CA2125959C - Bis(diallylamino) silanes - Google Patents
Bis(diallylamino) silanes Download PDFInfo
- Publication number
- CA2125959C CA2125959C CA002125959A CA2125959A CA2125959C CA 2125959 C CA2125959 C CA 2125959C CA 002125959 A CA002125959 A CA 002125959A CA 2125959 A CA2125959 A CA 2125959A CA 2125959 C CA2125959 C CA 2125959C
- Authority
- CA
- Canada
- Prior art keywords
- bis
- diallylamino
- copolymer
- flask
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000004756 silanes Chemical class 0.000 title claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 7
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 13
- 238000007334 copolymerization reaction Methods 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 5
- 229960004592 isopropanol Drugs 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920001384 propylene homopolymer Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XCENPWBBAXQVCG-UHFFFAOYSA-N 4-phenylpiperidine-4-carbaldehyde Chemical compound C=1C=CC=CC=1C1(C=O)CCNCC1 XCENPWBBAXQVCG-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FKLILKHHYDFNFD-UHFFFAOYSA-N sodium;1,3,4,5,7,8-hexahydroxy-9,10-dioxoanthracene-2,6-disulfonic acid Chemical compound [Na+].O=C1C2=C(O)C(O)=C(S(O)(=O)=O)C(O)=C2C(=O)C2=C1C(O)=C(S(O)(=O)=O)C(O)=C2O FKLILKHHYDFNFD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Bis(diallylamino) silanes of formula (I) where R1 and R2 are lower alkyl or phenyl groups are copolymerized with lower olefins and desilylated to exhibit amine functionality; they are receptive to dyes.
Description
BIS(DIALLYLAMINU) SILANES
Technical Field.
This invention relates to the use of bis(diallylamino) silanes of the general formula (CH2=CH-CH2)2N-Si-N(CH2-CH=CH2)2 where R1 and R2 are independently selected from alkyl and aryl groups having 1 to 6 carbon atoms as comonomers for lower olefins polymerized in highly active Ziegler-Natta catalyst systems.
Background Art In European Patent Publication 0423438, Sivak et al propose the use of protected diallyl amine monomers for copolymerization with ethylene, propylene, and other lower alpha-olefins having up to 8 carbon atoms. Protection of the otherwise vulnerable amine group is provided by a silyl group 2125J5~!
Technical Field.
This invention relates to the use of bis(diallylamino) silanes of the general formula (CH2=CH-CH2)2N-Si-N(CH2-CH=CH2)2 where R1 and R2 are independently selected from alkyl and aryl groups having 1 to 6 carbon atoms as comonomers for lower olefins polymerized in highly active Ziegler-Natta catalyst systems.
Background Art In European Patent Publication 0423438, Sivak et al propose the use of protected diallyl amine monomers for copolymerization with ethylene, propylene, and other lower alpha-olefins having up to 8 carbon atoms. Protection of the otherwise vulnerable amine group is provided by a silyl group 2125J5~!
having relatively bulky,substituents, such as lower alkyl or phenyl groups. Diallyl amines are proposed and several examples are given of silyl-protected diallyl amines. However, bis-diallyl amines are not contemplated.
Summary of Invention I have invented new compounds of the general formula (CH2=CH-CH2)2N-Si-N(CH2-CH=CH2)2 where R1 and R2 are independently selected from alkyl and aryl groups having 1 to 6 carbon atoms.
They may be used as cross-linking agents in polymers and find special utility as comonomers for lower olefins polymerized in highly active Ziegler-Natta catalyst systems.
Detailed Description cf the Invention My invention will be described with respect to two paradigms, namely bis(diallylamino)dimethylsilane and bis(diallylamino)diphenylsilane.
- ~ ~ ~ PCT/US93/10025 EXAMPLE I
Bis(diallylaminoldimethylsilane The equipment used for the synthesis of bis(diallylamino)dimethylsilane was set up in the following manner. A reflux condenser, mechanical stirrer and 125 ml addition funnel were placed on a 2000 ml 3-necked, round-bottomed flask. An argon inlet was connected to the top of the reflux condenser and a heating mantle was placed on the flask. The flask was flushed with argon (allowing the argon to exit the setup through the top of the addition funnel) until the atmosphere in the glassware was assured of being inert.
Heptane (400 ml), triethylamine (136.62 g, 1.350 moles, 188 ml) and diallylamine (98.36 g, 1.012 moles, 125 ml) were charged into the reaction flask. Dichlorodimethylsilane (43.55 g, 0.3375 moles, 41 ml) was placed in the addition funnel and added to the reaction mixture in the flask over a period of 70 minutes. The temperature of the reaction mixture reached 37.5°C (as measured by a thermocouple between the flask and heating mantle).
The reaction produces a large amount of salts (triethylamine hydrochloride and diallylamine hydrochloride) and twice during the reaction additional heptane had to be added (200 ml portions each time) in order to keep the slurry thinned to a stirrable consistency.
2iy595~
Summary of Invention I have invented new compounds of the general formula (CH2=CH-CH2)2N-Si-N(CH2-CH=CH2)2 where R1 and R2 are independently selected from alkyl and aryl groups having 1 to 6 carbon atoms.
They may be used as cross-linking agents in polymers and find special utility as comonomers for lower olefins polymerized in highly active Ziegler-Natta catalyst systems.
Detailed Description cf the Invention My invention will be described with respect to two paradigms, namely bis(diallylamino)dimethylsilane and bis(diallylamino)diphenylsilane.
- ~ ~ ~ PCT/US93/10025 EXAMPLE I
Bis(diallylaminoldimethylsilane The equipment used for the synthesis of bis(diallylamino)dimethylsilane was set up in the following manner. A reflux condenser, mechanical stirrer and 125 ml addition funnel were placed on a 2000 ml 3-necked, round-bottomed flask. An argon inlet was connected to the top of the reflux condenser and a heating mantle was placed on the flask. The flask was flushed with argon (allowing the argon to exit the setup through the top of the addition funnel) until the atmosphere in the glassware was assured of being inert.
Heptane (400 ml), triethylamine (136.62 g, 1.350 moles, 188 ml) and diallylamine (98.36 g, 1.012 moles, 125 ml) were charged into the reaction flask. Dichlorodimethylsilane (43.55 g, 0.3375 moles, 41 ml) was placed in the addition funnel and added to the reaction mixture in the flask over a period of 70 minutes. The temperature of the reaction mixture reached 37.5°C (as measured by a thermocouple between the flask and heating mantle).
The reaction produces a large amount of salts (triethylamine hydrochloride and diallylamine hydrochloride) and twice during the reaction additional heptane had to be added (200 ml portions each time) in order to keep the slurry thinned to a stirrable consistency.
2iy595~
After the addition of dichlorodimethyl-silane was complete, the mixture was heated to reflux for five hours. .The flask was then allowed to cool to room temperature.
The salts were removed by filtration using a buchner funnel covered with a latex dam to keep exposure to the atmosphere to a minimum. the product was isolated from the filtrate by distillation. The heptane and excess amines were removed at a vacuum of 40 mmHg with a temperature range from ambient to 93°C. The product distilled at 72.6-74.6°C at 1 mmHg.
61.2 g of bis(diallylamino)dimethylsilane was isolated by this technique which corresponds to a yield of 720 of theoretical after distillation.
EXAMPLE II
Bis(diallylamino)diphenylsilane The glassware setup used for the preparation of bis(diallylamino)diphenylsilane was the same as the equipment used for the synthesis of bis(diallylamino)dimethylsilane above except that a 1000 ml flask was used instead of a 2000 ml flask.
After the system was flushed with argon, triethylamine (159.84 g, 1.580 moles, 220.2 ml), diallylamine (84.48 g, 0.8699 moles, 107.3 ml) and toluene (200 ml) were added to the reaction flask.
Dichlorodiphenylsilane (100.75 g, 0.3980 moles, 83.7 ml) was charged into the addition funnel and added to the reaction mixture in the flask over a period of 15 minutes, the temperature rose to 60°C.
WO 94/10217 ~ 1 ~ ~ 9 ~ ~ PCT/US93/10025 A large amount of solid precipitated from the mixture. Toluene (100 ml) was added to the flask through the addition funnel to rinse out the remaining silane and make the reaction mixture more stirrable and the mixture was heated to reflux for two hours, then cooled to room temperature.
The salts were removed by filtration using a sealed pressure filter under an inert atmosphere.
The product was isolated from the filtrate by distillation. The heptane and excess amines were removed at a vacuum of 40 mmHg with a temperature range from ambient to 43°C. The product distilled in a range from 160°/0.3 mmHg to 160°/0.1 mmHg.
101.5 g of bis(diallylamino)diphenylsilane was isolated by this technique which corresponds to a yield of 68$ of theoretical after distillation.
Similar preparations may be made for the diethyl, dipropyl, dibutyl, dipentyl, dihexyl and methylphenyl variants.
My new monomers may be incorporated into chains of crystalline polypropylene and other lower olefin polymers as described in the above-mentioned Sivak et al patent. Thereafter, the silyl groups may be removed by hydrolysis or alcoholysis optionally promoted by acidic or basic catalysis and the remaining copolymers, which may be mildly cross-linked, will exhibit amine functionality or ammonium functionality in the presence of acids.
My monomers may be homopolymerized using Ziegler-Natta systems and/or copolymerized in amounts to yield copolymers having ratios of lower olefin to my monomer (m) of 0.1 mole ~ to 99.9 mole %.
The salts were removed by filtration using a buchner funnel covered with a latex dam to keep exposure to the atmosphere to a minimum. the product was isolated from the filtrate by distillation. The heptane and excess amines were removed at a vacuum of 40 mmHg with a temperature range from ambient to 93°C. The product distilled at 72.6-74.6°C at 1 mmHg.
61.2 g of bis(diallylamino)dimethylsilane was isolated by this technique which corresponds to a yield of 720 of theoretical after distillation.
EXAMPLE II
Bis(diallylamino)diphenylsilane The glassware setup used for the preparation of bis(diallylamino)diphenylsilane was the same as the equipment used for the synthesis of bis(diallylamino)dimethylsilane above except that a 1000 ml flask was used instead of a 2000 ml flask.
After the system was flushed with argon, triethylamine (159.84 g, 1.580 moles, 220.2 ml), diallylamine (84.48 g, 0.8699 moles, 107.3 ml) and toluene (200 ml) were added to the reaction flask.
Dichlorodiphenylsilane (100.75 g, 0.3980 moles, 83.7 ml) was charged into the addition funnel and added to the reaction mixture in the flask over a period of 15 minutes, the temperature rose to 60°C.
WO 94/10217 ~ 1 ~ ~ 9 ~ ~ PCT/US93/10025 A large amount of solid precipitated from the mixture. Toluene (100 ml) was added to the flask through the addition funnel to rinse out the remaining silane and make the reaction mixture more stirrable and the mixture was heated to reflux for two hours, then cooled to room temperature.
The salts were removed by filtration using a sealed pressure filter under an inert atmosphere.
The product was isolated from the filtrate by distillation. The heptane and excess amines were removed at a vacuum of 40 mmHg with a temperature range from ambient to 43°C. The product distilled in a range from 160°/0.3 mmHg to 160°/0.1 mmHg.
101.5 g of bis(diallylamino)diphenylsilane was isolated by this technique which corresponds to a yield of 68$ of theoretical after distillation.
Similar preparations may be made for the diethyl, dipropyl, dibutyl, dipentyl, dihexyl and methylphenyl variants.
My new monomers may be incorporated into chains of crystalline polypropylene and other lower olefin polymers as described in the above-mentioned Sivak et al patent. Thereafter, the silyl groups may be removed by hydrolysis or alcoholysis optionally promoted by acidic or basic catalysis and the remaining copolymers, which may be mildly cross-linked, will exhibit amine functionality or ammonium functionality in the presence of acids.
