RU2199773C2 - Photoresist composition - Google Patents

Abstract

FIELD: light-sensitive materials. SUBSTANCE: invention provides radiation-sensitive photoresist composition containing acid photoinitiator, optionally dissolution inhibitor, and copolymer, which contains at least two itineration polycyclic motifs, one of which bears side acid-labile group and the other side polar function. When irradiated by image-forming emission source, photoinitiator releases acid cleaving side acid-labile groups giving rise to reverse of polymer polarity, as a result of which polymer acquires solubility in basic water solution in sites exposed to image-forming emission source. EFFECT: enhanced image-forming effect. 29 cl, 1 tbl, 74 ex

Description

 The invention relates to polycyclic polymers and methods for their use as photoresists in the manufacture of integrated circuits. More specifically, the invention relates to photoresist compositions comprising a polycyclic polymer and a cationic photoinitiator. A polycyclic polymer contains repeating acid-labile side groups linked to the polymer backbone. Labile groups, i.e. sensitive to the action of acids, can be selectively cleaved with the formation of repeating polar groups in the main polymer chain. The polymers are transparent to shortwave imaging radiation and are resistant to reactive ion etching.

 The prior art.

 Integrated circuits (ICs) are central to the production of electronic device arrays. They are made by sequentially forming alternating and interconnected bands of conductive, semiconductor and non-conductive layers on a suitable substrate (e.g., silicon wafer), which are selectively modeled to form circuits and interconnections in order to perform specific electrical functions. The configuration of the IP is carried out by various lithography techniques known in the art. The main and important technological method in the manufacture of IC devices is photolithography using ultraviolet (UV) radiation and radiation from deep penetrating UV light or using other radiation. A photosensitive polymer layer (photoresist) is applied to the surface of the plate and dried. Then, a photomask containing the desired information in the form of a picture is placed close to the photoresist film. The photoresist is irradiated through the photomask layer with one or more types of imaging radiation, including UV radiation, electron radiation, x-ray radiation, or ion radiation. Under the influence of radiation, the photoresist undergoes chemical changes, leading to a change in its solubility. After irradiation, the plate is immersed in a solution showing a pattern on a photosensitive polymer film (i.e., selectively removing either the exposed or unexposed zones). Depending on the type of polymer used or the polarity of the developing solvent, either the exposed or unexposed areas of the film with the opening of the substrate below are removed during the development process, after which the opened or undesired substrate material with the applied configuration is removed or changed during etching while maintaining the desired pattern in the functional layer plates. Apply plasma etching, spray etching and reactive ion etching (RIT). The remaining photoresist material acts as a protective barrier during the etching process. Removing the remaining photoresist material results in printed patterns.

 In the manufacture of devices containing an IP pattern, the most critical stage is the etching of various layers on the wafer. One of the methods is immersion of the substrate and the patterned resist in a chemical bath in which the exposed surface of the substrate is exposed while the resist itself is intact. The disadvantage of such a wet chemical process is the difficulty in achieving well-defined edges on etched surfaces. This is due to chemical etching of the resist material and the formation of an isotropic image. In other words, a conventional chemical process does not provide directional selectivity (anisotropy), which is considered necessary to achieve optimal functionally specified sizes that meet existing technological requirements. In addition, a wet process leads to undesirable environmental and safety effects.

 To overcome the disadvantages of a wet chemical process, various "dry" processes have been proposed. Such dry processes include passing gas through the chamber and ionizing the gas by applying a potential difference between the two electrodes in the presence of gas. Plasma containing an ionized substance generated by generating voltage is used to etch a substrate placed in the chamber. The ionized substance generated in the plasma is directed onto an open substrate, where it interacts with the surface of the material to form volatile products that are removed from the surface. Typical examples of dry etching are plasma etching, spray etching and reactive ion etching.

 Reactive ion etching provides the formation on the substrate of profiles with well-defined vertical side walls, as well as uniform etching from substrate to substrate. Thanks to these advantages, reactive ion etching has become standard in IP manufacturing.

 Two types of photoresists are used in industry: negative and positive photoresists. Negative resists after exposure to imaging radiation polymerize, crosslink, or alter the solubility so that the irradiated regions become insoluble with respect to the developing solution. Non-irradiated areas remain soluble and washed out. Positive resistes act in the opposite way, acquiring solubility in the developing solution after exposure to imaging radiation.

 The basis of one of the types of positive resistive material are novolac phenol-formaldehyde polymers. A specific example is the Shipley AZ 1350 material used in industry, containing novolac m-cresol formaldehyde polymer composition and diazoketone (2-diazo-1-naphthol-5-sulfonic acid ester). When irradiated with imaging radiation, the diazoketone is converted to a carboxylic acid, which in turn converts the phenolic polymer into a polymer readily soluble in the developing aqueous solution of a weak base.

 US Pat. No. 4,491,628, issued to Ito et al., Describes positive and negative photoresist compositions containing acid-generating photoinitiators and polymers with acid labile side groups (i.e., acid-cleaving). Since each acid generated removes the protection in the form of a multitude of acid-cleaving groups, this approach is known as chemical amplification, which serves to increase the quantitative yield of the overall photochemical process. Described polymers include vinyl polymers, such as polystyrenes, polyvinyl benzoates and polyacrylates, substituted by repeating side groups susceptible to acidolysis to obtain products that differ in solubility from their predecessors. Preferred acid labile groups include tert. butyl esters of carboxylic acids and tert. butyl phenol carbonates. Depending on the nature of the developing solution used, positive or negative photoresists can be obtained.

 Trends in the development of the electronics industry continuously require ICs that are faster and use less energy. To meet these requirements, smaller ICs must be manufactured. Conducting lines (i.e., communication lines) should be thinner and placed closer to each other. A significant reduction in the size of transistors and lines contributes to an increase in the efficiency of ICs, for example, an increase in the amount of stored information and the speed of microcircuits. To achieve a finer line of the IP element, a higher image resolution is needed. Higher image resolution is possible with a shorter wavelength of the source used to irradiate the photoresist material. However, photoresists previously known in the art, such as novolac phenol-formaldehyde polymers and substituted styrene polymers, contain aromatic groups that by their nature become more optically dense at a light wavelength of less than about 300 nm (AXO Symposia Series 537, Polymers for Microelectronics, Resistors and Dielectrics , 203rd National Congress of the American Chemical Society, April 5-10, 1992, pp. 2-24; Polymers for use in electronics and photonics, edited by S.R. Wong, Academician Press, p.67-118 - ACS Symposium Series 537, Po lymers for Microelectronics, Resists and Dielectrics, 203-rd National Meeting of the American Chemical Society, 1992, April 5-10, p. 2-24; Polymers for Electronic and Photonic Applications, Edited by CP Wong, Academic Press, p. 67 -118). Sources with a shorter wavelength are usually less bright than traditional sources requiring chemical amplification using photoacids. The opacity of aromatic polymers with respect to light with a short wavelength is a disadvantage, since under the surface of the polymer, the photoacids are irregularly irradiated by the light source and, as a result, the polymer does not appear. To overcome the insufficient transparency of these polymers, the aromatic content in the photoresist polymers should be reduced. If transparency is required with respect to deep UV radiation (i.e., irradiation with a wavelength of 248 nm and, especially, 193 nm), the aromatic content in the polymer should be minimal.

 US Pat. No. 5,372,912 relates to a photoresist composition comprising an acrylate copolymer, a phenolic binder and a photosensitive acid generator. Acrylate copolymer is a product of the copolymerization of acrylic acid, alkyl acrylate or methacrylate and a monomer containing a lateral labile acid group. While the composition is sufficiently transparent with respect to UV radiation at a wavelength of about 240 nm, the use of an aromatic binder limits the use of radiation sources with a shorter wavelength. As is known in the polymer field, an improvement in one property is usually achieved through another property. When using acrylate polymers, an increase in transparency with respect to UV radiation with a shorter wavelength is achieved by reducing the resistance of the resist with respect to reactive ion etching.

 In many cases, improved transparency with respect to imaging short-wave radiation leads to erosion of the resist material in the subsequent dry etching process. Since photoresist materials are usually organic in nature, and the substrates used in the manufacture of ICs are usually inorganic, the photoresist material by its nature has a higher etching rate than the substrate material using reactive ion etching (RIT) technology. In this case, there is a need for a photoresist material of a greater thickness than the substrate located below. Otherwise, the photoresist material will be removed during erosion before the etching of the underlying substrate is completely completed. It follows that the resistive material with a lower erosion rate can be used in the form of thinner layers on the surface of the substrate to be etched. Thinner layers of resistive material make it possible to achieve a higher resolution, which ultimately allows one to achieve narrower conductive lines and smaller transistors.

 J.V. Crivello et al. (Chemically Amplified Electron-Beam Photoresists, Chem. Mater., 1996, 8, p. 376-381) describe a polymer mixture containing 20 wt.% Obtained from free radical polymerization of a norbornene homopolymer containing acid labile groups and 80 wt.% homopolymer of 4-hydroxy-alpha-methylstyrene containing acid-labile groups, intended for use in electron beam photoresists. As indicated by the authors, the increased optical density of aromatic groups (especially at high concentrations) gives these compositions opacity and makes them impossible to use when irradiated with imaging short-wave radiation with a wavelength of less than 200 nm.

 The described compositions are suitable only for electron beam photoresists and cannot be used to form images using deep UV radiation (especially for resistes with a wavelength of 193 nm).

 Crivello et al. they used mixed compositions because they found that oxygen plasma had an etching rate that was unacceptably high for homopolymers by free-radical polymerization of norbornene monomers containing acid labile groups.

 Therefore, there is a need for photoresist compositions that are compatible with the general scheme of chemical amplification and provide transparency with respect to the short-wavelength imaging radiation with sufficient resistance to reactive ion etching conditions.

SUMMARY OF THE INVENTION
The main technical objective of the invention is the creation of a photoresist composition containing a polycyclic polymer, the main chain of which contains side acid labile groups, and a photoinitiator.

 Another technical objective of the invention is the creation of polycyclic polymers having repeating acid-labile side groups that can be split to form polar groups.

 Another objective of the invention is the creation of polymer compositions that are transparent with respect to imaging short-wave radiation.

 The next technical task of the invention is the creation of polymer compositions that are resistant to the process of dry etching.

 Another objective of the invention is the creation of polymer compositions that are transparent with respect to imaging short-wave radiation and resistant to the process of dry etching.

 Another objective of the invention is the creation of polycyclic monomers containing acid-labile side groups capable of polymerizing to form polymers that can be manifested in aqueous solutions of the base.

 These and other technical objectives of the invention are achieved by polymerization of a reaction mixture containing a polycyclic monomer with functional acid labile groups, a solvent, a one- or multicomponent catalyst system containing a source of metal ions of group VIII of the Periodic system. In the multi-component catalyst systems of the invention, a Group VIII metal ion source is used in combination with one or two organometallic cocatalysts and a third component. Single and multicomponent catalyst systems can be used with an optimal chain transfer agent (APC) selected from compounds having a terminal olefinic double bond between adjacent carbon atoms, where at least one of these adjacent carbon atoms contains two atoms associated with it hydrogen. APCs are selected from unsaturated compounds, which are usually not capable of cationic polymerization, and therefore styrenes, vinyl ethers and conjugated dienes are excluded.

 The resulting polymers are used in photoresist compositions, including a radiation-sensitive acid generator.

Information confirming the possibility of carrying out the invention
The present invention relates to a radiation sensitive resist composition comprising an acid generating initiator and a polycyclic polymer containing repeating acid-labile side groups along the main polymer chain. The composition containing the polymer and the initiator is applied to the substrate in the form of a thin film, dried under controlled conditions, irradiated according to the simulated pattern configuration, and, if necessary, additionally dried under controlled conditions to facilitate further deprotection. In those places of the film that was irradiated, the repeating acid-labile side groups (i.e., those sensitive to the action of the acid) of the polymer chain are split to form repeating polar groups. The irradiated areas treated in this way are selectively removed by a developing alkaline solution. Alternatively, the non-irradiated sites of the polymer remain non-polar and can be selectively removed by treatment with an appropriate non-polar solvent for negative effects. Inversion of the image can be easily achieved by the appropriate choice of the developing solution due to the difference in solubility of the irradiated and unirradiated parts of the polymer.

Простейшим полициклическим мономером по изобретению является бициклический мономер бицикло[2.2.1] гепт-2-ен, обычно известный как нонборнен. В одном варианте воплощения изобретения функциональные кислотно-лабильные группы вводят в полимерную цепь полимеризацией реакционной смеси, содержащей один или более полициклических мономеров с кислотно-лабильными заместителями, приведенных ниже под формулой I, в случае необходимости, в сочетании с одним или более полициклическим мономером, представленных ниже под формулами II, III, IV и V, в присутствии каталитической системы металла группы VIII Периодической системы.The polymers of the present invention contain repeating units, some of which are substituted by acid labile groups. These polymers are prepared by polymerizing polycyclic monomers according to the invention. By the term “polycyclic” (such as norbornene or functional norbornene) is meant a monomer containing at least one portion of nonbornene, as shown below:

The simplest polycyclic monomer of the invention is the bicyclic monomer bicyclo [2.2.1] hept-2-ene, commonly known as nonbornene. In one embodiment of the invention, the functional acid labile groups are introduced into the polymer chain by polymerization of a reaction mixture containing one or more polycyclic monomers with acid labile substituents shown below under Formula I, optionally in combination with one or more polycyclic monomers represented below under formulas II, III, IV and V, in the presence of a catalytic system of a metal of group VIII of the Periodic system.

 Another embodiment of the invention is the copolymerization of one or more substituted polycyclic monomers of formula I containing acid labile substituents with one or more polycyclic monomers represented by formula II.

где R¹, R², R³, R⁴ независимо представляют собой заместители, выбранные из группы: -(A)_n-C(О)OR^*, -(A)_n-C(О)OR, -(A)_n-OR, -(A)_n-OC(О)R, -(A)_n-C(О)R, -(A)_n-OC(О)OR, -(A)_n-OCH₂C(О)OR^*, -(A)_n-C(О)О-A'-0(CH₂)C(О)OR^*, (A)_n-OC(О)-A'-C(О)OR^*, -(A)_n-C(R)₂CH(R)(C(О)OR^**) и -(A)_n-C(R)₂CH(C(О)OR_**)₂, при условии, что, по крайней мере, один из заместителей R¹-R⁴ выбирают из кислотно-лабильных групп -(A)_nC(О)OR^*. А и А' независимо представляют двухвалентную мостиковую связь или спейсерный радикал, которые выбирают из группы, включающей двухвалентные углеводородные радикалы, двухвалентные циклические углеводородные радикалы, двухвалентные радикалы, содержащие кислород, двухвалентные циклические простые эфиры и циклические простые диэфиры, а n является целым числом, равным 0 или 1. Если n равно 0, то очевидно, что А и А' являются простой ковалентной связью. Термин "двухвалентный" означает, что на каждом конце радикала имеется свободная связь, к каждой из которых присоединены две различные группы. Двухвалентные углеводородные радикалы могут быть представлены формулой -(С_dН_2d)-, где d является числом углеродных атомов в алкиленовой цепи и равно целому числу от 1 до 10. Двухвалентные углеводородные радикалы предпочтительно выбирают из нормальных или разветвленных (С₁-С₁₀) алкиленов, таких как метилен, этилен, пропилен, бутилен, пентилен, гексилен, гептилен, октилен, нонилен и децилен. Если рассматривается разветвленный алкиленовый радикал, следует понимать, что атом водорода в нормальной алкиленовой цепи замещен на нормальную или разветвленную (С₁-С₅) алкильную группу.Monomers
The polycyclic acid labile monomers used in the invention are selected from monomers having the following formula:

where R ¹ , R ² , R ³ , R ⁴ independently represent substituents selected from the group: - (A) _n -C (O) OR ^* , - (A) _n -C (O) OR, - (A) _n -OR, - (A) _n -OC (O) R, - (A) _n -C (O) R, - (A) _n -OC (O) OR, - (A) _n -OCH ₂ C ( O) OR ^* , - (A) _n -C (O) O-A'-0 (CH ₂ ) C (O) OR ^* , (A) _n -OC (O) -A'-C (O) OR ^* , - (A) _n -C (R) ₂ CH (R) (C (O) OR ^** ) and - (A) _n -C (R) ₂ CH (C (O) OR _** ) ₂ , provided that at least one of the substituents R ¹ -R ^{4 is} selected from acid labile groups - (A) _n C (O) OR ^* . A and A ′ independently represent a divalent bridging bond or spacer radical selected from the group consisting of divalent hydrocarbon radicals, divalent cyclic hydrocarbon radicals, divalent radicals containing oxygen, divalent cyclic ethers and cyclic ethers, and n is an integer equal to 0 or 1. If n is 0, then it is obvious that A and A 'are a simple covalent bond. The term “divalent” means that at each end of the radical there is a free bond, to each of which two different groups are attached. Divalent hydrocarbon radicals can be represented by the formula - (C _d H _2d ) -, where d is the number of carbon atoms in the alkylene chain and is an integer from 1 to 10. The divalent hydrocarbon radicals are preferably selected from straight or branched (C ₁ -C ₁₀ ) alkylene, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene. If a branched alkylene radical is considered, it should be understood that the hydrogen atom in the normal alkylene chain is substituted with a normal or branched (C ₁ -C ₅ ) alkyl group.

где а означает целое число от 2 до 7, a R^q, если присутствует, означает нормальные или разветвленные (С₁-С₁₀) алкильные группы. Предпочтительные двухвалентные циклоалкиленовые радикалы включают циклопентиленовые и циклогексиленовые остатки, представленные следующими структурами:

где R^q определено выше. Следует понимать, что изображенные здесь и далее во всем тексте описания и выходящие из циклических структур и/или формул линии химических связей, означают двухвалентную природу остатка и указывают позиции присоединения атома углерода к соседним фрагментам молекулы, определенным в соответствующих формулах. Как принято в данной области техники, диагональная линия связи, выходящая из центра циклической структуры, означает, что данная связь по выбору соединена с одним из атомов углерода в цикле. Следует также понимать, что данный атом углерода, который образует указанную связь, будет содержать на один атом водорода меньше в соответствии с четырехвалентной природой атома углерода.Divalent cyclic hydrocarbon radicals include substituted and unsubstituted (C ₃ -C ₈ ) cycloaliphatic residues, represented by the formula:

where a is an integer from 2 to 7, and R ^q , if present, means a straight or branched (C ₁ -C ₁₀ ) alkyl group. Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene radicals represented by the following structures:

where R ^{q is} defined above. It should be understood that the chemical bond lines depicted hereinafter throughout the text and coming out of cyclic structures and / or formulas indicate the divalent nature of the residue and indicate the positions of attachment of the carbon atom to neighboring fragments of the molecule defined in the corresponding formulas. As is customary in the art, a diagonal bond line extending from the center of the cyclic structure means that the bond is optionally connected to one of the carbon atoms in the cycle. It should also be understood that this carbon atom, which forms the indicated bond, will contain one hydrogen atom less in accordance with the tetravalent nature of the carbon atom.

Двухвалентные радикалы, содержащие кислород, включают (С₂-С₁₀) алкиленовые простые эфиры и простые полиэфиры. Термин (C₂-С₁₀) алкиленовые простые эфиры означает, что общее число атомов углерода в двухвалентном остатке простого эфира должно быть равно, по крайней мере, 2 и не превышать 10. Двухвалентные алкиленовые простые эфиры представлены формулой - алкилен-О-алкилен, где каждая из алкиленовых групп, присоединенных к атому кислорода, может быть одинаковой или различной, причем указанные алкилены выбирают из группы, включающей метилен, этилен, пропилен, бутилен, пентилен, гексилен, гептилен, октилен и нонилен. Простейшим двухвалентным алкиленовым простым эфиром в данной серии является радикал -СН₂-О-СН₂-. Предпочтительные остатки простых полиэфиров включают двухвалентные радикалы следующей формулы:

где х означает целое число от 0 до 5, а у означает целое число от 2 до 50 при условии, что концевой атом кислорода в полиэфирном спейсерном остатке не связан напрямую с кислородным атомом соседней группы с образованием пероксидной связи. Другими словами, пероксидные связи (т.е. -О-О-) не предполагаются, когда полиэфирные спейсеры связаны с любыми заместителями, содержащими концевой атом кислорода, представленными выше как R¹-R⁴.Preferred divalent cyclic ethers and diesters are represented by the following structures:

Divalent radicals containing oxygen include (C ₂ -C ₁₀ ) alkylene ethers and polyethers. The term (C ₂ -C ₁₀ ) alkylene ethers means that the total number of carbon atoms in the divalent ether residue must be at least 2 and not exceed 10. The divalent alkylene ethers are represented by the formula alkylene-O-alkylene, where each of the alkylene groups attached to the oxygen atom may be the same or different, and these alkylenes are selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene and nonylene. The simplest divalent alkylene ether in this series is the radical —CH ₂ —O — CH ₂ -. Preferred polyether residues include divalent radicals of the following formula:

where x is an integer from 0 to 5, and y is an integer from 2 to 50, provided that the terminal oxygen atom in the polyester spacer moiety is not directly bonded to the oxygen atom of a neighboring group to form a peroxide bond. In other words, peroxide bonds (i.e., —O — O—) are not intended when the polyester spacers are bonded to any substituents containing a terminal oxygen atom represented above as R ¹ —R ⁴ .

где R^p означает водород, нормальную или разветвленную (С₁-C₅) алкильную группу. Алкильные заместители включают метил, этил, пропил, изопропил, бутил, изобутил, трет-бутил, пентил, трет-пентил и неопентил. В указанных выше структурах линия простой связи, выходящая из циклических групп, указывает позицию атома углерода цикла, в которой защитные группы связаны с соответствующим заместителем. Примерами кислотно-лабильных заместителей являются 1-метил-1-циклогексил, изоборнил, 2-метил-2-изоборнил, 2-метил-2-адамантил, тетрагидрофуранил, тетрагидропираноил, 3-оксоциклогексанонил, лактонил мевалоновой кислоты, 1-этоксиэтил, 1-трет-бутоксиэтил, дициклопропилметил (ДЦПМ) и диметил-циклопропилметил (ДМЦП). Алкильные заместители защитных групп, указанных выше, выбирают из нормальных или разветвленных (С₁-C₅) алкильных групп. R^**, независимо друг от друга, означает R и R^*, значение которых указано выше. ДЦПМ и ДМЦП группы имеют, соответственно, следующие структуры:

Полициклические мономеры указанных выше формул, содержащие заместители, выбранные из группы: -(CH₂)_nC(R)₂CH(R)(C(О)OR^**) или -(CH₂)_nC(R)₂СН(С(О)ОR^**)₂, могут быть представлены следующими формулами:

где m определено выше, а n является целым числом от 0 до 10.In the above formulas, R is hydrogen, a straight or branched (C ₁ -C ₁₀ ) alkyl group, am is an integer from 0 to 5. R ^* represents residues (i.e. blocking or protecting groups) that are cleaved by photonic acid initiators wherein R ^{* is} selected from the group consisting of —C (CH ₃ ) ₃ , —Si (CH ₃ ) ₃ , —CH (R ^p ) OCH ₂ CH ₃ , —CH (R ^p ) OC (CH ₃ ) _3, or the following cyclic groups:

where R ^p means hydrogen, a straight or branched (C ₁ -C ₅ ) alkyl group. Alkyl substituents include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-pentyl and neopentyl. In the above structures, the single bond line leaving the cyclic groups indicates the position of the carbon atom of the ring in which the protecting groups are bonded to the corresponding substituent. Examples of acid labile substituents are 1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic acid lactonyl, 1-ethoxyethyl, 1- tert-butoxyethyl, dicyclopropylmethyl (DCM) and dimethyl cyclopropylmethyl (DMCP). Alkyl substituents of the protecting groups mentioned above are selected from straight or branched (C ₁ -C ₅ ) alkyl groups. R ^** , independently of one another, means R and R ^* , the meaning of which is indicated above. The cerebral palsy and cerebral palsy groups have, respectively, the following structures:

Polycyclic monomers of the above formulas containing substituents selected from the group: - (CH ₂ ) _n C (R) ₂ CH (R) (C (O) OR ^** ) or - (CH ₂ ) _n C (R) ₂ CH (C (O) OR ^** ) ₂ , can be represented by the following formulas:

where m is defined above, and n is an integer from 0 to 10.

где заместители от R¹ до R⁴ имеют указанное выше значение.In the above formulas, m is preferably 0 or 1, more preferably 0. If m is 0, then preferred structures can be represented by the following formula:

where the substituents from R ¹ to R ⁴ have the above meaning.

 It will be apparent to those skilled in the art that any group capable of photonic acid cleavage is suitable for practicing the invention, provided that they do not inhibit the polymerization reaction.

 Preferred acid labile groups are organic ester groups cleaving in the presence of acid. Preferred acid labile groups include ester groups and carbonate groups. Particularly preferred groups are tert. butyl esters of carboxylic acids.

 By polymerizing the monomers of Formula I, a polymer is obtained whose main chain contains acid-side acid groups which are then cleaved to give the polymer polarity or solubility.

где R⁵-R⁸ независимо представляют собой нейтральные или полярные заместители, которые выбирают из группы:
-(A)_n-C(О)OR", -(A)_n-OR", -(A)_n-OC(О)R", -(A)_n-OC(О)OR",
-(A_n)-C(О)R", -(A_n)-OC(О)C(О)OR"-, -(A)_n-О-A'-C(О)OR",
-(A)_n-OC(О)-A'-C(О)OR", -(A)_n-C(О)О-A'-C(О)OR",
-(A)_n-C(O)-A'-OR", -(A)_n-C(О)О-A'-OC(О)OR",
-(A)_n-C(О)О-A'-О-A'-C(О)OR", -(A)_n-C(О)О-A'-OC(О)C(О)OR",
-(A)_n-C(R")₂CH(R")(C(О)OR") и -(A)_n-C(R")₂CH(C(О)OR")₂. Остатки А и А' независимо представляют двухвалентную мостиковую связь или спейсерный радикал, которые выбирают из группы, включающей двухвалентные углеводородные радикалы, двухвалентные циклические углеводородные радикалы, двухвалентные радикалы, содержащие кислород, двухвалентные циклические простые эфиры и циклические простые диэфиры, а n является целым числом, равным 0 или 1. Если n равно 0, то очевидно, что А и А' являются простой ковалентной связью. Термин "двухвалентный" означает, что на каждом конце радикала имеется свободная связь, к каждой из которых присоединены две различные группы. Двухвалентные углеводородные радикалы могут быть представлены формулой -(С_dН_2d)-, где d является числом углеродных атомов в алкиленовой цепи, а n является целым числом от 1 до 10. Двухвалентные углеводородные радикалы предпочтительно выбирают из нормальных или разветвленных (С₁-С₁₀) алкиленов, таких как метилен, этилен, пропилен, бутилен, пентилен, гексилен, гептилен, октилен, нонилен и децилен. Если рассматривается разветвленный алкиленовый радикал, следует понимать, что атом водорода в нормальной алкиленовой цепи заменен на линейную или разветвленную (C₁-C₅) алкильную группу.A possible but optional second monomer may be represented by formula II:

where R ⁵ -R ⁸ independently represent neutral or polar substituents, which are selected from the group:
- (A) _n -C (O) OR ", - (A) _n -OR", - (A) _n -OC (O) R ", - (A) _n -OC (O) OR",
- (A _n ) -C (O) R ", - (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 ") ₂ CH (R") (C (O) OR ") and - (A) _n -C (R") ₂ CH (C (O) OR ") _2. Residues A and A ′ independently represent a divalent bridging bond or spacer radical selected from the group consisting of divalent hydrocarbon radicals, divalent cyclic hydrocarbon radicals, divalent radicals containing oxygen, divalent cyclic ethers and cyclic ethers, and n is an integer equal to 0 or 1. If n is 0, then it is obvious that A and A 'are a simple covalent bond. The term “divalent” means that on each con There is a free bond for each radical, each of which has two different groups. Divalent hydrocarbon radicals can be represented by the formula - (C _d H _2d ) -, where d is the number of carbon atoms in the alkylene chain and n is an integer from 1 to 10 Divalent hydrocarbon radicals are preferably selected from straight or branched (C ₁ -C ₁₀ ) alkylenes such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene. If a branched alkylene radical is considered, it should be understood that the hydrogen atom in the normal alkylene chain is replaced by a linear or branched (C ₁ -C ₅ ) alkyl group.

где а означает целое число от 2 до 7, a R^q, если присутствует, означает нормальные и разветвленные (С₁-С₁₀) алкильные группы. Предпочтительные двухвалентные циклоалкиленовые радикалы включают циклопентиленовые и циклогексиленовые остатки, представленные следующими структурами:

где R^q определено выше. Следует понимать, что изображенные здесь и далее во всем тексте описания и выходящие из циклических структур и/или формул линии химических связей означают двухвалентную природу остатка и указывают позиции присоединения атома углерода к соседним молекулярным остаткам, как определено в соответствующих формулах. Как принято в данной области техники, диагональная линия связи, выходящая из центра циклической структуры, означает, что данная связь по выбору соединена с одним из атомов углерода в цикле. Следует также понимать, что данный атом углерода, который образует указанную связь, будет содержать на один атом водорода меньше, в соответствии с четырехвалентной природой атома углерода.Divalent cyclic hydrocarbon radicals include substituted and unsubstituted (C ₃ -C ₈ ) cycloaliphatic residues, affixed by the following formula:

where a is an integer from 2 to 7, and R ^q , if present, means a straight and branched (C ₁ -C ₁₀ ) alkyl group. Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene radicals represented by the following structures:

where R ^{q is} defined above. It should be understood that the descriptions shown hereinafter throughout the text of the lines and leaving the cyclic structures and / or formulas of the chemical bonds indicate the divalent nature of the residue and indicate the positions of attachment of the carbon atom to neighboring molecular residues, as defined in the corresponding formulas. As is customary in the art, a diagonal bond line extending from the center of the cyclic structure means that the bond is optionally connected to one of the carbon atoms in the cycle. It should also be understood that this carbon atom, which forms the indicated bond, will contain one less hydrogen atom, in accordance with the tetravalent nature of the carbon atom.

Двухвалентные радикалы, содержащие кислород, включают (С₂-С₁₀) алкиленовые простые эфиры и простые полиэфиры. Термин "(С₂-С₁₀) алкиленовые простые эфиры" означает, что общее число атомов углерода в остатке двухвалентного простого эфира должно быть равно, по крайней мере, 2 и не превышать 10. Двухвалентные алкиленовые простые эфиры представлены формулой -алкилен-О-алкилен-, где каждая из алкиленовых групп может быть одинаковой или различной, причем указанные алкилены выбирают из группы, включающей метилен, этилен, пропилен, бутилен, пентилен, гексилен, гептилен, октилен и нонилен. Простейшим двухвалентным алкиленовым простым эфиром в данной серии является радикал -CH₂-O-CH₂-. Предпочтительные остатки простых полиэфиров включают двухвалентные радикалы следующей формулы:

где х означает целое число от 0 до 5, а у означает целое число от 2 до 50 при условии, что концевой атом кислорода в полиэфирном спейсерном остатке не должен быть напрямую связан с атомом кислорода соседней группы с образованием пероксидной связи. Другими словами, пероксидные связи (т.е. -О-О-) не предполагаются, если полиэфирные спейсеры связаны с любыми заместителями, содержащими концевой атом кислорода, представленными выше как R⁵-R⁸.Preferred divalent cyclic ethers and diesters are represented by the following structures:

Divalent radicals containing oxygen include (C ₂ -C ₁₀ ) alkylene ethers and polyethers. The term “(C ₂ -C ₁₀ ) alkylene ethers” means that the total number of carbon atoms in the residue of the divalent ether must be at least 2 and not exceed 10. The divalent alkylene ethers are represented by the formula -alkylene-O- alkylene-, where each of the alkylene groups may be the same or different, said alkylenes being selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene and nonylene. The simplest divalent alkylene ether in this series is the radical —CH ₂ —O — CH ₂ -. Preferred polyether residues include divalent radicals of the following formula:

where x is an integer from 0 to 5, and y is an integer from 2 to 50, provided that the terminal oxygen atom in the polyester spacer moiety does not have to be directly bonded to the oxygen atom of a neighboring group to form a peroxide bond. In other words, peroxide bonds (i.e., —O — O—) are not contemplated if the polyester spacers are bonded to any substituents containing a terminal oxygen atom represented above as R ⁵ —R ⁸ .

где х означает целое число от 0 до 5, у означает целое число от 2 до 50, а R^a представляет собой нормальный или разветвленный (С₁-С₁₀) алкил. Предпочтительные простые полиэфирные радикалы включают полиэтиленоксид и полипропиленоксид. Примерами моноциклических циклоалифатических остатков являются циклопропил, циклобутил, циклопентил, циклогексил и т.п. Примерами циклоалифатических полициклических остатков являются норборнил, адамантил, тетрагидродициклопентадиенил (трицикло[5.2.1.0^2,6] деканил) и т.п. Примерами циклических простых эфиров являются остатки тетрагидрофуранила и тетрагидропиранила. Примером циклического кетона является остаток 3-оксоциклогексанонила. Примером циклического сложного эфира или лактона является остаток лактонила мевалоновой кислоты.R ⁵ -R ⁸ can also be independently represented by hydrogen, a straight or branched (C ₁ -C ₁₀ ) alkyl group, provided that at least one of the remaining R ⁵ -R ⁸ substituents is selected from one of the above groups neutral or polar substituents. In the above formula, p is an integer from 0 to 5 (preferably 0 or 1, most preferably 0). R "independently represents hydrogen, straight or branched (C ₁ -C ₁₀ ) alkyl, straight or branched (C ₁ -C ₁₀ ) alkoxyalkylene, polyethers, monocyclic or polycyclic (C ₄ -C ₂₀ ) cycloaliphatic residues, cyclic ethers , cyclic ketones and cyclic esters (lactones). The term “(C ₁ -C ₁₀ ) alkoxyalkylene” means that the terminal alkyl group is bonded to the alkylene radical via an ether oxygen atom. This radical is a hydrocarbon-based ether residue which which can be represented in general terms as -alkylene-O-alkyl-, where alkylene and alkyl groups independently contain from 1 to 10 carbon atoms, each of which may be straight or branched. The polyether radical can be represented by the following formula:

where x is an integer from 0 to 5, y is an integer from 2 to 50, and R ^a is a straight or branched (C ₁ -C ₁₀ ) alkyl. Preferred polyether radicals include polyethylene oxide and polypropylene oxide. Examples of monocyclic cycloaliphatic residues are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Examples of cycloaliphatic polycyclic residues are norbornyl, adamantyl, tetrahydrodicyclopentadienyl (tricyclo [5.2.1.0 ^2,6 ] decanyl) and the like. Examples of cyclic ethers are tetrahydrofuranyl and tetrahydropyranyl residues. An example of a cyclic ketone is the residue of 3-oxocyclohexanonyl. An example of a cyclic ester or lactone is the mevalonic acid lactonyl residue.

Since the substituents defined for R ″ in formula II overlap with the acid labile or protecting groups described as R ^* in formula I, it should be understood that R ″ in formula II cannot be represented by an ester moiety containing an acid labile group . For example, if R "is a residue of norbornyl, adamantyl, tetrahydrodicyclopentadienyl (tricyclo [5.2.1. ^2,6 ] decanyl), tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanonyl or mevalonic acid lactone, then this residue should not be directly connected to the oxygen atom ester residue (—C (O) O).

Preferred neutral or polar substituents include carboxylic acid alkyl esters, moieties containing spacer oxalate groups (e.g. - (A) _n -OC (O) -A'-C (O) OR ") and oxalate moieties (e.g., - ( A) _n OC (O) C (O) OR "), the formulas of which are defined above. Esters, spacer oxalate groups and oxalate groups give the compound an extremely high hydrophilicity, provide good developer wettability and improve the mechanical properties of the film, without causing problems associated with an excess of functional residues of carboxylic acids.

где заместители R⁹ до R¹² независимо означают остатки карбоновой или сульфоновой кислот или их солей, которые выбирают из группы, включающей -(СН₂)_nС(О)ОН, -(СН₂)_nSО₃Н, -(CH₂)_nC(O)O^-X⁺, -(СН₂)_nSО₃ ^-Х⁺ где Х означает катионы тетраалкиламмония, алкильные заместители, связанные с атомом азота, которые независимо выбирают из нормальных или разветвленных (С₁-С₁₀) алкилов, q означает целое число от 0 до 5 (предпочтительно 0 или 1, более предпочтительно 0), а n означает целое число от 0 до 10 (предпочтительно 0). Заместители R⁹-R¹² независимо могут означать водород, нормальный или разветвленный (С₁-С₁₀) алкил, при условии, что, по крайней мере, один из оставшихся заместителей R⁹-R¹² выбирают из указанных выше кислот или их солей.An optional third monomer component is represented by the structure of formula III:

where the substituents R ⁹ to R ¹² independently mean residues of carboxylic or sulfonic acids or their salts, which are selected from the group consisting of - (CH ₂ ) _n C (O) OH, - (CH ₂ ) _n SO ₃ H, - (CH ₂ ) _n C (O) O ^- X ⁺ , - (CH ₂ ) _n SO ₃ ^- X ⁺ where X is tetraalkylammonium cations, alkyl substituents attached to the nitrogen atom, which are independently selected from straight or branched (C ₁ -C ₁₀ ) alkyls, q is an integer from 0 to 5 (preferably 0 or 1, more preferably 0), and n is an integer from 0 to 10 (preferably 0). The substituents R ⁹ -R ¹² may independently mean hydrogen, straight or branched (C ₁ -C ₁₀ ) alkyl, provided that at least one of the remaining substituents R ⁹ -R ^{12 is} selected from the above acids or their salts.

 Monomers containing a carboxyl functional group give the polymer hydrophilicity, which, as a result, contributes to the high rate of polymer manifestation in an aqueous solution of the base.

где заместители от R¹³ до R¹⁶, независимо друг от друга, означают нормальный или разветвленный алкил С₁-С₁₀, а r равно от 0 до 5, предпочтительно, 0 или 1, особенно предпочтительно, 0. Любой заместитель от R¹³ до R¹⁶ может означать водород, при условии, что по меньшей мере, один из оставшихся заместителей от R¹³ до R¹⁶ выбраны из указанных выше алкильных групп. Особенно предпочтительным алкильным заместителем является децил.A possible monomer of formula IV is represented by the following formula:

where the substituents from R ¹³ to R ¹⁶ , independently of one another, mean straight or branched C ₁ -C ₁₀ alkyl, and r is from 0 to 5, preferably 0 or 1, particularly preferably 0. Any substituent from R ¹³ to R ¹⁶ may be hydrogen, provided that at least one of the remaining substituents R ¹³ to R ^{16 is} selected from the above alkyl groups. A particularly preferred alkyl substituent is decyl.

 The polymerisation of alkyl substituted monomers in a polymer chain is a method for controlling the glass transition temperature (Tg) of a polymer, as described in US Pat. No. 5,468,819 to Goodall et al.

Другие полициклические аддукты получают термическим пиролизом дициклопентадиена в присутствии подходящего диена. Реакция протекает путем первоначального пиролиза дициклопентадиена (ДЦПД) в ЦПД с последующим взаимодействием ЦПД и диена по реакции Дильса - Альдера с образованием аддуктов по следующей схеме:

где заместители от R' до R"" независимо друг от друга имеют значения, указанные выше для заместителей от R¹ до R¹⁶ в формулах I, II, III и IV.An economical scheme for producing polycyclic monomers with functional and hydrocarbon substituents according to the invention is the Diels-Alder reaction, according to which cyclopentadiene (CPD) or substituted cyclopentadiene reacts with a correspondingly substituted diene at elevated temperatures to form a substituted polycyclic adduct according to the following reaction scheme:

Other polycyclic adducts are prepared by thermal pyrolysis of dicyclopentadiene in the presence of a suitable diene. The reaction proceeds by the initial pyrolysis of dicyclopentadiene (DCPD) in the CPD, followed by the interaction of the CPD and diene according to the Diels-Alder reaction with the formation of adducts according to the following scheme:

where the substituents from R 'to R "" independently from each other have the meanings indicated above for the substituents from R ¹ to R ¹⁶ in the formulas I, II, III and IV.

Соответствующий трет. бутиловый эфир карбоновой кислоты может быть получен взаимодействием функциональной карбоксильной группы с изобутиленом в присутствии небольшого количества кислоты при пониженной температуре (т.е. от (-30) до (-20)^oС) по следующей схеме:

Другим предпочтительным методом получения трет. бутилового эфира норборнен карбоновой кислоты является взаимодействие циклопентадиена с трет. бутилакрилатом по реакции Дильса - Альдера.For example, 2-norbornene-5-carboxylic acid (bicyclo [2.2.1] hept-5-en-2-carboxylic acid) can be obtained by the Diels – Alder reaction by reacting cyclopentadiene with acrylic acid according to the following reaction scheme:

The corresponding tert. butyl carboxylic acid ester can be prepared by reacting a functional carboxyl group with isobutylene in the presence of a small amount of acid at a reduced temperature (i.e., from (-30) to (-20) ^o C) according to the following scheme:

Another preferred method of obtaining tert. norbornene carboxylic acid butyl ether is the interaction of cyclopentadiene with tert. butyl acrylate according to the Diels-Alder reaction.

где заместители R¹⁷, R¹⁸ и R¹⁹ независимо друг от друга представлены нормальный или разветвленной С₁-C₅ алкильной группой или любой из R¹⁷, R¹⁸ и R¹⁹ вместе с атомом кислорода, к которому он присоединен, образует замещенное или незамещенное 5- - 10-членное циклическое или бициклическое кольцо, содержащее от 3 до 8 атомов (исключая замещающие группы), s равно от 0 до 5, предпочтительно, 0, a t равно от 1 до 5, предпочтительно, 1. Примерами структур, в которых s равно 0, t равно 1 и заместители R¹⁷, R¹⁸ и R¹⁹ вместе с атомами кислорода, к которым они прикреплены, образуют циклическое или бициклическое кольцо, приведены ниже в виде формул Va, Vb, Vc:

где заместители R¹⁷', R¹⁸' и R¹⁹' независимо друг от друга означают водород и нормальный, и разветвленный С₁-C₅ алкил. Мономеры, замещенные в орто-положении сложноэфирной группой по изобретению, могут быть получены согласно, так называемому, синтезу Пиннера (A.Pinner, Chem. Ber., (1883), 16, с. 1643) и способом, предложенным S.M. McElvain, J.T. Venerable (J. Am. Chem. Soc. , (1950), 72, с.1661); SM. McElvain, C.L Aldridge (J. Am. Chem. Soc. , (1953), 75, с.3987). Типичный пример синтеза соответствует представленной ниже реакционной схеме:

Альтернативный способ синтеза заключается в обработке алкилакрилата триалкилоксоний тетрафторборатной солью с последующей обработкой солью щелочного металла (алкоголятом натрия) с получением орто-триалкоксиметилового сложного эфира. (H.Meerwein, P. Borner, O.Fuchs, H.J.Sasse, H.Schrodt and J. Spille, Chem.Ber., (1956), 89, с.2060).Another method for the synthesis of monomers substituted with acid and ester groups of the present invention is to obtain polycyclic monomers substituted in the ortho position with ester groups, followed by hydrolysis of them to form functional carboxyl groups, or partial hydrolysis with the formation of ester functional groups. Carboxyl functional groups can be esterified to form the desired ester. The monomers of the invention substituted in the ortho-position with ester groups have the formula V:

where the substituents R ¹⁷ , R ¹⁸ and R ¹⁹ independently represent a normal or branched C ₁ -C ₅ alkyl group or any of R ¹⁷ , R ¹⁸ and R ¹⁹ together with the oxygen atom to which it is attached forms a substituted or unsubstituted A 5- to 10-membered cyclic or bicyclic ring containing from 3 to 8 atoms (excluding substituent groups), s is from 0 to 5, preferably 0, at is from 1 to 5, preferably 1. Examples of structures in which s is 0, t is 1 and the substituents R ¹⁷ , R ¹⁸ and R ¹⁹ together with the oxygen atoms to which they are attached, form t cyclic or bicyclic ring are given below in the form of formulas Va, Vb, Vc:

where the substituents R ¹⁷ ', R ¹⁸ ' and R ¹⁹ 'independently from each other mean hydrogen and normal and branched C ₁ -C ₅ alkyl. Monomers substituted in the ortho position with the ester group of the invention can be prepared according to the so-called Pinner synthesis (A. Pinner, Chem. Ber., (1883), 16, p. 1643) and the method proposed by SM McElvain, JT Venerable (J. Am. Chem. Soc., (1950), 72, p. 1661); SM. McElvain, CL Aldridge (J. Am. Chem. Soc., (1953), 75, p. 3987). A typical synthesis example corresponds to the following reaction scheme:

An alternative synthesis method consists in treating the trialkyloxonium alkyl acrylate with a tetrafluoroborate salt followed by treatment with an alkali metal salt (sodium alcoholate) to obtain an ortho-trialkoxymethyl ester. (H. Meerwein, P. Borner, O. Fuchs, HJ Sasse, H. Schrodt and J. Spille, Chem. Ber., (1956), 89, p. 2060).

Другим, более предпочтительным способом получения бифункциональных полициклических мономеров является гидролиз и частичный гидролиз ангидрида эндо-5-норнборнен-2,3-дикарбоновой кислоты (надиевого ангидрида). Надиевый ангидрид может быть полностью гидролизован в дикарбоновую кислоту, либо частично гидролизован до кислоты и сложного эфира или диэфира, как это показано ниже:

где R¹⁷ независимо означает прямой или разветвленный алкил С₁-С₅. Предпочтительно, R¹⁷ означает метил, этил или трет. бутил. Предпочтительно, при синтезе надиевого ангидрида в качестве исходного вещества используют экзо-изомер. Экзо-изомер легко получают нагреванием эндо-изомера при 190^oС с последующей рекристаллизацией из соответствующего растворителя (толуол). Для получения дикарбоновой кислоты по реакционной схеме 1 просто гидролизуют надиевый ангидрид в кипящей воде с получением почти что количественного выхода целевого продукта. Для получения смеси мономеров с карбоксильными и алкилэфирными группами согласно схеме 3 надиевый ангидрид нагревают с обратным холодильником в течение от 3 до 4 часов в присутствии соответствующего алифатического спирта (R¹⁷ОН). Альтернативно этот же продукт может быть получен взаимодействием сначала надиевого ангидрида с алифатическим спиртом и триалкиламином с последующей обработкой разбавленной соляной кислотой. Диэфир, замещенный идентичными алкильными группами (R¹⁷), может быть получен из дикарбоновой кислоты взаимодействием ее с триалкилоксоний тетраборатом, например, с R¹⁷ ₃O[BF₄] в метиленхлориде при комнатой температуре в присутствии диизопропилэтиламина. Для получения сложных эфиров с различными алкильными группами R¹⁷ в качестве исходного вещества используют смешанный продукт из кислоты и сложного эфира, полученный по схеме 3. В этом случае кислотные группы этерифицируют, как показано на реакционной схеме 2. Однако используют триалкилоксоний тетрафторборат с другими алкильными группами, отличными от алкильных групп, уже имеющихся в сложноэфирных функциональных группах.As noted above, the ortho-ether groups can undergo a hydrolysis reaction in the presence of a weak acid as a catalyst, such as hydrobromic, hydroiodic and acetic acid to form a carboxylic acid. Carboxylic acid, in turn, can be esterified in the presence of an aliphatic alcohol and an acid catalyst to form the corresponding ester. It should be understood that in the case of polycyclic monomers substituted in the ortho position by two or more ester groups, the latter can be partially hydrolyzed into acid groups to form an acid and a common ester of the same monomer:

Another, more preferred method for the preparation of bifunctional polycyclic monomers is the hydrolysis and partial hydrolysis of endo-5-norbornene-2,3-dicarboxylic acid anhydride (nadic anhydride). Nadium anhydride can be completely hydrolyzed to dicarboxylic acid, or partially hydrolyzed to acid and ester or diester, as shown below:

where R ¹⁷ independently means straight or branched alkyl C ₁ -C ₅ . Preferably, R ¹⁷ means methyl, ethyl or tert. butyl. Preferably, in the synthesis of nadium anhydride, the exo-isomer is used as the starting material. The exo-isomer is readily prepared by heating the endo-isomer at 190 ^{° C.} , followed by recrystallization from an appropriate solvent (toluene). To obtain dicarboxylic acid according to reaction scheme 1, nadium anhydride is simply hydrolyzed in boiling water to obtain an almost quantitative yield of the target product. To obtain a mixture of monomers with carboxyl and alkyl ether groups according to Scheme 3, nadium anhydride is heated under reflux for 3 to 4 hours in the presence of the corresponding aliphatic alcohol (R ¹⁷ OH). Alternatively, the same product can be obtained by first reacting nadium anhydride with aliphatic alcohol and trialkylamine, followed by treatment with dilute hydrochloric acid. A diester substituted with identical alkyl groups (R ¹⁷ ) can be obtained from dicarboxylic acid by reacting it with trialkyloxonium tetraborate, for example, R ¹⁷ ₃ O [BF ₄ ] in methylene chloride at room temperature in the presence of diisopropylethylamine. To obtain esters with various alkyl groups R ¹⁷ , a mixed product of acid and ester obtained according to Scheme 3 is used as the starting material. In this case, acid groups are esterified as shown in Reaction Scheme 2. However, trialkyloxonium tetrafluoroborate with other alkyl groups is used other than alkyl groups already present in the ester functional groups.

 It should be noted that the monomers of the previous stage containing functional groups corresponding to the previous stage can be converted into monomers with the desired functional groups before polymerization, or these monomers can be polymerized first, and then the corresponding polymers containing the same functional groups as substituents as in the previous stage, can be subjected to subsequent reactions to obtain the desired functional groups.

 Within the scope of this invention, it is assumed that for monomers of formulas I to V, where m, p, q, r and s are 0, the methylene bridge can be replaced by oxygen to give 7-oxo-norbornene derivatives.

It is also contemplated that for use at a wavelength of 248 nm, substituents R ⁵ to R ¹⁶ and R ¹¹ in formulas II, III, and IV may be aromatic, such as phenyl.

Polymers
One or more polycyclic monomers substituted with acid labile groups of formula I may be polymerized separately or in admixture with one or more polycyclic monomers of formula II, III, IV and V. It is also contemplated that polycyclic monomers of formula I-V may be copolymerized with carbon monoxide to obtain copolymers of polycyclic monomers and carbon monoxide. Norbornene copolymers having pendant carboxyl groups and carbon monoxide are described in US Pat. No. 4,960,857, which is incorporated herein by reference. The monomers of formulas IV and carbon monoxide are copolymerized in the presence of a palladium-containing catalyst system, as described in Chem. Rev. , (1996), 96, p. 663-681. It will be appreciated by those skilled in the art that copolymers of alternating units of polycyclic monomers and carbon monoxide may exist in a keto or spiroketal isomeric form. Accordingly, the present invention contemplates the use of homopolymers and copolymers containing randomly repeating units derived (polymerized) from a monomer or monomers of formula I, copolymers containing randomly repeating units derived (polymerized) from a monomer (s) of formula I, possibly in a mixture with any monomer (s) of formulas II-V. In addition, the present invention contemplates the use of copolymers containing repeating units derived (polymerized) from carbon monoxide and monomer (s) represented by formulas IV.

The inclusion of functional lateral carboxyl groups is important, because it gives the polymer chain hydrophilicity, adhesion characteristics and the ability to completely dissolve (manifest). However, in some applications of photoresistors, too high a carboxyl group content in the polymer is undesirable. Such polymers do not combine well with industry standard developers (0.26 N tetramethylammonium hydroxide, TMAH). The main disadvantages of such polymers with a high content of carboxyl groups are swelling of the polymer in unexposed areas, uncontrolled thinning during use and swelling of the polymer during dissolution during exposure. Accordingly, in cases where a high content of carboxyl groups is undesirable, but hydrophilicity and good wetting characteristics are of great importance, copolymers obtained by polymerization of the monomers of formula I in the required combination with the monomers of formula II are of great importance. Particularly preferred are the monomers of formula II containing residues of alkyl esters, alkyl carbonates, bridged alkyl oxalates and alkyl oxalates such as - (A) _n —C (O) OR ", - (A) _n —OC (O) OR ", - (A) _n -OC (O) O-A'-C (O) OR" and - (A) _n -OC (O) C (O) OR ", respectively, where A, A ', n and R "are defined above.

 The polymers of the present invention are the main component of the composition. The polymer typically contains from 5 to 100 mol% of a monomer (repeating unit) containing acid labile groups. Preferably, the polymer contains about 20-90 mol% of an acid labile monomer. More preferably, the polymer contains about 30-70 mol% of a monomer containing labile acid functional groups. The remainder of the polymer composition consists of repeating units, optionally polymerized from the monomers shown above in the form of formulas III-V. The selection and amount of specific monomers used in the polymer may vary in accordance with the desired properties. For example, by varying the number of carboxyl functional groups in the polymer chain, the desired solubility of the polymer in various developing solvents can be achieved. To improve the mechanical properties of the polymer and the radiation sensitivity of the system, monomers containing ester functional groups can be varied. Finally, it is possible to control the glass transition temperature of the polymer by incorporating into the polymer chain repeating cyclic units containing long chain alkyl groups such as decyl.

 There are several methods for the polymerization of cyclic olefin monomers, such as norbornene and higher cyclic (polycyclic) monomers containing norbornene groups. These include: (1) exchange polymerization (via the olefin metathesis mechanism) with ring opening (MPRC); (2) MPRC followed by hydrogenation; and (3) additive polymerization (polyaddition). Each of the above methods leads to the production of polymers with a specific structure, as shown below in scheme 1.

 The MPRC polymer has a structure different from the polymer obtained by the polyaddition reaction. The MPRC polymer contains repeating units containing one less cyclic unit compared to the starting monomer. The repeating units are interconnected in an unsaturated polymer chain, as shown in scheme 1 above. Due to this unsaturation, the polymer should preferably be subjected to subsequent hydrogenation to give the polymer chain oxidation stability. On the contrary, additive polymers (i.e., polymers obtained by the polyaddition reaction) do not have any C = C unsaturation in the polymer chain, despite the fact that they are obtained from the same monomer.

где заместители от R' до R"", независимо друг от друга, представляют собой радикалы от R¹ до R¹⁹, значение которых определено в приведенных выше формулах I-V, m равно от 0 до 5 и а означает количество повторяющихся звеньев в полимерной цепи.The monomers according to the invention can be polymerized by polyaddition and by the mechanism of metathesis of olefins with the opening of the cycle (MPRC), preferably followed by hydrogenation. The cyclic polymers of the present invention have the following structures:

where the substituents from R 'to R "", independently from each other, are radicals from R ¹ to R ¹⁹ , the value of which is defined in the above formulas IV, m is from 0 to 5 and a means the number of repeating units in the polymer chain.

 The MPRC polymers of the present invention are prepared by polymerization in the presence of a specific catalyst for such polymerization in an appropriate solvent. Methods of MPRC polymerization and subsequent hydrogenation of the polymers thus obtained are described in US Pat. Nos. 5,053,471 and 5,202,388, incorporated herein by reference.

In one embodiment of the MPRC, the polycyclic monomers of the invention can be polymerized in the presence of a one-component complex ruthenium or osmium carbene catalyst, such as described in WO 95-US 9655. The ratio of monomer to catalyst should be from about 100: 1 to about 2000: 1, advantageously about 500: 1. The reaction may be carried out in a halogenated hydrocarbon solvent such as dichloroethane, dichloromethane, chlorobenzene and the like, or in a hydrocarbon solvent such as toluene. The amount of solvent in the reaction medium should be sufficient to achieve a solids concentration of from about 5 wt.% To about 40 wt.%, Preferably from 6 wt.% To 25 wt.%. The reaction can be carried out at a temperature of from about 0 ^{° C.} to 60 ^{° C.} , preferably from 20 ^{° C.} to 50 ^° C.

A preferred metal carbene catalyst is bis (tricyclohexylphosphine) ruthenium benzylidene. It was unexpectedly found that this catalyst can be used as a catalyst for the initial reaction MPRs and as an effective catalyst for hydrogenation (hydrogenation) to obtain a practically saturated polymer MPRs. The use of any additional hydrogenation catalyst is not required. After the initial reaction of the MPRC for hydrogenation of the polymer chain, it is only necessary to maintain the hydrogen pressure above the reaction medium at a temperature above about 100 ^{° C.} but below about 220 ^{° C.} , preferably from about 150 ^{° C.} to about 200 ^° C.

 Additive polymers of the present invention can be obtained by standard methods of free radical polymerization in solution, well known in the art. The monomer of formula I-V may be homo- or copolymerized in the presence of maleic anhydride. Free radical polymerization methods are described in Encyclopedia of Polymer Science, Encyclopedia of Polymer Sciences, John Wiley & Sons, (1988), 13, p. 708.

 Alternatively, and preferably, the monomers of the present invention are polymerized in the presence of a single or multicomponent catalyst system containing a source of Group VIII metal ions, preferably palladium or nickel. It was unexpectedly found that the polymers thus obtained have excellent transparency with respect to deep UV light (193 nm) and exhibit excellent resistance to reactive ion etching.

 Preferred polymers of the present invention are polymerized from a reaction mixture containing at least one polycyclic monomer selected from monomers of formulas I and II, a solvent, a catalytic system containing a source of Group VIII metal ions and, if necessary, a transfer agent chains. The catalyst system may comprise a single component catalyst based on a metal of group VIII or a multicomponent catalyst based on a metal of group VIII.

Single component systems
According to one embodiment, the one-component catalyst system of the present invention contains a cationic complex of a Group VIII metal and a counter-anion weakly coupled to it by donor-acceptor bond, as represented by the following formula:
[L _y MX _Z ] [CA] _a
cationic complex anionion,
where L is a ligand containing 1,2 - or 3π-bonds; M is a transition metal of group VIII; X means a ligand containing one σ-bond and from 0 to 3 π-bonds; y is 0, 1 or 2 and z is 0 or 1, and y and z cannot both mean 0 and, if y is 0, then a is 2, and if y is 1, then a is 1; CA means a weakly bound anion.

 The expression "loosely coupled by a donor-acceptor bond counterion" means anion that is only weakly coordinated to the cation, as a result of which it remains practically labile for substitution with a neutral Lewis base. More specifically, this expression means anion, which, when acting as a stabilizing anion in the catalyst system of the present invention, does not transfer the anionic substituent or part thereof to the cation. The counter anion is non-oxidizing, non-reducing, non-nucleophilic and relatively inert.

L is a neutral ligand, weakly coordinated to the cationic complex of a metal of group VIII. In other words, the ligand is relatively inert and is easily replaced in the cationic metal complex by an intrinsic monomer in a growing polymer chain. Suitable π-bond ligands include C ₂ -C ₁₂ monoolefins (e.g., 2,3-dimethyl-2-butene), C ₄ -C ₁₂ diolefins (e.g., norbornadiene) and C ₆ -C ₂₀ aromatics. A preferred ligand L is a cyclo (C ₆ -C ₁₂ ) diolefin chelating bidentate, for example cyclooctadiene (DPC) or dibenzocyclooctadiene, or an aromatic compound such as benzene, toluene or mesitylene.

 Group VIII metal is selected from Group VIII metals of the Periodic System. Preferably, M is selected from the group consisting of nickel, palladium, cobalt, platinum, iron and ruthenium. The most preferred metals are nickel and palladium.

Ligand X is selected from (i) a group forming a single metal-carbon σ-bond in the cationic complex (in the absence of π-bonds) with a metal, or (ii) a group forming a single metal-carbon σ-bond in the cationic complex and 1- 3 π-bonds with metal. According to (i), the group is bonded to the Group VIII metal with a single metal-carbon σ bond in the absence of π bonds. Examples of ligands in this case are: C ₁ -C ₁₀ alkyl, such as methyl, ethyl, straight or branched alkyl, such as propyl, butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl and C ₇ -C ₁₅ aralkyl, such as benzyl. In the case of variant (ii) described above, the cation contains a hydrocarbon group directly bonded to the metal with a single metal-carbon σ-bond, as well as at least one but not more than three π-bonds. By a hydrocarbon group is meant a group capable of stabilizing the cationic complex of a metal of group VIII by forming a carbon-metal σ bond and from one to three π bonds, which can be conjugated and unconjugated. Representative hydrocarbon groups are C ₃ -C ₂₀ alkenyl, which may be non-cyclic, monocyclic or polycyclic and may be substituted with a straight or branched C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₁₅ aryloxy group or halogen (e.g. Cl and F).

-связь с металлом от отдаленного от центра углеродного атома, отделенного от олефинового углеродного атома, по меньшей мере, двумя простыми углерод-углеродными связями (вариант iii).Preferably, X is the only allylic ligand or its canonical form, forming a σ-bond and π-bond, or a compound forming at least one olefinic π-bond with a metal and

- bond with a metal from a carbon atom remote from the center, separated from the olefin carbon atom by at least two simple carbon-carbon bonds (option iii).

 It should be completely clear to a specialist that in the absence of a ligand L or X (i.e., y or z means 0), the metal cationic complex will be weakly bound to the solvent in which the reaction was carried out. Examples of solvents include, but are not limited to, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and aromatic solvents such as benzene, toluene, mesicylene, chlorobenzene and nitrobenzene and the like. A more detailed discussion of suitable solvents will be provided below.

 Some selected variants of cationic metal complexes of group VIII of one-component catalyst systems of the invention are shown below.

 Structure VII illustrates option (i) in which ligand X denotes a methyl group bonded to the metal with a single metal-carbon σ-bond, and ligand L is cyclooctadiene (DPC), weakly coordinated with the palladium metal by two olefinic π-bonds. In the structure below, M is preferably palladium or nickel.

Структуры VIII, IX и X иллюстрируют различные примеры варианта (ii), где Х является аллильной группой, связанной с металлом (палладий показан исключительно с целью иллюстрации) одинарной σ-связью металл-углерод и, по меньшей мере, одной, но не более чем тремя π-связями.

Structures VIII, IX, and X illustrate various examples of option (ii), where X is an allyl group bonded to a metal (palladium shown solely for the purpose of illustration) with a single metal-carbon σ bond and at least one but not more than three π-bonds.

 VIII L is absent in the structure, but the aromatic group creating three π bonds is poorly coordinated with respect to the palladium metal; X denotes an allyl group providing a single metal-carbon σ bond and an olefinic π bond with palladium.

 In the structure of IX, L means cyclooctadiene (DPC), and X is an allyl group providing a metal-carbon σ-bond and π-olefin bond with palladium.

 Structure X illustrates a variant in which ligand X is an unsaturated hydrocarbon group providing a metal-carbon σ bond, a conjugated π bond and two additional π bonds with palladium; L is absent.

Заместители R²⁰, R²¹, R²² будут подробно описаны ниже.

The substituents R ²⁰ , R ²¹ , R ²² will be described in detail below.

 Structures XI and XII illustrate examples of option (iii), where L is cyclootadiene and X is a ligand providing at least one olefinic π-bond with a metal of group VIII and a σ-bond with the metal from a carbon atom remote from the center, remote from any olefinic a carbon atom with at least two simple carbon-carbon bonds.

Описанные выше катионные комплексы металла группы VIII ассоциированы со слабо координирующим или не координирующим противоионом СА^-, который является относительно инертным, слабонуклефильным и обеспечивает получение катионного комплекса, значительно растворимого в растворителе реакционной смеси. Анион выбирают с учетом требований лабильности, стабильности и инертности по отношению к катионному комплексу металла группы VIII в конечном образце катализатора и придания однокомпонентному катализатору по изобретению растворимости в растворителях, используемых по настоящему изобретению. Анионы, стабильные при взаимодействии с водой или кислотами Бренстеда и не имеющие протонов кислоты, расположенных на наружной стороне аниона (т.е. анионные комплексы, не взаимодействующие с сильными кислотами или основаниями), обладают необходимой стабильностью для квалификации их в качестве стабильного аниона для каталитической системы. Свойства аниона, важные для максимальной лабильности, включают общий размер и форму (т.е. большой радиус кривизны) и нуклефильность.

The cationic metal complexes of group VIII described above are associated with weakly coordinating or non-coordinating counterion CA ^- , which is relatively inert, weakly nucleophilic and provides a cationic complex that is significantly soluble in the solvent of the reaction mixture. The anion is selected taking into account the requirements of lability, stability and inertness with respect to the cationic complex of a Group VIII metal in the final catalyst sample and imparting to the one-component catalyst of the invention solubility in the solvents used in the present invention. Anions that are stable when interacting with water or Bronsted acids and do not have acid protons located on the outside of the anion (i.e. anionic complexes that do not interact with strong acids or bases) have the necessary stability to qualify them as a stable anion for catalytic system. Anion properties important for maximum lability include overall size and shape (i.e. large radius of curvature) and nucleophilicity.

 In general terms, a suitable anion can be any stable anion that allows the catalyst to be dissolved in a selected solvent and satisfies the following requirements: (1) the anion must form stable salts with the above Lewis acids, Bronsted acids, reducing Lewis acids, protonated Lewis bases, thallium cations and silver; (2) the negative charge of the anion must be delocalized in the structure of the anion or localized in the nucleus of the anion; (3) the anion should be relatively weakly nucleophilic and (4) the anion should not be a strong reducing agent or oxidizing agent.

где R" независимо означает водород, фтор и трифторметил и n равно от 1 до 5.Anions satisfying these criteria are anions selected from the group consisting of tetrafluorides of Ga, Al or B; P, Sb or As hexafluorides; perfluoroacetates, propionates and butyrates, hydrogenated perchlorates, toluenesulfonates, trifluoromethyl sulfonates and substituted tetraphenylborates substituted on the phenyl ring with fluorine or trifluoromethyl. Selected examples of counter-anions include BF ₄ ^- , PF ₆ ^- , AlF ₃ O ₃ SCF ₃ ^- , SbF ₆ ^- , SbF ₅ SO ₃ F ^- , AsF ₆ ^- , trifluoroacetate (CF ₃ CO ₂ ^- ), pentafluoropropionate (C ₂ F ₅ CO ₂ ^- ), heptafluorobutyrate (CF ₃ CF ₂ CF ₂ CO ₂ ^- ), perchlorate (ClО ₄ ^- • H ₂ O), p-toluenesulfonate (p-CH ₃ C ₆ H ₄ SO ₃ ^- ) and tetraphenyl borate having the formula :

where R "independently means hydrogen, fluorine and trifluoromethyl and n is from 1 to 5.

Катализатор содержит π-аллильный комплекс металла группы VIII со слабокоординирующим противоанионом. Аллильные группы катионного комплекса металла создаются с помощью соединения, содержащего аллильные функциональные группы, связанные с атомом металла одинарной углерод-металл σ-связью и олефиновой π-связью. Металл М группы VIII, предпочтительно, выбран из никеля и палладия. Наиболее предпочтительным металлом является палладий. Было неожиданно найдено, что такие однокомпонентные катализаторы, у которых М является палладием и катионный комплекс не содержит других лигандов, кроме аллильных функциональных групп (т.е. L_y=0), проявляют превосходную активность при полимеризации функциональных полициклических мономеров, таких как мономеры, содержащие силильные функциональные группы, согласно изобретению. Как обсуждалось выше, должно быть понятно, что катализаторы сольватированы разбавителем в реакционной среде, который может рассматриваться как очень слабый лиганд по отношению к металлу группы VIII в катионном комплексе.A preferred one-component catalyst in the above embodiment has the formula:

The catalyst contains a π-allyl complex of a Group VIII metal with a weakly coordinating counteranion. Allyl groups of the metal cationic complex are created using a compound containing allyl functional groups bonded to the metal atom by a single carbon-metal σ-bond and olefinic π-bond. The metal of group VIII is preferably selected from nickel and palladium. The most preferred metal is palladium. It was unexpectedly found that such single-component catalysts in which M is palladium and the cationic complex does not contain ligands other than allyl functional groups (i.e., L _y = 0) exhibit excellent activity in the polymerization of functional polycyclic monomers, such as monomers, containing silyl functional groups according to the invention. As discussed above, it should be understood that the catalysts are solvated with a diluent in a reaction medium, which can be considered as a very weak ligand with respect to the Group VIII metal in the cationic complex.

The substituents R ²⁰ , R ²¹ and R ²² in the allyl group represented above in structures VIII, IX and XIII, independently of one another, are hydrogen, branched or unbranched C ₁ -C ₅ alkyl such as methyl, ethyl, n-propyl , isopropyl and tert-butyl, C ₆ -C ₁₄ aryl such as phenyl and naphthyl, C ₇ -C ₁₀ aralkyl such as benzyl, -COOR ¹⁶ , - (CH ₂ ) _n OR ¹⁶ , Cl and C ₅ cycloaliphatic radical —C ₆ , where R ¹⁶ is C ₁ -C ₅ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, and n is from 1 to 5.

где R²³ означает водород, нормальный или разветвленный алкил С₁-C₅, такой как метил, этил, н-пропил, изопропил, н-бутил, изобутил и пентил, R²⁴ означает метилкарбонил и R²⁵ означает нормальный или разветвленный алкил С₁-С₂₀. Противоанион СА^- охарактеризован выше.Any two substituents from R ²⁰ , R ²¹ and R ²² may be connected to each other to form cyclic and polycyclic ring structures, but not necessarily. The cyclic ring structure may be carbocyclic or heterocyclic. Preferably, any two substituents R ²⁰ , R ²¹ and R ^22, together with the carbon atoms to which they are bonded, form rings containing from 5 to 20 atoms. Representative heteroatoms are nitrogen, sulfur and carbonyl. Examples of cyclic groups with allyl functionality are the following structures:

where R ²³ means hydrogen, straight or branched C ₁ -C ₅ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and pentyl, R ²⁴ means methyl carbonyl and R ²⁵ means straight or branched C ₁ alkyl -C ₂₀ . Counter anion CA ^- characterized above.

, P.L.I. Nagy и G.N. Schrauzer в книге Достижения элементоорганической химии (Advances in Organometallic Chemistry, New York, Academic Press Inc. , 1964, том 2); W.T. Dent, R. Long и A.J. Wilkinson в Журнале химического общества (J. Chem. Soc., 1964, с. 1585); Н.С. Volger в Rec. Trav. Chim. Pay Bas, (1969), 88, с. 225, которые приведены здесь в качестве ссылки.Additional examples of π-allyl metal complexes are presented by RG Guy and BLShaw in Advances in Inorganic Chemistry and Radiochemistry, New York, Academic Press Inc., 1962, Volume 4); J. Birmingham, E. de Boer, MLH Green, RB King, R.

, PLI Nagy and GN Schrauzer in Achievements of Organoelemental Chemistry (Advances in Organometallic Chemistry, New York, Academic Press Inc., 1964, Volume 2); WT Dent, R. Long, and AJ Wilkinson in the Journal of the Chemical Society (J. Chem. Soc., 1964, p. 1585); N.S. Volger in Rec. Trav. Chim. Pay Bas, (1969), 88, p. 225, which are incorporated herein by reference.

 A one-component catalyst of the aforementioned embodiment can be prepared by combining a ligated halide component of a Group VIII metal with a salt, which creates a counterion for the subsequently formed cationic metal complex. The ligated compound of a Group VIII metal halide, a counter-anion forming salt, and optionally a compound containing a π bond, for example cyclooctadiene, are combined in a solvent capable of solvating the formed single-component catalyst. When this is used, preferably the same solvent as introduced into the reaction medium. The catalyst may be preformed in a solvent or directly (in situ) in the reaction medium.

Специфический катализатор [aллил-Pd-циклooктaдиeн]⁺PF₆ ^- получают предварительным образованием лигированного соединения галогенида палладия, например, бис(аллил Pd бромида), которое затем подвергают расщеплению агентом, отщепляющим галоген, в виде соли, создающей противоанион, т.е. TIPF₆, в присутствии циклооктадиена. Схема реакции может быть выражена следующим образом (см. в конце описания).Suitable counter anionic salts are any salts capable of providing the anions described above. For example, salts of sodium, lithium, potassium, silver, thallium and ammonium, in which the anion is selected from the counteranions (CA ^- ), described above. Examples of salt forming counteranions are TIPF ₆ , AgPF ₆ , AgSbF ₆ , LiBF ₄ NH ₄ , PF ₆ , KASF ₆ , AgC ₂ F ₅ CO ₂ , AgBF ₄ , AgCF ₃ CO ₂ , AgClO ₄ • H ₂ O, AgAsF ₆ , AgCF ₃ CF ₂ CF ₂ CO ₂ , AgC ₂ F ₅ CO ₂ , (C ₄ H ₉ ) ₄ NB (C ₆ F ₅ ) ₄ and

A specific catalyst [allyl-Pd-cycloactadiene] ⁺ PF ₆ ^{- is} obtained by preliminarily forming a ligated palladium halide compound, for example, bis (allyl Pd bromide), which is then cleaved with a halogen-cleaving agent in the form of a counter-anion salt, i.e. TIPF ₆ , in the presence of cyclooctadiene. The reaction scheme can be expressed as follows (see the end of the description).

 After cleavage, only one cyclooctadiene ligand remains, linked by two π-bonds to palladium. The allylic functional group is linked to palladium by one metal-carbon σ-bond and one π-bond.

 In order to obtain preferred one-component catalysts containing a group VIII / allyl metal complex compound of group VIII / counterion corresponding to structure XIII above, in which M is palladium, allylpalladium chloride is combined with the desired counterion to form a salt, preferably silver salt with a counteranion in an appropriate solvent . The chloride ligand comes from the allyl palladium complex in the form of precipitated silver chloride (AgCl), which can be filtered from the solution. A one-component catalyst containing an allyl palladium cationic complex / counter anion remains in solution. Palladium is devoid of any ligand other than the allyl functional group.

An alternative one-component catalyst used in the invention may be represented by the following formula:
Pd [R ²⁷ CN] ₄ [CA ^- ] ₂ ,
where R ²⁷ independently means a straight or branched alkyl C ₁ -C ₁₀ and CA ^- means the above-described counter-anion.

Another one-component catalytic system for producing polymers used in the invention corresponds to the formula:
E _n Ni (C ₆ F ₅ ) ₂ ,
where n is 1 or 2 and E is a neutral ligand - a donor of 2 electrons. When n = 1, E is preferably a π-arene ligand such as toluene, benzene and mesitylene. When n = 2, E preferably means diethyl ether, tetrahydrofuran (THF) and dioxane. The ratio of monomer to catalyst in the reaction medium may vary from about 2000: 1 to about 100: 1. The reaction can be carried out in a hydrocarbon solvent such as cyclohexane, toluene and the like at a temperature of from about 0 ^° C to about 70 ^° C, preferably from about 10 ^° C to 50 ^° C, and more preferably from about 20 ^° C to about 40 ^° C. Preferred catalysts of the above formula are: toluenebis (perfluorophenyl) nickel, mesitylenebis (perfluorophenyl) nickel, benzolbis (perfluorophenyl) nickel, bis (tetrahydrofuran) bis (perfluorophenyl) nickel and bis (dioxane) bis (perfluorophenyl) nickel.

Multicomponent Systems
The multicomponent catalyst systems of the invention comprise a Group VIII metal ion source in combination with one or more organometallic catalysts and a third component. The cocatalyst is selected from organoaluminum compounds, dialkylaluminum hydrides, dialkylzinc compounds, dialkyl magnesium compounds and alkyl lithium compounds.

 The Group VIII metal ion source is preferably selected from compounds containing nickel, palladium, cobalt, iron and ruthenium, most preferably nickel and palladium. There is no limitation on the compound of a metal of group VIII, provided that it is a source of catalytically active metal ions of group VIII. Preferably, the Group VIII metal compound is soluble or may become soluble in the reaction medium.

 The Group VIII metal compound contains an ionic and / or neutral ligand (s) bound to the Group VIII metal. Ionic or neutral ligands can be selected from various monodentates, bidentates or polyidentates, and combinations thereof.

Термин "замещенный углеводород" означает углеводородную группу, определение которой приведено выше, у которой один или более атомов замещены на атом галогена, такого как Cl, F, Вr и I (например, как в перфторфенильном радикале); гидроксил; амино; алкил; нитро; меркапто и подобные. Соединения металла группы VIII могут также содержать катионы, такие как, например, органоаммониевые, органоарсониевые, органофосфониевые и пиридиновые соединения, соответствующие формуле:

где А означает азот, мышьяк и фосфор, а радикалы R²⁸ могут быть независимо выбраны из водорода, разветвленнного или неразветвленного алкила С₁-С₂₀, разветвленного или неразветвленного алкенила С₂-С₂₀ и циклоалкила C₅-C₁₆, например, такого как циклопентил, циклогексил, циклогептил, циклооктил и подобные. R²⁹ и R³⁰ независимо друг от друга выбраны из водорода, разветвленного или неразветвленного алкила С₁-С₅₀, нормального или разветвленного алкенила C₂-C₅₀ и циклоалкильных групп C₅-С₁₆, таких как определено выше; n равно от 1 до 5, предпочтительно, 1, 2 или 3, наиболее предпочтительно, n равно 1. Радикалы R³⁰, предпочтительно, присоединены в положениях 3, 4 и 5 пиридинового кольца.Representative ionic ligands that can be bonded to a metal to form a Group VIII metal compound are anionic ligands selected from halogen ions such as chlorine, bromine, iodine and fluorine; like halogen-containing compounds, such as cyanides, cyanates, thiocyanates, hydrides; hydrocarbon anions, such as branched or unbranched C ₁ -C ₄₀ alkyl anions, phenyl anions; cyclopentadienylide anions, π-allyl groups; enolates of β-dicarbonyl compounds such as acetylacetonate, 4-pentanedionate, 2,2,6,6-tetramethyl-3,5-heptanedione and halogenated acetylacetonates such as 1,1, 1,5,5,5-hexafluoro-2 4-pentanedionate; 1,1,1-trifluoro-2,4-pentanedionate; anions of acid derivatives of carbon oxides such as carboxylates and halogenated carboxylates (e.g. acetates, 2-ethylhexanoates, neodecanoates, trifluoroacetates, etc.) and nitrogen oxides (e.g. nitrates, nitrites, etc.), bismuth (e.g. bismuthates, etc.), oxides of aluminum (e.g., aluminates, etc.), silicon (e.g., silicates, etc.), phosphorus (e.g., phosphates, phosphites, phosphines, etc.), oxides sulfur (e.g. sulfates such as triflate, p-toluenesulfonate, sulfites, etc.); ylides; amides; imides, oxides; phosphides; sulfides; C ₆ -C ₂₄ aryloxides, C ₁ -C ₂₀ alkoxides; hydroxides, hydroxyalkyls C ₁ -C ₂₀ ; catechols; oxalates; chelating alkoxides and aryloxides. Palladium compounds may also contain anions, such as PF ₆ ^- , AlF ₃ O ₃ SCF ₃ ^- , SbF ₆ ^- and compounds corresponding to the formula:
A1 (R`` ') ^- ₄ , B (X) ^- ₄ ,
where R ″ ″ and X, independently of one another, are a halogen atom selected from the group Cl, F, I and Br, or substituted or unsubstituted hydrocarbon groups. Representative hydrocarbon groups are C ₁ -C ₂₅ alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octodecyl , eicosyl, geneikosyl, docosyl, tricosyl, tetracosyl, pentacosyl and their isomers; C ₂ -C ₂₅ alkenyl, such as vinyl, allyl, crotyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nenodenyl, C ₆ -C ₂₅ aryl such as phenyl, tolyl, xylyl, naphthyl and the like; C ₇ -C ₂₅ aralkyl, such as benzyl, phenethyl, phenpropyl, phenbutyl, phenhexyl, naphthoctyl and the like; C ₃ -C ₈ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-norbornyl, 2-norbornyl and the like. In addition to the above values of X means a radical:

The term “substituted hydrocarbon” means a hydrocarbon group as defined above, in which one or more atoms are replaced by a halogen atom such as Cl, F, Br and I (for example, as in a perfluorophenyl radical); hydroxyl; amino; alkyl; nitro; mercapto and the like. Group VIII metal compounds may also contain cations, such as, for example, organoammonium, organoarsonium, organophosphonium and pyridine compounds corresponding to the formula:

where A means nitrogen, arsenic and phosphorus, and the radicals R ²⁸ can be independently selected from hydrogen, branched or unbranched alkyl C ₁ -C ₂₀ , branched or unbranched alkenyl C ₂ -C ₂₀ and cycloalkyl C ₅ -C ₁₆ , for example, such like cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. R ²⁹ and R ³⁰ are independently selected from hydrogen, branched or unbranched alkyl, C ₁ -C ₅₀ straight or branched alkenyl, C ₂ -C ₅₀ cycloalkyl groups and C ₅ -C _16, such as defined above; n is from 1 to 5, preferably 1, 2 or 3, most preferably n is 1. The radicals R ³⁰ are preferably attached at the 3, 4 and 5 positions of the pyridine ring.

It should be noted that an increase in the total number of carbon atoms in the radical R ²⁸ promotes better solubility of the transition metal compound in an organic medium, such as organic solvents and polycyclic monomers. Preferably, the R ²⁸ radicals are selected from C ₁ -C ₁₈ alkyl groups, the total number of carbon atoms in all R ²⁸ radicals being from 15 to 72, preferably from 25 to 48, more preferably from 21 to 42. The radical R ²¹ , preferably selected from straight or branched C ₁ -C ₅₀ alkyl, more preferably C ₁₀ -C ₄₀ alkyl. The radical R ³⁰ is preferably selected from straight or branched C ₁ -C ₄₀ alkyl, more preferably C ₂ -C ₃₀ alkyl.

 Specific examples of organoammonium cations include: tridecylammonium, methyltricaprylammonium, tris (tridecyl) ammonium and trioctylammonium. Specific examples of organo-arsonium and organophosphonium cations include tridedecylarsonium and phosphonium, methyltricaprylarsonium and phosphonium, tris- (tridecyl) arsonium and phosphonium, trioctylarsonium and phosphonium. Specific pyridinium cations include: eicosyl-4- (1-butylpentyl) pyridinium, docosyl-4- (13-pentacosyl) pyridinium and eicosyl-4- (1-butylpentyl) pyridinium.

где радикалы R³¹ независимо означают углеводородный или замещенный углеводородный радикал, определенный выше, и n равно от 2 до 10. Мочевины, нитрилы, такие как ацетонитрил, бензонитрил и их галогенпроизводные; органические простые эфиры, такие как диметиловый эфир диэтиленгликоля, диоксан, тетрагидрофуран, фурандиаллиловый эфир, диэтиловый эфир, циклические простые эфиры, такие как циклические олигомеры диэтиленгликоля; органические сульфиды, такие как простые тиоэфиры (диэтилсульфид); арсины; стибины; фосфины, такие как триарилфосфины (например, трифенилфосфин), триалкилфосфины (например, триметилфосфин, триэтилфосфин, трипропилфосфин, трипентакозилфосфин и их галогенпроизводные), бис(дифенилфосфино)этан, бис(дифенилфосфино)пропан, бис(диметилфосфино)пропан, бис(дифенилфосфино)бутан, (S)-(-)2,2'-бис(дифенилфосфино)-1,1'-бинафтил, (R)-(+)-2,2'-бис(дифенилфосфино)-1,1'-бинафтил и бис(2-дифенилфосфиноэтил)фенилфосфин; фосфиноксиды, галогениды фосфора; фосфиты формулы
P(OR³¹)₃,
где R³¹ независимо означает углеводородный или замещенный углеводородный радикал, такой как указано выше; оксигалогениды фосфора; фосфонаты; фосфониты; фосфиниты; кетоны; сульфоксиды, такие как алкилсульфоксиды С₁-С₂₀; арилсульфоксиды C₆-С₂₀; алкарилсульфоксиды С₇-C₄₀ и подобные. Должно быть понятно, что вышеназванные нейтральные лиганды могут быть использованы в качестве возможного третьего компонента, как это будет описано ниже.Suitable neutral ligands that may be associated with the transition metal, palladium, are olefins; acetylenes; carbon monoxide; nitric oxide; nitrogen containing compounds such as ammonia, alkyl isocyanide, alkyl isocyanate, alkyl isothiocyanate; pyridines and pyridine derivatives (e.g., 1,10-phenanthroline, 2,2 '- (dipyridyl), 1,4-dialkyl-1,3-diazabutadiene, 1,4-diaryl-1,3-diazabutadiene and amines such as represented by the formulas:

where the radicals R ³¹ independently mean a hydrocarbon or substituted hydrocarbon radical, as defined above, and n is from 2 to 10. Urea, nitriles, such as acetonitrile, benzonitrile and their halogen derivatives; organic ethers, such as diethylene glycol dimethyl ether, dioxane, tetrahydrofuran, furandiallyl ether, diethyl ether, cyclic ethers, such as cyclic diethylene glycol oligomers; organic sulfides such as thioethers (diethyl sulfide); arsines; stibines; phosphines such as triarylphosphines (e.g. triphenylphosphine), trialkylphosphines (e.g. trimethylphosphine, triethylphosphine, tripropylphosphine, tripentacosylphosphine and their halogen derivatives), bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane, bis (diphenylphosphino) propane, bis (bis) , (S) - (-) 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, (R) - (+) - 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl and bis (2-diphenylphosphinoethyl) phenylphosphine; phosphine oxides, phosphorus halides; phosphites of the formula
P (OR ³¹ ) ₃ ,
where R ³¹ independently means a hydrocarbon or substituted hydrocarbon radical, such as described above; phosphorus oxyhalides; phosphonates; phosphonites; phosphinites; ketones; sulfoxides, such as C ₁ -C ₂₀ alkyl sulfoxides; aryl sulfoxides C ₆ -C ₂₀ ; C ₇ -C ₄₀ alkarylsulfoxides and the like. It should be understood that the above neutral ligands can be used as a possible third component, as will be described below.

Examples of Group VIII transition metal compounds suitable as a source of Group VIII metal ions are: palladium ethyl hexanoate, trans-PdCl ₂ (PPh ₃ ) ₂ , palladium (II) bis (trifluoroacetate), palladium (II) bis (acetylacetonate), 2 palladium (II) ethylhexanoate, Pd- (acetate) ₂ (PPh ₃ ) ₂ , palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitrile tris (triphenylphosphine) palladium (II) ) tetrafluoroborate, tetrakis (acetonitrile) palladium (II) tetrafluoroborate, dichlorbis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), di lorbis (benzonitrile) palladium (II), palladium acetylacetonate, bis (acetonitrile) dichloride palladium bis (dimethylsulfoxide) palladium dichloride; Nickel acetylacetonates, Nickel carboxylates, Nickel dimethylglyoxime, Nickel ethylhexanoate, NiCl ₂ (PPh ₃ ) ₂ , NiCl ₂ (PPh ₂ CH ₂ ) ₂ , (P (cyclohexyl) ₃ ) N-Ni (Ph ₂ P (C ₆ H ₄ ) CO ₂ ), (PPh ₃ ) (C ₆ H ₅ ) Ni (Ph ₂ PCH = C (O) Ph), nickel (II) bis (2,2,6,6-tetramethyl-3,5-heptanedionate), nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, nickelocenes, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel bis, nickel oxide nickel, bis (cyclopentadienyl) nickel, neodymium cobalt ecanoate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, cobalt dichlorohexyl acetate, cobalt (II) cobaltate (II) stearate, tetraf , iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene; ruthenium tris (triphenylphosphine) dichloride, ruthenium tris (triphenylphosphine) hydridochloride, ruthenium trichloride, ruthenium tetrakis (acetonitrile) dichloride, ruthenium tetrakis (dimethyl sulfoxide) dichloride; rhodium chloride, rhodium tris (triphenylphosphine) trichloride.

The organoaluminum compounds of the multicomponent catalyst systems of the present invention can be represented by the formula
AlR ³² _{3 x} Q _x
where R ³² independently mean straight or branched alkyl C ₁ -C ₂₀ , aryl C ₆ -C ₂₄ , aralkyl C ₇ -C ₂₀ , cycloalkyl C ₃ -C ₁₀ ; Q means a halide compound or a pseudo-halide compound selected from chlorin, fluorine, bromine, iodine, straight or branched C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₄ aryloxy, and x is from 0 to 2.5, preferably from 0 to 2.

Representative organoaluminum compounds include trialkylaluminum, such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methyl-butylaluminum, tri-2-methylpentylaluminium-aluminum, tri-2-methylpentylaluminium-aluminum, tri-2-methyl-aluminum-tri-aluminum tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, trioctylaluminum, tris-2-norbornylaluminum and the like; dialkylaluminium halides such as dimethylaluminium chloride, diethylaluminium chloride, diisopropylaluminium chloride, diisobutylaluminium chloride and the like; monoalkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, ethylaluminium diiodide, propylaluminum dichloride, isopropylaluminum dichloride,
butylaluminum dichloride, isobutylaluminum dichloride and the like; alkylaluminum sesquichlorides, such as methylaluminum sulphate, ethylaluminum sulphate, propylaluminum sulphate, isobutylaluminum sulphate and the like.

Dialkylaluminium hydrides are selected from straight and branched dialkylaluminum hydrides (C ₁ -C ₁₀ ). Diisobutylaluminum hydride is preferred.

Dialkylzinc compounds are selected from straight and branched (C ₁ -C ₁₀ ) dialkylzinc compounds. Diethylzinc is preferred. The dialkyl magnesium compounds are selected from straight and branched (C ₁ -C ₁₀ ) dialkyl magnesium. Most preferred is dibutylmagnesium. Alkyl lithium compounds are selected from straight and branched (C ₁ -C ₁₀ ) alkyl lithium compounds. Butyl lithium is preferred.

Dialkyl aluminum hydrides are selected from straight or branched (C ₁ -C ₁₀ ) dialkyl aluminum hydrides. Diisobutylaluminum hydride is preferred.

Dialkylzinc compounds are selected from straight or branched (C ₁ -C ₁₀ ) dialkylzinc compounds. Diethylzinc is preferred. Dialkyl magnesium compounds are selected from straight or branched (C ₁ -C ₁₀ ) dialkyl magnesium. Dibutylmagnesium is preferred. Alkyl lithium is selected from straight or branched (C ₁ -C ₁₀ ) -alkyl lithium compounds. Butyl lithium is preferred.

 According to the present invention, a catalyst system obtained from a Group VIII metal ion source is used with one or two components selected from the group consisting of cocatalyst compounds and compounds of the third component.

Доноры электронов, такие как фосфины и фосфиты, и олефиновые доноры выбирают из алифатических С₄-С₁₂ и циклоалифатических диолефинов C₆-C₁₂, таких как бутадиен, циклооктадиен и норборнадиен.Examples of the third components are Lewis acids, such as BF ₃ • ether, TiCl ₄ , SbF ₅ , Tris (perfluorophenyl) boron, BC1 ₃ , B (OCH ₂ CH ₃ ) ₃ ; strong Bronsted acids such as hexafluoroboric acid (HSbF ₆ ), hydrate HPF ₆ , trifluoroacetic acid (CF ₃ CO ₂ H) and FSO ₃ H • SbF ₅ , H ₂ C (SO ₂ CF ₃ ) ₂ CF ₃ SO ₃ H and paratoluenesulfonic acid; halogenated compounds such as hexachloroacetone, hexafluoroacetone, 3,3-butenoic acid 2,2,3,4,4-pentachlorobutyl ester, hexafluorglutaric acid, hexafluoroisopropanol and chloranil, i.e. compound of the formula:

Electron donors such as phosphines and phosphites and olefin donors are selected from aliphatic C ₄ -C ₁₂ and cycloaliphatic C ₆ -C ₁₂ diolefins such as butadiene, cyclooctadiene and norbornadiene.

The acidity of strong Bronsted acids can be evaluated by determining their acidity function according to Hammett H _o , which can be found in FA Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Wiley-lnterscience, 1988, p. 107.

 As noted above, neutral ligands can be used as an optional third component with electron-donor properties.

 According to one embodiment of the invention, a multi-component catalyst system can be prepared by co-mixing the catalyst components, i.e. compounds of a metal of group VIII, a cocatalyst compound and a third component, if the latter is used, in a hydrocarbon or halogenated hydrocarbon solvent, followed by mixing the catalyst system obtained in the preliminary mixing process with components of the reaction medium containing at least one polycyclic monomer with strong functional group. Alternatively (if a possible third component is used), any two components of the catalyst system can be pre-mixed in a hydrocarbon or halocarbon solvent and then introduced into the reaction medium. The remaining catalyst component may be introduced into the reaction medium before or after the addition of the premixed components.

 In another embodiment, a multicomponent catalyst system can be prepared in situ by jointly mixing all of the catalyst components in a reaction medium. In this case, the mixing order does not matter.

According to one embodiment of the multicomponent catalyst system of the present invention, a typical catalyst system comprises a Group VIII transition metal salt, for example, nickel ethyl hexanoate, an organoaluminum compound, for example triethyl aluminum, and a mixture of third components, for example, BF ₃ • ether and hexafluorobutyric acid (HSbF ₆ ) in a preferred molar ratio A1 / BF ₃ • ether / Ni / acid 10: 9: 1: 0.5-2. The reaction scheme is as follows:
1. Nickel ethylhexanoate + HSbF ₆ + 9BF ₃ • ether + 10 triethylaluminium ->
Active catalyst
According to another embodiment of the multicomponent catalyst system of the invention, a typical catalyst system comprises a nickel salt, for example nickel ethyl hexanoate, an organoaluminum compound, for example triethylaluminium, and a third component, a Lewis acid, for example tris (perfluorophenyl) boron, as shown in the following scheme:
2. Nickel ethylhexanoate + tris (perfluorophenyl) boron + triethylaluminium ->
Active catalyst
In a further embodiment of the multi-component catalyst system of the invention, the third component is a halogenated compound selected from various halogenated activators. A typical catalyst system contains a Group VIII transition metal salt, organoaluminium, and a halogenated compound as a third component, as shown below:
3. Nickel ethylhexanoate + aluminum triethyl + chloranil ->
Active catalyst
In yet another embodiment of the multi-component catalyst system of the invention, no cocatalyst is present. The catalyst system contains a Group VIII metal salt (e.g., 3-allyl nickel bromide dimer and Lewis acid (e.g., Tris (perfluoro-phenyl) boron), as shown below:
4. η ^3- allyl nickel chloride + tris (perfluorophenyl) boron ->
Active catalyst
We found that the choice of a Group VIII metal in a cationic metal-containing complex of both one- and multicomponent catalyst systems according to the invention affects the microstructure and physical properties of the obtained polymers. For example, we have found that palladium catalysts usually produce norbornene units exclusively attached at position 2, 3 and exhibiting some degree of regularity. The polymers obtained in the presence of type 2 catalyst systems and in the presence of one-component catalyst systems of the formula E _n Ni (C ₆ F ₅ ) ₂ described above contain at least one of the two ends of the polymer chain a perfluorophenyl group. In other words, a perfluorophenyl residue can be located at one end or at both ends of the polymer. In any case, perfluorophenyl groups are linked by covalent bonds and are lateral to the terminal polycyclic repeating units of the main polymer chain.

 The reactions using the single and multicomponent catalysts of this invention are carried out in an organic solvent that does not adversely affect the catalyst system and which is a solvent for the monomer. Examples for organic monomers are aliphatic non-polar hydrocarbons such as pentane, hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, chlorobenzene, o-dichlorobenzene, toluene and xylene; polar halogenated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane , 1-chloro-2-methylpropane and 1-chloropentane.

 The choice of solvent for the reaction is carried out taking into account several factors, including the type of catalyst chosen and the type of polymerisation process (suspension polymerisation or polymerisation in solution). For most catalysts of the invention, preferred solvents are chlorinated hydrocarbons, such as methylene chloride and 1,2-dichloroethane, and aromatic hydrocarbons, such as chlorobenzene and nitrobenzene. Simple hydrocarbons are less preferred due to the lower conversion of monomers with NB-type functional groups. Unexpectedly, we found that some catalytic systems, most notably, multicomponent catalysts based on Group VIII metal compounds and alkyl aluminum halide, especially dihaloidal monoalkyl aluminum (e.g. ethyl aluminum dichloride) and type 2 catalysts mentioned above, also give excellent results (high degree monomer conversion) during the reaction in heptane, cyclohexane and toluene.

 The molar ratio of all monomers to Group VIII metal for single and multicomponent catalysts can be from 20: 1 to 100000: 1, preferably 50: 1 to 20,000: 1, and most preferably from 100: 1 to 10,000: 1.

 In multicomponent catalytic systems, the molar ratio of the metal of the cocatalyst (e.g. aluminum, zinc, magnesium and lithium) to the metal of group VIII is less than or equal to 100: 1, preferably less than or equal to 30: 1, and most preferably less than or equal to 20: 1.

 The third component is used in a molar ratio to the metal of group VIII from 0.25: 1 to 20: 1. In the case of using acids as the third component, the molar ratio of acid to metal of group VIII is less than or equal to 4: 1, preferably less than or equal to 2: 1.

The polymerization reaction of the present invention is usually carried out at a temperature of from (-100) ^° C to 120 ^° C, preferably from (-60) ^° C to 90 ^° C, most preferably from (-10) ^° C to 80 ^° C.

 The optimum temperature of the present invention depends on a number of changing factors, primarily on the choice of catalyst and diluent of the reaction mixture. Therefore, for any particular polymerization process, the optimum temperature is determined experimentally, taking into account the mentioned changing factors.

 When developing such catalysts and polymer systems, we found that the palladium-carbon bond connecting the palladium catalyst to the growing polymer chain is particularly stable. This is the main advantage in the polymerization of polycyclic monomers containing acid labile groups, ester and carboxyl functional groups, since palladium catalysts are especially resistant to such functional groups. However, this stability, on the other hand, greatly complicates the removal of the palladium catalyst from the obtained polymer. When developing such new components, we found that the palladium-carbon bond is conveniently cleaved (by precipitation of palladium, which can be removed by filtration or centrifugation) using carbon monoxide, preferably in the presence of a protic solvent such as alcohol, moisture or carboxylic acid .

The polymers obtained by the method in accordance with the invention have a molecular weight (M _n ) of from about 1000 to about 1,000,000, preferably from about 2,000 to about 700,000, and more preferably from about 5,000 to 500,000, and most preferably from about 10,000 to about 50,000.

где А означает ароматический заместитель и R означает углеводородный радикал.The molecular weight of the polymer can be controlled by changing the quantitative ratio of catalyst to monomer, i.e., by changing the ratio of initiator to monomer. Low molecular weight polymers and oligomers can also be obtained in the range of from about 500 to about 500,000 by carrying out the polymerization process in the presence of a chain transfer agent. Macromonomers and oligomers containing from 4 to 50 repeating units can be obtained in the presence of a chain transfer agent (APC) selected from compounds containing terminal olefinic double bonds between adjacent carbon atoms, in which at least one of adjacent carbon atoms has two hydrogen atoms associated with it. Chain transfer agents are compounds excluding styrenes (not styrenes), vinyl ethers (not vinyl esters), and conjugated dienes. Compounds other than styrenes and vinyl ethers (not styrenes and not vinyl ethers) mean compounds having the following structures that are excluded from chain transfer agents of the invention:

where A is an aromatic substituent and R is a hydrocarbon radical.

где R' и R", независимо друг от друга, означают водород, разветвленный или неразветвленный алкил С₁-С₄₀, разветвленный или неразветвленный алкенил C₂-С₄₀, галоген или группу.Preferred chain transfer agents of the invention are compounds corresponding to the following formula:

where R 'and R ", independently of one another, are hydrogen, C ₁ -C ₄₀ branched or unbranched alkyl, C ₂ -C ₄₀ branched or unbranched alkenyl, halogen or a group.

 Of the chain transfer agents provided, α-olefins containing from 2 to 10 carbon atoms, for example, ethylene, propylene, 4-methyl-1-pentene, 1-hexene, 1-decene, 1,7-octadiene and 1,6, are preferred -octadiene or isobutylene.

 Although the optimal conditions for achieving any predetermined result should be determined experimentally by a specialist, taking into account all the above factors, there are some general guidelines that may be suitable in appropriate cases. We have found that, in general, α-olefins (e.g. ethylene, propylene, 1-hexene, 1-decene, 4-methyl-1-pentene) are the most effective chain transfer agents compared to 1,1-disubstituted olefins that are less effective. In other words, ceteris paribus, to achieve a given molecular weight will require a much higher concentration of isobutylene than when using ethylene. Styrene olefins, conjugated dienes and vinyl ethers are not effective chain transfer agents because of their tendency to polymerize with the catalyst described above.

 The chain transfer agent can be used in an amount of from about 0.10 to more than 50 mol% of the number of moles of all NB-type monomers. Preferably, the chain transfer agent is used in an amount of from 0.10 to 10 mol% and, most preferably, from 0.1 to 5.0 mol%. As noted above, depending on the type of catalyst and sensitivity, the effectiveness of the chain transfer agent and the desired end groups, the concentration of the chain transfer agent can be over 50 mol. % (based on the total number of monomers with NB functionality present), for example, from 60 to 80 mol%. To obtain low molecular weight products of the invention, such as oligomers and macromonomers, a higher concentration of chain transfer agent (e.g., greater than 100 mol%) may be required. It is important to note that, surprisingly, even such high concentrations of chain transfer agents (with the exception of isobutylene) do not copolymerize into the main chain of the polymer, but are included in the form of end groups of each polymer chain. The method of the invention provides a route in which, in addition to chain transfer agents, terminal α-olefin groups can be included at the ends of the polymer chain.

The polymers of the present invention, obtained in the presence of a chain transfer agent, have a molecular weight (M _n ) of from about 1000 to about 500,000, preferably from about 2000 to about 300,000, and most preferably from about 5000 to about 200,000.

 The photoresist compositions of the present invention contain the described polycyclic compositions, a solvent, and a photosensitive acid generator (photoinitiator). If necessary, a dissolution inhibitor may be added in an amount up to about 20% by weight of the composition. A suitable dissolution inhibitor is tert. butylcholate (J.V. Crivello et al., Chemically Amplified Electron-Beam Photoresists, Chem. Mater., (1996), 8, pp. 376-381).

 When irradiated, a radiation-sensitive acid generator generates a strong acid. Suitable photoinitiators include triflates (for example triphenylsulfonium triflate), pyrogallol (for example pyrogallol trimesylate); onium layers, such as triarylsulfonium and diaryliumium hexafluoroantimonates, hexafluoroarsenates, trifluoromethanesulfonates; esters of hydroxyimides, α, α′-bis-sulfonyl-diazomethanes, sulfonate esters of nitro-substituted benzyl alcohol and naphthoquinone-4-diazides. Other suitable acid photoinitiators are described by Reichmanis et al., Chem. Mater., (1991), 3, p. 395. Compositions containing triarylsulfonium or diarylsulfonium salts are preferred because of their sensitivity to deep UV radiation (from 193 to 300 nm) and the very high resolution of the images. Most preferred are unsubstituted and symmetric or asymmetric substituted diaryliodium or triarylsulfonium salts. The content of the acid photoinitiator component is from about 1 to 100 wt. % polymer. A content of 5 to 50% by weight of the polymer is preferred.

 The photoresist compositions of the present invention optionally comprise a sensitizer capable of sensitizing an acid photoinitiator with respect to longer wavelengths in the region from medium wavelength UV radiation to visible light. Depending on the intended use, such sensitizers include polycyclic aromatic compounds such as perens and perlins. The sensitization of acid photoinitiators is well known and is described in US Pat. Nos. 4,250,053, 4,371,605 and 4,491,628, incorporated herein by reference. The invention is not limited to a specific class of sensitizers and acid photoinitiators.

 The present invention also relates to a method for generating positive resistive images on a substrate, the method comprising the steps of: a) coating the substrate with a film containing a resistive positive tone composition according to the invention, b) irradiating the film with image forming radiation, and c) developing the image.

The first step involves coating the substrate with a film obtained from a positive resist composition dissolved in a suitable solvent. Suitable substrates are made of silicone, ceramic, polymer, etc. Suitable solvents include: propylene glycol methyl ester acetate (AMEPG), cyclohexanone, butyrolactate, ethyl lactate and the like. The film is applied to a substrate by coating methods known in the art, such as centrifugation or spraying, or with a doctor blade. Preferably, before irradiation, the film is heated at an elevated temperature from about 90 ^{° C.} to 150 ^{° C.} for a short period of time of about 1 minute. In the second stage of the process, the film is irradiated with radiation forming an image, for example, electron beams or, preferably, electromagnetic radiation, such as UV or X-ray radiation, preferably UV radiation, for example, with a wavelength of about 193 to 514 nm, preferably about from 193 to 248 nm. Suitable radiation sources are: mercury, mercury / xenon and xenon lamps, x-ray and electron beam. The radiation-sensitive acid generator absorbs radiation to form free acid in the irradiated areas. Free acid breaks down the lateral acid-labile groups of the copolymer, as a result of which the copolymer is converted from a dissolution inhibitor to a dissolution enhancer, thereby increasing the solubility of the irradiated resistance composition in an aqueous base solution. Surprisingly, the irradiated resist composition readily dissolves in an aqueous solution of the base. This solubility is surprising and unexpected given the complex nature of the cycloaliphatic chain and the high molecular weight of the units of the norbornene monomer containing functional carboxyl groups. Preferably, after irradiation, the film is again heated at an elevated temperature of from about 90 ^{° C.} to 150 ^{° C.} for a short period of time of about 1 minute.

 The third stage is to obtain a positive tone image using a suitable solvent. Suitable solvents include, preferably, an aqueous solution of a base that does not contain metal ions, such as tetramethylammonium hydroxide or choline. The composition of the invention creates high contrast positive images with smooth walls. Uniquely, the solubility of the composition of the present invention can vary by a simple change in the composition of the copolymer.

 The present invention also relates to integrated circuit blocks, such as an integrated circuit, a multi-chip integrated circuit module or circuit board, manufactured by the method of the present invention. The integrated circuit block contains a circuit obtained on a substrate as a result of the steps of: a) coating the substrate with a film obtained from a positive resistive composition according to the invention; b) irradiating the film with radiation forming an image; c) developing an image for opening the substrate; g) the formation of the circuit on the developed film located on the substrate, by known methods.

 After the substrate has been opened at the opening points, a circuit image can be obtained by coating a conductive material, such as conductive metals, using known techniques such as vapor deposition, sputtering, metal plating, chemical vapor deposition, or laser deposition. The surface of the film can be rolled to remove excess conductive material. In the manufacturing process of circuits in a similar manner, dielectric materials can also be applied to the substrate. In the process of producing p or n doped circuit transistors, inorganic ions such as boron, phosphorus and arsenic ions can be implanted into the substrate. Other methods for producing schemes are well known to those skilled in the art.

 In the following examples, methods for preparing and using certain compositions of the invention are described in detail. A detailed description serves as an example embodiment of the invention, while more general preparation methods are set forth above. The examples are given for illustrative purposes only and do not limit the scope of the invention.

 As noted above, photoresists are used to create and multiply an image from a photomask to a substrate. The efficiency of image transfer is determined by the wavelength of the radiation forming the image, the sensitivity of the photoresist and its ability to withstand etching conditions, in which an image is created on the released areas of the substrate. Photoresists are most often used in consumer form, when photoresists are etched in places not exposed to radiation (for positive photoresists), and the substrate is etched in places of irradiation. Since the photoresist is an organic material and the substrate is a typical inorganic material, the photoresist inherently has a higher etching rate during reactive ion etching, which requires an increase in the thickness of the photoresist compared to the substrate material. The lower the etching rate of the photoresist substance, the thinner the photoresist layer should be. As a result, a high resolution image can be achieved. Therefore, the lower the rate of reactive ion etching of the photoresist, the more attractive it is from a technological point of view. The etching rate is primarily determined by the main polymer chain, as shown below for the chlorine plasma etching process, which is a commonly used method of reactive ion etching in the manufacture of semiconductors.

 In the examples and description, the molar ratio of monomer to catalyst is given.

Polymer - Reactive ion etching rate under normal conditions, μm / min
1 - Novolak resin - 1.0
2 - Polyhydroxy styrene resist - 0.98
3 - 248 nm (deep UV) (a mixture of acrylate terpolymer / novolak, US patent 5372912) - 1.14
4 - 193 nm (polyacrylate terpolymer, Allen et al., Proceedings SPE (1995), 2438 (1), pp. 474 - 1.96
5 - Homopolynorbornene - 0.83
Polymers 1 and 2 are initially aromatic, while polymer 3 is obtained by copolymerization with a small amount of acrylate, which increases the etching rate of the polymer. Polymer 4 is completely based on acrylate to provide transparency at 193 nm (aromatic rings give the material a light tightness in this area, so there are no practically acceptable resistance materials for 193 nm based on traditional novolacs or p-hydroxystyrenes). These polymers almost double the etching rate. Polymer 5 has an etching rate even lower than that of standard photoresist materials (1 and 2), in addition to providing transparency at 193 nm. Therefore, the main chain of polymer 5 (cyclic polyaddition olefin) obtained in the presence of a multicomponent nickel catalyst according to the invention represents the achievement, in comparison with all previous attempts described in the technical literature, to obtain a resistor operating at 193 nm with reactive ion etching characteristics, comparable to commercial materials irradiated at longer waves. Indeed, the cyclic olefin polymer obtained by the polyaddition reaction may offer advantages in terms of etch resistance also at longer wavelengths. It is known from the literature (N. Gokan, S. Esho and Y. Ohnishi, J. Electrochem. Soc., (1983), 130 (1), p. 143) that increasing the C / H ratio decreases the etching rate of polymeric materials. Based on this assumption, the etching rate of polymer 5 should be between the etching rate of aromatic-based systems and acrylate systems. It is surprising that the cyclic olefin obtained by polyaddition exhibits super-etching resistance even in comparison with aromatic systems.

Example 1
Into a glass tube with a capacity of 50 ml, equipped with a Teflon ^® coated stir bar was added tert. 5-norbornene-carboxylic acid butyl ether (carbo-tert-butoxynorbornene) (2.0 g, 10.3 mmol, exo, endo 44/56). To this stirred monomer, a catalyst solution was added at room temperature over 30 minutes, obtained by adding the dimer η ^3- allyl palladium chloride (38 mg, 103 μmol) in chlorobenzene (5 ml) to silver hexafluoroantimonate (99 mg, 290 μmol) in chlorobenzene (5 ml), then the mixture is filtered through a microporous filter (to remove precipitated silver chloride). The reaction is carried out for 36 hours. By this time, the reaction mixture is gelled, turning into a clear yellow gel. After adding the gel to an excess of methanol, the polymer precipitates as a white powder, the polymer is washed with an excess of methanol and dried. The polymer yield is 1.5 g (75%). The presence of monomer with ether groups in the polymer is confirmed by infrared analysis showing strong bands at 1728 cm ^-1 (C = O band), 1251 cm ^-1 (C-O-C band) and 1369 cm ^-1 and 1392 cm ^-1 (characteristic tert.butyl groups), and the absence of an unconverted monomer by proton NMR. The molecular weight of the polymer found (M _w ) is 22500. Thermogravimetric analysis (TGA) in a nitrogen atmosphere (heating rate of 10 ^o C / min) indicates the polymer is thermally stable up to about 210 ^o C and then the loss is approximately 28% of the mass at 260 ^o C ( manifested in the loss of tert.butyl groups in the form of isobutene to obtain a homopolymer of 5-norbornenocarboxylic acid) and polymer degradation (loss of 90% of the total mass) at about 400 ^o C.

Example 2
The glass vial 50 ml, equipped with a Teflon ^® coated stir bar was added norbornene (0.8 g, 8.6 mmol), 1,2-dichloroethane (8 ml) and tert. 5-norbornenocarboxylic acid butyl ether (carbo-tert. butoxynorbornene) (0.2 g, 1 mmol, exo, endo 44/56). Nickel ethylhexanoate (3 μmol), trisperfluorophenylboron (23 μmol) and triethylaluminium (27 μmol) are added to this stirred solution at room temperature. Under these conditions, a reaction immediately proceeds with precipitation from the polymer solution in less than 10 s. After 60 minutes of the reaction, the contents of the reactor were dissolved in cyclohexane and poured into excess methanol. The polymer was washed with an excess of methanol and dried overnight in a vacuum oven at 80 ^° C. The polymer yield was 0.9 g (90%). The molecular weight of the polymer found by gel permeation chromatography is 535,000 (M _w ) with a degree of polydispersity of 4.7.

Example 3
The glass vial 50 ml, equipped with a Teflon ^® coated stir bar was added tert. 5-norbornenocarboxylic acid butyl ether (carbo-tert-butoxynorbornene) (2.2 g, 11.3 mmol, exo, endo 44/56). To this stirred monomer, a catalyst solution was added at room temperature obtained by adding a dimer of η ^3- allyl palladium chloride (29 mg, 74 μmol) in dichloroethane (6 ml) to silver tetrafluoroborate (61 mg, 311 μmol) in dichloroethane (6 ml) over a period of 30 min followed by filtration through a microporous filter (to remove precipitated silver chloride). After carrying out the reaction for 36 hours, the mixture gelled to form a clear yellow gel. After adding the gel to an excess of methanol, the polymer precipitates as a white powder. The polymer is washed with an excess of methanol and dried. The polymer yield is 1.4 g (64%). The presence of monomer units with ether groups in the polymer is confirmed by infrared analysis showing strong bands at 1728 cm ^-1 (C = O band), 1251 cm ^-1 (C-O-C band) and 1369 cm ^-1 and 1392 cm ^-1 ( characteristic of tert.butyl groups), and the absence of an unconverted monomer or carboxyl functional groups (proton NMR and IR). The molecular weight of the polymer found (M _w ) is 54100. Thermogravimetric analysis (TGA) in a nitrogen atmosphere (heating rate of 10 ^o C / min) shows the polymer to be thermally stable up to about 210 ^o C and then lose about 29% of the mass at 250 ^o C (which indicates the loss of tert.butyl groups in the form of isobutene with the formation of a homopolymer of 5-norbornenocarboxylic acid) with subsequent degradation of the polymer (loss of 80% by weight) at about 400 ^o C.

Example 4
Into a glass vial 100 ml equipped with a Teflon ^® coated stir bar was added norbornene (1.16 g, 12.3 mmol), 1,2-dichloroethane (50 ml) and tert. 5-norbornenocarboxylic acid butyl ether (carbo-tert. butoxynorbornene) (0.6 g, 3.1 mmol, exo, endo 44/56). To this stirred solution, palladium bis (2,2,6,6-tetramethyl-3,5-pentadionate) (31 mmol), trisperfluorophenylboron (279 mmol) are added at room temperature. After 16 hours of reaction, the contents of the reactor were poured into excess methanol. The polymer was washed with an excess of methanol and dried overnight in a vacuum oven at 80 ^° C. The polymer yield was 0.54 g (31%).

Example 5
The glass vial 50 ml, equipped with a Teflon ^® coated stir bar was added tert. 5-norbornenocarboxylic acid butyl ether (carbo-tert-butoxynorbornene) (4.4 g, 22.7 mmol, exo, endo 44/56). To this stirred monomer, a catalyst solution was added at room temperature obtained by adding a dimer of η ^3- allyl palladium chloride (41.5 mg, 113 μmol) in dichloroethane (7 ml) to silver tetrafluoroborate (42 mg, 215 μmol) in dichloroethane (7 ml) for 30 minutes, followed by filtration through a microporous filter (to remove precipitated silver chloride). Then the reaction mixture is heated in an oil bath at 75 ^o C. After 90 minutes it is found that the mixture has solidified into a gray polymer mass. The mass is dissolved in acetone to obtain a dark-colored solution. Gaseous carbon monoxide was bubbled through the solution for 30 minutes, resulting in a fine precipitation of finely ground black precipitate (metallic palladium and possibly other catalyst residues). The precipitate was removed by centrifugation, and this process was repeated two more times. Finally, the resulting colorless solution was filtered through a 45 μm microdisk, and the polymer was precipitated by adding an acetone solution to an excess of hexane. The white polymer was separated by centrifugation and dried overnight to obtain a copolymer in the form of a white powder (2.21 g, 50%). Thermogravimetric analysis under nitrogen (heating rate of 10 ^o C / min) shows the thermal stability of the polymer up to about 210 ^o C and then the loss of its mass, approximately 28% at 260 ^o C (indicating the loss of tert. Butyl groups in the form of isobutene to obtain homopolymer of 5-norbornenocarboxylic acid) followed by degradation of the polymer (loss of 90% of the total mass) at approximately 400 ^o C. Molecular mass M _n 3300 g / mol and M _w equal to 6900 g / mol (found by gel permeation chromatography in tetrahydrofuran, polystyrene standards) .

Example 6
The glass vial 50 ml, equipped with a Teflon ^® coated stir bar was added the pure exo isomer of tert. 5-norbornenocarboxylic acid butyl ether (carbo-tert-butoxynorbornene) (0.6 g). To this stirred monomer, a catalyst solution was added at room temperature obtained by adding a dimer of η ^3- allyl palladium chloride (30 mg) in dichloroethane (10 ml) to silver hexafluoroantimonate (50 mg) in dichloroethane (20 ml) over 30 minutes, followed by filtration through a microporous filter (to remove precipitated silver chloride). After 15 hours of reaction, the mixture was added to an excess of methanol to precipitate the polymer as a white powder. The polymer is washed with an excess of methanol and dried, the polymer yield of 0.5 g (85%). The found molecular weight of the polymer (M _w ) is 46900 and the polydispersity of 2.4.

Example 7
Into a glass vial 100 ml equipped with a Teflon ^® coated stir bar was added norbornene (4.01 g, 42.6 mmol), 1,2-dichloroethane (50 ml) and tert. 5-norbornenocarboxylic acid butyl ether (carbo-tert. butoxynorbornene) (2 g, 10.3 mmol, exo, endo mixture). To this stirred solution at room temperature is added a catalyst solution obtained by reacting a η ³ -allyl palladium chloride dimer (10 mg, 27.3 μmol) with silver hexafluoroantimonate (19.6 mg, 57 μmol) in 1,2-dichloroethane (3 ml) for 30 minutes, followed by filtration through a microporous filter. After 20 hours of reaction, the contents of the reactor were poured into excess methanol. The polymer is washed with an excess of methanol and dried. The polymer yield is 4.15 g. The determined molecular weight of the copolymer determined by gel permeation chromatography (M _w ) is 618,000 with a polydispersity of 7.1.

Example 8
Into a glass vial 100 ml equipped with a Teflon ^® coated stir bar was added norbornene (3.75 g, 39.8 mmol), 1,2-dichloroethane (50 ml) and tert. 5-norbornenocarboxylic acid butyl ether (carbo-tert. butoxynorbornene) (2 g, 10.3 mmol, exo, endo mixture). Palladium ethylhexanoate (12 μmol, Tris (perfluorophenyl) boron (108 μmol) and triethylaluminium (120 μmol) were added to this stirred solution at room temperature. After 72 hours, the contents of the reactor were poured into excess methanol. The polymer was washed with excess methanol and dried, redissolved in chlorobenzene and precipitated with an excess of methanol, filtered and washed with methanol before final drying in a vacuum oven overnight at 80 ^o C. The yield of the copolymer is 1.66 g. The molecular weight of the copolymer, determined by gel permeation chromatography imaging (M _w ) is equal to 194000 with a polydispersity of 2.3. The presence of monomer with ether groups in the copolymer is confirmed by infrared analysis showing the bands at 1730 cm ^-1 (C = O band) and 1154 cm ^-1 (C-O-C band ) in the absence of an unconverted monomer (proton NMR).

Example 9
Into a glass vial 100 ml equipped with a Teflon ^® coated stir bar was added 1,2-dichloroethane (25 ml) and tert. 5-norbornenocarboxylic acid butyl ether (carbo-tert. butoxynorbornene) (10 g, 51.5 mmol, exo, endo mixture). To this stirred solution at room temperature is added a catalyst solution obtained by reacting a η ^3- allyl palladium chloride dimer (82 mg, 223 μmol) with silver hexafluoroantimonate (200 mg, 581 μmol) in 1,2-dichloroethane (10 ml) over 30 minutes followed by filtration through a microporous filter. After 48 hours of reaction, the contents of the reactor were poured into excess methanol. The polymer is washed with an excess of methanol and dried. Homopolymer yield 4.5 g.

Example 10
Into a glass vial 100 ml equipped with a Teflon ^® coated stir bar was added 1,2-dichloroethane (50 ml), tert. 5-norbornenocarboxylic acid butyl ester (carbo-tert. butoxynorbornene) (5 g, 25.8 mmol, exo, endo mixture) nonborne (0.82 g, 8.7 mmol) and 5-triethoxysilyl norbornene (0.47 g, 1 , 8 mmol). To this stirred solution at room temperature is added a catalyst solution obtained by reacting a η ^3- allyl palladium chloride dimer (47.2 mg, 128 μmol) with silver tetrafluoroborate (138 mg, 700 μmol) in 1,2-dichloroethane (10 ml) in for 30 minutes, followed by filtration through a microporous filter. After 48 hours of reaction, the contents of the reactor were poured into excess methanol. The polymer is washed with an excess of methanol and dried. The yield of the thermopolymer is 5.3 g. The molecular weight value found by gel permeation chromatography is 39900 (M _w ) with a polydispersity of 3.2.

Example 11
The glass vial 50 ml, equipped with a Teflon ^® coated stir bar was added 7.25 g (37.5 mmol) of tert. norbornene butyl ether, 1.9 g (12.5 mmol) of norbornene methyl ester, 50 ml of freshly distilled dichloroethane, and the solution was degassed under argon. A 10 ml glass vial equipped with a Teflon ^® coated stir bar was charged with 0.0365 g (0.1 mmol) of η ³ dimer -allilpallady chloride (to produce eventually a monomer to catalyst ratio of 500: 1) and 2 ml of dichloroethane. In another 10 ml glass tube, 0.0344 g (0.1 mmol) of silver hexafluoroantimonate and 2 ml of dichloroethane are charged. A catalyst solution is prepared by mixing a dimer of allyl palladium chloride with a solution of silver hexafluoroantimonate inside a box with a dried atmosphere. There is an immediate precipitation of silver chloride, which is filtered to obtain a clear yellow solution. The yellow active catalyst solution was added to the monomer solution with a syringe, and the reaction mixture was stirred for 20 hours at 60 ^° C. There was no significant increase in viscosity, but a solid precipitated from the solution. The solution was cooled, concentrated in a rotary evaporator and precipitated in hexane to give a white polymer. Yield 2.3 g, 26%. The polymer is dried in vacuo at room temperature and its molecular weight is determined by gel permeation chromatography in tetrahydrofuran with polystyrene standards. The found value of the molecular weight M _n = 1950 g / mol and M _w = 3150 g / mol. ¹ H NMR indicates the presence of both methyl and tert. norbornene butyl ether and a small amount of acid - tert. hydrolysis product butyl ether.

перемешивающим стержнем, загружают 0,0365 г (0,1 ммоль) димера аллилпалладий хлорида, при отношении мономера к катализатору 500:1, и 2 мл дихлорэтана. В другую 10 мл стеклянную пробирку загружают 0,0344 г (0,1 ммоль) гексафторалюмината серебра и 2 мл дихлорэтана. Раствор катализатора готовят смешением раствора димера аллилпалладий хлорида с раствором гексафторантимоната серебра внутри бокса с осушенной атмосферой. Наблюдается немедленное осаждение хлорида серебра, который отфильтровывают для получения прозрачного желтого раствора. Раствор активного желтого катализатора добавляют к раствору мономера шприцем, и реакционную смесь перемешивают в течение 20 ч при 60^oС. Какого-либо значительного увеличения вязкости не наблюдается, но из раствора осаждается твердое вещество. Раствор охлаждают, концентрируют в роторном испарителе и осаждают в гексане для получения белого полимера. Выход 2,05 г, 25%. Полимер сушат в вакууме при комнатной температуре и определяют его молекулярную массу методом гельпроникающей хроматографии в тетрагидрофуране с полистирольными стандартами. Найденное значение молекулярной массы М_n=1440 г/моль и М_w= 2000 г/моль. ¹H ЯМР указывает на присутствие как метилового, так и трет. бутилового эфира норборнена и небольшого количества кислоты - продукта гидролиза трет. бутилового эфира.Example 12
The glass vial 50 ml, equipped with a Teflon ^® coated stir bar was added 2.42 g (12.5 mmol) of tert. norbornene butyl ether, 5.7 g (37.5 mmol) of norbornene methyl ether, 50 ml of freshly distilled dichloroethane, and the solution was degassed under argon. In a 10 ml glass tube equipped with a coated

with a stirring rod, 0.0365 g (0.1 mmol) of allyl palladium chloride dimer is charged at a ratio of monomer to catalyst of 500: 1 and 2 ml of dichloroethane. In another 10 ml glass tube, 0.0344 g (0.1 mmol) of silver hexafluoroaluminate and 2 ml of dichloroethane are charged. The catalyst solution is prepared by mixing a solution of allyl palladium chloride dimer with a solution of silver hexafluoroantimonate inside a box with a dried atmosphere. There is an immediate precipitation of silver chloride, which is filtered to obtain a clear yellow solution. The yellow active catalyst solution was added to the monomer solution with a syringe, and the reaction mixture was stirred for 20 hours at 60 ^° C. There was no significant increase in viscosity, but a solid precipitated from the solution. The solution was cooled, concentrated in a rotary evaporator and precipitated in hexane to give a white polymer. Yield 2.05 g, 25%. The polymer is dried in vacuo at room temperature and its molecular weight is determined by gel permeation chromatography in tetrahydrofuran with polystyrene standards. The found value of the molecular weight M _n = 1440 g / mol and M _w = 2000 g / mol. ¹ H NMR indicates the presence of both methyl and tert. norbornene butyl ether and a small amount of acid - tert. hydrolysis product butyl ether.

Example 13
The glass vial 25 ml, equipped with a Teflon ^® coated stir bar was added 2 g (7.94 mmol) of pure bicyclo [2.2.1] hept-5-ene-exo-2-t. butyl-exo-3-methyl dicarboxylic acid ester, followed by 15 ml of freshly distilled methylene chloride and 10 ml of methanol, and the solution was degassed in an argon atmosphere. A 10 ml glass vial equipped with a Teflon ^® coated stir bar was charged with 0.00588 g (0.0158 mmol) of η ³ dimer -allilpallady chloride at a monomer to catalyst ratio of 500: 1, and 2 ml of methylene chloride. In another 10 ml glass tube, 0.0108 g (0.0312 mmol) of silver hexafluoroantimonate and 2 ml of methylene chloride are charged. The catalyst solution is prepared by mixing a solution of the η ³ -allyl palladium chloride dimer with a solution of silver hexafluoroantimonate inside a box with a dried atmosphere. There is an immediate precipitation of silver chloride, which is filtered to obtain a clear yellow solution. The yellow active catalyst solution was added to the monomer solution with a syringe at 50 ^{° C.} , and the reaction mixture was stirred for 16 hours at room temperature. No significant increase in viscosity was observed, and the solution was filtered through a 0.5 micron filter, and then concentrated in a rotary evaporator. A viscous solution is dissolved in methanol and precipitated in a mixture of methanol with water to obtain a white solid. Yield 65%. The found molecular weight value (determined by gel permeation chromatography in tetrahydrofuran with polystyrene standards) M _n = 10250 g / mol and M _w = 19700 g / mol. ¹ H NMR indicates the presence of both methyl and tert. norbornene butyl ether.

Example 14
The glass vial 25 ml, equipped with a Teflon ^® coated stir bar was added 3.06 g (12.8 mmol) of pure diethyl ether bicyclo [2.2.1] hept-5-ene-exo, exo-2,3-dicarboxylic acid 2.5 g (12.8 mmol) tert. norbornene butyl ether, followed by 15 ml of freshly distilled methylene chloride and 10 ml of methanol, and the solution was degassed in an argon atmosphere. A 10 ml glass vial equipped with a Teflon ^® coated stir bar was charged with 0.0188 g (0.052 mmol) of allylpalladium chloride dimer (in a ratio of monomer to catalyst of 500: 1) and 2 ml of methylene chloride. In another 10 ml glass tube, 0.0357 g (0.104 mmol) of silver hexafluoroantimonate and 2 ml of methylene chloride are charged. The catalyst solution is prepared by mixing a solution of allyl palladium chloride dimer with a solution of silver hexafluoroantimonate inside a box with a dried atmosphere. There is an immediate precipitation of silver chloride, which is filtered to obtain a clear yellow solution. The yellow active catalyst solution was added to the monomer solution with a syringe at 50 ^{° C.} , and the reaction mixture was stirred for 16 hours at room temperature. No significant increase in the viscosity of the solution is observed, and the solution is filtered through a 0.5 μm filter, and then concentrated in a rotary evaporator. The resulting viscous solution was dissolved in methanol and precipitated in a mixture of methanol with water to obtain a white solid. Yield 23%. The found molecular weight value (determined by gel permeation chromatography in tetrahydrofuran with polystyrene standards) M _n = 15700 g / mol and M _w = 32100 g / mol. Thermogravimetric analysis (TGA) under nitrogen (heating rate of 10 ^o C / min) indicates the thermal stability of the polymer up to about 155 ^o C followed by a loss of approximately 20% of the mass at 290 ^o C (indicating the loss of tert. Butyl groups in the form of isobutylene with the formation of a homopolymer of 5-norbornenocarboxylic acid) with subsequent degradation of the polymer at about 450 ^o C.

Example 15
Synthesis of bicyclo [2.2.1] hept-5-eno-exo-2,3-dicarboxylic acid diethyl ester
Exo, exo-diethyl ether of norbornene is synthesized from exo-5-norbornene-2,3-dicarboxylic acid. Exo isomer receive
thermal conversion of endo-5-norbornene-2,3-dicarboxylic acid anhydride at 190 ^° C followed by recrystallization several times from toluene to obtain pure exo-5-norbornene-2,3-dicarboxylic anhydride. Part of the exo-anhydride is hydrolyzed in boiling water, and the solution is cooled to obtain pure dicarboxylic acid in almost quantitative yield. Dicarboxylic acid is converted to diethyl ether using a triethyl oxonium salt, as described below.

In a 250 ml three-necked flask equipped with a magnetic stirring bar, 16.0 g (0.0824 mol) of pure exo-norbornene dicarboxylic acid and 35 g (0.1846 mol) of triethyloxonium tetrafluoroborate are charged. The flask is sealed with stoppers and 300 ml of dichloroethane are added under argon. Replace the cork with a condenser in a nitrogen atmosphere, and an additional funnel is inserted into the other neck. 35 ml of ethyldiisopropylamine are slowly added dropwise through this funnel. A slight heating is observed (exothermic reaction) and the solution is allowed to drain back. After completion of the introduction of the amine, the solution was kept at room temperature for 15 hours. Then the reaction mixture is extracted with three portions of 50 ml of each hydrochloric acid solution, followed by three times extraction with 50 ml of sodium bicarbonate each and finally washed twice with water. The organic solution is dried over magnesium sulfate, treated with charcoal, filtered and concentrated on a rotary evaporator. After purification of the residue by distillation at 110 ^{° C.} , 15 g (75%) of pure norbornene exo-diethyl ether are obtained in the form of a colorless viscous liquid with a fruity odor.

COO), d= 3,07 (2H; s, bridge head), d=4,10 (2H; m, CH₂), d=6,19 (2H; s, C=C), FI-MS (DIP) = M⁺ (238). ¹ H NMR (CDCl ₃ ): d = 1.22 (3H; t, CH ₃ ), d = 1.47 (1H), d = 2.15 (1H), d = 2.58 (2H; s, C

COO), d = 3.07 (2H; s, bridge head), d = 4.10 (2H; m, CH ₂ ), d = 6.19 (2H; s, C = C), FI-MS ( DIP) = M ⁺ (238).

Example 16
Synthesis of bicyclo [2.2.1] hept-5-ene-exo-2-tert. exo-3-carboxylic acid butyl ester
In a 50 ml round bottom flask with one neck equipped Teflonom ^® coated stir bar was added 1.5 g (9.15 mmol) of pure exo-nadikangidrida, 10 ml of freshly distilled methylene chloride and 20 ml of tert. butanol (0.209 mol). 7.5 g (0.061 mol) of dimethylaminopyridine was added to the solution, and the solution was heated under reflux at 75 ^{° C.} for 8 hours. At first, the anhydride does not dissolve, but after a certain period of time, the solid dissolves and the solution becomes brown. The solution was cooled, concentrated on a rotary evaporator to remove methylene chloride, and the viscous solution was slowly added to water acidified with hydrochloric acid. The solid precipitate is filtered off, washed with water and redissolved in ether treated with magnesium sulfate, followed by soot treatment. The solution is filtered on zeolite (Celite). The ether was removed on a rotary evaporator to obtain a solid. Yield 8.5 g, 60%.

COO), d=3,07 (2H; s, bridge head), d=6,19 (2H; s, C=C), d= 10,31 (1H; broad, COOH). ¹ H NMR (CDCl ₃ ): d = 1.47 (9H; s, tert-butyl), d = 1.60 (1H), d = 2.15 (1H), d = 2.58 (2H; m , C

COO), d = 3.07 (2H; s, bridge head), d = 6.19 (2H; s, C = C), d = 10.31 (1H; broad, COOH).

Example 17
Synthesis of bicyclo [2.2.1] hept-5-ene-exo-2-tert.butyl.exo-3-dicarboxylic acid methyl ester
In a 100 ml round bottom three-necked flask equipped with a magnetic stirring rod, 9.7 g (0.0408 mol) of pure exo-tert-butyl half-ester of norbornenecarboxylic acid and 6.05 g (0.0408 mol) of trimethyloxonium tetrafluoroborate are charged. The flask is sealed with stoppers and 100 ml of dichloromethane are added through a funnel in an argon atmosphere. Replace the rubber stopper with a condenser in an argon atmosphere, and an additional funnel is inserted into the other throat. 7.3 ml of ethyldiisopropylamine are slowly added dropwise through this funnel. An exothermic reaction is observed, and the solution is allowed to condense back. After completion of the introduction of the amine, the solution was kept at room temperature for 15 hours. Then the reaction mixture is extracted with three portions of 50 ml of each hydrochloric acid solution, followed by three times extraction with 50 ml of sodium bicarbonate each and finally washed twice with water. The organic solution is dried over magnesium sulfate, treated with charcoal, filtered and concentrated on a rotary evaporator. A colorless liquid is obtained, which begins to crystallize. The solid was washed with cold pentane, and the pentane solution was concentrated on a rotary evaporator to obtain a colorless liquid, which crystallized upon cooling. Yield 5.1 g.

COO), d=3,07 (2H; s, bridge head), d=3,65 (3H; s, СН₃), d= 6,19 (2H; s, C=C). ¹ H NMR (СОСl ₃ ): d = 1.45 (9Н; s, tert-butyl), d = 1.47 (1Н), d = 2.15 (1Н), d = 2.54 (2Н; m , C

COO), d = 3.07 (2H; s, bridge head), d = 3.65 (3H; s, CH ₃ ), d = 6.19 (2H; s, C = C).

Example 18
The glass vial 50 ml, equipped with Teflonom ^® coated stir bar was added 5-norbornene carboxylic acid (2.0 g, 14.5 mmol, exo, endo mixture) and dichloroethane (20 ml). To this stirred mixture at room temperature was added a catalyst solution obtained by adding a dimer of η ^3- allyl palladium chloride (6 mg, 16 μmol) in dichloroethane (5 ml) to silver hexafluoroantimonate (50 mg, 146 μmol) over 30 minutes, followed by filtration through microporous filter (to remove precipitated silver chloride). After 18 hours of carrying out the reaction, the mixture gelled to form a clear yellow gel. After adding the gel to an excess of hexane, the polymer precipitates as a white powder. The polymer is washed with excess hexane and dried. The polymer yield of 1.2 g (60%). The found molecular weight of the polymer (M _w ) is 22,000 and the polydispersity of 2.3.

 After adding part of this polymer (0.5 g) to a 0.1 N aqueous KOH solution (10 ml) with stirring, the polymer immediately dissolves to form an inviscid, colorless solution. This demonstrates the ability to manifest these materials in an aqueous solution of the base, since no other homopolymers tert. 5-norbornenocarboxylic acid butyl ester did not show a tendency to dissolve under the same conditions.

Example 19
Synthesis of the Pinner (The Pinner syntesis) of complex ortho-esters consists of two stages.

 Stage 1. Synthesis of imide ether hydrochloride.

The reaction is carried out in a two-neck round-bottomed flask with a capacity of 1 l, equipped with a stirrer, an oil bubbler and a tube with anhydrous calcium chloride. The following reagents were charged into the flask: 100 g (0.84 mol) of norbornenecarbonitrile (NB-CN), 37 ml (0.91 mol) of anhydrous methanol and 200 ml of anhydrous diethyl ether. The flask was placed in an ice bath and 61 g (1.67 mol) of dry hydrogen chloride were bubbled through the mixture with stirring for 1.5 hours. The flask is placed overnight in a refrigerator at 0 ^o C. In the morning, the mixture hardens in "cake". It is broken into pieces and another 200 ml of diethyl ether is added. The flask is kept in the refrigerator for another 10 days with periodic stirring. At the end of this process, the precipitated imidium ether hydrochloride is filtered off with suction and washed five times with approximately 300 ml of diethyl ether. About 20 g of unreacted NB-CN was isolated from the filtrate.

The yield of imidium ether hydrochloride is 76% (120 g, 0.64 mol). Product structures are confirmed by ¹ H NMR spectroscopy.

 Stage 2. Synthesis of ortho-esters.

56.7 g (0.30 mol) of imidium ether hydrochloride, 37 ml (0.91 mol) of anhydrous methanol and 250 ml of anhydrous petroleum ether are charged into a 0.5 L flask. The reaction is carried out at room temperature for 5 days with periodic stirring. The precipitated ammonium chloride is filtered off and washed three times with petroleum ether. The filtrate and washings were collected, the petroleum ether was distilled off and the product was fractionated by distillation in vacuo. A fraction with a boiling point of 68-69 ^o C / 3 mm Hg / cool. Yield 50%, 30 g, 0.15 mol). According to a ¹ H NMR spectrum, the product contains 97% 5-norbornene-2-trimethoxymethane (ortho ether).

Example 20
To a solution of 2.16 g (10.9 mmol) of C ₇ H ₉ C (OCH ₃ ) ₃ (norborno-trimethylorthoester) in 16 ml of 1,2-dichloroethane is added a solution of the reaction product obtained by mixing 1 mole of allyl palladium chloride dimer with 2 moles of silver hexafluoroantimonate in dichloroethane and filtering the precipitate of silver chloride formed. The amount of added catalyst corresponds to 0.08 mmol of palladium dissolved in 2 ml of dichloroethane. The stirred reaction mixture was placed in an oil bath at 70 ^{° C.} and the reaction was carried out for 20 hours.

 At the end of the reaction, 2 ml of methanol was added, the solvent was removed on a rotary evaporator, and the polymer was dried in vacuo to constant weight. Yield 1.28 g (60%).

Example 21
The glass vial 50 ml, equipped with Teflonom ^® coated stir bar was added bicyclo [2.2.1] hept-5-ene-2-methyl acetate (18.44 g, 0.1109 mol) and tert. norbornene butyl ether (21.55 g, 0.1109 mol) and 75 ml of toluene. A solution of the nickel catalyst [toluene complex of bis (perfluorophenyl) nickel, (Tol) NiC ₆ F ₅ ) ₂ ] is prepared in a box with a dried atmosphere by dissolving 0.5367 g (1.109 mmol (Tol) NiC ₆ F ₅ ) ₂ ) in 15 ml of toluene . The active catalyst solution is added to the monomer solution by syringe at room temperature. The reaction mixture was stirred for 6 hours at room temperature. The solution was diluted with toluene and the polymer was precipitated with an excess of methanol. The precipitated polymer is filtered, washed with acetone and dried overnight in vacuo. The yield of the isolated polymer is 24.9 g (63%). The molecular weight is determined by gel permeation chromatography. Found: M _n = 21000 and M _w = 52000. NMR analysis of the copolymer shows the presence of 51 mol. % tert butyl groups. IR analysis of the copolymer indicates the absence of acid groups.

Example 22
The glass vial 50 ml, equipped with Teflonom ^® coated stir bar was added bicyclo [2.2.1] hept-5-ene-2-methyl ethylcarbonate (4.03 g, 0.0205 mol) and tert. norbornene butyl ether (3.98 g, 0.0205 mol) and 50 ml of toluene. A solution of the nickel catalyst [toluene complex of bis (perfluorophenyl) nickel, (Tol) NiC ₆ F ₅ ) ₂ ] is prepared in a box with a dried atmosphere by dissolving 0.0991 g (0.2049 mmol (Tol) NiC ₆ F ₅ ) ₂ in 15 ml toluene. The active catalyst solution is added to the monomer solution through a funnel at room temperature. The reaction is carried out at room temperature. The solution was diluted with toluene and the polymer was precipitated with an excess of methanol. The precipitated polymer is filtered, washed with acetone and dried overnight in vacuo. The yield of the isolated polymer was 4.16 g (52%). The molecular weight of the polymer is determined by gel permeation chromatography. Found: M _n = 22000 and M _w = 58000. NMR analysis of the copolymer shows the presence of 50 mol.% Tert. butyl groups. IR analysis of the copolymer indicates the absence of acid groups.

Example 23
The glass vial 50 ml, equipped with Teflonom ^® coated stir bar was added bicyclo [2.2.1] hept-5-ene-2-methyl-butyl dicarbonate (17.15 g, 0.0764 mol) and tert. norbornene butyl ether (14.85 g, 0.0764 mol) and 72 ml of toluene. A solution of the nickel catalyst [bis (perfluorophenyl) nickel toluene complex, (Tol) NiC ₆ F ₅ ) ₂ ] is prepared in a box with a dried and purified atmosphere by dissolving 0.3699 g (0.7644 mmol (Tol) NiC ₆ F ₅ ) ₂ in 15 ml of toluene. The active catalyst solution is added to the monomer solution through a funnel at room temperature. The reaction is carried out with stirring for 6 hours at room temperature. The solution was diluted with toluene, and the polymer was precipitated with an excess of methanol. The precipitated polymer is filtered, washed with acetone and dried overnight in vacuo. The yield of the isolated polymer was 17.53 g (54%). The molecular weight of the polymer is determined by gel permeation chromatography. Found: M _n = 22000 and M _w = 58000. NMR analysis of the copolymer shows the presence of 54 mol.% Tert. butyl groups. IR analysis of the copolymer indicates the absence of acid groups.

Example 24
The glass vial 50 ml, equipped with Teflonom ^® coated stir bar was added t-butyl ester of norbornene (29.92 g, 0.154 mol) followed by addition of powdered maleic anhydride (15.10 g, 0.154 mol) and 90 ml chlorobenzene. This mixture is degassed three times to remove traces of oxygen. The reaction mixture is then heated to 80 ^° C. A degassed solution of benzoyl peroxide as a free radical polymerization initiator containing 0.9948 g (0.04 mol) of benzoyl peroxide in 10 ml of chlorobenzene is added to the reaction mixture using a dry syringe. After completion of the reaction, the polymer solution was poured directly into hexane to precipitate the polymer. A white precipitate precipitates. The precipitated polymer is separated from unreacted maleic anhydride, which may be present in the mixture. The polymer was then dried overnight in a vacuum oven at room temperature. The mass of the obtained dry polymer is equal to 20.62 g, yield 45.8%. The molecular weight of the polymer is determined by gel permeation chromatography. Found: M _n = 4200 and M _w = 8800. NMR analysis of the copolymer shows the presence as tert. butyl groups, and maleic anhydride groups.

Example 25
The glass vial 50 ml, equipped with Teflonom ^® coated stir bar was added bicyclo [2.2.1] hept-5-ene-2-methyl acetate (13.3 g, 0.0799 mol), tert. norbornene butyl ether (15.70 g, 0.0808 mol) followed by the addition of dry maleic anhydride (15.85 g, 0.162 mol) and 90 ml of chlorobenzene. This mixture is degassed three times to remove traces of oxygen. The reaction mixture is then heated to 80 ^° C. A degassed solution of benzoyl peroxide as a free radical initiator of polymerization containing 1.0438 g (0.041 mol) of benzoyl peroxide in 10 ml of chlorobenzene is added to the reaction mixture with a dry syringe. The reaction is carried out with stirring for 19 hours. After completion of the reaction, the polymer solution was poured directly into hexane to precipitate the polymer. A white precipitate precipitates. The precipitated polymer is separated from the unreacted maleic anhydride, which may be present there. The polymer was then dried overnight in a vacuum oven at room temperature. The mass of the obtained dry polymer is 21.89 g, yield 48.7%. The molecular weight of the polymer is determined by gel permeation chromatography. Found: M _n = 3000 and M _w = 6600. NMR analysis of the copolymer indicates the presence of acetate and tert. butyl groups. And K analysis of the copolymer indicates the presence of acetate, tert. butyl groups and maleic anhydride groups.

Example 26
The copolymer tert. norbornene butyl ether with norbornene carboxylic acid, 50:50.

In a 50 ml glass tube equipped with a magnetic stir bar, tert is added under nitrogen atmosphere. norbornene carboxylic acid butyl ether (2 g, 10 mmol) and norbornene carboxylic acid (1.38 g, 10 mmol). To this stirred mixture was added an initiator (tert. Butyl peroxide) (2.9 g) and the resulting mixture was heated to 130 ^° C. Stirring was continued for 16 hours. The resulting polymer (soluble in both tetrahydrofuran and toluene) is precipitated in hexane and filtered to give the product. The mass of the dried product is 2.91 g (86% conversion). The resulting solid polymer has a molecular weight of M _n = 3000 and M _w = 20,000. IR, NMR and TGA analyzes of the copolymers confirm that an additive copolymer of two monomers having an irregular structure is obtained.

Example 27
The copolymer tert. norbornene carboxylic acid butyl ether with norbornene carboxylic acid methyl ester, 50:50.

In a 50 ml glass tube equipped with a magnetic stir bar, tert is added under nitrogen atmosphere. norbornene carboxylic butyl ether (2 g, 10 mmol) and norbornene carboxylic acid methyl ester (1.5 g, 10 mmol). To this stirred mixture at room temperature was added an initiator (tert. Butyl peroxide) (2.9 g) and the resulting mixture was heated to 130 ^° C. Stirring was continued for 16 hours. The resulting polymer (toluene soluble) is precipitated in methanol and filtered to give the product. The mass of the dried product is equal to 0.82 g (degree of conversion of 23%). The resulting solid polymer has a molecular weight of M _n = 6000 and M _w = 35000. IR, NMR and TGA analyzes confirm that an additive copolymer of two monomers having an irregular structure is obtained.

Example 28
The copolymer tert. norbornene carboxylic acid butyl ether with tetracycline dodecene carboxylic acid ethyl ester, 50:50.

In a 100 ml glass tube equipped with a magnetic stir bar, toluene (40 ml) is added under nitrogen atmosphere, tert. norbornenecarboxylic acid butyl ether (1.94 g, 10 mmol) and tetracycline dodecenoic carboxylic acid ethyl ester (2.32 g, 10 mmol). To this stirred solution at room temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene. After 1 hour, ethyl vinyl ether (0.015 ml, 0.156 mmol) was added and stirred for 1 hour. The polymer solution was precipitated by the addition of excess methanol, collected by filtration and dried in vacuo. 3.46 g (81% yield) of the copolymer are released. Found: M _n = 133000 and M _w = 221000.

 The copolymer is redissolved in toluene and passed through a silica gel column. In this case, noticeable color (ruthenium) disappears. The polymer was again precipitated in excess methanol to give a pure white copolymer.

Example 29
The copolymer tert. norbornene butyl ether with tetracyclineododecene carboxylic acid ethyl ester, 50:50.

 In a 100 ml glass tube equipped with a magnetic stir bar, toluene (80 ml) is added under nitrogen atmosphere, tert. norbornenecarboxylic acid butyl ether (3.9 g, 20 mmol) and tetracycline dodecenoic carboxylic acid ethyl ester (4.64 g, 20 mmol). To this stirred solution at room temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (68 mg, 0.083 mmol) in 5 ml of toluene. After 2 hours, ethyl vinyl ether (0.030 ml, 0.31 mmol) was added and stirred for 2 hours.

The organo-resin solution is passed through a silica gel column to obtain a clear, colorless solution. The solution was precipitated by the addition of excess methanol, collected by filtration and dried in vacuo. 6.54 g (77% yield) of the copolymer are isolated. Found: M _n = 182000 and M _w = 244000. The glass transition temperature measured by the DSC method is 220 ^° C.

Example 30
The copolymer tert. norbornenecarboxylic acid butyl ether with tetracycline dodecenocarboxylic acid ethyl ester, 50:50.

In a 300 ml stainless steel reactor equipped with a mechanical stirrer and containing nitrogen, toluene (90 ml) was added, tert. norbornenecarboxylic acid butyl ether (3.9 g, 20 mmol) and tetracycline dodecenoic carboxylic acid ethyl ester (4.64 g, 20 mmol). To this stirred solution at room temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (68 mg, 0.083 mmol) in 5 ml of toluene. After 2 hours, ethyl vinyl ether (0.030 ml, 0.31 mmol) was added and stirred for 16 hours. Hydrogen (2410 kPa (350 psig) pressure) was fed into the reactor and the temperature was maintained at 175 ^{° C.} for 7 hours. At the end of the reaction, the solution was passed through a silica gel column and a hydrogenated copolymer was isolated. The NMR method determines that the degree of hydrogenation of the copolymer is 95%. Found: M _n = 163000 and M _w = 237000.

Example 31
The copolymer tert. norbornenecarboxylic acid butyl ether with tetracycline dodecenocarboxylic acid ethyl ester, 50:50.

In a 300 ml stainless steel steel reactor equipped with a mechanical stirrer and containing nitrogen, toluene (90 ml) was added, tert. norbornenecarboxylic acid butyl ether (2.9 g, 15 mmol) and tetracycline dodecenocarboxylic acid ethyl ester (3.5 g, 15 mmol). To this stirred solution at ambient temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (50 mg, 0.060 mmol) in 5 ml of toluene. After 2 hours, hydrogen was introduced into the reactor (pressure 5510 kPa (800 psig)) and the temperature was maintained at 175 ^{° C.} for 7 hours. At the end of the reaction, the solution was passed through a silica gel column and a hydrogenated copolymer was isolated. The NMR method determines that the polymer has a degree of hydrogenation of 96%. Found: M _n = 172000 and M _w = 278000.

Example 32
The copolymer tert. norbornenecarboxylic acid butyl ether with tetracycline dodecenocarboxylic acid ethyl ester, 50:50.

In a 100 ml glass tube equipped with a magnetic stir bar and containing nitrogen, toluene (40 ml) is added, tert. norbornenecarboxylic acid butyl ether (1.94 g, 10 mmol), tetracycline dodecenocarboxylic acid ethyl ester (2.32 g, 10 mmol) and 1-hexene (0.050 ml, 0.4 mmol). To this stirred solution at ambient temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene. After 2 hours, the polymer solution was added to excess methanol, collected by filtration and dried under vacuum. Obtain 3.1 g (yield 73%) of the polymer. Found: M _n = 22000 and M _w = 35000.

Example 33
The copolymer tert. norbornenecarboxylic acid butyl ether with tetracycline dodecenocarboxylic acid ethyl ester, 50:50.

In a 100 ml glass tube equipped with a magnetic stir bar and containing nitrogen, toluene (40 ml) is added, tert. norbornenecarboxylic acid butyl ether (1.94 g, 10 mmol), tetracycline dodecenocarboxylic acid ethyl ester (2.32 g, 10 mmol) and 1-hexene (0.275 ml, 2.2 mmol). To this stirred solution at ambient temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene. After 2 hours, the polymer solution was added to excess methanol, collected by filtration and dried under vacuum. 3.45 g (81% yield) of polymer are isolated. Found: M _n = 6000 and M _w = 8000.

Example 34
The copolymer tert. norbornenecarboxylic acid butyl ether with tetracycline dodecenocarboxylic acid ethyl ester, 50:50.

 In a 100 ml glass tube equipped with a magnetic stirring bar and containing nitrogen, toluene (40 ml) is added, tert. norbornenecarboxylic acid butyl ether (1.94 g, 10 mmol), tetracycline dodecenocarboxylic acid ethyl ether (2.32 g, 10 mmol) and 1-hexene (0.62 ml, 5.0 mmol). To this stirred solution at ambient temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene. After 2 hours, the polymer solution was added to excess methanol, collected by filtration and dried under vacuum. 2.75 g (65% yield) of the polymer are isolated.

Example 35
The copolymer tert. norbornenecarboxylic acid butyl ether with tetracycline dodecenocarboxylic acid ethyl ester, 50:50.

 In a 100 ml glass tube equipped with a magnetic stir bar and containing nitrogen, toluene (80 ml) is added, tert. norbornenecarboxylic acid butyl ester (3.9 g, 20 mmol), tetracycline dodecenocarboxylic acid ethyl ester (4.64 g, 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol). To this stirred solution at ambient temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (68 mg, 0.083 mmol) in 5 ml of toluene. After 2 hours, ethyl vinyl ether (0.030 ml, 0.31 mmol) was added and stirred for 2 hours.

Amber-orange polymer solution is passed through a silica gel column, eliminating the dark color (ruthenium). The solution was precipitated by the addition of excess methanol, collected by filtration and dried overnight at 80 ^{° C.} under vacuum. 2.6 g (30% yield) of polymer are isolated. Found: M _n = 3000 and M _w = 4000.

Example 36
The copolymer tert. norbornenecarboxylic acid butyl ether with tetracycline dodecenocarboxylic acid ethyl ester, 50:50.

In a 300 ml stainless steel reactor equipped with a mechanical stirrer and containing nitrogen, toluene (80 ml), tert. norbornenecarboxylic acid butyl ether (3.9 g, 20 mmol), tetracycline dodecenoic carboxylic acid ethyl ester (4.64 g, 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol). To this stirred solution at ambient temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (68 mg, 0.042 mmol) in 5 ml of toluene. After 2 hours, hydrogen was fed into the reactor (pressure 5170 kPa (750 psig)) and the temperature was maintained at 175 ^{° C.} for 20 hours.

The solution was precipitated by the addition of excess methanol, collected by filtration and dried overnight at 80 ^{° C.} under vacuum. About 5 g (59% yield) of polymer are recovered. Found: M _n = 20,000 and M _w = 30,000. The NMR method determines that the degree of hydrogenation of the copolymer is more than 99%.

Example 37
The copolymer tert. norbornenocarboxylic acid butyl ether with tetracycline dodecenocarboxylic acid ethyl ester, 65:35.

 In a 250 ml round bottom flask equipped with a magnetic stir bar and containing nitrogen, toluene (160 ml) was added, tert. norbornenecarboxylic acid butyl ether (10.1 g, 52 mmol), tetracycline dodecenoic carboxylic acid ethyl ester (6.5 g, 28 mmol) and 1-hexene (0.176 ml, 1.4 mmol). To this stirred solution at room temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (131 mg, 0.160 mmol) in 5 ml of toluene. After 16 hours, ethyl vinyl ether (0.060 ml, 0.62 mmol) was added and stirred for 1.5 hours. The polymer solution is passed through a silica gel column to remove ruthenium. The solution was added to excess methanol, collected by filtration and dried in vacuo. 9.69 g (58% yield) of polymer are isolated.

Found: M _n = 31000 and M _w = 42000. DSC methods are used to measure the glass transition temperature of the polymer. The found value of the glass transition temperature is 110 ^o C.

Example 38
In a 100 ml glass tube containing nitrogen, 5.0 g of the polymer of Example 37 was dissolved in tetrahydrofuran (80 ml). The solution was transferred to a 300 ml steel reactor. 2.25 g (5 wt%) of a palladium on aluminum catalyst (purchased from Aldrich) was added to the reactor. The reactor is then heated to 175 ^{° C.} and hydrogen is supplied at a pressure of 5510 kPa (800 psig). The temperature and pressure are maintained for 9.5 hours. The resulting polymer solution was centrifuged, the colorless solution was separated, and the polymer was precipitated in excess methanol. By NMR, it was found that the resulting copolymer has a degree of hydrogenation of more than 99%.

Example 39
The copolymer tert. norbornenecarboxylic acid butyl ether with tetracycline dodecenocarboxylic acid ethyl ester, 50:50.

In a 100 ml glass tube equipped with a magnetic stir bar and containing nitrogen, toluene (80 ml) is added, tert. norbornenecarboxylic acid butyl ether (3.9 g, 20 mmol), tetracycline dodecenoic carboxylic acid ethyl ester (4.64 g, 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol). To this stirred solution at ambient temperature is added a solution of bis (tricyclohexylphosphine) benzylidenruthenium dichloride (68 mg, 0.084 mmol) in 5 ml of toluene. After 2 hours, ethyl vinyl ether (30 μl) was added to suspend further reaction, and the mixture was stirred for 1.5 hours. The polymer solution was passed through a silica gel column to remove ruthenium residues, and the polymer was isolated by precipitation in methanol as a pure white solid. The found value of the molecular weight of the polymer is M _n = 33700 and M _w = 46000. The polymer is fully characterized by IR, NMR and TGA.

Example 40
Ethyl 2-methyl-4-pentanoate (99 g, 0.7 mol) and freshly cracked cyclopentadiene (46.4 g, 0.7 mol) are added to a stainless steel autoclave with an internal volume of 300 ml. The stirred mixture is heated to 200 ^o C and left overnight. Then the reactor is cooled and the contents are removed. The resulting norbornene with functional groups (norbornene-CH ₂ CH (CH ₃ ) C (O) OS ₂ H ₅ ) is purified by vacuum distillation and the boiling point is determined at about 46-47 ^° C at a pressure of 0.02 mm Hg. Using gas chromatography, it was determined that the product has a purity of 98.4-99.3% (various fractions). The yield of isolated highly pure product is about 33 g.

Example 41
The copolymer tert. butyl ether of norbornenocarboxylic acid with an ester of the formula (norbornene-CH ₂ CH (CH ₃ ) C (O) OC ₂ H ₅ ), 40:60.

In a 100 ml glass tube equipped with a magnetic stir bar in a nitrogen atmosphere, toluene (50 ml) is added, tert. norbornenocarboxylic acid butyl ether (2.7 g, 14 mmol) and the ester of Example 40 (norbornene-CH ₂ CH (CH ₃ ) C (O) OC ₂ H ₅ ) (4.4 g, 21 mmol). To this stirred solution at ambient temperature was added a solution of (toluene) Ni (C ₆ F ₆ ) ₂ in toluene (1 ml) and the resulting solution was heated to 50 ^° C. Stirring was continued for 3 hours. The polymer is precipitated in methanol and filtered. The resulting solid was redissolved in tetrahydrofuran, filtered and precipitated again with methanol and filtered. The resulting white solid polymer is dried. The mass of the obtained polymer is 2.66 g. The found value of the molecular weight of the polymer is M _n = 39800 and M _w = 70,000. The upper layer of the solution was evaporated to dryness to obtain an additional amount of a white polymer with a dry weight of 1.52 g. Found: M _n = 31000 and M _w = 60650. The total polymer yield indicates a degree of monomer conversion of 59%. IR, NMR and TGA analyzes of the copolymer confirm the preparation of an additive copolymer from two monomers with an irregular structure.

Example 42
The copolymer tert. norbornene butyl ether with an ether of the formula (norbornene-CH ₂ CH (CH ₃ ) C (O) OC ₂ H ₅ ), 40:60.

In a 250 ml glass tube equipped with a magnetic stir bar in a nitrogen atmosphere, dichloroethane (200 ml), tert. butyl ether of norbornenocarboxylic acid (7.76 g, 40 mmol), and the ether from example 40 (norbornene-CH ₂ CH (CH ₃ ) C (O) OC ₂ H ₅ ) (12.5 g, 60 mmol) and 2, 6-di-tert.butylpyridine (28.8 mg, 0.26 mmol). To this stirred solution at ambient temperature is added a catalyst solution obtained by mixing a dimer of allyl palladium chloride (0.183 g, 0.5 mmol) with silver hexafluoroantimonate (equivalent amount) in dichloroethane (3 ml) and filtering to remove precipitated silver chloride. The resulting solution was heated to 50 ^o C. Stirring was continued for 16 hours. The polymer solution is treated with carbon monoxide (pressure 28 kPa (4 psig)) for 48 hours to precipitate palladium, filtered through a filter with a mesh size of 0.45 μm, reduced in volume and precipitated with an excess of methanol to obtain 7.9 g of copolymer ( conversion rate 39%). The found molecular weight value is M _n = 7000 and M _w = 11600. The copolymer is fully characterized by IR, NMR and TGA analysis.

Example 43
Copolymerization of carbon monoxide with norbornene-5-tert. butyl ether.

A deoxygenated solution of bipyridine (0.025 g, 0.16 mmol) in methanol is added to palladium (II) acetate (0.012 g, 0.053 mmol) dissolved in deoxygenated methanol. To this solution was added p-toluenesulfonic acid (0.045 g, 0.27 mmol) dissolved in deoxygenated methanol. The resulting brown solution was added to a solution of benzoquinone (1.72 g, 1.59 mmol) in deoxygenated methanol. This solution is introduced into a stainless steel reactor preheated to 50 ^° C. Norbornene-5-tert is then added to this reactor. butyl ether (5.14 g, 0.027 mol) in 100 ml of methanol deoxygenated in argon. The pressure in the reactor was increased with carbon monoxide to 4130 kPa (600 psig) and heated to 65 ^° C. After 4.5 hours, carbon monoxide was removed from the reactor and the reactor was cooled. The pink solution was filtered to remove palladium residues and the solution was evaporated. The resulting mixture was dissolved in a minimum amount of tetrahydrofuran and slowly poured into a 25:75 mixture of water with methanol to precipitate the polymer. This procedure is repeated twice. The resulting white polymer was filtered and dried at room temperature in vacuo. Yield 2.9 g.

Example 44
Deoxygenated and dried tetrahydrofuran / methanol (35 ml / 15 ml) solution of benzoquinone (0.43 g, 0.40 mmol), bipyridine (0.0062 g, 0.0040 mmol) and Pd (MeCN) ₂ (p-toluenesulfonate) ₂ (0.0070 g, 0.0013 mmol) are placed in a dry 500 ml stainless steel reactor heated to 50 ^° C. Norbornene-5-tert-butyl ether (5.14 g, 0.027 mol) is added to the reactor 100 ml of THF (deoxygenated and dried. The reactor was filled with carbon monoxide to a pressure of 4130 kPa (600 psig) and heated to 65 ^o C. after 12.5 hours the reactor was heated to 90 ^o C for 1.5 hours. Then, oxide is removed from the reactor at the hydrogen chloride and the reactor are cooled. The solution from the purple reactor is filtered to remove palladium residues and evaporated. The resulting mixture is dissolved in a minimum amount of tetrahydrofuran and slowly poured into a mixture of water with methanol, 25:75 to precipitate the polymer. This procedure is repeated twice. The resulting white polymer is filtered and dried under vacuum Product yield 2.9 g.

Examples 45-51
Measurement of optical density of cyclic olefin homo- and copolymers at 193 nm.

 Optical density is a critical characteristic of effective photoresists, since it determines the uniformity of energy penetration through the film thickness. The polymer chain of polymers commonly used in lithography has an optical density of less than 0.2 optical units / micron before adding acidic photo-generators. (T. Neenan, E. Chandross, J. Kometani, and O. Nalamasu, “Styrylmethylsulfonamides: Variable Base Soluble Photoresist Gum Components,” p. 199 AXO Series 614 materials on Microelectronic Technology, Polymers for Enhanced Image and Packaging, Ed. E. Reichmanis, C. Ober, S. MacDonald, T. Iwayanagai and T. Nishikubo, April 1995 - T. Neenan, E. Chandross, J. Kometani and O. Nalamasu, "Styrylmethylsulfonamides: Versatile Base-Solubilizing Components of Photoresist Resins ", pg. 199 in Microelectronics Technology, Polymers for Advanced Imaging and Packaging, ACS Symposium Series 614, Eds: E. Reichmanis, C. Ober, S. MacDonald, T. Iwayanagai and T. Nishikubo, 1995, April) . Polyhydroxystyrene, the starting component of conventional long-wavelength 248 nm UV photoresists, has an optical density of 2.8 optical units / microns at 193 nm and is therefore unsuitable as the polymer chain of the resist at this wavelength.

Preparation of sample solution
Samples of various polymers given in the examples described above (0.016 ± 0.001 g of polymer) are weighed and dissolved in 4 ml of chloroform. Polymer solutions are pipetted and thin films are molded from them on clean, identical quartz slides. The films are dried overnight. The round films obtained on quartz slides are then dried at 70 ^{° C.} in a nitrogen purged oven for 10 minutes.

UV spectra of films are obtained on a Perkin-Elmer-Lambda 9UV / VIS / IR spectrophotometer at a scanning speed of 120 nm / min. The range of the spectrum is set from 300 nm to 180 nm. By measuring the optical density of the films at 193 nm and bringing it to normal film thickness, the optical density of the films is measured at 193 nm. The test results are shown in the following table:
Preparation of a resist solution, irradiation and manifestation.

 The polymers obtained in the examples described above are dissolved in propylene glycol monomethyl ether acetate (AMEPH) at a concentration of 15% by weight, based on the solid. To the resulting solutions add onium salt according to the examples in a concentration of 5% by weight of the polymer or 10% by weight of the polymer.

The solutions are filtered through a 0.2 micron Teflon ^® filter. On the surface primed with hexamethyldisilazane, a silicone plate, a resist layer is formed from each solution by centrifugation. The film coating is dried at 95 ^o C for 1 minute. The films are then irradiated through a quartz pattern with UV radiation on a Karl Suss MJB3 UV 250 device at a wavelength of 230 to 250 nm. Irradiated films are heated to 125-150 ^o C for 1 minute. Then, the irradiated and heat-treated films are developed in an aqueous solution of the base to obtain high-resolution images in a positive tone without reducing the film thickness in unirradiated zones.

 When developed in a non-polar solvent, negative operating systems can be easily obtained. Such materials are easily sensitized for longer wavelengths (365 nm) by adding a small amount of sensitizers, such as pyrene, perylene or thioxanthones, or for shorter waves (193 nm), since these materials, as shown above, have a very low optical density at 193 nm

Example 52
A copolymer of bicyclo [2.2.1] hept-5-en-2-methyl acetate with tert-butyl ether of norbornene (polymer according to example 2) with an arithmetic average molecular weight of 21,000 is dissolved in acetate of propylene glycol monomethyl ether at a concentration of 10 wt./vol.% Calculated on a solid. 10% by weight of the polymer triphenylsulfonium hexafluoroarsenate is added to the solution. The solution is filtered through a 0.2 μm Teflon ^® filter, and after filtration, a resist film is formed by centrifugation on a surface of a silicone plate primed with hexamethyldisilazane at 500 rpm for 30 s and then at 2000 rpm for 25 s. Get a layer with a thickness of 0.7 μm. The film is dried at 95 ^o C for 1 minute above the surface of the hot plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 50 mJ / cm ² . After post-heat treatment at 125 ^o C for 1 minute, in the process of manifestation in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 53
The copolymerization of bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate and norbornene tert-butyl ether using a NiArf catalyst.

Into a glass flask of 50 ml equipped with a Teflonom ^® coated stir bar was added bicyclo [2.2.1] hept-5-ene-2-metiletiloksalat (8.57 g, 0.0382 mmol), tert-butyl ester of norbornene (7, 42 g, 0.0392 mol) and 38 ml of toluene. A solution of the nickel catalyst [complex of toluene with bisperfluorophenyl nickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] is obtained in a dry vessel by dissolving 0.1854 g (0.382 mmol of (Tol) Ni (C ₆ F ₅ ) ₂ in 5 ml of toluene. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature, the reaction mixture was stirred at room temperature for 5 hours, the solution was diluted with toluene and the polymer was precipitated with excess methanol. The precipitated polymer was filtered, washed with acetone and dried in vacuo overnight. the resulting polymer sosta 7.62 g (48%). The molecular weight of the polymer was characterized by gel permeation chromatography (GPC) M _n = 28000 and M _w = 56000. It was shown by NMR that the composition of the copolymer is very close to the initial ratio of monomers. The absence of any acid groups in the copolymer confirmed by IR spectroscopy.

Example 54
A copolymer of bicyclo [2.2.1] hept-5-en-2-methyl acetate with tert-butyl norbornene ether (polymer according to example 21) with an arithmetic average molecular weight of 21,000 is dissolved in acetate of propylene glycol monomethyl ether at a concentration of 10% w / v, calculated as on a solid. Diaryl iodonium hexafluoroantimonate (Sartomer 1012) is added in an amount of 10% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter and, after filtration, the resist film is formed by centrifugation on a surface of a silicone plate primed with hexamethyldisilazane at 500 rpm for 30 s and then at 2000 rpm for 25 s. In this case, a coating layer thickness of 0.7 μm is obtained. The film is dried at 95 ^o C for 1 minute over a hot sheet, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 50 mJ / cm ² . After post-heat treatment at 125 ^o C for 1 minute and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 55
A copolymer of bicyclo [2.2.1] hept-5-en-2-methyl acetate with tert-butyl norbornene ether (polymer according to example 21) with an arithmetic average molecular weight of 21,000 is dissolved in acetate of propylene glycol monomethyl ether at a concentration of 10% w / v, calculated as on a solid. Diaryl iodonium hexafluoroantimonate (Sartomer 1012) is added to the solution in an amount of 10% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter and, after filtering, a resist film is formed on the surface of a hexamethyldisilazane-primed silicone wafer by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating with a layer thickness of 0.7 μm is obtained. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz photomask with UV radiation (240 nm) with a dose of 100 mJ / cm ² . After post-heat treatment at 125 ^o C for 1 minute and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 56
The copolymerization of bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate and norbornene tert-butyl ether (molar ratio 70/30) using a NiArf catalyst.

The glass vessel of 50 ml, equipped with Teflonom ^® coated stir bar was added bicyclo [2.2.1] hept-5-ene-2-metiletiloksalat (14.8 g, 0.0663 mol), tert-butyl ester of norbornene (5 52 g, 0.0284 mol) and 113 ml of toluene. A solution of a nickel catalyst [complex of toluene with bisperfluorophenyl nickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] is obtained in a dry vessel by dissolving 0.2296 g (0.474 mmol (Tol) Ni (C ₆ F ₅ ) ₂ in 5 ml of toluene. The active catalyst solution was added to the monomer solution using a syringe at ambient temperature, the reaction mixture was stirred at room temperature for 5 hours, the solution was diluted with toluene and the polymer was precipitated with excess methanol. The precipitated polymer was filtered, washed with acetone and dried in vacuo overnight. the resulting polymer sosta 10.15 g (50%). The molecular weight of the polymer was characterized by GPC. M _n = 35000 and M _w = 98000. It was shown by NMR that the composition of the copolymer is very close to the initial ratio of monomers. The absence of any acid groups in the copolymer is confirmed by IR spectroscopy .

Example 57
A copolymer of bicyclo [2.2.1] hept-5-en-2-methyl acetate with tert-butyl ether of norbornene (polymer according to example 21) with an arithmetic mean
with a molecular weight of 21,000 is dissolved in acetate of propylene glycol monomethyl ether at a concentration of 10% w / v, calculated on the solid. Triphenylsulfonium hexafluoroarsenate is added to the solution in an amount of 10% based on the solid. The solution is filtered through a 0.2 μm Teflon ^® filter and, after filtration, a resist film is formed on the surface of a hexamethyldisilazane-primed silicone wafer by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating with a layer thickness of 0.7 μm is obtained. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz photomask with UV radiation (240 nm) with a dose of 10 mJ / cm ² . After post-heat treatment at 125 ^o C for 1 minute and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 58
A copolymer of bicyclo [2.2.1] hept-5-en-2-methyl acetate with tert-butyl norbornene ether (polymer according to example 21) with an arithmetic average molecular weight of 21,000 is dissolved in acetate of propylene glycol monomethyl ether at a concentration of 10% w / v, calculated as on a solid. Triphenylsulfonium hexafluoroarsenate is added to the solution in an amount of 10% by weight of the polymer. The resulting solution is filtered through a Teflon ^® 0.2 μm filter, and after filtration, a resist film is formed on the surface of a silicone plate primed with hexamethyldisilazane by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 from. A film coating with a layer thickness of 0.7 μm is obtained. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 30 mJ / cm ² . After post-heat treatment at 125 ^o C for 1 minute and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 59
The copolymerization of bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate and 1- (1-ethoxy) ethyl 5-norbornene-2-carboxylic acid (molar ratio 50/50) using a NiArf catalyst.

Into a glass flask of 50 ml equipped with a Teflon ^® coated stir bar was added bicyclo [2.2.1] hept-5-ene-2-metiletiloksalat (0.5166 g, 2.304 mmol), 1- (1-ethoxy) ethyl 5 norbornene-2-carboxylic acid (0.4885 g, 2.304 mol) and 2.25 ml of cyclohexane. A solution of a nickel catalyst [complex of toluene with bisperfluorophenyl nickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] is obtained in a dry vessel by dissolving 0.0112 g (0.023 mmol (Tol) Ni (C ₆ F ₅ ) ₂ in 0.65 ml of ethyl acetate The active catalyst solution was added to the monomer solution using a syringe at ambient temperature, the reaction mixture was stirred at room temperature for 5 hours, the solution was diluted with toluene and the polymer was precipitated with excess methanol, the precipitated polymer was filtered, washed with acetone and dried in vacuo overnight. The yield of the obtained polymer comp It is 0.0315 g (3%). The molecular weight of the polymer was characterized by GPC. M _n = 52000 and M _w = 100000.

Example 60
A copolymer of maleic anhydride with tert. norbornene butyl ether obtained by the free radical polymerization method (polymer of Example 24) with an arithmetic average molecular weight of 4000 is dissolved in propylene glycol monomethyl ether acetate at a concentration of 15% w / v on a solid basis. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer CD 1010 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter and, after filtration, a resist film is formed on the surface of a hexamethyldisilazane-primed silicone wafer by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating with a layer thickness of 0.6 μm is obtained. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 30 mJ / cm ² . After post-heat treatment at 125 ^o C for 1 minute and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 61
A copolymer of maleic anhydride with tert. norbornene butyl ether obtained by the free radical polymerization method (polymer of Example 24) with an arithmetic average molecular weight of 4000 is dissolved in propylene glycol monomethyl ether acetate at a concentration of 15% w / v on a solid basis. To the resulting solution is added triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter and, after filtration, a resist film is formed on the surface of a hexamethyldisilazane-primed silicone wafer by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating with a layer thickness of 0.6 μm is obtained. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 30 mJ / cm ² . After post-heat treatment at 95 ^o C for 1 minute and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 62
The copolymerization of bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate and norbornene trimethylsilyl ether (molar ratio 50/50) using a NiArf catalyst.

Into a glass flask of 50 ml equipped with a Teflon ^® coated stir bar was added bicyclo [2.2.1] hept-5-ene-2-metiletiloksalat (1.5484 g, 6.904 mmol), trimethylsilyl ester of norbornene (1.4523 g, 6.905 mol) and 6.75 ml of cyclohexane. A nickel catalyst solution [complex of toluene with bisperfluorophenyl nickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] is obtained in a dry vessel by dissolving 0.0335 g (0.0691 mmol) of (Tol) Ni (C ₆ F ₅ ) ₂ in 1 95 ml of ethyl acetate. The active catalyst solution is added to the monomer solution by syringe at ambient temperature. The reaction mixture was stirred at room temperature for 5 hours. The polymer was precipitated with an excess of methanol. The precipitated polymer is filtered, washed with acetone and dried in vacuo overnight. The yield of the obtained polymer is 0.2675 g (9%). The presence of acid groups resulting from the release of trimethylsilyl groups is noted.

Example 63
The maleic anhydride terpolymer with bicyclo [2.2.1] hept-5-en-2-methyl acetate and with norbornene tert-butyl ether obtained by the free radical polymerization method (polymer according to Example 25) with an average molecular weight of 3000 is dissolved in monomethyl ether acetate propylene glycol at a concentration of 10 wt./vol.% calculated on the solid. To the resulting solution add diaryl iodonium hexafluoroantimonate (Sartomer 1012) in an amount of 10% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter and, after filtration, a resist film is formed on the surface of a hexamethyldisilazane-primed silicone wafer by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating with a layer thickness of 0.5 μm is obtained. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 50 mJ / cm ² . After post-heat treatment at 125 ^o C for 1 minute and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 64
A copolymer of bicyclo [2.2.1] hept-5-en-2-methylethyl carbonate with tert. norbornene butyl ether (polymer according to Example 22) with an arithmetic average molecular weight of 22,000 was dissolved in propylene glycol monomethyl ether acetate at a concentration of 15% w / v on a solid basis. To the resulting solution is added triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter, and after filtering, a resist film is formed from the solution on the surface of a hexamethyldisilazane-primed silicone plate by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating is obtained with a layer thickness of 1.1 μm. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 30 mJ / cm ² . After post-heat treatment at 95 ^o C for 1 minute and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 65
The copolymerization of bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate and norbornene tert-butyl ether.

Into a glass flask of 50 ml equipped with a Teflon ^® coated stir bar was added 2.42 g (12.5 mmol) of tert-butyl ester of norbornene, 8.57 g (38.2 mmol) of bicyclo [2.2.1] hept-5 en-2-methylethyl oxalate, 50 ml of freshly distilled dichloroethane and the solution is degassed under argon. Into a glass flask of 10 ml equipped with a Teflon ^® coated stir bar was added 0.0365 g (0.1 mmol) of allylpalladium chloride dimer in a ratio of monomer / catalyst equal to 500/1 and 2 ml of dichloroethane. 0.0344 g (0.1 mmol) of silver hexafluoroantimonate and 2 ml of dichloroethane are added to another 10 ml glass jar. The catalyst solution is obtained by mixing solutions of allyl palladium chloride dimer and silver hexafluoroantimonate in a dry container. In this case, an immediate precipitation of silver chloride is observed, which is filtered off and an active catalyst solution is obtained. The active catalyst solution was added to the monomer solution by syringe and the reaction mixture was stirred at 60 ^{° C.} for 20 hours. The polymer solution was cooled, concentrated on a rotary evaporator and precipitated with methanol.

Example 66
A copolymer of bicyclo [2.2.1] hept-5-en-2-methylethyl carbonate with tert. norbornene butyl ether (polymer of Example 22) with an arithmetic average molecular weight of 22,000 was dissolved in propylene glycol monomethyl ether acetate at a concentration of 15% w / v on a solid basis. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter, and after filtering, a resist film is formed from the solution on the surface of a hexamethyldisilazane-primed silicone plate by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating is obtained with a layer thickness of 1.1 μm. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 15 mJ / cm ² . After post-heat treatment at 95 ^o C for 1 minute and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 67
A copolymer of bicyclo [2.2.1] hept-5-en-2-methylbutyl carbonate with tert. norbornene butyl ether (polymer of Example 23) with an arithmetic average molecular weight of 22,000 was dissolved in propylene glycol monomethyl ether acetate at a concentration of 15% w / v on a solid basis. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter, and after filtering, a resist film is formed from the solution on the surface of a hexamethyldisilazane-primed silicone plate by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating with a layer thickness of 1 μm is obtained. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 30 mJ / cm ² . After post-heat treatment at 125 ^o C for 0.5 minutes and the manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 68
A copolymer of bicyclo [2.2.1] hept-5-en-2-methylbutyl carbonate with tert. norbornene butyl ether (polymer of Example 23) with an arithmetic average molecular weight of 22,000 was dissolved in propylene glycol monomethyl ether acetate at a concentration of 15% w / v on a solid basis. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter, and after filtering, a resist film is formed from the solution on the surface of a hexamethyldisilazane-primed silicone plate by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating with a layer thickness of 1.0 μm is obtained. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 30 mJ / cm ² . After post-heat treatment at 150 ^o C for 0.5 minutes and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 69
Hydrogenated copolymer of 35 mol.% Ethyl tetracyclodecene with 65 mol. % tert norbornene butyl ester (polymer according to example 37) with an arithmetic average molecular weight of 23,000, obtained by polymerization with rearrangement and ring opening, is dissolved in propylene glycol monomethyl ether acetate at a concentration of 15% w / v on a solid basis. To the resulting solution add triarylsulfonium hexafluoroantimonate (Sartomer SD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter and, after filtration, a resist film is formed on the surface of a hexamethyldisilazane-primed silicone wafer by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating is obtained with a layer thickness of 1.1 μm. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 30 mJ / cm ² . After post-heat treatment at 125 ^o C for 1 minute and manifestations in an aqueous solution of the base for 30 s receive positive images with high resolution.

Example 70
Unhydrogenated copolymer of 50 mol.% Ethyl tetracyclodecene with 50 mol.% Tert. norbornene butyl ester (polymer according to example 39) with an arithmetic average molecular weight of 34,000, obtained by polymerization with rearrangement and ring opening, was dissolved in propylene glycol monomethyl ether acetate at a concentration of 15 wt./vol.% based on solid. To the resulting solution is added triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) in an amount of 5% by weight of the polymer. The solution is filtered through a 0.2 μm Teflon ^® filter, and after filtering, a resist film is formed from the solution on the surface of a hexamethyldisilazane-primed silicone plate by centrifugation at 500 rpm for 30 s and then at 2000 rpm for 25 s. A film coating with a layer thickness of 1.25 μm is obtained. The film is dried at 95 ^o C for 1 minute above the hot surface of the plate, and then irradiated through a quartz pattern with UV radiation (240 nm) with a dose of 50 mJ / cm ² . After post-heat treatment at 150 ^o C for 30 s and manifestations in an aqueous solution of the base for 60 s receive positive images with high resolution.

Example 71
In a 50 ml glass vessel equipped with a Teflon-coated stirring bar, bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate (8.57 g, 0.0382 mol), norbornene tert-butyl ether (7.42) are added g, 0.0392 mol) and 38 ml of toluene. A solution of the nickel catalyst [complex of toluene with bisperfluorophenyl nickel, (Tol) Ni (C ₆ F ₅ ) ₂ ] is obtained in a dry container by dissolving 0.1854 g [0.382 mmol (Tol) Ni (C ₆ F ₅ ) ₂ ] in 5 ml of toluene . The active catalyst solution is added to the monomer solution by syringe at ambient temperature. The reaction mixture was stirred at room temperature for 5 hours. The solution was diluted with toluene and the polymer was precipitated with an excess of methanol. The precipitated polymer is filtered, washed with acetone and dried in vacuo overnight. The yield of the obtained polymer is 7.62 g (48%). The molecular weight of the polymer was characterized by GPC. M _n = 28000 and M _w = 56000. It was shown by NMR that the composition of the copolymer is very close to the initial ratio. The absence of any acid groups in the copolymer is confirmed by IR spectroscopy.

Example 72
The copolymer tert. norbornene carboxylic acid butyl ether with norbornene trimethylsilyl ether, 85:15.

159 ml of toluene, norbornene carboxylic acid tert-butyl ester (82.61 g, 0.425 mol) and norbornene trimethylsilyl ether (15.91 g, 0.0749 mol) are added to a 500 ml glass vessel equipped with a stirring magnetic rod under nitrogen atmosphere. ) To this stirred solution, a solution of (toluene) Ni (C ₆ H ₅ ) ₂ in 50 ml of toluene is added at ambient temperature and stirring is continued for 5 hours. The polymer solution is treated with glacial acetic acid (120 ml) and hydrogen peroxide (120 ml, 15 wt.%) And stirring is continued in this solution for 1.5 hours at a temperature of 80 ^° C. Wash water is separated from the organic phase and the resulting polymer solution is washed three times with deionized water. The polymer is precipitated with methanol and the precipitated polymer is filtered off. The resulting polymer is dried. The yield of the obtained polymer is 75.31 g (M _n = 7500 and M _w = 12800). The total copolymer yield represents 76% monomer conversion. The polymer was characterized using NMR spectroscopy.

Example 73
Norbornene methyl acetate copolymer with norbornene trimethylsilyl ether, 70:30.

In a 250 ml glass jar equipped with a stirring magnetic rod, toluene (82.25 ml), norbornene methyl acetate (11.67 g, 0.0702 mol) and norbornene trimethylsilyl ether (6.39 g, 0.0301) are added under nitrogen atmosphere. mole). To this stirred solution, a solution of (toluene) Ni (C ₆ H ₅ ) ₂ in 5 ml of toluene is added at ambient temperature and stirring is continued for 6 hours. To the polymer solution are added tetrahydrofuran (100 ml) and IRC-718 resin (30 ml ) and stirring is continued for 18 hours, then the resin is filtered off. Resin A-15 (30 ml) and deionized water (10 ml) were added to the resulting solution and stirred for another 18 hours, and then the polymer solution was filtered. The polymer was precipitated with a 90:10 methanol / water mixture and the precipitated polymer was filtered off. The resulting polymer is dried. The yield of the obtained polymer is 13.34 g (M _n = 31600 and M _w = 71500). The total copolymer yield represents 74% monomer conversion. The polymer is fully characterized using NMR and IR spectroscopy and gel chromatography.

Example 74
The copolymers synthesized according to Examples 72 and 73 are dissolved in propylene glycol monomethyl ether acetate, formulated, centrifuged and formed into a film, and completely processed as described in Example 64 of the initial description, except that diaryl iodononium hexafluoroantimonate is added instead of triarylsulfonium hexafluoroantimonate 1012) in an amount of 10% by weight of the polymer. After the base develops in an aqueous solution for 65 s, positive high-resolution images are obtained.

Claims (29)

1. A photoresist composition containing an acid photoinitiator, optionally a dissolution inhibitor and a copolymer, characterized in that the copolymer contains at least two types of repeating polycyclic units, one of which contains a lateral acid labile group, and the other contains a lateral polar functional group, moreover, a polymer containing polar functional groups, obtained by polymerization of a monomer of the formula

where R ⁵ -R ⁸ independently selected from the group consisting of hydrogen, straight or branched (C ₁ -C ₁₀ ) alkyl and a polar substituent, which is represented by one of the following groups:
- (A) _n -C (O) OR ", - (A) _n -OR", - (A) _n -OC (O) R ", - (A) _n -OC (O) OR",
-A _n -C (O) R ", -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 ") ₂ CH (R") (C (O) OR ") and - (A) _n -C (R") ₂ CH (C (O) OR ") ₂ , where n is 1;
p is an integer from 0 to 5;
-A- and -A'- independently represent a divalent radical selected from the group consisting of straight and branched (C ₁ -C ₁₀ ) alkylene, (C ₂ -C ₁₀ ) alkylene ethers, polyesters, cyclic ethers, cyclic diesters or cyclic group of the formula

where a is an integer from 2 to 7;
R "means a substituent selected from the group consisting of hydrogen, straight and branched (C ₁ -C ₁₀ ) alkyl, straight and branched (C ₁ -C ₁₀ ) alkoxyalkylene, polyesters, monocyclic and polycyclic (C ₄ -C ₂₀ ) cycloaliphatic residues cyclic ethers, cyclic diesters, cyclic ketones and cyclic ethers (lactones),
however, at least one of the substituents R ⁵ -R ⁸ must be selected from the specified side functional group, provided that if R "means an alkyl, lactone, cycloaliphatic group or cyclic ketone or if R ⁵ -R ^{8 are} represented by one from the groups - (A) _n -C (O) OR ", - (A) _n -OR", - (A) _n -OC (O) R ", - (A) _n -OC (O) OR", -A _n -C (O) R ", - (A) _n -C (R") ₂ CH (R ") (C (O) OR") and - (A) _n -C (R ") ₂ CH (C (O) OR ") ₂ , the group -A- cannot mean an alkylene radical. 2. The composition according to p. 1, characterized in that the repeating unit containing a side acid labile group is obtained by polymerizing the polycyclic (s) monomer (s) containing one or more acid labile groups as substituents and represented by the formula C (O ) OR, - (A) _n -OR, - (A) _n -OC (O) R, - (A) _n -C (O) R, - (A) _n -OC (O) OR, - (A ) _n -OCH ₂ C (O) OR ^* , - (A) _n -C (O) O-A'-O (CH ₂ ) C (O) OR ^* , - (A) _n -OC (O) - A'-C (O) OR ^* ,
- (A) _n -C (R) ₂ CH (R) (C (O) OR ^** ) and - (A) _n -C (R) ₂ CH (C (O) OR **) ₂ , where n = 0 or 1, am is a prime number from 0 to 5, -A- and -A'- independently mean a divalent radical selected from the group consisting of straight and branched (C ₁ - C ₁₀ ) alkylenes, (C ₂ -C ₁₀ ) alkylene ethers, polyesters, or a cyclic group of the formula

where a is an integer from 2 to 7;
R is hydrogen or straight and branched (C ₁ -C ₁₀ ) alkyl;
R * means an acid labile group which is cleaved by the action of an acid photoinitiator and which is selected from the group consisting of —C (CH ₃ ) ₃ , —Si (CH ₃ ) ₃ , —CH (R ^p ) OCH ₂ CH ₃ , - CH (R ^p ) OS (CH ₃ ) ₃ or the following cyclic groups:

where R ^p means hydrogen, a straight or branched (C ₁ -C ₅ ) alkyl group;
R ^** independently means R and R ^* ,
and at least one of the substituents R ¹ -R ⁴ must be selected from the group of substituents containing said acid labile group. 3. The composition according to claim 2, characterized in that said polycyclic copolymer contains repeating units, which are obtained by polymerization of one or more monomers represented by the formulas

where R ⁹ -R ¹⁶ independently selected from the group comprising hydrogen, straight and branched (C ₁ -C ₁₀ ) alkyl, provided that at least one of the substituents R ⁹ -R ¹² is a carboxyl substituent of the formula - (CH ₂ ) _n C (O) OH, where n is an integer from 0 to 10,
q and r are integers from 0 to 5.  4. A composition according to any one of claims 1, 2 or 3, characterized in that said monomers are polymerized by ring-opening polymerization to obtain a polymer with open rings.  5. The composition according to claim 4, characterized in that the said open-cycle polymer is hydrogenated.  6. The composition according to claim 2, characterized in that the said monomers are polymerized by free radical polymerization. 7. The composition according to any one of claims 1, 2 or 3, characterized in that the said copolymer contains repeating units represented by formulas

where R ¹ -R ⁸ , m and p are as previously defined. 8. The composition according to claim 7, characterized in that the said copolymer, in addition, contains at least one repeating unit, which is selected from the group presented below

where R ⁹ -R ¹⁶ as previously defined. 9. The composition according to claim 1, characterized in that the said copolymer is an open-loop polymer and contains repeating units represented by the formulas

where R ¹ -R ⁸ as previously defined. 10. The composition according to p. 9, characterized in that the said polymer with open cycles, in addition, contains at least one repeating unit, which is selected from the group represented by formulas

where R ⁹ -R ¹⁶ independently selected from the group consisting of hydrogen and straight and branched (C ₁ -C ₁₀ ) alkyl, provided that at least one of the substituents R ⁹ -R ¹² is a carboxyl substituent of the formula - (CH ₂ ) _n C (O) OH, where n is an integer from 0 to 10;
q and r are independently integers from 0 to 5. 11. The composition according to claim 9, characterized in that the said copolymer contains repeating units represented by formulas

where the substituent R ^* means a residue that is cleaved by the action of an acid photoinitiator and which is selected from the group consisting of —C (CH ₃ ) ₃ , —Si (CH ₃ ) ₃ , 1-methyl-1-cyclohexyl, isobornyl, 2-methyl- 2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanonyl, the residue of mevalonic acid lactone, 1-ethoxyethyl, 1-tert-butoxyethyl, dicyclopropylmethyl (DCMP) and dimethylcyclopropylmethyl (DMC);
R ″ substituents are selected from the group consisting of straight and branched (C ₁ -C ₁₀ ) alkyl. 12. The composition according to p. 11, characterized in that the substituents R ¹ -R ³ or R ⁵ -R ⁷ mean hydrogen, straight or branched (C ₁ -C ₁₀ ) alkyl, and the substituent R "means straight or branched (C ₁ -C ₁₀ ) alkyl. 13. The composition according to p. 12, characterized in that the said polymer with open cycles contains repeating units represented by formulas

where m and p are independently 0 or 1;
n = 1. 14. The composition of claim 13, wherein R ^* is tert-butyl, A is a methylene group, and R ″ is selected from straight or branched (C ₁ -C ₅ ) alkyl.  15. The composition according to any one of claims 9 to 14, characterized in that the unsaturated units in the side chain of said open ring polymer are hydrogenated.  16. The composition according to p. 15, characterized in that the unsaturated units in the side chain of the said polymer with open rings are hydrogenated, and the degree of hydrogenation is more than 90%.  17. The composition according to p. 16, characterized in that the unsaturated units in the side chain of said open-cycle polymer are almost completely hydrogenated, that is, the degree of hydrogenation is more than 99%. 18. The composition according to p. 1, characterized in that it contains an acid photoinitiator, optionally a dissolution inhibitor and a copolymer containing polycyclic repeating units represented by the formulas

where the substituents R ¹ -R ⁸ as previously defined. 19. The composition according to p. 18, characterized in that the said copolymer, in addition, contains at least one repeating unit, which is selected from the group represented by formulas

where R ⁹ -R ¹⁶ independently selected from the group consisting of hydrogen and straight and branched (C ₁ -C ₁₀ ) alkyl, provided that at least one of the substituents R ⁹ -R ¹² is a carboxyl substituent of the formula - (CH ₂ ) _n C (O) OH, where n is an integer from 0 to 10;
q and r are independently integers from 0 to 5. 20. The composition according to p. 18, characterized in that the said copolymer contains repeating units represented by formulas

where R ^* means a residue that is cleaved by the action of an acid photoinitiator and which is selected from the group consisting of -C (CH ₃ ) ₃ , -Si (CH ₃ ) ₃ , 1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2 -isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanonyl, the residue of mevalonic acid lactone, 1-ethoxyethyl, 1-tert-but-hydroxyethyl, dicyclopropylmethyl (DCMP) and dimethylcyclopropylmethyl (DMC);
R "is selected from the group consisting of straight and branched (C ₁ -C ₁₀ ) alkyl. 21. The composition according to claim 20, characterized in that the substituents R ¹ -R ³ and R ⁵ -R ⁷ mean hydrogen or straight or branched (C ₁ -C ₁₀ ) alkyl, and R "means straight or branched (C ₁ - C ₁₀ ) alkyl. 22. The composition according to p. 21, characterized in that the said copolymer contains repeating units represented by formulas

where m and p are independently 0 or 1;
n = 1. 23. The composition of claim 22, wherein R ^* is tert-butyl, A is a methylene group, and R "is straight or branched (C ₁ -C ₅ ) alkyl.  24. The composition according to one of claims 1 to 3, 5, 11-21, characterized in that said polymer contains from 5 to 100 mol% of repeating units containing said acid labile group.  25. The composition according to p. 24, characterized in that the said polymer contains from 20 to 90 mol.% Repeating units containing an acid-labile group.  26. The composition according A.25, characterized in that the said polymer contains from 30 to 70 mol.% Repeating units containing an acid-labile group.  27. The composition according to one of paragraphs.7, 8, 18-23, characterized in that said polymer has a lateral perfluorophenyl group at least at one end of the chain.  28. The composition according to any one of claims 1 to 3, characterized in that said polycyclic polymer contains repeating units obtained by polymerization of maleic anhydride. 29. The composition according to one of paragraphs.7, 8, 18-23, characterized in that the said polymer contains a repeating unit represented by the formula

-

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