Classifications

• • 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
• • 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
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
• • 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
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/40—Polymerisation processes
  • C08G2261/41—Organometallic coupling reactions
  • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

• the invention relates to a method of preparation of polydicyclopentadiene and use of ruthenium complexes acting as (pre)catalysts in ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD).
• ruthenium complexes acting as (pre)catalysts in ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD).
• Olefin metathesis is an important tool applied in organic synthesis (Handbook of Metathesis, Volume I-III, Editor: Grubbs, R. H.; Wiley- VCH, 2003).
• ruthenium complexes which actively catalyze olefin metathesis (see reviews by Vougioukalakis, G. C; Grubbs, R. H. Chem. Rev. 2010, 110, 1746. It was shown that III- generation complexes (such as Gru-III, Ind-III) are highly useful (pre)catalysts of ROMP reactions.
• Third generation catalysts initiate metathesis reactions very quickly, while in some applications of metathesis, such as, e.g., mold ROMP, it is preferred to use a (pre)catalyst which does not initiate the reaction immediately after it has been added to the substrate but only after an appropriate initiation by means of chemical agents, temperature or light.
• Complexes characterized by a delayed initiation are often referred to as "latent catalysts"; see reviews by Monsaert, S.; Vila, A. L.; Drozdzak, R.; Van Der Voort, P.; Verpoort, F., Chem. Soc. Rev., 2009, 38, 3360.
• Examples of "latent catalysts” are complexes, A-F, and also P-l and P-2 which were recently obtained (oral presentation of the results, ISOM XIX Renes, 10-15.07.2011).
• Mold ROMP allows to obtain finished products.
• Polydicyclopentadiene is characterized among others by low moisture absorption and resistance to tensions and high temperatures. Therefore, components of vehicles or specialized containers for the chemical industry are more often produced through (mold) ROMP of dicyclopentadiene.
• P-l complex catalyzes the ROMP reaction of cyclooctadiene carried out in dichloromethane, at room temperature. This reaction, however, proceeds with a very low conversion of the substrate. In the presence of a chemical activator, the reaction, however, proceeds much faster and with a higher conversion of the substrate. It should be noted, however, that such reactions were performed using 1 mol % of (pre)catalyst.
• DCPD dicyclopentadiene
• the type of an anionic ligand may be important for the effectiveness of a (pre)catalyst in ring-opening metathesis polymerization. It is suspected that high effectiveness of catalysts of formula D is due in a large part to a lesser degree of a bimolecular decomposition of an active complex, which in turn results from the presence of a phenoxylate ligand. Catalysts containing phenoxylate or carboxylate anionic ligands are obtained in the reaction of classic complexes (with chloride anionic ligands) with the appropriate phenoxylate or carboxylate salts. This creates additional synthetic problems, extends the time and increases the cost of obtaining a (pre)catalyst.
• the cost of a catalyst is however a key element determining the possibility of its application in the synthesis of polydicyclopentadiene on an industrial scale, due to its relatively low price.
• the ease of synthesis, a low price and the possibility to introduce a modified anionic ligand into the structure of complexes of formula 1 by adding the corresponding acid to its mixture with a monomer (e.g. , dicyclopentadiene) may determine its industrial utility.
• TsOH p-toluenesulfonic acid
• the object of the present invention is a method of preparation of polydicyclopentadiene in ring-opening metathesis polymerization in which dicyclopentadiene is polymerized in the presence of a ruthenium (pre)catalyst of general formula 1
• X is an anionic ligand
• L 1 and V 2 are neutral ligands
• R 1 is H, -C 1-20 alkyl, -C 2 - 2 0 alkenyl, -C 2 - 2 o alkynyl or -C 5 _ 10 aryl;
• R 2 , R 3 , R 4 and R 5 are, independently, H, halogen, CrC 16 alkyl, CrC 16 alkoxy , Cr C 16 perhalogenoalkyl, C 3 -C 7 cycloalkyl, C 2 -Ci 6 alkenyl, C 5 -C 14 aryl, C 5 -C 14 perhalogenoaryl, C3-12 heterocyclic, -OR 6 , -N0 2 , -COOH, -COOR 6 , -CONR 6 R 7 , -S0 2 NR 6 R 7 , -S0 2 R 6 , -CHO, -COR 6 , wherein R 6 and R 7 are, independently, Ci-C 6 alkyl, CrC 6 perhalogenoalkyl, C 5 -C 14 aryl, C 5 -C 14 perhalogenoaryl; R 2 , R 3 , R 4 and R 5 may be optionally linked together to form a substituted or unsubstitute
• R and R are, independently, C -C alkyl, C -C perhalogenoalkyl, Cs-Cio aryl, Cs-Cio perhalogenoaryl.
• NHC N-heterocyclic carbene ligand
• R are, independently, H, C C 12 alkyl, C 3 -C 12 cycloalkyl, C 5 -C 14 aryl, optionally substituted with one or more groups selected from CrC 12 alkyl, CrC 12 perhalogenoalkyl, CrC 12 alkoxy or with halogen;
• R 13 , R 14 , R 15 , R 16 are, independently, H, CrC 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 5 _ 14 aryl, optionally substituted with one or more groups selected from
• Q-C 12 alkyl, CrC 12 perhalogenoalkyl, CrC 12 alkoxy or with halogen, and R , R 14 , R 15 , R 16 may be optionally linked together to form a substituted or unsubstituted, fused -C 4 _g carbocyclic ring > or a substituted or unsubstituted, fused aromatic ring.
• R' is C 1-12 alkyl, C 3-12 cycloalkyl, C 5-14 aryl, C 5-12 heterocyclic, C 1-12 alkoxy, C 5-12 aryloxy.
• X is CI
• R 1 is H
• R 2 , R 3 , R 4 and R 5 are, independently, H or C 1-3 alkyl
• Y is H, C 1 -C 12 alkyl, -COOH, -COOR 8 , -CONR 8 R 9 , -S0 2 NR 8 R 9 , -S0 2 R 8 , -CHO, -
• R and R are, independently, C -C alkyl, Cs-Cio aryl;
• L 1 is tricyclohexylphosphine or triphenylphosphine
• L 2 is a ligand of formula 2a or 2b:
• R are, independently, H, C C 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C5-C 14 aryl, optionally substituted with one or more groups selected from CrC 6 alkyl, CrC 6 perhalogenoalkyl, CrC 6 alkoxy or with halogen;
• R 13 , R 14 , R 15 , R 16 are, independently, H, CrC 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 5 -C 14 aryl, optionally substituted with one or more groups selected from CrC 6 alkyl, CrC 6 perhalogenoalkyl, CrC 6 alkoxy or with halogen, and R 13 , R 14 , R 15 , R 16 may be optionally linked together to form a substituted or unsubstituted, fused -C 4 _8 carbocyclic ring > or a substituted or unsubstituted, fused aromatic ring.
• reaction is carried out without a solvent.
• a (pre)catalyst of general formula 1 is added to dicyclopentadiene as a solution in the least amount of an organic solvent.
• the organic solvent is dichloromethane or toluene.
• polymerization is initiated by heating a mixture of dicyclopentadiene and a (pre)catalyst of general formula 1 up to a temperature of 35°C or higher.
• polymerization is carried out in the presence of a chemical activator, more preferably, the chemical activator being a Br0nsted or Lewis acid or a halogen derivative of alkane or silane, most preferably, the chemical activator being hydrogen chloride, chlorotrimethylsilane or p-toluenesulfonic acid.
• a chemical activator being a Br0nsted or Lewis acid or a halogen derivative of alkane or silane, most preferably, the chemical activator being hydrogen chloride, chlorotrimethylsilane or p-toluenesulfonic acid.
• polymerization is carried out at a temperature within the range of 35 to 120°C.
• polymerization is carried out within the period of time ranging from 1 minute to 24 hours.
• polymerization is carried out in the presence of an addition of an agent promoting the formation of crosslinks.
• Suitable agents promoting the formation of crosslinks include but are not limited to tert-butyl peroxide, di-tert-butyl peroxide and also mixtures thereof.
• the starting material contains at least 94% of DCPD.
• polymerization is carried out using the amount of a (pre)catalyst equal to or less than 0.01 mol %.
• the object of the present invention is also use of a ruthenium complex of the general formula 1
• optionally substituted group means that any one or more hydrogen atoms of the group is replaced with the indicated groups, with the proviso that the substitution results in a stable compound.
• halogen means an element selected from F, CI, Br, I.
• carbene means a particle containing a neutral carbon atom of valency number being two and two unpaired valence electrons.
• carbene covers also carbene analogs in which a carbon atom is replaced with another chemical element; examples of such elements include but are not limited to boron, silicon, nitrogen, phosphorus, sulfur.
• alkyl group refers to a saturated linear or branched hydrocarbon substituent of the indicated number of carbon atoms.
• alkyl groups include but are not limited to methyl, ethyl, propyl, iso- propyl, butyl, sec-butyl, tert-butyl, pentyl.
• alkoxy group refers to an alkyl substituent as defined above connected by means of an oxygen atom.
• perhalogenoalkyl group means an alkyl group as defined above where all hydrogen atoms are replaced with halogen atoms, wherein halogen atoms may be the same or different.
• cycloalkyl group refers to a saturated mono- or polycyclic hydrocarbon substituent of the indicated number of carbon atoms.
• the non-limiting examples of a cycloalkyl substituent are -cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl.
• alkenyl group refers to a non-cyclic, linear or branched hydrocarbon chain of the indicated number of carbon atoms and containing at least one double carbon-carbon bond.
• alkenyl groups are vinyl, allyl, 1-butenyl, 2-butenyl.
• cycloalkenyl group refers to an aliphatic mono- or polycyclic hydrocarbon substituent of the indicated number of carbon atoms and containing at least one double carbon-carbon bond.
• the non-limiting examples of a cycloalkenyl substituent are -cyclopentenyl, -cyclopentadienyl, -cyclohexenyl, -cyclohexadienyl, -cycloheptenyl, -cycloheptadienyl, -cycloheptatrienyl.
• aryl group refers to an aromatic mono- or polycyclic hydrocarbon substituent of the indicated number of carbon atoms.
• the non-limiting examples of an aryl group are phenyl, mesityl, anthracene.
• heterocyclic group refers to an aromatic and non- aromatic cyclic substituent of the indicated number of carbon atoms, wherein one or more carbon atoms are replaced with a heteroatom such as nitrogen, phosphorus, sulfur, oxygen with the proviso that the ring of said group does not contain two adjacent oxygen or sulfur atoms.
• Non-aromatic heterocyclic groups may include from 4 to 10 atoms in a ring, while aromatic heterocyclic groups must have at least 5 atoms in a ring.
• the heterocyclic groups include also benzo- fused ring systems.
• non-aromatic heterocyclic groups are pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, dihydropyranyl, tetrahydrothiopyranyl, piperidino, morpholino, thiomorpholino 2-pyrrolinyl, indolinyl.
• aromatic heterocyclic groups are pyridinyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, furyl, thienyl.
• the foregoing groups may be C-attached or N- attached.
• a substituent derived from attaching pyrrol may be pyrrol- 1-yl (N-attached) or pyrrol-3-yl (C-attached).
• neutral ligand refers to an uncharged substituent, capable of coordinating with a ruthenium atom.
• the non-limiting examples of neutral ligands include but are not limited to N-heterocyclic carbene ligands, amines, imines, phosphines and oxides thereof, alkyl and aryl phosphites and phosphates, ethers, alkyl and aryl sulfides, coordinated hydrocarbons, alkyl and
• Neutral ligands L and L may be connected to a benzylidene ligand (also with a nitrogen atom forming a covalent bond with a ruthenium atom) and
• anionic ligand refers to a substituent capable of coordinating with a metallic center, having a charge capable of partial or complete compensation of a metallic center charge.
• anionic ligands include but are not limited to fluoride, chloride, bromide, iodide, anions of carboxylic acids, anions of alcohols and phenols, anions of thiols and thiophenols, anions of (organo)sulfuric acids and of (organo)phosphoric acids and esters
• An anionic ligand (X) and neutral ligands (L , L ) may be combined together, forming in result multidentate ligands.
• the non-limiting examples of multidentate ligands are a bidentate ligand (X 1 -!. 1 ), a tridentate ligand (X 1 -!. 1 - If).
• the non-limiting examples of neutral ligands are an acetylacetone anion and a salicylaldehyde anion.
• Dicyclopentadiene (1 g, 7.56 mmol) was introduced into a polymerization vial on air and after melting it was placed in an
• Dicyclopentadiene (1 g, 7.56 mmol) was introduced into a polymerization vial on air and after melting it was placed in an oil bath of a temperature of 35°C. Then, catalyst P-2 (0.01 mol %) was added as a solution in dichloromethane and the vial was transferred to an oil bath of a temperature of 60°C and left therein for 15 minutes. Then, toluene was added to the vial and it was brought to the boiling temperature to wash out the unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure for 12 h. Conversion of dicyclopentadiene was >99%.
• Dicyclopentadiene (1 g, 7.56 mmol) was introduced into a polymerization vial on air and after melting it was placed in an oil bath of a temperature of 35°C. Then, catalyst P-2 (0.005 mol %) was added as a solution in dichloromethane and hydrogen chloride (0.005 mol %, 4M solution in 1,4-dioxane). The vial was transferred to an oil bath of a temperature of 60°C and left therein for 25 minutes. Then, toluene was added to the vial and it was brought to the boiling temperature to wash out the unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure for 12 h. Conversion of dicyclopentadiene was >99 .
• Dicyclopentadiene (1 g, 7.56 mmol) was introduced into a polymerization vial on air and after melting it was placed in an oil bath of a temperature of 35°C. Then, catalyst P-2 (0.005 mol %) was added as a solution in dichloromethane and chlorotrimethylsilane (TMSC1) (0.005 mol %) dissolved in a small amount of dichloromethane. The vial was transferred to an oil bath of a temperature of 60°C and left therein for 60 minutes. Then, toluene was added to the vial and it was brought to the boiling temperature to wash out the unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure for 12 h. Conversion of dicyclopentadiene was >99 .
• Dicyclopentadiene (1 g, 7.56 mmol) was introduced into a polymerization vial on air and after melting it was placed in an oil bath of a temperature of 35°C. Then, catalyst P-2 (0.005 mol %) was added as a solution in dichloromethane and p-toluenesulfonic acid (p-TsOH) (0.005 mol %) dissolved in a small amount of methanol.
• the vial was transferred to an oil bath of a temperature of 60°C and left therein for 30 minutes. Then, toluene was added to the vial and it was brought to the boiling temperature to wash out the unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure for 12 h. Conversion of dicyclopentadiene was >99 .
• Dicyclopentadiene (1 g, 7.56 mmol) was introduced into a polymerization vial on air and after melting it was placed in an oil bath of a temperature of 35°C. Then, catalyst P-l (0.01 mol %) as was added a solution in dichloromethane and chlorotrimethylsilane (TMSC1) (0.01 mol %) dissolved in a small amount of dichloromethane. The vial was transferred to an oil bath of a temperature of 60°C and left therein for 120 minutes. Then, toluene was added to the vial and it was brought to the boiling temperature to wash out the unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure for 12 h. Conversion of dicyclopentadiene was >99 .
• Dicyclopentadiene (1 g, 7.56 mmol) was introduced into a polymerization vial on air and after melting it was placed in an oil bath of a temperature of 35°C. Then, catalyst P-l (0.01 mol %) was added as a solution in dichloromethane and hydrogen chloride (0.01 mol , 4M solution in 1,4-dioxane). The vial was transferred to an oil bath of a temperature of 60°C and left therein for 120 minutes. Then, toluene was added to the vial and it was brought to the boiling temperature to wash out the unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure for 12 h. Conversion of dicyclopentadiene was 90%.
• complexes of formula 1 efficiently promote ring-opening metathesis polymerization (ROMP) of dicyclopentadiene.
• Chemical activation of complexes of formula 1 using acids allows to easily introduce various anionic ligands to the structure of an activated complex.
• Some complexes of general formula 1 (such as, e.g., P-2) can also be thermally activated.
• the possibility of dual activation and "in situ" introduction of anionic ligands makes it possible to control precisely the start of the polymerization process as well as to control the time in which polymerization is ended.

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