My monomers may be homopolymerized using Ziegler-Natta systems and/or copolymerized in amounts to yield copolymers having ratios of lower olefin to my monomer (m) of 0.1 mole ~ to 99.9 mole %.
Following are examples of propylene copolymerizations with bis(diallylamino)dimethylsilane ("BDMS") and bis(diallylamino)diphenylsilane ("BDPS").
_General Copolymerization Procedure Standard inert atmosphere techniques were used to exclude moisture and oxygen throughout the manipulations.
An apparatus consisting of a round bottom flask fitted with a side arm, magnetic stirring bar and a stopper was assembled hot from a drying oven and was then either evacuated and refilled with inert gas several times or (and) purged with inert gas for at least 15 minutes. The flask was charged with a given amount of solvent, heptane or toluene, usually 125 mL. The solvents were freshly distilled from sodium and triethyl-aluminum (TEA) over which they had been refluxed for at least 18 hours under an inert atmosphere.
At this point the inert gas atmosphere in the flask was replaced with the gaseous comonomer by a minimum of three cycles of evacuation and refilling back to atmospheric pressure with the comonomer. After the third cycle the solution was stirred for at least ten minutes (usually longer) to allow the solvent to become saturated with the comonomer. Pressure was maintained at one atmosphere via a bubbler.
Next was added an "external donor", which was diphenyldimethoxysilane. Phenyltrimethoxysilane may alternatively be used. Then the other comonomer 7 .-2 ~ ~ ~ 9 5 ~ P~/US93/10025 _7_ was added. A given amount of alkyl aluminum co-catalyst, which was in the form of a heptane solution of about 25$ by weight (0.715 g/mL in heptane), was also added to the flask.
The polymerization was initiated by the addition of the transition metal containing co-catalyst, which was a titanium tetrachloride on a magnesium chloride support. At this point the flask was lowered into a thermostated oil bath and magnetic stirring was begun.
An excess of gaseous comonomer was passed into the flask in order to replace any that was consumed. Excess gaseous comonomer was allowed to pass from the reaction vessel via a bubbler, maintaining a pressure in the flask of one atmosphere.
After a specified period of time the reaction was quenched by the addition of acidified alcohol (HC1 in iso-propanol, ethanol and/or methanol). The quenched reaction slurry was combined with the alcohol solution of volume at least twice the original volume of the inert reaction solvent. The resultant slurry was stirred for at least 45 minutes and then filtered. This treatment not only stopped the reaction, it dissolved catalyst residues and removed silyl groups and thus regenerated the amino groups.
If the filtration proceeded very slowly, the slurry was combined with enough water to make the filtration proceed at a convenient rate.
The polymer was resuspended in alcohol, a stirred, filtered and vacuum dried overnight.
2~2~~59 _8_ Boiling heptane soluble content was determined by standard methods.
Homopolymerization of propylene under these conditions produces polypropylene with yields in the range of 200-220 g polymer/g , titanium-containing catalyst. The extent of reduction in polymer yield in the copolymerizations relative to this homopolymer yield is used as a rough guide to the utility of the comonomers in the copolymerization systems.
Copolymerizations of Propylene with Bis(diallylamino) dimethylsilane (BDMS) Example III
The general copolymerization procedure above was followed using the following quantities of reagents and reaction conditions in the polymerization.
Solvent heptane 100 mL
External Donor DPMS 75 NL
Comonomer BDMS 3.85 g Cocatalyst triethylaluminum 4.3 mL (25 wt ~) TiCl4/MgCl2 Catalyst 91 mg Reaction Temperature 50°C
Reaction Time 2 hr Alcohol Used in Work Up iso-propanol The polymerization yielded 8.3 g of polymer which is a yield of 91.2 g polymer/g catalyst. This corresponds to about 40% of the yield of a homopolymerization of propylene under these conditions.
_g_ Example IV
This polymerization was done using the following quantities of reagents and reaction conditions with the general copol ymerization procedure from above.
Solvent heptane 75 mL
External Donor DPMS 225 NL
Comonomer BDMS 11.12 g Cocatalyst triethylaluminum 12.9 mL (25 wt ~) TiCl4/MgCl2 Catalyst 104 mg Reaction Temperature 50C
Reaction Time 2 hr Alcohol Used in Work Up iso-propanol Polymer (5.8 g) was produced in this polymerization which is a yield of 55.5 g polymer/g catalyst which is approximately 25% of a comparable homopolymerization.
Copolymerizations of Propylene with Bis(diallylamino) diphenylsilane (BDPS) Example V
The following quantities of reagents and reaction conditions were used with the general copolymerization procedure.
Solvent heptane 100 mL
External Donor DPMS 220 NL
Comonomer BDPS 18.19 g Cocatalyst triethylaluminum 12.5 mL (25 wt %) TiCl4/MgCl2 Catalyst 137 mg Reaction Temperature 50C
Reaction Time 2 hr Alcohol Used in Work Up iso-propanol ~~2~g59 The polymerization yielded 15.4 g of polymer which is a yield of 112.4 g polymer/g catalyst which is in the range of 51-57$ of a comparable propylene homopolymerization. 98.40 of a tested sample was insoluble in boiling heptane.
Example VI
The following quantities of reagents and reaction conditions were used with the general copolymerization procedure.
Solvent heptane 50 mL
External Donor DPMS 400 NL
Comonomer BDPS 31.97 g Cocatalyst triethylaluminum 23.5 mL (25 wt ~k) TiCl4/MgCl2 Catalyst 117 mg Reaction Temperature 50C
Reaction Time 2 hr Alcohol Used in Work Up iso-propanol Copolymer (17.0 g) was produced by this copolymerization which corresponds to a yield of 145.3 g polymer/g catalyst. This is about 70~ of what is produced in a comparable propylene homopolymerization.
The fraction insoluble in boiling heptane was 91.8 of the tested sample.
Uptake of an Acid Dye by Polymer Samples as a Test for Amine Incorporation Example VII
A sample of propylene homopolymer was prepared using the general polymerization conditions given above and used as a blank in the dye uptake experiments described below.
A stock solution of dye was prepared by dissolving Acid Alizarin Blue BB dye (1.00 g) and ammonium acetate (7.0 g) in water to obtain 80 grams of solution.
~~2~~5.~
Samples (200 mg) of the propylene homopolymer and each of the four propylene/amine copolymers produced iri Examples 1-4 above were placed in test tubes and 10 mL of the stock dye solution was added.
The samples were sealed and shaken to assure dispersion of the polymer powder in the dye and placed in a 60°C water bath. The temperature of the bath was increased to 100°C over a period of 30 minutes and held at that temperature for 1 hour and then cooled to room temperature.
The samples were filtered and rinsed repeatedly with water until the rinsings were clear and the color of the powder did not appear to change. The rinsings were then continued with an equivalent amount of water. The total amount of water used was about 500 ml. The samples were then suspended in boiling water for about one minute and then filtered and this hot wash was repeated two more times.
After the samples were dried, their color intensities were compared and are described in Table 1 below.
Table 1 Dyed Propylene/Amine Copolymers Sample Color Propylene homopolymer very pale pink/
purple color Example III slightly more intense purple than propylene homopolymer Example IV pale purple Example V pale purple Example VI reasonably intense purple/blue color
_General Copolymerization Procedure Standard inert atmosphere techniques were used to exclude moisture and oxygen throughout the manipulations.
An apparatus consisting of a round bottom flask fitted with a side arm, magnetic stirring bar and a stopper was assembled hot from a drying oven and was then either evacuated and refilled with inert gas several times or (and) purged with inert gas for at least 15 minutes. The flask was charged with a given amount of solvent, heptane or toluene, usually 125 mL. The solvents were freshly distilled from sodium and triethyl-aluminum (TEA) over which they had been refluxed for at least 18 hours under an inert atmosphere.
At this point the inert gas atmosphere in the flask was replaced with the gaseous comonomer by a minimum of three cycles of evacuation and refilling back to atmospheric pressure with the comonomer. After the third cycle the solution was stirred for at least ten minutes (usually longer) to allow the solvent to become saturated with the comonomer. Pressure was maintained at one atmosphere via a bubbler.
Next was added an "external donor", which was diphenyldimethoxysilane. Phenyltrimethoxysilane may alternatively be used. Then the other comonomer 7 .-2 ~ ~ ~ 9 5 ~ P~/US93/10025 _7_ was added. A given amount of alkyl aluminum co-catalyst, which was in the form of a heptane solution of about 25$ by weight (0.715 g/mL in heptane), was also added to the flask.
The polymerization was initiated by the addition of the transition metal containing co-catalyst, which was a titanium tetrachloride on a magnesium chloride support. At this point the flask was lowered into a thermostated oil bath and magnetic stirring was begun.
An excess of gaseous comonomer was passed into the flask in order to replace any that was consumed. Excess gaseous comonomer was allowed to pass from the reaction vessel via a bubbler, maintaining a pressure in the flask of one atmosphere.
After a specified period of time the reaction was quenched by the addition of acidified alcohol (HC1 in iso-propanol, ethanol and/or methanol). The quenched reaction slurry was combined with the alcohol solution of volume at least twice the original volume of the inert reaction solvent. The resultant slurry was stirred for at least 45 minutes and then filtered. This treatment not only stopped the reaction, it dissolved catalyst residues and removed silyl groups and thus regenerated the amino groups.
If the filtration proceeded very slowly, the slurry was combined with enough water to make the filtration proceed at a convenient rate.
The polymer was resuspended in alcohol, a stirred, filtered and vacuum dried overnight.
2~2~~59 _8_ Boiling heptane soluble content was determined by standard methods.
Homopolymerization of propylene under these conditions produces polypropylene with yields in the range of 200-220 g polymer/g , titanium-containing catalyst. The extent of reduction in polymer yield in the copolymerizations relative to this homopolymer yield is used as a rough guide to the utility of the comonomers in the copolymerization systems.
Copolymerizations of Propylene with Bis(diallylamino) dimethylsilane (BDMS) Example III
The general copolymerization procedure above was followed using the following quantities of reagents and reaction conditions in the polymerization.
Solvent heptane 100 mL
External Donor DPMS 75 NL
Comonomer BDMS 3.85 g Cocatalyst triethylaluminum 4.3 mL (25 wt ~) TiCl4/MgCl2 Catalyst 91 mg Reaction Temperature 50°C
Reaction Time 2 hr Alcohol Used in Work Up iso-propanol The polymerization yielded 8.3 g of polymer which is a yield of 91.2 g polymer/g catalyst. This corresponds to about 40% of the yield of a homopolymerization of propylene under these conditions.
_g_ Example IV
This polymerization was done using the following quantities of reagents and reaction conditions with the general copol ymerization procedure from above.
Solvent heptane 75 mL
External Donor DPMS 225 NL
Comonomer BDMS 11.12 g Cocatalyst triethylaluminum 12.9 mL (25 wt ~) TiCl4/MgCl2 Catalyst 104 mg Reaction Temperature 50C
Reaction Time 2 hr Alcohol Used in Work Up iso-propanol Polymer (5.8 g) was produced in this polymerization which is a yield of 55.5 g polymer/g catalyst which is approximately 25% of a comparable homopolymerization.
Copolymerizations of Propylene with Bis(diallylamino) diphenylsilane (BDPS) Example V
The following quantities of reagents and reaction conditions were used with the general copolymerization procedure.
Solvent heptane 100 mL
External Donor DPMS 220 NL
Comonomer BDPS 18.19 g Cocatalyst triethylaluminum 12.5 mL (25 wt %) TiCl4/MgCl2 Catalyst 137 mg Reaction Temperature 50C
Reaction Time 2 hr Alcohol Used in Work Up iso-propanol ~~2~g59 The polymerization yielded 15.4 g of polymer which is a yield of 112.4 g polymer/g catalyst which is in the range of 51-57$ of a comparable propylene homopolymerization. 98.40 of a tested sample was insoluble in boiling heptane.
Example VI
The following quantities of reagents and reaction conditions were used with the general copolymerization procedure.
Solvent heptane 50 mL
External Donor DPMS 400 NL
Comonomer BDPS 31.97 g Cocatalyst triethylaluminum 23.5 mL (25 wt ~k) TiCl4/MgCl2 Catalyst 117 mg Reaction Temperature 50C
Reaction Time 2 hr Alcohol Used in Work Up iso-propanol Copolymer (17.0 g) was produced by this copolymerization which corresponds to a yield of 145.3 g polymer/g catalyst. This is about 70~ of what is produced in a comparable propylene homopolymerization.
The fraction insoluble in boiling heptane was 91.8 of the tested sample.
Uptake of an Acid Dye by Polymer Samples as a Test for Amine Incorporation Example VII
A sample of propylene homopolymer was prepared using the general polymerization conditions given above and used as a blank in the dye uptake experiments described below.
A stock solution of dye was prepared by dissolving Acid Alizarin Blue BB dye (1.00 g) and ammonium acetate (7.0 g) in water to obtain 80 grams of solution.
~~2~~5.~
Samples (200 mg) of the propylene homopolymer and each of the four propylene/amine copolymers produced iri Examples 1-4 above were placed in test tubes and 10 mL of the stock dye solution was added.
The samples were sealed and shaken to assure dispersion of the polymer powder in the dye and placed in a 60°C water bath. The temperature of the bath was increased to 100°C over a period of 30 minutes and held at that temperature for 1 hour and then cooled to room temperature.
The samples were filtered and rinsed repeatedly with water until the rinsings were clear and the color of the powder did not appear to change. The rinsings were then continued with an equivalent amount of water. The total amount of water used was about 500 ml. The samples were then suspended in boiling water for about one minute and then filtered and this hot wash was repeated two more times.
After the samples were dried, their color intensities were compared and are described in Table 1 below.
Table 1 Dyed Propylene/Amine Copolymers Sample Color Propylene homopolymer very pale pink/
purple color Example III slightly more intense purple than propylene homopolymer Example IV pale purple Example V pale purple Example VI reasonably intense purple/blue color
Claims (15)
1. A copolymer of about 0.1% to about 99.9%
lower alpha-olefin having 2 to 8 carbon atoms and a bis(diallylamino) silane of the formula where R1 and R2 are independently selected from alkyl and aryl groups having 1 to 6 carbon atoms.
lower alpha-olefin having 2 to 8 carbon atoms and a bis(diallylamino) silane of the formula where R1 and R2 are independently selected from alkyl and aryl groups having 1 to 6 carbon atoms.
2. Copolymer of claim 1 wherein the alpha-olefin is propylene.
3. Copolymer of claim 1 wherein the silane is bis(diallylamino) dimethylsilane.
4. Copolymer of claim 1 wherein the silane is bis(diallylamino) diphenylsilane.
5. A desilanated copolymer of claim 1.
6. A desilanated copolymer of claim 2.
7. A desilanated copolymer of claim 3.
8. A desilanated copolymer of claim 4.
9. A dyed copolymer of claim 5.
10. A dyed copolymer of claim 6.
11. A dyed copolymer of claim 7.
12. A dyed copolymer of claim 8.
13. Bis(diallylamino) silanes of the formula where R1 and R2 are independently selected from alkyl and aryl groups having 1 to 6 carbon atoms.
14. A silane of claim 13 wherein R1 and R2 are CH3.
15. A silane of claim 13 wherein R1 and R2 are phenyl groups.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US96532092A | 1992-10-23 | 1992-10-23 | |
US965,320 | 1992-10-23 | ||
PCT/US1993/010025 WO1994010217A1 (en) | 1992-10-23 | 1993-10-21 | Bis(diallylamino) silanes |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2125959A1 CA2125959A1 (en) | 1994-05-11 |
CA2125959C true CA2125959C (en) | 2000-02-22 |
Family
ID=25509804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002125959A Expired - Fee Related CA2125959C (en) | 1992-10-23 | 1993-10-21 | Bis(diallylamino) silanes |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0620831A4 (en) |
JP (1) | JPH07502565A (en) |
CA (1) | CA2125959C (en) |
WO (1) | WO1994010217A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7956207B2 (en) * | 2006-09-28 | 2011-06-07 | Praxair Technology, Inc. | Heteroleptic organometallic compounds |
JP2011256120A (en) * | 2010-06-07 | 2011-12-22 | Toho Titanium Co Ltd | Process for producing organoaminosilane compound |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5239030A (en) * | 1987-05-08 | 1993-08-24 | Aristech Chemical Corporation | Amine/propylene copolymers |
-
1993
- 1993-10-21 EP EP93923952A patent/EP0620831A4/en not_active Withdrawn
- 1993-10-21 CA CA002125959A patent/CA2125959C/en not_active Expired - Fee Related
- 1993-10-21 WO PCT/US1993/010025 patent/WO1994010217A1/en not_active Application Discontinuation
- 1993-10-21 JP JP6511142A patent/JPH07502565A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
WO1994010217A1 (en) | 1994-05-11 |
EP0620831A1 (en) | 1994-10-26 |
CA2125959A1 (en) | 1994-05-11 |
EP0620831A4 (en) | 1995-04-19 |
JPH07502565A (en) | 1995-03-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7348388B2 (en) | Copolymers of olefins and vinyl- and allylsilanes | |
JP2001509827A (en) | Catalyst composition for the production of olefin polymers | |
EP3480221A1 (en) | Ethylene/alpha-olefin copolymer | |
EP0509233B1 (en) | Process for producing ethylene-alpha-olefin copolymers | |
EP0773241B1 (en) | Solid catalyst component for polymerizing olefins and catalyst for polymerization of olefins | |
US5008421A (en) | Silyl derivatives of 2,6-dimethyl-4-allyl phenol | |
CA2125959C (en) | Bis(diallylamino) silanes | |
US5280094A (en) | Bis (diallylamino) silanes | |
US4916248A (en) | Silyl derivatives of 2, 6-dimethyl-4-allyl phenol | |
Wendt et al. | Ethene Co‐and Terpolymerizations with TIBA‐Protected Norbornenemethanol and TIBA‐Protected Norbornenecarboxylic Acid Using Homogeneous Metallocene/MAO Catalyst Systems | |
WO1988008856A1 (en) | Incorporation of functional groups in polymers | |
US5248737A (en) | Method of making amine/propylene copolymers | |
US5110971A (en) | Silyl derivatives of eugenol | |
CA2015493C (en) | Liquid catalyst component, catalyst system containing the same, and process for producing ethylene-a-olefin copolymers using the catalyst system | |
US5556822A (en) | Catalyst system for polyermization of olefin | |
EP0423438B1 (en) | Amine/propylene copolymers | |
US6214950B1 (en) | Process for preparation of polyolefin using an olefin polymerization catalyst | |
CA2024895C (en) | Silyl derivatives of 2-allyl phenol | |
US5266663A (en) | Silyl derivatives of eugenol | |
JP2775501B2 (en) | Propylene-silicon compound random copolymer and method for producing the same | |
US5258533A (en) | Bis(diallylamino) silanes | |
US5206323A (en) | Silyl derivatives of eugenol | |
US5200542A (en) | Diallyl silyl amines | |
EP0846706B1 (en) | Olefin polymerization catalyst and preparation process of polyolefin using the same | |
CA1318454C (en) | Process for polymerizing 4-methylpentene-1 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |