 , R 2 0 and R 21 have 10 the meanings given above with respect to the formula (V).
16. Process according to claim 15, characterized in that the hydroxylated organic compounds (*') of formula (X) in which R 27 is the radical CH 3 HO-C-it k~22 g 15 with g being a number other than zero, and R 22 , B 3 , R 18 , R 19 , R 20 and R 21 have the meanings indicated, are prepared by linking together the following 3 stages: 57 (1) chlorination with HCl of the alcohol of formula: R1 8 CH2,=CRII -C-OH 9 gi9 then (2) condensation of the chlorinated compound obtained with the amine R 2 1 -NHR 2 0 in order to result in an ethylenically unsaturated amine, and then (3) 5 hydration in sulphuric acid medium of the double bond of the amine obtained.
17. Process according to claim 15, characterized in that the hydroxylated organic compounds ('I) of formula (X) in which R 27 is the radical CH HO-CH 10 (in this case, R22 = H and g = 0), and R 18 , R 19 , R 2 0 and R 21 have the meanings indicated, are prepared by linking together the following 4 stages: (1) chlorination with HCl of the alcohol of formula: R18 CH=-C-OH R1 9 then (2) condensation of the chlorinated compound 15 obtained with the amine R 2 1 -NHR 2 0 in order to result in an acetylenically unsaturated amine, then (3) hydration in sulphuric acid medium of the triple bond of the 58 amine, and then (4) reduction of the ketone formed to an alcohol in the presence of a suitable metallic reducing agent.
18. As means for implementing the process 5 according to claim 14, a novel hydroxylated amine (') of formula: IB 1- 20 21 1-C-NN R (X) I9 in which: - the symbol R 27 is a hydroxylated radical of formula: CH3 HO-C--B ?2 10 the symbols R 2 2 , B 3 , g, R 18 , R 19 , R 2 0 and R 21 have the meanings given above with respect to the formula (V).
19. Use of an effective amount of an optionally mixed polyorganosiloxane according to any one of claims 15 1 to 9, as stabilizers in combating light, oxidative and thermal degradation of organic polymers.
20. Use according to claim 19, characterized in that the organic polymers to be stabilized are chosen from polyolefins, polyurethanes, polyamides, 20 polyesters, polycarbonates, polysulphones, 59 polyethersulphones, polyetherketones, acrylic polymers, their copolymers and their mixtures.
21. Organic polymer composition stabilized against light, oxidative and thermal degradation, 5 characterized in that it comprises: - per 100 g of organic polymers to be stabilized, - an amount of mixed polyorganosiloxane according to any one of claims 1 to 9 which introduces from 0.04 to 20 milliequivalents of sterically hindered amine 10 functional group(s).
22. Composition according to claim 21, characterized in that the organic polymers to be stabilized are chosen from polyolefins, polyurethanes, polyamides, polyesters, polycarbonates, polysulphones, 15 polyethersulphones, polyetherketones, acrylic polymers, their copolymers and their mixtures.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9414054 | 1994-11-18 | ||
| FR9414054A FR2727121B1 (en) | 1994-11-18 | 1994-11-18 | NOVEL SILICON COMPOUNDS WITH STERICALLY HALFLED LINEAR AMINE FUNCTIONS, USEFUL FOR LIGHT AND THERMAL STABILIZATION OF POLYMERS |
| PCT/FR1995/001502 WO1996016127A1 (en) | 1994-11-18 | 1995-11-15 | New silicon compounds with sterically hindered linear amine functions, useful for the heat and light stabilization of polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU4180396A true AU4180396A (en) | 1996-06-17 |
Family
ID=9469086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU41803/96A Abandoned AU4180396A (en) | 1994-11-18 | 1995-11-15 | New silicon compounds with sterically hindered linear amine functions, useful for the heat and light stabilization of polymers |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0792324A1 (en) |
| JP (1) | JPH10509757A (en) |
| AR (1) | AR000253A1 (en) |
| AU (1) | AU4180396A (en) |
| BR (1) | BR9510402A (en) |
| CA (1) | CA2207109A1 (en) |
| FR (1) | FR2727121B1 (en) |
| IL (1) | IL116028A0 (en) |
| TR (1) | TR199501444A2 (en) |
| WO (1) | WO1996016127A1 (en) |
| ZA (1) | ZA959789B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2735481B1 (en) * | 1995-06-16 | 1997-08-22 | Rhone Poulenc Chimie | NOVEL SILICONE COMPOUNDS WITH STERICALLY HALF CYCLIC AMINE FUNCTIONS, USEFUL FOR LIGHT AND THERMAL STABILIZATION OF POLYMERS |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1218004B (en) * | 1988-05-27 | 1990-03-30 | Enichem Sintesi | UV STABILIZERS FOR ORGANIC POLES |
| US4895885A (en) * | 1988-09-06 | 1990-01-23 | Union Carbide Chemicals And Plastics Company Inc. | Polymer compositions stabilized with polysiloxanes containing sterically hindered heterocyclic moiety |
-
1994
- 1994-11-18 FR FR9414054A patent/FR2727121B1/en not_active Expired - Fee Related
-
1995
- 1995-11-15 EP EP95940315A patent/EP0792324A1/en not_active Withdrawn
- 1995-11-15 WO PCT/FR1995/001502 patent/WO1996016127A1/en not_active Application Discontinuation
- 1995-11-15 BR BR9510402A patent/BR9510402A/en not_active Application Discontinuation
- 1995-11-15 JP JP8516615A patent/JPH10509757A/en active Pending
- 1995-11-15 CA CA002207109A patent/CA2207109A1/en not_active Abandoned
- 1995-11-15 AU AU41803/96A patent/AU4180396A/en not_active Abandoned
- 1995-11-16 IL IL11602895A patent/IL116028A0/en unknown
- 1995-11-17 TR TR95/01444A patent/TR199501444A2/en unknown
- 1995-11-17 AR AR33426895A patent/AR000253A1/en unknown
- 1995-11-17 ZA ZA959789A patent/ZA959789B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AR000253A1 (en) | 1997-06-18 |
| FR2727121A1 (en) | 1996-05-24 |
| IL116028A0 (en) | 1996-01-31 |
| BR9510402A (en) | 1997-12-23 |
| TR199501444A2 (en) | 1996-06-21 |
| WO1996016127A1 (en) | 1996-05-30 |
| FR2727121B1 (en) | 1997-01-03 |
| JPH10509757A (en) | 1998-09-22 |
| EP0792324A1 (en) | 1997-09-03 |
| ZA959789B (en) | 1996-05-29 |
| CA2207109A1 (en) | 1996-05-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK5 | Application lapsed section 142(2)(e) - patent request and compl. specification not accepted |