A method of obtaining a polycyclic polymer (options) and the method for attaching the ligand-acceptor of electrons to the terminal site of the polycyclic polymer

 

(57) Abstract:

The invention relates to polycyclic polymer that is used as a photoresist in the manufacture of integrated circuits. Describes how to obtain a polycyclic polymer and the method for attaching the ligand-acceptor of electrons to the terminal site of the polycyclic polymer by polymerization of a Monomeric composition containing acid photoinitiator and polycyclic polymer containing the repeating unit with side splitting under the action of acid groups. When exposed to the imaging radiation source acid photoinitiator generates acid that breaks down the side of the acid-labile group, which leads to a change of polarity of the polymer. The polymer becomes soluble in an aqueous solution of the base in places exposure to the imaging radiation source and provides transparency with respect to short-wave to the imaging radiation while simultaneously sufficient resistance to the process of reactive ion etching. 4 C. and 8 C.p. f-crystals, 17 tab., 3 Il.

Description text in facsimile form (see graphic part).

1. The method of obtaining p the IPA polycyclic monomers, one of which contains a side split under action of an acid group, in the presence of the previously prepared catalyst containing a transition metal of group VIII, characterized in that the polymerization is carried out at a ratio of monomer: catalyst from 50000:1 to 50:1, as a catalyst choose compound represented by formula

EnM(Q)f(Rz)g,

where M is a transition metal of group VIII;

Q is a ligand-acceptor of electrons, which is chosen from the group comprising normal or branched group (C1-C10) perhalogenated, (C7-C24) perhalogenated and perhalogenated;

n is an integer 0, 1, 2 or 3;

f is an integer 1, 2 or 3;

g is an integer of 0 or 1;

if f= 1, there must be a group, Rz; and E, if present, are selected from the group including monodentate or bidentate ligands, and mentioned monodentate ligand selected from the group comprising arena; ethers and thioethers of the formula Ri-O-Riand Ri-S-Riwhere Rimay be the same or different meaning and presents a normal or branched (C1-C10) alkyl group; groups RCSOs ring, containing from 4 to 8 carbon atoms; cyclic ethers containing from 3 to 6 carbon atoms; ketones represented by the formula, Ri-C(O)-Riwhere substituent Ridefined above; substituted or unsubstituted cyclic ketones containing from 5 to 8 carbon atoms, where said substituents are selected from normal or branched (C1-C10) alkyl and (C6-C24) aryl groups; amines of the formula N(Rd)3where Rdindependently represented by a normal or branched (C1-C10) alkyl, (C7-C10) arallel, (C6-C24) aryl, and cycloaliphatic groups containing from 5 to 8 carbon atoms, where the above-mentioned alkyl, aryl and cycloaliphatic substituents on the selection contain halogen atoms selected from chlorine, bromine, fluorine and iodine; pyridine and substituted pyridine containing normal and branched (C1-C10) alkyl groups; phosphines of the formula P(Rd)3; phosphine oxides of the formula (Rd)3RO; phosphites of the formula P(ORd)3where Rdin each of the formulas, phosphine, phosphine oxide and phosphite defined above; ester compounds of formula RiC(O)ORiwhere Ridefined above; LACT is lactoovo ring contains from 3 to 8 carbon atoms, as mentioned bidentate ligand selected from the group hemilabile chelate ligands containing phosphorus, oxygen, nitrogen and sulfur, represented by formula

< / BR>
where Y and Z independently denote phosphorus, oxygen, carbonyl, nitrogen, and sulfur, which substituted choice of normal and branched (C1-C10) alkyl and (C6-C24) aryl groups, and means To balance unsubstituted or substituted hydrocarbon chain containing from 2 to 25 carbon atoms, or a divalent residue alkalinous simple ether, where alkylene radicals independently contain from 1 to 10 carbon atoms, and said substituents, if present, is chosen from the group comprising normal and branched (C1-C10) alkyl, (C5-C15) alicyclic and (C6-C24) aryl groups, Halogens, and amine, and Rzis a substituted or unsubstituted allyl ligand represented by the formula

< / BR>
where R20, R21and R22independently mean hydrogen, normal or branched (C1-C5)alkyl, (C6-C14)aryl, (C7-C10)kalkilya group,

such as benzyl, -COOR38, -(CH2)nOR38, Cl and (SS5)alkyl group, and n is from 1 to 5, and any two of the substituent R20, R21and R22can be joined together with formation of an alicyclic group, and the aforementioned polycyclic monomers represented by the formula

< / BR>
< / BR>
where R1-R4independently represented by the substituents, which are selected from the group comprising -(A)n-C(O)OR*, -An-OCH2C(O)OR*, -(A)n-C(O)O-A'-OCH2C(O)OR SIG*, -(A)n-OC(O)-A'-C(O)OR*, -(A)n-C(R)2CH(R)(C(O)OR*, and -(A)n-C(R)2CH(C(O)OR SIG*)2where n is 0 or 1; m is an integer from 0 to 5; and-And - and-And' independently represent a bivalent radical selected from the group consisting of normal and branched (C1-C10) alkylene, (C2-C10) alkilinity ethers, polyethers, or a cyclic group of formula

< / BR>
moreover, a is an integer from 2 to 7;

R* represents an acid-labile group which is cleaved under the action of motocicletas initiator selected from the group consisting of-C(CH3)3, -Si(CH3)3, -CH(Rp)OCH2CH3, -CH(Rp)OS(CH3)3or the following cyclic groups:

< / BR>
< / BR>
< / BR>
< / BR>
where Rpmeans hydrogen or a normal or RA is ctionality substituents, which is selected from the group comprising -(A)n-C(O)OR", -(A)n-OR", -(A)n-OC(O)R", -(A)n-OC(O)OR", -An-C(O)R", -An-OC(O)-C(O)OR",

(A)n-O-A'-C(O)OR", -(A)n-OC(O)-A'-C(O)OR", -(A)n-C(O)O-A'-C(O)OR", -An-C(O)-A'-OR", -(A)n-C(O)O-A'-OC(O)OR", -(A)n-C(O)O-A'-O-A'-C(O)OR", -(A)n-C(O)O-A'-OC(O)C(O)OR", -(A)n-C(R')2CH(R") C(O)OR") and -(A)n-C(R')2CH(C(O)OR")2where n is 0 or 1; p is an integer from 0 to 5, a R" represents a Deputy chosen from the group comprising normal and branched (C1-C10) alkoxyalkyl, polyethers, monocyclic and polycyclic (C4-C20) cycloaliphatic residues, cyclic ethers, cyclic diesters, cyclic ketones, and cyclic esters (lactones), provided that if R" means a lactone, cycloaliphatic or cyclic ketone, there must be a group-And-non alkilinity radical.

2. The method according to p. 1, wherein M is chosen from the group comprising Nickel, palladium, platinum, iron, rhodium and cobalt; Q is chosen from the group of ligands, including trifluoromethyl, pentafluorophenyl, pentachlorophenyl, pentabromophenyl, 2,4,6-Tris(triptoreline), and E is chosen from the group comprising benzene, toluene and mesites, the tetrahydrothiophene, dioxane, acetone, methyl ethyl ketone and methylvinylketone, pyridine, trialkyl, theperformance and triarylphosphine, phosphites P(ORd)3and phosphine oxides (Rd)3RO, ethyl acetate, propiolactone and-butyrolactone, and allyl.

3. The method according to p. 1, characterized in that the said catalyst is chosen from the group comprising bis(2,4,6-Tris(triptoreline))Nickel, (toluene)bis(perftoralkil)Nickel, (mesitylene)bis(perftoralkil)Nickel, (benzene)bis(perftoralkil)Nickel, bis(tetrahydrofuran) bis(perftoralkil)Nickel, (dimethylethoxysilane)bis(perftoralkil)Nickel, (dimethoxyethane)bis(2,4,6-Tris(triptoreline))Nickel, bis(dioxane) bis(perftoralkil)Nickel, bis(diethyl ether)-bis(perftoralkil)Nickel, (methallyl)Nickel(pentafluorophenyl)(three-phenylphosphine), (methallyl)Nickel(pentafluorophenyl)(tricyclohexyl-phosphine) and the compound [Ni(C6F5)2Cl]22-.

4. The method according to p. 3, characterized in that the ratio of monomer:catalyst is from 2000:1 to 50:1.

5. The method according to p. 4, characterized in that the reaction composition further comprises a system of mixed solvents comprising two-component solvent system containing non-polar uglevodorodnyi solvent: polar organic solvent is in the range from 75:25 to 25:75 (wt./wt.).

6. The method according to p. 5, characterized in that the monomer concentration in the solvent is in the range from 5 to 50 wt.%.

7. The method according to p. 6, characterized in that the ratio of monomer:catalyst is in the range from 500:1 to 100:1, and the concentration of monomer in the solvent is in the range from 10 to 30 wt.%.

8. A method of obtaining a polycyclic polymer comprising the polymerization of Monomeric reactive composition containing at least two types of polycyclic monomers, one of which contains a side split under action of an acid group, in the presence of a transition metal, characterized in that the polymerization is carried out at a ratio of monomer:catalyst from 50000: 1 to 50:1, as the transition metal is chosen metal ion of group VIII, group IVB, group VA, group VB, and group of the lanthanides and the compound containing the transition metal which is selected from the group of compounds of formula (C6X5)2ZnLig, where X is a halogen selected from the group comprising fluorine, bromine and chlorine, a Lig means essential ligand selected from the group comprising dimethyl ether (DME), diethyl ether, methyl tert-butyl ether, glyme, diglyme, trislim, tetralin, Tris(perftoralkil)boron, Tris(per the practical monomers represented by the formula

< / BR>
< / BR>
where R1-R4independently represented by the substituents, which are selected from the group comprising -(A)n-C(O)OR*, -An-OCH2C(O)OR*, -(A)n-C(O)O-A'-OCH2C(O)OR*, -(A)n-OC(O)-A'-C(O)OR*, -(A)n-C(R)2CH(R)(C(O)OR*, and -(A)n-C(R)2CH(C(O)OR*)2where n is 0 or 1; m is an integer from 0 to 5; and-And - and-And'- independently represents a bivalent radical selected from the group consisting of normal and branched (C1-C10) alkylene, (C2-C10) alkilinity ethers, polyethers, or a cyclic group of formula

< / BR>
moreover, a is an integer from 2 to 7; R* represents an acid-labile group which is cleaved under the action of motocicletas initiator selected from the group consisting of-C(CH3)3, -Si(CH3)3, -CH(Rp)OCH2CH3, -CH(Rp)OS(CH3)3or the following cyclic groups:

< / BR>
< / BR>
< / BR>
< / BR>
where Rpmeans hydrogen or a normal or branched (C1-C5)alkyl and R5-R8independently are lateral polar functional substituents that are selected from the group comprising -(A)n-C(O)OR", -(A)n-OR", -(A)n-OC(O)R", -(A)n-OCA'-OR", (A)n-C(O)O-A'-OC(O)OR", -(A)n-C(O)O-A'-O-A'-C(O)OR", -(A)n-C(O)O-A'-OC(O)C(O)OR", -(A)n-C(R')2CH(R") C(O)OR") and -(A)n-C(R')2CH(C(O)OR")2where n is 0 or 1; p is an integer from 0 to 5, a R" represents a Deputy chosen from the group comprising normal and branched (C1-C10) alkoxyalkyl, polyethers, monocyclic and polycyclic (C4-C20) cycloaliphatic residues, cyclic ethers, cyclic diesters, cyclic ketones, and cyclic esters (lactones), provided that if R" means a lactone, cycloaliphatic or cyclic ketone, there must be a group-And-non alkilinity radical.

9. The method according to p. 8, characterized in that the compound of the metal of group VIII selected from the following group: ethylhexanoate, palladium, TRANS-dl2(h3)2, bis(triptorelin)palladium (II) bis(acetylacetonate) palladium (II) 2-ethylhexanoate, palladium (II), PD(acetate)2(h3)2, bromide, palladium (II) chloride, palladium (II) iodide, palladium (II), monoclonal-Tris(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine) pbis(dimethylsulfoxide)dichloride, palladium, the Nickel acetylacetonates, Nickel carboxylates, Nickel dimethylglyoxime, Nickel ethylhexanoate, NiCl2(h3)2, NiCl2(PPh2CH2)2, (P(cyclohexyl)3)Ni(PH2P(C6H4)CO2), (h3)(C6H5)Ni(PH2RSN= C(O)PH),

bis(2,2,6,6-tetramethyl-3,5-heptanedionato) Nickel (II), hexafluoroacetylacetonate tetrahydrate Nickel (II), cryptorchidectomy the dihydrate, Nickel (II) acetylacetonate tetrahydrate Nickel (II), nickelocene, acetate Nickel (II), Nickel bromide, Nickel chloride, Nickel lactate, tetracarbonyl Nickel, bis(allyl)Nickel, bis(cyclopentadienyl) Nickel, neodecanoate cobalt acetate cobalt (II) acetylacetonate, cobalt (II) acetylacetonate, cobalt (III) benzoate, cobalt (II), cobalt chloride, bromide cobalt, dichloracetate cobalt stearate, cobalt (II), tetrafluoroborate cobalt (II), iron naphthenate, iron chloride (II) chloride iron (III) bromide, iron (II) bromide iron (III) acetate, iron (II) acetylacetonate Fe (III), ferrocene, rhodium chloride and Tris(triphenylphosphine)trichloride rhodium.

10. A method of obtaining a polycyclic polymer comprising the polymerization of Monomeric reactive composition containing polycyclic(s) monomer(s), PR is the, the polymerization is carried out at a ratio of monomer: catalyst from 50000:1 to 50:1, as a catalyst choose compound represented by formula

EnM(Q)f(Rz)g,

where M is a transition metal of group VIII;

Q is a ligand-acceptor of electrons, which is chosen from the group comprising normal or branched group (C1-C10) perhalogenated, (C7-C24) perhalogenated and perhalogenated;

n is an integer 0, 1, 2 or 3;

f is an integer 1, 2 or 3;

g is an integer of 0 or 1;

if f is 1, there must be a group, Rzand, if present, are selected from the group including monodentate or bidentate ligands, and mentioned monodentate ligand selected from the group comprising arena; ethers and thioethers of the formula Ri-O-Riand Ri-S-Riwhere Rimay be the same or different meaning and presents a normal or branched (C1-C10) alkyl group; groups Riattached to the heteroatom of oxygen or sulfur, can be combined to form heterocyclic rings containing from 4 to 8 carbon atoms; cyclic ethers, Staropramen above; substituted or unsubstituted cyclic ketones containing from 5 to 8 carbon atoms, where said substituents are selected from normal or branched (C1-C10) alkyl and (C6-C24) aryl groups; amines of the formula N(Rd)3where Rdindependently represented by a normal or branched (C1-C10) alkyl, (C7-C10) arallel, (C6-C24) aryl, and cycloaliphatic groups containing from 5 to 8 carbon atoms, where the above-mentioned alkyl, aryl and cycloaliphatic substituents on the selection contain halogen atoms selected from chlorine, bromine, fluorine and iodine; pyridine and substituted pyridine containing normal and branched (C1-C10) alkyl groups; phosphines of the formula P(Rd)3; phosphine oxides of the formula (Rd)3RO; phosphites of the formula P(ORd)3where Rdin each of the formulas, phosphine, phosphine oxide and phosphite defined above; ester compounds of formula RiC(O)ORiwhere Ridefined above; lactones and normal and branched (C1-C6) alkyl - and (C6-C15) aryl-substituted lactones, where lactoovo ring contains from 3 to 8 carbon atoms, and the bidentate ligand of the formula

< / BR>
where Y and Z independently denote phosphorus, oxygen, carbonyl, nitrogen, and sulfur, which substituted choice of normal and branched (C1-C10) alkyl and (C6-C24) aryl groups, and means To balance unsubstituted or substituted hydrocarbon chain containing from 2 to 25 carbon atoms, or a divalent residue alkalinous simple ether, where alkylene radicals independently contain from 1 to 10 carbon atoms, and said substituents, if present, is chosen from the group comprising normal and branched (C1-C10) alkyl, (C5-C15) alicyclic and (C6-C24) aryl groups, Halogens, and amine, and Rzis a substituted or unsubstituted allyl ligand represented by the formula

< / BR>
where R20, R21and R22independently mean hydrogen, normal or branched (C1-C5)alkyl, (C6-C14)aryl, (C7-C10)kalkilya group,

such as benzyl, -COOR38, -(CH2)nOR38, Cl and (C5-C6) cycloaliphatic group, and R38is normal and branched (C1-C5)alkyl group, and n is from 1 to 5, the koi group, as mentioned polycyclic monomers represented by the formula

< / BR>
where R40, R41, R42and R43independently denote a substituted and unsubstituted hydrocarbon radical (C5-C12)cycloalkyl, or anhydride, or dicarboximido group;

-(B)n-SiR34R35R36,

where means the divalent bridging bond or spacer elements radical selected from the group comprising normal and branched (C1-C10)alkylene; n is an integer 0 or 1;

R34, R35and R36independently denote halogen, normal or branched (C1-C20) alkyl, normal or branched (C1-C20)alkoxy, substituted or unsubstituted (C6-C20)aryloxy, normal or branched (C1-C20) alkylcarboxylic and (C1-C20) alkylperoxy; -(A)n-C(O)OR", -(A)nOR", -(A)n-OC(O)R", -(A)n-OC(O)OR", -(A)n-C(O)R", -(A)n-OCH2C(O)OR*, -(A)n-C(O)O-A'-OCH2C(O)OR*, -(A)n-OC(O)C(O)OR", -(A)n-O-A'-C(O)OR", -(A)n-OC(O)-A'-C(O)OR", -(A)n-C(O)O-A'-C(O)OR", -(A)n-C(O)-A'-OR", -(A)n-C(O)O-A'-OC(O)OR", -(A)n-C(O)O-A'-O-A'-C(O)OR", -(A)n-C(O)O-A'-OC(O)C(O)OR", -(A)n-C(R')2CH(R") C(O)OR") and -(A)n-C(R')2CH(C(O)OR")10) alkyl or (C6-C15) aryl where n is 0 or 1; m is an integer from 0 to 5; and-And - and-And'- independently denote a divalent radical selected from the group comprising normal and branched (C1-C10) alkylene, (C2-C10) alkylene ethers, polyethers, or a cyclic group of the formula

< / BR>
where and is an integer from 2 to 7;

R ' means hydrogen or normal and branched (C1-C10) alkyl, -C(CH3)3, -Si(CH3)3, -CH(Rp)OCH2CH3, -CH(Rp)-OC(CH3)3,

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
where Rpmeans hydrogen or a normal or branched (C1-C5)alkyl, normal or branched (C1-C10) alkoxyalkyl, polyethers, monocyclic and polycyclic (C4-C20) cycloaliphatic residues, cyclic ethers, cyclic diesters, cyclic ketones, and cyclic esters (lactones),

if any R40-R43is succinoyl or carboxyimide residue and n is 1, And can be represented only normal or branched (C1-C10) alkalinous group.

11. The method for attaching the ligand-acceptor of electrons to copaciu polycyclic monomer of the formula

< / BR>
in the presence of a catalyst of the formula

EnM(Q)f(Rz)g,

where E, n, M, Q, f, Rz, g, R40-R43and m is defined above.

12. The method according to p. 11, characterized in that the said ligand is performanceline group.

 

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22 cl, 1 tbl, 14 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: additive copolymer 3,3,4-tris(trimethylsilyl)tricyclononene-7 and 3-trimethylsilyltricyclononene-7 of the formula (I), where n and m are the proportion of these monomeric units, Me - methyl, the weight-average molecular weight Mw=(3.5-4.5)×105 g/mol, the polydispersity index Mw/Mn=2.5-2.8, the content of 3,3,4-tris (trimethylsilyl) tricyclononene - 7 to 20 mol %. A method of producing the said copolymer and a method for separating gas mixtures using a selectively permeable membrane are also provided, the material of which is said to be an additive copolymer.

EFFECT: increasing the gas permeability of membranes on the basis of the received polymers.

3 cl, 3 dwg, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method includes at least a stage of the ethylene polymerization in the presence of a metal complex selected from the following structural formulae I

,

where M is metal of group 4 of the Periodic Table of the Elements, R1a, R1aa, R2a, R2aa, R3a, R3aa, and R4a, R4aa, R5a, R5aa, R6a, R6aa, and R7a, R7aa, R8a, R8aa, R9a, R9aa, R11a, R11aa, R12a, R12aa, R14a, R14aa, R15a, R15aa independently in each case represent a hydrogen atom, a halogen atom, hydrocarbon, each of R10a, R10aa, R13aa, and R13a independently represents (C1-C40) hydrocarbyl, X independently represents (C1-C20) hydrocarbyl, Z represents O, Y represents hydrocarbyl, L represents (C1-C40) hydrocarbilen. A polymer based on ethylene, a composition, an article, and a metal complex are also provided.

EFFECT: invention makes it possible to obtain high molecular weight polymers at lower viscosities in the reactor.

13 cl, 5 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry, specifically to a method of preparing a catalyst for metathesis polymerisation of dicyclopentadiene -[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-N,N-dimethylaminomethylphenyl methylene)ruthenium. The method involves reacting a triphenylphosphine complex of ruthenium with 1,1-diphenyl-2-propin-1-ol in tetrahydrofuran while boiling in an inert atmosphere, and then with tricyclohexylphosphine at room temperature in an inert atmosphere. The indenylidene ruthenium complex formed is separated and successively reacted in a single reactor with 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dimethylaminomethyl)styrene in toluene while heating in an inert atmosphere.

EFFECT: method increases output of product.

3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis and preparation of dicyclopentadiene metathesis polymerisation catalysts. The metathesis polymerisation catalyst has the formula: , where L is a substitute selected from the group: , , . Several methods of preparing the catalyst are disclosed. The method of preparing the catalyst having formula , where , , is characterised by that, a second generation Grubbs catalyst is reacted with N,N-dialkyl-(2-vinylbenzyl)amine or 4-(2-vinylbenzyl)morpholine in an inert atmosphere at 60-85°C in the presence of a solvent, where the dialkyl- is methylethyl- or methyl(2-methoxyethyl). The method of preparing the catalyst formula , where L is a substitute selected from the group: , , , , involves reacting a ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propyn-1-ol in tetrahydrofuran at boiling point of the solvent in an inert atmosphere and then with tricyclohexylphosphine at room temperature in an inert atmosphere. The ruthenium indenylidene complex formed is extracted and then, successively in the same reactor, reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and 2-(N,N-dialkylaminomethyl)styrene or 1-(2-vinylbenzyl)pyrrolidine or 4-(2-vinylbenzyl)morpholine in toluene while heating to 60-70°C in an inert atmosphere. The dialkyl- is diethyl-, methylethyl- or methyl(2-methoxyethyl)-. A dicyclopentadiene metathesis polymerisation method is disclosed, which involves polymerisation using the catalyst in paragraph 1 in molar ratio substrate: catalyst ranging from 70000:1 to 200000:1.

EFFECT: invention increases catalyst output and simplifies synthesis by reducing the number of steps, and also enables to obtain polydicyclopentadiene with good application properties.

4 cl, 1 tbl, 22 ex

FIELD: chemistry.

SUBSTANCE: invention describes a method of producing polydicyclopentadiene (PDCPD) by mixing diclopentadiene (DCPD) with a catalyst in molar ratio of catalyst to DCPD ranging from 1:70000 to 1:1000000 and polymerisation by heating the reaction mixture from 30°C to 200°C. Described also is a method of producing polymer materials based on PDCPD, involving further addition of modifying additives selected from cycloolefin comonomers, cyclopentadiene oligomers in form of a mixture of trimmers and tetramers, dicarboxylic acid esters, alkylphenols or combinations thereof. The catalyst used for production of PDCPD and polymer materials based on PDCPD is a compound of formula: where L is a substitute selected from the group:

, , , , , .

EFFECT: low catalyst consumption, possibility of controlling time for onset of polymerisation, improved physical and mechanical properties of the obtained product.

6 cl, 51 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organometallic chemistry, in particular to novel complexes of group 8 transition metals, which are used as polymerisation catalysts of cyclic olefins, particularly dicyclopentadiene (DCPD). The catalyst is a ruthenium complex compound of general formula (1), having ligands in form of 1,3-dimesitylimidazolidinylidene, two chlorine atoms and substituted benzylidene. The substitute in the benzylidene ligand is an amino-substituted methyl group, where the amine is a di(hydroxyalkyl)amino group, as well as piperidine. The amine-containing substitute also coordinates to the ruthenium atom and forms a six-member chelate ring where X=N (Alk-OH)2, (CH2)5N , where Alk is a straight saturated hydrocarbon chain containing 2 carbon atoms. The method of preparing the catalyst involves successive reaction in a single reactor of 1,3-dimesityl-4,5-dihydro-imidazolium chloride with potassium tert-butoxide, first generation Grubb's catalyst (GrI) and then amino-containing styrene.

EFFECT: simple technology of obtaining an efficient catalyst for metathesis polymerisation of dicyclopentadiene.

2 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel complexes of group 8 transition metals, which are used as polymerisation catalysts for cyclic olefins, particularly dicyclopentadiene (DCPD). Described is a catalyst for metathesis polymerisation of dicyclopentadiene which is a ruthenium complex compound, having ligands in form of 1,3-bis-(2,6-dimethylphenyl)-2-imidazolidinylidene, two chromium atoms and ortho-substituted benzylidene. The substitute in the benzylidene ligand is an amino-substituted methyl group, where the amine is a dialkylamino-, di(2-hydroxyethyl)amino-, alkylphenylamino-group, as well as cyclic amines, particularly piperidine and morpholine; the catalyst has general formula: , where X=(Alk)2N, N(CH2-CH2-OH)2, piperidine, morpholine, NAlkPh; Alk=CH3, C2H5; Ph is phenyl. Described also is a catalyst for metathesis polymerisation of dicyclopentadiene, which is a ruthenium complex compound having ligands in form of 1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene, two chromium atoms and ortho-substituted benzylidene. The substitute in the benzylidene ligand is an alkylphenylamino-substituted methyl group. The catalyst has general formula: Alk=CH3, C2H5; Ph=phenyl. The invention describes methods of producing polydicyclopentadiene, involving polymerisation of dicyclopentadiene in the presence of the described catalysts, as well as catalysts which are compounds of [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(2-(N,N-bis(2-hydroxyethyl)aminomethyl)benzylidene)ruthenium or a compound of [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-9piperidin-1-ylmethyl)benzylidene)ruthenium with molar ratio of monomer: catalyst ranging from 70000:1 to 250000:1.

EFFECT: reduced unit consumption of catalyst, which leads to low cost of polydicyclopentadiene, possibility of controlling the starting time of the polymerisation process.

5 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: elastomers contain at least two or more cyclic olefin monomers. Said elastomers are obtained as a result of metathesis ring-opening polymerisation in the presence of Grubbs catalyst or a metathesis ring-opening polymerisation catalyst based on ruthenium or osmium. The elastomer interpolymers are characterised by lack of crystallinity, glass transition temperature (Tg) less than 80°C, and number-average molecular weight (Mn) equal to at least 40 kg/mol. To obtain the elastomer interpolymers, characterised by lack of crystallinity, at least two cyclic olefin monomers are used, said monomers being selected from a group consisting of cyclopropene, cyclobutene, benzocyclobutene, cyclopentene, norbornene, norbornadiene, cycloheptene, cyclooctene, 7-oxanorbornene, 7-oxanorbornadiene, cyclodecene, 1,3-cyclooctadiene, 1,5-cyclooctadiene, 1,3-cycloheptadiene, [2.2.1]bicycloheptenes, [2.2.2]bicyclooctenes, cyclohexenyl norbornenes, norbornene dicarboxylic anhydrides, cyclododecene, 1,5,9-cyclododecatriene and mixtures thereof. The elastomer interpolymers are used in rubber mixtures for making covers and cores of golf balls etc.

EFFECT: invention enables to obtain elastomer interpolymers having a suitable balance between dynamic rigidity and hysteresis and satisfactory balance between collision coefficient and compression response.

22 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis and preparation of dicyclopentadiene polymerisation catalysts. Described is a polymerisation catalyst having the formula: The structure of the catalyst employs a fundamentally new L substitute which gives the catalyst new properties. Described is a method of producing the catalyst by reacting a ruthenium triphenylphosphine complex with 1,1-diphenyl-2-propyn-1-ol in tetrahydrofuran or dioxane at boiling point of the solvent in an inert atmosphere, and then with tricyclohexylphosphine at room temperature in an inert atmosphere; the formed ruthenium indenylidene complex is separated and then successively reacted with 1,3-bis-(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine and the corresponding 2-vinylbenzylamine to form the end product.

EFFECT: high output of the catalyst and obtaining polydicyclopentadiene with improved application properties.

3 cl, 26 ex

FIELD: chemistry.

SUBSTANCE: described is material (version) which contains 1-99.8 wt % polydicyclopentadiene, 0.05-0.99 wt % antioxidant selected from: sterically hindered phenols, phenol derivatives, sterically hindered amine bases, 0.05-0.99 wt % saturated or unsaturated elastomer, 0.000018-0.00010 wt % catalyst; the rest of the amount of the material is modifying additives, which can be contained both separately and together in form of their different combinations, wherein the modifying additives are selected from a group A) cyclopentene, cyclooctene, cyclooctadiene, norbornene, norbornadiene; B) cyclopentadiene trimers and/or tetramers; C) dyes; D) compounds which alter activity of the catalyst system, selected from: amines, phosphines, phosphites, phosphoramides, organoaluminium compounds; E) filler materials, selected from: chopped glass or carbon fibres with diameter of 6-17 mcm and length 4-24 m, as well as structural glass, carbon and basalt fabric with thickness of 0.20-0.87 mm and density of 250-900 g/m2; F) multi-wall carbon nanotubes with 2-20 walls and diameter of 7-30 nm. Described is a method of producing said material, which contains polydicyclopentadiene, involving mixing, in any sequence, dicyclopentadiene, catalyst, antioxidant, elastomer and modifying additives with subsequent polymeriseation of the obtained reaction mass while heating from 30 to 210°C. Described also is material (version) which contains 1-98.9 wt % polycyclopentadiene and 1-98.9 wt % "полиэндикатов", and containing an antioxidant, an elastomer, a catalyst and modifying additives, the quality and amount of which correspond to said version of the material. Described is a method of obtaining said material, which involves further addition of "полиэндикатов" to the reaction mass before polymerisation.

EFFECT: high impact viscosity and glass-transition temperature of the obtained material owing to addition of small amounts of elastomer into the reaction mass, reduced amount of antioxidant used, high rate of polymerisation and possibility of using starting material with different purity.

30 cl, 26 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer proppant material which is a metathesis-radially cross-linked mixture of oligocyclopentadienes and methylcarboxy norbornene esters. Described is a method of producing said material, which includes preparing a mixture of oligocyclopentadienes and methylcarboxy norbornene esters by cross-linking dicyclopentadiene with methacrylic esters and polymer stabilisers given in claim 2 of the invention, heating said mixture to temperature of 150-220°C and holding at said temperature for 15-360 min, followed by cooling to 20-50°C. A radical initiator and a catalyst given in claim 2 of the invention are successively added to the obtained mixture of oligocyclopentadienes and methylcarboxy norbornene esters. Further, the obtained polymer matrix is heated to temperature of 50-340°C, held at said temperature for 1-360 minutes and then cooled to room temperature.

EFFECT: high heat resistance of the proppant material.

4 cl, 36 ex

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