CN1276884A - 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 photoacid initiator and a polycyclic polymer comprising repeating units that contain pendant acid labile groups. Upon exposure to an imaging radiation source the photoacid initiator generates an acid which cleaves the pendant acid labile groups effecting a polarity change in the polymer. The polymer is rendered soluble in an aqueous base in the areas exposed to the imaging source.

Description

The photoetching compositions that contains the polycyclic polymers that comprises acid labile pendant groups

Background of invention

1. invention field

The present invention relates to polycyclic polymers and as the method for the photoresist in the integrated circuit preparation.More specifically, the invention describes the photoetching compositions that contains polycyclic polymers and cation light initiator.This polycyclic polymers contains the repetition acid-unstable group of side joint on main polymer chain.Acid-unstable group can selective splitting, forms to repeat polar group on main polymer chain.Radiation is transparent and shows anti-ion etching activity polymkeric substance to the shortwave image.

2. background of invention

Integrated circuit (IC) is the highest array of making electronic equipment.They be by a series of on suitable base plate (as silicon wafer) alternately and interconnective conductor, semiconductor and insulator pipe fitting, according to the arranged in patterns on the base plate, interconnected formation circuit and produce special electric function.The pattern of IC is to make of the imprint lithography of existing technology.The light path imaging of using ultraviolet ray (UV) and more deep UV (UV) or other radiation is production IC Equipment Foundations and important techniques.Photopolymer film (photoresist) is used in wafer surface and drying.The photomask that will comprise the pattern of requirement then is placed on apart from the very near place of photoresist film.Photoresist by on the photomask that covers comprised ultraviolet ray by several image-forming radiation light, electron ray, a kind of irradiation in x-ray or the ion irradiation.Expose in radiant light, the chemical change of dissolving variation has taken place to follow in photosensitizer.After overshoot, wafer is immersed in the solution graphic design that forms design on the photopolymer film (promptly select to remove radiation or the zone of radiation not).According to the type of used polymkeric substance or the polarity of developer solution, in developing process, remove light-sensitive surface exposed areas or unexposed zone and make the base exposure, make pattern exposure in process, after removing unwanted base material or etch process, on the functional layer of wafer, retain the pattern of requirement and obtain changing.Etching comprises plasma etching, sputter etching and reactive ion etching (RIE).The effect of the photoresist that remains is to make protective seam in etch process.Obtain the layout circuit after removing the photoresist material that keeps.

When making the pattern of IC equipment, the technology of etched wafer different aspects is institute's middle most criticals in steps.A kind of method is that base plate and protected pattern are immersed in the chemical bath, and the backplate surface of chemical etching exposure intactly keeps protected portions.The chemical technology that " wets " method is difficult in the corner that the backplate surface of etching obtains designing.This is because chemical method etching erosion resistant has formed isotropic pattern.Just, traditional chemical technology can not the provider to selectivity (anisotropy), do not consider the consistance that reaches the optimum dimension technical specification with existing technological requirement.In addition, to be eliminated be because do not meet environment and safety requirements to wet processing.

Developed multiple " doing " method technology to overcome the shortcoming of wet chemical process.These dry process generally comprise and make gas pass through a compartment, and when having gas to exist between two electrodes, voltage makes gas ionization.The plasma that contains the ion thing by electric field action produces can be used for the base plate of placing in the etching compartment.The ion thing direct irradiation base plate of plasma generation, they and material surface interactions form volatilizable product, from surface removal.The exemplary of dry etching is a plasma etching, sputter etching and reactive ion etching.

Reactive ion etching can produce the good vertical sidewall profile that limits on base plate, become with base plate to face toward the same good homogeneity of base plate etching.Because have these advantages, the reactive ion etching technology has become the standard technique of making IC.

The two class photoresists that are used for industry are negative-type photoresist and positive type photoresist.The negative-type photoresist, by in image-forming radiation, exposing, polyreaction, crosslinked, or change dissolubility and make exposed areas soluble to developer.Unexposed portion has kept dissolubility and has been washed off.The effect against corrosion of positive type is just in time opposite, and the zone in image-forming radiation after the exposure becomes solvable in developer solution.

A kind of positive type photoresist material is to be principal ingredient with thermoplastic phenolic varnish gum polymkeric substance.The example of an industrial applications is a Shipley AZ1350 material, and it comprises metacresol formaldehyde phenolic resin varnish polymer composition and diazo-ketones (2-diazonium-1-naphthol-5-sulfonic acid ester).When exposing in image-forming radiation, diazo-ketones is transformed into carboxylic acid, is transformed into novolac polymer afterwards, can dissolving rapidly in moisture alkalescent developer.

United States Patent (USP) the 4th, 491, No. 628 (Ito etc.) have been described and have been had the polymkeric substance that acid causes the positive type and the negative-type photoetching compositions of light trigger and has acid labile pendant groups.Because each generation acid all causes producing a plurality of acid labile groups and goes protection, this method is called chemistry amplifies, and it can be used to increase the quantum yield of all photochemistry technologies.Disclosed polymkeric substance comprises vinyl class in polymer such as polystyrene, and polyvinyl benzoic ether and polyacrylate, these polymkeric substance are repeated side group and replace, and the product of process acidolysis has the dissolubility different with their precursor.Preferred acid labile pendant groups comprises the positive butyl ester of carboxylic acid and the phenol carbonic acid tert-butyl ester.It still is that negative film can be decided according to the performance of used developing solution that photoresist is made positive.

The trend that electronics industry requires IC is faster and consumes lower energy.In order to cater to this performance requirement, IC must do forr a short time.Lead (as circuit) must be done narrowlyer, arranges closelyr.The transistor of making and the size of circuit obviously dwindle the efficient that correspondingly improves IC, for example, make computer chip have the stronger storage and the ability of process information.In order to make line width narrower, need higher photoimaging resolution.Higher resolution makes short wavelength's radiating light source more may be used for the irradiation of photoresist material.Yet, the photoresist of early stage technology for example novolac resin polymkeric substance and substituted phenylethylene polymkeric substance contains when optical wavelength is lower than about 300nm the aryl that it has intrinsic high-absorbable (is seen 5-10 day in April, 1992, No. 537, the 203rd national proceeding of American Chemical Society, " be used for microelectronics, the polymkeric substance of against corrosion and medium "; " polymkeric substance that is used for electronics and photonics ", C.P.Wong edits, Academic publishing house, 67-118 page or leaf).The light source than traditional is dark usually for the shorter light source of wavelength, needs to use the chemical enhancement methods of photic acid (photoacid).These aromatic polymers are opaque to short wavelength's more light, and its shortcoming is that the photic acid under the polymer surfaces can not evenly expose under light source, and then polymkeric substance can not develop.In order to overcome the bad shortcoming of these polymkeric substance transparencys, must reduce the aromatics component content in the photoresist polymkeric substance.If wish that the aromatic character part of polymkeric substance should be at minimum level to deep UV transparent (for example, being used for 248nm, especially 193nm wavelength exposure).

United States Patent (USP) the 5th, 372 relates to a kind of photoetching compositions and contains the acrylate base co-polymer, phenolic bonding agent and photosensitive acid propellant for No. 912.The acrylate base co-polymer is by acrylic acid, and the acrylic or methacrylic acid alkyl ester forms with the monomer polymerization that contains acid labile pendant groups.This composition is fully transparent to the ultraviolet radiation line of the about 240nm of wavelength, can not use more short wavelength's radiating light source but the use of aromatic species bonding agent has limited it.Normally like this, the cost that strengthens a kind of performance generally is to reduce another kind of performance in polymer process.When using the acrylate based polyalcohol, be that cost obtains to reduce diaphragm to the anti-etching performance of reactive ion etch process to the transparency of more short wavelength ultraviolet radiation.

In a lot of examples, improved the transparency in short wavelength's image-forming radiation, but reduced the etch-resistance in dry method etch technology subsequently.Because the normally organic property of photoresist material, the normally inorganic material of manufacturing IC base plate, the photoresist material is than baseboard material intrinsic higher rate of etch when using the RIE technology.This needs photoresist thinner than following baseboard material.Otherwise, be corroded before the abundant etching of photoresist material base plate below.Can in thin layer more, use the photoresist material of lower rate of etch to make the base plate can be etched.Use thinner photoresist material can obtain higher resolution, final, allow to use narrower wire line and littler transistor.

J.V.Crivello et al. (chemical amplification electron-X-ray lithography X glue, chemical material, 1996 the 8th phases, the 376-381 page or leaf) described a kind of polymeric blends and contained the free radical polymerization homopolymer of the norbornene monomer that has acid-unstable group of 20% (weight) and the homopolymer of 80% the 4-hydroxyl-α-Jia Jibenyixi that contains acid-unstable group, as the electron ray photoresist.From above discussion as can be known, aromatic group enhanced absorption when high concentration (especially) makes these compositions opaque, can not be used for the image-forming radiation that wavelength is lower than 200nm.

Disclosed composition only is applicable to the electron ray photoresist and can not be used for deep ultraviolet imaging (can not be used for 193nm especially) anticorrosion protection.

Crivello et al. has investigated blend compositions, because they find that oxygen plasma is too high to the rate of etch of the free radical polymerization homopolymer of the norbornene monomer that has acid labile group, can not be accepted.

Therefore, need a kind of photoetching compositions, it can either amplify that operation is compatible with general chemistry again can be transparent to short wavelength's image-forming radiation, and fully anti-etching under the reactive ion etch process condition.

Summary of the invention

General objects of the present invention provides a kind of polycyclic polymers that has the acid labile group side chain on the main chain and photoetching compositions of light trigger of comprising.

Another object of the present invention provide the acid-unstable group that has repeat side chain can be cleaved and form the polycyclic polymers of polar group.

The present invention also has another purpose to provide the transparent polymer composition of short wavelength's image-forming radiation.

Further object of the present invention provides polymer composition anti-etching in dry method etch technology.

The present invention also have one further purpose provide to short wavelength's image-forming radiation transparent and in dry method etch technology anti-etching polymer composition.

The polycyclic monomer that has acid labile pendant groups that the present invention also has another purpose to provide can be aggregated, the polymkeric substance of formation is applicable to the water base developing agent.

These purposes of the present invention and other purpose are to comprise the functionalized many cyclenes monomer of acid labile group by polymerization, and solvent has that the reaction mixture of the one-component of VIII family metal ion source or multicomponent catalyst system realizes.VIII family ion in the multicomponent catalyst system of the present invention is by being used in combination with in organic metal promotor and the 3rd component one or both.In one-component and multicomponent catalyst system, can use the optional chain-transferring agent (CTA) that is selected from the compound that has terminal olefinic double bond between the adjacent carbon atom, have at least one to have two coupled hydrogen atoms in the wherein above-mentioned adjacent carbon atom.Chain-transferring agent (CAT) be selected from typically can not cationic polymerization unsaturated compound, therefore, can not use styrene, vinyl ether and conjugated diolefine.

The polymkeric substance that obtains is useful in comprising the photoetching compositions of radiosensitive acid forming agent.

Detailed Description Of The Invention

The radiosensitive photoetching compositions that the present invention relates to comprise acid generation initiating agent and on main polymer chain, have the polycyclic polymers of repetition acid labile pendant groups group.The polymkeric substance that contains initiating agent is painted film on base plate, toast under the condition of control, carries out the radiation of pattern configuration, and any under controlled conditions after-bake impels further goes protective effect.In the part of having exposed on the film, the repetition acid-unstable group cracking on the main polymer chain has formed the polarity recurring group.Exposed areas is handled with the alkali developer, is selectively removed.Or the unexposed area of polymkeric substance kept nonpolar, can handle with the non-polar solvent that is suitable for of the toner, developer agent of suitable negative film, with selective removal.Image inversion can realize by suitable selection developer at an easy rate, because the polymkeric substance exposure is different with the dissolubility of unexposed portion.

Polymkeric substance of the present invention comprises many rings repetitive composition that part is replaced by acid labile group.This polymkeric substance is by polymerization polycyclic monomer preparation of the present invention.Term " many ring " (norbornene-type or norborene official can) be meant monomer contain at least one following shown in the norborene part:

The simplest polycyclic monomer is the dicyclo monomer among the present invention, and dicyclo [2.2.1] hept-2-ene" is commonly referred to norborene.In a specific embodiments of the present invention, the unstable functional group of acid is by making, comprise the unstable reaction medium that replaces polycyclic monomer of one or more acid as shown in the formula I with optional combining form under VIII family metal catalyst system and as shown in the formula II, III, in IV and the V polycyclic monomer one or more carry out polymerization, are introduced into polymer chain.

In another specific embodiments of the present invention, one or more are suc as formula acid unstable replacement polycyclic monomer and one or more the polycyclic monomer copolymerization as shown in the formula II of I.

Monomer

The sour unstable polycyclic monomer that is used for the present invention's practice is selected from as shown in the formula the monomer of representing:

R wherein ¹To R ⁴Represent independently to be selected from-(A) _nC (O) OR ^*,-(A) _nC (O) OR ,-(A) _n-OR ,-(A) _nOC (O) R ,-(A) _nC (O) R ,-(A) _nOC (O) OR ,-(A) _nOCH ₂C (O) OR ^*,-(A) _nC (O) O-A '-OCH ₂C (O) OR ^*,-(A) _nOC (O)-A '-C (O) OR ^*,-(A) _nC (R) ₂CH (R) (C (O) OR ^*) and-(A) _nC (R) ₂CH (C (O) OR ^*) ₂The substituting group of group, collateral condition are R at least ¹To R ⁴In a kind of acid-unstable group-(A) of being selected from _nC (O) OR ^*A and A ' represent independently and are selected from bivalent hydrocanbon radical, and divalence cyclic hydrocarbon radical, divalence contain the divalent abutment or the interval base of oxygen base and divalence cyclic ethers and ring diether, and n is integer 0 or 1.When on behalf of A and A ', n 0 represent single covalent bond.Divalence is meant that the free valence of the end of each group has two different groups.Bivalent hydrocanbon radical can be suc as formula-(C _dH _2d)-expression, wherein d represents the carbon number in the alkylidene chain, is from 1 to 10 integer.Bivalent hydrocanbon radical is preferably selected from the (C of line style and branching ₁To C ₁₀) alkylidene such as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl and inferior decyl.When using sub-branched alkyl, can be understood as hydrogen atom on the line style alkylidene chain by the (C of line style or branching ₁To C ₅) the alkyl replacement.

The divalence cyclic hydrocarbon radical comprise replacement with unsubstituted as shown in the formula (C ₃To C ₈) alicyclic part: Wherein a is 2 to 7 integer, works as R ^q(the C that has interval scale line style and branching ₁To C ₁₀) alkyl.Preferred divalence cycloalkylidene comprises cyclopentylene and cyclohexylidene part, and structure is as follows:

R wherein ^qAs above definition.From diagram with describe in detail as can be known, the key of drawing from ring structure and/or formula represent divalent moiety, and has represented ring carbon atom and the position of the adjacent molecule part bonding that defines in formula separately.According to the technology routine, the key table of being drawn by the ring structure center shows this key arbitrary ring carbon atom on the coupling ring arbitrarily.Should be understood that the ring carbon atom that links to each other with key holds a hydrogen atom at the most, to satisfy the price of carbon atom.

Preferred divalence cyclic ethers and diether are following structure:

Divalence contains the oxygen base and comprises (C ₂To C ₁₀) alkylene ether and polyethers.(C ₂To C ₁₀) alkylene ether is meant that the total number of carbon atoms of divalence ether moiety is 2 at least, but is no more than 10.Divalent alkyl ether is suc as formula-alkylidene-O-alkylidene-expression, and wherein each alkylidene can be identical or different, connects by oxygen atom, and is to be selected from methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji and inferior nonyl.The simplyst in the series divalent alkyl ether be-CH ₂-O-CH ₂-, bivalent radical that preferred polyether moiety comprises is suc as formula  CH ₂(CH ₂) _XO) _Y-wherein x is 0 to 5 integer, and y is 2 to 50 integer, and collateral condition is that the terminal oxygen atom of polyethers compartment can not directly be connected to form the peroxidating key with the terminal oxygen atom on the adjacent group.That is to say basic at interval and as above-mentioned R when polyethers ¹To R ⁴When the contained terminal oxygen of the substituting group of definition connects, the peroxidating chain can not be arranged (O-O-).

R represents hydrogen in following formula, (the C of line style or branching ₁To C ₁₀) alkyl, m is 0 to 5 integer.R ^*Representative can be selected from-C (CH by the part of photic sour initiating agent cracking (END CAPPED GROUP or protecting group) ₃) ₃,-Si (CH ₃) ₃,-CH (R ^p) OCH ₂CH ₃,-CH (R ^p) OC (CH ₃) ₃, or following cyclic group:

R wherein ^pRepresent hydrogen or line style or branching (C ₁To C ₅) alkyl.Alkyl substituent comprises methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group, amyl group, tertiary pentyl and neopentyl.In said structure, the singly-bound of being drawn by cyclic group is represented the carboatomic ring position that protecting group links to each other with substituting group separately.The example of acid labile group comprises 1-methyl isophthalic acid-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, the tetrahydrofuran base, THP trtrahydropyranyl, 3-oxygen hexamethylene ketone group, mevalonolactone base (mevalonic lactonyl), the 1-ethoxyethyl group, uncle 1--butoxyethyl group, two ring third methyl (Dcpm) and diformazan basic ring third methyl (Dmcp).Alkyl substituent on the protecting group as above is selected from (the C of line style and branching ₁To C ₅) alkyl.R ^*Represent above-mentioned R and R independently ^*Dcpm and Dmcp are expressed as follows formula respectively:

Have substituent polycyclic monomer in the following formula, substituting group is selected from group-(CH ₂) _nC (R) ₂CH (R) (C (O) OR ^*), or-(CH ₂) _nC (R) ₂CH (C (O) OR ^*) ₂, this polycyclic monomer can be as shown in the formula expression:

Wherein m such as above-mentioned definition, n ' is 0 to 10 integer.

M preferred 0 or 1 in the following formula, and more preferably m is 0.When m is 0, preferred construction is expressed as follows: R wherein ¹To R ⁴As mentioned above.

Those of ordinary skills can see that any photic sour cleavable part all is suitable for using, as long as it is to the essentially no inhibition of polyreaction in the present invention's practice.

Preferred acid labile group is organic ester group of protection, and wherein protecting group or END CAPPED GROUP in the presence of acid cracking take place.Carboxylic acid tertiary butyl ester especially preferably.

When polyreaction occurs on the main polymer chain, provide suc as formula the described monomer of I and to have repeated acid-sensitive sense side group unit, cracking subsequently makes polymkeric substance have polarity or dissolubility.

The second optional monomer is by representing as shown in the formula the II structure:

R wherein ⁵To R ⁸Representative is selected from group independently :-(A) _n-C (O) OR " ,-(A) _nOR " ,-(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 ") ₂CH (R ") (C (O) OR ") and-(A) _n-C (R ") ₂CH (C (O) OR ") ₂Neutrality or polar substituent.Part A and A ' represent independently and are selected from bivalent hydrocanbon radical, and divalence cyclic hydrocarbon radical, divalence contain the divalent abutment or the interval base of oxygen base and divalence cyclic ethers and ring diether; N is integer 0 or 1.When n is 0, can see that A and A ' represent single covalent bond.Divalence is meant that the terminal free valence of each base has two different groups.Bivalent hydrocanbon radical can be represented suc as formula-(C _dH _2d)-, wherein d represents carbon number in the alkylidene chain, and is 1 to 10 integer.Bivalent hydrocanbon radical is preferably selected from the (C of line style and branching ₁To C ₁₀) alkylidene, as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl and inferior decyl.When prepare using sub-branched alkyl, can be understood as is that hydrogen atom on the line style alkylidene chain is by (the C of line style or branching ₁To C ₅) the alkyl replacement.

The divalence cyclic hydrocarbon radical comprises and replacing and unsubstituted (C ₃To C ₈) the cyclic aliphatic part, be expressed as follows formula:

Wherein a is 2 to 7 integer, works as R ^qWhen existing, represent (the C of line style and branching ₁To C ₁₀) alkyl.Preferred divalence cycloalkylidene comprises cyclopentylene and cyclohexylidene part, is expressed as follows structure:

R wherein ^qAs above definition.By diagram and technical descriptioon herein, be appreciated that the key of drawing represents the divalence neutral fraction from ring structure and/or formula, and express the position that defined adjacent molecule partly links to each other in ring carbon atom and each formula.In the technology routine, the taper key of being drawn by the ring structure center is represented the arbitrary ring carbon atom on any abutment ring of this key.Also can be understood as on the ring carbon atom that is connected with this key no more than one of hydrogen atom, to satisfy the price of carbon.

Preferred divalence cyclic ethers and diether are expressed as follows structure:

Divalence contains the oxygen base and comprises (C ₂To C ₁₀) alkylene ether and polyethers.(C ₂To C ₁₀) alkylidene be meant the total number of carbon atoms of divalence ether molecular moiety minimum be 2, but be no more than 10.Divalent alkyl ether represent suc as formula-alkylidene-O-alkylidene-, wherein each alkylidene that connects with oxygen atom can be identical also can be different, and be selected from methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji and inferior nonyl.The simplest divalent alkyl ether is-CH in the series ₂-O-CH ₂-.Preferred polyether moiety comprises the bivalent radical of following formula:

 CH ₂(CH ₂) _xO _YWherein x is 0 to 5 integer, and y is 2 to 50 integer, and collateral condition is that the oxygen atom end on the polyethers compartment can not be directly links to each other with terminal oxygen atom on the adjacent group and forms peroxidating and link.Just, connect above-mentioned R when polyethers is basic at interval ⁵To R ⁸During described arbitrary terminal oxygen-containing substituents, can not be the peroxidating link (promptly-O-O-).

R ⁵To R ⁸Also can represent hydrogen independently, line style and branching (C ₁To C ₁₀) alkyl, as long as the R of at least a reservation ⁵To R ⁸Substituting group is selected from one of the neutrality of above-mentioned representative or polar group.P is 0 to 5 integer (preferred 0 or 1, more preferably 0) in following formula.R " represent hydrogen, line style and branching (C independently ₁To C ₁₀) alkyl, line style and branching (C ₁To C ₁₀) the alkoxy alkylidene, polyethers, monocycle and many ring (C ₄To C ₂₀) alicyclic moiety, cyclic ethers, cyclic ketones and cyclic ester (lactone).(C ₁To C ₁₀) the alkoxy alkylidene is meant that end alkyl is connected with alkylene moiety by ether oxygen atom.This group is a kind of generally can being expressed as-alkylidene-O-alkyl hydrocarbon ether moiety, and wherein alkylidene and alkyl contain 1 to 10 carbon atom respectively, and are line style or branching.Polyether-based can represent suc as formula:

 CH ₂(CH ₂) _xO _YR ^aWherein x is 0 to 5 integer, and y is 2 to 50 integer, and R ^aRepresent (the C of hydrogen or line style and branching ₁To C ₁₀) alkyl.Preferred polyether-based comprises poly-(oxirane) and poly-(epoxypropane).The example of monocycle alicyclic ring monocycle part comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or the like.The example of the many loop sections of alicyclic ring comprises norbornene, adamantyl, tetrahydrochysene dicyclopentadienyl (three ring [5.2.1.0 ^2.6] decyl) or the like.The example of cyclic ethers comprises tetrahydrofuran base and oxinane base section.The example of cyclic ketones is a 3-oxygen hexamethylene ketone group.The example of cyclic ethers or lactone is the mevalonolactone part.

With regard to the R that describes among the formula II " R that describes among substituting group and the formula I ^*Acid labile group or protecting group scope are overlapping, are appreciated that the R among the formula II " can not represent the ester moiety that contains acid labile group.For example, work as R " be norbornene, adamantyl, tetrahydrochysene dicyclopentadienyl (three ring [5.2.1.0 ^2.6] decyl), tetrahydrofuran base, THP trtrahydropyranyl, when 3-oxygen hexamethylene ketone group or mevalonolactone part, R " can not be directly link to each other with oxygen atom in the ester moiety (C (O) O).

Preferred neutrality or polar substituent comprise alkyl carboxylates, contain oxalate at interval part (as-(A) _n-OC (O)-A '-C (O) OR ") and contain oxalate part (as-(A) _n-OC (O) C (O) OR "), wherein the formula definition is as mentioned above.Ester, oxalate at interval and contain the functional group of oxalate and obtain excellent water wettability promotes good wetting of developer and the physical property of promoting film, does not contain the negative interaction that too much carboxylic acid functional produces and do not have.

The 3rd optional monomer component is expressed as follows the structure of formula III:

R wherein ⁹To R ¹²Represent carboxylic acid or sulfonic acid substituting group or common salt independently, be selected from formula-(CH ₂) _nC (O) OH ,-(CH ₂) _nSO ₃H ,-(CH ₂) _nC (O) O ^-X ⁺,-(CH ₂) _nSO ₃ ^-X ⁺, wherein X represents tetraalkyl ammonium kation, and the alkyl substituent that is connected on the nitrogen-atoms is independently selected from line style and branching (C ₁To C ₁₀) alkyl, q is that 0 to 5 integer (preferred 0 or 1, more preferably 0) and n are 0 to 10 integers (preferred 0).R ⁹To R ¹²Can represent hydrogen independently, line style and branching (C ₁To C ₁₀) alkyl, as long as the R that keeps ⁹To R ¹²At least a one of above-mentioned acid or hydrochlorate of being selected from of substituting group.

Contain the water wettability that the carboxylic acid functional monomer can constantly keep polymkeric substance, make polymkeric substance in water-based system, have the development capability of two-forty.

The optional monomer suc as formula IV is expressed as follows structure:

R wherein ¹³To R ¹⁶Represent line style or branching (C independently ₁To C ₁₀) alkyl, r is 0 to 5 integer (preferred 0 or 1, more preferably 0).Any R ¹³To R ¹⁶Can represent hydrogen, the R of reservation ¹³To R ¹⁶One of at least be selected from the alkyl of above-mentioned definition in the substituting group.In the abovementioned alkyl substituting group, preferred especially decyl.

Can be with the polyreaction of alkyl substituted monomer on the main polymer chain a kind of method as the glass transition temperature of control polymkeric substance, referring to United States Patent (USP) the 5th, 468, No. 819 (Goodall et al.).

A kind of economic route for preparing the polycyclic monomer of functional group of the present invention replacement or alkyl replacement relates to diels-alder reaction, wherein cyclopentadiene (CPD) or substituted-cyclopentadienyl and suitable replacement dienophile at high temperature react, form to replace to encircle adducts, general course of reaction is as follows more:

Other many ring adducts can pass through the thermal cracking preparation of bicyclopentadiene (DCPD) in the presence of suitable dienophile.This course of reaction is to obtain CPD by the DCPD thermal cracking earlier, and the Di Ersi-A Deer addition reaction that carries out CPD and dienophile then obtains adduct, and process is shown below:

Wherein R ' is to R " " represent as above-mentioned formula I II, III, the R among the IV independently ¹To R ¹⁶The substituting group of definition.

For example 2-norborene-5-carboxylic acid (dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid) can prepare according to following reaction equation by cyclopentadiene and acrylic acid diels-alder reaction:

The corresponding carboxylic acid tertiary butyl ester can be descended prepared in reaction according to following reaction equation low temperature (as-30 to-20 ℃) by carboxylic acid functional and isobutylene in the presence of triflic acid:

The route of another preferred preparation norborene carboxylic acid tertiary butyl ester comprises the diels-alder reaction of cyclopentadiene and tert-butyl acrylate.

The route of the monomer that another synthetic the present invention acid and ester replace is that the polycyclic monomer by the ortho esters replacement is hydrolyzed to carboxylic acid functional in succession or partial hydrolysis is the functional group of ester.The ester that carboxylic acid functional can esterifiedly obtain wishing.The monomer that ortho esters of the present invention replaces is expressed as follows formula V:

R wherein ¹⁷, R ¹⁸And R ¹⁹Represent line style or branching (C independently ₁To C ₅) alkyl, perhaps any R ¹⁷, R ¹⁸And R ¹⁹Combine with oxygen, form replacement or unsubstituted 5 to 10 Yuans dicyclos that encircle or contain 3 to 8 carbon atoms (not comprising substituting group), s is 0 to 5 integer (preferred 0), and t is 1 to 5 integer (preferred 1).S is 0 in typical structure, and t is 1, R ¹⁷, R ¹⁸And R ¹⁹With oxygen combine form ring or dicyclo as shown in the formula:

R wherein ¹⁷, R ¹⁸And R ¹⁹Represent hydrogen and line style and branching (C independently ₁To C ₅) alkyl.Ortho esters of the present invention can synthesize (A.Pinner, chemistry report (Chem.Ber.), 16 according to so-called Pinner synthetic method, 1643, (1883), technological process is seen S.M.McElvain and J.T.Veneralbe, JACS (J.Am.Chem.Soc.) 72.1661 (1950); SM.McElvain and C.L.Aldridge, JACS (J.Am.Chem.Soc.), 75,3987 (1953)) typical synthetic as following reaction equation:

Select in the synthetic route at another, alkyl acrylate is handled the back with tetrafluoro boric acid trialkyl oxonium salt and is handled with alkaline metal (sodium alcoholate), obtain tri-alkoxy methyl ortho esters (H.Meerwein, P.Borner, O.Fuchs, H.J.Sasse, H.Schrodt, and J.Spille, chemistry report (Chem.Ber.), 89,2060 (1956)).

Above-mentioned ortho esters can be hydrolyzed to react in the presence of the diluted acid catalyzer and obtain carboxylic acid, acid catalyst such as hydrobromic acid, hydroiodic acid and acetic acid.Carboxylic acid can be successively in the presence of fatty alcohol and acid catalyst esterification obtain different esters.Can see that if polycyclic monomer is under ortho acid ester group two or the polysubstituted situation, ortho esters part can partial hydrolysis, obtains acid and traditional ester on same monomer, react as shown in the formula:

The route of another preferred preparation two functionality polycyclic monomers is to be undertaken by the hydrolysis and the partial hydrolysis of carbic anhydride (interior-5-norborene-2, the 3-dicarboxylic anhydride).Carbic anhydride can all be hydrolyzed into dicarboxylic acid or partial hydrolysis becomes acid and ester functional group or diester functional group, as shown in the formula:

R wherein ¹⁷Represent line style and branching (C independently ₁To C ₅) alkyl.Preferred R ¹⁷Be methyl, the ethyl or the tert-butyl group.In a kind of preferred synthesis technique, the starting material of carbic anhydride is outer isomeride.Outer isomeride is easy to by at 190 ℃ internal (position) isomer being heated, recrystallization preparation in appropriate solvent (toluene) again.In order in course of reaction 1, to obtain diacid, only need carbic anhydride hydrolysis in boiling water can be obtained the almost diacid product of quantitative yield.Mixed carboxylic acid-Arrcostab the functional group that is shown in flow process 3 can pass through at suitable fatty alcohol (R ¹⁷OH) exist down, the heating carbic anhydride refluxes and obtained in 3 to 4 hours.In another selection scheme, same product can be used watery hydrochloric acid (HCl) Processing of Preparation again by earlier with carbic anhydride starting material and fatty alcohol and trialkylamine reaction.By identical alkyl R ¹⁷The diester product that replaces can be by diacid by diacid and tetrafluoro boric acid trialkyl oxygen such as R ¹⁷ ₃O[BF ₄], in methylene chloride, in the presence of diisopropylethylamine, in room temperature, react.In order to obtain having the R of being different from ¹⁷The ester of alkyl uses acid mixture one ester products that obtains in the flow process 3 to make starting material.In this embodiment, acidic group is pressed reaction process 2 esterifications.Yet, tetrafluoro boric acid trialkyl oxygen have with used ester functional group on the different alkyl of alkyl.

Can notice that the above-mentioned monomer that contains precursor functional group can change into desired functional groups before polymerization, perhaps monomer can first polymerization, and each polymkeric substance that contains the precursor sense substituent can obtain desired functional groups by late phase reaction again.

Can expect within the scope of the present invention, in the monomer that formula I to V describes, m, p, q, r and s are 0, the methylene bridge unit can be replaced by oxygen, obtains 7-oxygen norbornene derivative.

Also can be expected under the 248nm wavelength condition and use, above-mentioned formula II, III, the R among the IV ⁵To R ¹⁶And R ¹¹Can be aromatics as phenyl.

Polymkeric substance

Unstable polycyclic monomers that replace of one or more acid that formula I describes copolymerization or combine copolymerization separately with one or more polycyclic monomers that formula II describes, optional and III, one or more polycyclic monomers of IV and V description are in conjunction with copolymerization.Can expect that also formula I can form the alternating copolymer of many rings and carbon monoxide with CO-copolymerization to the polycyclic monomer of formula V.The norbornene copolymer that contains carboxylic acid side group and carbon monoxide is at United States Patent (USP) the 4th, 960, description arranged in No. 857, and it openly is incorporated herein for referencial use.Formula I to the monomer of formula V and carbon monoxide can copolymerization in the presence of the palladium-containing catalyst system, referring to chemistry comment (Chem.Rev.) 1996,96,663-681.Those skilled in the art are readily appreciated that many ring/carbon monoxide alternating copolymers both can be that keto-acid also can be a spiral ketal isomeride.Therefore, the present invention expection by the multipolymer that contains random repetitive of a kind of monomer of formula I and formula II representative or multiple monomer derived (polymerization) can be arbitrarily with combine to the monomer that formula V represents by formula II.In addition, the alternating copolymer of the present invention expection contains by carbon monoxide with by formula I and forms to the monomer derived (polymerization) of formula V representative.

The carboxylic-acid functional side group is for making the main polymer chain possess hydrophilic property, and cohesive and pure dissolubility (development) are very important.Yet, in the application of some photoresists, do not wish that polymkeric substance has too much carboxylic acid functional.These polymkeric substance can not be in the developer of industrial standard applications well (the 0.26N tetramethyl ammonium hydroxide, TMAH).The unexposed portion swelling polymer, can not control thickness and polymkeric substance swelling in exposure solution in application is the intrinsic shortcomings of these peracidity polymkeric substance.Therefore, do not wishing that excess carboxylic acid functional group exists but when essential possess hydrophilic property and good soakage, be preferred with the multipolymer that formula II monomer necessity combines polymerization by formula I monomer.Particularly preferred formula II monomer contains Arrcostab, alkyl carbonate at interval the oxalic acid Arrcostab and oxalic acid Arrcostab substituting group as-(A) _nC (O) OR " ,-(A) _n-OC (O) OR " ,-(A) _n-OC (O)-A '-C (O) OR " and-(A) _n-OC (O) C (O) OR ", A wherein, A ', n and R " as mentioned above.

Polymkeric substance of the present invention is the key component of composition.Polymkeric substance generally contains the monomer that contains the acid labile group component (repetitive) of about 5 to 100% (moles).Preferred polymkeric substance contains about 20 to 90% (moles) and contains the acid-unstable group monomer.More preferably polymkeric substance contains the monomeric unit that about 30 to 70% (moles) contain sour unstable functional group.The remainder of polymer composition is made up of the optional repetitive that monomer polymerization to formula V becomes from above-mentioned formula III.Select to be used in concrete monomeric species and consumption in the polymkeric substance according to the performance wanted.For example,, can change the dissolubility of polymkeric substance, developer solution is regulated as required by changing the content of the carboxylic acid functional in the main polymer chain.Can change and contain the ester monomer with the mechanical property that strengthens polymkeric substance and system susceptibility to radiation.At last, the glass transition temperature of polymkeric substance can be by combining adjusted with the ring-type repetitive that contains chain alkyl such as decyl etc.

There are several the routes can the polymerized cycloolefins monomer such as norborene and contain senior ring-type (many rings) monomer of norborene part.These routes comprise: (1) open loop metathesis polymerizable (ROMP); (2) hydrogenation after the ROMP polymerization; (3) polyaddition reaction.Every kind of above-mentioned path of preparing has the concrete structure polymkeric substance, represents as process 1:

Process 1

The ROMP polymkeric substance is different with the structure of addition polymer.The ROMP polymkeric substance contains the repetitive compared with the few ring element of beginning monomer.Repetitive as mentioned above in unsaturated main chain key connect together.Owing to have a unsaturation, this polymkeric substance is answered hydrogenation subsequently and is made main chain have stability to oxygen.On the other hand, although addition polymer is made by identical monomer, in main polymer chain, there is not the C=C unsaturated link.

Monomer of the present invention can preferably carry out afterwards hydrogenation by polyaddition reaction with by open loop metathesis polymerizable reaction (ROMP) polymerization.Cyclopolymer of the present invention is represented by following structure:

Wherein R ' is to R " " R that defines to the formula V of representative as above-mentioned formula I independently ¹To R ¹⁹, m is 0 to 5 integer, and the number of repeat unit in the representation polymer main chain.

ROMP polymkeric substance among the present invention is polymerization in the presence of the catalyzer in the displacement ring-opening polymerization in appropriate solvent.The polymerization of ROMP polymerization and the hydrogenation of follow-up gained ring-opening polymerization polymer is disclosed in United States Patent (USP) the 5th, 053, No. 471 and 5,202, No. 388, is incorporated herein for reference.

In the embodiment of a ROMP, polycyclic monomer of the present invention is to carry out polyreaction in the presence of one-component ruthenium or osmium metal carbene composition catalyst, and catalyzer is referring to WO95-US9655.Monomer compares at about 100: 1 to about 2000: 1 preferably approximately 500: 1 with catalyst system therefor.Reaction can be at halogenated hydrocarbon solvent such as ethylene dichloride, and methylene chloride carries out in chlorobenzene etc. or varsol such as the toluene.Used quantity of solvent will be enough to obtain the solid constituent that relative solvent is about 5 to 40% (weight) in the reaction medium, preferably obtains the solid of 6 to 25% (weight).Reaction can be carried out at about 0 ℃ to about 60 ℃, preferably at about 20 ℃ to 50 ℃.

A kind of preferred metal carbene catalysts is two (tricyclohexyl phosphine) benzal rutheniums.Wondrous and found that advantageously this catalyzer can obtain saturated substantially ROMP polymkeric substance as the start catalysts of ROMP reaction and as a kind of effective hydrogenation catalyst.Do not need to use other additional hydrogenation catalyst.According to this initial ROMP reaction, the whole requirements that need impact polymer main chain hydrogenation are exactly still to be lower than about 220 ℃ about more than 100 ℃ by temperature, and preferred temperature keeps the pressure of hydrogen on the reaction medium at about 150 ℃ to about 200 ℃.

Addition polymer of the present invention can be by standard free radical solution polymerization reactive mode preparation well known by persons skilled in the art.Formula I to the monomer of formula V can be in homopolymerization in the presence of the maleic anhydride or copolymerization.The Raolical polymerizable technology sees " polymer science encyclopedia ", John Wiley ﹠amp; Sons, 13,708 (1988).

Alternative preferred version is monomer of the present invention polymerization in the presence of list that comprises VIII family metal ion source (preferred palladium or nickel) or multicomponent catalyst system.Found that surprisingly the addition polymer for preparing thus has the excellent transparency of deep ultraviolet (193nm) and shows excellent anti-reactive ion etching.

The preferred polymkeric substance of the present invention is polymerized by reaction mixture, and this potpourri comprises at least a polycyclic monomer that is selected from formula I and formula II, a kind of solvent, a kind of catalyst system and optional chain-transferring agent that contains VIII family metal ion source.Catalyst system can be ready-made one-component VIII family's metal-based catalyst or many components VIII family metallic catalyst.

The single-component catalyst system

In one embodiment, single-component catalyst system of the present invention comprises VIII family metal cation complex and slightly co-ordinating counter negative ion, is expressed as follows formula:

Wherein L representative contains 1,2 or the ligand of 3JI-key; M represents the VIII group 4 transition metal; The X representative contains the ligand of 1 σ-key and 0 to 3JI-key; Y is 0,1, or 2 and z be 0 or 1, wherein y and z can not be 0 simultaneously, when y was 0, a was 2, when y was 1, a was 1; And CA is the slightly co-ordinating counter negative ion.

Phrase " slightly co-ordinating counter negative ion " thus only mean and faintly leave the instable negative ion of enough being replaced by neutral Lewis base with the kation coordination.More specifically, thus this phrase means to rise to stablize in catalyst system of the present invention anionicly to be done the time spent and anion substituent or its fragment not to be converted to the negative ion that kation forms neutral products.Described counter anion is not oxidation, do not reduce, not nucleophilic and relative inertness.

L be with described VIII family metal cation complex a little less than the neutral ligand of coordination.In other words, this ligand relative inertness, easily the insertion monomer in the polymer chain that is increased is replaced from described metal cation complex.π-key the ligand that contains that is suitable for comprises (C ₂-C ₁₂) mono-olefin (for example 2,3-dimethyl-2-butylene), diolefin (C ₄-C ₁₂) (for example norbornadiene) and (C ₆-C ₂₀) aromatic portion.Preferably, ligand L is two ring gear (C of chelating ₆-C ₁₂) diene, for example cyclo-octadiene (COD) or dibenzo cyclo-octadiene, or aromatic such as benzene, toluene or 1,3,5-trimethylbenzene.

VIII family metal M is selected from group VIII metal in the periodic table of elements.Preferred L is selected from nickel, palladium, cobalt, platinum, iron and ruthenium.Most preferred metal is nickel and palladium.

Ligand X is selected from the part that (i) provides the part of single metal-carbon σ-key (no π-key) for the metal in the cationic complexes or single metal-carbon σ-key and 1 to 3 π-key (ii) are provided for the metal in the cationic complexes.(i) part does not have π-key and VIII family metal binding by single metal-carbon σ-key in force.Comprise (C in the undefined representative ligand of this embodiment ₁-C ₁₀) moieties, be selected from part such as propyl group, butyl, amyl group, neopentyl, hexyl, heptyl, octyl group, nonyl and decyl and the (C of methyl, ethyl, linearity and side chain ₇-C ₁₅) aralkyl such as benzyl.(ii) generally as defined above, described kation has by single metal-carbon σ-key, also by at least 1 but the alkyl that no more than 3 π-keys and direct bonded metal close in this embodiment.This alkyl means and can stablize the group of VIII family metal cation complex by metal-carbon σ-key and 1 to 3 alkene π-key (can be conjugation or unconjugated) are provided.Representational alkyl is (C ₃-C ₂₀) alkenyl, it can be acyclic, monocycle or polycyclic, and can be by (the C of linear and side chain ₁-C ₂₀) alkoxy, (C ₆-C ₁₅) aryloxy group or halogen (as Cl and F) replacement.

Preferred X is monoene propyl group ligand or its canonical form, and it provides σ-key and π-key; Or with this metal form at least one olefinic π-key, by with each olefinic carbon atom at interval the distally carbon atom of at least two carbon-to-carbon singly-bounds and the compound that this metal forms a σ-key (embodiment iii).

Those skilled in the art are apparent: when there be not (being that y or z are zero) in ligand L or X, used solvent will make described metal cation complex form weak complex in reacting.Representational solvent includes but not limited to halogenated hydrocarbons such as phenixin, chloroform, methylene chloride, 1,2-ethylene dichloride and aromatic solvent such as benzene, toluene, 1,3,5-trimethylbenzene, chlorobenzene and nitrobenzene etc.The back will be discussed suitable solvent in more detail.

The selected embodiment of the VIII family metal cation complex of single component catalyst system of the present invention is shown in hereinafter.

Structure VII illustrates embodiment (i), and wherein ligand X is the COD by two alkene π-keys and the weak coordination of palladium metal for methyl and ligand L by single metal-carbon σ-key and metallic bonding.In following structure, M preferably represents palladium or nickel.

Structure VIII, IX and X explanation embodiment various examples (ii), wherein X is for by single metal-carbon σ-key and at least one but the allyl of no more than three π-keys and metal (shown in palladium only be used for illustrating) bonding.

In structure VIII, there is not L, but the aryl and the weak coordination of palladium metal of three π-keys are provided; X is the allyl that forms single metal-carbon σ-key and olefinic π-key with palladium.

In structure I X, L is COD, and X is the allyl that forms a metal-carbon σ-key and an olefinic π-key with palladium.

Structure X illustrates a kind of embodiment, and wherein ligand X is the unsaturated alkyl that forms metal-carbon σ-key, a conjugated pi-key and two other π-keys with palladium; L does not exist. Substituent R ²⁰, R ²¹, R ²²To describe in detail in the back.

Structure XI and XII explanation embodiment example (iii), wherein L be COD and X for VIII family metal form at least one olefinic π-key and by with each olefinic carbon atom the distally carbon atom of at least two carbon-to-carbon singly-bounds and the ligand that this metal forms a σ-key at interval.

Above-mentioned VIII family cationic complexes relates to the counter anion CA of weak coordination or non-coordination ^-, it is relative inertness, nucleophilic not, and is formed on the cationic complexes that is necessary solubleness in the reaction dissolvent.The key of suitable anion design is its mutability of requirement, and in final catalyst material for kation VIII family metal complex reaction be stable and inertia, and require it to make described single component catalyst dissolve in solvent of the present invention.For with water or Bronsted acid reaction be stable and the negative ion (promptly not with the anionic complex of strong acid or alkali reaction) that is not arranged in the acid proton of negative ion outside has and qualifiedly stablizes the required stability of negative ion as this catalyst system.For maximum instability is that important negative ion performance comprises overall dimensions, shape (being larger radius of curvature) and nucleophilicity.

Usually, the negative ion of Shi Yonging can be any stable negative ion that makes catalyzer be dissolvable in water in the selected solvent and following characteristic is arranged: (1) this negative ion should form stable salt with above-mentioned lewis acid, Bronsted acid, reducible lewis acid, protonated Lewis base, thallium and silver-colored kation; (2) negative charge on this negative ion should not be positioned on the anionic skeleton or be positioned at anionic in-core; (3) this anionic nucleophilicity is relatively poor relatively; (4) this negative ion should not be strong reduction or oxygenant.

The negative ion that satisfies above-mentioned restriction can be selected from the tetrafluoride negative ion of Ga, Al or B; The hexafluoride negative ion of P, Sb or As; Perfluor-acetate, propionate and butyric acid root, the perchloric acid hydrate root; Tosylate and trifluoromethane sulfonic acid root; With the tetraphenylboron acid group that replaces, wherein phenyl ring is partly replaced by fluorine or trifluoromethyl.The example of selected counter anion comprises BF ₄ ^-, PF ₆ ^-, AlF ₃O ₃SCF ₃ ^-, SbF ₆ ^-, SbF ₅SO ₃F ^-, AsF ₆ ^-, trifluoroacetic acid root (CF ₃CO ₂ ^-), five fluorine propionate (C ₂F ₅CO ₂ ^-), hyptafluorobutyric acid root (CF ₃CF ₂CF ₂CO ₂ ^-), perchlorate (ClO ₄ ^-H ₂O), p-toluenesulfonic acid root (p-CH ₃C ₆H ₄SO ₃ ^-) and the tetraphenylboron acid group of following formula representative: R wherein " _nRepresenting hydrogen, fluorine and trifluoromethyl and n independently is 1 to 5.

Following formula is represented preferred single component catalyst in the above-mentioned embodiment:

This catalyzer comprise with counter anion a little less than the π-allyl VIII family metal complex of coordination.The allyl of this metal cation complex is provided by the compound that contains allyl functionality, and this functional group is by single carbon-metal σ-key and olefinic π-key and M bonding.VIII family metal M is preferably selected from nickel and palladium, most preferably palladium.Unexpectedly, found that M wherein is that the ligand of not having of palladium and cationic complexes (is L except that described allyl functionality _y=0) these single component catalysts show advantages of high activity to the polymerization that contains silyl group monomer among sense polycyclic monomer such as the present invention.As mentioned above, will understand reaction diluent and make these catalyzer solvations, can think that thinning agent is the very weak ligand of VIII family metal in the cationic complexes.

Substituent R on the allyl that proposes among top structure VIII, IX and the XIII ²⁰, R ²¹And R ²²Be hydrogen independently, side chain or unbranched (C ₁-C ₅) alkyl such as methyl, ethyl, n-pro-pyl, isopropyl and the tert-butyl group, (C ₆-C ₁₄) aryl such as phenyl and naphthyl, (C ₇-C ₁₀) aralkyl such as benzyl ,-COOR ¹⁶,-(CH ₂) _nOR ¹⁶, Cl and (C ₅-C ₆) cycloaliphatic radical, wherein R ¹⁶Be (C ₁-C ₅) alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl and isobutyl and n be 1 to 5.

Alternatively, R ²⁰, R ²¹And R ²²In any two can be bonded together and form ring or multiring structures.This ring structure can be carbocyclic ring or heterocycle.Preferred R ²⁰, R ²¹And R ²²In any two connect together by carbon atom and to form the ring of 5 to 20 atoms.Representational heteroatoms comprises nitrogen, sulphur and carbonyl.The illustrative example that the cyclic group of allyl functionality is arranged is following structure: R wherein ²³(C for hydrogen, linearity or side chain ₁-C ₅) alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl and amyl group, R ²⁴Be the methyl carbonyl, and R ²⁵(C for linearity or side chain ₁-C ₂₀) alkyl.Counter anion CA ^-As defined above.

Other example of π-allyl metal complex is seen R.G.Guy and B.L.Shaw, inorganic chemistry and radiochemistry progress (Advances in Inorganic Chemistry andRadiochemistry), 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, organometallic chemistry progress (Advances in OrganometallicChemistry), Vol.2, Academic Press Inc., New York, 1964; W.T.Dent, R.Long and A.J.Wilkinson, chemistry meeting will (J.Chem.Soc.), (1964) 1585; And H.C.Volger, " Dutch chemical paper collection (Rec.Trav.Chim.) " Pay Bas, 88 (1969) 225; These documents are all introduced for reference.

The single component catalyst of above-mentioned embodiment can prepare like this: make into the halogenation VIII family metal component of complex and the salt chemical combination that counter anion is provided for the metal cation complex that forms subsequently.Become complex halogenation VIII family metal component, the salt of counter anion is provided and optionally contains component (as COD) chemical combination in the solvent of the single component catalyst solvate that can make formation of π-key.Solvent for use is preferably identical with the selected solvent of reaction medium.This catalyzer can form in solvent in advance, perhaps can form on the spot in reaction medium.

The salt that counter anion is provided that is suitable for is any salt that above-mentioned counter anion can be provided.For example, sodium, lithium, potassium, silver, thallium and ammonia salt, wherein negative ion is selected from previously defined counter anion (CA ^-).Provide the illustrative example of the salt of counter anion to comprise TlPF ₆, AgPF ₆, AgSbF ₆, LiBF ₄, NH ₄PF ₆, KAsF ₆, AgC ₂F ₅CO ₂, AgBF ₄, AgCF ₃CO ₂, AgClO ₄H ₂O, AgAsF ₆, AgCF ₃CF ₂CF ₂CO ₂, AgC ₂F ₅CO ₂, (C ₄H ₉) ₄NB (C ₆F ₅) ₄With

Concrete catalyzer [allyl-Pd-COD] ⁺PF ₆ ^-So pre-formation: at first form the halogenation palladium component of complex, promptly two (the bromination allyl closes palladium) is then with the salt that counter anion is provided-be TlPF ₆The halogenide extraction agent of form makes it cracking in the presence of COD.Response hierarchy is as follows: During division, only stay next COD ligand, it is by two π-keys and palladium bonding.Allyl functionality is by metal-carbon σ-key and π-key and palladium bonding.

Be the preferred π-allyl VIII family metal/counter anion single component catalyst for preparing top structure XIII representative, when M is palladium, make chlorination Allylpalladium and desired salt (silver salt of preferred counter anion) chemical combination in the solvent that is fit to that counter anion is provided.The chlorion ligand leaches from solution as silver chloride (AgCl) precipitation and breaks away from the Allylpalladium complex.Allylpalladium cationic complexes/counter anion single component catalyst is stayed in the solution.This palladium metal is no any ligand except that described allyl functionality.

Be used for a kind of selective single-component catalyst of the present invention and be expressed as follows formula:

Pd[R ²⁷CN] ₄[CA ^-] ₂R wherein ²⁷Represent (the C of line style and branching independently ₁To C ₁₀) alkyl, and CA ^-It is the counter anion of above-mentioned definition.

The another kind of single-component catalyst system that is used to prepare the used polymkeric substance of the present invention represent as shown in the formula:

E _nNi (C ₆F ₅) ₂Wherein n is 1 or 2, and E represents neutral 2 electronation ligands.When n is 1, the preferred π of E-aromatic hydrocarbons ligand such as toluene, benzene and 1,3,5-trimethylbenzene.When n was 2, E was preferably selected from diethyl ether, and (THF) is with diox for tetrahydrofuran.The ratio of monomer and catalyzer was at about 2000: 1 to about 100: 1 in the reaction medium.Reaction can be as cyclohexane, and in the varsols such as toluene, at about 0 ℃ to about 70 ℃, preferred 10 ℃ to about 50 ℃, more preferably about 20 ℃ are carried out to about 40 ℃ of temperature.Preferred catalyzer is (toluene) two (perfluorophenyl) nickel in the following formula, (1,3, the 5-trimethylbenzene) two (perfluorophenyl) nickel, (benzene) two (perfluorophenyl) nickel, two (tetrahydrofurans) two (perfluorophenyl) nickel and two (diox) two (perfluorophenyl) nickel.

Multi-component catalyst systems

The embodiment of multi-component catalyst systems of the present invention comprises VIII family metal ion source, in organic promoter and the 3rd component one or both of.Promotor is selected from organo-aluminum compound, dialkyl aluminum hydride, dialkyl zinc compounds, dialkyl magnesium compound and alkyl lithium compounds.

VIII family metal ion source is preferably selected from nickeliferous, palladium, cobalt, the compound of iron and ruthenium, most preferably nickeliferous and palladium compound.For containing VIII family metallic compound without limits, as long as it provides the VIII family metal ion source of catalytic activity.Preferably, this VIII family metallic compound is dissolved in reaction medium, maybe can make it to be dissolved in reaction medium.

VIII family metallic compound comprises ion and/or the neutral ligand with VIII family metallic bonding.Ion and neutral ligand can be selected from various monodentates, bidentate or multiple tooth part and combination thereof.

The representative example that can form the ionic ligand of VIII family metallic compound with metallic bonding is an anion ligand, is selected from halogen ion such as chlorine, bromine, iodine or fluorine ion; Intend halogen ion such as cryanide ion, cyanate radical, thiocyanate radical, hydride ion; Carbanion such as side chain and unbranched (C ₁-C ₄₀) alkyl negative ion, phenyl negative ion; Cyclopentadienyl anion; π-allylic; The enolate of beta-dicarbonyl compound such as diacetone negative ion, (4-glutarate), 2,2,6,6-tetramethyl-3,5-heptadione and halo diacetone negative ion be as 1,1, and 1,5,5,5-hexafluoro-2,4-glutarate, 1,1,1-three fluoro-2,4-glutarate; The negative ion of the acidic oxide of carbon such as carboxylate radical and halogenated carboxylic acid root are (as acetate, the 2 ethyl hexanoic acid root, the neodecanoic acid root, trifluoroacetic acid root etc.) and the nitrogen oxides negative ion (as nitrate radical, nitrite anions etc.), the oxide negative ion of bismuth (as bismuthic acid root etc.), the oxide negative ion of aluminium (as aluminate etc.), the oxide negative ion of silicon (as silicate etc.), the oxide negative ion of phosphorus is (as phosphate radical, orthophosphite, phosphine etc.), the sulfur oxide negative ion is (as sulfate radical such as triflate, the p-toluenesulfonic acid root, inferior sulfate radical etc.); Inner salt; Acid amides; Acid imide; Oxide; Phosphide; Sulfide; (C ₆-C ₂₄) aryl oxide, (C ₁-C ₂₀) alkoxide, oxyhydroxide, hydroxyl (C ₁-C ₂₀) alkyl; Catechol; Oxalate; Chelating alkoxide and aryl oxide.Palladium compound also can contain complex anion such as PF ₆ ^-, AlF ₃O ₃SCF ₃ ^-, SbF ₆ ^-Compound with the following formula representative:

Al (R ) ^- ₄, B (X) ^- ₄Wherein R and X represent the halogen atom that is selected from Cl, F, I and Br independently, or replacement or unsubstituted alkyl.The representative example of alkyl is (C ₁-C ₂₅) alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl and isomeric form thereof; (C ₂-C ₂₅) alkenyl such as vinyl, allyl, crotyl, butenyl group, pentenyl, hexenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic, tridecylene base, tetradecene base, 15 carbene bases, cetene base, heptadecene base, vaccenic acid base, 19 carbene bases, ppentacosene base and isomeric form thereof.(C ₆-C ₂₅) aryl such as phenyl, tolyl, xylyl, naphthyl etc.; (C ₇-C ₂₅) aralkyl such as benzyl, phenethyl, phenylpropyl, benzene butyl, benzene hexyl, naphthalene octyl group etc.; (C ₃-C ₈) naphthenic base such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, 2-norborny, 2-norbornene etc.Except that above definition, the following base of X representative:

The term substituted hydrocarbon radical means alkyl as defined above, and wherein one or more hydrogen is by halogen atom such as Cl, F, Br and I (for example in perfluorophenyl); Hydroxyl; Amino; Alkyl; Nitro; Replacements such as sulfydryl.

VIII family metallic compound also can contain organic ammonium, organo-arsenic, organophosphorus and the pyridine compounds of kation as shown in the formula representative:

Wherein A represents nitrogen, arsenic and phosphorus, and R ²⁸Base can be independently selected from hydrogen, side chain or unbranched (C ₁-C ₂₀) alkyl, side chain or unbranched (C ₂-C ₂₀) alkenyl and (C ₅-C ₁₆) naphthenic base, as cyclopentyl, cyclohexyl, suberyl, ring octyl group etc.R ²⁹And R ³⁰Be independently selected from hydrogen, side chain and unbranched (C ₁-C ₅₀) (the C of alkyl, line style and side chain ₂-C ₅₀) alkenyl and (C ₅-C ₁₆) naphthenic base, as defined above; With n be 1 to 5, preferred n is 1,2 or 3, most preferably n is 1.R ³⁰Base preferably is connected in 3,4 and 5 of pyridine ring.

It should be noted that increases R ²⁸The summation of institute's carbon atoms can make the solubleness of transistion metal compound in organic media such as organic solvent and polycyclic monomer higher in the base.Preferably, R ²⁸Base is selected from (C ₁-C ₁₈) alkyl, wherein all R ²⁸The carbon number summation of base is 15 to 72, and is preferred 25 to 48, more preferably 21 to 42.R ²¹Base is preferably selected from line style and side chain (C ₁-C ₅₀) alkyl, more preferably (C ₁₀-C ₄₀) alkyl.R ³⁰Be preferably selected from (the C of line style and side chain ₁-C ₄₀) alkyl, more preferably (C ₂-C ₃₀) alkyl.

The cationic object lesson of organic ammonium comprises three (dodecyl) ammonium ion, methyl trioctylammonium ion, three (tridecyl) ammonium ions and trioctylammonium ion.The cationic object lesson of organo-arsenic and organophosphorus comprise three (dodecyl) Zhong with Phosphonium, Jia base San Xin Ji Arsonium He Phosphonium, three (tridecyl) Zhong He Phosphonium and trioctylphosphine Zhong with Phosphonium.Concrete pyridylium comprises eicosyl-4-(1-butyl phenyl) pyridine, docosyl-4-(13-pentacosyl) pyridine and eicosyl-4-(1-butyl amyl group) pyridine.

What be suitable for can be olefines with the neutral ligand of palladium transition metal bonding; The acetylene class; Carbon monoxide; Nitrogen oxide, nitrogen compound such as ammonia, alkyl isocyanide thing, alkyl isocyanate, alkylisothiocyanate; Pyridine and pyridine derivate (for example 1,10-phenanthroline, 2,2 '-dipyridine), 1,4-dialkyl group-1,3-diaza butadiene, 1,4-diaryl-1, the amine of 3-diaza butadiene and following formula representative:

R wherein ³¹Be that alkyl and n as defined alkyl in front or replacement is 2 to 10 independently.The urea class; Nitrile such as acetonitrile, benzonitrile and halo derivatives thereof; The cyclic oligomer of the dimethyl ether of organic ethers such as diglycol, diox, tetrahydrofuran, furanodiene propyl ether, diethyl ether, cyclic ethers such as diglycol; Organic sulfide such as thioether (diethyl thioether); Arsine; ; Phosphine such as triaryl phosphine (for example triphenyl phasphine), trialkyl phosphine (for example trimethyl, triethyl, tripropyl, three pentacosyls and halo derivatives thereof), two (diphenyl phosphine) ethane, two (diphenyl phosphine) propane, two (diformazan phosphino-) propane, two (diphenyl phosphine) butane, 2,2 (S)-(-) '-two (diphenyl phosphine)-1,1 '-dinaphthalene, (R)-(+)-2,2 '-two (diphenyl phosphine)-1,1 '-dinaphthalene and two (2-diphenyl phosphine ethyl) phosphniline; Phosphinoxides, halogenation is Phosphorus; The phosphite ester of following formula representative:

P (OR ³¹) ₃R wherein ³¹Representative is as the alkyl of defined alkyl in front or replacement independently; Phosphorus oxyhalide; Phosphonate ester; Phosphinate, phosphinic acid ester, ketone; The sulfoxide class is as (C ₁-C ₂₀) alkyl sulfoxide; (C ₆-C ₂₀) aryl sulfoxide and (C ₇-C ₄₀) the alkaryl sulfoxide etc.Should know that above-mentioned neutral ligand can be used as optional the 3rd component, as hereinafter described.

The example that is suitable for use as the VIII group transition metal compound of VIII family metal ion source comprises: the thylhexoic acid palladium, and trans-PdCl ₂(PPh ₃) ₂, two (trifluoroacetic acid) palladium (II), two (diacetone) palladium (II), 2 ethyl hexanoic acid palladium (II), Pd (acetate) ₂(PPh ₃) ₂, palladium bromide (II), palladium bichloride (II), palladium iodide (II); palladium oxide (II), tetrafluoro boric acid one acetonitrile three (triphenylphosphine) closes palladium (II), and tetrafluoro boric acid four (acetonitrile) closes palladium (II); the dichloro diacetonitrile closes palladium (II), and dichloro two (triphenylphosphine) closes palladium (II), and dichloro two (benzonitrile) closes palladium (II); palladium acetylacetonate, dichloride two (acetonitrile) is closed palladium, and dichloride two (dimethyl sulfoxide) is closed palladium; pentanedione nickel, nickel carboxylate, nickel carboxylate; Nickel Dimethylglyoxime, thylhexoic acid nickel, NiCl ₂(PPh ₃) ₂, NiCl ₂(PPh ₂CH ₂) ₂, (P (cyclohexyl) ₃) HNi (Ph ₂P (C ₆H ₄) CO ₂), (PPh ₃) (C ₆H ₅) Ni (Ph ₂PCH=C (O) Ph), two (2,2,6,6-tetramethyl-3, the 5-heptadione) nickel (II), hydrogen fluoro diacetone four hydration nickel (II), three fluoro diacetones, two hydration nickel (II), diacetone four hydration nickel (II), dicyclopentadienyl nickel, nickel acetate (II), nickelous bromide, nickel chloride, dichloro hexylacetic acid nickel, lactic acid nickel, nickel oxide, tetrafluoro boric acid nickel, two (allyl) nickel, two (cyclopentadiene) nickel, new cobalt decanoate, cobalt acetate (II), acetylacetone cobalt (II), acetylacetone cobalt (III), cobalt benzoate (II), cobalt chloride, cobaltous bromide, dichloro hexylacetic acid cobalt, cobaltous octadecanate (II), tetrafluoro is for cobalt borate (II), naphthenic acid (napthenate) iron, iron chloride (II), iron chloride (III), ferric bromide (II), ferric bromide (III), ferric acetate (II), ferric acetyl acetonade (III), ferrocene, dichloride three (triphenyl phasphine) ruthenium, hydrochlorinate three (triphenyl phasphine) ruthenium, ruthenium trichloride, dichloride four (acetonitrile) ruthenium, dichloride four (dimethyl sulfoxide (DMSO)) ruthenium, radium chloride, tri-chlorination three (triphenyl phasphine) rhodium.

The organo-aluminium component of multi-component catalyst systems of the present invention is represented by following formula:

AlR ³² _3-xQ _xR wherein ³²Represent (the C of line style and side chain independently ₁-C ₂₀) alkyl, (C ₆-C ₂₄) aryl, (C ₇-C ₂₀) aralkyl, (C ₃-C ₁₀) naphthenic base; Q is halogenide or the pseudohalide that is selected from chlorine, fluorine, bromine, iodine, (the C of line style and side chain ₁-C ₂₀) alkoxy, (C ₆-C ₂₄) aryloxy group; With x be 0 to 2.5, preferred 0 to 2.

Representational organo-aluminum compound comprises trialkylaluminium such as trimethyl aluminium, aluminium triethyl, tri-propyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, three-2-methyl butyl aluminium, three-3-methyl butyl aluminium, three-2-methyl amyl aluminium, three-3-methyl amyl aluminium, three-4-methyl amyl aluminium, three-2-methyl hexyl aluminium, three-3-methyl hexyl aluminium, trioctylaluminum, three-2-norborny aluminium etc.

Aluminum dialkyl monohalide such as chlorodimethylalumiu, diethylaluminum chloride, chlorination diisopropyl aluminium, di-isobutyl aluminum chloride etc.

Dihalide alkyl aluminium such as methylaluminium dichloride, ethylaluminium dichloride, two iodate aluminium ethides, dichloride propyl group aluminium, dichloride isopropyl aluminium, dichloride butyl aluminium, aluminium isobutyl dichloride etc.

Sesquialter alkyl aluminium halide such as sesquialter methyl chloride aluminium, sesquialter ethylaluminium chloride, sesquialter chlorination propyl group aluminium, sesquialter chlorination aluminium isobutyl etc.

The hydrogenation aluminum dialkyl is selected from the (C of line style and branching ₁-C ₁₀) the hydrogenation aluminum dialkyl, diisobutylaluminium hydride is preferred hydrogenation aluminum dialkyl compound.

Dialkyl zinc compounds is selected from the (C of line style or branching ₁-C ₁₀) dialkyl zinc compounds, preferred diethyl zinc.Dialkyl magnesium compound is selected from the (C of line style and branching ₁-C ₁₀) dialkyl magnesium, preferred dibutylmagnesium.Alkyl lithium compounds is selected from the (C of line style and branching ₁-C ₁₀) alkyl lithium compounds, preferred butyl lithium.

In enforcement of the present invention, use with one or both components that are selected from cocatalyst compound, the 3rd component composition by the catalyst system and catalyzing of described VIII family metal ion source gained.

The example of described the 3rd component is lewis acid such as BF ₃Etherate, TiCl ₄, SbF ₅, three (perfluorophenyl) boron, BCl ₃, B (OCH ₂CH ₃) ₃Strong Bronsted acid such as hexafluoro-antimonic acid (HSbF ₆), HPF ₆Hydrate, trifluoroacetic acid (CF ₃CO ₂H) and FSO ₃HSbF ₅, H ₂C (SO ₂CF ₃) ₂CF ₃SO ₃H and p-toluenesulfonic acid; Halogenated compound such as hexachloroacetone, Hexafluoro acetone, 3-butyric acid-2,2,3,4,4-pentachloro-butyl ester, hexafluoro glutaric acid, hexafluoroisopropanol and chloranil, promptly

Electron donor such as phosphine and phosphite and be selected from (C ₄-C ₁₂) aliphatic series and (C ₆-C ₁₂) the olefinic electron donor of cyclic aliphatic diolefin such as butadiene, cyclo-octadiene and norbornadiene.

The acidity of strong Bronsted acid can be by measuring their Hammett's acidity function H ₀Metering.F.A.Cotton and G.Wilkinson is seen in the definition of Hammett's acidity function, modern inorganic chemistry (Advanced Inorganic Chemistry), and Wiley-Interscience, 1988, p.107.

As previously mentioned, neutral ligand can be used as optional the 3rd component that the sub-performance of power supply is arranged.

In a kind of embodiment of the present invention, described multi-component catalyst systems can prepare by the following method, this method comprises: catalytic component-be VIII family metallic compound, cocatalyst compound and the 3rd component (as using) are mixed in hydrocarbon or halogenated hydrocarbon solvent together, then the catalyst system of described premix is sneaked in the reaction medium that comprises at least a silyl functional polycyclic monomer.Perhaps, (supposing to use optional the 3rd component) can add any two kinds of premixs in hydrocarbon or halogenated hydrocarbon solvent of catalyst system component in the reaction medium then.Remaining catalytic component can add in the reaction medium before or after the premix component adds in the reaction medium.

In another embodiment, all catalytic components can be mixed together in the reaction medium, prepare described multi-component catalyst systems on the spot.The order that adds is inessential.

In a kind of embodiment of multicomponent catalyst system of the present invention, typical catalyst system comprises VIII group 4 transition metal salt (as thylhexoic acid nickel), and the potpourri of organo-aluminum compound (as aluminium triethyl) and the 3rd component is (as BF ₃Etherate and hexafluoro-antimonic acid (HSbF ₆)), preferred Al/BF ₃Etherate/Ni/ acid mol ratio is 10/9/1/0.5-2.Reaction equation is as follows:

1. thylhexoic acid nickel+HSbF ₆+ 9BF ₃Etherate+10 aluminium triethyls → active catalyst

In the embodiment of another kind of multicomponent catalyst system of the present invention, catalyst system comprises nickel salt (as thylhexoic acid nickel), and organo-aluminum compound (as aluminium triethyl) and the 3rd component lewis acid (as three (perfluorophenyl) boron) are shown below:

2. thylhexoic acid nickel+three (perfluorophenyl) boron+aluminium triethyl → active catalyst

In the embodiment of another kind of multicomponent catalyst system of the present invention, the 3rd component of catalyst system is the halogenated compound that is selected from different halogenation activators.Typical catalyst system comprises VIII group 4 transition metal salt, and organo-aluminium and the 3rd component halogenide are shown below:

3. thylhexoic acid nickel+aluminium triethyl+chloranil → active catalyst

In the embodiment of another multicomponent catalyst system of the present invention, do not use promotor.Catalyst system comprises VIII family slaine (as bromination 3-allyl nickel dimer) and lewis acid (as three (perfluorophenyl) boron), as shown in the formula:

4. chlorination η ³Allyl nickel+three (perfluorophenyl) boron → active catalyst

The inventor finds no matter one-component still is the multicomponent catalyst system among the present invention, and the microstructure and the physical property of the polymkeric substance that the VIII family metal pair of selecting in the metal cation complex obtains are influential.For example, the inventor observes typical palladium catalyst and makes exclusive 2,3 norborene unit chaining and show certain stereoregularity.By above-mentioned the 2nd kind of catalyst system and formula E _nNi (C ₆F ₅) ₂Polymkeric substance at least one end in the polymer chain two ends of single-component catalyst catalysis comprise a perfluorophenyl.That is to say that the perfluorophenyl part can be positioned at an end or two ends of polymkeric substance.In above-mentioned any scheme, perfluorophenyl all is to connect by the terminal many ring repetitive sides on covalent bond and the main polymer chain.

Use the present invention's list and being reflected in the organic solvent of multicomponent catalyst to carry out, described organic solvent reply catalyst system has no adverse effect and is the solvent of monomer.Representative examples of organic is aliphatic series (nonpolar) hydrocarbon such as pentane, hexane, heptane, octane and decane; Clicyclic hydrocarbon such as cyclopentane and cyclohexane; Aromatic hydrocarbon such as benzene, chlorobenzene, neighbour-dichloro-benzenes, toluene and dimethylbenzene; Halo (polarity) hydrocarbon such as methylene chloride, chloroform, phenixin, ethyl chloride, 1,1-ethylene dichloride, 1,2-ethylene dichloride, 1,2-dichloroethene, n-propyl chloride, 2 cbloropropane isopropyl chloride, 1-chlorobutane, Sec-Butyl Chloride, 1-chloro-2-methylpropane and 1-chloropentane.

Based on many factor choice reaction solvents, comprise selection of catalysts and whether need by slurry or solwution method polymerization.For most of catalyzer of the present invention, preferred solvent is chlorohydrocarbon such as methylene chloride and 1, and 2-ethylene dichloride and aromatic hydrocarbons such as chlorobenzene and nitrobenzene, simple hydrocarbon are not preferred, because the conversion ratio of gained official energy NB-type monomer is lower.Unexpectedly, the inventor finds some catalyst system, be based on the particularly multicomponent catalyst of dihalide alkyl aluminium (as ethylaluminium dichloride) of VIII family metallic compound and aluminum alkyl halide the most significantly, and above-mentioned the 2nd kind of catalyzer, when in simple hydrocarbon such as heptane, cyclohexane and toluene, moving, also obtain fabulous result (with the high monomer conversion ratio).

For list and multicomponent catalyst, the mol ratio of total monomer and VIII family metal can be 20: 1 to 100,000: 1, and preferred 50: 1 to 20,000: 1, and most preferably 100: 1 to 10,000: 1.

In multi-component catalyst systems, the mol ratio of promoter metal (as aluminium, zinc, magnesium and lithium) and VIII family metal preferably is less than or equal to 30: 1 in being less than or equal to 100: 1 scope, most preferably be less than or equal to 20: 1.

The mol ratio of the 3rd component and VIII family metal is in 0.25: 1 to 20: 1 scope.With acid during as the 3rd component, the scope of acid and the ratio of VIII family metal preferably is less than or equal to 2: 1 for being less than or equal to 4: 1.

The temperature of carrying out polyreaction of the present invention typically in-100 ℃ to 120 ℃ scope, preferred-60 ℃ to 90 ℃, most preferably-10 ℃ to 80 ℃.

Optimum temperature of the present invention depends on many variablees, mainly is the selection of selection of catalysts and reaction diluent.Therefore, for given polymerization, will consider that these variablees are by the definite optimum temperature of experiment.

In development these catalyzer and polymeric system process, it is very stable that the present inventor finds to connect the palladium-carbon bond of palladium catalyst and growing polymer chain.This has acid labile group to polymerization, and the polycyclic monomer of ester and carboxylic acid functional is very beneficial, because palladium catalyst will be compatible to these functional groups to greatest extent.Yet stable so also making is difficult to remove the palladium catalyst remants thing from the polymkeric substance that makes.In the process of developing these new compositions, the present inventor finds can be with carbon monoxide preferably at proton solvent such as alcohol, and moisture or carboxylic acid exist down, disconnects palladium-carbon bond (obtain and can precipitate by the palladium metal of filtering or centrifugation is removed) at an easy rate.

The molecular weight of the polymkeric substance that the inventive method obtains (Mn) is about 1,000 to 1,000,000 scope, preferably approximately 2,000 to 700,000, more preferably about 5,000 to 500,000 and most preferably about 10,000 to 50,000.

Can control molecular weight as the ratio of regulating initiating agent and monomer by the ratio that changes catalyzer and monomer.Also can form low-molecular weight polymer and the oligomer of molecular weight by in the presence of chain-transferring agent, implementing polyreaction in about 500 to 500,000 scopes.The macromonomer or the oligomer that comprise 4 to 50 repetitives can prepare in the presence of CTA (chain-transferring agent).Described chain-transferring agent (CTA) is selected from the compound of the terminal olefinic double bond between adjacent carbon atom, and wherein said adjacent carbon atom one of at least has two hydrogen atoms to be attached thereto.Described CTA does not comprise styrene (non-styrene), vinyl ether (non-vinyl ether) and conjugated diolefine.Non-styrene, non-vinyl ether mean the compound that chain-transferring agent of the present invention does not include following structure:

Wherein A is that aromatic substituent and R are alkyl.

The preferred CTA compound of the present invention is expressed from the next:

R wherein ₁And R ₁₁Represent hydrogen, side chain or unbranched (C independently ₁-C ₄₀) alkyl, side chain or unbranched (C ₂-C ₄₀) alkenyl and halogen.

In the above-mentioned chain-transferring agent, preferably have the alpha-olefin of 2 to 10 carbon atoms, for example ethene, propylene, 4-methyl-1-pentene, 1-hexene, 1-decene, 1,7-octadiene and 1,6-octadiene or isobutylene.

Though those skilled in the art consider above-mentioned all factors, should several general principles that can utilize easily in suitable occasion be arranged by the definite top condition of experiment for given result.We know that usually, alpha-olefin (for example ethene, propylene, 1-hexene, 1-decene, 4-methyl-1-pentene) is the most effective chain-transferring agent, and 1, the dibasic alkene of 1-(as isobutylene) effect is relatively poor.In other words, at other all situations homogeneous phase simultaneously, the concentration that obtains the required isobutylene of given molecular weight will be more much higher than selecting ethene.Styrene belongs to alkene, conjugated diolefine and vinyl ether can not effectively be used as chain-transferring agent, because they tend to and polymerization catalyst described herein.

The consumption of CTA with respect to the molal quantity of total NB-type monomer at about 0.10 mole of % to the scope that is higher than 50 moles of %.The consumption of preferred CTA in the scope of 0.10 to 10 mole of %, 0.1 to 5.0 mole of % more preferably.As mentioned above, depend on efficient and the desired end group of the type of catalyzer and susceptibility, CTA, the concentration of CTA can surpass 50 moles of % (based on the total NB-functional monomer meter that exists), for example 60 to 80 moles of %.Obtain low-molecular-weight embodiment of the present invention as in oligomer and macromonomer application, may need higher CTA concentration (for example greater than 100 moles of %).Important and notice unexpectedly, even high like this CTA concentration (except the isobutylene), described CTA is not copolymerized in the main polymer chain yet, but inserts as the end group on each polymer chain.Except that chain-transferring agent, the inventive method provides a kind of method that terminal alpha-alefinically end group can be placed on the polymkeric substance end of the chain.

CTA directly in the presence of polymer molecular weight of the present invention (Mn) scope of preparation about 1,000 to 500,000, preferably approximately 2,000 to 300,000 and most preferably about 5,000 to 200,000.

Photoetching compositions of the present invention comprises disclosed many ring composition, solvent and photosensitive acid forming agent (photoinitiators).Optional, can add the dissolution inhibitor that accounts for composition 20% (weight) at most.A kind of suitable dissolution inhibitor be the cholic acid tert-butyl ester (J.V.Crivello et al., chemical amplification electron X-ray lithography X glue, Chem.Mater, 1996,8,376-381).

Be exposed under the radiation, radiosensitive acid forming agent produces strong acid.Suitable light trigger comprises fluoroform sulphonate (triflates) (as the trifluoromethanesulfonic acid triphenylsulfonium), 1,2,3,-thrihydroxy-benzene (as the methylsulfonyl 1,2,3,-thrihydroxy-benzene); Salt such as hexafluoro metaantimmonic acid triaryl matte and diaryl group iodized salt (diaryliodium), hexafluoro arsenate, fluoroform sulphonate; The inferior carboxylic acid amide esters of hydroxyl, α, α '-disulfonyl basic weight n-formyl sarcolysine alkane, benzylalcohol sulphonic acid ester and naphthoquinones-4-two nitrine that nitro replaces.Other suitable photic sour initiating agent sees Reichmanis et al., chemical material (Chem.Mater.) 3,395, (1991).It preferably contains triarylsulfonium salt or diaryl group iodized salt composition, because to deep ultraviolet (193 to 300nm) sensitivity, can access the image of high definition.Most preferably do not replace and symmetry or asymmetric substituted diaryl salt compounded of iodine or triarylsulfonium salt.Photic sour initiating agent component accounts for about 1 to 100% (weight) of polymkeric substance.Preferred concentration is in 5 to 50% (weight) scope.

Photoetching compositions of the present invention is chosen wantonly to contain and can be made the light activated photosensitizer of photic sour initiating agent to the more long wavelength scope from the moderate ultraviolet ray to visible light.According to predetermined purposes, these photosensitizers comprise polynuclear aromatic compound such as pyrene and perlene.The photosensitization of photic sour initiating agent is that present technique field personnel are known, and at United States Patent (USP) the 4th, 250, No. 053; Description is arranged, quote for reference at this for 4,371, No. 605 and 4,491, No. 628.The invention is not restricted to specific photosensitizer or photic sour initiating agent.

The present invention also relates to form on base the technology of positive picture, step comprises: (a) film on base with positive type corrosion-resistant composition of the present invention; (b) under radiation, make film by image exposure; (c) image developing.

The first step relates to the positive type composition of the present invention that is dissolved in the appropriate solvent films on base.Suitable base is by silicon, compositions such as pottery or polymkeric substance.Appropriate solvent comprises propylene glycol methyl ether acetate (PGMEA) cyclohexanone, butyrolactone, ethyl lactate etc.Film can be coated on the base with known technology such as spin coating or spraying or blade coating.Preferably, film high temperature before exposure is heated to about 90 ℃ to 150 ℃ about blinks of 1 minute.In second step of technology, film is exposed in the radiation as suitable electron ray or electromagnetic radiation by image format, preferred electromagnetic radiation such as ultraviolet ray or x-ray, preferred ultraviolet ray, its appropriate wavelength is about 193 to 514nm, optimal wavelength 193 to 248nm.Suitable radiation source comprises mercury lamp, mercury/xenon lamp and xenon lamp, x-ray or electron beam.Radiation is absorbed by radiosensitive acid forming agent, generates free acid in the exposure area.Free acid impels the acid labile pendant groups cracking on the multipolymer, makes multipolymer change dissolution enhancers into by dissolution inhibitor thus, therefore, has increased the solubleness of corrosion-resistant composition in water base of exposure.Unexpectedly, the corrosion-resistant composition of exposure dissolving rapidly in water base.According to the alicyclic ring main chain with have the complicated character of the high molecular norbornene monomer unit of carboxylic acid functional, this solubleness is unexpected and at beyong contemplation.Preferably, film is heated to about 90 ℃ to 150 ℃ blinks of 1 minute again after exposure.

The 3rd step related to positive type image and develops in appropriate solvent.Appropriate solvent comprises water base, preferred water base non-metallic ion such as tetramethyl ammonium hydroxide or choline.The present composition provides high-contrast and has had the positive picture of vertical etching wall.Uniquely, the solubility property of the present composition can change by the composition that changes multipolymer simply.

The present invention also relates to integrated circuit package such as integrated circuit (IC) chip, multi-chip module or circuit board etc. with technology manufacturing of the present invention.Integrated circuit package is included in the circuit of making on the base, and step is: (a) be coated with film forming with positive type corrosion-resistant composition of the present invention on base; (b) film is pressed image exposure under radiation; (c) develop at exposure base epigraph; (d) make the film that develops on the base make circuit with technology known in the art.

After base exposure, make at exposed areas coated with conductive material such as conducting metal and to make circuit pattern, paint-on technique known in the art such as evaporation are filmed, sputter coating, chemical vapour deposition is filmed or laser induced deposition is filmed.Can finish grind the surface of filming to remove unnecessary conductive material.Also can be with making dielectric deposition with manufacturing circuit similar methods.Making p, or in the technology of n doping circuit semiconductor pipe, can be in base boron implant, inorganic ions such as phosphorus or arsenic.Other method of making circuit is well known by persons skilled in the art.

The following examples are described preparation in detail and are used concrete method for compositions of the present invention.Classify giving an example of detailed preparation method down as, more generally describe as previously mentioned for the preparation method.For example just in order to illustrate, rather than to the restriction of scope of the present invention.

As mentioned above, making is at the pattern that produces on the base and duplicate on the photomask with photoresist.The effect of this transformation depends on the image-forming radiation light wavelength, and the susceptibility of photoresist and photoresist bear the ability of exposure image zone etching condition on the base.Photoresist is the most normal to be used in consumable mode, and wherein photoresist is at unexposed area etching (to positive type photoresist), and base is in the exposure area etching.Because photoresist is that organically base is inorganic usually, thus photoresist intrinsic higher etch-rate in reactive ion etching (RIE) technology, and necessarily require photoresist thinner than base material.The etch-rate of photoresist material is low more, requires photoresist coating thin more.Therefore can obtain higher resolution.Therefore, the reactive ion etching speed of photoresist is low more, and is just attractive more from the angle of technology.Etch-rate depends primarily on main polymer chain, and following chlorine plasma etch process is the reactive ion etching technology that is usually used in semiconductor technology.

Be used for the monomer in embodiment and all explanations and the ratio of catalyzer and be meant mol ratio.

Sequence number polymkeric substance normalization RIE speed (micron/minute)

1 novolac resin resist 1.0

2 polycarboxylated styrene resists 0.98

3 248nm (deep ultraviolet) 1.14

(acrylate trimer/novolac resin potpourri,

United States Patent (USP) the 5th, 372, No. 912)

4 193nm (polyacrylate trimer, 1.96

Allen et al., SPIE technology

2438(1)，474(1995))

5 norborene homopolymer 0.83

Polymkeric substance 1 and 2 mainly is an aromatic polymer, and polymkeric substance 3 and a small amount of acrylic ester copolymer are to improve its etch-rate.Polymkeric substance 4 is a raw material based on the acrylic ester fully, and transparent under the 193nm ultraviolet ray (aromatic ring makes material opaque in these zones, is that raw material is in the next no feasible resist alternative materials of 193nm based on traditional novolac resin or para hydroxybenzene ethene therefore).This etch-rate almost twice is in this polymkeric substance.Polymkeric substance 5 is except transparent at 193nm, and its etch-rate is lower than the photoresist material (No. 1 and No. 2 polymkeric substance) of standard.Therefore, main chain with the polymkeric substance 5 (addition cycloolefin) of polycomponent Raney nickel of the present invention preparation all has improvement than early stage all documents, the resist that provides can play the effect suitable with business-like material with regard to the characteristic of reactive ion etching under 193nm, can use under longer wavelength.In fact, the addition cyclic olefin polymer can be provided in more long wavelength's etch-resistance.Talk about in document (H.Gokan, S.Esho, and Y.Ohnishi, galvanochemistry meeting will (J.Electrochem.Soc.) 130 (1), 143 (1983)), higher C/H ratio has reduced the etch-rate of polymeric material.According to this hypothesis, the etch-rate of polymkeric substance 5 will be between based on aromatics system with between based on the acrylate based material.The etch-resistance of this addition cyclic olefin material performance even better surprisingly than aromatics based material.

Embodiment 1

Having Te Fulong (Teflon ^) add 5-norborene-carboxylic acid (carbon-tert-butoxy norborene) tert-butyl ester (2.0 grams, 10.3 mMs, outer, interior 44/56) in 50 milliliters of vials of stirring rod of coating.Add catalyst solution under the room temperature in this stirring monomer, the catalyst solution preparation is the η that will be dissolved in the chlorobenzene (5 milliliters) ³-Allylpalladium chlorine dipolymer (38 milligrams, 103 micromoles) joins in the hexafluoro metaantimmonic acid silver (99 milligrams, 290 micromoles) that is dissolved in chlorobenzene (5 milliliters), through 30 minutes, filters (removal silver nitride precipitation) with millipore filter again.After the polyreaction 36 hours, the potpourri gel becomes limpid yellow gel.Gel is put into excessive methyl alcohol, and polymer precipitation becomes white powder.Polymkeric substance is with excessive methanol wash, drying.The yield of polymkeric substance is 1.5 grams (75%).With containing the monomer that has ester in the infrared analysis polymkeric substance, show strong bands of a spectrum and be positioned at 1728 centimetres ^-1(C=O), 1251 centimetres ^-1(C-O-C) and 1369 and 1392 centimetres ^-1(tertiary butyl groups feature), and do not have unreacted monomer (proton magnetic resonance (PMR)).Obtaining polymer molecular weight (Mw) is 22,500.Carry out thermogravimetry (TGA) (10 ℃ of rate of heat addition per minutes) in the blanket of nitrogen and show that polymkeric substance is heat-staple at about 210 ℃, at 260 ℃ about 28% the loss in weight (showing the net loss of tertiary butyl groups as the isobutylene of 5-norborene-homopolymer of carboxylic acid) is arranged, then in about 400 ℃ of polymer degradations (loss total weight 90%).

Embodiment 2

Having Te Fulong (Teflon ^) add norborene (0.8 gram, 8.6 mMs) in 50 milliliters of vials of stirring rod of coating, 1,2-ethylene dichloride (8 milliliters) and 5-norborene-carboxylic acid (carbon-tert-butoxy norborene) tert-butyl ester (0.2 gram, 1 mM, outward, interior 44/56).At room temperature in the solution that stirs, add thylhexoic acid nickel (3 micromole), three perfluorophenyl boron (23 micromole) and aluminium triethyl (27 micromole).Reaction is carried out immediately, obtains the white polymer precipitation in less than 10 seconds in solution.Reaction was carried out 60 minutes, afterwards reactive component was dissolved in the thiacyclohexane, poured in the excessive methyl alcohol again.Polymkeric substance washs with excessive methanol, dried overnight in 80 ℃ of vacuum drying ovens.Copolymer yield is 0.9 gram (90%).Measure with the GPC method, molecular weight of copolymer is 535,000 (Mw), polydispersity 4.7.

Embodiment 3

Having Te Fulong (Teflon ^) add 5-norborene-carboxylic acid (carbon-tert-butoxy norborene) tert-butyl ester (2.2 grams, 11.3 mMs, outer, interior 44/56) in 50 milliliters of vials of stirring rod of coating.Add catalyst solution under the room temperature in this stirring monomer, the catalyst solution preparation is the η that will be dissolved in the ethylene dichloride (6 milliliters) ³-Allylpalladium chlorine dipolymer (29 milligrams, 74 micromoles) joins in the silver tetrafluoroborate (61 milligrams, 311 micromoles) that is dissolved in ethylene dichloride (6 milliliters), through 30 minutes, filters (removal silver nitride precipitation) with millipore filter.After the polyreaction 36 hours, the potpourri gel becomes limpid yellow gel.Gel is put into excessive methyl alcohol, and polymer precipitation becomes white powder.Polymkeric substance is with excessive methanol wash, drying.The yield of polymkeric substance is 1.4 grams (64%).Show with infrared analysis to contain the monomer that has ester in the polymkeric substance, show strong bands of a spectrum and be positioned at 1728 centimetres ^-1(C=O), 1251 centimetres ^-1(C-O-C) and 1369 and 1392 centimetres ^-1(tertiary butyl groups feature), and do not have unreacted monomer or carboxylic acid functional (proton magnetic resonance (PMR) and IR).Obtaining polymer molecular weight (Mw) is 54,100.Carry out thermogravimetry (TGA) (10 ℃ of rate of heat addition per minutes) in the blanket of nitrogen and show that polymkeric substance is heat-staple at about 210 ℃, at 250 ℃ about 29% the loss in weight (showing the net loss of tertiary butyl groups as the isobutylene of 5-norborene-homopolymer of carboxylic acid) is arranged, in about 400 ℃ of polymer degradations (loss total weight 80%).

Embodiment 4

Having Te Fulong (Teflon ^) add norborene (1.16 grams, 12.3 mMs), 1 in 100 milliliters of vials of stirring rod of coating, 2-ethylene dichloride (50 milliliters) and 5-norborene-carboxylic acid (carbon-tert-butoxy norborene) tert-butyl ester (0.6 gram, 3.1 mM is outer, and interior 44/56).In the solution that stirs, add two (2,2,6,6-tetramethyl-3,5-pentanedione) palladium (31 micromole), three perfluorophenyl boron (279 micromole) under the room temperature.Reaction was carried out 16 hours, afterwards reactive component was poured in the excessive methyl alcohol.Polymkeric substance washs with excessive methanol, dried overnight in 80 ℃ of following vacuum drying ovens.Copolymer yield is 054 gram (31%).

Embodiment 5

Having Te Fulong (Teflon ^) add 5-norborene-carboxylic acid (carbon-tert-butoxy norborene) tert-butyl ester (4.4 grams, 22.7 mMs, outer, interior 44/56) in 50 milliliters of vials of stirring rod of coating.Add catalyst solution under the room temperature in this stirring monomer, the catalyst solution preparation is the η that will be dissolved in the ethylene dichloride (7 milliliters) ³-Allylpalladium chlorine dipolymer (41.5 milligrams, 113 micromoles) joins in the silver tetrafluoroborate (42 milligrams, 215 micromoles) that is dissolved in ethylene dichloride (7 milliliters), through 30 minutes, filters (removal silver nitride precipitation) with micro-filter.Reaction mixture is incubated in 75 ℃ of oil baths.Find mixture solidified after 90 minutes, obtain the grey polymeric material.It is dissolved in obtains dark solution in the acetone.In solution, feed CO gas 30 minutes, obtain a large amount of superfine little black precipitates (Metal Palladium and other possible catalyst residue).Remove precipitation by centrifuging, and can repeat repeatedly.The colourless solution that obtains at last filters with 45 microns micropore dishes, and the acetone soln of polymkeric substance joins in the excessive hexane, polymer precipitation.The white polymer centrifuging, dried overnight afterwards obtains the white powder (2.21 grams, 50%) of multipolymer.Carry out thermogravimetry (TGA) (10 ℃ of rate of heat addition per minutes) in the blanket of nitrogen and show that polymkeric substance is heat-staple at about 210 ℃, at 260 ℃ about 28% the loss in weight (showing the net loss of tertiary butyl groups as the isobutylene of 5-norborene-homopolymer of carboxylic acid) is arranged, in about 400 ℃ of polymer degradations (loss total weight 90%).Observing polymer molecular weight is Mn=3,300 gram/moles, Mw=6,900 gram/moles (gel permeation chromatography in the tetrahydrofuran, polystyrene standard sample).

Embodiment 6

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add 5-norborene-carboxylic acid the tert-butyl ester pure outer isomeric compound (carbon-tert-butoxy norborene) (0.6g).Under environment temperature this stirs in the monomer, and adding will be at the η in the ethylene dichloride (10ml) ³Allylpalladium chlorine dipolymer (30mg) is added in the hexafluoro-antimonic acid silver (50mg) in the ethylene dichloride (20ml) 30 minutes, and filters the catalyst solution of (precipitation separation silver chloride) preparation again by millipore filter.Reaction was carried out 15 hours, and potpourri added and to make the polymer precipitation powder that is white in color in the excessive methanol this moment.With excessive methanol washing copolymer and dry.The output of polymkeric substance is 0.5g (85%).Recording polymer molecular weight is that 46900 (Mw) and polydispersity are 2.4.

Embodiment 7

To being furnished with coating Teflon ^The 100ml vial of stirring rod in, add norborene (4.01 grams, 42.6mmol), 1, the tert-butyl ester of 2-ethylene dichloride (50ml) and 5-norborene-carboxylic acid (carbon-tert-butoxy norborene) (2g, 10.3mmol, outer/inner potpourri).In this agitating solution under environment temperature, add catalyst solution: make η by following method preparation ³Allylpalladium chlorine dipolymer (10mg, 27.3 μ mol) and hexafluoro-antimonic acid silver (19.6mg, 57 μ mol) are 1, and reaction is 30 minutes in the 2-ethylene dichloride (3ml), filters by millipore filter then.Reaction was carried out 20 hours, then material in the reactor is injected excessive methanol.With excessive methanol washing copolymer and dry.The output of multipolymer is 4.15g.The molecular weight of multipolymer is determined as 618,000 (Mw) with the GPC method, and polydispersity is 7.1.

Embodiment 8

To being furnished with coating Teflon ^The 100ml vial of stirring rod in, add norborene (3.75g, 39.8mmol), 1, the tert-butyl ester of 2-ethylene dichloride (50ml) and 5-norborene-carboxylic acid (carbon-tert-butoxy norborene) (2g, 10.3mmol, outer/inner potpourri).In this agitating solution under environment temperature, add thylhexoic acid palladium (12 μ mol, three (perfluorophenyl boron (108 μ mol) and aluminium triethyls (120 μ mol).Reaction was carried out 72 hours, then material in the reactor is injected excessive methanol.With excessive methanol washing copolymer and dry, dissolving and precipitate again again in chlorobenzene with excessive methanol, filter and in the end dry before use methanol wash, and in 80 ℃ of vacuum drying chambers dried overnight.The output of multipolymer is 1.66g.The molecular weight of multipolymer is to be determined as 194,000 (Mw) with the GPC method, and polydispersity is 2.3.By containing the existence of ester monomer in the infrared analysis check multipolymer, show that bands of a spectrum are at 1730cm ^-1(C=O) and 1154cm ^-1(C-O-C), there is not unconverted monomer (proton N MR).

Embodiment 9

To being furnished with coating Teflon ^The 100ml vial of stirring rod in, add 1, the tert-butyl ester of 2-ethylene dichloride (25ml) and 5-norborene-carboxylic acid (carbon-tert-butoxy norborene) (10g, 51.5mmol, outer/inner potpourri).In this agitating solution under environment temperature, add catalyst solution: make η by following method preparation ³Allylpalladium chlorine dipolymer (82mg, 223 μ mol) and hexafluoro-antimonic acid silver (200mg, 581 μ mol) are 1, and reaction is 30 minutes in the 2-ethylene dichloride (10ml), filters by millipore filter then.Reaction was carried out 48 hours, then material in the reactor is injected excessive methanol.With excessive methanol washing and dry polymer.The output of homopolymer is 4.5g.

Embodiment 10

To being furnished with coating Teflon ^The 100ml vial of stirring rod in, add 1,2-ethylene dichloride (50ml), the tert-butyl ester of 5-norborene-carboxylic acid (carbon-tert-butoxy norborene) (5g, 25.8mmol, outer/inner potpourri), norborene (0.82g, 8.7mmol) and 5-triethoxy benzene silicyl norborene (0.47g, 1.8mmol).In this agitating solution under environment temperature, add catalyst solution: make η by following method preparation ³Allylpalladium chlorine dipolymer (47.2mg, 128 μ mol) and silver tetrafluoroborate (138mg, 700 μ mol) are 1, and reaction is 30 minutes in the 2-ethylene dichloride (10ml), filters by millipore filter then.Reaction was carried out 48 hours, then material in the reactor is injected excessive methanol.With excessive methanol washing and dry polymer.Trimeric output is 5.3g.It is 3.2 with polydispersity that the molecular weight of multipolymer is determined as 39,900 (Mw) with the GPC method.

Embodiment 11

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add the tert-butyl ester of 7.25g (37.5mmol) norborene, the methyl ester of 1.9g (12.5mmol) norborene is newly distilled ethylene dichloride 50ml, and makes solution exhaust under argon atmospher.Is furnished with coating Teflon ^The 10ml vial of the stirring rod η that packs into ³Allylpalladium chlorine dipolymer 0.0365g (0.1mmol) (ratio that finally obtains monomer and catalyzer is 500/l) and 2ml ethylene dichloride.Hexafluoro-antimonic acid silver 0.0344g (0.1mmol) and ethylene dichloride 2ml pack in another 10ml vial.Catalyst solution is mixed with in drying box by chlorination Allylpalladium bipolymer solution and hexafluoro-antimonic acid silver solution.Observe the precipitation of chlorination silver salt immediately, filter then, obtain glassy yelloe solution.This active yellow catalyst solution joins in the monomer solution through injection and under 60 ℃ reaction mixture was stirred 20 hours.Can't see viscosity has tangible increase, but solid precipitates in solution, and the solution cooling concentrates with rotary evaporator (rotovap).And precipitation obtains white polymer in hexane.Output=2.3g, 26%.Polymkeric substance is dry and record molecular weight with CPC in the room temperature vacuum.In THF, obtain GPC with polystyrene standard.Observing molecular weight is Mn=1950g/mole and Mw=3150g/mole. ¹HNMR shows the methyl esters that exists norborene and the acid of tertiary butyl ester and a spot of tert-butyl group hydrolysate.

Embodiment 12

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add the tert-butyl ester of 2.42g (12.5mmol) norborene, the methyl ester of 5.7g (37.5mmol) norborene, the ethylene dichloride 50ml of new distillation also makes solution exhaust under argon atmospher.Is furnished with coating Teflon ^The 10ml vial of stirring rod in pack into chlorination Allylpalladium dipolymer 0.0365g (0.1mmol) (monomer is 500/1 with the ratio of catalyzer) and 2ml ethylene dichloride.Hexafluoro-antimonic acid silver and the ethylene dichloride 2ml of 0.0344g (0.1mmol) pack in another 10ml vial.Catalyst solution is mixed with in drying box by chlorination Allylpalladium bipolymer solution and hexafluoro-antimonic acid silver solution.Observe the precipitation of chlorination silver salt immediately, filter then, obtain glassy yelloe solution.This active yellow catalyst solution joins in the monomer solution through injection and under 60 ℃ reaction mixture was stirred 20 hours.Can't see viscosity has tangible increase, but solid precipitates in solution, and the solution cooling concentrates with rotovap, and precipitation obtains white polymer in hexane.Output=2.05g, 25%.Polymkeric substance is dry and record molecular weight with CPC in the room temperature vacuum.In THF, obtain GPC with polystyrene standard.Observing molecular weight is Mn=1440g/mole and Mw=2000g/mole. ¹HNMR shows the methyl esters that exists norborene and the acid of tertiary butyl ester and a spot of tert-butyl group hydrolysate.

Embodiment 13

To being furnished with coating Teflon ^The 25ml vial of stirring rod in, add pure two rings [2.2.1] of 2g (7.94mmol) heptan-5-alkene-outer ,-2-the tert-butyl group, outer-3-methyl-dicarboxylic ester, add the methylene chloride and the 10ml methyl alcohol of the new distillation of 15ml then, under argon atmospher, make the solution degassing.To being furnished with coating Teflon ^The 10ml vial of stirring rod in, the 0.00588g that packs into (0.0158mmol) η ³-Allylpalladium chlorine dipolymer (monomer is 500/1 with the ratio of catalyzer) and 2ml methylene chloride.In another 10ml vial, the 0.0108g that packs into (0.0312mmol) hexafluoro-antimonic acid silver and 2ml methylene chloride.In drying box, make this η ³-Allylpalladium chlorine bipolymer solution and hexafluoro-antimonic acid silver solution mixing system are equipped with catalyst solution.Observe chlorination silver salt precipitation immediately, filter and obtain yellow transparent solution.50 ℃ should activity by syringe yellow catalyst solution add in the monomer solution, reaction mixture was at room temperature stirred 16 hours.Not observing viscosity significantly increases, and this solution is filtered by 0.5 μ filtrator, concentrates with rotovap.The gained strong solution is dissolved in the methyl alcohol, makes it precipitation and obtain white solid in methanol/water mixture, and productive rate is 65%.The measurement molecular weight is M _n=10,250g/mol and M _w=19,700g/mol (GPC in THF, polystyrene standard). ¹H NMR shows the methyl esters and the tert-butyl ester that has norborene.

Embodiment 14

To being furnished with coating Teflon ^The 25ml vial of stirring rod in, add pure two rings [2.2.1] of 3.06g (12.8mmol) heptan-5-alkene-outer, outward-2, the methylene chloride and the 10ml methyl alcohol of the tert-butyl ester of 3-diethyl dicarboxylate, 2.5g (12.8mmol) norborene, the new distillation of 15ml make the solution degassing under argon atmospher.To being furnished with coating Teflon ^The 10ml vial of stirring rod in, the 0.0188g that packs into (0.052mmol) chlorination Allylpalladium dipolymer (monomer is 500/1 with the ratio of catalyzer) and 2ml methylene chloride.In another 10ml vial, the 0.0357g that packs into (0.104mmol) hexafluoro-antimonic acid silver and 2ml methylene chloride.In drying box, make this chlorination Allylpalladium bipolymer solution and hexafluoro-antimonic acid silver solution mixing system be equipped with catalyst solution.Observe chlorination silver salt precipitation immediately, filter and obtain yellow transparent solution.50 ℃ should activity by syringe yellow catalyst solution add in the monomer solution, reaction mixture was at room temperature stirred 16 hours.Not observing viscosity significantly increases, and this solution is filtered by 0.5 μ filtrator, concentrates with rotovap.The gained viscosity solution is dissolved in the methyl alcohol, makes it precipitation and obtain white solid in methanol/water mixture, and productive rate is 23%.The measurement molecular weight is M _n=15,700g/mol and M _w=32,100g/mol (GPC in THF, polystyrene standard). ¹H NMR shows the methyl esters and the tert-butyl ester that has norborene.Thermogravimetry (TGA under nitrogen, 10 ℃ of the rates of heat addition/min) show this polymkeric substance to about 155 ℃ be heat-staple, and 290 ℃ of losses (showing the net loss of tertiary butyl groups as the isobutylene of 5-norborene homopolymer of carboxylic acid) that show about 20wt.%, then in about 450 ℃ of polymer degradations.

Embodiment 15

In two rings [2.2.1] heptan-5-alkene-outer, outer-2, the 3-diethyl dicarboxylate's is synthetic:

Outside the norborene, outer diethylester is by outer-5-norborene-2, and the 3-dicarboxylic acid synthesizes.Outer isomeride is by interior-5-norborene-2, the 3-dicarboxylic anhydride 190 ℃ of following thermal transitions then by the toluene recrystallization repeatedly (as in the reference paper 1) obtain pure outside-5-norborene-2, the 3-dicarboxylic anhydride.The hydrolysis and solution is cooled off in boiling water of the outer acid anhydride of part obtains the pure diacid of almost quantitative output.Diacid is as described below with triethyl  salt conversion diethylester:

The pure exonorborn docosene dicarboxylic acid of 16.0g (0.0824mole) and the tetrafluoro boric acid triethyl  of 35g (0.1846mole) pack in the 250ml three neck round-bottomed flasks that magnetic stirring bar is arranged.Bottleneck is jumped a queue and add the methylene chloride of 300ml with sleeve pipe under argon atmospher, and rubber plug is changed to condenser under argon atmospher.And have charging hopper at another eck.The ethyl diisopropyl amine of 35ml is added funnel, make its slow slow-motion go into reaction vessel.Seeing that slight exotherm solution is little has a backflow.This solution at room temperature kept 15 hours after adding amine.Processing procedure is with three parts of each 50ml extractive reaction potpourris of hydrochloric acid solution, with three parts of each 50ml extractions of sodium bicarbonate, washes with water at last twice afterwards.The organic solution dried over mgso is handled with carbon black, filters, and concentrates on rotary evaporator.110 ℃ down the distillation purifications of carrying out residue obtain 15g (75%) pure norborene outside-diethylester is a liquid colourless, thickness, that send fruity. ¹HNMR (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, end of the bridge), d=4.10 (2H; M, CH ₂), d=6.19 (2H; S, C=C), FI-MS (DIP)=M ⁺(238).

Embodiment 16

Two rings [2.2.1] heptan-5-alkene-outer-2-tertiary butyl ester, outer-3-carboxylic acid synthetic:

To being furnished with coating Teflon ^The single neck round-bottomed flask of 50ml of stirring rod in, add 1.5g (9.15mmol) pure outer-(carbic anhydride), new distilled dichloromethane 10ml, tert-butyl alcohol 20ml (0.209mole).Dimethyl amine pyridine 7.5g (0.061moles) is added this solution.And this solution was refluxed 8 hours down at 75 ℃.The beginning acid anhydride is soluble, but later stage solid dissolving and solution are transformed into brown.The cooling reaction concentrates the solid of removing methylene chloride and strong solution slowly being added filtering-depositing in the water (HCL) that contains acid in rotovap, wash and further be dissolved in MgSO with water ₄In the ether of handling, with after the carbon black processing solution is filtered with Celite.Remove ether with rotovap and obtain white solid (productive rate 8.5g60%). ¹HNR (CDCl ₃): d=1.47 (9H; S, the tert-butyl group), d=1.60 (1H), d=2.15 (1H), d=2.58 (2H; M, CHCOO), d=3.07 (2H; S, end of the bridge), d=6.19 (2H; S, C=C), d=10.31 (1H; Wide, COOH).

Embodiment 17

Two rings [2.2.1] heptan-5-alkene-outer-2-tertiary butyl ester, dicarboxylic acid is outer-3-methyl esters synthetic:

In the 100ml three neck round-bottomed flasks of being furnished with magnetic stirring bar, outside the pure norbornene dicarboxylic acids of adding 9.7g (0.0408mol)-tert-butyl group half ester and tetrafluoro boric acid trimethyl .Bottleneck is jumped a queue, and adds the methylene chloride of 100ml under argon atmospher with sleeve pipe, and rubber plug is changed to condenser and has charging hopper at another eck under argon atmospher.The ethyl diisopropyl amine of 7.3ml is added funnel, make it slowly enter reaction vessel.Seeing that slight exotherm solution is little has a backflow.This solution at room temperature kept 15 hours after adding amine.Processing procedure is with three parts of each 50ml extractive reaction potpourris of hydrochloric acid solution, with three parts of each 50ml extractions of sodium bicarbonate, washes twice at last with water afterwards, and the organic solution dried over mgso is handled with carbon black, filters, and concentrates on rotary evaporator.Obtain colourless liquid, the beginning crystallization.Solid is washed with cold pentane and pentane solution is concentrated in rotovap and obtains colourless liquid, crystallisation by cooling then.Product 5.1g. ¹HNMR (CDCl ₃): d=1.45 (9H; S, the tert-butyl group), d=1.47 (1H), d=2.15 (1H), d=2.54 (2H; M, CHCOO), d=3.07 (2H; S, end of the bridge), d=3.65 (3H; S, CH ₃), d=6.19 (2H; S, C=C).

Embodiment 18

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add 5-norborene-carboxylic acid (2.0g, 14.5mmol, outer, interior potpourri) and ethylene dichloride (20ml).During under environment temperature this stirs the mixture, add by with the η in the ethylene dichloride (5ml) ³Allylpalladium chlorine dipolymer (6mg, 16 μ mol) is added in the hexafluoro-antimonic acid silver (50mg, 146 μ mol) in the ethylene dichloride (5ml) 30 minutes, filters the catalyst solution of (removing the precipitation silver chloride) preparation then by millipore filter.Reaction was carried out 18 hours, and this moment, the potpourri gel formed the glassy yelloe colloid.Polymer precipitation is a white powder when this glue joins in the excessive hexane.Polymkeric substance is also dry with excessive hexane wash.The output of polymkeric substance is 1.2g (60%).Recording polymer molecular weight is that 22000 (Mw) and polydispersity are 2.3.

When partly this polymkeric substance (0.5) joins in the KOH aqueous solution (10ml) of a 0.1N stirring, polymkeric substance dissolve immediately cannot not obtain stickingly, colourless solution, this proves that these materials are that available bases is developed because there is not the homopolymer of the tert-butyl ester of 5-norborene-carboxylic acid to demonstrate any tendency under identical condition.

Embodiment 19

The Pinner of ortho esters is synthetic to be that two steps are synthetic: step 1, imino-ester hydrochloride synthetic.

Reaction is to finish in the 1L two neck round-bottomed flasks of the pipe that is equipped with a stirring rod, oily bubbler and band anhydrous calcium chloride.Put following reagent into flask: 100g (0.84mol) norborene nitrile (NB-CN), 37ml (0.9mol) absolute methanol and the anhydrous Anaesthetie Ether of 200ml.Flask is put into ice-water bath, make the dry hydrogen chloride of 61g (1.67mol) pass through the potpourri bubbling 1.5 hours under stirring.Flask spends the night in 0 ℃ of refrigerator.In morning, potpourri is frozen into " cake ".Broken in flakes and add Anaesthetie Ether 200ml.Flask kept in refrigerator 10 days again and stirred every now and then.Last imino-ester hydrochloride precipitation is washed 5 times through suction strainer and with about 300ml Anaesthetie Ether.Reclaiming unreacted NB-CN from filtrate is about 20g.

The productive rate of imino-ester hydrochloride be 79% (120g, 0.64mol).The structure of product by ¹HNMR spectrum is confirmed.

Step 2, ortho esters synthetic

In the 0.5L flask, put into 56.7g (0.30mol) imino-ester hydrochloride, 37ml (0.91mol) absolute methanol and 250ml dry oil ether.Reaction mixture insulation at room temperature 5 days is also constantly stirred.Filter out chloride precipitation and use petroleum ether 3 times.Merging filtrate and washing lotion distill out sherwood oil, and with product fractionation in a vacuum.Collecting boiling point is the cut of 68-69 ℃/3mmHg.Productive rate 50% (30g, 0.15mol).According to ¹HNMR spectrum product as can be known is 97+%5-norborene-2-trimethoxy-methane (ortho esters).

Embodiment 20

To 2.16g (10.9mmol) C ₇H ₉(OCH ₃) ₃(norborene trimethyl ortho esters) at 16ml1, add in the solution in the 2-ethylene dichloride hexafluoro-antimonic acid silver 2moles that is used in the ethylene dichloride and 1mole chlorination Allylpalladium dipolymer reaction product mixture solution and leach silver nitride precipitation.Add the palladium that catalytic amount is equivalent to 0.08mmol and be dissolved in the 2ml ethylene dichloride.In 70 ℃ of following oil baths, add stirred reaction mixture and reacted 20 hours.

Reaction is last, adds 2ml methyl alcohol, and solvent steams on rotary evaporator, and polymkeric substance is dried to constant weight in a vacuum.

Output-1.28g (60%).

Embodiment 21

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add two rings [2.2.1] heptan-5-alkene-2-methylene diacetate ester (18.44g, 0.1109mol) and the tert-butyl ester of norborene (21.55g, 0.1109mol) and toluene 75ml, nickel catalyst solution [the toluene complex of two perfluorophenyl nickel, (Tol) Ni (C ₆F ₅) ₂] be by 0.5367g (1.109mmol (Tol) Ni (C ₆F ₅) ₂] in drying box, be dissolved in and prepare in the 15ml toluene.The active catalytic agent solution joins in the monomer solution at ambient temperature by syringe.At room temperature stirred 6 hours.Solution precipitates in excessive methyl alcohol with dilution with toluene and polymkeric substance.The polymkeric substance washing with acetone of filtering-depositing, dried overnight in the vacuum.The polymer yield that separates is 24.9g (63%).Polymkeric substance characterizes with the GPC determining molecular weight.Mn=21,000 and Mw=52,00.The NMR of multipolymer the analysis showed that the tertiary butyl groups that has 51mol%.The IR of multipolymer the analysis showed that no acidic group.

Embodiment 22

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add two rings [2.2.1] heptan-5-alkene-2-Methylethyl carbonic ester (4.03g, 0.0205mol) and the tert-butyl ester of norborene (3.98g, 0.0205mol) and toluene 50ml, nickel catalyst solution [the toluene complex of two perfluorophenyl nickel, (Tol) Ni (C ₆F ₅) ₂] be by 0.0991g (0.2049mmol (Tol) Ni (C ₆F ₅) ₂] in drying box, be dissolved in and prepare in the 15ml toluene.The active catalytic agent solution joins in the monomer solution at ambient temperature by syringe.At room temperature stirred 6 hours.Solution precipitates in excessive methyl alcohol with dilution with toluene and polymkeric substance.The polymkeric substance washing with acetone of filtering-depositing, dried overnight in the vacuum.The polymer yield that separates is 4.16g (52%).Polymkeric substance characterizes with the GPC determining molecular weight.Mn=22,000 and Mw=58,000.The NMR of multipolymer the analysis showed that the tertiary butyl groups that has 50mol%.The IR of multipolymer the analysis showed that and not contain acidic group.

Embodiment 23

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add two rings [2.2.1] heptan-5-alkene-2-methyl butyl carbonic ester (17.15g, 0.0764mol) and the tert-butyl ester of norborene (14.85g, 0.0764mol) and toluene 72ml, nickel catalyst solution [the toluene complex of two perfluorophenyl nickel, (Tol) Ni (C ₆F ₅) ₂] be by 0.3699g (0.7644mmol (Tol) Ni (C ₆F ₅) ₂] in drying box, be dissolved in and prepare in the 15ml toluene.The active catalytic agent solution joins in the monomer solution at ambient temperature by syringe.At room temperature stirred 6 hours.Solution precipitates in excessive methyl alcohol with dilution with toluene and polymkeric substance.The polymkeric substance washing with acetone of filtering-depositing, dried overnight in the vacuum.The polymer yield that separates is 17.53g (54%).Polymkeric substance characterizes with the GPC determining molecular weight.Mn=22,000 and Mw=58,000.The NMR of multipolymer the analysis showed that the tertiary butyl groups that has 54mol%.The IR of multipolymer the analysis showed that no acidic group.

Embodiment 24

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add norborene tertiary butyl ester (29.92g, 0.154mol), add then dry maleic anhydride (15.10g, 0.154mol) and the 90ml chlorobenzene.This potpourri degassing is removed trace oxygen three times.Reaction mixture is heated to 80 ℃ then.The degassing benzoyl peroxide solution of being made up of in the 10ml chlorobenzene 0.9948g (0.04mol) benzoyl peroxide free radical initiating agent adds in the reaction mixture with the dry injection device.Behind the stirring reaction 19 hours.After the reaction, polymer solution is directly poured the hexane precipitation polymers into.Obtain white depositions.The stripping precipitation polymers is removed the unreacted maleic anhydride that may exist.Polymkeric substance is dried overnight under the room temperature in a vacuum.The weight of dry polymer is 20.62g, productive rate 45.8%.Polymkeric substance characterizes with the GPC determining molecular weight.Mn=4,200 and Mw=8,800.The NMR of multipolymer the analysis showed that and has tertiary butyl groups.The IR of multipolymer the analysis showed that and both exists the tert-butyl group also to have the maleic anhydride group.

Embodiment 25

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add two rings [2.2.1] heptan-5-alkene-2-methylene diacetate ester (13.3g, 0.0799mol), tertiary butyl ester (the 15.70g of norborene, 0.0808mol), (15.85g is 0.162mol) with the 90ml chlorobenzene to add dry maleic anhydride then.This potpourri degassing is removed trace oxygen three times.Reaction mixture is heated to 80 ℃ then.The degassing benzoyl peroxide solution of being made up of in the 10ml chlorobenzene 1.0438g (0.041mol) benzoyl peroxide free radical initiating agent adds in the reaction mixture with the dry injection device.Stirring reaction 19 hours.After the reaction, polymer solution is directly poured the hexane precipitation polymers into.Obtain white depositions.The stripping precipitation polymers is removed the unreacted maleic anhydride that may exist.Polymkeric substance is dried overnight under the room temperature in a vacuum.The weight of dry polymer is 21.89g, productive rate 48.7%.Polymkeric substance characterizes with the GPC determining molecular weight.Mn=3,000 and Mw=6600.The NMR of multipolymer the analysis showed that and has acetic acid esters and tertiary butyl groups.The IR of multipolymer the analysis showed that and has acetate, the tert-butyl group and maleic anhydride group.

Embodiment 26

50: 50 multipolymers of t-BuNB ester/NB-COOH

In the 50ml vial of being furnished with magnetic stirring bar, under blanket of nitrogen, add norborene carboxylic acid tertiary butyl ester (2g, 10mmol) and the norborene carboxylic acid (1.38g, 10mmol).Stir the mixture to this at ambient temperature and add initiating agent (tert-butyl peroxide) (2.9g) and mixture heated to 130 ℃ and continue to stir 16 hours.Polymkeric substance (solvable in THF and toluene) precipitates in hexane and filters and draws product, and dry weight is 2.91g (86% conversion ratio).Solid polymer molecular weight Mw is 20,000, and Mn is 3,000).The IR of multipolymer, NMR and TGA analyze and confirm that its composition is the random addition copolymer of two kinds of monomers.

Embodiment 27

50: 50 multipolymers of t-BuNB ester/NB-MeNB ester

In the 50ml vial of being furnished with magnetic stirring bar under blanket of nitrogen, add norborene carboxylic acid tertiary butyl ester (2g, 10mmol) and the methyl esters of norborene carboxylic acid (1.5g, 10mmol).Stir the mixture to this at ambient temperature and add initiating agent (tert-butyl peroxide) (2.9g) and mixture heated to 130 ℃ and continue to stir 16 hours.Polymkeric substance (dissolving in toluene) precipitates in methyl alcohol and filters and draws product, and dry weight is 0.82g (23% conversion ratio).Solid polymer molecular weight Mw is 35,000, and Mn is 6,000).The IR of multipolymer, NMR and TGA analyze and confirm that its composition is the random addition copolymer of two kinds of monomers.

Embodiment 28

50: 50 multipolymers of t-BuNB ester/EtTD ester

In the 100ml vial of being furnished with magnetic stirring bar under blanket of nitrogen, add toluene (40ml) norborene carboxylic acid tertiary butyl ester (1.94g, 10mmol) and the ethyl ester of tetracyclododecane carboxylic acid (2.32g, 10mmol).Add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (34mg, 0.042mmol) solution in the toluene of 5ml at ambient temperature to this agitating solution.Add after 1 hour ethyl vinyl ether (0.015ml, 0.156mmol) and stirred 1 hour.In polymer solution, add excessive MeOH and make its precipitation, filter and collect and drying under vacuum.Reclaim multipolymer 3.46g (81% productive rate) (Mw221,000, Mn133,000).

Multipolymer is dissolving and make color obviously fade (Ru) by a silicagel column again in toluene.Polymkeric substance precipitates once more in excessive MeOH and obtains a kind of pure white multipolymer.

Embodiment 29

50: 50 multipolymers of t-BuNB ester/EtTD ester

In the 100ml vial of being furnished with magnetic stirring bar under blanket of nitrogen, add toluene (80ml) norborene carboxylic acid tertiary butyl ester (3.9g, 20mmol) and the ethyl ester of tetracyclododecane carboxylic acid (4.64g, 20mmol).In this agitating solution, add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (68mg, 0.083mmol) solution in the toluene of 5ml at ambient temperature.Add after 2 hours ethyl vinyl ether (0.030ml, 0.31mmol) and stirred 2 hours.

Orange-yellow solution obtains transparent colourless solution by silicagel column.Add excessive MeOH at this solution and make it precipitation, filter and collect and drying under vacuum.Reclaim multipolymer 6.54g (productive rate 77%) (Mw244,000, Mn182,000).Measure glass temperature and be defined as 220 ℃ with the DSC method.

Embodiment 30

50: 50 multipolymers of t-BuNB ester/EtTD ester

In the 300ml stainless steel reactor of being furnished with magnetic stirring bar, under blanket of nitrogen, add toluene (90ml), norborene carboxylic acid tertiary butyl ester (3.9g, 20mmol) and the ethyl ester of tetracyclododecane carboxylic acid (4.64g, 20mmol).In this agitating solution, add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (68mg, 0.083mmol) solution in 5ml toluene at ambient temperature.Add after 2 hours ethyl vinyl ether (0.030ml, 0.31mmol) and stirred 16 hours.Be added to hydrogen (350psig) in the reactor and temperature remain on 175 ℃ following 7 hours.Reaction back solution is by silicagel column and separate the multipolymer of hydrogenation.Determine multipolymer hydrogenation 95% (Mw237,000, Mn163,000) with the NMR method.

Embodiment 31

50: 50 multipolymers of t-BuNB ester/EtTD ester

In the 300ml stainless steel reactor of being furnished with magnetic stirring bar, under blanket of nitrogen, add toluene (90ml), norborene carboxylic acid tertiary butyl ester (2.9g, 15mmol) and the ethyl ester of tetracyclododecane carboxylic acid (3.5g, 15mmol).Stir the mixture to this at ambient temperature and add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (50mg, 0.060mmol) solution in 5ml toluene.Be added to hydrogen (800psig) in the reactor after 2 hours and temperature remain on 175 ℃ following 7 hours.Reaction back solution is by silicagel column and separate the multipolymer of hydrogenation.Determine multipolymer hydrogenation 96% (Mw278,000, Mn172,000) with the NMR method.

Embodiment 32

50: 50 multipolymers of t-BuNB ester/EtTD ester

In the 100ml vial of being furnished with magnetic stirring bar, under blanket of nitrogen, add toluene (40ml), norborene carboxylic acid tertiary butyl ester (1.94g, 10mmol) and the ethyl ester of tetracyclododecane carboxylic acid (2.32g, 10mmol) and the 1-hexene (0.050ml, 0.4mmol).Add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (34mg, 0.042mmol) solution in 5ml toluene to this agitating solution at ambient temperature.After 2 hours polymer solution is added among the excessive MeOH, filter and collect and drying under vacuum.Obtain the polymkeric substance (Mw35,000, Mn22,000) of 3.1g (productive rate 73%).

Embodiment 33

50: 50 multipolymers of t-BuNB ester/EtTD ester

In the 100ml vial of being furnished with magnetic stirring bar, under blanket of nitrogen, add toluene (40ml), norborene carboxylic acid tertiary butyl ester (1.94g, 10mmol), the ethyl ester (2.32g of tetracyclododecane carboxylic acid, 10mmol) and the 1-hexene (0.275ml, 2.2mmol).Add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (34mg, 0.042mmol) solution in 5ml toluene to this agitating solution at ambient temperature.Polymer solution adds among the excessive MeOH after 2 hours, filters and collects and drying under vacuum.Obtain the polymkeric substance (Mw8,000, Mn6,000) of 3.45g (productive rate 81%).

Embodiment 34

50: 50 multipolymers of t-BuNB ester/EtTD ester

In the 100ml vial of being furnished with magnetic stirring bar, under blanket of nitrogen, add toluene (40ml), norborene carboxylic acid tertiary butyl ester (1.94g, 10mmol), the ethyl ester of tetracyclododecane carboxylic acid (2.32g, 10mmol) and the 1-hexene (0.62ml, 5.0mmol).In this agitating solution, add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (34mg, 0.042mmol) solution in 5ml toluene at ambient temperature.Polymer solution adds among the excessive MeOH after 2 hours, filters and collects and drying under vacuum.Obtain the polymkeric substance of 2.75g (productive rate 65%).

Embodiment 35

50: 50 multipolymers of t-BuNB ester/EtTD ester

In the 100ml vial of being furnished with magnetic stirring bar, under blanket of nitrogen, add toluene (80ml), norborene carboxylic acid tertiary butyl ester (3.9g, 20mmol), the ethyl ester of tetracyclododecane carboxylic acid (4.64g, 20mmol) and the 1-hexene (0.088ml, 0.7mmol).In this agitating solution, add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (68mg, 0.083mmol) solution in 5ml toluene at ambient temperature.Add after 2 hours ethyl vinyl ether (0.030ml, 0.31mmol) and stirred 2 hours.

Orange-faint yellow polymer solution is by the silicagel column dark colour (Ru) of decorporating.Solution added among the excessive MeOH precipitate, filter and collect and dried overnight under 80 ℃ of vacuum.Obtain polymkeric substance 2.6g (productive rate 30%) (Mw4,000, Mn3,000).

Embodiment 36

50: 50 multipolymers of t-BuNB ester/EtTD ester

In the 300ml stainless steel reactor of being furnished with magnetic stirrer, under blanket of nitrogen, add toluene (80ml), norborene carboxylic acid tertiary butyl ester (3.9g, 20mmol), the ethyl ester (4.64g of tetracyclododecane carboxylic acid, 20mmol) and the 1-hexene (0.088ml, 0.7mmol).In this agitating solution, add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (68mg, 0.042mmol) solution in 5ml toluene at ambient temperature.Hydrogen (750psig) adds reactor and 175 ℃ insulation 20 hours down after 2 hours.

Solution added in the excessive methanol precipitate filtered and recycled and dried overnight under 80 ℃ of vacuum.Obtain the polymkeric substance (Mw30,000, Mn20,000) of about 5g (productive rate 59%).Determine that with the NMR method multipolymer hydrogenation is greater than 99%.

Embodiment 37

65: 35 multipolymers of t-BuNB ester/EtTD ester

Add toluene (160ml) to being furnished with magnetic stirring bar and containing in the 250ml round-bottomed flask of nitrogen, norborene carboxylic acid tertiary butyl ester (10.1g, 52mmol), the ethyl ester (6.5g of tetracyclododecane carboxylic acid, 28mmol) and the 1-hexene (0.176ml, 1.4mmol).In this agitating solution, add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (131mg, 0.160mmol) solution in 5ml toluene at ambient temperature.Add after 16 hours ethyl vinyl ether (0.060ml, 0.62mmol) and stirred 1.5 hours.Polymer solution is removed Ru by silicagel column.This solution is added in the excessive methanol, filter and collect and drying under vacuum.Obtain polymkeric substance 9.69g (productive rate 58%) (Mw42,000, Mn31,000).Measure glass temperature (110 ℃) with the DSC method.

Embodiment 38

In containing the 100ml vial of nitrogen with the polymer dissolution of 0.5g embodiment 37 in THF (80ml).This solution is transferred in the 300ml stainless steel reactor.Palladium-aluminium oxide catalyst the 2.25g (available from Aldrich) that drapes over one's shoulders of 5wt% adds reactor.Be heated to 175 ℃ then also with hydrogen 800psig pressurization.Temperature and pressure was kept 9.5 hours.The centrifuging polymer solution is also told colourless solution, and polymkeric substance precipitates in excessive methanol.The demonstration of NMR method obtains multipolymer hydrogenation greater than 99%.

Embodiment 39

50: 50 multipolymers of t-BuNB ester/EtTD ester

Add toluene (80ml) to being furnished with magnetic stirring bar and containing in the 100ml vial of nitrogen, norborene carboxylic acid tertiary butyl ester (3.9g, 20mmol), the ethyl ester of tetracyclododecane carboxylic acid (4.64g, 20mmol) and the 1-hexene (0.088ml, 0.7mmol).Add two (tricyclohexyl phosphine)-benzylidene ruthenous chloride (68mg, 0.084mmol) solution in 5ml toluene to this agitating solution at ambient temperature.Add ethyl vinyl ether (30 μ l) after 2 hours and temporarily stop further to react and stirred 1.5 hours.Polymer solution is removed the Ru residue by silicagel column.Polymkeric substance is collected as the cleaning white solid by precipitation in methyl alcohol then.Predicting polymkeric substance Mw is 46,600, (Mn33,700).And using IR, NMR and TGA method are fully characterized.

Embodiment 40

To internal capacity be add in the stainless steel cauldron of 300ml 2-methyl-4-penetenoic acid ethyl ester (99g, 0.7mol) and new cracking cyclopentadiene (46.4g, 0.7mol).Stir the mixture and be heated to 200 ℃ and spend the night.The reactor cooling is also emitted material.Functionalized norborene (the NB-CH that obtains ₂CH (CH ₃) C (O) OC ₂H ₅) purify and predict under 0.02mmHg the about 46-47 of boiling point ℃ by vacuum distillation.Show that with this material of GC methods analyst purity is 98.4% to 99.3% (different fractions).The output of the high purity product that separates is 33g.

Embodiment 41

T-BuNB ester (NB-CH ₂CH (CH ₃) C (O) OC ₂H ₅) 40: 60 multipolymers

Under blanket of nitrogen, add toluene (50ml) in the 100ml vial of being furnished with magnetic stirring bar, (2.7g is 14mmol) with by the ester (NB-CH of embodiment 40 for norborene carboxylic acid tertiary butyl ester ₂CH (CH ₃) C (O) OC ₂H ₅) (4.4g, 21mmol).In this agitating solution, add (toluene) Ni (C at ambient temperature ₆F ₅) ₂Solution in toluene (1ml).The solution that obtains is heated to 50 ℃ also to be continued to stir 3 hours.Polymkeric substance precipitates in methyl alcohol and filters.The solid that obtains is dissolving again in THF, filters and once more with the methanol solution precipitation and filter.Obtaining white solid polymkeric substance drying and predicting weight is 2.66g (Mw70,000; Mn39,800).Supernatant liquor is evaporated to dried, obtains more white polymer, and dry weight is 1.52g (Mw60,650, Mn31,000).The overall yield of multipolymer is expressed as 59% monomer conversion.The IR of multipolymer, NMR and TGA analyze and determine that it consists of the random addition copolymer of two kinds of monomers.

Embodiment 42

T-BuNB ester (NB-CH ₂CH (CH ₃) C (O) OC ₂H ₅) 40: 60 multipolymers

In the 250ml vial of being furnished with magnetic stirring bar, under blanket of nitrogen, add ethylene dichloride (200ml), and norborene carboxylic acid tertiary butyl ester (7.76g, 40mmol) and the ester (NB-CH of embodiment 40 ₂CH (CH ₃) C (O) OC ₂H ₅) (12.5g, 60mmol) with 2,6-two-tert-butyl pyridine (28.8mg, 0.26mmol).Add in this agitating solution at ambient temperature that (0.183g 0.5mmol) mixes in ethylene dichloride (3ml) with hexafluoro-antimonic acid silver (equivalent amount) and removes by filter the catalyst solution that silver nitride precipitation makes by chlorination Allylpalladium dipolymer.The solution that obtains was heated to 50 ℃ of continuous stirring 16 hours.This polymer solution is handled with carbon monoxide (4psi pressure) and was made palladium residue precipitation in 48 hours, filters by 0.45 μ filtrator, reduces in a vacuum and obtains multipolymer 7.9g (39% conversion ratio), Mw11,600 with excessive methanol extraction; Mn7,000.Multipolymer IR, NMR and TGA method are fully characterized.

Embodiment 43

The copolymerization of CO and norborene-5-tertiary butyl ester

With dipyridine deoxidation methanol solution (0.025g, 0.16mmol) add the acid chloride (II) be dissolved in deoxidation methyl alcohol (0.012g, 0.053mmol).In this kind solution, add the right-toluenesulfonic acid be dissolved in the deoxidation methyl alcohol (0.045g, 0.27mmol).Brown solution adding benzoquinones methyl alcohol (deoxidation) solution that obtains (1.72g, 1.59mmol).Be preheated to 50 ℃ in this solution adding stainless steel reactor.(5.14g 0.027mol) (uses the argon gas deoxidation) to be incorporated in norborene-5-tertiary butyl ester among the 100ml MeOH to this reactor.Reactor is pressurized to 600psig with carbon dioxide and is heated to 65 ℃.4.5 after hour, discharge carbon dioxide and make the reactor cooling.Pink solution in the filtration reactor is removed remaining palladium and evaporation.The potpourri that obtains is dissolved among a spot of THF and slowly pours 25: 75 water into: precipitation polymers in the methanol solution.Repeat this step twice.The white polymer that obtains is filtered and is dry under the room temperature vacuum.Output=2.9g.

Embodiment 44

With benzoquinones (0.43g, 0.40mmol), dipyridine (0.0062g, 0.0040mmol) and Pd (MeCN) ₂(p-toluenesulfonic acid) ₂(0.0070g 0.0013mmol) is heated to 50 ℃ in the stainless steel reactor of the adding of the solution in the deoxidation THF/ of drying methyl alcohol (35ml/15ml) 500ml drying.To reactor be incorporated in norborene-5-tertiary butyl ester among the 100ml THF (deoxidation and dry) (5.14g, 0.027mol).Reactor is pressurized to 600psig with carbon monoxide and is heated to 65 ℃.12.5 after hour, reactor be heated to 90 ℃ 1.5 hours.Discharge carbon monoxide and make the reactor cooling.The solution of purple in the filtration reactor is removed remaining palladium and evaporation.The potpourri that obtains is dissolved among a spot of THF and slowly pours 25: 75 water into: precipitation polymers in the methanol solution.Repeat this step twice.The white polymer that obtains is filtered and drying under the room temperature vacuum.Output=2.9g.

Embodiment 45-51 is based on the test of optical density under 193nm of the homopolymer and the multipolymer of cycloolefin

Optical density is the key characteristic of effective photoresist, because its decision is by the homogeneity of the energy of film thickness.The optical density of main polymer chain before adding Photoacid generators useful on a kind of typical photoetching technique is less than 0.2 absorbance units/micron (T.Neenan, E.Chandross, J.Kometani and O.Nalamasu, " styryl sulfonyloxy methyl amine: the alkali increase-volume components of using of photoresist resin " pg199 more, microelectric technique, modern imaging and packing polymkeric substance, ACS collection of thesis 614, publish: E.Reichmanis, C.Ober, S.MacDonald, T.Iwayanagai and T.Nishikubo, April nineteen ninety-five).Optical density is 2.8 absorbance units/microns under the 193nm of polycarboxylated styrene (principal ingredient of 248nmDUV photoresist usually), under this wavelength, is useless as the resist main chain therefore.

The preparation sample solution

(polymkeric substance of 0.016 ± 0.001g also is dissolved in the 4ml chloroform to weigh up various polymer samples described in the above embodiment.Polymer solution take out with suction pipe and on the even quartzy slide plate of cleaning curtain coating become film.Film drying is spent the night.Circular membrane on the quartzy slide plate that obtains in baking oven under the nitrogen 70 ℃ further dry 10 minutes.

With Perkin-Elmer Lambda 9UV/VIS/IR spectrophotometer,, record the UV spectrum of this film with 120nm/ minute sweep velocity.Spectral range is set at 300nm to 180nm.By the absorptance of this film under the mensuration 193nm, and press film thickness normalization, record the optical density of this film at 193nm.The results are shown in following table:

Normalization embodiment polymkeric substance absorptivity (A) (micron) absorptivity (/micron) 45 50,/50 two ring [2.2.1] heptan-5-alkene-2-methylene diacetate ester/norborene 1.0173 25.39 0.0400 of the film thickness of 193nm under 193nm

The multipolymer of the tert-butyl ester (polymkeric substance of embodiment 21) 46 50,/50 2 ring [2.2.1] heptan-5-alkene-2-Methylethyl carbonic ester/norborene 0.1799 30.47 0.0059

The multipolymer of the tert-butyl ester (polymkeric substance of embodiment 22) 47 50,/50 2 ring [2.2.1] heptan-5-alkene-2-methyl butyl carbonic ester/norborene 0.2808 33.01 0.0085

Multipolymer (polymkeric substance of embodiment 24) 1.1413 38.09 0.029949 2 ring [2.2.1] of the multipolymer of the tert-butyl ester (polymkeric substance of embodiment 23) 48 maleic anhydrides/norborene tert-butyl ester heptan-5-alkene-2-methylene diacetate ester/maleic anhydride/norborene tert-butyl ester 0.8433 17.78 0.04743

Tertiary butyl ester/the tetracyclododecen 0.4693 33.01 0.0142 of trimer (polymkeric substance of embodiment 25) 50 50/50 norborene

The tertiary butyl ester/tetracyclododecen 0.4146 35.55 0.0117 of ethyl ester multipolymer (polymkeric substance of embodiment 29) 51 50/50 norborene

The preparation of ethyl ester multipolymer (polymkeric substance of embodiment 30) resist solution, exposure and developing

The solid content of polymkeric substance in the foregoing description with 15w/v% is dissolved in the propylene glycol monomethyl ether (PGMEA), add therein with respect to polymkeric substance be 5 or the foregoing description of 10w/w% in salt.

By 0.2 μ Teflon ^Filtrator filters this solution, is spin-coated on the silicon wafer that is coated with hexamethyldisilazane (HMDS) bottom by each solution and makes resist layer.Filmed 1 minute 95 ℃ of oven dry.By the quartz mask wavelength is that the ultraviolet ray that 230 to 250nm Karl Suss MJB3 UV250 instrument produces makes the film exposure.The film that exposed be heated to 125 ℃ to 150 ℃ 1 minute.In buck, develop, provide high-resolution positive tone illustration to resemble, in the free of losses of unexposed portion film thickness.

This system can easily carry out the processing of negative film image by developing in non-polar solvent.Can have low-down optical density with these materials finding under 193nm the same (as mentioned above) by adding a spot of photosensitizer such as Bi, perylene or thioxanthones etc. make these materials to long wavelength (365nm) or short wavelength (193nm) sensitivity.

Embodiment 52

The multipolymer (embodiment 21) (number-average molecular weight 21,000) of the tertiary butyl ester of two rings [2.2.1] heptan-5-alkene-2-methyl acetic acid ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 10w/v%.In polymkeric substance, add the hexafluoroarsenate triphenyl sulfonium with 10w/w% load.Etchant resist is by 0.2 μ lTeflon ^Filtrator filters, and filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain 0.7 μ thick film layers.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 50mj/cm ²The UV ray of dosage (240nm makes its exposure.The back oven dry is 1 minute under 125 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 53

With under the NiArf catalyzer two the ring [2.2.1] heptan-5-alkene--the copolymerization of the tertiary butyl ester of 2-Methylethyl oxalate/norborene

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add two rings [2.2.1] heptan-5-alkene-2-Methylethyl oxalate (8.57g, 0.0382mol) and the tertiary butyl ester of norborene (7.42g, 0.0392mol) and toluene 38ml.Nickel catalyst solution [the toluene complex of two perfluorophenyl nickel, (Tol) Ni (C ₆F ₅) ₂] by 0.1854g (0.382mmol (Tol) Ni (C ₆F ₅) ₂] in drying box, be dissolved in and prepare in the 15ml toluene.The active catalytic agent solution joins in the monomer solution at ambient temperature by syringe.At room temperature stirred 5 hours.Solution precipitates in excessive methyl alcohol with dilution with toluene and polymkeric substance.The polymkeric substance washing with acetone of filtering-depositing, dried overnight in the vacuum.The productive rate of isolating polymer is 7.62g (48%).Polymkeric substance characterizes determining molecular weight Mn=28 with GPC, and 000 and Mw=56,000.The NMR of multipolymer the analysis showed that the multipolymer composition approaches charge ratio.The IR of multipolymer the analysis showed that no acidic group.

Embodiment 54

The tertiary butyl ester multipolymer (embodiment 21) (number-average molecular weight 21,000) of two rings [2.2.1] heptan-5-alkene-2-methyl acetic acid ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 10w/v%.In polymkeric substance, add hexafluoro-antimonic acid two fragrant salt compounded of iodine (Sartomer1012) with 10w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters, and this filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain 0.7 μ thick film layers.This film was dried 1 minute under on the heat dish 95 ℃, then by quartz mask 50mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 1 minute under 125 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 55

The tertiary butyl ester multipolymer (embodiment 21) (number-average molecular weight 21,000) of two rings [2.2.1] heptan-5-alkene-2-methyl acetic acid ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 10w/v%.In this polymkeric substance, add hexafluoro-antimonic acid two fragrant salt compounded of iodine (Sartomer1012) with 10w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 0.7 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 100mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 1 minute under 125 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 56

With under the NiArf catalyzer two the ring [2.2.1] heptan-5-alkene--the copolymerization of the tertiary butyl ester (70/30 mol ratio) of 2-Methylethyl oxalate/norborene

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add two rings [2.2.1] heptan-5-alkene-2-Methylethyl oxalate (14.8g, 0.0663mol) and the tertiary butyl ester of norborene (5.52g, 0.0284mol) and toluene 113ml.Nickel catalyst solution [the toluene complex of two perfluorophenyl nickel, (Tol) Ni (C ₆F ₅) ₂] by 0.2296g (0.474mmol (Tol) Ni (C ₆F ₅) ₂] in drying box, be dissolved in and prepare in the 15ml toluene.The active catalytic agent solution joins in the monomer solution at ambient temperature by syringe.At room temperature stirred 5 hours.Solution precipitates in excessive methyl alcohol with dilution with toluene and polymkeric substance.The polymkeric substance washing with acetone of filtering-depositing, dried overnight in the vacuum.The polymer yield that separates is 10.15g (50%).Polymkeric substance characterizes determining molecular weight with GPC.Mn=35,000 and Mw=98,000.The NMR of multipolymer the analysis showed that the multipolymer composition approaches charge ratio.The IR of multipolymer the analysis showed that no acidic group.

Embodiment 57

The multipolymer (embodiment 21) (number-average molecular weight 21,000) of the tertiary butyl ester of two rings [2.2.1] heptan-5-alkene-2-methyl acetic acid ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 10w/v%.In polymkeric substance, add the hexafluoroarsenate triphenyl sulfonium with 10w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters, and this filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 0.7 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 10mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 1 minute under 125 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 58

The multipolymer (embodiment 21) (number-average molecular weight 21,000) of the tertiary butyl ester of two rings [2.2.1] heptan-5-alkene-2-methyl acetic acid ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 10w/v%.In this polymkeric substance, add the hexafluoroarsenate triphenyl sulfonium with 10w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 0.7 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 30mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 1 minute under 125 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 59

With under the NiArf catalyzer two the ring [2.2.1] heptan-5-alkene--the copolymerization of 2-Methylethyl oxalate/1-(1-ethoxy) ethyl 5 norborene-2-carboxylic esterification (50/50 mol ratio)

To being furnished with coating Teflon ^The 50ml vial of stirring rod in, add two rings [2.2.1] heptan-5-alkene-2-Methylethyl oxalate (0.5166g, 2.304mmol) and 1 (1-ethoxy) ethyl 5-norborene-2 carboxylate (0.4885g, 2.304mol) and cyclohexane 2.25ml.Nickel catalyst solution [the toluene complex of two perfluorophenyl nickel, (Tol) Ni (C ₆F ₅) ₂] by 0.0112g (0.023mmol (Tol) Ni (C ₆F ₅) ₂] in drying box, be dissolved in and prepare in the 0.65ml ethyl acetate.The active catalytic agent solution joins in the monomer solution at ambient temperature by syringe.At room temperature stirred 5 hours.Solution precipitates in excessive methyl alcohol with dilution with toluene and polymkeric substance.The polymkeric substance washing with acetone of filtering-depositing, dried overnight in the vacuum.The polymer yield that separates is 0.0315g (3%).Polymkeric substance characterizes determining molecular weight with GPC.Mn=52,000 and Mw=100,000.

Embodiment 60

The multipolymer (embodiment 24) (number-average molecular weight 4,000) that obtains the tertiary butyl ester of maleic anhydride/norborene by free radical polymerization is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 15w/v%.In this polymkeric substance, add hexafluoro-antimonic acid triaryl sulfonium (Sartomer CD1010,50% solution in propylene carbonate) with 5w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 0.6 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 30mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 1 minute under 125 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 61

The multipolymer (embodiment 24) (number-average molecular weight 4,000) that obtains the tertiary butyl ester of maleic anhydride/norborene by free radical polymerization is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 15w/v%.In this polymkeric substance, add hexafluoro-antimonic acid triaryl sulfonium (Sartomer CD1010,50% solution in propylene carbonate) with 5w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filter.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 0.6 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 30mj/cm ²The UV ray (240nnm) of dosage make its exposure.The back oven dry is 1 minute under 95 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 62

With under the NiArf catalyzer two the ring [2.2.1] heptan-5-alkene--the copolymerization of 2-Methylethyl oxalate/norborene trimethyl silyl ester (50/50 mol ratio)

To being furnished with coating Teflon ^The 50ml vial of stirring rod in add two rings [2.2.1] heptan-5-alkene-2-Methylethyl oxalate (1.5484g, 6.904mmol) and norborene trimethyl silyl ester (1.4523g, 6.905mol) and cyclohexane 6.75ml.Nickel catalyst solution [the toluene complex compound of two perfluorophenyl nickel, (Tol) Ni (C ₆F ₅) ₂] by 0.0335g (0.0691mmol (Tol) Ni (C ₆F ₅) ₂] in drying box, be dissolved in and prepare in the 1.95ml ethyl acetate.The active catalytic agent solution joins in the monomer solution at ambient temperature by syringe.At room temperature stirred 5 hours.Polymkeric substance precipitates in excessive methyl alcohol.The polymkeric substance washing with acetone of filtering-depositing, dried overnight in the vacuum.The polymer yield that separates is 0.2675g (9%).It shows acid functionality's existence, this be owing to trimethyl silyl go the protection cause.

Embodiment 63

The ter-polymers (embodiment 25) (number-average molecular weight 3,000) of the maleic anhydride that obtains by free radical polymerization/two rings [2.2.1] heptan-5-alkene--the tertiary butyl ester of 2-methyl acetic acid ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 10w/v%.In this polymkeric substance, add hexafluoro-antimonic acid triphenyl sulfonium (Sartomer 1012) with 10w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 0.5 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 50mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 1 minute under 125 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 64

The tertiary butyl ester (embodiment 22) (number-average molecular weight 22,000) of two rings [2.2.1] heptan-5-alkene-2-Methylethyl carbonic ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 15w/v%.In this polymkeric substance, add hexafluoro-antimonic acid triaryl sulfonium (Sartomer CD 1010,50% solution in propylene carbonate) with 5w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters, and this filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 1.1 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 30mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 1 minute under 95 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 65

Two rings [2.2.1] heptan-copolymerization of 5-alkene-2-Methylethyl oxalate/norborene tertiary butyl ester

To being furnished with coating Teflon ^The 50ml vial of stirring rod in add the tert-butyl ester of 2.42g (12.5mmol) norborene, in 8.57g (38.2mmol) two rings [2.2.1] heptan-5-alkene--2-Methylethyl oxalate, newly distill ethylene dichloride 50ml, and make solution exhaust under argon atmospher.Is being furnished with coating Teflon ^The 10ml vial of stirring rod in pack into chlorination Allylpalladium dipolymer 0.0365g (0.1mmol) (monomer is 500/1 with the ratio of catalyzer) and 2ml ethylene dichloride.Hexafluoro-antimonic acid silver 0.0344g (0.1mmol) and ethylene dichloride 2ml pack in another 10ml vial.Catalyzer is mixed with in drying box by chlorination Allylpalladium bipolymer solution and hexafluoro-antimonic acid silver solution.Observe the precipitation of chlorination silver salt immediately, filter then, obtain the active catalytic agent solution.Join this active catalytic agent solution in the monomer solution and under 60 ℃, reaction mixture was stirred 20 hours with syringe.The polymer solution cooling concentrates with rotovap.And in methyl alcohol, precipitate.

Embodiment 66

The multipolymer (embodiment 22) (number-average molecular weight 2,000) of the tertiary butyl ester of two rings [2.2.1] heptan-5-alkene-2-Methylethyl carbonic ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 15w/v%.In this polymkeric substance, add hexafluoro-antimonic acid triphenyl sulfonium (Sartomer CD 1010,50% solution in propylene carbonate) with 5w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 1.1 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 15mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 1 minute under 95 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 67

The tertiary butyl ester multipolymer (embodiment 23) (number-average molecular weight 22,000) of two rings [2.2.1] heptan-5-alkene-2-methyl butyl carbonic ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 15w/v%.In this polymkeric substance, add in the hexafluoro-antimonic acid triphenyl sulfonium (Sartomer CD 1010,50% solution in propylene carbonate) with 5w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 1.0 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 30mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 0.5 minute under 125 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 68

The tertiary butyl ester multipolymer (embodiment 23) (number-average molecular weight 22,000) of two rings [2.2.1] heptan-5-alkene-2-methyl butyl carbonic ester/norborene is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 15w/v%.In this polymkeric substance, add hexafluoro-antimonic acid triaryl sulfonium (Sartomer CD 1010,50% solution in propylene carbonate) with 5w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 1.0 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 30mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 0.5 minute under 150 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 69

The multipolymer (embodiment 37) (number-average molecular weight 23,000) of the 35/65mole% hydrogenation of the tertiary butyl ester of the ethyl ester/norborene of the tetracyclododecane that obtains with ring-opening metathesis polymerization is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 15w/v%.In this polymkeric substance, add hexafluoro-antimonic acid triaryl sulfonium (Sartomer CD 1010,50% solution in propylene carbonate) with 5w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.The film that obtains 1.1 μ thickness was dried this film 1 minute under on the heat dish 95 ℃, then by quartz mask 30mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 1 minute under 125 ℃, and developing in buck obtained high-resolution just as pattern in 30 seconds.

Embodiment 70

The unhydrided multipolymer of 35/65mole% (embodiment 39) (number-average molecular weight 34,000) of the tertiary butyl ester of the ethyl ester/norborene of the tetracyclododecane that obtains with ring-opening metathesis polymerization is dissolved in the propylene glycol monomethyl ether (PGMEA) with the solid content of 15w/v%.In this polymkeric substance, add hexafluoro-antimonic acid triaryl sulfonium (Sartomer CD 1010,50% solution in propylene carbonate) with 5w/w% load.Etchant resist is by 0.2 μ Teflon ^Filtrator filters.This filtrate is with the spin coating 30 seconds on the silicon wafer of hexamethyldisilazane priming operation of 500rpm speed, with 2000rpm spin coating 25 seconds.Obtain the rete of 1.25 μ thickness.On a heat dish, dried this film 1 minute down for 95 ℃, then by quartz mask 50mj/cm ²The UV ray (240nm) of dosage make its exposure.The back oven dry is 30 seconds under 150 ℃, and developing in buck obtained high-resolution just as pattern in 60 seconds.

Embodiment 71

To being furnished with coating Teflon ^The 50ml vial of stirring rod in add two rings [2.2.1] heptan-5-alkene-2-Methylethyl oxalate (8.57g, 0.0382mol) and the tertiary butyl ester of norborene (7.42g, 0.0392mol) and toluene 38ml.Nickel catalyst solution [the toluene complex of two perfluorophenyl nickel, (Tol) Ni (C ₆F ₅) ₂] by 0.1854g (0.382mmol (Tol) Ni (C ₆F ₅) ₂] in drying box, be dissolved in and prepare in the 5ml toluene.The active catalytic agent solution joins in the monomer solution at ambient temperature by syringe.At room temperature stirred 5 hours.Solution precipitates in excessive methyl alcohol with dilution with toluene and polymkeric substance.The polymkeric substance washing with acetone of filtering-depositing, dried overnight in the vacuum.The polymer yield that separates is 7.62g (48%).Polymkeric substance characterizes determining molecular weight with GPC.Mn=28,000 and Mw=56,000.The NMR of multipolymer the analysis showed that the multipolymer composition approaches charge ratio very much.The IR of multipolymer the analysis showed that no acidic group.

Claims (30)

1. photoetching compositions, comprise photic sour initiating agent, optionally dissolution inhibitor and contain at least two classes encircle more repetitive wherein a class contain acid labile pendant groups and the another kind of multipolymer that contains the polar functional side group, the repetitive that wherein contains the polar functional base is by the monomer polymerization of following formula structure representative:

R wherein ⁵To R ⁸Representative is selected from the (C of hydrogen, linearity and branching independently ₁To C ₁₀) substituting group of alkyl and polar substituent, be expressed as follows :-(A) _n-C (O) OR " ,-(A) _nOR " ,-(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 ") ₂CH (R ") (C (O) OR ") and-(A) _n-C (R ") ₂CH (C (O) OR ") ₂, wherein n is 0 or 1, p is by 0 to 5 integer ,-A-and-A-' represents that independently one is selected from linear and branching (C ₁To C ₁₀) alkylidene, (C ₂To C ₁₀) divalent group of cyclic group of alkylene ether, polyethers, cyclic ethers, ring diether or following formula:

Wherein a is 2 to 7 integer, and R " representative is selected from hydrogen, linear and branching (C ₁To C ₁₀) alkyl, linear and branching (C ₁To C ₁₀) the alkoxy alkylidene, polyethers, monocycle and many ring (C ₄To C ₂₀) alicyclic part, cyclic ethers, the ring diether, cyclic ketones, and cyclic ester (lactone), condition is work as R " be a kind of alkyl, must have when lactone, alicyclic or cyclic ketones base-the A-group exists and can not represent alkylidene.

2. polycyclic monomer is polymerized shown in the following formula that the composition of claim 1, wherein said polymkeric substance are replaced by one or more acid labile groups:

R wherein ¹To R ⁴Representative is selected from hydrogen independently, linear and branching (C ₁To C ₁₀) alkyl ,-(A) _nC (O) OR ^*,-(A) _nC (O) OR ,-(A) _n-OR ,-(A) _nOC (O) R ,-(A) _nC (O) R ,-(A) _nOC (O) OR ,-(A) _nOCH ₂C (O) OR ^*,-(A) _nC (O) O-A '-OCH ₂C (O) OR ^*,-(A) _nOC (O)-A '-C (O) OR ^*,-(A) _nC (R) ₂CH (R) (C (O) OR ^*) and-(A) _nC (R) ₂CH (C (O) OR ^*) ₂The substituting group of group, wherein n is 0 or 1, m is by 0 to 5 integer ,-A-and-A-' represent independently and is selected from linearity and branching (C ₁To C ₁₀) alkylidene, (C ₂To C ₁₀) alkylene ether, polyethers, or the bivalent radical of the cyclic group of following formula:

Wherein a is 2 to 7 integer, and R represents hydrogen or linear and branching (C ₁To C ₁₀) alkyl, and R ^*Expression is by the fissionable acid labile group of photic sour initiating agent and be selected from-C (CH ₃) ₃,-Si (CH ₃) ₃,-CH (R ^P) OCH ₂CH ₃,-CH (R ^P) OC (CH ₃) ₃, or following cyclic group:

R wherein ^PExpression hydrogen or linearity or branching (C ₁To C ₅) alkyl, and R ^*Represent R and R independently ^*And R ¹To R ⁴At least aly must be selected from the substituting group that contains described acid labile group.

3. the composition of claim 2, wherein said polycyclic polymers comprise the repetitive by one or more monomer polymerizations of being represented by the following formula structure:

R wherein ⁹To R ¹⁶Represent hydrogen and linear and branching (C independently ₁To C ₁₀) alkyl, condition is R ⁹To R ¹²One of be by formula-(CH ₂) _nThe carboxylic acid substituent that C (O) OH represents, wherein n is 0 to 10 integer; And q and r are 0 to 5 integers.

4. claim 1,2 or 3 composition, wherein said monomer obtains ring-opening polymerization polymer by the ring-opening polymerization polymerization.

5. the composition of claim 4, the wherein described ring-opening polymerization polymer of hydrogenation.

6. the composition of claim 2, wherein said monomer is by the Raolical polymerizable polymerization.

7. claim 1,2 or 3 composition, wherein said polymkeric substance comprises the repetitive that is expressed from the next:

R wherein ¹To R ⁸, m and p are as defined above.

8. the composition of claim 7, wherein said polymkeric substance also comprise at least a repetitive that is selected from as shown in the formula the group of expression: R wherein ⁹To R ¹⁶Define as the front.

9. the composition of claim 1, wherein said polymkeric substance is the ring-opening polymerization polymer that comprises the repetitive of being represented by following structure:

R wherein ¹To R ⁴Representative is selected from hydrogen independently, linear and branching (C ₁To C ₁₀) alkyl ,-(A) _nC (O) OR ^*,-(A) _nC (O) OR ,-(A) _n-OR ,-(A) _nOC (O) R ,-(A) _nC (O) R ,-(A) _nOC (O) OR ,-(A) _nOCH ₂C (O) OR ^*,-(A) _nC (O) O-A '-OCH ₂C (O) OR ^*,-(A) _nOC (O)-A '-C (O) OR ^*,-(A) _nC (R) ₂CH (R) (C (O) OR ^*) and-(A) _nC (R) ₂CH (C (O) OR ^*) ₂The substituting group of group, R ⁵To R ⁸Representative is selected from hydrogen, linearity and branching (C independently ₁To C ₁₀) substituting group and the R of alkyl ⁵To R ⁸In must be selected from one of at least by-(A) _n-C (O) OR " ,-(A) _nOR " ,-(A) _n-OC (O) R " ,-(A) _n-OC (O) OR " ,-(A) _n-C (O) R " ,-(A) _n-O (O) C (O) OR " ,-(A) _n-O-A '-C (O) OR " ,-(A) _n-OC (O)-A '-C (O) OR " ,-(A) _n-C (O) O-A '-C (O) OR " ,-(A) _n-C (O)-A '-OR " ,-(A) _n-C (O) O-A '-OC (O) OR " ,-(A) _n-C (O) O-A '-O-A '-C (O) OR " ,-(A) _n-C (O) O-A '-OC (O) C (O) OR " ,-(A) _n-C (R ") ₂CH (R ") (C (O) OR ") and-(A) _n-C (R ") ₂CH (C (O) OR ") ₂The polar substituent of expression ,-A-and-expression of A '-independently is selected from linear and branching (C ₁To C ₁₀) alkylidene, (C ₂To C ₁₀) divalent group of cyclic group of alkylene ether, polyethers, cyclic ethers, ring diether or following formula: Wherein a is 2 to 7 integer, and n is 0 or 1 independently, and m and p are 0 to 5 integer independently, and R represents hydrogen or linear and branching (C ₁To C ₁₀) alkyl, and R ^*Expression is by being selected from-C (CH ₃) ₃,-Si (CH ₃) ₃,-CH (R ^P) OCH ₂CH ₃,-CH (R ^P) OC (CH ₃) the fissionable acid labile group of photic sour initiating agent:

R wherein ^PExpression hydrogen or linearity or branching (C ₁To C ₅) alkyl, and R ^*Represent R and R independently ^*And R ¹To R ⁴At least aly must be selected from the substituting group that contains described acid labile group, and R " representative is selected from hydrogen, linear and branching (C ₁To C ₁₀) alkyl, linear and branching (C ₁To C ₁₀) the alkoxy alkylidene, polyethers, monocycle and many ring (C ₄To C ₂₀) alicyclic part, cyclic ethers, cyclic ketones, and the substituting group of cyclic ester (lactone), condition is to work as R " be a kind of alkyl, must have when lactone, alicyclic or cyclic ketones-the A-group exists and can not represent alkylidene.

10. the composition of claim 9, wherein said ring-opening polymerization polymer also comprises at least a repeating unit represented that is selected from: R wherein ⁹To R ¹⁶Represent hydrogen and linear and branching (C independently ₁To C ₁₀) alkyl, condition is R ⁹To R ¹²One of at least be by formula-(CH ₂) _nThe carboxylic acid substituent that C (O) OH represents, wherein n is 0 to 10 integer; And q and r are respectively 0 to 5 integers.

11. the composition of claim 9, wherein said multipolymer comprises the repetitive of being represented by following structure:

R wherein ^*Expression is by being selected from-C (CH ₃) ₃,-Si (CH ₃) ₃, 1-methyl isophthalic acid-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuran base, THP trtrahydropyranyl, 3-oxygen hexamethylene ketone group, mevalonolactone base, 1-ethoxyethyl group, 1-tert-butoxy ethyl, contrast name (check nomenclature) bicyclic methyl propyl (Dcpm) and dimethyl cyclopropyl methyl (Dmcp), and R " be selected from linear and branching (C ₁To C ₁₀) alkyl.

12. the composition of claim 11, wherein R ¹To R ³And R ⁵To R ⁷Be hydrogen or linearity or branching (C ₁To C ₁₀) alkyl, and R " be linearity or branching (C ₁To C ₁₀) alkyl.

13. the composition of claim 12, wherein said ring-opening polymerization polymer comprises the repetitive of being represented by following structure:

Wherein m and p are 0 or 1 independently, n be 1 and A be the methylene group that contains 1 to 10 carbon atom.

14. the composition of claim 13, wherein R ^*Be the tert-butyl group, A is a methylene and R " be selected from linearity or branching (C ₁To C ₅) alkyl.

15. claim 9,10,11,12,13, or 14 composition, unsaturated part is hydrogenated in the wherein said ring-opening polymerization polymer main chain.

16. surpassing 90%, the polymkeric substance of claim 15, the unsaturated part in the wherein said ring-opening polymerization polymer main chain be hydrogenated.

17. the polymkeric substance of claim 16,100% hydrogenation basically of the unsaturated part in the wherein said ring-opening polymerization polymer main chain.

18. a photoetching compositions comprises photic sour initiating agent, optionally dissolution inhibitor and multipolymer comprise the many rings repetitive as shown in the formula expression: R wherein ¹To R ⁴Representative is selected from hydrogen independently, linear and branching (C ₁To C ₁₀) alkyl ,-(A) _nC (O) OR ^*,-(A) _nC (O) OR ,-(A) _n-OR ,-(A) _nOC (O) R ,-(A) _nC (O) R ,-(A) _nOC (O) OR ,-(A) _nOCH ₂C (O) OR ^*,-(A) _nC (O) O-A '-OCH ₂C (O) OR ^*,-(A) _nOC (O)-A '-C (O) OR ^*,-(A) _nC (R) ₂CH (R) (C (O) OR ^*), and R ⁵To R ⁸Representative is selected from linear and branching (C independently ₁To C ₁₀) substituting group and the R of alkyl ⁵To R ⁸In one of at least must be selected from by-(A) _n-C (O) OR " ,-(A) _nOR " ,-(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 ") ₂CH (R ") (C (O) OR ") and-(A) _n-C (R ") ₂CH (C (O) OR ") ₂The expression polar substituent ,-A-and-A-' represent independently to be selected from the linearity and branching (C ₁To C ₁₀) alkylidene, (C ₂To C ₁₀) the divalent group R of cyclic group of alkylene ether, polyethers, cyclic ethers, ring diether or following formula ⁵To R ⁸-(A) _nC (R) ₂CH (C (O) OR ^*) ₂The substituting group of group, wherein n is 0 or 1, m is by 0 to 5 integer ,-A-and-A-' represent independently and is selected from linearity and branching (C ₁To C ₁₀) alkylidene, (C ₂To C ₁₀) alkylene ether, polyethers, cyclic ethers, the bivalent radical of the cyclic group of ring diether or following formula:

Wherein a is 2 to 7 integer, and n is 0 or 1 independently, and m and p are 0 to 5 integer independently, and R represents hydrogen or linear and branching (C ₁To C ₁₀) alkyl, and R ^*Expression is by being selected from-C (CH ₃) ₃,-Si (CH ₃) ₃,-CH (R ^P) OCH ₂CH ₃,-CH (R ^P) OC (CH ₃) the fissionable acid labile group of photic sour initiating agent, or following cyclic group: R wherein ^PExpression hydrogen or linearity or branching (C ₁To C ₅) alkyl, and R ^*Represent R and R independently ^*And R ¹To R ⁴At least aly must be selected from the substituting group that contains acid labile group, and R " representative is selected from hydrogen, linear and branching (C ₁To C ₁₀) alkyl, linear and branching (C ₁To C ₁₀) the alkoxy alkylidene, polyethers, monocycle and many ring (C ₄To C ₂₀) alicyclic part, cyclic ethers, the ring diether, cyclic ketones, and the substituting group of cyclic ester (lactone), condition is work as R " be a kind of alkyl, must have when lactone, alicyclic or cyclic ketones base-the A-group exists and can not represent alkylidene.

19. the composition of claim 18, wherein said multipolymer also comprise at least a repetitive that is selected from as shown in the formula the group of expression:

R wherein ⁹To R ¹⁶Represent hydrogen and linear and branching (C independently ₁To C ₁₀) alkyl, condition is R ⁹To R ¹²One of be by formula-(CH ₂) _nThe carboxylic acid substituent that C (O) OH represents, wherein n is 0 to 10 integer; And q and r are respectively 0 to 5 integers.

20. the composition of claim 18, wherein said multipolymer comprises the repetitive of being represented by following structure:

R wherein ^*Expression is by being selected from-C (CH ₃) ₃,-Si (CH ₃) ₃, 1-methyl isophthalic acid-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuran base, THP trtrahydropyranyl, 3-oxygen hexamethylene ketone group, mevalonolactone base, 1-ethoxyethyl group, 1-tert-butoxy ethyl, bicyclic methyl propyl (Dcpm) and dimethyl cyclopropyl methyl (Dmcp), and R " be selected from linear and branching (C ₁To C ₁₀) alkyl.

21. the composition of claim 20, wherein R ¹To R ³And R ⁵To R ⁷Be hydrogen or linearity or branching (C ₁To C ₁₀) alkyl, and R " be linearity or branching (C ₁To C ₁₀) alkyl.

22. the composition of claim 21, wherein said multipolymer comprises the repetitive of being represented by following structure:

Wherein m and p are 0 or 1 independently, n be 1 and A be the alkylidene that contains 1 to 10 carbon atom.

23. the composition of claim 22, wherein R ^*Be the tert-butyl group, A is a methylene and R " be selected from linearity or branching (C ₁To C ₅) alkyl.

24. claim 1,2,3,5,11,12,13,14,15,16,17,18,19,20, or 21 composition, wherein said polymkeric substance comprises 5 to 100mole% the repetitive that contains described acid labile group.

25. the composition of claim 24, wherein said polymkeric substance comprise 20 to 90mole% the repetitive that contains described acid labile group.

26. the composition of claim 25, wherein said polymkeric substance comprise 30 to 70mole% the repetitive that contains described acid labile group.

27. the composition of claim 25, wherein said polymkeric substance comprise 5 to 100mole% the repetitive that contains described acid labile group.

28. claim 7,8,18,19,20,21,22, or 23 polymkeric substance, wherein said polymkeric substance has the perfluorophenyl side group on its at least one end.

29. claim 1,2, or 3 polymkeric substance, the polymkeric substance of wherein said many rings comprises the repetitive by the maleic anhydride polymerization.

30. claim 7,8,18,19,20,21,22, or 23 polymkeric substance, wherein said polymkeric substance comprises the repetitive as shown in the formula representative: