CA2180725C - Polymerisation of cycloalkenes - Google Patents
Polymerisation of cycloalkenes Download PDFInfo
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- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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Abstract
Polyalkenamers are produced by the ring-opening polymerization of cycloalkenes. The polymerization is conducted in the presence of a homogeneous catalyst system comprising (a) a salt of a transition metal selected from the Group VIb of the periodic table; (b) an organometallic compound of a metal selected from Groups IIIa and IVa of the periodic table; and (c) an organo-silicon compound having the formula: RxSi (OR')y(OSiR3)z(Ia), (R2SiO)3 (Ib) or (R3Si)2NH (Ic), wherein R is identical or different and represents a hydrogen atom, a C1-C4 alkyl or phenyl group; R' represents a C1-C4 alkyl or phenyl group; O<x molar ratio of component (c) to component (a) is at least about 0.5:1. The catalyst system of the invention enables one to significantly increase the rate of polymerization.
Description
~ Wo 95/20GI3 2 l 8 ~ 7 ~ 5 PCT/CA9J/00060 -" POLYMERI ZAT I ON OF CYCLOALKENES "
TECHNICAL FIELD
The present invention pertains to improvements in the field of polymerization catalysts. More particularly, the invention relates to an improved catalyst system for the ring-opening polymerl2ation of cycloalkenes to produce polyalkenamers as well as to a process for the production of polyalkenamers utilizing such a catalyst system.
;3ACKGROUND ART
Polyalkenamers play an important role in the rubber industry as they enter in the manufac-ture of synthetic rubbers. Some of these polymers are produced by a catalyzed ring-opening polymerization of cycloalkenes. The catalysts employed are generally two-component catalytic systems comprising a salt of a transition metal from Group VIb or VIIb of the Periodic Table and an organometallic compound of a metal from Groups Ia to IVa of the Periodic Table. The most common catalyst systems are based on tungsten or molybde-num salts, such as the well known system WCl6/Sn (CH3~ 4 . However, the ring-opening polymeri-zation of cycloalkenes such as cyclooctene with this system may take from several days to several weeks to reach completion.
In order to accelerate the polymeriza-tion, it is known to add a third catalyst compo-nent containing oxygen, such as water or an alcohol. For instance, the use of ethanol as an accelerator with the catalyst system WCl6/C2HsAlCl2 for polymerizing cyclopentene in Wo 95/20G13 2 1 c~ 0 ~ ~ ~ PC~/CA9~/00060 benzene~ has been reported by E. A. Ostead et al in Die Makromolekulare Chemie, Vol. 154 (1972), pages 21-3g. The amount of ethanol added must be strictly controlled as too little ethanol does not provide the desired accelerating effect and the reaction is extremely slow. Too much ethanol, on the other hand, has been found to terminate the reaction and inhibit same so that the polymeriza-tion cannot be re-initiated.
DISCI,OSURE OF THE INVENTION
It is therefore an object of the present invention to overcome the above drawbacks and to provide an improved catalyst system for the ring-opening polymerization of cycloalkenes, whereby to increase the rate of polymerization.
It is another object of the invention to provide a catalyst system which does not adversely affect_ the polymerization if an excess of the catalyst system is used.
~ In accordance with the present inven-tion, there is thus provided a homogeneous catalyst system for the ring-opening polymeriza-tion of cyrl ..~l k~n~c to produce polyalkenamers, comprising:
a) a salt of a transition metal selected from the Group VIb of the Periodic Table;
b) an organometallic compound of a metal selected from Groups IIIa and IVa of the Periodic Table; and c) an organosilicon compound having the formula:
RXSi~oR')y(OSiR3j ~ (Ia) 2 ~ ~Q7~5 .
~R2Si~1 3 (Ib) or (R3Si~ 2NH ( Ic) wherei~:
R is ident~ cal or different and repre-sents a hydrogen at~m, a C1-C4 alkyl or phenyl g~up;
R' reoresents a C1-C4 alkyl or ohenyl ~roup;
0 < x 5 3;
0 S y < 4;
z=0 or 1;
y+z 2 1;
x+y+z=4;
wlth the proviso that x=1 and y=3 when z=0;
and where~n the molar ratio of component (c) to component ~a) is at least about 0.5:1.
~pplicant has found quite unexpectedly that organosilicon compounds of formula (Ia), (Ib) or (Ic) as defined above can be used to activate kno~n two-component catalytic systems, such as the system WC16/Sn (CH3) 4, thereby increasing the rate of poly~Lerization of cycloalkenes. These organosil con compounds may be used in excess relative to the other catalyst components without adversely affecting the polymerization.
The catalyst system of the invention is prepared by first reacting component (a) with component (b), and thereafter adding component (c). The reaction of the transition metal salt wi.h the organometallic cQmpound is known to generate a carbene ligand.
.
AMEN~3 SH~ET
~ Wo 9~/20613 2 ~ ~ ~ 7 ~ 5 PCT1CA9~/00060 Representative examples of the transi-tion metal salts which may be used as the first catalyst component (a) are tungsten and molybdenum halides, such as molybdenum trichloride, molybde-num tetrachloride, molybdenum pentachloride, tungsten dichloride, tungsten tetrachloride, tungsten pentachloride, tungsten hexachloride, molybdenum dibromide, molybdenum tribromide, molybdenum tetrabromide, tungsten dibromide, lO tungsten pentabromide, tungsten hexabromide, molybdenum hexafluoride, tungsten hexafluoride, tungsten dliodide and tungsten tetraiodide. It is usually preferred to employ tungsten hexachloride.
Representative examples of organo-metallic compounds useful as the second catalyst component (b) include aluminum and tin compounds.
Representative of such compounds are trialkylalu-minums such as trimethylaluminum, triethylalumi-num, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tri-hexylaluminum, trioctylaluminum and the like;
dialkylaluminum halides such as diethylaluminum chloride, di-n-propylaluminum chloride, diiso-butylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diethylaluminum fluoride and the like; alkylaluminum dihalides such as ethylaluminum dichloride, ethylaluminum dibromide, propylaluminum dichloride, isobutylaluminum di-chloride, ethylaluminum diiodide and the like; and tetraalkyltins such as tetramethyltin, tetra-ethyltins, tetra-n-propyltin, tetra-n-butyltin, tetraisopropyltin, tetraisobutyltin, tetra-hexyltin, tetraoctyltin and the like. It is usually preferred to employ tetramethyltin.
~ WO 95/20613 2 1 ~ ~ 7 ~ 5 PCT/CAg~/00060 Examples of suitable organosiloxanes of formula (Ia) or (Ib) which may be used as the third catalyst component ~c) include phenyl-triethoxysiloxane, 1,1, 3, 3-tetramethyldisiloxane, hexamethyldisiloxane aIrd hexamethylcyclotri-siloxane. It is also possible to use an organo-silazane of formula (Ic), such as 1,1, 3, 3-tetramethyldisilazane, 1, 3-diphenyl-1, 1, 3, 3-tetra-methyldisilazane or hexamethyldisilazane.
The molar ratio of the organosilicon compound to the transition metal salt must be at least 0.5 (iO.1) :1, since at a lesser molar ratio the organosilicon compound does not have any sub-stantial activating effect. Preferred molar ratios of cn~rnnPnts (a): (b): (c) are 1:2:2.3 and 1:2:4.7.
T~e ring-opening polymerization of cycloalkenes with the catalyst system of the invention is generally carried out at a tempera-ture ranging from about 0 to about 160C. At a temperature above 160C, there is a tendency for the catalyst system to decompose. The polymeriza-tion can be carried out in bulk or in solution since the catalyst system is homogeneous and thus soluble in the monomer or solvent.
Applicant has also found quite unexpect-edly that satura~ed polycyclic oligomers can be produced by conducting the polymerization of cycloalkenes in the presence of the above catalyst system, but containing no organometallic compound.
It is believed that the polymerization proceeds through a mechanism different than ring-opening, such as a cationic m~ h~n; Sm The saturated poly-cyclic oligomers produced are stable at high Wo 95/20613 PCT/CA9~/00060 2 1 8Q7~ ~
temperature and can thus be used as lubricants or release agents.
The present invention therefore provi~es, in another aspect thereof, a homo-geneous catalyst system for.. the polymerization of cycloalkenes to produce saturated polycyclic oligomers, comprising:
a) a salt of a transition metal selec~ed from the Group VIb of the Periodic 10 Table, and b) an organosilicon compound having the f ormuIa:
RXSi(OR')y(OSiR3)z (Ia) (R2SiO) 3 (Ib) or ~R3Si) 2NH (Ic) 20 wherein:
R is identical ~r di~ferent and repre-sents a hydro~en atom, a C1-C4 alkyl or phenyl group;
R' represents a C1-C4 alkyl or phenyl 25 group;
0 < x < 3;
0 < y < 4 z=0 or l;
y+z ~ l;
TECHNICAL FIELD
The present invention pertains to improvements in the field of polymerization catalysts. More particularly, the invention relates to an improved catalyst system for the ring-opening polymerl2ation of cycloalkenes to produce polyalkenamers as well as to a process for the production of polyalkenamers utilizing such a catalyst system.
;3ACKGROUND ART
Polyalkenamers play an important role in the rubber industry as they enter in the manufac-ture of synthetic rubbers. Some of these polymers are produced by a catalyzed ring-opening polymerization of cycloalkenes. The catalysts employed are generally two-component catalytic systems comprising a salt of a transition metal from Group VIb or VIIb of the Periodic Table and an organometallic compound of a metal from Groups Ia to IVa of the Periodic Table. The most common catalyst systems are based on tungsten or molybde-num salts, such as the well known system WCl6/Sn (CH3~ 4 . However, the ring-opening polymeri-zation of cycloalkenes such as cyclooctene with this system may take from several days to several weeks to reach completion.
In order to accelerate the polymeriza-tion, it is known to add a third catalyst compo-nent containing oxygen, such as water or an alcohol. For instance, the use of ethanol as an accelerator with the catalyst system WCl6/C2HsAlCl2 for polymerizing cyclopentene in Wo 95/20G13 2 1 c~ 0 ~ ~ ~ PC~/CA9~/00060 benzene~ has been reported by E. A. Ostead et al in Die Makromolekulare Chemie, Vol. 154 (1972), pages 21-3g. The amount of ethanol added must be strictly controlled as too little ethanol does not provide the desired accelerating effect and the reaction is extremely slow. Too much ethanol, on the other hand, has been found to terminate the reaction and inhibit same so that the polymeriza-tion cannot be re-initiated.
DISCI,OSURE OF THE INVENTION
It is therefore an object of the present invention to overcome the above drawbacks and to provide an improved catalyst system for the ring-opening polymerization of cycloalkenes, whereby to increase the rate of polymerization.
It is another object of the invention to provide a catalyst system which does not adversely affect_ the polymerization if an excess of the catalyst system is used.
~ In accordance with the present inven-tion, there is thus provided a homogeneous catalyst system for the ring-opening polymeriza-tion of cyrl ..~l k~n~c to produce polyalkenamers, comprising:
a) a salt of a transition metal selected from the Group VIb of the Periodic Table;
b) an organometallic compound of a metal selected from Groups IIIa and IVa of the Periodic Table; and c) an organosilicon compound having the formula:
RXSi~oR')y(OSiR3j ~ (Ia) 2 ~ ~Q7~5 .
~R2Si~1 3 (Ib) or (R3Si~ 2NH ( Ic) wherei~:
R is ident~ cal or different and repre-sents a hydrogen at~m, a C1-C4 alkyl or phenyl g~up;
R' reoresents a C1-C4 alkyl or ohenyl ~roup;
0 < x 5 3;
0 S y < 4;
z=0 or 1;
y+z 2 1;
x+y+z=4;
wlth the proviso that x=1 and y=3 when z=0;
and where~n the molar ratio of component (c) to component ~a) is at least about 0.5:1.
~pplicant has found quite unexpectedly that organosilicon compounds of formula (Ia), (Ib) or (Ic) as defined above can be used to activate kno~n two-component catalytic systems, such as the system WC16/Sn (CH3) 4, thereby increasing the rate of poly~Lerization of cycloalkenes. These organosil con compounds may be used in excess relative to the other catalyst components without adversely affecting the polymerization.
The catalyst system of the invention is prepared by first reacting component (a) with component (b), and thereafter adding component (c). The reaction of the transition metal salt wi.h the organometallic cQmpound is known to generate a carbene ligand.
.
AMEN~3 SH~ET
~ Wo 9~/20613 2 ~ ~ ~ 7 ~ 5 PCT1CA9~/00060 Representative examples of the transi-tion metal salts which may be used as the first catalyst component (a) are tungsten and molybdenum halides, such as molybdenum trichloride, molybde-num tetrachloride, molybdenum pentachloride, tungsten dichloride, tungsten tetrachloride, tungsten pentachloride, tungsten hexachloride, molybdenum dibromide, molybdenum tribromide, molybdenum tetrabromide, tungsten dibromide, lO tungsten pentabromide, tungsten hexabromide, molybdenum hexafluoride, tungsten hexafluoride, tungsten dliodide and tungsten tetraiodide. It is usually preferred to employ tungsten hexachloride.
Representative examples of organo-metallic compounds useful as the second catalyst component (b) include aluminum and tin compounds.
Representative of such compounds are trialkylalu-minums such as trimethylaluminum, triethylalumi-num, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tri-hexylaluminum, trioctylaluminum and the like;
dialkylaluminum halides such as diethylaluminum chloride, di-n-propylaluminum chloride, diiso-butylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diethylaluminum fluoride and the like; alkylaluminum dihalides such as ethylaluminum dichloride, ethylaluminum dibromide, propylaluminum dichloride, isobutylaluminum di-chloride, ethylaluminum diiodide and the like; and tetraalkyltins such as tetramethyltin, tetra-ethyltins, tetra-n-propyltin, tetra-n-butyltin, tetraisopropyltin, tetraisobutyltin, tetra-hexyltin, tetraoctyltin and the like. It is usually preferred to employ tetramethyltin.
~ WO 95/20613 2 1 ~ ~ 7 ~ 5 PCT/CAg~/00060 Examples of suitable organosiloxanes of formula (Ia) or (Ib) which may be used as the third catalyst component ~c) include phenyl-triethoxysiloxane, 1,1, 3, 3-tetramethyldisiloxane, hexamethyldisiloxane aIrd hexamethylcyclotri-siloxane. It is also possible to use an organo-silazane of formula (Ic), such as 1,1, 3, 3-tetramethyldisilazane, 1, 3-diphenyl-1, 1, 3, 3-tetra-methyldisilazane or hexamethyldisilazane.
The molar ratio of the organosilicon compound to the transition metal salt must be at least 0.5 (iO.1) :1, since at a lesser molar ratio the organosilicon compound does not have any sub-stantial activating effect. Preferred molar ratios of cn~rnnPnts (a): (b): (c) are 1:2:2.3 and 1:2:4.7.
T~e ring-opening polymerization of cycloalkenes with the catalyst system of the invention is generally carried out at a tempera-ture ranging from about 0 to about 160C. At a temperature above 160C, there is a tendency for the catalyst system to decompose. The polymeriza-tion can be carried out in bulk or in solution since the catalyst system is homogeneous and thus soluble in the monomer or solvent.
Applicant has also found quite unexpect-edly that satura~ed polycyclic oligomers can be produced by conducting the polymerization of cycloalkenes in the presence of the above catalyst system, but containing no organometallic compound.
It is believed that the polymerization proceeds through a mechanism different than ring-opening, such as a cationic m~ h~n; Sm The saturated poly-cyclic oligomers produced are stable at high Wo 95/20613 PCT/CA9~/00060 2 1 8Q7~ ~
temperature and can thus be used as lubricants or release agents.
The present invention therefore provi~es, in another aspect thereof, a homo-geneous catalyst system for.. the polymerization of cycloalkenes to produce saturated polycyclic oligomers, comprising:
a) a salt of a transition metal selec~ed from the Group VIb of the Periodic 10 Table, and b) an organosilicon compound having the f ormuIa:
RXSi(OR')y(OSiR3)z (Ia) (R2SiO) 3 (Ib) or ~R3Si) 2NH (Ic) 20 wherein:
R is identical ~r di~ferent and repre-sents a hydro~en atom, a C1-C4 alkyl or phenyl group;
R' represents a C1-C4 alkyl or phenyl 25 group;
0 < x < 3;
0 < y < 4 z=0 or l;
y+z ~ l;
3 0 x+y+ z=4;
and wherein the molar ratio of component (b) to component (a) is at least about 0 . 5 :1.
~ WO~5/20613 2 ~ 8~725 PCT/CAg~/00060 BRIEF DESCRIPTION OF DRi~WINGS
Further features and advantages of the invention will become more readily apparent from the following non-limiting examples and the accompanying drawings, in which:
Figure 1 graphically illustrates the degree of converslon with time for the bulk poly-merization of cyclooctene at 45. 0C catalyzed with WC16/Sn (CH3) 4/HMDS having a molar ratio of 1:2:4.7, where HMDS represents hexamethyl-disiloxane;
Figure 2 graphically illustrates the degree of conversion with time for the bulk poly-merization of cyclooctene at 103.3C catalyzed with WC16/Sn (CH3) 4/HMDS having a molar ratio of 1:2:4 .7;
Figure 3 graphically illustrates the degree of conversion with time for the bulk poly-merization of cyclooctene at 157.3C catalyzed with WC16/Sn (CH3) 4/HMDS having a molar ratio of 1:2:4.7;
Figure 4 graphically illustrates the relation between the molar ratio of HMDS:WC16 and I n t, where t is the time required to reach equi-librium;
Figure 5 graphically illustrates the relation between I n (HMDS/WC16) and I n t; and Figure 6 which is on the same sheet of drawings as Fig. 3, graphically illustrates the degree of conversion with time for the bulk poly-merization of cyclooctene at 100C catalyzed with WC16/Sn (CH3) 4/HMDS having a molar ratio of 1:2:0.01.
WO 9~/20G13 2 1 8 0 7 25 PCTICAs~/00060 EXA~PLE 1 The bulk polymerization of cyclooctene was carried out under dry argon in order to elimi-nate water and oxygen which react with WC16 and destroys its activity. The monomer (99% pure) was distill~d and dried over calcium hydride for at least one hour prior to its use. WC16 99 . 9~ pure was kept under dry argon. Sn (CH3) 4 99% pure was used without further purification and kept under dry argon. Hexamethyldisiloxane (H~IDS) 99% pure was also kept under dry argon.
For the polymerization, WCl6 was trans-ferred into a dry ampoule through a side arm and then closed with a septum. Sn (CH3) 4 was added with a syringe through the septum. The mixture was cooled, the side arm sealed and removed~ The mixture was warmed up to room temperature and allowed to react for about 20 seconds. Then the monomer containing 4.7 moles of ~DS was trans-ferred into the ampoule, cooled down and the ampoule sealed off. The ampoule was plunged into water, five minutes being necessary for melting of the mixture. The ampoule was then shaken in order to ensure homogeneity of the mixture and placed in a thermoregulated bath set at a temperature of 45C ~
The polymerization was stopped by the addition of methanol. The polymer samples were analyzed through nuclear magnetic resonance, gel permeation chromatography and mass spectometry.
The samples comprised high-molecular-weight un-saturated Linear polymer and unsaturated oligomers. The proportion of oligomers varied with polymerization time. In this case, the proportion Wo 95/20613 2 1 8 0 7 2 ~ PCT/CAg J/00060 -- g _ was very high ~as high as 80%) in the first fcw minutes and decreased with time.
In the experiment, 3 g of cyclooctene were polymerized using 10 mg of WCl6. The molar composition of the catalyst system WCl6/Sn(CH3)3/HMDS was 1:2:4.7.
As shown in Figure 1, the degree of conversion is plotted against time for the poly-merization at 45C. After approximately 5 minutes (0.1 h), the % conversion reached 50%. The %
conversion levelled off at about 80%. The conver-sion did not go higher due to the formation of a gel, the monomer being trapped in the gel, pre-venting higher conversion.
The same polymerization as described in Example 1 was carried out at 103C and 157C.
Figures 2 and 3 show the conversion against time.
At these temperatures, the % conversion reached almost 100~. At 103C, the conversion was approxi-mately 65~ after 3 min. and about 80% at 157C
af ter the same time .
EX~MPLE 3 The bulk polymerization of cyclooctene was carried out between 100 and 115C using the following organosilicon compounds as accelerators:
- phenyltriethoxysiloxane (PTEOS) - l, l, 3, 3-tetramethyldisiloxane (TMDS) - hexamethyldisiloxane (~DS) - hexamethylcyclotrisiloxane ~HMCTS) - hexamethyldisilane (HMDSi) - 1,1,3,3-tetramethyldisilazane ~TMDZ) - hexamethyldisilazane (HMDZ) - heptamethyldisilazane ~HPMDZ ) 2 1 8 ~ 7 ~ 5 PCT/CA9-1/ 0 ~ ~
The molar composition of the catalyst system WCl6/Sn (CH3 ) 4/accelerator was~ 1:2: 5 .
The efficiency of the accelerators in activating the system WCl6/Sn (CX3) 4 and accelerat-ing the rate of polymerization was obtained through comparison of the yield obtained after 8 hours. The following data were obtained:
Accelerator Yield ( ~ ) H~iDS 65 HPMDZ inactive XMDSi inactive Based on the above results, the follow-ing qualitative efficiency scale was obtained:
TMDS > XMCTS > PTEOS, XMDS >
XMDZ, TMDZ >> HPMDZ, XMDSi = O
As it is apparent, the presence of a methyl group on the nitrogen atom in heptamethyl-disilazane inactivates the compound. The absence of a Si-O bond in hexamethyldisilane has also the same effect. Thus, a Si-O or a Si-NX-Si bond must be present in order to form an accelerator.
Using the same technique as described in Example 1, the polymerization of norbornene was carried out in cyclohexane. The catalyst system ~ WO 95120613 2 ~ 8 0 7 ~ 5 PCT/CA9.1/00060 used was WC16/Sn (CH3~ 4/E~DS with a molar ratio of 1: 2: 4 . 7 . The monomer concentration was 1. 88 g in 10.0 ml of cyclohexane. The amount of WC16 was 10 mg. At room temperature, the % conversion reached 95% in approximately two minutes. No oligomers were found and the molecular weight of the polymer produced was about 106.
EXEMPLE S
The polymerization of cyclopentene was carried out ln benzene, in the same manner as described in Example 1. The polymerization temperature was 0C. The catalyst system used was nC16/Sn(CH3)4/HMDS with a molar ratio of 1:2:2.3.
The monomer concentration was 33% and the WC16 concentration was 10 mg in 6 ml of monomer-solvent mixture. Because of a monomer-polymer equilibrium in this system, the polymerization never reached completion. It is known that for the polymeriza-tion of cyclopentene at 0C, the maximum yield is 70% conversion. In the present case~ this was easily achieved within 24 hours. No oligomers are found and the molecular weight O e the polymer produced was about 10 6 EXA~SPLE 6 The bulk polymerization of cyclooctene at 160C using the catalyst system WC16/HMDS with a molar ratio of 1: 4 . 7 led to the formation of low-molecular-weight polymer (< 103). The polymer produced comprised a mixture of dimers, trimers and higher oligomers. The polymer yield was 50%
and was made of saturated and unsaturated:
oligomers. The proportion of saturated polycyclic oligomer was about 80% and reached 90% upon repeating the experiment at 100C.
WO 9~/20613 PCT/CA9~100060 2~ ~Q725 The bulk polymerization of cyclooctene was carried out at 103C in the same manner as described in E~cample l, using the catalyst system WCl6/Sn ~CH3) 4/HMDS. The WCl6/Sn ~CH3) 4 molar ratio was l:æ The lIMDS/WC16 ratio was allowed to vary and the time required to - obtain equilibrium, measured ;~ r~li ngly, The HMDS/WC16 ratio is plotted againt I n t (time in hours) in Figure 4. ~s shown in Figure 5, when I n ~HMDS/WCl6) is plotted against I n t, using the same data and interpolated values between 5. 0 and 7 . 0 for I n t, then two straight lines are obtained with a break-up point corresponding to a molar ratio of E~DS/WC16 equal to D.5 ~t O.l). This molar ratio is the minimum ratio at which the organosilicon compound provides a substantial activating effect on the polymerization .
COMPARATIVE EXAMPLE
The polymerization described in Example l was repeated, but the proportion of ~DS was reduced to a molar ratio o~ ~DS/WCl6 equal to 0 . Ol . Figure 6 shows the ~ conversion with time in terms of days. This can be compared with Figure 2 which shows that for nearly the same temperature, the ~ conversion is about 65% within 5 minutes, using a HMDS/WCl6 molar ratio equal to 4 . 7 .
and wherein the molar ratio of component (b) to component (a) is at least about 0 . 5 :1.
~ WO~5/20613 2 ~ 8~725 PCT/CAg~/00060 BRIEF DESCRIPTION OF DRi~WINGS
Further features and advantages of the invention will become more readily apparent from the following non-limiting examples and the accompanying drawings, in which:
Figure 1 graphically illustrates the degree of converslon with time for the bulk poly-merization of cyclooctene at 45. 0C catalyzed with WC16/Sn (CH3) 4/HMDS having a molar ratio of 1:2:4.7, where HMDS represents hexamethyl-disiloxane;
Figure 2 graphically illustrates the degree of conversion with time for the bulk poly-merization of cyclooctene at 103.3C catalyzed with WC16/Sn (CH3) 4/HMDS having a molar ratio of 1:2:4 .7;
Figure 3 graphically illustrates the degree of conversion with time for the bulk poly-merization of cyclooctene at 157.3C catalyzed with WC16/Sn (CH3) 4/HMDS having a molar ratio of 1:2:4.7;
Figure 4 graphically illustrates the relation between the molar ratio of HMDS:WC16 and I n t, where t is the time required to reach equi-librium;
Figure 5 graphically illustrates the relation between I n (HMDS/WC16) and I n t; and Figure 6 which is on the same sheet of drawings as Fig. 3, graphically illustrates the degree of conversion with time for the bulk poly-merization of cyclooctene at 100C catalyzed with WC16/Sn (CH3) 4/HMDS having a molar ratio of 1:2:0.01.
WO 9~/20G13 2 1 8 0 7 25 PCTICAs~/00060 EXA~PLE 1 The bulk polymerization of cyclooctene was carried out under dry argon in order to elimi-nate water and oxygen which react with WC16 and destroys its activity. The monomer (99% pure) was distill~d and dried over calcium hydride for at least one hour prior to its use. WC16 99 . 9~ pure was kept under dry argon. Sn (CH3) 4 99% pure was used without further purification and kept under dry argon. Hexamethyldisiloxane (H~IDS) 99% pure was also kept under dry argon.
For the polymerization, WCl6 was trans-ferred into a dry ampoule through a side arm and then closed with a septum. Sn (CH3) 4 was added with a syringe through the septum. The mixture was cooled, the side arm sealed and removed~ The mixture was warmed up to room temperature and allowed to react for about 20 seconds. Then the monomer containing 4.7 moles of ~DS was trans-ferred into the ampoule, cooled down and the ampoule sealed off. The ampoule was plunged into water, five minutes being necessary for melting of the mixture. The ampoule was then shaken in order to ensure homogeneity of the mixture and placed in a thermoregulated bath set at a temperature of 45C ~
The polymerization was stopped by the addition of methanol. The polymer samples were analyzed through nuclear magnetic resonance, gel permeation chromatography and mass spectometry.
The samples comprised high-molecular-weight un-saturated Linear polymer and unsaturated oligomers. The proportion of oligomers varied with polymerization time. In this case, the proportion Wo 95/20613 2 1 8 0 7 2 ~ PCT/CAg J/00060 -- g _ was very high ~as high as 80%) in the first fcw minutes and decreased with time.
In the experiment, 3 g of cyclooctene were polymerized using 10 mg of WCl6. The molar composition of the catalyst system WCl6/Sn(CH3)3/HMDS was 1:2:4.7.
As shown in Figure 1, the degree of conversion is plotted against time for the poly-merization at 45C. After approximately 5 minutes (0.1 h), the % conversion reached 50%. The %
conversion levelled off at about 80%. The conver-sion did not go higher due to the formation of a gel, the monomer being trapped in the gel, pre-venting higher conversion.
The same polymerization as described in Example 1 was carried out at 103C and 157C.
Figures 2 and 3 show the conversion against time.
At these temperatures, the % conversion reached almost 100~. At 103C, the conversion was approxi-mately 65~ after 3 min. and about 80% at 157C
af ter the same time .
EX~MPLE 3 The bulk polymerization of cyclooctene was carried out between 100 and 115C using the following organosilicon compounds as accelerators:
- phenyltriethoxysiloxane (PTEOS) - l, l, 3, 3-tetramethyldisiloxane (TMDS) - hexamethyldisiloxane (~DS) - hexamethylcyclotrisiloxane ~HMCTS) - hexamethyldisilane (HMDSi) - 1,1,3,3-tetramethyldisilazane ~TMDZ) - hexamethyldisilazane (HMDZ) - heptamethyldisilazane ~HPMDZ ) 2 1 8 ~ 7 ~ 5 PCT/CA9-1/ 0 ~ ~
The molar composition of the catalyst system WCl6/Sn (CH3 ) 4/accelerator was~ 1:2: 5 .
The efficiency of the accelerators in activating the system WCl6/Sn (CX3) 4 and accelerat-ing the rate of polymerization was obtained through comparison of the yield obtained after 8 hours. The following data were obtained:
Accelerator Yield ( ~ ) H~iDS 65 HPMDZ inactive XMDSi inactive Based on the above results, the follow-ing qualitative efficiency scale was obtained:
TMDS > XMCTS > PTEOS, XMDS >
XMDZ, TMDZ >> HPMDZ, XMDSi = O
As it is apparent, the presence of a methyl group on the nitrogen atom in heptamethyl-disilazane inactivates the compound. The absence of a Si-O bond in hexamethyldisilane has also the same effect. Thus, a Si-O or a Si-NX-Si bond must be present in order to form an accelerator.
Using the same technique as described in Example 1, the polymerization of norbornene was carried out in cyclohexane. The catalyst system ~ WO 95120613 2 ~ 8 0 7 ~ 5 PCT/CA9.1/00060 used was WC16/Sn (CH3~ 4/E~DS with a molar ratio of 1: 2: 4 . 7 . The monomer concentration was 1. 88 g in 10.0 ml of cyclohexane. The amount of WC16 was 10 mg. At room temperature, the % conversion reached 95% in approximately two minutes. No oligomers were found and the molecular weight of the polymer produced was about 106.
EXEMPLE S
The polymerization of cyclopentene was carried out ln benzene, in the same manner as described in Example 1. The polymerization temperature was 0C. The catalyst system used was nC16/Sn(CH3)4/HMDS with a molar ratio of 1:2:2.3.
The monomer concentration was 33% and the WC16 concentration was 10 mg in 6 ml of monomer-solvent mixture. Because of a monomer-polymer equilibrium in this system, the polymerization never reached completion. It is known that for the polymeriza-tion of cyclopentene at 0C, the maximum yield is 70% conversion. In the present case~ this was easily achieved within 24 hours. No oligomers are found and the molecular weight O e the polymer produced was about 10 6 EXA~SPLE 6 The bulk polymerization of cyclooctene at 160C using the catalyst system WC16/HMDS with a molar ratio of 1: 4 . 7 led to the formation of low-molecular-weight polymer (< 103). The polymer produced comprised a mixture of dimers, trimers and higher oligomers. The polymer yield was 50%
and was made of saturated and unsaturated:
oligomers. The proportion of saturated polycyclic oligomer was about 80% and reached 90% upon repeating the experiment at 100C.
WO 9~/20613 PCT/CA9~100060 2~ ~Q725 The bulk polymerization of cyclooctene was carried out at 103C in the same manner as described in E~cample l, using the catalyst system WCl6/Sn ~CH3) 4/HMDS. The WCl6/Sn ~CH3) 4 molar ratio was l:æ The lIMDS/WC16 ratio was allowed to vary and the time required to - obtain equilibrium, measured ;~ r~li ngly, The HMDS/WC16 ratio is plotted againt I n t (time in hours) in Figure 4. ~s shown in Figure 5, when I n ~HMDS/WCl6) is plotted against I n t, using the same data and interpolated values between 5. 0 and 7 . 0 for I n t, then two straight lines are obtained with a break-up point corresponding to a molar ratio of E~DS/WC16 equal to D.5 ~t O.l). This molar ratio is the minimum ratio at which the organosilicon compound provides a substantial activating effect on the polymerization .
COMPARATIVE EXAMPLE
The polymerization described in Example l was repeated, but the proportion of ~DS was reduced to a molar ratio o~ ~DS/WCl6 equal to 0 . Ol . Figure 6 shows the ~ conversion with time in terms of days. This can be compared with Figure 2 which shows that for nearly the same temperature, the ~ conversion is about 65% within 5 minutes, using a HMDS/WCl6 molar ratio equal to 4 . 7 .
Claims (24)
1. A homogeneous catalyst system for the ring-opening polymerization of cycloalkenes to produce polyalkenamers, comprising:
a) a salt of a transition metal selected from the Group VIb of the Periodic Table;
b) an organometallic compound of a metal selected from Groups IIIa and IVa of the Periodic Table; and c) an organosilicon compound having the formula:
R x Si(OR')y(OSiR3)z (Ia) (R2SiO)3 (Ib) or ~(R3Si) 2NH (Ic) wherein:
R is identical or different and represents a hydrogen atom, a C1-C4 alkyl or phenyl group:
R' represents a C1-C4 alkyl or phenyl group:
0 < x ~ 3;
0 ~ y < 4;
z=0 or 1;
y + z ~ 1;
x+y+z=4;
with the proviso that x=1 and y=3 when z=0;
and wherein the molar ratio of component (c), to component (a) is at least about 0.5:1.
a) a salt of a transition metal selected from the Group VIb of the Periodic Table;
b) an organometallic compound of a metal selected from Groups IIIa and IVa of the Periodic Table; and c) an organosilicon compound having the formula:
R x Si(OR')y(OSiR3)z (Ia) (R2SiO)3 (Ib) or ~(R3Si) 2NH (Ic) wherein:
R is identical or different and represents a hydrogen atom, a C1-C4 alkyl or phenyl group:
R' represents a C1-C4 alkyl or phenyl group:
0 < x ~ 3;
0 ~ y < 4;
z=0 or 1;
y + z ~ 1;
x+y+z=4;
with the proviso that x=1 and y=3 when z=0;
and wherein the molar ratio of component (c), to component (a) is at least about 0.5:1.
2. A catalyst system according to claim 1, wherein component (a) is a tungsten or molybdenum halide.
3. A catalyst system according to claim 2, wherein component (a) is tungsten hexachloride.
4. A catalyst system according to claim 1, wherein component (b) is an organoaluminum or organotin compound.
5. A catalyst system according to claim 4, wherein component (b) is tetramethyltin.
6. A catalyst system according to claim 3, wherein component (b) is tetramethyltin.
7. A catalyst system according to claim 1, wherein component (c) is an organosiloxane selected from the group consisting of phenyl-triethoxysiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane and hexamethylcyclotrisiloxane.
8. A catalyst system according to claim 7, wherein component (c) is hexamethyldisiloxane.
9. A catalyst system according to claim 6, wherein component (c) is hexamethyldisiloxane.
10. A catalyst system according to claim 9, wherein the molar ratio of components (a):(b):(c) is 1:2:2.3 or 1:2:4.7.
11. A catalyst system according to claim 1, wherein component (c) is an organosilazane selected from the group consisting of 1,1,3,3-tetramethyldisilazane, 1,3-phenyl-1,1,3,3-tetra-methyldisilazane and hexamethyldisilazane.
12. A process for the production of polyalkenamers by the ring-opening polymerization of cycloalkenes, which comprises conducting the polymerization at a temperature ranging from about 0° to about 160°C in the presence of a homogeneous catalyst system comprising:
a) a salt of a transition metal selected from the Group VIb of the Periodic Table;
b) an organometallic compound of a metal selected from Groups IIIa and IVa of the Periodic Table; and c) an organosilicon compound having the formula:
R x Si(OR')y(OSiR3)z (Ia) (R2SiO)3 (Ib) or (R3Si)2NH (Ic) wherein:
R is identical or different and represents a hydrogen atom, a C1-C4 alkyl or phenyl group;
R' represents a C1-C4 alkyl or phenyl group;
0 < x ~ 3;
0 ~ y < 4;
z=0 or 1;
y+z ~ 1;
x+y+z=4;
with the proviso that x=1 and y=3 when z=0;
and wherein the molar ratio of component (c) to component (a) is at least about 0.5:1.
a) a salt of a transition metal selected from the Group VIb of the Periodic Table;
b) an organometallic compound of a metal selected from Groups IIIa and IVa of the Periodic Table; and c) an organosilicon compound having the formula:
R x Si(OR')y(OSiR3)z (Ia) (R2SiO)3 (Ib) or (R3Si)2NH (Ic) wherein:
R is identical or different and represents a hydrogen atom, a C1-C4 alkyl or phenyl group;
R' represents a C1-C4 alkyl or phenyl group;
0 < x ~ 3;
0 ~ y < 4;
z=0 or 1;
y+z ~ 1;
x+y+z=4;
with the proviso that x=1 and y=3 when z=0;
and wherein the molar ratio of component (c) to component (a) is at least about 0.5:1.
13. A process according to claim 12, wherein component (a) of said catalyst system is a tungsten or molybdenum halide.
14. A process according to claim 13, wherein component (a) of said catalyst system is tungsten hexachloride.
15. A process according to claim 12, wherein component (b) of said catalyst system is an organoaluminum or organotin compound.
16. A process according to claim 15, wherein component (b) of said catalyst system is tetramethyltin.
17. A process according to claim 14, wherein component (b) of said catalyst system is tetramethyltin.
18. A process according to claim 12, wherein component (c) of said catalyst system is an organosiloxane selected from the group consisting of phenyltriethoxysiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane and hexamethylcyclotrisiloxane.
19. A process according to claim 18, wherein component (c) of said catalyst system is hexamethyldisiloxane.
20. A process according to claim 17, wherein component (c) of said catalyst system is hexamethyldisiloxane.
21. A process according to claim 20, wherein the molar ratio of components (a):(b):(c) of said catalyst system is 1:2:2.3 or 1:2:4.7.
22. A process according to claim 12, wherein component (c) of said catalyst system is an organosilazane selected from the group consisting of 1,1,3,3-tetramethyldisilazane, 1,3-diphenyl-1,1,3,3-tetramethyldisilazane and hexamethyldisilazane.
23. A process according to claim 12, wherein the cycloalkene is selected from the group consisting of cyclopentene, cyclooctene and norbornene.
24. A process according to claim 12, wherein the cycloalkene is cyclooctene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002284237A CA2284237C (en) | 1994-01-31 | 1994-01-31 | Catalysis of cycloalkenes to saturated polycyclic oligomers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CA1994/000060 WO1995020613A1 (en) | 1994-01-31 | 1994-01-31 | Polymerisation of cycloalkenes |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002284237A Division CA2284237C (en) | 1994-01-31 | 1994-01-31 | Catalysis of cycloalkenes to saturated polycyclic oligomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2180725A1 CA2180725A1 (en) | 1995-08-03 |
| CA2180725C true CA2180725C (en) | 2000-06-13 |
Family
ID=4173009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002180725A Expired - Fee Related CA2180725C (en) | 1994-01-31 | 1994-01-31 | Polymerisation of cycloalkenes |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU5997094A (en) |
| CA (1) | CA2180725C (en) |
| WO (1) | WO1995020613A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1244104A (en) * | 1968-03-07 | 1971-08-25 | Bayer Ag | Process for the polymerisation of cyclomonoolefines |
| US5082909A (en) * | 1990-10-12 | 1992-01-21 | Hercules Incorporated | Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts |
| GB9117744D0 (en) * | 1991-08-16 | 1991-10-02 | Shell Int Research | Polymerization of cycloolefins and catalytic system suitable for use therein |
| US5198511A (en) * | 1991-12-20 | 1993-03-30 | Minnesota Mining And Manufacturing Company | Polymerizable compositions containing olefin metathesis catalysts and cocatalysts, and methods of use therefor |
-
1994
- 1994-01-31 CA CA002180725A patent/CA2180725C/en not_active Expired - Fee Related
- 1994-01-31 WO PCT/CA1994/000060 patent/WO1995020613A1/en not_active Ceased
- 1994-01-31 AU AU59970/94A patent/AU5997094A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO1995020613A1 (en) | 1995-08-03 |
| AU5997094A (en) | 1995-08-15 |
| CA2180725A1 (en) | 1995-08-03 |
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