Cycloolefin polymer compound and method of preparing the same
This invention relates to a cycloolefin copolymer, which is prepared via ring-opening metathesis polymerization using, as monomers, dicyclopentadiene obtained by chemically bonding two cyclopentadiene molecules using a Diels-Alder reaction and tricyclopentadiene obtained by chemically bonding three cyclopentadiene molecules using a Diels-Alder reaction, in which the cyclopentadiene is a C5-fraction of naphtha cracking, and to a method of preparing the same. This copolymer is a non-crystalline transparent resin and is useful for a variety of end uses.
1. A cycloolefin polymer compound having a repeating unit represented by Chemical Formula 1 below:
wherein a molar ratio of x:y is 99:1-1:99, and z has an average value of 10-20,000.
2. The cycloolefin polymer compound of claim 1 , wherein the molar ratio of x:y is 90:10-50:50, and z has an average value of 10-3,000.
3. A method of preparing a cycloolefin polymer compound having a repeating unit represented by Chemical Formula 1 below, comprising:
subjecting a compound represented by Chemical Formula 2 below to ring-opening metathesis polymerization with dicyclopentadiene and a compound represented by Chemical Formula 3 below as a molecular weight controller in presence of a catalyst resulting from activating a compound represented by Chemical Formula 4 below using an alkyllithium compound represented by R 4 Li (wherein R 4 is a C1-C20 hydrocarbyl radical) as a co-catalyst,
wherein a molar ratio of x:y is 99:1-1:99, and z has an average value of 10-20,000,
wherein R 1 is a C1˜C20 alkyl group,
wherein M is Mo or W; R 2 s, which are same as or different from each other, are a hydrogen radical, C1-C20 alkyl, alkenyl or alkynyl; and R 3 s, which are same as or different from each other, are a hydrogen radical, C1-C20 alkyl, alkenyl or alkynyl.
4. The method of claim 3 , wherein the compound represented by Chemical Formula 4 is configured such that M is W, all of R 2 s are a methyl group, and all of R 3 s are a hydrogen radical; and R 4 of the alkyllithium represented by R 4 Li is a butyl group.
5. A cycloolefin polymer compound having a repeating unit represented by Chemical Formula 5 below,
wherein a molar ratio of x:y is 99:1-1:99, and z has an average value of 10-20,000.
6. The cycloolefin polymer compound of claim 5 , wherein the molar ratio of x:y is 90:10-50:50, and z has an average value of 10-3,000.
7. A method of preparing a cycloolefin polymer compound having a repeating unit represented by Chemical Formula 5 below, comprising:
hydrogenating double bonds of a main chain and a ring moiety of a cycloolefin polymer having a repeating unit represented by Chemical Formula 1 below in presence of a compound represented by Chemical Formula 6 below as a catalyst,
wherein a molar ratio of x:y is 99:1-1:99, and z has an average value of 10-20,000,
wherein a molar ratio of x:y is 99:1-1:99, and z has an average value of 10-20,000,
(L) a (X) b Ru Chemical Formula 6
wherein L is a neutral electron donor ligand selected from among oxygen, water, carbonyl, amine, pyridine, ether and phosphine; and X is an anionic ligand selected from among halogen, hydride, acetylacetonate, alkyl and aryl, and a and b are independently an integer of 1-4.
8. The method of claim 7 , wherein the compound represented by Chemical Formula 6 is configured such that L is bistricyclohexylphosphine or carbonyl, and X is a hydrogen radical or Cl.
9. A method of preparing a cycloolefin polymer compound having a repeating unit represented by Chemical Formula 5 below, comprising:
hydrogenating double bonds of a main chain and a ring moiety of a cycloolefin polymer having a repeating unit represented by Chemical Formula 1 below in presence of a catalyst resulting from activating a compound represented by Chemical Formula 7 below using a compound represented by Al(R 5 ) 3 (wherein R 5 s which are same as or different from each other are a halogen radical or a C1-C20 hydrocarbyl radical) as a co-catalyst,
wherein a molar ratio of x:y is 99:1-1:99, and z has an average value of 10-20,000,
wherein a molar ratio of x:y is 99:1-1:99, and z has an average value of 10-20,000,
M(acac) n Chemical Formula 7
wherein M is Ni or Co; acac is acetylacetonate, and n is 2 or 3.
10. The method of claim 9 , wherein the compound represented by Chemical Formula 7 is configured such that M is Ni and n is 2; and R 5 of the compound represented by Al(R 5 ) 3 is an isobutyl group.