KR20010023940A - Photoresist compositions comprising polycyclic polymers with acid labile pendant groups - Google Patents

Abstract

The present invention relates to a radiation sensitive photoresist composition comprising a polycyclic polymer comprising a repeating unit containing an acid labile pendant group and a photoacid initiator. The photoacid initiator generates an acid which degrades the acid labile pendant group that affects the polarity change of the polymer upon exposure to the imaging radiation source. Such a polymer can be dissolved in an aqueous base in the exposed area to an imaging source.

Description

[0001] PHOTORESIST COMPOSITIONS COMPRISING POLYCYCLIC POLYMERS WITH ACID LABILE PENDANT GROUPS [0002]

Background of the Invention Integrated circuits (ICs) are excellent for manufacturing arrays of electronic devices. They may be fabricated from the continuous formation of alternating conductive and semi-conductive and nonconductive layers and interconnecting bands on a suitable substrate (e.g., silicon wafer) that is selectively patterned to form circuits and interconnects to produce a particular electrical action do. The patterning of the IC is performed according to various lithographs known in the art. Photolithography using ultraviolet (UV) light and progressively deep UV light or other radiation is essential and is an important technology utilized in the production of IC devices. The light sensitive polymer film (photoresist) is applied to the wafer surface and dried. The photomask containing the desired patterning information is then located in close proximity to the photoresist film. The photoresist is irradiated through an overlying photomask by radiation of one form of several types of imaging radiation, including UV light, e-beam, x-ray or ion beam. Upon exposure to radiation, the photoresist is chemically altered with simultaneous changes in solubility. After irradiation, the wafer is immersed in a solution that develops the patterned image in the photosensitive polymer film (i. E., Selectively removes exposed or unexposed areas). Depending on the type of polymer used or the polarity of the developing solvent, the exposed or unexposed areas of the film may be removed during development to expose the underlying substrate, and then the patterned exposed or undesired substrate material may act on the wafer Layer is removed or changed by an etching process that leaves a desired pattern in the layer. Etching is accomplished by plasma etching, sputter etching and reactive ion etching (RIE). The remaining photoresist material acts as a protective barrier against the etching process. Removal of the remaining photoresist material provides a patterned circuit.

The process of etching a different layer on a wafer in manufacturing a patterned IC device is the most important step among the included steps. One approach is to immerse the substrate and the patterned resist in a chemical bath that attacks the exposed substrate surface while keeping the resist intact. This " wet " chemical treatment is difficult to achieve well-defined edges on the etched surface. This difficulty is due to the chemical undercutting of resist materials and the formation of isotropic images. In other words, conventional chemical treatments do not provide a degree of orientation (isotropy) selectivity that is deemed necessary to achieve optimal dimensional specifications consistent with current treatment requirements. In addition, the wetting treatment is permitted due to the unsolicited environmental and safety consequences.

Various " dry " treatments have been developed to overcome defects in wet chemical treatments. This drying process generally involves passing the gas through a chamber and ionizing the gas by providing a potential across the two electrodes in the presence of a gas. Plasma containing ion species generated by dislocation is used to etch the substrate placed in the chamber. The ionic species generated in the plasma are directed to an exposed substrate that interacts with a surface material that forms volatile products that are removed from the surface. Typical examples of dry etching include plasma etching, sputter etching and reactive ion etching.

Reactive ion etching provides well defined vertical sidewall shapes within the substrate as well as substrate to substrate etch uniformity. Because of these advantages, reactive ion etching technology has become a standard in IC manufacturing.

Two types of photoresists are used in the industry: negative and positive photoresists. The negative resist changes the solubility characteristics so that the exposed, polymerized, crosslinked, or exposed areas do not dissolve in the developer. The unexposed areas are maintained in a soluble state and washed. The positive resist acts in reverse and dissolves in the developing solution after exposure to the imaging radiation.

One type of positive resist material is based on phenol-formaldehyde novolac polymers. A specific example is a commercially available Shipley AZ1350 material comprising m-cresol formaldehyde novolak polymer composition and diazo ketone (2-diazo-1-naphthol-5-sulfonic acid ester). The diazoketone is converted to carboxylic acid when exposed to imaging radiation, which converts the phenolic polymer into a substance that is readily soluble in a weak aqueous base developer.

U.S. Patent No. 4,491,628 to Ito et al. Describes positive and negative photoresist compositions having an acid-generating photoinitiator and polymers having acid-unstable pendant groups. This approach is known as chemical amplification, which serves to increase the yield of a particular amount of whole photochemical treatment, since each acid generated causes the deprotection of many acid labile groups. Such polymers include polystyrenes, polyvinyl benzoates, and vinyl-based polymers such as polyacrylates substituted with a recurrence pendant group that is cracked to yield a different product in solubility than the precursor. Preferred acid-labile pendant groups include t-butyl esters of carboxylic acids and t-butyl carbonates of phenols. The photoresist can be made positive or negative depending on the nature of the suspension solution used.

The trend in the electronics industry is constantly demanding ICs that are faster and consume less power. In order to meet these specifications, the IC must be made smaller. The conduction path (i. E., Line) should be made thinner and closer together. Significant reduction in the size of the generated lines and transistors simultaneously increases the efficiency of the IC, for example, to increase the ability to process and store information on a computer chip. High photo image resolution is required to achieve thinner line widths. The high resolution is made possible by an exposure source of short wavelength used to irradiate the photoresist material. However, conventional photoresists and substituted styrenic polymers, such as phenol-formaldehyde novolac polymers, contain aromatic groups that gradually become absorbent when the wavelength of light falls below about 300 nm [Reference: ACS Symposium Series 537 , Polymers for Microelectronics, Resists and Dielectrics, 203rd National Meeting of the American Chemical Society, April 5-10, 1992, pages 2-24; Polymers for Electronic and Photonic Applications, Edited by C.P. Wong, Academic Press, p. 67-118]. Short wavelength sources are typically less vivid than conventional sources that require a chemical amplification method that uses a photoacid. The opacity of these aromatic polymers to short wavelength light is a defect in that the photoacid under the polymer surface is not uniformly exposed to the light source and ultimately the polymer can not be developed. In order to overcome the lack of transparency of these polymers, the aromatic content of the photoresist must be reduced. When deep UV transparency is desired (i.e., 248 nm and especially 193 nm wavelength exposure), the polymer should contain minimal aromatic properties.

U.S. Patent No. 5,372,912 relates to a photoresist composition containing an acrylate-based polymer, a phenolic-type binder and a photo-sensitive acid generator. The acrylate-based copolymer is polymerized from monomers having acrylic acid, alkyl acrylate or methacrylate, and acid-labile pendant groups. When such a composition is sufficient to transmit UV radiation at a wavelength of about 240 nm, the use of short wavelength radiation sources is limited by the use of aromatic type binders. As is common in polymer technology, an increase in one characteristic is generally achieved at the expense of another. In the case of using an acrylate based polymer, the gain in transparency to short wavelength UV is achieved by sacrificing the resistance of the resistor to the reactive ion etching process.

In many cases, improvement in transparency to short wavelength imaging radiation results in corrosion of the resist material during the subsequent dry etch process. The photoresist material has a higher etch rate than the substrate material when using the RIE technique because the photoresist material is typically organic in nature and the substrate used in the manufacture of ICs is typically inorganic. This requires a requirement for a photoresist material that is much thicker than the underlying substrate. If not, the photoresist material will corrode before the bottom substrate is completely etched. Thin layers of resist material allow for high resolution, ultimately allowing more limited conduction lines and smaller transistors.

J.V. J. V. Crivello et al., Chemically Amplified Electron-Beam Photoresists, Chem. Mater., 1996, 8, 376-381) discloses a photoresist composition comprising 20% by weight of a homopolymer polymerized with a free radical of a norbornene monomer containing an acid labile group and 4-hydroxy- RTI ID = 0.0 > 80% < / RTI > by weight of a-a-methylstyrene homopolymer. As noted above, increased absorption of aromatics (especially at high concentrations) makes these compositions opaque and unstable for short wavelength imaging radiation below 200 nm.

The above compositions are suitable only for electron-beam photoresists and can not be utilized for deep UV imaging (especially for 193 nm resist).

Creevel et al. Studied the blend composition because it was observed that the oxygen plasma etch rate was unacceptably high for homopolymers polymerized with free radicals of norbornene monomers containing acid labile groups.

Thus, there is still a need for photoresist compositions that are compatible with common chemical amplification methods and that are sufficiently resistant to reactive ion etch processing environments and that provide transparency to short wavelength imaging radiation.

The present invention relates to polycyclic polymers and methods of using them as photoresists in the manufacture of integrated circuits. More particularly, the present invention relates to a photoresist composition comprising a polycyclic polymer and a cationic photoinitiator. The polycyclic polymer contains a group that is unstable in the recurrent acid which is a pendant group of the polymer backbone. An acid labile group can be selectively cleaved to form a recurring polar group with the backbone of the polymer. The polymer transmits short wavelength imaging radiation and is resistant to reactive ion etching.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a photoresist composition comprising a polycyclic polymer skeleton having an acid-labile pendant group and a photoinitiator.

Another object of the present invention is to provide a polycyclic polymer having an unstable pendant group in the regenerated acid which can be cleaved to form a polar group.

It is another object of the present invention to provide a transparent polymer composition for short wavelength imaging radiation.

Another object of the present invention is to provide a polymer composition which is resistant to dry etching treatment.

It is another object of the present invention to provide a polymer composition which is transparent to short wavelength imaging radiation and is resistant to dry etching treatment.

Another object of the present invention is to provide a polycyclic monomer containing an acid-labile pendant group capable of being polymerized and capable of forming a polymer that can be developed in an aqueous base.

These and other objects of the present invention are achieved by polymerizing a reaction mixture comprising a monocomponent or multi-component catalyst system containing an acid labile group-terminated polycycloolefin-based monomer, a solvent, and a source of a Group VIII metal ion, respectively. In the multi-component catalyst system of the present invention, the Group VIII ion source is used in combination with one or both of the organometallic cocatalyst and the third component. Single-component and multi-component catalyst systems can be used with any chain transfer agent (CTA) selected from compounds having terminal olefinic double bonds of adjacent carbon atoms (two hydrogen atoms attached to at least one carbon of these carbon atoms) do. CAT is typically selected from unsaturated compounds capable of polymerizing with a cation to exclude styrene, vinyl ethers and conjugated dienes.

The resulting polymer is useful in photoresist compositions comprising an acid generator that is sensitive to radiation.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a radiation-sensitive resist composition comprising an acid generation initiator and a polycyclic polymer containing a pendant group unreactive to a recurrent acid along the polymer backbone. The polymer containing the initiator is coated as a thin film on a substrate, baked under controlled conditions, exposed to radiation in a patterned shape, and optionally baked under controlled conditions to further promote deprotection. In the portion of the film exposed to the radiation, the recurrent pendant groups that are unstable to the acid on the polymer backbone break up to form a recurring group of polarity. The exposed areas treated in this manner are selectively removed with an alkaline developer. Alternatively, the non-exposed regions of the polymer remain in the non-polar state and can be selectively removed by treatment with a non-polar solvent suitable for negative tendency phenomena. Image reversal can be easily accomplished by appropriate selection of the developer due to the difference in solubility characteristics of the exposed and unexposed portions of the polymer.

The polymer of the present invention comprises a polycyclic repeating unit substituted with an acid labile group. These polymers are prepared by polymerizing the polycyclic monomers of the present invention. The term " polycyclic " (norbornene type or norbornene functionality) means that the monomers contain one or more norbornene moieties as shown below:

The simplest polycyclic monomer of the present invention is the bicyclic monomer, bicyclo [2.2.1] hept-2-ene, commonly referred to as norbornene. In one embodiment of the invention, acid labile functional groups are optionally combined with one or more polycyclic monomers of the following formulas (II), (III), (IV) and (V) in the presence of a Group VIII metal catalyst system, Is introduced into the polymer chain by polymerization reaction of a reaction medium comprising a substituted polycyclic monomer of the formula (I) < Desc / Clms Page number 12 >

In another embodiment of the present invention, the substituted polycyclic monomers of formula (I) that are labile to one or more acids are copolymerized with one or more of the following polycyclic monomers of formula (II).

Monomer

Acid-labile polycyclic monomers useful in the practice of the present invention are selected from monomers represented by the formula (I)

Wherein R, R ¹ to R ⁴ are independently a _{- (A) n C (O} ) OR *, - (A) n -C (O) 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 ' ^{_{-OCH 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 with the proviso that at least one group of R ¹ to R ⁴ is an acid (A) _n C (O) OR ^* . A and A 'independently represent a divalent bridging or spacer selected from a divalent hydrocarbon radical, a divalent cyclic hydrocarbon radical, a divalent oxygen containing radical, and bivalent cyclic ethers and cyclic diethers, And n is an integer of 0 or 1. When n is 0, A and A 'represent a single covalent bond. 2 < / RTI > means that free valencies at each terminal end of the radical are attached to two distinct groups. The divalent hydrocarbon radical may be represented by the formula - (C _d H _2d ) - wherein _d represents the number of carbon atoms in the alkylene chain and is an integer of 1 to 10. The divalent hydrocarbon radicals are preferably selected from straight and branched (C ₁ to C ₁₀ ) alkylenes such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, Is selected. When side-chain alkylene radicals are contemplated, it is to be understood that the hydrogen in the straight chain alkylene is replaced by a straight-chain or branched (C ₁ to C ₅ ) alkyl group.

Dicyclic hydrocarbon radicals include substituted and unsubstituted (C ₃ to C ₈ ) alicyclic moieties represented by the formula:

Wherein a is an integer from 2 to 7 and R ^q , when present, represents a straight chain and branched (C ₁ to C ₁₀ ) alkyl group. Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene moieties represented by the formula:

Wherein R ^q is as defined above. As here and generally illustrated herein, the bonding line projecting from the cyclic structure and / or formula represents the divalent nature of the moiety and the point at which the carbocyclic moiety is bonded to adjacent moieties defined in each formula ≪ / RTI > As is conventional in the art, the diagonal line of engagement protruding from the center of the cyclic structure indicates that the bond is optionally attached to either of the carbocyclic atoms in the ring. It is also to be understood that the carbocyclic atom to which the bond is connected will accommodate less than one hydrogen atom to meet the valence requirements of the carbon.

Preferred dicyclic ethers and diethers are represented by the formula:

Divalent oxygen containing radicals include (C ₂ to C ₁₀ ) alkylene ethers and polyethers. (C ₂ to C ₁₀ ) alkylene ether means that the total number of carbon atoms in the divalent ether moiety is at least 2 and can not exceed 10. The divalent alkylene ether may be the same or different and each alkylene group bonded to the oxygen atom may be the same or different and is selected from methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene and nonylene. -Alkylene-O-alkylene-. Of these, the simplest divalent alkylene ether is the radical -CH ₂ -O-CH ₂ -. Preferred polyether moieties include divalent radicals of the formula:

Wherein x is an integer from 0 to 5 and y is an integer from 2 to 50 with the proviso that the terminal oxygen atom on the polyether spacer residue is directly connected to the terminal oxygen atom on the adjacent group to form a peroxide bond . In other words, a peroxy bond (i.e., -OO-) is not taken into account when the polyether spacer is also bonded to any of the terminal oxygen containing substituents described in R ¹ to R ⁴ above.

In the above formulas, R represents hydrogen or straight chain and side chain (C ₁ to C ₁₀ ) alkyl, and m is an integer of 0 to 5. R ^* is _{-C (CH 3) 3 -,} -Si (CH 3) 3, -CH (R p) OCH 2 CH 3, -CH (R p) OC (CH 3) 3 or selected from the following compounds (I. E., A blocking or protecting group) that can be cleaved by a photoacid initiator: < RTI ID = 0.0 >

Wherein R ^p represents hydrogen or a straight chain or branched (C ₁ to C ₅ ) alkyl group. Alkyl substituents include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, t-pentyl and neopentyl. In the above formulas, the single bond line protruding from the cyclic group represents a carbon atom ring position at which the protective group is bonded to each substituent. Examples of acid labile groups include 1-methyl-1-cyclohexyl, isobonyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuran, tetrahydropyranyl, Cyclohexanonyl, mevalonic lactonyl, 1-ethoxyethyl, 1-t-butoxyethyl, dicyclopropylmethyl (Dcpm) and dimethylcyclopropylmethyl (Dmcp) groups. Alkyl substituents on the above protecting groups are selected from straight and branched (C ₁ to C ₅ ) alkyl groups. R ^** independently represent R and R ^* as defined above. The Dcpm and Dmcp groups are respectively represented by the following structures:

_{- (CH 2) n C (} R) 2 CH (R) (C (O) OR **) or _{- (CH 2) n C (} R) 2 CH (C (O) OR **) ₂ substituents selected from ≪ / RTI > may be represented as follows: < RTI ID = 0.0 >

Wherein m is as defined above, and n 'is an integer of 0 to 10.

In the above formula, m is preferably 0 or 1, more preferably 0. When m is 0, the preferred structure is as follows:

Wherein R ¹ to R ⁴ are as defined above.

It will be apparent to those skilled in the art that any photoacid-cleavable moiety is suitable for practicing the present invention as long as the polymerization is not substantially hampered by the practice of the present invention.

Preferred acid labile groups are protected organic ester groups in which the protecting or blocking group is cleaved in the presence of an acid. Particular preference is given to tertiary butyl esters of carboxylic acids.

When the monomers described under formula (I) are polymerized into the polymer backbone, these monomers provide a recurrent pendant acid sensitive group that is subsequently cleaved to provide polarity or solubility to the polymer.

An optional second monomer is represented by the following formula (II): < RTI ID = 0.0 >

Wherein, R ⁵ to R ⁸ is independently _{- (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 ") indicates a substituent, neutral or polar is selected from ₂ . Residues A and A 'independently represent a divalent bridging or spacer selected from a divalent hydrocarbon radical, a divalent cyclic hydrocarbon radical, a divalent oxygen containing radical and a divalent cyclic ether and a cyclic diether, and n is 0 or Lt; / RTI > When n is 0, it is clear that A and A 'represent a single covalent bond. 2 means that the free valence at each terminal end of the flanking radical is attached to two distinct groups. The divalent hydrocarbon radical may be represented by the formula - (C _d H _2d ) - wherein _d represents the number of carbon atoms in the alkylene chain and is an integer of 1 to 10. The divalent hydrocarbon radicals are preferably selected from straight and branched (C ₁ to C ₁₀ ) alkylenes such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, Is selected. When side-chain alkylene radicals are contemplated, it is to be understood that the hydrogen in the straight chain alkylene is replaced by a straight-chain or branched (C ₁ to C ₅ ) alkyl group.

The divalent cyclic hydrocarbon radicals include substituted and unsubstituted (C ₃ to C ₈ ) alicyclic moieties represented by the formula:

Wherein a is an integer from 2 to 7 and R ^q , when present, represents a straight chain and branched (C ₁ to C ₁₀ ) alkyl group. Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene moieties represented by the formula:

Wherein R ^q is as defined above. As here and generally illustrated herein, the bonding line projecting from the cyclic structure and / or formula represents the divalent nature of the moiety and the point at which the carbocyclic moiety is bonded to adjacent moieties defined in each formula ≪ / RTI > As is conventional in the art, the diagonal line of engagement protruding from the center of the cyclic structure indicates that the bond is optionally attached to either of the carbocyclic atoms in the ring. It is also to be understood that the carbocyclic atom to which the bond is connected will accommodate less than one hydrogen atom to meet the valence requirements of the carbon.

Preferred dicyclic ethers and diethers are represented by the formula:

Divalent oxygen containing radicals include (C ₂ to C ₁₀ ) alkylene ethers and polyethers. (C ₂ to C ₁₀ ) alkylene ether means that the total number of carbon atoms in the divalent ether moiety is at least 2 and can not exceed 10. The divalent alkylene ether may be the same or different and each alkylene group bonded to the oxygen atom may be the same or different and is selected from methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene and nonylene. -Alkylene-O-alkylene-. Of these, the simplest divalent alkylene ether is the radical -CH ₂ -O-CH ₂ -. Preferred polyether moieties include divalent radicals of the formula:

Wherein x is an integer from 0 to 5 and y is an integer from 2 to 50 with the proviso that the terminal oxygen atom on the polyether spacer residue is directly connected to the terminal oxygen atom on the adjacent group to form a peroxide bond . In other words, a peroxy bond (i.e., -OO-) is not taken into account when the polyether spacer is also bonded to any of the terminal oxygen containing substituents described in R ¹ to R ⁴ above.

R ⁵ to R ⁸ can independently represent hydrogen or straight-chain and branched (C ₁ to C ₁₀ ) alkyl, as long as at least one of the remaining R ⁵ to R ⁸ substituents is selected from one of the above neutral or polar groups . In the above formula, p is an integer of 0 to 5 (preferably 0 or 1, more preferably 0). R " is independently hydrogen or a linear or branched (C ₁ to C ₁₀ ) alkyl, linear or branched (C ₁ to C ₁₀ ) alkoxyalkylene, polyether, monocyclic and polycyclic (C ₄ to C ₂₀ ) (C ₁ to C ₁₀ ) alkoxyalkylene means that a terminal alkyl group is bonded to an alkylene residue through an ether oxygen atom. The radical is a hydrocarbon-based ether residue, which may be generically represented as -alkylene-O-alkyl, where the alkylene and alkyl groups each independently contain 1 to 10 carbon atoms, which may be linear or branched. The radical may be represented by the formula:

Wherein x is an integer from 0 to 5, y is an integer from 2 to 50, and R ^a represents hydrogen or a straight chain or branched (C ₁ to C ₁₀ ) alkyl. Preferred polyether radicals are poly (ethylene oxide) and poly (propylene oxide). Examples of monocyclic alicyclic monocyclic moieties include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Examples of alicyclic polycyclic moieties include norbornyl, adamantyl, tetrahydrodicyclopentadienyl (tricyclo [5.2.1.0 ^2,6 ] decanyl, etc. Examples of cyclic ethers include tetrahydrofuranyl and Tetrahydropyranyl residue. An example of a cyclic ketone is a 3-oxocyclohexanonyl residue. An example of a cyclic ester or lactone is a mevalonic lactonyl residue.

R " of formula (II) is an ester containing an acid labile group, as long as the substituent described for R " of formula (II) is unstable or counterproductive to the acid described for R ^* in formula (I) It should be understood that the residue can not be represented. For example, when R " is a norbonyl, adamantyl, tetrahydropyranyl, 3-oxocyclohexanonyl or mevalonic lactonyl moiety, it is directly attached to the oxygen atom in the ester moiety (-C (O) O) It can not be attached.

Preferred neutral or polar substituents are alkyl esters of carboxylic acids, isolated oxalate containing moieties such as - (A) _n -OC (O) -A'-C (O) OR ' Containing residues (e.g., - (A) _n -OC (O) C (O) OR "). The esters, spaced apart oxalate and oxalate containing functionalities provide exceptional hydrophilicity without problems associated with excessive carboxylic acid functionalities, promote wetting of the developer and improve film mechanical properties.

An optional third monomer component is represented by the following formula (III): < RTI ID = 0.0 >

Wherein, R ⁹ to R ¹² are independently _{- (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 ⁺ , wherein X represents a tetraalkylammonium cation and the alkyl substituent is selected from the group consisting of straight and branched (C ₁ to C ₁₀ ) alkyl , Q is an integer of 0 to 5 (preferably 0 or 1, more preferably 0), and n is an integer of 0 to 10 (preferably 0). R ⁹ to R ¹² may independently represent hydrogen or straight-chain and branched (C ₁ to C ₁₀ ) alkyl, as long as at least one substituent in the remaining R ⁹ to R ¹² substituents is selected from one of the above-mentioned acids or acid salts have.

Monomers containing carboxylic acid functional groups contribute to the hydrophilicity of the polymer and allow the polymer to develop at high speed in an aqueous base system.

Any monomer of formula (IV) is represented by the formula:

Wherein R ¹³ to R ¹⁶ independently represent a straight-chain or branched (C ₁ to C ₁₀ ) alkyl, and r is an integer of 0 to 5 (preferably 0 or 1, more preferably 0). R ¹³ to R ¹⁶ is any of one selected from the remaining R ¹³ to R is an alkyl group defined above, at least one of ^16, may represent a independently hydrogen. Among these alkyl substituents, decyl is particularly preferred.

Polymerization of the alkyl substituted monomers into the polymer backbone is a method of controlling the Tg of the polymer as described in Goodall et al., U.S. Patent No. 5,468,819.

An economical method for preparing the functionalized or hydrocarbyl substituted polycyclic monomers of the present invention comprises reacting a cyclopentadiene (CPD) or substituted CPD with a dienophile suitably substituted at elevated temperature to produce a Alder reaction which forms the substituted polycyclic adduct product generally indicated.

Other polycyclic adducts can be prepared by pyrolysis of dicyclopentadiene (DCPD) in the presence of a suitable dienophile. The reaction is initially pyrolyzed with DCPD to CPD, followed by treatment with CPD and dienophyll with a Diels-Alder addition reaction to yield an adduct of the formula:

In the above formulas, R 'to R "' independently represent a substituent group defined for R ¹ to R ¹⁶ in the above formulas (I), (II), (III) and (IV).

For example, 2-norbornene-5-carboxylic acid (bicyclo [2.2.1] hept-5-ene-2-carboxylic acid) can be prepared by subjecting a cyclopentadiene to the Diels- do:

The t-butyl esters of the corresponding carboxylic acids can be prepared by reacting isobutylene and carboxylic acid functionality in the presence of a triflic acid as shown in the following scheme:

Another more preferred method for preparing t-butyl esters of norbornene carboxylic acids involves the Diels-Alder reaction of t-butyl acrylate and cyclopentadiene.

Another synthetic method for the acid and ester substituted monomers of the present invention is carried out via ortho ester substituted polycyclic monomers with subsequent hydrolysis to the carboxyl functionality or partial hydrolysis moiety to the ester functionality. The carboxylic acid functionality can be esterified with the desired ester. The orthoester substituted monomers of the present invention are represented by the formula (V)

Wherein R ¹⁷ , R ¹⁸ and R ¹⁹ independently represent a straight or branched (C ₁ to C ₅ ) alkyl group, or R ¹⁷ , R ¹⁸ and R ¹⁹ together with the oxygen atom to which they are attached represent a substituted or unsubstituted , A 5- to 10-membered cyclic or bicyclic ring having 3 to 8 carbon atoms (excluding substituents), s is an integer of 0 to 5 (preferably 0), t is an integer of 1 to 5 (Preferably 1). Representative formulas wherein s is 0, t is 1, R ¹⁷ , R ¹⁸ and R ¹⁹ together with the oxygen atom to which they are attached form a cyclic or bicyclic ring are shown below:

Wherein R ^{17 '} , R ^18' and R ^{19 '} independently represent hydrogen and straight-chain and branched (C ₁ to C ₅ ) alkyl. The orthoester of the present invention can be synthesized by a pinner synthesis method (reference: A. Pinner, Chem. Ber., 16, 1643 (1883), and SM McElvain and JT Venerable, J. Am. Chem. Soc., 72, 1661 (1950); SM McElvain and CL Aldridge, J. Am. Chem. Soc., 75, 3987 (1953). A typical synthesis is illustrated by the following scheme:

An alternative synthetic method is to treat an alkyl acrylate with a trialkyloxonium tetrafluoroborate salt followed by treatment with an alkali metal (sodium alcoholate) to yield a trialkoxymethyl orthoester (see H. Meerwein , P. Borner, O. Fuchs, HJ Sasse, H. Schrodt, and J. Spille, Chem. Ber., 89, 2060 (1956)].

As described above, the orthoester is subjected to a hydrolysis reaction in the presence of a dilute acid catalyst such as hydrobromic acid, hydroiodic acid, and acetic acid to produce a carboxylic acid. Alternatively, the carboxylic acid can be esterified in the presence of an aliphatic alcohol and an acid catalyst to produce the esters, respectively. It should be appreciated that in the case of di- or multisubstituted polycyclic monomers with orthoester groups, the orthoester moieties can be partially hydrolyzed to form acids and conventional esters on the same monomers as shown below.

Another and more preferred synthesis method for the bifunctional polycyclic monomers is by hydrolysis and partial hydrolysis of nadic anhydride (endo-5-norbonene-2,3-dicarboxylic anhydride). The nadic anhydride can be fully hydrolyzed to form the dicarboxylic acid or partially hydrolyzed to produce acid and ester or diester functionalities as shown below:

Wherein R ¹⁷ independently represents straight and branched (C ₁ to C ₅ ) alkyl. Preferably, R ¹⁷ is methyl, ethyl or t-butyl. In a preferred synthesis, the nadic anhydride starting material is an exo isomer. The exo isomer is readily prepared by heating the endo isomer at < RTI ID = 0.0 > 190 C < / RTI > and recrystallizing from a suitable solvent (toluene). In order to obtain the disac- tions under Scheme (1), the nadic anhydride is hydrolyzed in boiling water in a simple manner to give a nearly quantitative yield of the diacid product. The mixed carboxylic acid-alkyl ester functionality shown in Scheme (3) is obtained by heating nadik anhydride with refluxing in the presence of a suitable aliphatic alcohol (R ¹⁷ OH) for 3 to 4 hours. Alternatively, the same product may be prepared by first reacting the aliphatic alcohol and trialkylamine and natric anhydride starting materials followed by treatment with dilute HCl. The diester product substituted with the same alkyl (R ¹⁷ ) group can be reacted with trialkyloxonium tetrafluoroborate in methylene chloride, for example, R ¹⁷ ₃ O [BF ₄ ] and diacid in the presence of diisopropylethylamine at ambient temperature ≪ / RTI > To obtain an ester having different R < ¹⁷ > alkyl groups, the mixed acid-ester product obtained in scheme (3) is used as a starting material. In this embodiment, the acid group is esterified as shown in Scheme (2). However, trialkyloxonium tetrafluoroborates having an alkyl group that is different from the alkyl groups already present in the ester functionality are used.

The foregoing monomers containing the precursor functional group can be converted to the desired functional groups before the polymerization or the respective polymer containing the substituent acting as a precursor after the monomer is first polymerized is reacted to form the desired functional group It should be noted that

It is within the scope of the present invention that the monomers, the methylene bridge units, described under (I) through (V) below in which m, p, q, r and s are 0 can be replaced by oxygen to produce a 7-oxo-norbornene derivative. . ≪ / RTI >

It is also considered to be within the scope of the present invention that the application at a wavelength of 248 nm and that R ⁵ to R ¹⁶ and R ^{11 in} formulas (II), (III) and (IV) may be aromatic compounds such as phenyl.

polymer

The at least one acid labile substituted polycyclic monomer described under formula (I) may be used alone or in combination with one or more of the polycyclic monomers described under formula (II), optionally one or more of the policies described under (III), (IV) Lt; RTI ID = 0.0 > monomers. ≪ / RTI > The polycyclic monomers of formulas (I) through (V) may be copolymerized with carbon monoxide to produce alternating copolymers of polycyclic and carbon monoxide. Copolymers of norbornene and carbon monoxide having a pendant carboxylic acid are described in U.S. Patent No. 4,960,857, which is incorporated herein by reference. The monomers and carbon monoxide of formulas (I) to (V) are described in Chem. 1996, 96, 663-681, incorporated herein by reference. It should be readily understood by those skilled in the art that alternating copolymers of polycyclic / carbon monoxide can exist in keto or spiroketa isomeric forms. Alternatively, the present invention relates to a process for the preparation of (polymerized) polymers derived from at least one monomer represented by formulas (I) and (II) in any combination with any of the monomers represented by formulas (II) Consider a copolymer containing random repeating units. The present invention also contemplates alternating copolymers containing repeating units (polymerized) derived from at least one monomer represented by formulas (I) through (V) and carbon monoxide.

Pendant carboxylic acid functional groups are important in terms of providing the polymer backbone with hydrophilic, adhesion and degradation properties. However, in some photoresist applications, polymers containing excess carboxylic acid functional groups are not preferred. These polymers do not perform well in industry standard developers (.26 N tetramethylammonium hydroxide, TMAH). Swelling of the polymer in unexposed areas, unregulated thinning during application, and swelling of the polymer during exposure decomposition are disadvantageous with respect to these acidic polymers. Thus, copolymers polymerized from the monomers of the formula (II) and optionally the monomers of the monomers (I) are preferred in situations where an excess of carboxylic acid functionality is undesirable, but hydrophilicity and good wetting properties are essential . Alkyl ester, alkyl carbonate spaced alkyl oxalate, and _{- (A) n -C (O} ) OR "-, - (A) n -OC (O) OR", - (A) n -OC (O) - A'-C (O) OR ", and - (a) _n -OC (O) C (O) OR" alkyl oxalate, such as (wherein, a, a ', n, and R "is as defined above) Monomers of formula (II) containing a substituent are particularly preferred.

The polymers of the present invention are an important component of the composition. The polymer will generally contain from about 5 to 100 mole percent of monomers (repeating units) containing an acid labile group. Preferably, the polymer contains from about 20 to 90 mole percent of monomers containing acid labile groups. More preferably, the polymer contains from about 30 to 70 mole percent of monomers containing an acid labile functional group. The remaining polymer composition is composed of repeating units polymerized from any of the monomers described above under the formulas (III) to (V). The amount and selection of the particular monomers used in the polymer may vary depending on the desired properties. For example, by varying the amount of carboxylic acid functionality in the polymer backbone, the solubility of the polymer in a variety of developing solvents can be tailored to desired. Monomers containing ester functional groups can be varied to increase the radiation sensitivity of the system and the mechanical properties of the polymer. Finally, the glass transition temperature characteristics of the polymer can be adjusted by incorporating a cyclic repeating unit containing a long chain alkyl group such as decyl.

There are several ways to polymerize high-grade cyclic (polycyclic) monomers containing cyclic olefinic monomers such as norbornene and norbornene moieties. These include (1) ring opening metathesis polymerization (ROMP); (2) ROMP followed by a hydrogenation reaction; And (3) addition polymerization. Each of the above methods produces a polymer having a specific structure as shown in Scheme (1) below:

The ROMP polymer has a structure different from that of the addition polymer. The ROMP polymer contains repeating units having one less cyclic unit than the starting monomer. The repeat units are joined together at the unsaturated skeleton as shown above. Because of this unsaturation state, it is desirable that the polymer is subsequently hydrogenated to provide oxidation stability to the backbone. On the other hand, the addition polymer has no C = C unsaturation in the polymer backbone, although it is formed from the same monomer.

The monomers of the present invention can be polymerized by addition polymerization and by ring opening metathesis polymerization (ROMP), preferably with subsequent hydrogenation reactions. The cyclic polymers of the present invention are represented by the following structure:

In the above formulas, R 'to R "" independently represent R ¹ to R ¹⁹ as defined in the above formulas (I) to (V), m is an integer of 0 to 5, .

The ROMP polymer of the present invention is polymerized in the presence of a metathesis ring opening polymerization catalyst in a suitable solvent. The method of polymerization via ROMP and the subsequent hydrogenation of the resulting ring-opened polymer are described in U.S. Patent Nos. 5,053,471 and 5,202,388, which are incorporated herein by reference.

In one ROMP embodiment, the polycyclic monomers of the present invention can be polymerized in the presence of a single component ruthenium or osmium metal carbene complex catalyst as described in WO 95-US 9655. The ratio of monomer to catalyst used should range from about 100: 1 to about 2,000: 1, preferably about 500: 1. The reaction may be carried out in a halogenated hydrocarbon such as dichloroethane, dichloromethane, dichlorobenzene or the like, or a hydrocarbon catalyst such as toluene. The amount of solvent used in the reaction medium should be sufficient to achieve a solids content of solids of from about 5 to about 40 wt.%, Preferably from 6 to 25 wt.%, Based on the solvent. The reaction may be carried out at a temperature ranging from about 0 캜 to about 60 캜, preferably from about 20 캜 to 50 캜.

A preferred metal carbene catalyst is bis (tricyclohexylphosphine) benzylidene ruthenium. Surprisingly and advantageously, it has been found that such a catalyst can be used as an initial ROMP reaction catalyst and as an efficient hydrogenation catalyst to produce an essentially saturated ROMP polymer. No additional hydrogenation catalysts need to be used. Following the initial ROMP reaction, all that is needed to hydrogenate the polymer backbone is to maintain the hydrogen pressure throughout the reaction medium at a temperature higher than about 100 DEG C but lower than about 220 DEG C, preferably about 150 to about 200 DEG C will be.

The addition polymers of the present invention can be prepared by standard free radical solution polymerization methods well known to those skilled in the art. The monomers of formulas (I) to (V) may be homopolymerized or copolymerized in the presence of maleic anhydride. The free radical polymerization reaction technique is described in Encyclopedia of Polymer Science, John Wiley & Sons, 13, 708 (1988).

Alternatively, and preferably, the monomers of the present invention are polymerized in the presence of a single or multi-component catalyst system comprising a Group VIII metal ion source (preferably palladium or nickel). Surprisingly, the present inventors have found that an addition polymer produced in this way has excellent transparency to deep UV light (193 nm) and shows excellent resistance to reactive ion etching.

Preferred polymers of the present invention are polymerized from a reaction mixture comprising at least one polycyclic monomer selected from formulas (I) and (II), a solvent, a catalyst system containing a source of Group VIII metal ion, and optional chain transfer agent. The catalyst system may be preformed from a single component VIII metal based catalyst or a multi-component VIII metal catalyst.

Single component catalyst system

In one embodiment, the single component catalyst system of the present invention comprises a Group VIII metal cation complex and a weakly coordinated counter anion as represented by the following formula:

Wherein L represents a ligand containing 1, 2 or 3 pi bonds; M represents a Group VIII transition metal; X represents a ligand containing one sigma bond and 0 to 3 pi bonds; y is 0,1 or 2; z is 0 or 1, where both y and z can not be 0 at the same time; when y is 0, a is 2 and when y is 1, a is 1; CA is a counter anion that is weakly coordinated.

As used herein, the expression " weakly coordinating counter anion " refers to an anion that remains stable enough to be displaced by a neutral Lewis base by only weakly coordinating to the cation. More particularly, the expression refers to anions which, when acting as stabilizing anions in the catalyst system of the present invention, convert anionic substituents or fragments thereof to cations to form a neutral product. The counter anion is a non-oxidizing, non-reducing, non-nucleophilic, relatively inert material.

L is a neutral ligand that is weakly coordinated to the Group VIII metal cation complex. In other words, the ligand is relatively inert and is easily replaced from the metal cation complex by inserting the monomer into the growing polymer chain. Suitable? Bond-containing ligands include, but are not limited to, (C ₂ to C ₁₂ ) monoolefinic (eg, 2,3-dimethyl-2-butene), diolefinic (C ₄ to C ₁₂ ) ₆ to C ₂₀ ) aromatic moieties. Preferably, the ligand L is an aromatic compound such as a chelated bidentate cyclo (C ₆ to C ₁₂ ) diolefin such as cyclooctadiene (COD) or benzo-COD, or benzene, toluene or mesitylene.

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

The ligand X is selected from the group consisting of (i) a moiety that provides a single metal-carbon sigma bond (without pi bond) to the metal in the form of a cation complex, or (ii) a single metal-carbon sigma bond and 1 to 3 pi bonds, Lt; RTI ID = 0.0 > metal. ≪ / RTI > Under this embodiment (i), the moiety is bonded to the Group VIII metal by a single metal-carbon sigma bond that does not have a pi bond. Typical ligands defined in these embodiments include methyl, ethyl and straight and branched chain residues such as propyl, butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl, and (C ₇ to C ₁₅ ) (C ₁ to C ₁₀ ) alkyl residues selected from aralkyl. Under the generally defined embodiment (ii) above, the cation has a hydrocarbyl group bonded directly to the metal by one single metal-carbon sigma bond and one to three pi bonds. Hydrocarbyl means a group capable of stabilizing a Group VIII metal cation complex by providing one carbon-metal sigma bond and one to three olefinic pi bonds that can be conjugated or nonconjugated. Typical hydrocarbyl groups may be bicyclic, monocyclic or polycyclic and include straight and branched (C ₁ to C ₂₀ ) alkoxy, (C ₆ to C ₁₅ ) aryloxy or halo groups such as Cl and F, (C ₃ to C ₂₀ ) alkenyl.

Preferably, X is a single allyl ligand that provides sigma bonds and pi bonds or is canonical form thereof; Providing one or more olefinic π bonds to the metal and providing a σ bond to the metal from a terminal carbon atom remote from the olefinic carbon atom by two or more carbon-carbon single bonds (embodiment iii).

It should be readily apparent to those skilled in the art that when the ligands L or X are absent (i.e., when y or z is zero), the metal cation complex will be weakly ligated by the solvent in which the reaction is performed. Typical 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, mesitylene, chlorobenzene and nitrobenzene . A more detailed description of suitable solvents will be provided below.

Selected embodiments of Group VIII metal cation complexes of the single component catalyst system of the present invention are shown below.

(VII) below represents embodiment (i) wherein the ligand X is a methyl group bonded to the metal through a single metal-carbon sigma bond, and the ligand L is a COD that is weakly coordinated to the palladium metal through two olefinic π bonds . In the structure below, M preferably represents palladium or nickel:

The compounds of formulas (VIII), (IX) and (X) are those wherein X is an allyl group which is bonded to a metal (palladium is shown for illustrative purposes only) through one single metal-carbon bond and one to three pi bonds Various examples of the example (ii) are shown.

In formula (VIII), an aromatic compound that does not exist L but provides three pi bonds is weakly coordinated to the palladium metal; X is an allyl group that provides one single metal-carbon sigma bond and an olefinic [pi] bond to palladium.

In formula (IX), L is COD and X is an allyl group that provides palladium with a metal-carbon sigma bond and an olefinic pi bond.

The following formula (X) represents an embodiment in which ligand X is an unsaturated hydrocarbon which provides one metal-carbon sigma bond, one conjugated pi bond and two additional pi bonds to palladium and no L is present:

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

(XI) and < RTI ID = 0.0 > (XII) < / RTI > wherein L is COD and X provides at least one olefin pi linkage to a Group VIII metal, and from at least two carbon- carbon single bonds a distal carbon atom remote from the olefin carbon atom (Iii) which provides? -Conjugation in the following formula:

The above VIII family cation complexes are associated with weakly coordinated or non-coordinating counter anions (CA ^- ) that are relatively inert and have poor nucleophilicity and provide the cationic complex with the requisite solubility in the reaction solvent. The solution to a suitable anion design should be unstable, stable and inert to reaction with the cationic Group VIII metal complex in the final catalyst species, and the single component catalyst should be soluble in the solvent of the present invention. Anions that are stable to the reaction with water or Bronsted acid and do not have acidic protons (that is, anionic complexes that do not react with strong acids or strong bases) that are external to the anion have the stability needed to qualify them as stable anions against the catalyst system I have. The properties of anions important for maximum instability include overall size and shape (i.e., large radius of curvature) and nucleophilicity.

In general, suitable anions can be any suitable anions in which the catalyst dissolves in the selected solvent and has the following characteristics: (1) the anions include the Lewis acid, the Bronsted acid, the reduced Lewis acid, the protonated Lewis acid, Thallium and silver should form a stable salt with the cation; The negative charge on the anion must be delocalized across the rim of the anion or be localized in the core of the anion; (3) the anion must be a relatively poor nucleophile; (4) Anions should not be strong reducing agents or oxidizing agents.

Anions meeting the above criteria may be tetrafluoride of Ga, Al or B; Hexafluoride of P, Sb or As; Perfluoro-acetate, propionate and butyrate, hydrated perchlorate; Toluenesulfonate and trifluoromethylsulfonate; And substituted tetraphenylborates wherein the phenyl ring is substituted with a fluorine or trifluoromethyl moiety. 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 ^- (C ₂ F ₅ CO ₂ ^- ), heptafluorobutyrate (CF ₃ CF ₂ CF ₂ CO ₂ ^- ), perchlorate (ClO ₄ ^-. H ₂ O), p-toluene-sulfonate -CH ₃ C ₆ H ₄ SO ₃ ^- ) and tetraphenyl borates of the formula:

Wherein R " is independently hydrogen, fluorine, and trifluoromethyl, and n is 1-5.

Preferred single component catalysts of the above embodiments are represented by the following formulas:

The catalyst comprises a π-allyl group VIII metal complex with a counter anion that is weakly coordinated. The allyl group of the metal cation complex is provided by a compound containing an allyl functional group in which the functional group is bonded to M by a single carbon-metal sigma bond and an olefin pi bond. The Group VIII metal M is preferably selected from nickel and palladium, and the most preferred metal is palladium. Surprisingly, the present inventors have found that these monocomponent catalysts in which M is palladium and the cation complex is free of other ligands other than the allyl functional groups (i.e., L _y = 0) are useful for the polymerization of functional polycyclic monomers such as silyl containing monomers of the present invention And exhibit excellent activity. As noted above, it should be understood that the catalyst is solvated by a reactive diluent, which diluent can be considered to be a very weak ligand to the Group VIII metal in the cationic complex.

The substituents R ²⁰ , R ²¹ and R ^{22 on} the allyl group in the formulas (VIII), (IX) and (XIII) are each independently hydrogen or a substituent such as methyl, ethyl, n-propyl, isopropyl and t- such as a branched or unbranched (C ₁ to C ₅₎ alkyl, or phenyl, and naphthyl (C ₆ to C ₁₄₎ aryl, or _{^{benzyl, -COOR 16, - (CH 2}} ) n oR 16, Cl and (C ₅ (C ₇ to C ₁₀ ) aralkyl such as C ₆ to C ₆ alicyclic, wherein R ¹⁶ is methyl, ethyl, n-propyl, isopropyl, n-butyl and I- )to be.

Optionally, any two of R ²⁰ , R ²¹ and R ²² may be joined together to form a single ring or multiple cyclic ring structure. The cyclic ring structure may be carbocyclic or heterocyclic. Preferably, any two of R < ²⁰ >, R < ²¹ >, and R < ²² > taken together with the carbon atom to which they are attached form a ring of 5 to 20 atoms. Typical heteroatoms include nitrogen, sulfur and carbonyl. Representative cyclic groups with allyl functional groups are:

Wherein R ²³ is hydrogen or straight or branched (C ₁ to C ₅ ) alkyl such as methyl, ethyl, n-propyl, isopropyl and pentyl, R ²⁴ is methylcarbonyl and R ²⁵ is a straight or branched (C ₁ -C ₂₀ ) alkyl. Counter anion, CA ^- is as defined above.

Additional examples of π-allyl metal complexes are described in RG et al. Guy and B.L. Shaw, Advances in Inorganic Chemistry and Radiochemistry, Vol. 4, Academic Press Inc., New York, 1962; J. Birmingham, E. de Boer, M.L.H. Green, R.B. King, R. Koster, P.L.I. Nagy, G.N. Schrauzer, Advances in Organometallic Chemistry, Vol. 2, Academic Press Inc., New York, 1964; W.T. Dent, R. Long and A.J. Wilkinson, J. Chem. Soc., (1964) 1585; and H.C. Volger, Rec. Trav. Chim. Pay Bas, 88 (1969) 225; All of which are incorporated herein by reference.

The single component catalyst of the foregoing embodiments can be prepared by combining a ligand VIII metal halide component coupled with a salt that provides a counter anion for the subsequently formed metal cation complex. The ligand VIII metal halide component, the counter anion providing the salt, and any π bond containing component, such as COD, are combined in a solvent capable of solvating the formed single component catalyst. The solvent used is preferably the same solvent as the solvent selected for the reaction medium. The catalyst may be preformed in a solvent or may be formed in situ in a reaction medium.

Suitable counter anions which provide a salt are any salts capable of providing the counter anions described above. For example, there are sodium, lithium, potassium, silver, tantalum, and salts of ammonia in which the anions are selected from the previously defined counter anions (CA ^- ). Examples of counter anions that provide a salt include TlPF 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 .

The specific catalyst [allyl-Pd-COD] ⁺ PF ₆ ^- is preformed by forming a ligand palladium halide component, namely bis (allyl Pd bromide), which is then converted to a salt, ₆ in the form of a counter anion. The reaction sequence is as follows:

When split, only one COD ligand remains bound to the palladium by two pi bonds. The allyl functional group is bonded to palladium by one metal-carbon sigma bond and one pi bond.

For the preparation of the preferred π-allyl group VIII metal / counter anion monocomponent catalyst represented by the above formula (XIII), ie, where M is palladium, the desired relative anion providing the salt in the presence of a suitable solvent, It is combined with silver salts of anions and allylpalladium chloride. Chloride ligands are formed from allylpalladium complexes as precipitates of silver chloride (AgCl) that can be filtered from solution. The allyl palladium cation complex / counter anion single component catalyst remains in solution. The palladium metal lacks any ligands that are distinct from the allyl functional groups.

An alternative single component catalyst useful in the present invention is represented by the formula:

Wherein R ²⁷ independently represents straight and branched (C ₁ to C ₁₀ ) alkyl and CA ^- is a counter anion as defined above.

Another single component catalyst system useful for preparing the polymers used in the present invention is represented by the formula:

Wherein n is 1 or 2 and E represents two electron donating ligands which are neutral. When n is 1, π-arene ligands such as toluene, benzene and mesitylene are preferred. When n is 2, E is preferably selected from diethyl ether, tetrahydrofuran (THF) and dioxane. The range of monomer to catalyst ratios in the reaction medium may be from about 2000: 1 to about 100: 1. The reaction may be carried out in a hydrocarbon solvent such as cyclohexane, toluene and the like at a temperature of from about 0 째 C to about 70 째 C, preferably from 10 째 C to about 50 째 C, more preferably from about 20 째 C to about 40 째 C. Preferred catalysts having the above chemical formula include (toluene) bis (perfluorophenyl) nickel, (mesitylene) bis (perfluorophenyl) nickel, (benzene) bis (perfluorophenyl) nickel, bis ) Bis (perfluorophenyl) nickel and bis (dioxane) bis (perfluorophenyl) nickel.

Multi-component system

The multi-component catalyst system embodiments of the present invention include a Group VIII metal ion source in combination with one or both of the organometallic cocatalyst and the third component. The cocatalyst is selected from organoaluminum compounds, dialkylaluminum hydrides, dialkylzinc compounds, dialkylmagnesium compounds and alkylaluminum compounds.

The Group VIII metal ion source is preferably selected from compounds containing nickel, palladium, cobalt, iron and ruthenium, with nickel and palladium being most preferred. There is no restriction on a Group VIII metal compound so long as the Group VIII metal compound provides a catalytically active source of a Group VIII metal ion. Preferably, the Group VIII metal compound is soluble or may be soluble in the reaction medium.

Group VIII metal compounds include at least one ionic and / or neutral ligand bonded to a Group VIII metal. The ionic and neutral ligands may be selected from various monodentate, bidentate or multidentate moieties and combinations thereof.

Typical ionic ligands capable of binding to a metal ion to form a Group VIII compound include halides such as chloride, bromide, iodide, or fluoride; Caustic halides such as cyanide, cyanate, thiocyanate, hydride; Side chain and non-side chain (C ₁ to C ₄₀ ) alkyl anions, phenyl anions; Cyclopentadienylid anions; π-allyl group; Acetyl acetonate (4-pentanedionate), 2,2,6,6-tetramethyl-3,5-heptanedionate, and 1,1,1,5,5,5-hexafluoro-2,4 - enolates of? -Carbonyl compounds such as pentanedionate and halogenated acetylacetonoates such as 1,1,1, -trifluoro-2,4-pentanedionate; Acidic oxides of carbon and oxides of nitrogen such as carboxylate and halogenated carboxylate (e.g., acetate, 2-ethylhexanoate, neodecanoate, trifluoroacetate, etc.) (E.g., nitrite), oxides of bismuth (e.g., bismuthate), oxides of aluminum (e.g., aluminate), oxides of silicon (e.g., silicate) , p-toluenesulfonate, sulfite, etc.); One lead; amides; Oxides; Phospholide; Sulfide; (C ₆ to C ₂₄ ) aryloxides, (C ₁ to C ₂₀ ) alkoxides, hydroxides, hydroxy (C ₁ to C ₂₀ ) alkyls; Catechol; Oxalate; Chelating alkoxides and aryl oxides. The palladium compound may also contain complex anions such as PF ^- ₆ , AlF ₃ O ₃ SCF ^- ₆ , SbF ^- ₆ and compounds represented by the formula:

Wherein R "'and X independently represent a halogen atom or a substituted or unsubstituted hydrocarbyl group selected from Cl, F, I, and Br. Typical examples of hydrocarbyl include methyl, ethyl, propyl, butyl, But are not limited to, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, (C ₁ -C ₂₅ ) alkyl such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, hexyl, hexyl, octenyl, decenyl, undecenyl (C ₂ to C ₂₅ ) alcohols such as dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, pentacosenyl and isomeric forms thereof (C ₆ to C ₂₅ ) aryl such as pentyl, tolyl, xylyl, naphthyl and the like, benzyl, Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-norbornyl, 2-norbornenyl (C ₇ to C ₂₅ ) such as cyclopropyl, (C ₃ to C ₈ ) cycloalkyl, such as, for example,

As used herein, the term " substituted hydrocarbyl " means that at least one hydrogen is replaced by a halogen atom (such as, for example, perfluorophenyl radical) such as Cl, F, Br and I; Hydroxyl; Amino; Alkyl; Nitro; Means a hydrocarbyl group as defined above substituted by mercapto and the like.

The Group VIII metal compounds may also contain, for example, cations such as organic ammonium, organic arsonium, organophosphonium and pyridinium represented by the formula:

(C ₁ to C ₂₀ ) alkyl, branched or unbranched (C ₂ to C ₂₀ ) alkenyl, and (C ₅ to C ₂₀ ) alkenyl, and wherein the R ²⁸ radical is selected from the group consisting of hydrogen, branched or unbranched _C16 ) cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. R ²⁹ and R ³⁰ are independently selected from hydrogen, branched and unbranched (C ₁ to C ₅₀ ) alkyl, straight and branched (C ₂ to C ₅₀ ) alkenyl and (C ₅ to C ₁₆ ) cycloalkyl groups as defined above Selected; n is 1 to 5, preferably 1, 2 or 3, most preferably 1. The R < ³⁰ > radical is preferably attached to positions 3, 4 and 5 on the pyridine ring.

It should be noted that an increase in the total amount of carbon atoms contained in the R ²⁸ radical improves the solubility of the transition metal compound and the polycyclic monomer in an organic medium such as an organic solvent. Preferably, the R ²⁸ radical is selected from (C ₁ -C ₁₈ ) alkyl groups wherein the sum of the carbon atoms for all R ²⁸ radicals is from 15 to 72, preferably from 25 to 48, more preferably from 21 to 42. The R ²¹ radical is preferably selected from straight and branched (C ₁ to C ₅₀ ) alkyl, more preferably (C ₁₀ to C ₄₀ ) alkyl. R ³⁰ is selected from straight chain and branched (C ₁ to C ₄₀ ) alkyl, more preferably (C ₂ to C ₃₀ ) alkyl.

Specific examples of the organic ammonium cations include tridodecylammonium, methyltricaprylammonium, tris (tridecyl) ammonium, and trioctylammonium. Specific examples of organoarsenium and organophosphonium cations include tridodecylarsonium and phosphonium, methyltricarylrhonium and phosphonium, tris (tridecyl) arsonium and phosphonium, and trioctylarsonium and phosphonium have. Specific examples of the pyridinium cation include eicosyl-4- (1-butylpentyl) pyridinium, docosyl-4- (13-pentacosyl) pyridinium, and eicosyl 4- (1-butylpentyl) have.

Suitable neutral ligands that can be bonded to the palladium transition metal include olefins; acetylene; carbon monoxide; Nitrogen oxides, and nitrogen compounds such as ammonium, alkyl isocyanides, alkyl isocyanates, alkyl isothiocyanates; Pyridine and pyridine derivatives (e.g., 1,10-phenanthroline, 2,2'-dipyridyl), 1,4-dialkyl-1,3-diazabutadiene, 1,4- - diazabutadiene and an amine represented by the formula:

Wherein R ³¹ is independently hydrocarbyl or substituted hydrocarbyl as defined above, and n is 2 to 10. Urea; Nitriles such as acetonitrile, benzonitrile and halogenated derivatives thereof; Organic ethers such as dimethyl ether of diethylene glycol, cyclic ethers such as dioxane, tetrahydrofuran, furandialyl ether, diethyl ether, and diethylene glycol cyclic oligomer; Organic sulfides such as thioether (diethyl sulfide); Arsine; antimony; Triphenylphosphine), trialkylphosphine (e.g., triphenylphosphine), trialkylphosphine (e.g., trimethyl, triethyl, tripropyl, tripentacosyl, and halogenated derivatives thereof), bis (diphenylphosphino) (Diphenylphosphino) propane, bis (dimethylphosphino) propane, bis (diphenylphosphino) butane, (S) - (-) - 2,2'- (R) - (+) - 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl and bis (2-diphenylphosphinoethyl) phenylphosphine pin; Phosphine oxide, phosphorous halide; There is a phosphite represented by the formula:

Wherein R ³¹ is independently hydrocarbyl or substituted hydrocarbyl as defined above; Phosphorus oxyhalide; Phosphonates; Phosphonites, phosphinites, ketones; (C ₁ to C ₂₀ ) alkyl sulfoxides; (C ₆ to C ₂₀ ) aryl sulfoxide, (C ₇ to C ₄₀ ) alkaryl sulfoxide, and the like. It should be appreciated that the neutral ligand described above can be used as any third component as described below.

Examples of Group VIII transition metal compounds as Group VIII metal ion sources include palladium ethyl hexanoate, trans-PdCl ₂ (PPh ₃ ) ₂ , palladium (II) bis (trifluoroacetate), palladium (II) carbonate), palladium (II) 2- ethylhexanoate, Pd (acetate) ₂ (PPh _{3) 2,} palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide (II) tetrafluoroborate, tetrakis (acetonitrile) palladium (II) tetrafluoroborate, dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (Acetonitrile) dichloride, palladium bis (dimethylsulfoxide) dichloride, nickel acetylacetonate, nickel acetylacetonate, triphenylphosphine palladium (II), dichlorobis (benzonitrile) palladium (II), palladium acetylacetonate, Nickel carboxylates, nickel-dimethyl glyoxime and nickel _{ethylhexanoate, NiCl 2 (PPh 3) 2} , NiCl 2 (PPh 2 CH 2) 2, (P ( _{cyclohexyl) 3) H Ni (Ph 2} P (C _{6 H 4) CO 2),} (PPh 3) (C 6 H 5) Ni (Ph 2 PCH = C (O) Ph), bis (2,2,6,6-tetramethyl-3,5-heptanedionite Nickel (II) acetylacetonate dihydrate, nickel (II) acetylacetonate dihydrate, nickel (II) hexafluoroacetylacetonate dihydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel ) Acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, bis (allyl) nickel, bis (cyclopentadienyl) nickel, cobalt neodecanoate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt Iron (III) chloride, iron (II) bromide, iron (III) chloride, iron (II) chloride, (Triphenylphosphine) dichloride, ruthenium tris (triphenylphosphine) hydridochloride, ruthenium trichloride, ruthenium tetrakis (triphenylphosphine) dichloride, bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, ruthenium tris (Acetonitrile) dichloride, ruthenium tetrakis (dimethylsulfoxide) dichloride, rhodium chloride, rhodium tris (triphenylphosphine) trichloride.

The organoaluminum component of the multi-component catalyst system of the present invention is represented by the formula:

Wherein R ³² independently represents straight and branched (C ₁ -C ₂₀ ) alkyl, (C ₆ -C ₂₄ ) aryl, (C ₇ -C ₂₀ ) aralkyl, (C ₃ -C ₁₀ ) ; Q is a halide or caustic halide selected from chlorine, fluorine, bromine, iodine, straight chain and branched (C ₁ to C ₂₀ ) alkoxy, (C ₆ to C ₂₄ ) aryloxy; x is 0 to 2.5, preferably 0 to 2.

Typical examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri- Trialkylaluminum such as aluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, aluminum; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and the like; Monoalkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, ethyl aluminum diiodide, propyl aluminum dichloride, isopropyl aluminum dichloride, butyl aluminum dichloride, isobutyl aluminum dichloride and the like; Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, propyl aluminum sesquichloride, isobutyl aluminum sesquichloride and the like.

Dialkyl aluminum hydrides are selected from linear and branched (C ₁ to C ₁₀ ) dialkyl aluminum hydrides, of which diisobutyl aluminum hydride is the preferred dialkyl aluminum hydride.

The dialkyl zinc compound is selected from linear and branched (C ₁ to C ₁₀₎ dialkyl zinc compounds, diethyl zinc is preferred among them. The dialkylmagnesium compounds are selected from linear and branched (C ₁ to C ₁₀ ) dialkylmagnesiums, of which dibutylmagnesium is most preferred. Alkyl lithium is selected from straight and branched (C ₁ to C ₁₀ ) alkyl lithium compounds. Of these, butyllithium is the preferred alkyllithium.

In practicing the present invention, a catalyst system obtained from a Group VIII metal ion source is used in combination with one or two of the components selected from the group consisting of the cocatalyst compound and the third component.

Examples of the third component include Lewis acids such as BF ₃ .Eterate, TiCl ₄ .SbF ₅ , tris (perfluorophenyl) boron, BCl ₃ , B (OCH ₂ CH ₃ ) ₃ ; (HSbF ₆ ), HPF ₆ hydrate, 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 para toluenesulfonic acid; Halogenated compounds such as hexachloroacetone, hexafluoroacetone, 3-butenoate-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutamic acid, hexafluoroisopropanol and chloranil, i. E. , (C ₄ to C ₁₂ ) aliphatic and (C ₆ to C ₁₂ ) alicyclic diolefins, such as butadiene, cyclooctadiene and norbornadiene, as well as olefinic electron donors .

The acidity of strong Bronsted acids can be evaluated by determining their Hammett acidity function H ₀ . The definition of the Hammett acid function is described in Advanced Inorganic Chemistry by FA Cotton and G. Wilkinson, Wiley-Interscience, 1988, p. 107].

As described above, the neutral ligand can be used as any third component having electron donating properties.

In one embodiment of the present invention, the multi-component catalyst system is prepared by mixing together the catalyst components, i.e., the Group VIII metal compound, the cocatalyst compound and the third component (if used) in a hydrocarbon or halohydrocarbon solvent, And mixing the premixed catalyst system in a reaction medium comprising a silyl functional polycyclic monomer. Alternatively, any two components of the catalyst system components may be premixed in the hydrocarbon or halohydrocarbons and then introduced into the reaction medium (assuming that any third component can be utilized). The remaining catalyst component may be added to the reaction medium before or after the addition of the premixed component.

In another embodiment, a multi-component catalyst system can be prepared in situ by mixing all of the catalyst components together in a reaction medium. The order of addition is not so important.

In one embodiment of the multi-component catalyst system of the invention, a typical catalyst system is 10/9/1 / 0.5-2 Al / BF ₃ · etherate / Ni / acid group VIII transition metal salt to the desired molar ratio of, for example, nickel Ethylhexanoate, an organoaluminum compound such as triethylaluminum, and a third component such as a mixture of BF ₃ · etherate and hexafluoroantimonic acid (HSbF ₆ ). The reaction is as follows:

1. Nickel ethyl hexanoate + HSbF ₆ + 9BF ₃ · Etherate + 10 triethyl aluminum → Active catalyst

In another embodiment of the multi-component catalyst system of the present invention, the catalyst system comprises a nickel salt such as nickel ethylhexanoate, an organoaluminum compound such as triethylaluminum and a third component Lewis acid such as tris Fluorophenyl) boron, the reaction scheme of which is as follows:

2. Nickel ethyl hexanoate + tris (perfluorophenyl) boron + triethyl aluminum → active catalyst

In another embodiment of the multi-component catalyst system of the present invention, the third component is a halogenated compound selected from various halogenated activators. Typical catalyst systems include Group VIII transition metal salts, organoaluminum and third component halogenated compounds, the reaction of which is as follows:

3. Nickel ethyl hexanoate + triethyl aluminum + chloranil → active catalyst

As another embodiment of the multi-component catalyst system of the present invention, there are no promoters. The catalyst system comprises a Group VIII metal salt (e.g., 3-allyl nickel bromide dimer) and a Lewis acid (e.g., tris (perfluorophenyl) boron)

4. η ³ -Allyl nickel chloride + tris (perfluorophenyl) boron → active catalyst

The present inventors have found that the selection of a Group VIII metal in the metal cation complexes of both the single and multi-component catalyst systems of the present invention affects the physical properties and microstructure of the resulting polymer. For example, the inventors have found that palladium catalysts are typically only chained to a few positions and provide norbornene with some degree of tacticity. A polymer catalyzed by a Type 2 catalyst system and a single component catalyst system of the above formula E _n Ni (C ₆ F ₅ ) ₂ contains a perfluorophenyl group at at least one end of the two terminal ends of the polymer chain. In other words, the perfluorophenyl moieties may be oriented at one or both ends of the polymer end-ends. In either case, the perfluorophenyl group is covalently bonded to and attached to the terminal polycyclic repeating unit of the polymer backbone.

The reaction using the single and multi-component catalyst systems of the present invention is carried out in an organic solvent which is a solvent for the monomers, without interfering with the catalyst system. Examples of organic solvents include 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; Methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1- chloropropane, 2- chloropropane, 1- Halogenated (polar) hydrocarbons such as chlorobutane, 1-chloro-2-methylpropane and 1-chloropentane.

The choice of reaction solvent is made based on a number of factors including whether the catalyst is desired and whether it is desired to polymerize as a slurry or solution treatment. For most of the catalysts described in this invention, preferred solvents are chlorinated hydrocarbons such as methylene chloride and 1,2-dichloroethane and aromatic hydrocarbons such as chlorobenzene and nitrobenzene, while simple hydrocarbons are functional NB-type monomers ( Lt; RTI ID = 0.0 > (e. ≪ / RTI > Surprisingly, the inventors of the present invention have found that by using a specific catalyst system, most notably a Group VIII metal compound and an alkyl aluminum halide, especially a monoalkyl aluminum dihalide (e.g., ethyl aluminum dichloride) Yields excellent results (and high monomer conversion) when the component catalyst is carried out in simple hydrocarbons such as heptane, cyclohexane and toluene.

The molar ratio of Group VIII metal to total monomers versus single- and multi-component catalysts can range from 20: 1 to 100,000: 1, preferably from 50: 1 to 20,000: 1, and most preferably from 100: 1 to 10,000: .

In a multi-component catalyst system, the molar ratio of cocatalyst metal (e.g., aluminum, zinc, magnesium and lithium) to Group VIII metal is in the range of 100: 1 or less, preferably 30: 1 or less, most preferably 20: .

The third component is used in a molar ratio ranging from 0.25: 1 to 20: 1 with respect to the Group VIII metal. When an acid is used as the third component, the molar ratio of the acid to the Group VIII metal is 4: 1 or less, preferably 2: 1 or less.

The temperature at which the polymerization reaction of the present invention is carried out is typically in the range of -100 ° C to 120 ° C, preferably -60 ° C to 90 ° C, and most preferably -10 ° C to 80 ° C.

The optimum temperature for the present invention depends on a number of variables, primarily the choice of catalyst and the choice of the reaction diluent. Thus, for the proposed polymerization reactions, the optimum temperature will be determined experimentally taking these parameters into account.

In developing these catalysts and polymer systems, the inventors have observed that the palladium-carbon bonds that bind the palladium catalyst to the growing polymer chain are particularly stable. This is very advantageous for polymerizing polycyclic monomers containing acid labile groups, esters and carboxylic acid functional groups, because the palladium catalyst is very resistant to these functional groups. However, due to this stability, it is very difficult to remove the palladium catalyst residue from the resulting polymer. In the course of developing these novel compositions, the present inventors have found that palladium-carbon bonds can be easily removed (by filtration or centrifugation) by using carbon monoxide, preferably in the presence of a solvent such as alcohol, Precipitating the palladium metal).

The polymer obtained by the process of the present invention has a molecular weight (M _n ) of from about 1,000 to about 1,000,000, preferably from about 2,000 to about 700,000, more preferably from about 5,000 to about 500,000, and most preferably from about 10,000 to about 50,000. Lt; / RTI >

The molecular weight can be controlled by changing the ratio of catalyst to monomer, i. E. The ratio of initiator to monomer. The low molecular weight polymer and the oligomer may be formed in the range of about 500 to about 500,000 by performing the polymerization reaction in the presence of the chain transfer agent. Oligomers or macromonomers comprising from 4 to 50 repeating units can be prepared in the presence of a CTA (chain transfer agent) selected from compounds having a terminal olefinic double bond between adjacent carbon atoms, and at least one of the adjacent carbon atoms And has two hydrogen atoms attached thereto. CTA excludes styrene (non-styrene), except vinyl ether (non-vinyl ether) and conjugated dienes. Non-styrene, non-vinyl ether means that a compound having the following structure is excluded from the chain transfer agent of the present invention:

Wherein A is an aromatic substituent and R is hydrocarbyl.

A preferred CTA compound of the present invention is represented by the following formula:

Wherein R _' and R _" independently represent hydrogen, branched or unbranched (C ₁ to C ₄₀ ) alkyl, branched or unbranched (C ₂ to C ₄₀ ) alkenyl, and halogen.

Of the above chain transfer agents, α-olefins having 2 to 10 carbon atoms are particularly preferred, and examples thereof include ethylene, propylene, 4-methyl-1-pentene, 1-hexene, 1-decene, 1,6-octadiene or isobutylene.

Although the optimum conditions for any given result should be determined experimentally by those skilled in the art in view of the above factors, there are a number of general guidelines that can be readily used where appropriate. We have found that while alpha-olefins (e.g. ethylene, propylene, 1-hexene, 1-decene, 4-methyl-1-pentene) are the most effective chain transfer agents, the present inventors have found that 1,1- Butylene) is a less effective chain transfer agent. In other words, if all else is equal, the concentration of isobutylene required to achieve the stated molecular weight will be much higher than if ethylene were chosen. Styrene olefins, conjugated dienes, and vinyl ethers are not effective as chain transfer agents due to their tendency to polymerize by the catalysts described herein.

CTA may be used in an amount ranging from about 0.10 mole% to more than 50 mole% based on the mole of the total NB-type monomer. The CTA is preferably used in the range of 0.10 mol% to 10 mol%, more preferably 0.1 to 5.0 mol%. As noted above, the concentration of CTA is greater than 50 mole% (based on the total NB functional monomer present), such as from 60 to 80 mole%, based on the type and sensitivity of the catalyst, CTA efficiency and desired terminal group, Lt; / RTI > High concentrations of CTA (e.g., greater than 100 mole percent) may be required to achieve the low molecular weight embodiments of the present invention, such as in oligomeric and macromonomer applications. It is important and surprising to note that even at high concentrations, CTA (except for isobutylene) is not polymerized into the polymer backbone rather than inserted as a terminal group on each polymer chain. Except for the chain transfer agent, the process of the present invention provides a method by which the terminal? -Olefin end group can be positioned at the end of the polymer chain.

The molecular weight (M _n ) of the polymers of the present invention prepared in the presence of the CTA of the present invention is from about 1,000 to about 500,000, preferably from about 2,000 to about 300,000, and most preferably from about 5,000 to about 200,000.

The photoresist compositions of the present invention include the described polycyclic compositions, solvents and photo-sensitive acid generators (photoinitiators). Optionally, the decomposition inhibitor may be added in an amount up to about 20% by weight of the composition. A suitable decomposition initiator is t-butylcholate [Reference: J.V. Crivello et al., Chemically Amplified Electron-Beam Photoresists, Chem. Mater., 1996, 8, 376-381].

The radiation sensitive acid generator generates strong acid upon exposure to radiation. Suitable photoinitiators include triflates (e. G., Triphenylsulfonium triflate), pyrogallol (e. G., Trimesylate of pyrogallol); Onium salts such as triarylsulfonium and diaryliodonium hexafluoroantimonate, hexafluoroarsenate, and trifluoromethanesulfonate; α, α'-bis-sulfonyl-diazomethane, esters of hydroxyimides, nitro-substituted benzyl alcohols and sulfonate esters of naphthoquinone-4-diazides. Other suitable photoinitiator are described in Reichmanis et al., Chem. Mater. 3, 395, (1991). Compositions containing a triaryl sulfonium or diaryl iodonium salt are preferred because of their sensitivity to deep UV light (193-300 nm) and provide very high resolution images. The most preferred compositions are diaryliodonium or triarylsulfonium salts which are unsubstituted and symmetrically or asymmetrically substituted. The photoacid initiator component comprises about 1 to 100 w / w% based on the polymer. The preferred concentration is 5 to 50 w / w%.

The photoresist composition of the present invention optionally contains a photosensitizer capable of sensitizing the photoacid initiator to a long wavelength in the range of intermediate UV light to visible light. Depending on the intended application, the photosensitizer comprises a polycyclic aromatic compound such as pyrene and perylene. The sensitization of photoacid initiators is well known and is described in U.S. Patent Nos. 4,250,053, 4,371,605 and 4,491,628, both of which are incorporated herein by reference. The present invention is not limited to any particular class of photosensitizer or photoacid initiator.

The present invention also provides a method of manufacturing a semiconductor device, comprising: (a) coating a substrate with a film comprising a resist composition of a positive tone of the present invention; (b) imagewise exposing said film to radiation; And (c) developing the image. ≪ Desc / Clms Page number 3 >

The first step involves coating the substrate with a film comprising a positive torque resist composition dissolved in a suitable solvent. Suitable substrates include silicon, ceramics, polymers, and the like. Suitable solvents include propylene glycol methyl ether acetate (PGMEA) cyclohexanone, butyrolactate, ethyl lactate, and the like. The film may be coated on a substrate using conventional techniques known in the art, such as spin or spray coating, or doctor blading. Preferably, the film is heated to an elevated temperature of about 90 DEG C to 150 DEG C for about one minute before being exposed to radiation. In the second step of the method, the film is irradiated with a radiation, suitably an electron beam or an electromagnetic radiation, preferably an electron such as ultraviolet or x-rays, preferably with a wavelength of from about 193 to 514 nm, preferably from about 193 nm to 248 nm And is exposed imagewise to ultraviolet light. Suitable sources of radiation include mercury, mercury / xenon, and xenon lamps, x-rays or e-beams. The radiation is absorbed by the radiation sensitive acid generator to produce free acid in the exposed area. The liberated acid catalyzes the decomposition of acid labile pendant groups in the copolymer which converts the polymer from the decomposition inhibitor into the decomposition increasing agent, thereby increasing the solubility of the exposed resist composition in an aqueous base. Surprisingly, the exposed resist composition readily dissolves in aqueous bases. This solubility is surprising and unexpected in terms of the complex nature of the alicyclic skeleton and the high molecular weight norbornene monomer units containing carboxylic acid functional groups. Preferably, the film is exposed to radiation and then heated again at an elevated temperature of 90 DEG C to 150 DEG C for about one minute.

The third step involves the development of a positive-toned image by a suitable solvent. Suitable solvents include aqueous bases, preferably aqueous bases free of metal ions such as tetramethylammonium hydroxide or choline. The compositions of the present invention provide high contrast and straight walls for positive images. Uniquely, the degradation characteristics of the composition of the present invention can be varied only by changing the composition of the copolymer.

The present invention also relates to an integrated circuit assembly, such as an integrated circuit board, an integrated circuit chip, or an integrated circuit multi-chip module manufactured by the present invention. The integrated circuit assembly comprises: (a) coating a substrate with a film comprising the positive tone resist composition of the present invention; (b) imagewise exposing said film to radiation; (c) developing the image to expose the substrate; And (d) circuitry formed on the substrate by forming the circuitry in the form of a film developed on the substrate by known techniques.

After the substrate is exposed, a circuit pattern may be formed in the exposure area by coating the substrate with a conductive material, such as a conductive metal, by conventional techniques known in the art, such as evaporation, sputtering, plating, chemical vapor deposition or laser induced deposition. The surface of the film may be ground to remove any excess conductive material. The dielectric material can be deposited by similar methods during fabrication of the circuit. Inorganic ions such as boron, phosphorus, or arsenic may be implanted into the substrate when making p or n doped circuit transistors. Other methods of forming the circuit are well known in the art.

The following examples are a detailed description of methods of making certain compositions of the invention and their uses. The detailed process belongs to the scope of the general process described above and serves to illustrate this. The following examples are illustrative only and are not intended to limit the scope of the invention.

As noted above, photoresist is used to create and replicate patterns from the photomask to the substrate. The efficacy of this transfer is determined by the wavelength of the imaging radiation, the sensitivity of the photoresist, and the ability of the photoresist to withstand the etching conditions that pattern the substrate in the exposure area. The photoresist is most commonly used in the form of a consumable when etched in a non-exposed region (for a positive-tone photoresist) and when the substrate is etched in the exposed region. Because the photoresist is an organic material and the substrate is typically an inorganic material, the photoresist has a high etch rate in a reactive ion etching (RIE) process where the photoresist must be thicker than the substrate material. The smaller the etch rate of the photoresist material, the thicker the photoresist layer. As a result, a high resolution can be obtained. Thus, the smaller the RIE rate of the photoresist, the more interesting it is from a method standpoint. The etch rate is largely determined by the polymer backbone as described below for the chlorine plasma etch process, which is the RIE technology typically used in semiconductor processing.

The molar ratios of monomer to catalyst used throughout the examples and specification are based on mole to mole.

No. Polymer Standardized RIE rate (占 퐉 / min)

1 novolac Resist 1.0

2 polyhydroxystyrene resist 0.98

3 248 nm (Deep UV) 1.14

(Acrylate terpolymer / novolak blend,

U.S. Patent No. 5,372,912)

4 193 nm (polyacrylate terpolymer, 1.96

[Allen et al., Proceedings SPIE,

2438 (1), 474 (1995)]

5 Homo polynorbornene 0.83

Polymers 1 and 2 were predominantly aromatic, while Polymer 3 was co-polymerized with a small amount of acrylate to increase its etch rate. Polymer 4 is based on acrylate that is transmitted at 193 nm (any aromatic polymer present at 193 nm on the basis of conventional novolac or p-hydroxystyrene because the aromatic ring makes the material opaque in this region I never do that). The etch rate was almost double for this polymer. Polymer 5 had a much lower etch rate than standard photoresist materials 1 and 2, in addition to passing a wavelength of 193 nm. Thus, Polymer 5 (cycloaddition olefin) prepared by the nickel multi-component catalyst of the present invention was found to be superior to all of the previously conducted studies to provide RIE characteristics to photoresists operating at 193 nm as compared to commercially available materials exposed at longer wavelengths It is more improved. Indeed, the cycloaddition olefin polymers provide advantages by etching resistance even at long wavelengths. H. Gokan, S. Esho, and Y. Ohnishi, J. Electrochem. Soc. 130 (1), 143 (1993), it is described that the higher the C / H ratio, the lower the etch rate of the polymeric material. Based on this assumption, the etch rate of polymer 5 should be between the aromatic based system and the acrylate system. What is surprising is that cyclic olefins show even better etch resistance than aromatic systems.

Example 1

Butyl ester (carbo-t-butoxynorbornene) (2.0 g, 10.3 mmol, 10 mmol) was added to a 50 ml glass bottle with a Teflon (TM) coated stir bar, Exo, endo 44/56). The η ³ -alylpalladium chloride dimer (38 mg, 103 μmol) in chlorobenzene (5 ml) was added to the silver hexafluoroantimonate (99 mg, 290 μmol) in chlorobenzene (5 ml) for 30 minutes and then filtered through a microporous filter (To remove precipitated silver chloride) was added to the stirred monomer at ambient temperature. The reaction was continued for 36 hours to gel the mixture to yield a clear yellow gel. When the gel was added to an excess of methanol, the polymer precipitated as a white powder. The polymer was washed with methanol and dried. The polymer yield was 1.5 g (75%). The presence of ester-containing monomers in the polymer was evidenced by IR analysis showing a strong band at 1728 cm ^-1 (C = O stretching), 1251 cm ^-1 (COC stretching) and 1369 and 1392 cm ^-1 And the absence of unconverted monomers was demonstrated by proton NMR. The molecular weight (Mw) of the polymer was 22,500. Thermogravimetric analysis (TGA) under a nitrogen atmosphere (heating rate: 10 DEG C per minute) showed that the polymer was thermally stable at 210 DEG C and a loss of about 28 wt.% Up to 260 DEG C Is apparently lost to produce a homopolymer of the 5-norbornene-carboxylic acid), confirming that the polymer decomposes (90% total weight loss) at about 400 ° C.

Example 2

(0.8 g, 8.6 mmol), 1,2-dichloroethane (8 ml), and t-norbornene-carboxylic acid in a 50 ml glass bottle with a Teflon (TM) Butyl ester (carbo-t-butoxynorbornene) (0.2 g, 1 mmol, exo, endo 44/56) was added. Nickel ethyl hexanoate (3 μmol), triperfluorophenylboron (23 μmol) and triethylaluminum (27 μmol) were added to the stirred solution at ambient temperature. It was then immediately reacted with the white polymer and precipitated from solution within less than 10 seconds. After carrying out the reaction for 60 minutes, the reactor contents were dissolved in cyclohexane and poured into excess methanol. The polymer was washed with excess methanol and dried overnight in a vacuum oven at 80 占 폚. The yield of the copolymer was 0.9 g (90%). The molecular weight (Mw) of the copolymer determined using the GPC method was 535,000 and the polydispersity was 4.7.

Example 3

Butyl ester (carbo-t-butoxynorbornene) (2.2 g, 11.3 mmol, exo, t-butyloxycarbonyl) was added to a 50 ml capacity vial equipped with a Teflon (TM) Endo 44/56). The η ³ -alylpalladium chloride dimer (29 mg, 74 μmol) in dichloroethane (6 ml) was added to the silver tetrafluoroborate (61 mg, 311 μmol) in dichloroethane (6 ml) for 30 min and then filtered through a microporous filter To remove the silver chloride) was added to the stirred monomer at ambient temperature. The reaction was carried out for 36 hours to gel the mixture to yield a clear yellow gel. When the gel was added to an excess of methanol, the polymer precipitated as a white powder. The polymer was washed with excess methanol and dried. The yield of the polymer was 1.4 g (64%). The presence of ester-containing monomers in the polymer was evidenced by IR analysis showing a strong band at 1728 cm ^-1 (C = O stretching), 1251 cm ^-1 (COC stretching) and 1369 and 1392 cm ^-1 And the absence of unconverted monomer or carboxylic acid functionality was demonstrated by proton NMR and IR. The molecular weight (Mw) of the polymer was 54,100. Thermogravimetric analysis (TGA) under a nitrogen atmosphere (heating rate: 10 DEG C per minute) showed that the polymer was thermally stable at 210 DEG C and a loss of about 29 wt% up to 250 DEG C Is apparently lost to produce a homopolymer of 5-norbornene-carboxylic acid), it was confirmed that the polymer decomposed (80% total weight loss) at about 400 ° C.

Example 4

(1.16 g, 12.3 mmol), 1,2-dichloroethane (50 ml), and t-norbornene-carboxylic acid in a 100 ml glass bottle with a Teflon (TM) Butyl ester (carbo-t-butoxynorbornene) (0.6 g, 3.1 mmol, exo, endo 44/56). Palladium bis (2,2,6,6-tetramethyl-3,5-pentanedionate (31 μmol) and trisperfluorophenylboron (279 μmol) were added to the stirred solution at ambient temperature. The reactor contents were poured into excess methanol. The polymer was washed with excess methanol and dried overnight in a vacuum oven at 80 DEG C. The yield of the copolymer was 0.54 g (31%).

Example 5

Butyl ester (carbo-t-butoxynorbornene) (4.4 g, 22.7 mmol, exo, t-butyloxycarbonyl) was added to a 50 ml glass bottle equipped with a Teflon (TM) Endo 44/56). The η ³ -alylpalladium chloride dimer (41.5 mg, 113 μmol) in dichloroethane (7 ml) was added to silver tetrafluoroborate (42 mg, 215 μmol) in dichloroethane (42 ml) for 30 minutes and then filtered To remove precipitated silver chloride) was added to the stirred monomer at ambient temperature. The reaction mixture was then warmed to 75 < 0 > C in an oil bath. After 90 minutes, it was observed that the mixture solidified to a gray polymer mass. The mass was dissolved in acetone to produce a dark colored solution. Gaseous carbon monoxide was bubbled through the solution for 30 minutes to produce a large amount of finely divided black precipitate (metal palladium and possibly other catalyst residues). The precipitate was removed by centrifugation and this procedure was repeated two more times. Finally, the resulting colorless solution was filtered through a 45 micron microdisk and the polymer was precipitated by adding acetone to an excess of hexane. The white polymer was isolated using a centrifuge and dried overnight to yield the copolymer as a white powder (2.21 g, 50%). Thermogravimetric analysis (TGA) under a nitrogen atmosphere (heating rate: 10 DEG C per minute) showed that the polymer was thermally stable at 210 DEG C and a loss of about 28 wt.% Up to 260 DEG C Is apparently lost to produce a homopolymer of the 5-norbornene-carboxylic acid), confirming that the polymer decomposes (90% total weight loss) at about 400 ° C. The molecular weight was observed to be Mn = 3,300 g / mol and Mw = 6,900 g / mol (GPC in THF, polystyrene standard).

Example 6

Butyl ester (carbo-t-butoxynorbornene) (0.6 g) of 5-norbornene-carboxylic acid was added to a 50 ml capacity vial equipped with a Teflon (TM) coated stir bar. The η ³ -alylpalladium chloride dimer (30 mg) in dichloroethane (10 ml) was added to silver tetrafluoroantimonate (50 mg) in dichloroethane (20 ml) for 30 min and then filtered through a microporous filter Was added to the stirred monomer at ambient temperature. The reaction was carried out for 15 hours, during which time the mixture was added to excess methanol to precipitate the polymer as a white powder. The polymer was washed with excess methanol and dried. The yield of the polymer was 0.5 g (85%). The molecular weight (Mw) of the polymer was 46,900 and the polydispersity was 2.4.

Example 7

(4.01 g, 42.6 mmol), 1,2-dichloroethane (50 ml), and t-norbornene-carboxylic acid in a 100 ml capacity glass bottle equipped with a Teflon (TM) Butyl ester (carbo-t-butoxynorbornene) (2 g, 10.3 mmol, exo, endo mixture) was added. Reaction of η ³ -allylpalladium chloride dimer (10 mg, 27.3 μmol) with silver hexafluoroantimonate (19.6 mg, 57 μmol) in 1,2-dichloroethane (3 ml) followed by filtration through a microporous filter The catalyst solution was added to the stirred solution at ambient temperature. After carrying out the reaction for 20 hours, the reactor contents were poured into excess methanol. The polymer was washed with excess methanol and dried. The yield of the polymer was 4.15 g. The molecular weight (Mw) of the copolymer determined using the GPC method was 618,000 and the polydispersity was 7.1.

Example 8

(3.75 g, 39.8 mmol), 1,2-dichloroethane (50 ml), and t-norbornene-carboxylic acid in a 100 ml capacity glass bottle equipped with a Teflon (TM) Butyl ester (carbo-t-butoxynorbornene) (2 g, 10.3 mmol, exo, endo mixture) was added. Palladium ethyl hexanoate (12 μmol), tris (perfluorophenylboron) (108 μmol) and triethylaluminum (120 μmol) were added to the stirred solution at ambient temperature. After the reaction was carried out for 72 hours, the reactor contents were poured into excess methanol. The polymer was washed with excess methanol, dried, redissolved in chlorobenzene and reprecipitated with excess methanol, filtered, washed with methanol and finally dried overnight in a vacuum oven at 80 占 폚. The yield of the copolymer was 1.66 g. The molecular weight (Mw) of the copolymer determined using the GPC method was 194,000 and the polydispersity was 2.3. The presence of ester-containing monomers in the copolymer was evidenced by IR analysis with bands emerging at 1730 cm ^-1 (C = O stretching), 1154 cm ^-1 (COC stretching), and the absence of unconverted monomers proved by proton NMR Respectively.

Example 9

To a 100 ml glass bottle equipped with a Teflon (TM) coated stir bar were added 1,2-dichloroethane (25 ml), and a t-butyl ester of 5-norbonenecarboxylic acid (carbo-t-butoxynor Borane) (10 g, 51.5 mmol, exo, endo mixture). The η ³ -alylpalladium chloride dimer (82 mg, 223 μmol) was reacted with silver hexafluoroantimonate (200 mg, 581 μmol) in 1,2-dichloroethane (10 ml) for 30 minutes and then filtered through a microporous filter Was added to the stirred solution at ambient temperature. After carrying out the reaction for 48 hours, the reactor contents were poured into excess methanol. The polymer was washed with excess methanol and dried. The yield of the homopolymer was 4.5 g.

Example 10

To a 100 ml glass bottle equipped with a Teflon (registered trademark) coated stir bar was added 1,2-dichloroethane (50 ml), t-butyl ester of 5-norbornene-carboxylic acid (carbo-t-butoxynorbornene ) (5 g, 25.8 mmol, exo, endo mixture), norbornene (0.82 g, 8.7 mmol) and 5-triethoxysilylnorbornene (0.47 g, 1.8 mmol). The η ³ -alylpalladium chloride dimer (47.2 mg, 128 μmol) was prepared by reacting silver tetrafluoroborate (138 mg, 700 μmol) in 1,2-dichloroethane (10 ml) for 30 minutes and filtering through a microporous filter The catalyst solution was added to the stirred solution at ambient temperature. After carrying out the reaction for 48 hours, the reactor contents were poured into excess methanol. The polymer was washed with excess methanol and dried. The yield of the terpolymer was 5.3 g. The molecular weight (Mw) of the copolymer measured by the GPC method was 39,900 and the polydispersity was 3.2.

Example 11

(37.5 mmol) of t-butyl ester of norbornene, 1.9 g (12.5 mmol) of methyl ester of norbornene, 50 ml of freshly distilled dichloroethane Was added and the resulting solution was degassed under an argon atmosphere. Teflon (R) η ³ in glass bottles of 10ml capacity, provided with a coated stir bar-allyl palladium chloride dimer 0.0365g (0.1mmol) (intended to be ultimately of the monomer to catalyst ratio of 500/1), and dichloroethane 2 ml. Another 10 ml glass bottle was charged with 0.0344 g (0.1 mmol) of silver hexafluoroantimonate and 2 ml of dichloroethane. The catalyst solution was prepared by mixing an allylpalladium chloride dimer solution with a silver hexafluoroantimonate solution in a dry box. A precipitate of silver chloride was observed immediately, which was filtered to give a clear yellow solution. The active yellow catalyst solution was added via a syringe to the monomer solution and the reaction mixture was stirred at 60 C for 20 hours. No increase in viscosity was observed, but solids precipitated in 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 was dried in vacuo at room temperature and analyzed using the GPC method to determine the molecular weight. GPC was obtained in THF using a polystyrene standard. The observed molecular weights were Mn = 1950 g / mol and Mw = 3150 g / mol. ¹ H NMR indicates the presence of both methyl and t-butyl esters of norbornene and indicates the presence of a small amount of t-butyl hydrolyzed product, i.e., an acid.

Example 12

(12.5 mmol) of t-butyl ester of norbornene, 5.7 g (37.5 mmol) of methyl ester of norbornene and 50 ml of freshly distilled dichloroethane were placed in a 50 ml capacity glass bottle equipped with a Teflon (TM) coated stir bar Was added and the resulting solution was degassed under an argon atmosphere. A 10 ml glass bottle with a Teflon (TM) coated stir bar was charged with 0.0365 g (0.1 mmol) of allylpalladium chloride dimer (to make the ratio of monomer to catalyst 500/1) and 2 ml of dichloroethane. Another 10 ml glass bottle was charged with 0.0344 g (0.1 mmol) of silver hexafluoroantimonate and 2 ml of dichloroethane. The catalyst solution was prepared by mixing an allylpalladium chloride dimer solution with a silver hexafluoroantimonate solution in a dry box. A precipitate of silver chloride was observed immediately, which was filtered to give a clear yellow solution. The active yellow catalyst solution was added via a syringe to the monomer solution and the reaction mixture was stirred at 60 C for 20 hours. No increase in viscosity was observed, but solids precipitated in 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 was dried in vacuo at room temperature and analyzed using the GPC method to determine the molecular weight. GPC was obtained in THF using a polystyrene standard. The observed molecular weights were Mn = 1440 g / mol and Mw = 2000 g / mol. ¹ H NMR indicates the presence of both methyl and t-butyl esters of norbornene and indicates the presence of a small amount of t-butyl hydrolyzed product, i.e., an acid.

Example 13

2-t-butyl, exo-3-tert-butylphenoxy) hept-5-ene-exo of pure dicarboxylic acid was added to a 25 ml glass bottle equipped with a Teflon (TM) After addition of 2 g (7.94 mmol) of methyl ester, 15 ml of freshly distilled methylene chloride and 10 ml of methanol were added and the solution was degassed under an argon atmosphere. Teflon (R) η ³ in glass bottles of 10ml capacity, provided with a coated stir bar-allyl palladium chloride dimer 0.00588g (0.0158mmol) (intended to be the monomer to catalyst ratio is 500/1) and a methylene chloride 2ml I filled it. Another 10 ml glass bottle was charged with 0.0108 g (0.0312 mmol) of silver hexafluoroantimonate and 2 ml of methylene chloride. A catalyst solution was prepared by mixing a solution of? ³ -allylpalladium chloride dimer in a dry box with silver hexafluoroantimonate solution. A precipitate of silver chloride was observed immediately, which was filtered to give a clear yellow solution. The active yellow catalyst solution was added to the monomer solution via a syringe at 50 캜, and the reaction mixture was stirred at room temperature for 16 hours. No increase in viscosity was observed, and the solution was filtered through a 0.5 mu filter and concentrated using a rotary evaporator. The thick solution was dissolved in methanol and precipitated in a methanol / water mixture to give a white solid (65%). The observed polymer molecular weights were Mn = 10,250 g / mol and Mw = 19,700 g / mol (GPC in THF, polystyrene standard). ¹ H NMR indicates the presence of both methyl and t-butyl esters of norbornene.

Example 14

To a 25 ml glass bottle equipped with a Teflon (registered trademark) coated stir bar was added 3.06 g of pure bicyclo [2.2.1] hept-5-en-exo, exo-2,3-dicarboxylic acid diethyl ester (12.8 mmol) of t-butyl ester of norbornene were added and then 15 ml of freshly distilled methylene chloride and 10 ml of methanol were added and the solution was degassed under an argon atmosphere. 0.0218g (0.052mmol) of allylpalladium chloride dimer (to make the ratio of monomer to catalyst 500/1) and 2ml of methylene chloride were charged to a 10ml glass bottle with a Teflon (TM) coated stir bar. Another 10 ml glass bottle was charged with 0.0357 g (0.104 mmol) of silver hexafluoroantimonate and 2 ml of methylene chloride. The catalyst solution was prepared by mixing an allylpalladium chloride dimer solution with a silver hexafluoroantimonate solution in a dry box. A precipitate of silver chloride was observed immediately, which was filtered to give a clear yellow solution. The active yellow catalyst solution was added to the monomer solution via a syringe at 50 캜, and the reaction mixture was stirred at room temperature for 16 hours. No increase in viscosity was observed, and the solution was filtered through a 0.5 mu filter and concentrated using a rotary evaporator. The resulting viscous solution was dissolved in methanol and precipitated in a methanol / water mixture to give a white solid (23%). The observed polymer molecular weights were Mn = 15,700 g / mol and Mw = 32,100 g / mol (GPC in THF, polystyrene standard). ¹ H NMR indicates the presence of both methyl and t-butyl esters of norbornene. By thermogravimetric analysis (TGA) (heating rate: 10 ° C per minute) under a nitrogen atmosphere, the polymer is thermally stable at about 155 ° C and exhibits a loss of about 28% by weight up to 290 ° C -Butyl group apparently disappeared to produce a homopolymer of 5-norbornene-carboxylic acid), it was confirmed that the polymer decomposed at about 450 ° C.

Example 15

Synthesis of bicyclo [2.2.1] hept-5-en-exo, exo-2,3-dicarboxylic acid diethyl ester:

Exo, exo diethyl ester of norbornene was synthesized from exo-5-norbornene-2,3-dicarboxylic acid. The endo-5-norbonen-2,3-dicarboxylic anhydride was thermally converted at 190 ° C and then recrystallized several times from toluene as in reference 1 to obtain pure exo-5-norbornene-2,3-dicar The exo isomer was prepared by obtaining the carboxylic acid anhydride. A portion of the exo anhydride was hydrolyzed in boiling water and the solution was cooled to yield a nearly quantitative yield of pure diacid. The diacid was converted to the diethyl ester using triethyloxonium as shown below:

16.0 g (0.0824 mol) of pure exonorbornenedicarboxylic acid and 35 g (0.1846 mol) of triethyloxonium tetrafluoroborate were charged to a 250 ml three necked round bottom flask equipped with a magnetic stir bar. The flask was capped and 300 ml of dichloromethane was added via a cannula under an argon atmosphere. The rubber stopper was replaced with a condenser under an argon atmosphere and an additional funnel was secured to the remaining neck. To the additional funnel is added 35 ml of ethyl diisopropylamine and slowly dipped in the reaction vessel. A small amount of exotherm was observed and the solution was refluxed mildly. After all of the amine was added, the solution was allowed to stand at room temperature for 15 hours. After extracting the reaction mixture in three portions of 50 ml of HCl, the three extracts of 50 ml each were extracted with sodium bicarbonate and finally washed twice with water. The organic solution was dried over magnesium sulfate, treated with carbon black, filtered and concentrated on a rotary evaporator. The residue was purified by distillation at 110 DEG C to give 15 g (75%) of exo-diethyl ester of pure norbornene as a colorless viscous fruit flavor liquid.

_{^{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, CHCOO), 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

Bicyclo [2.2.1] hept-5-en-exo-2-t-butyl ester, exo-3-carboxylic acid:

1.5 g (9.15 mmol) of pure exo-nadic anhydride, 10 ml of freshly distilled methylene chloride, 20 ml (0.209 mol) of t-butanol were added to a 50 ml one necked round bottom flask equipped with a Teflon (TM) Was added. To this solution was added 7.5 g (0.061 mol) of dimethylaminopyridine and the resulting solution was refluxed at 75 DEG C for 8 hours. Initially, the anhydride was not dissolved, but during that time the solids dissolved and the solution became brown. The reaction was cooled and concentrated in a rotary evaporator to remove methylene chloride and the thick solution was slowly added to acidic water (HCl). After dissolving by adding the filtered, the precipitated solid was washed, and then treated with MgSO ₄ and carbon black with water, ether, and the solution was filtered over Celite. The ether was removed on a rotary evaporator to give a white solid (Yield = 8.5 g, 60%).

_{^{1 H NMR (CDCl 3):}} d = 1.47 (9H; s, t- butyl), d = 1.60 (1H) , d = 2.15 (1H), d = 2.58 (2H; m, CHCOO), d = 3.07 ( 2H, s, bridge head), d = 6.19 (2H, s, C = C), d = 10.31 (1H; br, COOH).

Example 17

Synthesis of bicyclo [2.2.1] hept-5-en-exo-2-t-butyl, exo-3-methyl ester of dicarboxylic acid:

To a 100 ml three necked round bottom flask equipped with a magnetic stir bar was added 9.7 g (0.0408 mol) of exo-butyl half ester of pure norbornenedicarboxylic acid and 6.05 g (0.0408 mol) of trimethyloxonium tetrafluoroborate (0.0408 mol). The flask was capped and 100 ml of dichloromethane was added via a cannula under an argon atmosphere. The rubber stopper was replaced with a condenser under an argon atmosphere and an additional funnel was secured to the remaining neck. Add 7.3 ml of ethyl diisopropylamine to the additional funnel and slowly drown in the reaction vessel. A small amount of exotherm was observed and the solution was refluxed mildly. After all of the amine was added, the solution was allowed to stand at room temperature for 15 hours. After extracting the reaction mixture in three portions of 50 ml of HCl, the three extracts of 50 ml each were extracted with sodium bicarbonate and finally washed twice with water. The organic solution was dried over magnesium sulfate, treated with carbon black, filtered and concentrated on a rotary evaporator. A colorless liquid was obtained and crystallized. The solid was washed with cold pentane and the pentane solution was concentrated in a rotary evaporator to give a colorless liquid which crystallized upon cooling. Yield 5.1g.

_{^{1 H NMR (CDCl 3):}} d = 1.45 (9H; s, t- butyl), d = 1.47 (1H) , d = 2.15 (1H), d = 2.54 (2H; m, CHCOO), d = 3.07 ( 2H; s, bridge head), d = 3.65 (3H; s, CH 3), d = 6.19 (2H; s, C = C).

Example 18

5-norbonenecarboxylic acid (2.0 g, 14.5 mmol, exo-endo mixture) and dichloroethane (20 ml) were added to a 50 ml glass bottle equipped with a Teflon (TM) coated stir bar. The η ³ -alylpalladium chloride dimer (6 mg, 16 μmol) in dichloroethane (5 ml) was added to the silver hexafluoroantimonate (50 mg, 146 μmol) in dichloroethane (50 ml) for 30 min and then filtered through a microporous filter (To remove precipitated silver chloride) was added to the stirred mixture at ambient temperature. The reaction was carried out for 18 hours to gelify the mixture to yield a clear yellow gel. When the gel was added to an excess of hexane, the polymer precipitated as a white powder. The polymer was washed with excess hexane and dried. The yield of the polymer was 1.2 g (60%). The polymer had a molecular weight (Mw) of 22,000 and a polydispersity of 2.3.

When a portion (0.5 g) of this polymer was added to the stirred 0.1 N KOH (10 ml) aqueous solution, the polymer was immediately dissolved and an achromatic colorless solution was produced. This demonstrates the base evolution of these materials since none of the homopolymers of the t-butyl ester of 5-norbornene-carboxylic acid show a tendency to be solubilized under the same conditions.

Example 19

The pinner synthesis of orthoester is a two-step synthesis:

Step 1. Synthesis of imide ester hydrochloride.

The reaction was carried out in a 1 L capacity two necked round bottomed flask equipped with a stirrer, one oil bubbler and a tube filled with anhydrous calcium chloride. The following reagents were placed in 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 kept in a refrigerator overnight at < RTI ID = 0.0 > 0 C. < / RTI > In the morning, the mixture was solidified into a " cake ". The flask was kept in the refrigerator for an additional 10 days with occasional stirring. At the end of this period, the precipitated imide ester hydrochloride was filtered off by suction and washed five times with ~ 300 mL of diethyl ether. About 20 g of unreacted NB-CN was recovered from the filtrate.

Yield of imide ester hydrochloride - 76% (120 g, 0.64 mol). The structure of the product was confirmed by ¹ H NMR spectroscopy.

Step 2. Synthesis of Orthoester

In a 0.5 L flask, 56.7 g (0.30 mol) of imide ester hydrochloride, 37 ml (0.91 mol) of anhydrous methanol and 250 ml of anhydrous petroleum ether were added. The reaction mixture was allowed to stand at room temperature for 5 days with occasional stirring. The precipitated ammonium chloride was filtered off and washed three times with petroleum ether. The filtrate and washings were combined, the petroleum ether was distilled off and the product was fractionally distilled in vacuo. Fractions having a boiling point of 68-69 DEG C / 3 mmHg were collected. Yield - 50% (30 g, 0.15 mol). According to ¹ H NMR spectrum, 97% of the product was 5-norbonen-2-trimethoxymethane (orthoester).

Example 20

16ml of 1,2-dichloroethane _{C 7 H 9 C (OCH 3} ) 3 ( norbornene-trimethyl orthoester) 2.16g (10.9mmol) was added, 1 mol of palladium chloride dimer with 2 moles of allyl anti-hexafluoro The resulting reaction product solution was added by mixing the monate in dichloroethane and filtering the resulting silver chloride precipitate. The amount of catalyst added 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 캜 and reacted for 20 hours.

At approximately 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 - 1.28g (60%).

Example 21

Cyclo [2.2.1] hept-5-en-2-methyl acetate (18.44 g, 0.1109 mol) and t-butyl ester of norbornene in a 50 ml capacity vial equipped with a Teflon (TM) (21.55 g, 0.1109 mol) and 75 ml of toluene were added. In toluene _{15ml (Tol) Ni (C 6} F 5) 2 0.5367g (1.109mmol) was dissolved by the nickel catalyst [toluene complex of the bis-phenyl nickel _{perfluoroalkyl, (Tol) Ni (C 6} F 5) 2] A solution Lt; / RTI > The active catalyst solution was added to the monomer solution via a syringe at ambient temperature. The reaction was stirred at room temperature for 6 hours. The solution was diluted with toluene and the polymer was precipitated in an excess of methanol. The precipitated polymer was filtered, washed with acetone and dried under vacuum overnight. The yield of the isolated polymer was 24.9 g (63%). The polymer was characterized using GPC to determine its molecular weight. Mn = 21,000 and Mw = 52,000. NMR analysis of the copolymer confirmed that 51 mol% of t-butyl group was present. IR analysis of the copolymer revealed no acid groups.

Example 22

Butylcyclo [2.2.1] hept-5-en-2-methylethyl carbonate (4.03 g, 0.1109 mol) and t-butyl norbornene in a 50 ml capacity vial equipped with a Teflon (TM) Ester (3.98 g, 0.0205 mol) and 50 ml of toluene were added. In toluene _{15ml (Tol) Ni (C 6} F 5) 2 0.0991g (1.2049mmol) was dissolved by the nickel catalyst [toluene complex of the bis-phenyl nickel _{perfluoroalkyl, (Tol) Ni (C 6} F 5) 2] A solution Lt; / RTI > The active catalyst solution was added to the monomer solution via a syringe at ambient temperature. The reaction was stirred at room temperature for 6 hours. The solution was diluted with toluene and the polymer was precipitated in an excess of methanol. The precipitated polymer was filtered, washed with acetone and dried under vacuum overnight. The yield of the isolated polymer was 4.16 g (52%). The polymer was characterized using GPC to determine its molecular weight. Mn = 22,000 and Mw = 58,000. NMR analysis of the copolymer confirmed that 50 mol% of t-butyl groups were present. IR analysis of the copolymer revealed no acid groups.

Example 23

Bicyclo [2.2.1] hept-5-en-2-methylbutyl carbonate (17.15 g, 0.0764 mol) and t-butyl norbornene in a 50 ml capacity glass bottle equipped with a Teflon (TM) Ester (14.85 g, 0.0764 mol) and 72 ml of toluene. In toluene _{15ml (Tol) Ni (C 6} F 5) 2 nickel catalyst [toluene complex of the bis-phenyl nickel _{perfluoroalkyl, (Tol) Ni (C 6} F 5) 2] by dissolving 0.3699g (0.7644mmol) and the solution Lt; / RTI > The active catalyst solution was added to the monomer solution via a syringe at ambient temperature. The reaction was stirred at room temperature for 6 hours. The solution was diluted with toluene and the polymer was precipitated in an excess of methanol. The precipitated polymer was filtered, washed with acetone and dried under vacuum overnight. The yield of the isolated polymer was 17.53 g (54%). The polymer was characterized using GPC to determine its molecular weight. Mn = 22,000 and Mw = 58,000. NMR analysis of the copolymer confirmed that 54 mol% of the t-butyl group was present. IR analysis of the copolymer revealed no acid groups.

Example 24

Butyl ester (29.92 g, 0.154 mol), followed by a solution of maleic anhydride (15.10 g, 0.154 mol) in dry state and 90 ml of chlorobenzene in a 50 ml capacity glass bottle equipped with a Teflon (TM) Was added. This mixture was degassed three times to remove all traces of oxygen. The reaction mixture was then heated to 80 < 0 > C. A degassed benzoyl peroxide solution consisting of 0.9948 g (0.04 mol) of benzoyl peroxide free radical initiator in 10 ml of chlorobenzene was added to the reaction mixture via a dry syringe. The reaction mixture was stirred for 19 hours. After the reaction, the polymer solution was poured directly onto hexane to precipitate the polymer. A white precipitate was thus obtained. The precipitated polymer was then removed from unreacted maleic anhydride, which may be present. The polymer was then dried overnight at room temperature in a vacuum oven. The weight of the polymer obtained in the dry state was 20.62 g (yield: 45.8%). The polymer was characterized using GPC to determine the molecular weight. Mn = 4,200 and Mw = 8,800. NMR analysis of the copolymer confirmed the presence of the t-butyl group. IR analysis of the copolymer confirmed the presence of both t-butyl and maleic anhydride groups.

Example 25

Bicyclo [2.2.1] hept-5-en-2-methyl acetate (13.3 g, 0.0799 mol) and t-butyl ester of norbornene were added to a 50 ml capacity vial equipped with a Teflon (TM) (15.70 g, 0.0808 mol), followed by addition of dry maleic anhydride (15.85 g, 0.162 mol) and chlorobenzene 90 ml. This mixture was degassed three times to remove all traces of oxygen. The reaction mixture was then heated to 80 < 0 > C. A degassed benzoyl peroxide solution consisting of 1.0438 g (0.041 mol) of benzoyl peroxide free radical initiator in 10 ml of chlorobenzene was added to the reaction mixture via a dry syringe. The reaction mixture was stirred for 19 hours. After the reaction, the polymer solution was poured directly onto hexane to precipitate the polymer. A white precipitate was thus obtained. The precipitated polymer was then removed from unreacted maleic anhydride, which may be present. The polymer was then dried overnight at room temperature in a vacuum oven. The weight of the polymer obtained in the dry state was 21.89 g (yield: 48.7%). The polymer was characterized using GPC to determine the molecular weight. Mn = 3,000 and Mw = 6600. NMR analysis of the copolymer confirmed the presence of the t-butyl group. IR analysis of the copolymer confirmed the presence of acetate, t-butyl and maleic anhydride groups.

Example 26

A 50:50 copolymer of t-BuNB ester / NB-COOH

Butyl ester (2 g, 10 mmol) and norbornenecarboxylic acid (1.38 g, 10 mmol) were added to a 50 ml glass bottle equipped with a magnetic stir bar under a nitrogen atmosphere. An initiator (t-butyl peroxide) (2.9 g) was added to the stirred mixture at ambient temperature and the resulting mixture was heated to 130 캜 and stirred continuously for 16 hours. The resulting polymer (soluble in both THF and toluene) was precipitated into hexane and filtered to produce the product, which was dried and weighed to give 2.91 g (86% conversion). The resulting solid polymer had Mw = 20,000 and Mn = 3,000. IR, NMR and TGA analysis of the copolymer revealed that these compositions are random addition copolymers of two monomers.

Example 27

A 50:50 copolymer of t-BuNB ester / NB-MeNB ester

Butyl ester (2 g, 10 mmol) of norbornenecarboxylic acid and methyl ester (1.5 g, 10 mmol) of norbornenecarboxylic acid were added to a 50 ml capacity glass bottle equipped with a magnetic stir bar under a nitrogen atmosphere. An initiator (t-butyl peroxide) (2.9 g) was added to the stirred mixture at ambient temperature and the resulting mixture was heated to 130 캜 and stirred continuously for 16 hours. The resulting polymer (soluble in toluene) was precipitated into methanol and filtered to produce the product, which was dried and weighed to give 0.82 g (conversion: 23%). The resulting solid polymer had Mw = 35,000 and Mn = 6,000. IR, NMR and TGA analysis of the copolymer revealed that these compositions are random addition copolymers of two monomers.

Example 28

A 50:50 copolymer of t-BuNB ester / EtTD ester

(100 ml), t-butyl ester of norbornenecarboxylic acid (1.94 g, 10 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (2.32 g, 10 mmol) in a 100 ml capacity glass bottle equipped with a magnetic stirring bar under a nitrogen atmosphere , 10 mmol). A solution of bis (tricyclohexylphosphine) -benzylidene ruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. 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 addition with excess MeOH, collected by filtration, and dried under vacuum. 3.46 g (yield 81%) of the copolymer was recovered (Mw 221,000, Mn 133,000).

The copolymer was redissolved in toluene and passed through a column packed with silica gel to remove the significant color (Ru) produced. The polymer was again precipitated in excess MeOH to yield a pure white copolymer.

Example 29

A 50:50 copolymer of t-BuNB ester / EtTD ester

To a 100 ml glass bottle equipped with a magnetic stir bar under a nitrogen atmosphere were added toluene (80 ml), t-butyl ester of norbornenecarboxylic acid (3.9 g, 20 mmol) and ethyl ester of tetracyclododecenecarboxylic acid , 20 mmol). A solution of bis (tricyclohexylphosphine) -benzylidene ruthenium dichloride (68 mg, 0.083 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. After 2 hours, ethyl vinyl ether (0.030 ml, 0.31 mmol) was added and stirred for 2 hours.

The orange-amber solution was passed through a silica gel column to give a clear colorless solution. The solution was precipitated by addition of excess MeOH, collected by filtration, and dried under vacuum. 6.54 g (yield 77%) of the copolymer was recovered (Mw 244,000, Mn 182,000). The glass transition temperature was 220 캜 as measured by the DSC method.

Example 30

A 50:50 copolymer of t-BuNB ester / EtTD ester

To a 300 ml capacity stainless steel reactor equipped with a mechanical stirrer under a nitrogen atmosphere were added toluene (90 ml), t-butyl ester of norbornenecarboxylic acid (3.9 g, 20 mmol) and ethyl ester of tetracyclododecenecarboxylic acid , 20 mmol). A solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (68 mg, 0.31 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. Hydrogen (350 psig) was added to the reactor and the temperature was maintained at 175 C for 7 hours. After the reaction, the solution was passed through a silica gel column and the hydrogenated copolymer was separated. NMR method was used to confirm that the copolymer was 95% hydrogenated (Mw 237,000, Mn 163,000).

Example 31

A 50:50 copolymer of t-BuNB ester / EtTD ester

To a 300 ml stainless steel reactor equipped with a mechanical stirrer under a nitrogen atmosphere were added toluene (90 ml), t-butyl ester of norbornenecarboxylic acid (2.9 g, 15 mmol) and ethyl ester of tetracyclododecenecarboxylic acid , 15 mmol). A solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (50 mg, 0.060 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. After 2 hours, hydrogen (800 psig) was added to the reactor and the temperature was maintained at 175 C for 7 hours. After the reaction, the solution was passed through a silica gel column and the hydrogenated copolymer was separated. The NMR method was used to confirm that the copolymer was 96% hydrogenated (Mw 278,000, Mn 172,000).

Example 32

A 50:50 copolymer of t-BuNB ester / EtTD ester

Toluene (40 ml), t-butyl ester of norbornenecarboxylic acid (1.94 g, 10 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (2.32 g, 10 mmol) were added to a 100 ml capacity glass bottle equipped with a mechanical stir bar under a nitrogen atmosphere. , 10 mmol) and 1-hexene (0.050 ml, 0.4 mmol). A solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. After 2 hours, the polymer solution was added to excess MeOH, collected by filtration, and dried under vacuum. 3.1 g (yield 73%) of polymer were recovered (Mw 35,000, Mn 22,000).

Example 33

A 50:50 copolymer of t-BuNB ester / EtTD ester

Toluene (40 ml), t-butyl ester of norbornenecarboxylic acid (1.94 g, 10 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (2.32 g, 10 mmol) were added to a 100 ml capacity glass bottle equipped with a mechanical stir bar under a nitrogen atmosphere. , 10 mmol) and 1-hexene (0.275 ml, 2.2 mmol). A solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. After 2 hours, the polymer solution was added to excess MeOH, collected by filtration, and dried under vacuum. 3.45 g (yield 81%) of the polymer was recovered (Mw 8,000, Mn 6,000).

Example 34

A 50:50 copolymer of t-BuNB ester / EtTD ester

Toluene (40 ml), t-butyl ester of norbornenecarboxylic acid (1.94 g, 10 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (2.32 g, 10 mmol) were added to a 100 ml capacity glass bottle equipped with a mechanical stir bar under a nitrogen atmosphere. , 10 mmol) and 1-hexene (0.62 ml, 5.0 mmol). A solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (34 mg, 0.042 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. After 2 hours, the polymer solution was added to excess MeOH, collected by filtration, and dried under vacuum. 2.75 g (65% yield) of the polymer was recovered.

Example 35

A 50:50 copolymer of t-BuNB ester / EtTD ester

Toluene (80 ml), t-butyl ester of norbornenecarboxylic acid (3.9 g, 20 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (4.64 g, 20 mmol) were added to a 100 ml capacity glass bottle equipped with a mechanical stirring bar under a nitrogen atmosphere. , 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol). A solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (68 mg, 0.083 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. After 2 hours, ethyl vinyl ether (0.030 ml, 0.31 mmol) was added and stirred for 2 hours.

The orange-amber solution was passed through a silica gel column to remove the dark color (Ru). The solution was precipitated by the addition of excess MeOH, collected by filtration and dried under vacuum at 80 < 0 > C overnight. 2.6 g of polymer (yield 30%) was recovered (Mw 4,000, Mn 3,000).

Example 36

A 50:50 copolymer of t-BuNB ester / EtTD ester

To a 300 ml capacity stainless steel reactor equipped with a mechanical stirrer under a nitrogen atmosphere were added toluene (80 ml), t-butyl ester of norbornenecarboxylic acid (3.9 g, 20 mmol), ethyl ester of tetracyclododecenecarboxylic acid , 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol). A solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (68 mg, 0.042 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. After 2 hours hydrogen (750 psig) was added to the reactor and the temperature was maintained at 175 C for 20 hours.

The solution was precipitated by addition of excess methanol, collected by filtration and dried under vacuum at 80 < 0 > C overnight. About 5 g (59% yield) of the polymer was recovered (Mw 30,000, Mn 20,000). NMR was used to confirm that the copolymer was hydrogenated in excess of 99%.

Example 37

A 65:35 copolymer of t-BuNB ester / EtTD ester

(160 ml), t-butyl ester of norbornenecarboxylic acid (10.1 g, 52 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (6.5 ml) in a 250 ml capacity round bottom flask equipped with a mechanical stir bar under nitrogen atmosphere g, 28mmol) and 1-hexene (0.176ml, 1.4mmol). A solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (131 mg, 0.160 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. After 16 h, ethyl vinyl ether (0.060 ml, 0.62 mmol) was added and stirred for 1.5 h. The polymer solution was passed through a silica gel column to remove Ru. The solution was added to an excess of methanol, collected by filtration and dried under vacuum. 9.69 g of polymer (yield 58%) was recovered (Mw 42,000, Mn 31,000). The glass transition temperature (110 캜) was measured using the DSC method.

Example 38

In a 100 ml glass bottle containing nitrogen, 5 g of the polymer from Example 37 was dissolved in 80 ml of THF. The solution was transferred to a 300 ml stainless steel reactor. 2.25 g of a 5 wt% palladium catalyst on aluminum (purchased from Aldrich) was added to the reactor. The reactor was then heated to 175 DEG C and pressurized with 800 psig hydrogen. Temperature and pressure were maintained for 9.5 hours. The resulting polymer solution was centrifuged, the colorless solution was separated, and the polymer was precipitated in an excess of methanol. NMR was used to confirm that the resulting copolymer was hydrogenated at over 99%.

Example 39

A 50:50 copolymer of t-BuNB ester / EtTD ester

Toluene (80 ml), t-butyl ester of norbornenecarboxylic acid (3.9 g, 20 mmol) and ethyl ester of tetracyclododecenecarboxylic acid (4.64 g, 20 mmol) were added to a 100 ml capacity glass bottle equipped with a mechanical stirring bar under a nitrogen atmosphere. , 20 mmol) and 1-hexene (0.088 ml, 0.7 mmol). A solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (68 mg, 0.084 mmol) in 5 ml of toluene was added to the stirred solution at ambient temperature. After 2 h, ethyl vinyl ether (30 [mu] l, 0.31 mmol) was added to the reaction to pause further reaction and the mixture was stirred for 1.5 h. The polymer solution was passed through a silica gel column to remove Ru residues and then the polymer was recovered as a clear white solid by precipitation into methanol. The polymer had a Mw of 46,600 (Mn 33,700) and was fully characterized by IR, NMR and TGA methods.

Example 40

Ethyl 2-methyl-4-pentanoate (99 g, 0.7 mole) and freshly cracked cyclopentadiene (46.4 g, 0.7 mole) were added to a stainless steel autoclave having an internal volume of 300 ml. The stirred mixture was heated to 200 < 0 > C and allowed to stand overnight. The reactor was then cooled and its contents removed. The resulting functionalized norbornene (NB-CH ₂ CH (CH ₃ ) C (O) OC ₂ H ₅ ) was purified by vacuum distillation and found to have a boiling point of about 46-47 ° C at 0.02 mmHg . The material was analyzed by GC method and it was confirmed that the material had a purity of 98.4 to 99.3% (different fraction). The yield of isolated high purity product was about 33 g.

Example 41

t-BuNB ester _{(NB-CH 2 CH (CH} 3) C (O) OC 2 H 5) in 40: 60 copolymer

Ester (NB-CH ₂ CH from toluene (50ml) in a glass bottle of 100ml capacity, Nord t- butyl ester of norbornene carboxylic acid (2.7g, 14mmol), and Example 40 with a magnetic stirring bar under a nitrogen atmosphere ( the _{CH 3) C (O) OC} 2 H 5) (4.4g, 21mmol) was added. A (toluene) Ni (C ₆ F ₅ ) ₂ solution (1 ml) in toluene was added to the stirred solution, and the resulting solution was heated to 50 ° C and stirred continuously for 3 hours. The polymer was precipitated into methanol and filtered. The resulting solids were then redissolved in THF, filtered, re-precipitated with methanol and filtered. The resulting white solid polymer was dried to give 2.66 g (Mw 70,000; Mn 39,800) and the supernatant was evaporated to dryness to yield a white polymer which was dried to yield 1.52 g (Mw 60,650; Mn 31,000). The overall yield of the copolymer showed a monomer conversion of 59%. IR, NMR and TGA analyzes of the copolymers revealed that these compositions were random addition copolymers of both monomers.

Example 42

t-BuNB ester _{(NB-CH 2 CH (CH} 3) C (O) OC 2 H 5) in 40: 60 copolymer

(7.76 g, 40 mmol) of norbornenecarboxylic acid and the ester from Example 40 (NB-CH ₂ CH (CH _{3) 2} ) in a 250 ml capacity glass bottle equipped with a magnetic stirring bar under a nitrogen atmosphere, a _{(CH 3) C (O)} OC 2 H 5) (12.5g, 60mmol) and 2,6-di -t- butyl-pyridine (28.8mg, 0.26mmol) was added. The resulting catalyst solution was added to the stirred solution at ambient temperature by mixing silver hexafluoroantimonate and allyl palladium chloride dimer (0.183 g, 0.5 mmol) in dichloroethane (3 ml) and filtering to remove the silver chloride precipitate . The resulting solution was heated to 50 < 0 > C and stirred continuously for 16 hours. The polymer solution was treated with carbon monoxide (4 psi pressure) for 48 hours to precipitate the palladium residue, filtered through a 0.45 mu filter, reduced in volume and precipitated with excess methanol to give 7.9 g (39% conversion) of the copolymer . Mw 11,600, Mn 7,000. The copolymer was fully characterized using IR, NMR and TGA methods.

Example 43

Copolymerization of CO and norbornene-5-t-butyl ester

A methanol solution of deoxygenated bipyridine (0.025 g, 0.16 mmol) was added to palladium (II) acetate (0.012, 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 methanol (deoxygenated) solution of benzoquinone (1.72 g, 1.59 mmol). This solution was added to a stainless steel reactor pre-treated at 50 占 폚. To this reactor was added norbornene-5-t-butyl ester (5.14 g, 0.027 mol) in 100 ml of MeOH (oxygen-depleted by argon). The reactor was pressurized with carbon monoxide to 600 psig and allowed to warm to 65 < 0 > C. After 4.5 hours, the carbon monoxide was vented and the reactor was cooled. The pink solution from the reactor was filtered off to remove the palladium residue and evaporated. The resulting mixture was dissolved in a minimal amount of THF and slowly poured into a 25:75 mixture of water: methanol to precipitate the polymer. This process was repeated twice. The resulting white polymer was filtered and dried in vacuo at room temperature. Yield = 2.9 g.

Example 44

(0.70 g, 0.40 mmol), bipyridine (0.0062 g, 0.0040 mmol) and Pd (MeCN) ₂ (p-toluenesulfonate) ₂ (0.0070 g, 0.0013 mmol) in THF / methanol (35 ml / 15 ml) was added to a dry 500 ml stainless steel reactor heated to 50 < 0 > C. Norbornene-5-t-butyl ester (5.14 g, 0.027 mol) in 100 ml of anhydrous (deoxygenated and dried) THF was added to the reactor. The reactor was pressurized to 600 psig with carbon monoxide and allowed to warm to 65 [deg.] C. After 12.5 hours, the reactor was heated to 90 DEG C for 1.5 hours. Then, carbon monoxide was discharged and the reactor was cooled. The purple solution from the reactor was filtered to remove the palladium residue and evaporate. The resulting mixture was dissolved in a minimum amount of THF and slowly poured into a 25:75 mixture of water: methanol to precipitate the polymer. This process was repeated twice. The resulting white polymer was filtered and dried in vacuo at room temperature. Yield = 2.9 g.

Examples 45 to 51

Optical density measurement of cyclic olefin based homopolymers and copolymers at 193 nm.

Optical density is an important characteristic of an effective photoresist because it determines the uniformity of energy over film thickness. Typical polymeric scaffolds useful in lithographic techniques have an optical density of less than 0.2 absorbance units / micron prior to the addition of the photoacid generator (see 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. Reichmains, C. Ober, S. MacDonald, T. Iwayanagai and T. Nishikubo, April, 1995]. The polyhydroxystyrene, the primary component of a typical 248 nm DUV photoresist, is unstable as a resist skeleton at such wavelengths because it has an optical density of 2.8 absorbance units per micron at 193 nm.

Preparation of sample solution

The weight of the various polymer samples (polymers of .016 +/- .001) described in the previous examples was measured and dissolved in 4 ml of chloroform. The polymer solution was removed by pipetting and the thin film was cast on a clear and uniform quartz slide. The film was allowed to dry overnight. The resulting circular film on the quartz slide was further dried at 70 [deg.] C in an oven for 10 minutes under nitrogen.

A UV spectrum of the film was obtained using a Perkin-Elmer lambda 9 UV / VIS / IR spectrophotometer at a scan rate of 120 nm / min. The spectral range was set to 300 nm to 180 nm. The optical density of the film was measured at 193 nm by measuring the absorbance of the film at 193 nm and normalizing it to the thickness of the film. The results are shown in the following table:

Example polymer Absorbance at 193 nm (A) Film thickness (microns) Absorbance normalized at 193 nm (A / micron) 45 A 50/50 copolymer of the t-butyl ester of bicyclo [2.2.1] hept-5-en-2-methyl acetate / norbornene (polymer of Example 21) 1.0173 25.39 0.0400 46 A 50/50 copolymer of the t-butyl ester of bicyclo [2.2.1] hept-5-en-2-methylethyl carbonate / norbornene (polymer of Example 22) 0.1799 30.47 0.0059 47 A 50/50 copolymer of the t-butyl ester of bicyclo [2.2.1] hept-5-en-2-methylbutyl carbonate / norbornene (polymer of Example 23) 0.2808 33.01 0.0085 48 A copolymer of t-butyl ester of maleic anhydride / norbornene (polymer of Example 24) 1.1413 38.09 0.0299 49 Bicyclo [2.2.1] hept-5-en-2-methyl acetate terpolymer of t-butyl ester of maleic anhydride / norbornene (polymer of Example 25) 0.8433 17.78 0.04743 50 A 50/50 copolymer of the t-butyl ester of norbornene / ethyl ester of tetracyclododecene (polymer of Example 29) 0.4693 33.01 0.0142 51 A 50/50 copolymer of the t-butyl ester of norbornene / ethyl ester of tetracyclododecene (polymer of Example 30) 0.4146 35.55 0.0117

Preparation of resist solution, exposure and development

The polymer obtained in the above Examples was dissolved in propylene glycol monomethyl ether acetate (PGMEA) in an amount of 15 w / v% solids, and 5 or 10 w / w% of the onium salt described in the above- Lt; / RTI > to the polymer.

The solution was filtered through a 0.2 mu Teflon (TM) filter. A resist layer was formed from each solution by spin coating on hexamethyldisilazane (HMDS) primed silicon wafers. The coated money film was baked at 95 for 1 minute. The film was then exposed to UV radiation from a Karl Suss MJB3 UV 250 instrument at a wavelength of 230-250 nm through a quartz mask. The exposed film was heated to 125 < 0 > C to 150 < 0 > C for 1 hour. The exposed and heated film was then developed in an aqueous base to produce a high resolution positive tone image without loss of film thickness in unexposed areas.

The system can be easily negatively treated by development in a non-polar solvent. These materials are sensitive to long wavelengths by adding small amounts of photosensitizers such as pyrene, perylene or thioxanthone and to short wavelengths (193 nm) (these materials were observed with very low optical density at 193 nm .

Example 52

(Polymer of Example 21) (number average molecular weight 21,000) of t-butyl ester of bicyclo [2.2.1] hept-5-en-2-methyl acetate / norbornene in an amount of 10 w / v% solids Propylene glycol monomethyl ether acetate (PGMEA). Triphenylsulfonium hexafluoroarsenate was added to the polymer while being loaded in an amount of 10 w / w%. The resist film was filtered through a 0.2 mu Teflon (TM) filter and the filtered solution was transferred from the solution at a rate of 500 rpm for 30 seconds and then at a rate of 2000 rpm for 25 seconds onto a hexamethyldisilazane primed silicon wafer And coated in a rotating manner. Thus, a layer with a thickness of 0.7 mu m was produced. After baking the film at 95 ℃ for 1 minute in hot plate, it was exposed to UV radiation (240nm) at a dose of 50mJ / cm ² through a quartz mask. After the next baking at 125 占 폚 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 53

Copolymerization of t-butyl esters of bicyclo [2.2.1] hept-5-ene-2-methylethyl oxalate / norbornene with NiArf catalyst.

Bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate (8.57 g, 0.0382 mol) and t-butyl norbornene in a 50 ml capacity vial equipped with a Teflon (TM) Butyl ester (7.42 g, 0.0392 mol) and 38 ml of toluene were added. (Tol) Ni (C ₆ F ₅ ) _2] solution of a nickel catalyst [bisperfluorophenyl nickel] was dissolved by dissolving 0.1854 g (0.382 mmol) of (Tol) Ni (C ₆ F ₅ ) _{2 in 5} ml of toluene. Lt; / RTI > The active catalyst solution was added to the monomer solution via a syringe at ambient temperature. The reaction was stirred at room temperature for 5 hours. The solution was diluted with toluene and the polymer was precipitated in an excess of methanol. The precipitated polymer was filtered, washed with acetone and dried under vacuum overnight. The yield of the isolated polymer was 7.62 g (48%). The polymer was characterized using GPC to determine its molecular weight. Mn = 28,000 and Mw = 56,000. NMR analysis of the copolymer confirmed that the copolymer composition was very close to the feed ratio. IR analysis of the copolymer revealed no acid groups.

Example 54

Butyl ester of a bicyclo [2.2.1] hept-5-en-2-methyl acetate / norbornene) (number average molecular weight 21,000) was dissolved in a 10 w / v% 0.0 > (PGMEA). ≪ / RTI > Diaryl iodonium hexafluoroantimonate (Sartomer 1012) was added to the polymer with loading in an amount of 10 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer with a thickness of 0.7 mu m was produced. After baking the film at 95 ℃ for 1 minute on the hot plate, it was exposed to UV radiation (240nm) at a dose of 50mJ / cm ² through a quartz mask. After a subsequent baking at 125 캜 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 55

The copolymer of the t-butyl ester of bicyclo [2.2.1] hept-5-en-2-methyl acetate / norbornene (polymer of Example 21) (number average molecular weight 21,000) was added in an amount of 10 w / v% And dissolved in propylene glycol monomethyl ether acetate (PGMEA). Diaryl iodonium hexafluoroantimonate (Sartomer 1012) was added to the polymer with loading in an amount of 10 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer with a thickness of 0.7 mu m was produced. After baking the film at 95 ℃ for 1 minute on the hot plate, it was exposed to UV radiation (240nm) at a dose of 100mJ / cm ² through a quartz mask. After a subsequent baking at 125 캜 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 56

(70/30 molar ratio) of t-butyl ester of bicyclo [2.2.1] hept-5-ene-2-methylethyl oxalate / norbornene.

Bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate (14.8 g, 0.0663 mol), t-butylperoxybenzoate in a 50 ml capacity vial equipped with a Teflon (TM) Butyl ester (5.52 g, 0.0284 mol) and 113 ml of toluene were added. Nickel catalyst [bis perfluorophenyl nickel complexes of toluene to, _{(toluene) Ni (C 6 F 5)} 2] A solution, (toluene) Ni of 0.2296g (0.474mmol) in toluene of 5ml (C ₆ F _{5) 2} ≪ / RTI > in a dry box. At room temperature the active catalyst solution was added via syringe to the monomer solution. The reaction was stirred at room temperature for 5 hours. The solution was diluted with toluene and the polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone and dried under vacuum overnight. The yield of the isolated polymer was 10.15 g (50%). The polymer was characterized for molecular weight using GPC. Mn = 35,000 and Mw = 98,000. NMR analysis of the copolymer confirmed that the copolymer composition was very close to the feed ratio. IR analysis of the copolymer revealed no acid groups.

Example 57

The copolymer of the t-butyl ester of bicyclo [2.2.1] hept-5-en-2-methyl acetate / norbornene (polymer of Example 21) (number average molecular weight 21,000) was added in an amount of 10 w / v% And dissolved in propylene glycol monomethyl ether acetate (PGMEA). Triphenylsulfonium hexafluoroarsenate was added to the polymer while being loaded in an amount of 10 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer with a thickness of 0.7 mu m was produced. After baking the film at 95 ℃ for 1 minute on the hot plate, it was exposed to UV radiation (240nm) at a dose of 10mJ / cm ² through a quartz mask. After a subsequent baking at 125 캜 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 58

The copolymer of the t-butyl ester of bicyclo [2.2.1] hept-5-en-2-methyl acetate / norbornene (polymer of Example 21) (number average molecular weight 21,000) was added in an amount of 10 w / v% And dissolved in propylene glycol monomethyl ether acetate (PGMEA). Triphenylsulfonium hexafluoroarsenate was added to the polymer while being loaded in an amount of 10 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer with a thickness of 0.7 mu m was produced. The film was baked on a hot plate at 95 DEG C for 1 minute and exposed to UV radiation (240 nm) through a quartz mask at a dose of 30 mJ / cm < ^{2 &} gt ;. After a subsequent baking at 125 캜 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 59

Copolymerization reaction of bicyclo [2.2.1] hept-5-ene-2-methylethyl oxalate / 1- (1-ethoxy) ethyl 5-norbornene-2-carboxylate using NiArf ratio).

Bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate (0.5166 g, 2.304 mol), 1- (1- Ethoxy) ethyl 5-norbonen-2-carboxylate (0.4885 g, 2.304 mol) and 2.25 ml cyclohexane. Nickel catalyst [bis perfluorophenyl nickel complexes of toluene to, _{(toluene) Ni (C 6 F 5)} 2] A solution, (toluene) Ni (C ₆ F ₅ of 0.0112g (0.023mmol) in 0.65ml of ethyl acetate ) &_Lt; / RTI > At room temperature the active catalyst solution was added via syringe to the monomer solution. The reaction was stirred at room temperature for 5 hours. The solution was diluted with toluene and the polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone and dried under vacuum overnight. The yield of the isolated polymer was 0.0315 g (3%). The polymer was characterized for molecular weight using GPC. Mn = 52,000 and Mw = 100,000.

Example 60

Butyl ester of maleic anhydride / norbornene (the polymer of Example 24) (number average molecular weight: 4,000) obtained by radical polymerization of propylene was dissolved in propylene glycol monomethyl ether in an amount of 15 w / v% Acetate (PGMEA). Triarylsulfonium hexafluoroantimonate (Sartomer 1010, 50% solution in propylene carbonate) was added to the polymer with loading in an amount of 5 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer with a thickness of 0.6 mu m was produced. The film was baked on a hot plate at 95 DEG C for 1 minute and exposed to UV radiation (240 nm) through a quartz mask at a dose of 30 mJ / cm < ^{2 &} gt ;. After a subsequent baking at 125 캜 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 61

Butyl ester of maleic anhydride / norbornene (the polymer of Example 24) (number average molecular weight: 4,000) obtained by radical polymerization of propylene was dissolved in propylene glycol monomethyl ether in an amount of 15 w / v% Acetate (PGMEA). Triarylsulfonium hexafluoroantimonate (Sartomer 1010, 50% solution in propylene carbonate) was added to the polymer with loading in an amount of 5 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer with a thickness of 0.6 mu m was produced. The film was baked on a hot plate at 95 DEG C for 1 minute and exposed to UV radiation (240 nm) through a quartz mask at a dose of 30 mJ / cm < ^{2 &} gt ;. After subsequent baking at 95 占 폚 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 62

(50/50 molar ratio) of trimethylsilyl ester of bicyclo [2.2.1] hept-5-ene-2-methylethyl oxalate / norbornene.

Bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate (1.5484 g, 6.904 mol), trimethylsilyl of norbornene in a 50 ml capacity vial equipped with a Teflon (TM) Ester (1.4523 g, 6.905 mol) and 6.75 ml of cyclohexane. Nickel catalyst [bis perfluorophenyl nickel complexes of toluene to, _{(toluene) Ni (C 6 F 5)} 2] solution, 0.0335g of the 1.95ml of ethyl acetate (0.0691mmol of (toluene) Ni (C ₆ F ₅ ) ₂ ). ≪ / RTI > At room temperature the active catalyst solution was added via syringe to the monomer solution. The reaction was stirred at room temperature for 5 hours. The polymer was precipitated in an excess of methanol. The precipitated polymer was filtered, washed with acetone and dried under vacuum overnight. The yield of the isolated polymer was 0.2675 g (9%). It was confirmed that there is an acid functional group derived from the deprotection of the trimethylsilyl group.

Example 63

Butyl ester of a maleic anhydride / bicyclo [2.2.1] hept-5-en-2-methyl acetate / norbornene (number average molecular weight 3,000) Lt; / RTI > in propylene glycol monomethyl ether acetate (PGMEA). Diaryl iodonium hexafluoroantimonate (Sartomer 1012) was added to the polymer with loading in an amount of 10 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer with a thickness of 0.5 mu m was produced. After baking the film at 95 ℃ for 1 minute on the hot plate, it was exposed to UV radiation (240nm) at a dose of 50mJ / cm ² through a quartz mask. After a subsequent baking at 125 캜 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 64

Butyl ester of a bicyclo [2.2.1] hept-5-en-2-methylethyl carbonate / norbornene (the polymer of Example 22) (number average molecular weight: 22,000) was dissolved in a 15 w / v% And dissolved in propylene glycol monomethyl ether acetate (PGMEA). Triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) was added to the polymer with loading in an amount of 5 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer having a thickness of 1.1 占 퐉 was produced. The film was baked on a hot plate at 95 DEG C for 1 minute and exposed to UV radiation (240 nm) through a quartz mask at a dose of 30 mJ / cm < ^{2 &} gt ;. After subsequent baking at 95 占 폚 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 65

Copolymerization of t-butyl esters of bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate / norbornene.

(12.5 mmole) of t-butyl ester of norbornene, 8.57 g (38.2 mmole) of bicyclo [2.2.1] hept-5-ene in a 50 ml capacity glass bottle equipped with a Teflon (TM) -En-2-methylethyl oxalate, 50 ml of directly distilled dichloroethane, and the solution degassed under an argon atmosphere. A 10 ml glass bottle with a Teflon (TM) coated stir bar was charged with 0.0365 g (0.1 mmol) of allyl palladium chloride dimer with a monomer to catalyst ratio of 500/1 and 2 ml of dichloroethane. Another 10 ml glass bottle was filled with 0.0344 g (0.1 mmol) of silver hexafluoroantimonate and 2 ml of dichloroethane. The catalyst solution was prepared by mixing an allylpalladium chloride dimer solution with a silver hexafluoroantimonate solution in a dry box. An immediate precipitation of silver chloride was observed, which was filtered to obtain an active catalyst solution. The active catalyst solution was then added via a syringe to the monomer solution, and the reaction was stirred at 60 占 폚 for 20 hours. The polymer solution was allowed to cool, which was concentrated on a rotary evaporator and precipitated with methanol.

Example 66

Butyl ester of a bicyclo [2.2.1] hept-5-en-2-methylethyl carbonate / norbornene (the polymer of Example 22) (number average molecular weight: 22,000) was dissolved in a 15 w / v% And dissolved in propylene glycol monomethyl ether acetate (PGMEA). Triphenylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) was added to the polymer with loading in an amount of 5 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer having a thickness of 1.1 占 퐉 was produced. After baking the film at 95 ℃ for 1 minute on the hot plate, it was exposed to UV radiation (240nm) at a dose of 15mJ / cm ² through a quartz mask. After subsequent baking at 95 占 폚 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 67

Butyl ester of a bicyclo [2.2.1] hept-5-ene-2-methylbutyl carbonate / norbornene (the polymer of Example 23) (number average molecular weight: 22,000) was dissolved in a 15 w / v% And dissolved in propylene glycol monomethyl ether acetate (PGMEA). Triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) was added to the polymer with loading in an amount of 5 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer with a thickness of 1.0 mu m was produced. The film was baked on a hot plate at 95 DEG C for 1 minute and exposed to UV radiation (240 nm) through a quartz mask at a dose of 30 mJ / cm < ^{2 &} gt ;. After subsequent baking at 125 占 폚 for 0.5 minutes, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 68

Butyl ester of a bicyclo [2.2.1] hept-5-ene-2-methylbutyl carbonate / norbornene (the polymer of Example 23) (number average molecular weight: 22,000) was dissolved in a 15 w / v% And dissolved in propylene glycol monomethyl ether acetate (PGMEA). Triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) was added to the polymer with loading in an amount of 5 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer with a thickness of 1.0 mu m was produced. The film was baked on a hot plate at 95 DEG C for 1 minute and exposed to UV radiation (240 nm) through a quartz mask at a dose of 30 mJ / cm < ^{2 &} gt ;. After subsequent baking at 150 캜 for 0.5 minutes, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 69

A hydrogenated 50/50 mole% copolymer (polymer of Example 37) (number average molecular weight 23,000) of t-butyl ester of ethyl ester / norbornene of tetracyclodecene obtained by ring opening metathesis polymerization was reacted with 15 w / v % Solids in propylene glycol monomethyl ether acetate (PGMEA). Triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) was added to the polymer with loading in an amount of 5 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. Thus, a layer having a thickness of 1.1 占 퐉 was produced. The film was baked on a hot plate at 95 DEG C for 1 minute and exposed to UV radiation (240 nm) through a quartz mask at a dose of 30 mJ / cm < ^{2 &} gt ;. After a subsequent baking at 125 占 폚 for 1 minute, a high resolution positive image was obtained by development in an aqueous base for 30 seconds.

Example 70

(Non-hydrogenated 50/50 mole% copolymer (the polymer of Example 39) (number average molecular weight 34,000) of t-butyl ester of ethyl ester / norbornene of tetracyclodecene obtained by ring opening metathesis polymerization was changed to 15 w / v% solids in propylene glycol monomethyl ether acetate (PGMEA). Triphenylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution in propylene carbonate) was added to the polymer with loading in an amount of 5 w / w%. The resist film was filtered through a 0.2 mu Teflon (registered trademark) filter and the filtered solution was spun at a rate of 500 rpm for 30 seconds and then at 2000 rpm for 25 seconds to remove the hexamethyldisilazane-primed silicone Coated on a wafer. In this way, a layer with a thickness of 1.25 mu m was produced. After baking the film at 95 ℃ for 1 minute on the hot plate, it was exposed to UV radiation (240nm) at a dose of 50mJ / cm ² through a quartz mask. After subsequent baking at 150 캜 for 30 seconds, a high resolution positive image was obtained by development in an aqueous base for 60 seconds.

Example 71

Bicyclo [2.2.1] hept-5-en-2-methylethyl oxalate (8.57 g, 0.0382 mol), t-butylperoxybenzoate in a 50 ml capacity vial equipped with a Teflon (TM) Butyl ester (7.42 g, 0.0392 mol) and 38 ml of toluene. Nickel catalyst [bis perfluorophenyl nickel complexes of toluene to, _{(toluene) Ni (C 6 F 5)} 2] solution, 0.1854g of the 5ml of toluene [0.382mmol of _{(toluene) Ni (C 6 F 5)} 2 ] In a dry box. At room temperature the active catalyst solution was added via syringe to the monomer solution. The reaction was stirred at room temperature for 5 hours. The solution was diluted with toluene and the polymer was precipitated in excess methanol. The precipitated polymer was filtered, washed with acetone and dried under vacuum overnight. The yield of the isolated polymer was 7.62 g (48%). The polymer was characterized with respect to molecular weight using GPC. Mn = 28,000 and Mw = 56,000. NMR analysis of the copolymer confirmed that the copolymer composition was very close to the feed ratio. IR analysis of the copolymer revealed no acid groups.

Claims (30)

A photoinitiator, an optional dissolution inhibitor, and a polar pendant functional group in which one repeating unit contains an acid-unstable pendant group and the other repeating unit contains a polar functional group is polymerized from a monomer of the following formula (II) A photoresist composition comprising a copolymer comprising at least two kinds of polycyclic repeating units containing: In this formula, R ⁵ to R ⁸ are independently selected from hydrogen, linear and branched (C ₁ to C ₁₀₎ alkyl, the following polar _{substituents: - (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 , wherein n is 0 or 1, p is an integer from 0 to 5, -A- and -A'- are independently selected from the group consisting of straight and branched C ₁ to C ₁₀ ) alkylene, (C ₂ to C ₁₀ ) alkylene ether, polyether, cyclic ether, cyclic diether, (C ₁ to C ₁₀ ) alkyl, linear and branched (C ₁ to C ₁₀ ) alkyl, linear or branched (C ₁ to C ₁₀ ) ₍ C ₁ to C ₁₀ ) alkoxyalkylene, polyether, monocyclic and polycyclic (C ₄ to C ₂₀ ) cycloaliphatic moieties, cyclic ethers, cyclic diethers, cyclic ketones and cyclic esters , Provided that when R "is an alkyl, lactone, alicyclic or cyclic ketone group, -A- is always present and can not represent an alkylene radical. The composition of claim 1, wherein the polymer is polymerized from a polycyclic monomer substituted with at least one acid labile group of formula (I) In this formula, R ¹ to R ⁴ are independently hydrogen, linear and branched (C ₁ to C _{10) alkyl, - (A) n C (} O) OR *, - (A) n -C (O) OR, - (A) _{n -OR, - (A) n} -C (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'-OCH 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 **) from the group consisting of ₂ -A- and -A'- are independently straight and branched (C ₁ to C ₁₀ ) alkylene, (C ₂ to C ₁₀ ) alkylene, To C ₁₀ ) alkylene ethers, polyethers, (Where a is an integer from 2 to 7), R represents hydrogen or straight-chain or branched (C ₁ to C ₁₀ ) alkyl, R ^* represents a divalent radical selected from the group consisting of is capable of decomposing by the Acid initiator and _{-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 Of the cyclic group: (Wherein R ^p represents hydrogen or a linear or branched (C ₁ to C ₅ ) alkyl group), R ^** independently represents R and R ^* , and R ¹ To R < ⁴ > must be selected from substituents containing groups that are unstable to the acid. The composition of claim 2, wherein the polycyclic polymer comprises repeating units polymerized from one or more monomers of the formula: , In this formula, R ⁹ to R ¹⁶ independently represent hydrogen and linear and branched (C ₁ to C ₁₀ ) alkyl, with the proviso that at least one of R ⁹ to R ¹² is a group of the formula - (CH ₂ ) _n C (O) OH; < / RTI > q and r are an integer of 0 to 5; The composition according to any one of claims 1, 2 or 3, wherein the monomer is polymerized by ring opening polymerization to give a ring-opened polymer. 5. The composition of claim 4, wherein the ring-opened polymer is hydrogenated. 3. The composition of claim 2, wherein the monomer is polymerized by free radical polymerization. 4. The composition according to any one of claims 1 to 3, characterized in that the polymer comprises repeating units of the formula: In this formula, R ¹ to R ⁸ , m and p are as defined above. The composition of claim 7, wherein the polymer further comprises at least one repeating unit selected from the group consisting of: In this formula, R ⁹ to R ¹⁶ are as defined above. The composition of claim 1, wherein the polymer is a ring-opened polymer comprising repeating units of the formula: In this formula, R ¹ to R ⁴ are independently hydrogen, linear and branched (C ₁ to C _{10) alkyl, - (A) n C (} O) OR *, - (A) n -C (O) 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'-OCH 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 **) denotes a substituent selected from the group consisting of _2, R ⁵ to R ⁸ represents independently a substituent selected from the group consisting of hydrogen, straight chain and branched (C ₁ to C ₁₀ ) alkyl, and at least one group of R ⁵ to R ⁸ is - (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 , Wherein -A- and -A'- are independently selected from the group consisting of straight and branched (C ₁ to C ₁₀ ) alkylene, (C ₂ to C ₁₀ ) alkylene ether, polyether, Diether, or a compound represented by formula (Where a is an integer from 2 to 7), n is independently 0 or 1, m and p are independently an integer of 0 to 5, R is a straight or branched (C ₁ to C ₁₀ ) alkyl, and R ^* is -C (CH ₃ ) ₃ , -Si (CH ₃ ) ₃ , -CH (R ^p ) OCH ₂ CH ₃ , -CH ^p) OC (CH _3), or during of the formula cyclic ring group: (Where R ^p represents hydrogen or a linear or branched (C ₁ to C ₅ ) alkyl group), and R ^** represents an acid-labile group which may be decomposed by a photoacid initiator selected from the group consisting of R and R ^* , and at least one of R ¹ to R ⁴ is selected from substituents containing an acid labile group, and R "is selected from the group consisting of hydrogen, straight and branched (C ₁ to C ₁₀ ) alkyl, linear and branched ₍ C ₁ to C ₁₀ ) alkoxyalkylene, polyether, monocyclic and polycyclic (C ₄ to C ₂₀ ) cycloaliphatic moieties, cyclic ethers, cyclic ketones, and cyclic esters (lactones) Provided that when R " is an alkyl, lactone, alicyclic or cyclic ketone group, -A- is always present and can not represent an alkylene radical. The composition of claim 9, wherein the ring-opened polymer further comprises at least one repeating unit selected from the group consisting of: In this formula, R ⁹ to R ¹⁶ independently represent hydrogen and straight and branched chain (C ₁ to C ₁₀ ) alkyl, with the proviso that at least one group of R ⁹ to R ¹² is a group of the formula - (CH ₂ ) _n C (O) OH; < / RTI > q and r are independently an integer of 0 to 5; 10. The composition of claim 9, wherein the copolymer comprises repeating units of the formula: In this formula, R ^* is selected from the group consisting of -C (CH ₃ ) ₃ -, -Si (CH ₃ ) ₃ , 1-methyl-1-cyclohexyl, isobonyl, (Dmcp) group and a group selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, And R " is selected from straight chain and branched (C ₁ to C ₁₀ ) alkyl. A compound according to claim 11, characterized in that R ¹ to R ³ and R ⁵ to R ⁷ are hydrogen or straight or branched (C ₁ to C ₁₀ ) alkyl and R "is linear or branched (C ₁ to C ₁₀ ) / RTI > 13. A composition according to claim 12, wherein the ring-opened polymer comprises a repeating unit of the formula: In this formula, m and p are independently 0 or 1, n is 1, and A is an alkylene group containing 1 to 10 carbon atoms. 14. The composition of claim 13, wherein R ^* is t-butyl, A is a methylene group, and R " is selected from straight or branched (C ₁ to C ₅ ) alkyl. A polymer according to any one of claims 9 to 14, wherein the unsaturated moiety is hydrogenated within the framework of the ring opened polymer. 16. The copolymer of claim 15, wherein the unsaturated moiety is hydrogenated in greater than 90% of the framework of the ring opened polymer. 17. The copolymer of claim 16, wherein the unsaturated moiety within the framework of the ring-opened polymer is substantially 100% hydrogenated. A photoresist composition comprising a photoacid initiator, an optional dissolution inhibitor, and a copolymer comprising a polycyclic repeating unit of the formula: In this formula, R ¹ to R ⁴ are independently hydrogen, linear and branched (C ₁ to C _{10) alkyl, - (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'-OCH 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 **) selected from the group consisting of ₂ And R ⁵ to R ⁸ independently represent a substituent selected from the group consisting of hydrogen, straight-chain and branched (C ₁ to C ₁₀ ) alkyl, and at least one of R ⁵ to R ⁸ is - (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") polar-substituted, represented by ₂ Must be selected from, in which -A- and -A'- is independently selected from linear and branched (C ₁ to C ₁₀₎ alkylene, (C ₂ to C ₁₀₎ alkylene ethers, polyethers, cyclic ethers, when Cl-diether or a compound of formula Cyclic group during the (here, a is 2 to an integer from 7) 2 is selected from the group consisting represents the radical, p is independently an integer from 0 to 5, R is hydrogen or linear and branched (C ₁ to C ₁₀₎ represents alkyl, R ^* is _{-C (CH 3) 3, -Si} (CH 3) 3, -CH (R p) OCH 2 CH 3, -CH (R p) OC (CH 3) or following Lt; RTI ID = 0.0 > (Where R ^p represents hydrogen or a linear or branched (C ₁ to C ₅ ) alkyl group), and R ^** represents an acid-labile group which may be decomposed by a photoacid initiator selected from the group consisting of R and R ^* , and at least one of R ¹ to R ⁴ is selected from substituents containing groups unstable to the acid, R "is selected from the group consisting of hydrogen, straight and branched (C ₁ to C ₁₀ ) alkyl, linear and branched (C ₁ to C ₁₀ ) alkoxyalkylene, polyether, monocyclic and polycyclic (C ₄ to C ₂₀ ) cycloaliphatic moieties, cyclic ethers, cyclic ketones and cyclic esters (lactones) Provided that when R " is an alkyl, lactone, alicyclic or cyclic ketone group, -A- must be present and can not represent an alkylene radical. The composition according to claim 18, wherein the copolymer further comprises at least one repeating unit selected from the group consisting of compounds represented by the following formulas: In this formula, R ⁹ to R ¹⁶ independently represent hydrogen and straight and branched chain (C ₁ to C ₁₀ ) alkyl, with the proviso that at least one group of R ⁹ to R ¹² is a group of the formula - (CH ₂ ) _n C O) OH, and q and r are independently an integer of 0 to 5. 19. The composition of claim 18, wherein the copolymer comprises repeating units of the formula: Wherein R ^* is selected from the group consisting of -C (CH ₃ ) ₃ , Si (CH ₃ ) ₃ , 1-methyl-1-cyclohexyl, isobonyl, (1-ethoxyethyl, 1-t-butoxyethyl, dicyclopropylmethyl (Dcpm), and dimethylcyclohexyl (Dmcp) group, and R " is selected from straight chain and branched (C ₁ to C ₁₀ ) alkyl. A compound according to claim 20, characterized in that R ¹ to R ³ and R ⁵ to R ⁷ are hydrogen or straight or branched (C ₁ to C ₁₀ ) alkyl and R "is linear or branched (C ₁ to C ₁₀ ) / RTI > 22. The composition of claim 21, wherein the copolymer comprises repeating units of the formula: In this formula, m and p are independently 0 or 1, n is 1, and A is an alkylene group containing 1 to 10 carbon atoms. 23. The composition of claim 22, wherein R ^* is t-butyl, A is a methylene group, and R " is selected from straight or branched (C ₁ to C ₅ ) alkyl. The composition according to any one of claims 1 to 3, 5 and 11 to 21, wherein the polymer contains from 5 to 100 mol% of recurring units containing acid labile groups. 25. The composition of claim 24, wherein the polymer comprises from 20 to 90 mole percent repeat units containing acid labile groups. 26. The composition of claim 25, wherein the polymer comprises from 30 to 70 mole percent of repeat units containing acid labile groups. 26. The composition of claim 25, wherein the polymer comprises from 5 to 100 mole percent of repeat units containing acid labile groups. A polymer according to any one of claims 7, 8 and 18 to 23, wherein the polymer has a pendant perfluorophenyl group at one or more ends thereof. The polymer according to any one of claims 1 to 3, wherein the polycyclic polymer comprises repeating units polymerized from maleic anhydride. A polymer according to any one of claims 7, 8 and 18 to 23, wherein the polymer comprises recurring units of the formula: