TW315374B - - Google Patents

Description

Printed 315374 at B7 by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (/) The present invention relates to the polymerization method of cyclocane, which uses a catalytic amount of a titanium catalyst (containing at least two metal-bound Group or two mono-substituted methyl groups, the substituents of which do not contain hydrogen atoms at the position) for photochemical ring-opening replacement reaction and a polymerization composition containing such an amount of olefin and catalyst. Thermally induced ring-opening displacement polymerization (using a catalytic amount of metal catalyst) has long been known and described in the literature [(refer to KJJvin, Displacement of Dilute Hydrocarbons 1-12, Academic Press, London, (1983)]. Such thermal polymers have been produced industrially and are commercially available, such as Vestenamer®. Conversely, photochemically induced ring-opening displacement polymerization reactions are less well known and have not been used commercially so far. US Patent US4 , 060,468 olefin replacement polymerization is carried out, that is, a mixture of two different compositions (a metal salt selected from tungsten salt, molybdenum salt, chain salt and tantalum salt and substituted benzene or benzyl alcohol used as a cocatalyst) In a reactor with monomeric olefins, it is irradiated with UV-rays. Among the olefins, only cyclic and non-cyclic hydrocarbons (no functional groups and substituents) are mentioned. The catalyst components are separated and stored directly in The method step of mixing the catalyst components before the reaction makes the known method technically expensive and very troublesome. Tanielan (Tanielan) in [Tanielan, C., Kieffer, R., Harfouch, People, Tetrahedron Letters No. 52: 4589 · 4592 (1977)] describes the catalyst system W (C0) 6 / CC14, which can be used for the replacement polymerization of cyclopentane and raw norbornene after UV-ray irradiation. Carbonyl Metals are volatile and toxic, so when using this substance, it is necessary to make physiologically necessary protective measures, and the cost is high. In addition, a fierce competitive addition reaction has been observed, resulting in 1- This paper size is suitable for China Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling in this page) Order A7 315374 B7 5. Description of the invention (>) Chloro-2-trichloromethane-cycloalkane. Tao Yi ( Thoi) in [Thoi, HH, Ivin, KJ, Rooney, JJ, J. Mol. Catal_15: 245-270 (1982)]

(Please read the precautions on the back before filling in this page) Phenyl / c = w (co) 5 ch3o Tungsten pentacarbonyl carbene complex is a thermal catalyst for the ring-opening displacement polymerization of dimethylorbornene, and with Phenylacetylene (as a cocatalyst) is also a photocatalyst system for the same polymerization reaction. This type of catalyst system has its serious drawbacks, that is, when it is used as a finished product, the safety is very low, the carbonyl compound is physiologically concerned, and the tolerance of the functional group on the cycloolefin is very low. Feldmann (Feldmann) in [Feldmann, C., et al., In: Stephan J. Lippard (Ed) Progress in Inorganic Chemistry, 39: 3-73 (1991)] describes the alkylene complex of molybdenum and crane It is weak when used alone, but when combined with Lewis acid (Lewis-S, such as ren), it is a powerful thermal catalyst for cycloolefin polymerization. Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Known photochemically activated catalysts always require a cocatalyst, so the quality of the polymer produced (determined by the nature of the cocatalyst selected and the order of the reactants) varies greatly. With known polymerization methods, cycloolefin polymers (via photochemical ring-opening displacement polymerization) can only be produced in a costly and uneconomical manner. The lack of stability during storage is a special shortcoming (because of the stability before mixing) 'Another major shortcoming is the lack of tolerance for cycloolefin functionality, and the need for -5- This paper scale is applicable to the Chinese National Standard (CNS) A4 Specifications (210X297mm1 Printed by the Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperative A7 B7 V. Invention description (3) Use two components as a catalytic system. From the technical, economic and environmental ecological point of view, it is necessary to have a cycloolefin (Through photochemical ring-opening displacement polymerization) An improved and feasible method for manufacturing polymers. In W93 / 13171, molybdenum compounds containing carbonyl-based single-component and two-component catalysts for air stability and water stability are described. And tungsten compounds, ruthenium compounds and hungry compounds, with at least one polyene ligand for thermal displacement polymerization and photoreaction displacement polymerization of cyclic olefins, especially orthobornenes and derivatives of orthobornenes. Other polycyclic (especially It is a non-condensed polycyclic cyclic olefin. It is not mentioned. The single-component catalyst of the ruthenium compound used is [(C6H6) Ru (CH3CN) 2C1] + PFr and [Ru (Cumene) Cl2] 2 can be activated by UV-irradiation; however, the storage stability of the composition containing pro-norbornene is not enough. This kind of catalyst cannot fully replace the known two components. Catalyst. Patasis and Fu described in [Patasis, NA, Fu, D., J. Am. Chem. Soc. 1 l5: 72〇8-72l4 (l " 3), using dimeroyl -Di (trimethylsilyl) methyl-titanium (IV) as a thermally active catalyst for thermal ring-opening displacement polymerization of raw norbornene. The photochemical activity is not mentioned. It has been found that if the composition contains a titanium (IV) compound (It contains at least two methyl groups bonded to the metal or two mono-substituted methyl groups, and the substituent does not contain a hydrogen atom at the position), the composition of the tightened cycloolefin and a single-component catalyst can be used Photochemical polymerization. Surprisingly, it was found that this thermally stable compound proved to be an effective catalyst for light-induced ring-opening displacement polymerization, and despite its photochemical activity, the storage stability of the mixture of cycloolefin and titanium compound remained unchanged. This paper scale is applicable to China National Standard (CNS) Α4 specifications 210Χ297mm) (Please read the precautions on the back before filling out this page),? Τ Economy. -SP Central Standards Bureau staff consumer cooperative printed 315374 A7 A7 B7 V. Description of invention () More surprised to find that the above The tightened catalyst can be used as a thermal catalyst after a short period of irradiation in the presence of cyclic olefins, so that photochemical and thermal polymerization reactions can be used in combination. The subject of the present invention is that in the presence of a metal compound catalyst, photocatalytic monocyclic olefins Or at least two different cyclic olefin polymerization methods characterized by performing a photochemical ring-opening displacement polymerization in the presence of at least a pair of thermally stable titanium (IV) compounds in a catalytic amount, such compounds containing at least For two methyl groups bonded to a metal or two mono-substituted methyl groups, the substituents do not contain hydrogen atoms in position. The remaining titanium valence is preferably saturated with thermally stable neutral ligands, which are known. The number of neutral ligands can exceed the stoichiometrically possible number (solvent). The cyclic olefin used may be a monocyclic or polycyclic condensation or bridged ring system, for example, 2 to 4 rings, which are unsubstituted or substituted, and condensed aromatic or on one or more rings Heteroaromatic rings, for example, o-phenylene, o-naphthyl, o-pyridyl, o-pyridyl, contain heteroatoms such as 0, S, N, or Si. The number of rings of each cycloolefin may be 3-16 member rings, preferably 3-12 member rings, and most preferably 3-8 member rings. Cyclic olefins may further contain non-aromatic double bonds, depending on the size of the ring, preferably containing 2-4 additional double bonds. The substituents of the ring are inert substituents, that is, those that do not harm the chemical stability and thermal stability of the titanium compound. Cycloolefins are tension rings and ring systems. The thermal stability in the present invention means that the photocatalytically active titanium compound does not form an active species for ring-opening displacement polymerization under heating. The catalyst is heated at room temperature to a slight temperature, such as +4 (TC, under a few weeks to several paper scales, the Chinese National Standard (CNS) 84 specifications (210X297 mm) are applicable (please read the precautions on the back before filling this page ) Order A7 B7 V. Description of the invention () Within a month, without light irradiation, it will not cause ring-opening displacement polymerization, and during this period, less than 0.2 ° / ❶ weight is converted into monomer. Thermal stability can be The decision method is, for example, a toluene solution containing 20% by weight of the monomer and 0.33% by weight of the titanium catalyst, placed in the dark at 50 ° C for 96 hours, the amount of polymer that may be formed (can be (The determination of the amount of filtering and drying of the precipitating agent such as the precipitate in ethanol) is not more than 0.5%, preferably not more than 0.2% (by weight). If the cyclic olefin contains more than one double bond, such as 2-4 double bonds, Depending on the reaction conditions, the amount of selected monomers and catalyst, a networked polymer is formed. In one of the preferred examples of the method of the present invention, cycloolefin is equivalent to formula (I), (please read the precautions on the back before filling in this page)

CQ; (I), stipulated in the printed form (I) of the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

Qi is a free radical with at least one carbon atom, which forms an alicyclic ring of at least 3 members with the base _ch = Cq2_B. The alicyclic ring may contain one or more heteroatoms (composed of silicon, phosphorus, oxygen, nitrogen and sulfur Selected from the group); unreplaced or halogenated, = 0, -CN, _N02, Zhafeng and Lang -⑼》-, -C00M ^ -SOM '-PO3M--COOCMOxa .-S03 (M〇1 / 2-· ρα (Μ〇1 / 2, Cl_c2 (r alkyl, CrC2e-hydroxyalkyl, g-cv haloalkyl, cv c6-cyanoalkyl, cvcv cycloalkyl, c6-c16-aryl, C7-C16-aralkyl, c3-c6-heterocycloalkyl, C3_Cur heteroaryl, c4_Cur heteroaralkyl or reverse ^ _This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of invention () Substitute; or replaced by -co-o-co- -co-nr5-co- on two adjacent carbon atoms; or in fat An alicyclic, aromatic or heteroaromatic ring is condensed on adjacent carbon atoms of the ring, which is unsubstituted or halogen, -CN, -N02, R «R7R« Si- (0) u-, -COOM, -SO3M, -PO3M, -C00 (Mi) i / 2, -SCMM ^, P03 () ^) 1/2, cvcv alkyl, crc2e-haloalkyl, cvcv hydroxyl Group, CrC6-cyanoalkyl, C3-C8-cycloalkyl, C6-C16-aryl, Or c16-aralkyl, c3-c6-heterocycloalkyl, c3-c16-heteroaryl, c4-c16 -Heteroaralkyl or R13-Xr substitution; X and Xι are independent of each other ΔΔ ′ is 0 ·, -S-, -CO ·, · 80-, -S〇2-, -OC (O)-, _C (0 ) -0-, -C (0) -NR5 ·, -NRi〇-C (0)-, _S〇2_0_ or -O-SO2-; Z, R2 and Ra are independent of each other, CrC12 · alkyl, (VCu -Perfluorohydrocarbyl, phenyl or benzyl; R4 and R13 are each independently (VCV alkyl, CVCV haloalkyl, CrCV hydroxyalkyl, C3-C8-cycloalkyl, C6-C16-aryl, CVCV aromatic Alkyl; Rw and Rw are independent of each other, and are hydrogen, CVC12-homoyl, phenyl or benzyl, the alkyl is unsubstituted or substituted by crc12-homooxy or C3-C, -cycloalkyl; &, R7 and R * are independent of each other and are CrC12-alkyl, CrC12-perfluorohydrocarbyl, phenyl or benzyl; Μ stands for an alkali metal, stands for an alkaline earth metal; u stands for 〇 or 1; used to constitute the fat The ring may contain non-aromatic double bonds; Q2 is ammonia, C1-C2D-yuan, Cl_C2D_ 歯 院 基, Cl-Ci2_yuan-oxygen, cyclin, -CN, Rn-X2-; this paper size applies to China National Standard (CNS ) A4 specification (210X297mm) (Please read the precautions on the back before filling in this page) Order The Central Bureau of Standards of the Ministry of Economic Affairs *: Printed by the Industrial and Consumer Cooperatives 315374 A7 B7 V. Description of invention ()

Ru is CrCV alkyl, CrCV haloalkyl, CrCV hydroxyalkyl, c3-c8-cycloinstitution, c6-c16-aryl or occ16-aralkyl; x2 is -c (o) -o- or- c (o) -nr12-; r12 is hydrogen, cvc12-homoyl, phenyl or benzyl; the aforementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl Is unsubstituted or substituted by CrCV alkyl, CrCu-alkoxy, -N02, -CN or halogen, the heteroatoms of the aforementioned heterocycloalkyl, heteroaryl and heteroaralkyl are selected from -Ο-, -S -, -NR9- and -N = selected from the group consisting of: R9 is hydrogen, CVCu-homoyl, phenyl or benzyl. The condensed alicyclic ring contains 3-8 carbon atoms (4-7 is better, 5-6 is best). For example, there is an asymmetric center in the compound of formula (I). As a result, the compound can be presented as an optical isomer. Some compounds of formula (I) may be produced as tautomers (for example, keto-enol -Tautomers). If there is an aliphatic-C = C-double bond, geometric isomers (E-form or Z-form) may appear. Even more advanced, the outward-inward configuration is also possible. Formula (I) includes all possible stereoisomers (in the form of enantiomers, tautomers, diastereomers, E / Z-isomers or mixtures thereof). The alkyl, alkenyl and alkynyl groups in the definition of substituents may be linear or branched. The same applies to alkoxy, alkylthio, alkoxycarbonyl, and every other alkyl group containing alkyl groups. The monoalkyl group preferably contains 1-12 carbon atoms, more preferably 1-8 carbon atoms, especially 1-4 carbon atoms. The monoalkenyl and alkynyl groups preferably contain 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and most preferably 2 to 4 carbon atoms. -10- This paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) (please read the precautions on the back before filling this page)

* 1T A7 _B7__ printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention () Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, second Butyl, tertiary butyl and different isomeric pentyl, hexyl, heptyl-, octyl-, nonyl-, decyl-, undecyl-, dodecyl-, tridecyl -, Tetradecyl-, pentadecyl-, hexadecyl-, heptadecyl-, octadecyl-, nonadecyl- and eicosyl-radicals. Hydroxyalkyl groups include, for example, hydroxymethyl, hydroxyethyl, 1-hydroxy-isopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-isobutyl, 1-hydroxy -Second butyl, 1-hydroxy-third butyl, and various isomeric pentyl-, hexyl-, heptyl-, octyl-, nonyl-, decyl-, undecyl-, Dodecyl-, tridecyl-, tetradecyl, fifteen-, hexadecyl-, heptadecyl-, octadecyl-, nonadecyl- and eicosyl-radicals. Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2 · trifluoroethyl, 2-fluoroethyl Group, 2-chloroethyl, 2,2,2-trichloroethyl and halogenated, especially fluorinated or chlorinated alkanes, such as, for example, isopropyl-, n-propyl-, n-butyl-, Isobutyl-, second-butyl, third-butyl, and various isomeric pentyl-, hexyl-, heptyl-, octyl-, nonyl-, decyl-, undecyl- , Dodecyl-, tridecyl-, tetradecyl-, pentadecyl-, hexadecyl-, heptadecyl-, octadecyl-, nineteen-yl and eicosyl-radicals. Alkenyl groups include, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-pent-2,4-dienyl, 3-methyl-but-2-enyl , N-oct-2-yl, n-dodec-2-enyl, iso-dodecenyl, n-octadec-2-enyl, n-octadec-4-enyl. C5-C * -cycloalkyl is preferred for cycloalkyl, especially C5 • or CV cycloalkane-11-This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) (please read the notes on the back first (Fill in this page again)

, 1T A7 B7 315374 V. Description of invention () base. There are several examples of cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. (Please read the precautions on the back before filling in this page) Cyanoalkyl includes, for example, cyanomethyl (methylnitrile), cyanoethyl (ethylnitrile), 1-cyanoisopropyl, 1-cyano-n Propyl, 2-cyano-n-butyl, 1-cyano-isobutyl, 1-cyano-second butyl, 1-cyano-third butyl and various isomeric cyanopentyl- and -hexyl groups -Free radicals. The aralkyl group preferably contains 7-12 carbon atoms, and preferably contains 7-10 carbon atoms. It may be, for example, benzyl, phenethyl, 3-phenylpropyl, α-methylbenzyl, phenylbutyl and π, dimethylbenzyl. The aryl group preferably contains 6-10 carbon atoms. It may be, for example, phenyl, pentadiene, indene, naphthalene, husk and anthracene. Heteroaryl groups preferably contain 4 or 5 carbon atoms and one or two heteroatoms selected from oxygen, sulfur and nitrogen. It may be, for example, pyrrole, furan, thiophene, thiazole, thiazole, pyridine, pyridine, pyrimidine, tagen, indole, purine and quinine. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Heterocycloalkyl contains 4 or 5 carbon atoms and contains one or two heteroatoms selected from 〇, S and Ν. It may be, for example, ethylene oxide, azacyclopropene, 1,2-thiol, pyrazoline, pyrrolidine, hexahydropyridine, morpholine, tetrahydrofuran and tetrahydrothiophene. The alkoxy group is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy and third butoxy. The alkali metals in the present invention are lithium, sodium, potassium, rubidium and planing, and in particular, lithium, sodium and potassium. The alkaline earth metals referred to in the present invention are beryllium, magnesium, calcium, calcium and barium, and the special -12 · This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ 297 mm). System A7 B7 5. Description of the invention () Do not refer to magnesium and calcium. The halogens defined above are fluorine, chlorine, bromine and iodine, and fluorine, chlorine and bromine are preferred. The most suitable compound of formula (I) in the method of the present invention is one in which q represents hydrogen. A further more suitable polymer compound is a compound of formula (I), and its Q, and the alicyclic ring formed with the group -CH = CQ2- is preferably containing 3-16 ring atoms, more preferably 3-12 ring atoms, especially Preferably, it contains 3 or 8 ring atoms, which can be, for example, a monocyclic, bicyclic, tricyclic or tetracyclic ring system. The particular advantage of the method of the present invention is that it can be carried out with a compound of formula (I) below, of which

Qi is a free radical with at least one carbon atom, which forms a 3-20 membered alicyclic ring with the group -CH = CQ2-, which may contain one or more heteroatoms (composed of one of silicon, oxygen, nitrogen and sulfur Selected from the group); unsubstituted or halogen, = 0, -CN, -N02, RJ ^ SKO) »-, -COOM, -SO3M--PO, Μ--COOCMOw, -S〇3 ( M〇i / 2--P〇3 (M〇1 / 2 'Ci-C, 2-alkyl, (VCu-haloalkyl, OCV hydroxyalkyl, (VCV cyanoalkyl, C3-CV cycloalkyl , (VC12_aryl, C? _Cl2 aralkyl, C3_C6 • heterocycloalkyl, c3-c12-heteroaryl, c4-C12-heteroaralkyl or R4_X-substituted; or in the radical Qi two Substituted by _co-o-co- or -C0-NR5-CO- on adjacent carbon atoms; or condensing an alicyclic, aromatic or heteroaromatic ring on adjacent carbon atoms, which is Unsubstituted or halogen, -CN, _N02, R «R7R * Si_, -COOM, -S03M, -PO3M, -COCKMO ^, -SC ^ OVI ^, _P〇3 (M such as, CrCu-alkyl, cvcv Haloalkyl, CrCu- -13- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page) Standards Agency employees consumer cooperatives printed

Sl5374 at B7 5. Description of the invention () Hydroxyalkyl, crc4-cyanoalkyl, c3-c6-cycloalkyl, c6-c12-aryl, c7-c12-aralkyl, C3-C6-heterocycloalkyl , C3- (V heteroaryl, OCu-heteroaralkyl or Rn-Xi- substituted; X and Xi are independent of each other and are -0-, -8-,-(: 0-, -80-, -802 -, -0-C (0)-, -C (0) -0-, -C (0) -NR5_, -NR1 < rC (0)-, -S02-0- or -0-S〇2- , Private, gen and R3 are independent of each other and are CrCV-based, cvcv perfluorohydrocarbyl, phenyl or benzyl; Μ is a metal test, a soil-based metal; and Rl3 is independent of each other 1L 'is CrCu-based, Ci-Cl2- 愯 焼 group, Cl-Cl2- via alkyl group, c3-cv cycloalkyl group, c6-c12-aryl group, cvc12-aralkyl group; each and R1 () are independently hydrogen, CrC6-yuan , Phenyl or benzyl, the alkyl group of which is unsubstituted or substituted by CVC6-hodoxy or (VC6-cycloalkyl; private, R? And R «independent _ll, Ci-Ce-ho Group, Ci-CV all-nitronicotinyl group, phenyl group or benzyl group; u represents 0 or 1; the alicyclic ring composed of 4 may contain non-aromatic double bonds; _Q2 is ammonia, C1-C12-hospital group, C1 -C12-dentate base, Ci-CV oxy group, dentin, -CN, Rn-X2-;

Rn is (VCr alkyl, CrC12 haloalkyl, CrC12-hydroxyalkyl, C3-C6-cycloalkyl, Ce-Ci2 · square or C7-Ci2_square courtyard; x2 is -c (o) -o -Or-c (o) -nr12-; R12 is hydrogen, CrC «r, phenyl or benzyl; wherein the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and Miscellaneous • 14 · This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297mm) (please read the precautions on the back before filling in this page) '1. Order A7 B7 5. Description of invention () The alkyl is Unsubstituted or substituted by CVCV alkyl, CVCe-alkyloxy, -no2, -CN or halogen, the heteroatoms of the aforementioned heterocycloalkyl, heteroaryl and heteroaralkyl are selected from -0-, -S- , -NRg- and -N = selected from the group consisting of '~; R9 is hydrogen, cvcv phenyl, phenyl or benzyl. The preferred free radical-containing compounds of formula (I) are, of which

Qi is a radical with at least one carbon atom, which forms a 3-10 membered alicyclic ring with the group -CH = CQ2-, which may contain one or more heteroatoms (composed of one of silicon, oxygen, nitrogen and sulfur Selected from the group); unsubstituted or halogen, -CN, -N02, RjRJ ^ Si-, -COOM, -SOjM, -P03M, -COCXM ^ -SCMM ^, -CVC6-alkyl, CV CV Haloalkyl, (VC6-hydroxyalkyl, CVCr cyanoalkyl, C3-C6-cycloalkyl, phenyl, benzyl or R4-X-substituted; or condensing an alicyclic ring on adjacent carbon atoms , Aromatic or heteroaromatic ring, which is unsubstituted or halogen, -CN, _N02, R6R7R * Si_, -C00M, -S03M, -Ρ03Μ, -COOOV ^ V, -POaCM ^, crc6-alkyl , Cvcv haloalkyl, cvcv hydroxyalkyl, cvcv cyanoalkyl, c3-c6-cycloalkyl, phenyl, benzyl or R13-Xr replacement; Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please print first Read the notes on the back and fill in this page) Private, R2 and Gen are independent of each other and are CVCr-based, CrC4-perfluorohydrocarbyl, phenyl or benzyl; Μ is a metal test and 1 ^ is an earth metal test; Κ and R13 are independent of each other, CVCV alkyl, CrCV halo , CVG-hydroxyalkyl or C3-C6-cycloalkyl; X and X wave alone are -0-, -S-, -CO-, -SO- or -S〇2-, -15-this paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) 315374 A7 5. Description of the invention () Private, 117 and Rs are independent of each other, and are CrCr alkyl, CrC4-perfluoroalkyl, phenyl or benzyl; Q2 is hydrogen. The method of the present invention is particularly suitable for the polymerization of pro-norbornene. The best pro-norbornene derivative is represented by formula (Π),

Xj

Where X3 is -CHRis-, oxygen or sulfur; R14 and R15 are independent of each other and are hydrogen, -CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3Si- or -COOR17; R16 and Rn are mutually Independent, hydrogen, crc12-alkenyl, phenyl or benzyl; or represented by formula (m), (please read the precautions on the back before filling this page) Employee consumption cooperation Duin of the Central Standards Bureau of the Ministry of Economic Affairs System X »

Among them, X4 is -CHR19-, oxygen or sulfur; Rl9 is ammonia, Cl-Cl2-homoyl, phenyl or benzyl; hydrogen, CVCV molybdenum or halogen; -16- This paper scale is applicable to Chinese national standards ( CNS) A4 specification (210X297mm) ΚΊ Β7 5. Description of invention () or X5 represented by formula (IV)

Wherein x5 is -d-, oxygen or sulfur; r22 is hydrogen, crc12-homoyl, phenyl or benzyl; R2. And R21 are independent of each other, and are hydrogen, -CN, trifluoromethyl, (CH3) 3Si-0-, (CH3) 3Si-, or -COOR23; R23 is hydrogen, (VCu-homoyl, phenyl, or benzyl; Or as represented by formula (V), (please read the precautions on the back before filling in this 1),? Τ 〇

Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy where Xβ is-^-, oxygen or sulfur; R24 is ammonia, Ci-Cn-homoyl, phenyl or benzyl; Y is oxygen or = N-R25, and R25 is ammonia, methyl, ethyl or phenyl. The following compounds of formula (I) are particularly suitable for the polymerization method of the present invention, in which the bicyclic and polycyclic systems can be obtained from diene-acetaldehyde via Diels-Alder reaction: -17- This paper scale is applicable to Chinese national standards (CNS) Α4 specification (210Χ297mm) V. Description of invention (A7 B7 Printed by the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs

In nn nfl ^ i tm mu ^ ^ Ί square, v 'mouth (please read the precautions on the back before filling this page) 〇

〇

〇

〇

〇

⑶, οCOOCHr phenyl COOCHr phenyl COO (CH2) 3CH3 coo (ch2> 3ch3 COO (CH2) 9CH3 COO (CH2) 9CH3 Αχ P (C6H5) 2P (C6H5) 2 ⑷, ⑹, ⑻, (10), ( 12),

ο

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cooch2ch3 cooch2ch3 COO (CH2) 5CH3 COO {CH2) 5CH3 COOiCHjin ^ 000 (^ 2)! ch2o (ch2) 5och3

Si (CH3) 3 ⑶, ⑺, ⑼, (11), (13), -18- This paper scale is applicable to the Chinese National Standard (CN'S) A4 specification (210X297 mm)

A 7 β V. Description of the invention (ch2nhch3 ch2nhch3 (14),

(15),

3 6),

(17), --------- r: clothing-- (please read the notes on the back before filling this page)

Ho

3 H c 3 8),

(19), ch2ch3 D Printed by Employee Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs

(20 2 (2 19 The paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297mm)

3

Phenyl (21) ’(23), 315374 Αν B7 5. Description of the invention ()

This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm) A7 B7

GXX} i ⑽), printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (44). The titanium (IV) compounds used in the invention are those containing a metal atom. The methyl group or mono-substituted methyl group bonded to the metal is at least twice (preferably two to six times, preferably two to three times) for ligand binding. This ligand is represented by the formula (νπ), -CH2-R (νπ) where R is Η, -CF3, -C R26R27R28, unsubstituted or C6 substituted by CVCV alkyl or CrC6-hodoxy -C16-aryl group or C4-C15-heteroaryl group having 1 to 3 heteroatoms in a group consisting of 0, S and N; and R26, R27 and R2 * represent CrCur courtyard groups independent of each other, not It is substituted or substituted by CV CV oxy group, or R26 and R27 have this meaning, and R28 is C6-C1 (> -aryl or C4-C9-heteroaryl, unsubstituted or G-CV Or G-CV oxy substituted; -21-^^ 1 i ^^^ 1 In — ^ n ^^^ 1 I ^^^ 1 nfn n ^ i —ϋ ^^^ 1 ^ J.; ", \ 呑 (Please read the precautions on the back before filling out this page) This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 _____ B7_ printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs () And R29, R3e and L represent independent CrCir alkyl, C5_ or C6_cycloalkyl 'or phenyl or benzyl which is unsubstituted or substituted by CrCV yalyl or Cl-C6-alkoxy B to R «represents an alkyl group, which may be linear or branched, preferably containing 1 carbon atom (1-4 Good). R28 to! ^ Represents an aryl group, with particular preference for phenyl or naphthyl. R represents an aryl group in formula (VII), with particular preference for phenyl or naphthalene. R represents a heteroaryl group in formula (ΥΠ), with preference Pyridyl, furyl, sialyl or pyrrolyl. Preferred substituents for R26 to R31 are methyl, ethyl, methoxy and ethoxy. Examples of free radicals for R26 to R »are compounds of formula (I) In the preferred embodiment, the radical R in formula (VH) represents Η, -C (CH3) 3, -CXCB ^ CeHs' unsubstituted or methyl, ethyl, methoxy Or ethoxy substituted phenyl, -CF3 or -Si (CH3) 3. The remaining valence of the titanium (IV) atom can be saturated from the same or different ligands, for example, containing 2 to 18 carbon atoms Second amines, mono-anion ligands and neutral ligands such as 2〇-, R ^ S-, halogen, alkylene, bridged dialkylene, tri-coordinated ligands, such as ethers, amines, where R «Is a linear or branched CVCV alkyl group that is independently unsubstituted or substituted with (VCV alkoxy or halogen, C5- or unsubstituted or substituted with CVGr, CrC6-alkoxy or halogen (V cycloalkyl, not Phenyl substituted or substituted by CrC6-alkyl, CVC6-alkoxy, CV C6-oxomethyl, CrCV alkoxyethyl or halogen, or unsubstituted or substituted by Crc6-alkyl, CrC6-alkyl Oxygen, CVC6-alkoxymethyl, (VCer alkoxyethyl or halogen-substituted benzyl or phenethyl; -22 · I .-- II II-J Pack --------- (Please read the precautions on the back before filling out this page) This paper scale is applicable to the Chinese National Standard (CNS) 84 specifications (2! 〇X297 male thin) A7 B7__ printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs () The second amine preference is the one shown in the formula Rs4R35N-, where R34 and R35 are independent linear or branched CVCur groups; C5- or C6-cycloalkyl, unsubstituted or CVC6-alkoxy Group or halogen-substituted benzyl group or phenethyl group or (CVCV alkyl) 3 Si group; or together are tetramethylene, pentamethylene or 3-oxopentyl-1,5-diyl. The alkyl group preferably contains 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). Some examples are dimethyl, diethyl, di-n-propyl, di-iso-propyl, di-n-butyl, methyl-ethyl-, benzhydryl-, benzyl-methyl -, Diphenyl-, benzene-methylamino and bis (trimethylsilyl) amino groups. The halogen as a ligand or substituent is preferably F or α (C1 is preferred). The alkylene group may be unsubstituted or substituted with 1 to 5 CVCV alkyl groups, especially methyl groups, or -Si (CVCr alkyl groups), especially -Si (CH3) 3. The bridged mercapto group is particularly represented by the formula R36-A-R36 *, where R36 is unsubstituted or substituted with 1 to 5 G-Cr burned groups, especially methyl, or -Si (CrC4-alkyl) , In particular -Si (CH3) 3-substituted alkylene, and A is -CH2-, -CH2-CH2-, _Si (CH3) 2-, -Si (CH3) 2-Si (CH3) a- or -SKCHA- The ethers with O-SiCCH and 〇 as neutral ligands include dialkyl ethers (containing 2 to 8 carbon atoms) or cyclic ethers (containing 5 to 6 ring members). Some examples are diethyl ether, methyl ether, diethyl ether, di-n-propyl ether, di-iso-propyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, and dimethane. The third amine as a neutral ligand is one containing 3 to 24 carbon atoms (preferably 3 to 18). Some examples are trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, triphenylamine, tricyclohexylamine, xylylenediamine, xylylenediamine, 3,5-xylyl- Dimethylamine. -23- This paper scale is applicable to Chinese National Standard (CNS) 8.4 specifications (210X297mm) n '^ n— ^^^ 1 n 4 In K ^^^ 1 n ^ i nn nn l J fi (please read first (Notes on the back and then fill in this page) 315374 at B7 V. Description of the invention () The tri-anionic mono-anion ligand is, for example, hydrogen (tripyrazol-1-yl) borate or alkane (tripyrazole -1-yl) borate, which is unsubstituted or substituted with 1 to 3 CrC4-alkyl groups [refer to Trofimenko, S., Chem. Rev., 93: 943-980 (1993)], or is [C5 ( R'5) Co (R37R3 * Ρ = 0) 3] θ, where R is Η or methyl and R37 and R38 are independent of each other Crc4-homoyl, CrCr alkoxy or phenyl [refer to Klaui, W ,, Angew. Chem. 102: 601-670 (1990)]. The halogen as the radical substituent of R32 is preferably fluorine, more preferably chlorine. The substituent alkyl, alkylhydrogen and alkoxy in alkoxymethyl or -ethyl preferably contain 1 to 4 carbon atoms (preferably 1 to 2). Examples are methyl, ethyl, n- and -isopropyl, n-, iso- and tributyl, methoxy, ethoxy, n- and iso-propoxy and n-, iso and tributoxy base. The heart alkyl group preferably contains 1 to 12 carbon atoms, preferably 1 to 8, more preferably 1 to 4 carbon atoms. It is preferably a branched alkyl group. Examples of RM are methoxy, ethoxy, n- and iso-propoxy, n-, iso- and third butoxy, hexafluoro-iso-propoxy and hexan- and perfluorobutoxy base. I ----- IJ: Clothing --- I--ordered by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) R32 substituted phenyl and benzyl Examples are p-methyl-phenyl or benzyl, p-fluoro- or p-chlorophenyl or -benzyl, p-ethylphenyl or -benzyl, p-n- or iso-propyl Phenyl or -benzyl, p-iso-butylphenyl or -benzyl, 3-methyl-phenyl or -benzyl, tricumyl or 3,5-dimethylphenyl , 3,5-iso-propylphenyl or -benzyl, 3,5-n- or tertiary-butylphenyl or -benzyl. In the preferred embodiment, the titanium (IV) compound is particularly represented by the formula (VH〇, • 24 · This paper scale is applicable to the Chinese National Purlin Ratio (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (

At least two of the free radicals R »to Rc (preferably 2 or 3) are printed as a free radical -CH2-R of formula (VII) by the Employee Consumer Cooperative of the Central Purlin Bureau of the Ministry of Economic Affairs, R is Η, _CF3,- CR26 R27R28, -SiR ^ oR ^, unsubstituted or substituted with CrC6-alkyl or CrC6-alkoxy, c6-C1 (r aryl or with 1-3 heteroatoms selected from 0, S and N C4-C15-heteroaryl; R2eR27 and R2S are independent CVCV groups, unsubstituted or substituted by Cr alkyl, or R26 and R27 have this meaning and r28 is C < rCl (raryl or c4_c · »-Heteroaryl, unsubstituted or substituted by CrC6_alkyl or CrC < r oxy; L, RM and RS1 are CVCV burned groups that are independent of each other, C5_ or C6-cycloalkyl, unsubstituted or Phenyl or benzyl substituted by CVC6-alkyl or (VCV oxy); and the remaining radicals to R42 are the second amine group containing 2-18 carbon atoms, or R32s-, halogen, alkylene or bridge Linked dimerocyl or a neutral ligand 'where R32 is a linear or branched Cl-c18-alkyl group that is independently unsubstituted or substituted by Cl_Ce_alkoxy or halogen, unsubstituted or Ci_C (rCy or oxo or halogen substituted C r ^ C6 cycloalkyl, unsubstituted or Cr 6-homo group, Ci-C6-cyclo-homo group, CrC6-ho-oxymethyl group, CrC6-homo-oxyethyl group, one VCV home) amine group, di (( : 1 _ (: 6_alkyl) amine "3_yuan or halogen-substituted phenyl 'is not substituted or is CrCV alkyl, cvc6-alkoxy, CVCV alkoxymethyl-25- CN-S) Eight 4 Lin_ (210x297mm).

In ^^ 1----^^ 1 ^^ 1 J ——i In J ", vs (please read the precautions on the back before filling out this page) Printed 315374 at B7 by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 2. Description of the invention () group, CrC6-alkoxyethyl group, di (CrG-alkyl) amine group, di (CrGralkyl) amine-CV C3-homoyl group or halogen substituted benzyl group or phenethyl group. The free radical R ^ R26gR32 is suitable for the above preference. In a more preferred embodiment of the method of the present invention, a titanium (IV) compound of (vm) is used, wherein a) R39 to one of formula (VII) is a radical -CH2-R, or b) Rs9 to IU is the formula (νΠ) One of the radicals -CH2-R, R «and R42 represent independently unsubstituted or substituted alkylene, R32-〇- or halogen, or c) R39, R4◦ and IU are of the formula (νπ) A free radical -CH2-R, R «is an unsubstituted or substituted alkylene group, R32-0- or halogen, where R, R32 and R32 have the aforementioned meanings. R and R32 apply to the aforementioned preference. The method according to the invention prefers to use the titanium (IV) compound of formula (IXa) or OXB),

R33 to R «is a radical of formula (VII) -CH2-R ch2-r ch2-r

Rn-Ti-R42 (Ka), R-H2c-Ti- (DCb), CH2-R ch2-r where R represents H, -C (CH3) 3, -C (CH3) 2-C6H5, -CdH5 or- SKCVCU-alkyl) 3, and 1 ^ and 1142 in formula (IXa) or (IXb) represent F, Cl, Br independently of each other, unsubstituted or fluorine-substituted linear or branched CrC4-hospital oxygen基 ， 未 -26- This paper scale is applicable to the Chinese National Standard (CN'S) A4 specification (21〇Χ297mm)-'^ ------ Order (please read the precautions on the back before filling this page y Α7 Β7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of invention () Phenoxy substituted or substituted by cvcv or CVC4-hodoxy, or unsubstituted or (^-(: 4-hodyl Substituted alkylene; this alkoxy group is particularly favored as a branched alkoxy group, which is partially or completely substituted with fluorine, such as iso-propoxy, iso- and -third butoxy, hexafluoropropoxy and nine Fluoropropoxy. If the radical R in the group -CH2-R is -SiR ^ RaoRa ^, the titanium (IV) compound in the preferred embodiment includes a halogen atom bonded to titanium, especially C1 or Br. A particularly preferred compound is the one represented by formula (X) CH2-Si (R29R30R31) 3 R41 Ti CH2-Si (R29R30R31) 3 (X), I Υι where Yi is F, Cl or Br, R29, R3. And Rm represent C: -C18-alkyl independently of each other or unsubstituted or CVCV-based Or G-CV oxo substituted phenyl or benzyl; and IU represents the group -CH ^ SiRwRsoR ^, F, Cl, Br, unsubstituted or fluorine-substituted linear or branched (^- (: 4-alkyloxy, unsubstituted or phenoxy substituted by CVCU-alkyl or CVCV oxo, or unsubstituted or substituted by CVCr alkyl. R29, Rso and & 1 In particular, it represents CrCV-homoyl, phenyl or benzyl, and R41 is C1, or unsubstituted or C3 or C4-alkenyl substituted by fluorine, unsubstituted or substituted by CrCr-homoyl or CVCr oxy Phenyl or benzyl. -27- (please read the notes on the back before filling this page)

The size of L-β Dingben paper is applicable to the Chinese National Standard (CNS) A4 specification (210Χ297mm). 315374 A7 A7 B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy. V. Description of invention () Examples of titanium (IV) compounds are as follows [ Cp means molybdenum]:

Ti [CH2Si (CH3) 3] 4, Ti [OCH (CF3) 2] 2 [(CH2Si (CH3) 3] 2,

CpTi [(CH2C (CH3) 2-C6H5)] 2a, CpTi [(CH2-C6H5) 3,

TiCl2 [CH2Si (CH3) 3)] 2, [OCH (CF3) 2] Ti [(CH2-C6H5) 3,

CpBrTi [(CH2C (CH3) 2-CeH5)] 2, CpTi [2,6 · DimethylCeftO)] [CH2Si (CH3) 3)] 2, Ti [OCH (CH3) 2] 2 [(CH2-C6H5 )]2,

ClTi [OCH (CH3) 2] [CH2Si (CH3) 3)] 2, CpTi [OCH (CF3) 2] [(CH2-C6H5)] 2, CpTi (methyl) 3, CpTi (methyl) 2 [OCH (CH3) 2], Ti [CH2Si (CH3) 3] 2Br2,

Ti (2,6-xylyloxy) 2 (CH3) 2, Cp2Ti (CH3) 2, Ti [CH2Si (CH3) 3] 3 [OCH (CH3)] and Ti (2,6-dicumyloxy基) 2 (CH3) 2. The titanium (IV) compound used in the present invention is known or prepared according to known and similar methods from metal halides through Grignard reaction or from other known substitution reactions [Ref. Clauss, K., Bestian, H., Justus Liebigs Ann. Chem. 654: 8-19 (1962)]. The method of the present invention can be carried out in the presence of an inert solvent. The advantage of the method of the present invention is that the use of liquid monomers does not require the use of solvents. Inert means that the choice of solvent is based on the reaction of the titanium compound. For example, when the intended substitution reaction such as alkoxy exchange of halogen, protic polar solvents cannot be used. Suitable inert solvents are, for example, protic polar and aprotic solvents, which can be used alone or mixed with at least two solvents. Examples: Ethers (dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether or ethylene glycol dimethyl ether, ethylene glycol monoethyl ether or ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether Methyl ether), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, U, l-trichloroethane, 1,1,2,2-tetrachloroethane), carbonates And Propyl Ester (Acetic Acid-28-This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210Χ25Πmm) (please read the notes on the back before filling this page). Printed A7 B7 V. Description of the invention () Ethyl ester, methyl propionate, ethyl benzoate, 2-methoxyethyl ethyl ester, r-butyrolactone, valerolactone, pivalolactone), amine carbonate And internal amide (N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, tetramethylurea, hexamethylphosphoric acid triamine, r -butyramidine, e-caprolactam, N-methylpyrrolidone, N-acetampyrrolidone, N-methylcaprolactam), submill (dimethyl submillone) , Milling (two-class milling, two-class milling, three-class milling, four-class milling , Third ammonia (N-methylhexahydropyridine, N-methylmorpholine), aliphatic and aromatic hydrocarbons, such as petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane Alkane, benzene or substituted benzene (chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene, toluene, mixed xylene) and nitrile (acetonitrile, propionitrile, benzonitrile, phenyl Acetonitrile). The preferred solvents are protic polar and non-polar solvents. The particularly preferred solvents are aliphatic and aromatic hydrocarbons and mixtures of these solvents. Particularly remarkable are the substituted cycloolefins and catalysts in the process of the invention The composition is not sensitive to oxygen, so no protective gas is needed during storage and reaction. However, it is best to be isolated from moisture and use dry reaction and storage conditions. In the method of the invention, the monomer and the formula (I) are added The catalyst can be stored as a mixture or separately, because the catalyst used is highly stable. The mixture can be stored at any time before the photochemical polymerization reaction. This is the scientific and technological advantage of the method of the present invention. Light has a high sense It is best to store it under light isolation. Another subject of the present invention is a photopolymerizable composition containing ⑻ a cyclic olefin or at least two different cyclic olefins, and (b)-a catalytic amount of at least -29 — This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) I- .........-!-—-II -J-Cloth II I. N (Please read the notes on the back first Please fill in this page again) 315374 Α7 — Β7 V. Description of invention () A pair of thermally stable titanium (IV) -compounds, which contain at least two methyl groups or two mono-substituted methyl groups bonded to the metal, in which the substituents It does not contain a hydrogen atom at the position. Another subject of the present invention is a composition containing one cyclic olefin or at least two different cyclic olefins and an effective catalytic amount of a heat stabilized titanium (IV) compound (wherein at least Contains two metal-bound methyl groups or two mono-substituted methyl groups, in which the substituent does not contain a hydrogen atom at the position), the exception is dimercyl · bis (trimethylsilyl) methyl-titanium mixed with the original norbornene (IV). The composition of the present invention further contains non-volatile monomers for open-chain copolymerization. They form a copolymer with the tensioned cycloolefin. For example, combined with diene can form a network polymer. Examples of such monomers for copolymerization are olefin mono- or di-unsaturated compounds, such as olefins and dienes, such as from pentene, hexene, heptene, octene, decene, dodecene, propylene Diene of acids and methacrylic acid, its esters and amides, vinyl ethers, styrene, butadiene, isoprene and chloroprene. In addition, the replaceable polymerized olefin contains 80% by weight (preferably 0.1-80%, more preferably 0.5-60%, more preferably 5-40%) of the compound of formula (I) and replaceable in the composition of the present invention The total amount of polymerized olefins. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ----- II ---! '* Clothing --- order (please read the precautions on the back before filling in this page) The composition of the present invention may contain Polymerization auxiliary substances. Known auxiliary substances are antistatic agents, antioxidants, opacifiers, softeners, dyes, pigments, fillers, reinforcing agents, slip agents, adhesives, tackifiers and mold release agents. »% Material can be added in a very high proportion without impairing the polymerization, such as 70% (by weight), the preferred is 1-7〇%, 5.6% is better, 10-50% is better, 10.40% is best (subject to composition). Fillers and reinforced fillers are known to be -30- This paper scale is applicable to China National Standards (CNS) Α4 inspection (210X297 mm) A7 __B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Description of the invention , Physical and mechanical electronic properties, some examples are powdered, spherical and fibrous glass and quartz, metal and semi-metal oxides, carbonates such as MgC03, CaC03, dolomite, metal sulfates such as gypsum and barium sulfate, Natural and artificial silicates such as talc, zeolite, wollastonite, feldspar, clays such as porcelain clay, stone powder, moustache, carbon fiber, artificial fiber or artificial powder and artificial carbon black. Viscosity-enhancing agents are especially replacement polymers, which can prove to have olefinic unsaturation and form a polymer during the polymerization reaction. This replacement polymer is known and can be purchased on the market under the registered trademark Vestenamere®. Other viscosity enhancing substances are polybutadiene, polyisoprene or polychloroprene, as well as copolymers made from butadiene, isoprene and chloropentadiene with olefins. The viscosity enhancing substance may contain 0.1-50% by weight of the composition, preferably 1-30%, preferably 1-20%. The purpose of the filler is to have optical transparency in the polymerization reaction or to polymerize in a thin layer. In the method of the present invention, it is not necessary to maintain the irradiation of the reaction mixture with light throughout the reaction time. Once the polymerization reaction is initiated by photochemistry, the reaction process can be completed automatically even in the dark. The wavelength of the irradiated light is preferably 200 nm to 50 nm, preferably 200 nm to 500 nm, and most preferably depends on the light source in the uv range. According to the method of the present invention, UV-laser or UV-lamp irradiation is preferred. The irradiation of the catalyst can be carried out before, during or after the addition of the monomer. Proper irradiation is from 1 minute to 8 hours, especially from 5 minutes to 4 hours. The order of adding monomers and catalyst is not important. The monomer can be added first or after the introduction of the catalyst. Similarly, the catalyst can be irradiated first and then 50% into the monomer. It can also irradiate the solution containing catalyst and monomer. This: the method of the invention is implemented at a temperature from room temperature to slight heating. • 31- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X: 297 mm)-. In I In-i InJ ' —...... 11— ......-= I -I— n (Please read the precautions on the back before filling in this page) A7 B7 5. Description of invention () Good, for example around 50 ° C . The increase in temperature only increases the reaction rate, because the catalyst used will only initiate thermal polymerization in exceptional circumstances. The polymerization reaction mainly takes place at a temperature selected to accelerate the reaction. It should be mentioned that the catalyst can be converted into a hot catalyst after sufficient irradiation. The method of the present invention is carried out especially at -20 ° C to 50 ° C. Above 50 ° C, such as 110 ° C, can be used effectively after sufficient irradiation time. One of the surprising advantages of the method of the present invention is that the titanium compound used can become a thermal catalyst after irradiation. It is therefore possible that after a short period of irradiation, the polymerization reaction can be continued or terminated by heating, which has economic and technical advantages in the field of manufacturing various molds and coatings. This integrated method is particularly advantageous in terms of manufacturing thermoplastics. Another subject of the present invention is a method using photocatalytic initiation and subsequent thermal polymerization of cyclic olefins or at least two different cyclic olefins in the presence of a metal compound catalyst, which is characterized by printing H.I! , A I ϋir (please read the precautions on the back before filling in this page) a) First, combine cycloolefin with a catalytic amount of at least one pair of thermally stable titanium (IV) compounds (containing at least two methyl groups or two Metallized mono-substituted methyl groups, the substituents of which do not contain hydrogen atoms at the Λ-position) are irradiated with light; or a catalytic amount of at least one pair of thermally stable titanium (IV) compounds (having at least two methyl groups or two single The substituted methyl group is combined with the metal, and its substituent does not contain a hydrogen atom in position), irradiated in an inert solvent, and then mixed with a cycloolefin; and b) The polymerization reaction is then terminated by heating and without irradiation. The aforementioned preference applies to method a). The irradiation time mainly depends on the desired reaction. For example, if we only use the heating caused by irradiation -32- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 315374 A7 _________B7_ V. Description of the invention () To terminate the polymerization reaction, use a short irradiation time. The so-called short irradiation time may be 60 seconds, preferably 5-60 seconds, and particularly preferred is 1040 seconds. If we want to complete the polymerization reaction under irradiation, and the final polymerization reaction is terminated by annealing, then use a longer irradiation time. In step b) of the method, the heating temperature is preferably 50-200 ° C, preferably 50-150 ° C, especially 70-120 ° C. In the present invention, the so-called catalytic amount is preferably 0.001-20% Mohr fraction, especially 0.01-15% Mohr fraction is better, especially preferred is 0.1-10% Mohr fraction (in terms of monomer Amount). Another subject of the present invention is a method for manufacturing a thermal catalyst for cycloolefin replacement polymerization, which is characterized by a titanium (TV) compound (containing at least two methyl groups or two mono-substituted methyl groups bonded to a metal , Its substituent does not contain a hydrogen atom at the position) irradiated with light in a substance or solvent. Tightened cycloolefins are suitable for the method of the present invention and have a wide range of applications. Cyclohexene generally cannot be replaced with olefins to achieve homopolymerization. This exception is well known to professionals, such as Ivin in KJ Ivin, KJ Saegusa Τ. (Hrsg ·), Ring Opening Polymerisation Vol 1, No. 1 : 139-144, described in Elsevier Applied Science Publishers, London and New York (1984). Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs.-.Ί i-I il ^^ 1 ί---------I 1 1 I (Please read the precautions on the back before filling this page) With the method of the present invention, it is possible to manufacture structural units with the same or different chemical formula (XI) that are hardened by irradiation

-33- This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). The A7 B7 is printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy. V. Description of invention () (of which there is the definition of formula (I) ) Oligomers and polymers. The aforementioned preference is for such polymers. It can be homopolymers and copolymers (with statistically distributed structural units) or agglomerated polymers. Its average molecular weight is 500-2 million Daltons, preferably 1000-1 million Daltons (depending on the comparison between GPC and narrow polystyrene standards). Thermoforming materials for the production of various castings, coatings and reliefs can be manufactured by the method of the present invention. The properties of the polymers produced by the method of the present invention may vary greatly depending on the monomers used. Several are characterized by high oxygen permeability, low dielectric constant, high thermal stability, and low water absorption. Others have outstanding optical properties, such as high transparency and low refractive index. For the more advanced, the low shrinkage rate is particularly noticeable. Therefore, it can be used in different technical fields. The polymer composition of the present invention has a characteristic of high viscosity to the surface of the carrier material. The coating material has the characteristics of smooth and bright surface. In terms of excellent mechanical properties, its low shrinkage, high impact strength and thermal stability are its characteristics. The more advanced, it is easy to open the mold and has high stability of the solvent. This polymer composition is suitable for the manufacture of medical appliances, implants or contact lenses; suitable for the manufacture of electronic parts; as an adhesive for lacquers; it can be used as a light-hardening composition in mold engineering or as a substrate and low energy Adhesives for surfaces (eg, Teflon, polyethylene, and polypropylene), and photopolymerizable compositions for stereolithography. The composition of the present invention can be used to produce lacquers (using photopolymerization), in which colorless, transparent or even colored materials can be used. The color material can be white or variegated pigments. Furthermore, the manufacture of various types of castings is carried out by means of thermoforming. -34- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm)---I m In----I — —-:------ I inn 1 ^ 1 ( Please read the precautions on the back before filling in this page) A7 B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () The invention can be hardened with light or with light and heat hardened composition, which is particularly suitable for protective layer and Manufacture of relief statues. Another subject of the present invention is various methods for manufacturing the coating material and the relief statue on the substrate by the method of the present invention. These methods are to coat a layer of cycloolefin, catalyst and (sometimes) solvent composition on a carrier, For example, use the immersion method, smear method, casting method, extrusion method, scraping method, remove the solvent if necessary, and irradiate the coating with light for polymerization, or irradiate the coating through a photomask, and then irradiate the unexposed The part is removed with a solvent. The surface of the substrate can be modified or protected by this method, or used to manufacture printed circuits, printed boards or printing cylinders. When manufacturing printed circuits, the polymer composition of the present invention can be used as a solder retarder (Lotstopplacke). Other possible uses are the manufacture of mesh printing masks, which can be used as radiation-curable printing pigments (lithography, mesh printing and Flexodruck). Another subject of the present invention is a carrier material which can be coated with the oligomer or polymer produced by the present invention and contains a reticulated polymerizing agent. Another subject of the present invention is a carrier material which can be coated with the oligomer or polymer produced by the present invention and contains a reticulated polymerizing agent. This material is suitable for the production of protective layers or reliefs (through irradiation and subsequent layer development with solvents). Suitable reticulated polymerizer content, for example, 0.001-20% by weight, is mainly organic bis-azide, especially commercially available 2,6-bis (4-azidobenzylidene> 4 -Methyl-cyclohexanone. Another subject of the present invention is a coated carrier material, characterized in that a substrate is coated with a) a layer of at least one cyclocane and b) a catalytic amount of thermally stable titanium (IV) Compounds (containing at least two metal-bound methyl groups or -35- The paper size is applicable to China National Standard Falcon (CNS) M specifications (210X 297mm) (Please read the precautions on the back before filling this page ) Installed., Tr A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention () Two mono-substituted methyl groups whose substituents do not contain hydrogen atoms in position). Suitable carrier materials are, for example, glass, minerals, ceramics, artificial materials, wood, semi-metals, oxidized metals and metal nitrides. The thickness of the coating is mainly determined by the desired application, for example, from 001 to 1000 township, preferably 005-500 sound, the best. The coating material is characterized by its adhesion and excellent thermal and mechanical properties. The production of the coating material of the present invention can be carried out by a known method, for example, painting with a rubber squeegee, and casting methods such as curtain casting or centrifugal casting. If photo-substituted polymerized cyclic hydrocarbons are used, a better coating result will be produced. The cyclic olefin contains 1-3, preferably 1 double bonds, and in the present invention is a polycyclic condensation ring system. The following example further illustrates the method of the present invention. Examples 1 to 7: Polymerization of cycloolefins. Place the catalyst in the solvent in a shaker. Then inject the cycloolefin into the same solvent and close the shake tube. This mixture was irradiated with light while stirring. After 60 seconds, catalyst B was used to observe the rise of its viscosity. After reaching the reaction time shown in Table 1, the reaction mixture was poured into 100 ml of ethanol. The precipitated polymer was filtered out, washed with ethanol, and then dried in vacuum. The polymer is separated by gel permeation chromatography [GPC; tetrahydrofuran solvent, the molecular weight and the weight average (Mw) figures will be determined relative to polystyrene-g ten-volume standard] and 1H-NMR (Bruker 300 MH2; solvent CDCI3) Characterize. In the same experiment (but without light irradiation), there was no increase in viscosity at 45 ° C, and there was no precipitation of polymer after the addition of ethanol. -36 · This paper scale is applicable to China National Standard (CNS) Α4 specification (210X 297mm) (please read the precautions on the back before filling this page)

、 1T 315374 A 7 B7 V. Description of the invention () Add the following catalyst (Cp stands for the carboxyl group): A = Cp2Ti (CH3) 2 B = CpTi (CH2-C6H5) 3 C = [(CH3) 2CHO] TiCl [CH2-Si (CH3) 3] 2 Add compounds (1) and (23) as monomers. Light source used: AR-UV laser (331, 351, 364nm), 500mW / mm2 The results are listed in Table 1. Example 5 is for comparison. Printed example of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Catalyst exposure time Placement time / yield 1 3 mg A 20 minutes 96 hours 5 (TC 17% 2 3 mg A 20 minutes 96 hours 50 ° C 19% 3 3 mg A 20 50 ° C 12% 4 10 mg A in 96 hours 10 minutes 14 hours 50 ° C 21% 5 10 mg A… 6 3 mgB 6 minutes 96 hours 50 ° C 15% 7 3 mgB 6 minutes 48 hours 50 ° C 100% 8 3 mg A — 96 hours 50 ° C ___ 9 3 mgC 5 minutes 1 small poem 50 ° c 70% 10 3 mg C… 2 hours 50 ° C ___ Molecular weight (MG) Mn = 11.8k NL = 9.8 k M , = 11.4 k Ma = 1.65 k 4.8 k: 15 k Monomer: 500 mg in Examples 1-3 and 8-10 ⑴; 100 mg in Examples 4 and 5 (23); 600 mg in Examples 6 and 7 (1) Solvent: 3 ml of toluene in Example 1; 3 ml of hexane in Example 2; 3 ml of diethyl ether in Example 3; 1 ml of Tetrahydrofuran in Examples 4 and 5; in Examples 6, 7, 9, and 10 Toluene 6ml; • 37 · The paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm) --------- < Pack— (please read the precautions on the back before filling this page)

. • IT A7 B7 Fifth, the description of the invention () Irradiation and storage time at 25 ° C: before processing MG: molecular weight (GPC, g / mol) (please read the precautions on the back before filling in this page) Central Ministry of Economic Affairs Printed by the Staff Consumer Cooperative of the Bureau of Standards-38- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

Patent application scope 1. A photocatalytically induced cycloolefin of one of formula (Π), (ΠΙ>, (IV) or (V) or at least two of formula (II), (ΠΙ), (IV) or (V) Ring-opening replacement polymerization method for different cyclic olefins, Χ3 (Π), where Χ3 is -CHRI6-, oxygen or sulfur; and R15 is independent of each other, is hydrogen, -CN (CH3> 3Si- or -COOR17; and trifluoromethyl, (CH3) 3Si-0-R16 and R17 Independent of each other, hydrogen, cvc12 alkyl, phenyl or benzyl; X * (ΙΠ),. I binding (please read the precautions on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 8 where X4 is -CHR19-, oxygen or sulfur; hydrogen, CrC12 Group, phenyl or benzyl group; and R18 is ammonia, Ci-Ce group or D group; Xs Among them, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 315374 A8 B8 C8 D8 Patent scope X5 is -CHR22-, oxygen or sulfur; R22 is hydrogen, CrC12, phenyl or benzyl ; R2. And R21 are independent of each other, and are hydrogen, -CN, trifluoromethyl, (CHASi-O- (CH3) 3Si- or -COORD; and R23 is hydrogen, (VCu courtyard, phenyl or benzyl; 〇 0 (V), printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economy where Xβ is -CHRm-, oxygen, or sulfur; R24 is hydrogen, CrCu, phenyl, or benzyl; Y is oxygen or / N-R25 , And r25 is hydrogen, methyl, ethyl or phenyl. The polymerization method is carried out in the presence of a metal compound catalyst of formula (\ ^ 111) with a fraction of 0.001 to 20 moles of cycloolefin content, «42 R41 where There are at least two bases of formula (VII) -CH2-R (VII) in R39 to R »2, where II — ^ is packed with II I (please read the precautions on the back before filling in this page). Printed using the Chinese National Standard (CNS) A4 specification (210X297mm) 315374 A8 B8 C8 D8 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 6. The patent application scope R is Η, -SiR29R3〇R31 or it has not been replaced or has been replaced C6-C16 aryl substituted with CrC6 alkyl or CrC6 alkoxy; R29, Rso, and R31 are independent of each other, and are CVC ^ courtyard groups; and the remaining groups of R39 to R3 are independent of each other, and are R320 · or carboxyl; wherein R32 is Straight-chain or branched-chain CrC18 base, the method is characterized by the cycloolefin, at least a pair of thermal stability of a catalytic amount of formula (VII I) in the presence of Ti (IV) compounds, irradiated with light; or a catalytic amount of at least one pair of thermally stable Ti (IV) compounds of formula (Vffl), sometimes irradiated with light in an inert solvent, It is then mixed with at least one cyclic olefin. 2. A photo-catalyzed ring-opening displacement polymerization and follow-up heating polymerization such as a cyclic olefin of formula (Π), (ΙΠ), (IV) or (V) of the first item of the patent application scope or as the patent application scope The method of at least two different cyclic olefins in the formula (II), (ΠΙ), (IV) or (V) of item 1, the method is based on the 0.001 to 0 mole fraction of the amount of cyclic olefins. The formula (vm) of the first item in the scope is carried out in the presence of a metal compound catalyst, which is characterized by: 1) First, cycloolefin is irradiated with light in the presence of at least a pair of thermally stable Ti (IV) compounds in a catalytic amount ; Or a catalytic amount of at least one pair of thermally stable Ti (IV) compounds, sometimes irradiated with light in an inert solvent, and then mixed with at least one cyclic olefin, and 2) then heated without light irradiation to complete polymerization. 3. The method as claimed in item 1 of the patent scope is characterized in that the R group in formula (νπ) is Η or -Si (CH3) 3. --------, installed — (Please read the precautions on the back before filling out this page) The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 8888 ABCD S15374 Yuan 4. The method as claimed in item 1 of the patent scope 'is characterized in that Ti (IV) compounds of formula (VIII) are used in velvet, wherein (1) Xin 9 to R42 are the bases of formula (VH) -CH2- R, or ⑺Xin 9 and, the radicals of formula (VII) -CH2-R 'r41 and r42, which are independently, is a methylene group or R32〇-, or (3)%, Xin and r41 are the radicals of formula (VII) -avR, r42 is a mercapto group or% 〇_, where R and R32 are as defined in item 1 of the patent application scope. 5. The method as claimed in item 1 of the patent scope is characterized in that Ti (IV) compound of formula (IXa) or (Dft) is used, ch2-r ch2-r R41—-R42 (iXa) > R -tfeC Λ R41 (] Xb), ch2-r ch2-r where R is H, -C6H5 or -Si (CrC4 alkyl) 3, and R «in formulas (IXa) and (IXb) are independent of each other, are Cl, straight chain or branched chain CrC4 oxo or alkylene. 6. The method of claim 1 is characterized by the following Ti (IV) compounds: Ti [CH2SKCH3) 3] 4, CpTi (methyl> 2 [OCH (CH3) 2], ΟρΊ ^ α ^ -αΗ ^, Ti [OCH (CH3) 2] 2 [(CH2-C6H5)] 2, CpTi (methyl) 3, Cp2Ti (CH3) 2 or Ti [CH2Si (CH3) 3] 3 [OCH (CH3)], where Cp means Mercki. II-nn I * H * Pack—1 ^ 11-I Order (please read the notes on the back before filling this page) Printed copy of the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The paper scale adopts the Chinese National Standard (CNS) A4 specification (210X297mm) »Si7 # 153T4 A8 B8 C8 D8 6. Scope of patent application 7. If the method of patent application item 1, it is used to manufacture oligomers Or polymers to make coated carrier materials. 8. If the method of patent application item 1 is used to manufacture coating materials or reliefs on a carrier, the method is to apply the olefin and the patent application item 1 The catalyst is coated on the carrier, sometimes the solvent must be removed, and the coating is irradiated with light to polymerize, sometimes heat hardened, or the coating is irradiated through light shielding, sometimes hardened by heating Chemical treatment, and then remove the unirradiated part with a solvent. -------- / install ^ ------ order ------ (please read the precautions on the back before filling in This page) The paper standard printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs conforms to the Chinese National Standard (CNS) A4 specification (210X297mm)! No ,: 丨 —Pu,