Polymeric compositions and uses therefor

专利摘要:
The present invention relates to polycyclic polymers, methods of making polycyclic polymers, and methods for using such polymers as photoresists in the manufacture of integrated circuits. In one embodiment, the invention relates to a photoresist composition formed from the polymerization of one or more halogenated polycyclic monomers or hydrohalogenated polycyclic monomers. In another embodiment, the present invention relates to a photoresist composition formed from the copolymerization of one or more halogenated polycyclic monomers or hydrohalogenated polycyclic monomers with one or more non-halogenated polycyclic monomers. The invention also relates to a method of post-treating such photoresist composition to obtain one or both of (1) reducing the optical density of the polymer composition and (2) reducing the amount of residual metal and / or monomer in the polymer composition. It is about. Also disclosed herein is a catalyst system that enables the control of the molecular weight of a photoresist product, which is used to prepare the photoresist composition of the present invention.
公开号:KR20040065209A
申请号:KR10-2004-7005844
申请日:2002-12-12
公开日:2004-07-21
发明作者:래리 에프. 로드즈；리처드 비카리；레아 제이. 랭스도르프；앤드류 에이. 소벡；에드윈 피. 보이드；브라이언 벤네트
申请人:스미토모 베이클라이트 가부시키가이샤；
IPC主号:

专利说明:

POLYMERIC COMPOSITIONS AND USES THEREFOR}
[2] Fabrication of integrated circuits (ICs) is typical for array fabrication of electronic and microelectronic devices. Integrated circuits are fabricated by sequentially forming a plurality of conductive, semiconducting, and nonconductive layers on a suitable substrate (e.g., silicon wafer) that is selectively patterned to form circuits and interconnects to exhibit specific electrical functions. . Patterning of the IC is performed according to various lithographic techniques known in the art. Photolithography using ultraviolet (UV) light and even deeper UV light (eg, 193 and 157 nm) or other radiation is a fundamental and important technique used in the manufacture of IC devices. A photosensitive polymer film (photoresist) is applied on the wafer surface and dried. Subsequently, a photomask containing the desired patterning information is positioned between the radiation or light source and the photoresist film. The photoresist is irradiated through a photomask overlying one of several types of imaging radiation, including UV light, x-rays, electrons or ion beams. Upon exposure to radiation, the photoresist causes a chemical change and a change in solubility. After irradiation and / or optional post-exposure bake, the wafer is immersed in a solution that develops the patterned image in the photosensitive polymer film (ie, selectively removes exposed or unexposed areas). Depending on the type of polymer used or the polarity of the developing solvent, exposed or unexposed areas of the film are removed during the development process to expose the underlying substrate, followed by patterned and exposed substrate material or unwanted substrate material. Removing or changing by the etching process leaves the desired pattern in the working layer of the wafer. Etching is accomplished by plasma etching, sputter etching, and reactive ion etching (RIE). The remaining photoresist material acts as a protective barrier for the etching process. Removal of the remaining photoresist material yields a patterned circuit.
[3] In the manufacture of patterned IC devices, the process of etching the various layers on a wafer is one of the most important steps involved. One method is to immerse the substrate and patterned resist in a chemical bath that attacks the exposed substrate surface while keeping the resist itself intact. However, such "wet" chemical processes have difficulty creating very distinct edges on the etched surface. It is due to the chemical undercutting of the resist material and the formation of isotropic images. In other words, conventional chemical processes do not provide selectivity (anisotropy) in the directions that are considered necessary to achieve optimal dimensional specifications consistent with current processing requirements. Wet processes also suffer from undesirable environmental and safety derivatives.
[4] Various "dry" processes have been developed to overcome the drawbacks of wet chemical processes. This dry process generally involves passing gas through the chamber and ionizing the gas by applying a potential across the two electrodes in the presence of the gas. Plasma containing ionic species generated by the potential is used to etch the substrate positioned in the chamber. The ionic species generated in the plasma are directed towards the exposed substrate, where the ionic species interact with the surface material to form volatile products, which are removed from the surface. Typical examples of dry etching are plasma etching, sputter etching and reactive ion etching.
[5] Reactive ion etching provides not only substrate to substrate etch homogeneity but also very distinct vertical sidewall profiles in the substrate. Because of these advantages, reactive ion etching techniques have become a standard technology in IC manufacturing.
[6] Two types of photoresists are used in the industry, negative and positive photoresists. Negative resists polymerize, crosslink, or vary in solubility properties such that upon exposure to imaging radiation, the exposed area is insoluble in the developer. Unexposed areas remain soluble and are cleaned. The positive resist acts in the opposite way, becoming soluble in the developer solution after exposure to imaging radiation.
[7] One type of positive photoresist material is based on phenol-formaldehyde novolac polymers. A specific example is a commercially available Shipley AZ1350 material comprising m-cresol formaldehyde novolac polymer composition and diazoketone (2-diazo-1-naphthol-5-sulfonic acid ester). Exposure to imaging radiation converts the diazoketone to carboxylic acid, which converts the phenolic polymer into a material that is readily soluble in weak aqueous base developing agents.
[8] US Patent No. 4,491,628 to Ito et al. Discloses positive and negative photoresist compositions containing acid generating photoinitiators and polymers containing acid degradable pendant groups. Since each generated acid leads to deprotection of multiple acid decomposable groups, this method is known as a chemical amplification process which serves to increase quantum yield in the entire photochemical process. Disclosed polymers include vinyl-based polymers such as polystyrene, polyvinylbenzoate, and polyacrylates substituted with repeatable pendant groups that produce acid-degraded products with differing solubility relative to precursors. Preferred acid degradable pendant groups are t-butyl ester of carboxylic acid and t-butyl carbonate of phenol. The photoresist can be made positive or negative depending on the nature of the developing solution used.
[9] The trend in the electronics industry continues to demand ICs that are constantly faster and consume less power. To meet these requirements, ICs must be smaller. Conductive paths (ie lines) should be made thinner and placed closer to each other. Significant reductions in the size of the transistors and the resulting lines concomitantly increase the efficiency of the IC, for example, making storage and processing of information on computer chips more excellent. In order to make the width of the line thinner, higher optical imaging resolution is required. Higher resolution is possible when the wavelength of the exposure source used to irradiate the photoresist material is shorter. However, conventional photoresists, such as phenol-formaldehyde novolac polymers and substituted styrene polymers, contain aromatic groups that are increasingly absorbing in nature when the wavelength of light falls below about 300 nm (ACS Symposium Series 537, Polymers for Microelectronics, Resists and Dielectrics , 203rd National Meeting of the American Chemical Society, Apr. 5-10, 1992, p.2-24; Polymers for Electronics and Photonic Applications , Edited by CP Wong, Academic Press, p. 67-118) . Shorter wavelengths are typically less bright than conventional sources requiring chemical amplification using photoacids. The opacity of such aromatic polymers for short wavelength light is a drawback in that the polymer cannot be developed by inhomogeneously exposing the photoacid below the polymer surface to the light source. To overcome the lack of transparency of such polymers, the aromatics content of the photoresist polymer should be reduced. If raw UV transparency is desired (ie 248 nm, in particular for 193 nm and / or 157 nm wavelength exposure), the polymer should contain minimal aromatic character.
[10] Low molecular weight polymers are widely known as preferred photoresist matrix materials because they exhibit higher degradation rates than high molecular weight materials even after exposure and post-exposure heat treatment. Higher resolution is desired to increase wafer throughput in a manufacturing environment. Unfortunately, it is also known that low molecular weight materials may also exhibit higher optical densities than lower molecular weight materials when the end groups of the polymer are absorbable at the wavelength of interest (Barclay, et al., Macromolecules 1998, 31, 1024). : See discussion of poly (4-hydroxystyrene), which is the preferred material for 248 nm photoresist.
[11] The molecular weight of the polycyclic polymer can be reduced by polymerizing the desired polycycloolefin monomer in the presence of a single component or multicomponent transition metal catalyst and an α-olefin chain transfer agent, as taught in US Pat. No. 5,468,819. In addition, α-olefin chain transfer agents have been used to control the molecular weight of polymerized polycyclic polymers from functional groups containing polycycloolefin monomers with selected transition metal catalysts. US Patent No. 6,136,499 discloses the use of such polymers in chemically amplified photoresist compositions. It is known from the above description that the polymers prepared according to this teaching contain olefinic unsaturations at their terminal ends. As discussed above, unsaturation increases the optical density of the polymer, resulting in a less transparent polymer.
[12] The optical density (OD) of the matrix resin for photoresist at the exposure wavelength defines the usefulness of the resin at that particular wavelength. Polymers with high optical density at the exposure wavelength will limit the resolution performance of the resulting photoresist. For 193 nm and 157 nm resist systems, low optical densities are desirable not only to increase the resolution but also to reduce the exposure dose for imaging the wafer. Therefore, it is highly desirable that 193 nm and 157 nm resist systems have the lowest OD possible.
[13] U. S. Patent No. 5,372, 912 relates to a photoresist composition containing an acrylate based copolymer, a phenol type binder, and a photosensitive acid generator. The acrylate based copolymers are polymerized from acrylic acid, alkyl acrylates or methacrylates, and monomers having acid degradable pendant groups. Such compositions are sufficiently transparent to UV radiation at wavelengths of about 240 nm, but the use of aromatic type binders limits the use of radiation sources of shorter wavelengths. As is common in the polymer art, an improvement in one property usually comes at the expense of another. When using acrylate based polymers, the enhancement of transparency to shorter wavelengths of UV is at the expense of resist resistance to reactive ion etching processes.
[14] In many cases, the improvement in transparency to short wavelength imaging radiation results in corrosion of the resist material during subsequent dry etching processes. This is due to the fact that resist materials with slower etching rates can be used for thinner layers compared to the substrate to be etched. The thinner layer of resist material allows for higher resolution, resulting in narrower conducting lines and miniaturization of transistors.
[15] second. V. JV Crivello et al., Chemically Amplified Electron-Beam Photoresists , Chem. Mater., 1996, 8, 376-381 discloses 20% by weight of free-radically polymerized homopolymers of norbornene monomers containing acid-decomposable groups and 4-hydroxy containing acid-decomposable groups for use in electron-beam photoresists. A polymer blend is disclosed which comprises 80% by weight homopolymer of -α-methylstyrene. As discussed above, the increased absorption of aromatic groups (especially at high concentrations) makes these compositions opaque and unusable for short wavelength imaging radiation below 200 nm. The disclosed compositions are suitable only for electron-beam photoresists and cannot be used for raw UV imaging (particularly for 193 nm or 157 nm resists).
[16] Krivelo et al. Investigated the formulation composition because they observed that the oxygen plasma etch rate was unacceptably high for free-radically polymerized homopolymers of norbornene monomers containing acid-decomposable groups.
[17] Accordingly, there is a need for photoresist compositions that conform to general chemical amplification schemes and provide transparency for short wavelength imaging radiation while being sufficiently resistant to reactive ion etching process environments. There is also a need for a method for producing such photoresist compositions and a method for reliably controlling their molecular weight in a wider range.
[18] Summary of the Invention
[19] Embodiments according to the present invention comprise a single polymerization reaction of one monomer according to formula (I); Copolymerization of two or more different monomers according to formula (I); And a photoresist composition formed from the copolymerization of at least one monomer according to formula (I) with at least one monomer according to formula (II).
[20]
[21] Wherein R ¹ to R ⁸ , Z and m are as defined below.
[22] In another embodiment, the present invention contains olefinic end groups via treatment with a post-functionalized reagent (e.g., post-treatment with a peracid, hydrosilation agent, hydrogenation agent, hydroformylating agent). A method of reducing the optical density of a polymer.
[23] In another embodiment, the present invention relates to polymers via postfunctionalization of olefinic end groups with postfunctionalizing agents such as epoxidizing agents, hydrogen additives, hydroformylating agents, hydrosylating agents and / or cyclopropaneating agents. A method for reducing the optical density of any polycyclic polymer containing olefinic end group (s) that may be present in the product.
[24] In another embodiment, the present invention is directed to a process for removing residual monomers and / or catalysts from one or more polycyclic polymers through suitable post-treatment agents and mechanisms.
[25] The present invention is advantageous in that it provides a polymer composition useful for photoresist compositions in 193 nm and 157 nm applications. Such compositions have better performance properties than currently available photoresist compositions. For example, lower OD at the exposure wavelength reduced swelling in the aqueous base developer and reduced P _ka similarly to P _ka of poly (para-hydroxystyrene).
[26] In addition, one embodiment of the present invention is advantageous in that it provides a method of simultaneously controlling the reduction of molecular weight, optical density, and reduction of residual monomer and catalyst metal from the polymer composition.
[27] The foregoing and other features of the invention will be described in detail below, particularly with reference to the following description and the accompanying drawings which illustrate one or more embodiments of the invention in detail, although the principles of the invention It only shows some of the many ways that can be applied.
[1] The present invention generally relates to polycyclic polymers, methods of making polycyclic polymers, and methods for using such polymers in photoresists used in the manufacture of electronic and microelectronic devices.
[28] 1 is a diagram showing palladium bis (tri-i-propylphosphine) di (acetate) in ORTEP;
[29] FIG. 2 shows the optical density (OD) versus molecular weight of a homopolymer of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol prepared using a palladium catalyst. Plot;
[30] FIG. 3 shows the optical density (OD) versus molecular weight of a homopolymer of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol prepared using a nickel catalyst. Plot;
[31] 4 shows the effect of post-treatment with acetic acid and hydrogen peroxide on optical density (OD) in various α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol. It is a graph shown;
[32] 5 is a ¹ H NMR spectrum of Ni and Pd-based α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol homopolymers before and after peracetic acid treatment;
[33] Fig. 6 shows α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol and 5-produced using a palladium catalyst before and after treatment with acetic acid and hydrogen peroxide; It is a plot of optical density (OD) versus molecular weight for a copolymer of t-butylester of norbornene carboxylic acid.
[34] It should be noted that in the following description and claims, range and ratio limits and / or range and time limits may be combined. In addition, as used throughout the specification, the term halogenated polycyclic compound means a polycyclic compound containing one or more halogen atoms (eg, chlorine, fluorine or bromine) instead of hydrogen atoms. One or more halogen atoms may be present in one or more rings present in the polycyclic compound. In addition, one or more halogen atoms may be present in pendant groups or substituents attached to one or more rings of the polycyclic compound. In one embodiment, the halogenated substituents (eg halohydrocarbyl, perhalohydrocarbyl) are at least one-(C ₆ F ₅ ), at least one -CF ₃ (trifluoromethyl) group or as defined below It may be one or more other fluorohydrocarbyl groups.
[35] The present invention generally relates to polycyclic polymers, methods of making polycyclic polymers, and methods for using such polymers as photoresists in the manufacture of integrated circuits. In particular, the present invention relates to compositions formed from the polymerization of one or more non-halogenated polycyclic monomers or one or more halogenated polycyclic monomers or mixtures thereof. One or more non-halogenated polycyclic monomers or halogenated polycyclic monomers may contain one or more acid decomposable groups along the polymer backbone. In another embodiment, the polycyclic polymers and halogenated polycyclic polymers contain olefinic end groups, which are subsequently worked up to remove unsaturation. Non-halogenated polycyclic polymers mean that the polymer does not have repeating units containing halogen atoms. Halogenated polycyclic polymers mean that at least some of the repeating units contained in the polymer backbone contain halogen atoms.
[36] In another embodiment, the present invention relates to a polymer suitable for use in a photoresist composition formed from the polymerization of one or more non-halogenated polycyclic monomers, one or more halogenated polycyclic monomers, or mixtures thereof. In either case, one or both of these monomers may contain one or more acid degradable pendant groups.
[37] The present invention also relates to methods for controlling molecular weight, residual metal content, residual monomer content and optical density of polycyclic polymers and polycyclic polymers suitable for use in photoresist compositions.
[38] Polymers of the present invention include polycyclic repeating units. In one embodiment, the polycyclic polymers may be substituted with acid degradable groups. Such polymers are prepared by the polymerization of polycyclic monomers of the invention.
[39] The term "polycyclic" (norbornene-type or norbornene-functional) means that the monomer contains one or more norbornene moieties as shown below:
[40]
[41] The simplest polycyclic monomer of the present invention is bicyclo [2.2.1] hept-2-ene, a bicyclic monomer commonly referred to as norbornene. As noted above, in one aspect, the present invention relates to a polycyclic polymer formed from the polymerization of one or more polycyclic fluorinated monomers according to formula (I). One or more monomers according to formula (I) optionally (and independently of one another) contain acid degradable functionalities (groups). In another embodiment, at least one polycyclic fluorinated monomer according to formula (I) is combined with at least one monomer according to formula (II). In one embodiment, the polymerization reaction of the present invention is carried out in the presence of Group 8, 9 or 10 (latest notation system) transition metal catalyst system.
[42] Monomers:
[43] Polycyclic monomers useful in the practice of the present invention are selected from monomers represented by formula (I):
[44]
[45] Wherein R ¹ to R ⁴ are independently hydrogen, linear or branched (C ₁ to C ₃₀ ) alkyl, linear and branched (C ₁ to C ₂₄ ) halohydrocarbyl, linear or branched (C ₂ to C ₃₀ ) olefins; -(CH ₂ ) _n -C (O) OR ^* ,-(CH ₂ ) _n -C (O) OR,-(CH ₂ ) _n -OR,-(CH ₂ ) _n -OC (O) R,- (CH ₂ ) _n -C (O) R,-(CH ₂ ) _n -OC (O) OR,-(CH ₂ ) _n -C (R) ₂ -CH (R) (C (O) OR ^** ),-(CH ₂ ) _n- (CR ₂ ) _n -CH (R) (C (O) OR ^** ),-(CH ₂ ) _n C (OR ^*** )-(CF ₃ ) ₂ ,- (CR ′ ₂ ) _n —OR— and — (CH ₂ ) _n —C (R) ₂ —CH (C (O) OR ^** ) ₂ , where R is hydrogen, linear and branched (C ₁ to C ₁₀ ) alkyl, and-(CH ₂ ) _s -OH, R 'represents hydrogen or halogen (ie fluorine, chlorine, bromine, and / or iodine), n is an integer from 0 to 10, m Is an integer from 0 to 5, s is an integer from 1 to 10, Z represents oxygen, sulfur, -NR "-or-(CR" ₂ ) _p -where R "is hydrogen and p is 1 Or 2. In one embodiment of the invention, at least one of R ¹ to R ⁴ is a halohydrocarbyl and / or perhalocarbyl group In one embodiment, n is 0. R ^* is a photoinitiator Acid degradable moiety which can be cleaved by Shows a circuit breaker or a protective group), R ^*** is _{-CH 2 OR, -C (O)} OR , or represents a -C (O) R. The known acid-lifter any one can be used with the present invention. R ^* Moieties may represent tertiary (C ₄ -C ₂₀ ) alkyl and cycloalkyl groups, tri (C ₁ -C ₆ ) alkylsilyl groups and oxoalkyl groups of 4 to 20 carbon atoms. Tert-butyl, tert-amyl and 1,1-diethylpropyl, but are not limited to: tertiary cycloalkyl groups include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamant There are, but are not limited to, these. Typical trialkylsilyl groups include, but are not limited to, trimethylsilyl, triethylsilyl and dimethyl tert-butylsilyl. Examples of oxoalkyl groups are 3-oxocyclohexyl, 4-methyl-2-oxooxan-4-yl, and 5-methyl-2-oxooxolalan-5-yl. Other acid degradable groups include isobornyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanyl, mevalonic lactonyl, dicyclopropylmethyl (Dcpm), and dimethylcyclopropylmethyl (Dmcp) groups. have. R ^** independently represents R or R ^* as defined above. Dcpm and Dmcp groups are each represented by the following structural formula:
[46]
[47] The term halohydrocarbyl, as used in this section and throughout this specification, refers to one or more hydrogens on a hydrocarbyl group such as alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and aralkyl groups such as chlorine, bromine, iodine And halogen atoms selected from fluorine and combinations thereof (eg haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, haloaryl, and haloaralkyl). Halohydrocarbyl groups may contain 1 to 24 carbon atoms. The term fluorohydrocarbyl means that one or more hydrogen atoms on the hydrocarbyl group have been replaced with fluorine. The degree of halogenation refers to the degree of halogenation in which at least one hydrogen atom is replaced by a halogen atom (e.g. a monofluoromethyl group), in which all hydrogen atoms on the hydrocarbyl group are replaced by a halogen atom (e.g., trihalogenation) Perhalocarbyl, such as rhomethyl (perfluoromethyl). The fluorinated hydrocarbyl and perfluorocarbyl groups contain 1 to 24 carbon atoms in one embodiment. In another embodiment, the fluorinated hydrocarbyl and perfluorocarbyl groups contain 1-12 carbon atoms. In another embodiment, the fluorinated hydrocarbyl and perfluorocarbyl groups contain six carbon atoms and can be linear or branched, cyclic, or aromatic. Fluorinated hydrocarbyl and perfluorocarbyl groups include fluorinated and perfluorinated linear and branched C ₁ -C ₂₄ alkyl, fluorinated and perfluorinated C ₃ -C ₂₄ cycloalkyl, fluorinated and perfluorinated C ₂ -C ₂₄ alkenyl, fluorinated and perfluorinated C ₃ -C ₂₄ cycloalkenyl, fluorinated and perfluorinated C ₆ -C ₂₄ aryl, and fluorinated and perfluorinated C ₇ -C ₂₄ are Alkyl, but not limited to these. Fluorinated and perfluorocarbyl ether substituents are each represented by the formula-(CH ₂ ) _q OR ''', or (CF ₂ ) _q OR''', where R '''is the fluorinated hydro as defined above. Carbyl or perfluorocarbyl group and q is an integer from 0 to 5.
[48] In one embodiment, the perhalohydrocarbyl group includes overhalogenated phenyl and alkyl groups. Halogenated alkyl groups useful in the present invention are partially or fully halogenated and are linear or branched and are represented by the formula C _r X '' _{2r + 1} , wherein X '' is independently from fluorine, chlorine, bromine and / or iodine Halogen is selected and r is selected from an integer from 1 to 20.
[49] In one embodiment, perfluorinated substituents are perfluorophenyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl and perfluorohexyl. In addition to halogen substituents, the cycloalkyl, aryl, and aralkyl groups of the present invention may be further substituted with linear and branched C ₁ -C ₅ alkyl and haloalkyl groups, aryl groups and cycloalkyl groups.
[50] In one embodiment, m in formula (I) is 0 or 1. In another embodiment, m is zero in formula (I). When m is 0, the structural formula is represented by the formula (la):
[51]
[52] Wherein R ₁ to R ₄ and Z are as defined above. It will be apparent to those skilled in the art that any photocleavable moiety is suitable for the practice of the present invention unless the polymerization is substantially inhibited.
[53] In one embodiment, the acid decomposable group is an organic ester group in which a cleavage reaction occurs in the presence of an acid. In another embodiment, the acid decomposable groups include ester groups and carbonate groups. In another embodiment, the acid decomposable group is t-butyl ester of carboxylic acid.
[54] In another embodiment, R ¹ to R ³ are hydrogen, R ⁴ is-(CH ₂ ) _n -C (OR ^*** )-(CF ₃ ) ₂ , m is 0, n is 0 to 10 Is an integer of and Z is -CH-. In this case, the structure of formula (I) is represented by the following formula (Ib):
[55]
[56] Wherein R ^*** is -CH ₂ OR, -C (O) OR or -C (O) R, wherein R is as defined above.
[57] In another embodiment, R ¹ and R ² are hydrogen and R ³ and R ⁴ are C _r X '' _{2r + 1} wherein X '' is independently a halogen selected from fluorine, chlorine, bromine and / or iodine R is selected from an integer of 1 to 20), and Z is -CH-. In this case, the structure of formula (I) is represented by the following formula (Ic):
[58]
[59] In one embodiment, the monomer according to one of formulas (I), (la), (lb) and (lc) uses a catalyst system containing a Group 8, 9 metal ion source, as described below. By polymerization to form a homopolymer. In another embodiment, two or more different monomers according to formulas (I), (la), (lb) and (lc) can be polymerized to form a copolymer. In addition, this polymerization is carried out using a catalyst system containing a Group 8, 9 or 10 transition metal ion source as discussed below. In another embodiment, one or more monomers according to formulas (I), (la), (lb) and (lc) may be copolymerized with one or more monomers according to formula (II):
[60]
[61] Wherein R ⁵ to R ⁸ are independently hydrogen, linear or branched (C ₁ -C ₃₀ ) alkyl, linear or branched (C ₂ -C ₃₀ ) olefin,-(CH ₂ ) _n -C (O) OR ^* ,-(CH ₂ ) _n -C (O) OR,-(CH ₂ ) _n -OR,-(CH ₂ ) _n -OC (O) R,-(CH ₂ ) _n -C (O) R ,-(CH ₂ ) _n -OC (O) OR,-(CH ₂ ) _n -C (R) ₂ -CH (R) (C (O) OR ^** ),-(CH ₂ ) _n- (CR ₂ ) _n -CH (R) (C (O) OR ^** ),-(CR ' ₂ ) _n -OR- and-(CH ₂ ) _n -C (R) ₂ -CH (C (O) OR ^{* *} ) ₂ ; Wherein R represents hydrogen, linear and branched (C ₁ to C ₁₀ ) alkyl, and — (CH ₂ ) _s —OH, and R ′ represents hydrogen or halogen (ie fluorine, chlorine, bromine, and / or iodine ), N is an integer from 0 to 10, m is an integer from 0 to 5, s is an integer from 1 to 10, Z is oxygen, sulfur, -NR "-or-(CR" ₂ ) _p- Wherein R ″ is hydrogen and p is 1 or 2. In one embodiment, n is 0. R ^* represents any of the known acid decomposable moieties as defined above. In an example, at least one of R ⁵ to R ⁸ contains a halohydrocarbyl or perhalocarbyl group as defined above In another embodiment, at least one of R ⁵ to R ⁸ is a halogenated acid decomposable group. The degree of halogenation is determined by the fact that all or more hydrogen atoms on the hydrocarbyl group are replaced by one or more hydrogen atoms. It can be up to complete halogenation (perhalogenation) in which the hydrogen atom is replaced by a halogen atom.
[62] Monomers according to any one of formulas (I), (Ia), (Ib), (Ic) and (II) can be prepared by various methods. This method as well as catalyst systems for the polymerization of the aforementioned monomers are discussed in detail in US Pat. No. 6,136,499 and US Pat. No. 6,232,417, the entire contents of which are incorporated herein by reference.
[63] The polymers prepared according to the invention comprise addition polymerized polycyclic repeating units linked via 2,3-chaining. The polymer comprises one or more repeating units selected from structures represented by the formula:
[64]
[65] Wherein R ¹ to R ⁸ are as defined above.
[66] Catalytic System for Polymerization
[67] The polymers of the present invention comprise (1) one monomer according to one of formulas (I), (la), (lb) and / or (lc); (2) at least two different monomers according to formulas (I), (la), (lb) and / or (lc); And (3) polymerization of a reaction mixture comprising at least one monomer according to formulas (I), (la), (lb) and / or (lc) and at least one monomer according to formula (II). The desired reaction mixture is combined with a solvent, a catalyst system containing a Group 8, 9 or 10 transition metal ion source, and any chain transfer agent. The catalyst system may be a preformed single component Group 8, 9 or 10 transition metal based catalyst or multicomponent Group 8, 9 or 10 transition metal catalyst.
[68] Single component system:
[69] In one embodiment of the present invention, a single component catalyst system useful for preparing the polymers used in the present invention is represented by the following formula:
[70] E _n Ni (C ₆ F ₅ ) ₂
[71] Wherein n is 1 or 2 and E represents a neutral 2 electron donor ligand. In one embodiment when n is 1, E is a π-arene ligand such as toluene, benzene, and mesitylene. In another embodiment when n is 2, E is selected from diethyl ether, tetrahydrofuran (THF), ethyl acetate and dioxane.
[72] In one embodiment, the single component catalyst used in the present invention is bis (ethylacetate) bis (perfluorophenyl) nickel, (toluene) bis (perfluorophenyl) nickel, (mesitylene) bis (perfluoro) Phenyl) nickel, (benzene) bis (perfluorophenyl) nickel, bis (tetrahydrofuran) bis (perfluorophenyl) nickel and bis (dioxane) bis (perfluorophenyl) nickel.
[73] In single component catalyst embodiments, the molar ratio of total monomers to catalyst (based on metal) in the reaction medium is from about 5: 1 to about 100,00: 1, or from about 50: 1 to about 20,000: 1, or about 100: 1 to about 10,000: 1, or about 100: 1 to about 2,000: 1.
[74] Another catalyst system:
[75] In another embodiment, catalyst systems useful for preparing polymers are disclosed in WO 00/20472. One catalyst system that can be used to polymerize the polycyclic monomers of the present invention is represented by the following general formula:
[76] [(R ¹⁸ ) _z M (L ') _x (L'') _y ] _b [WCA] _d III
[77] Wherein M represents a Group 10 transition metal; R ¹⁸ represents anionic hydrocarbyl containing ligands; L 'represents a group 15 neutral electron donor ligand; L '' represents an unstable neutral electron donor ligand; z is 0 or 1; x is 1 or 2; y is 0, 1, 2 or 3; the sum of x, y, and z is 4; b and d represent multiples of the counter-anion complex (WCA), each of which weakly coordinates with the cationic complex, which is taken to balance the electron charge on the entire catalyst complex. The monomer charge may be pure or charge in solution and is contacted with a preformed catalyst of the above formula. The catalyst may also be formed in situ by mixing the catalyst forming component in the monomer charge.
[78] Weakly coordinating counteranionic complexes are only very weakly coordinating anions to the cationic complex. It is unstable enough to be replaced by a neutral Lewis base, solvent or monomer. More specifically, the WCA anion acts as a stabilizing anion for the cationic complex and is not delivered to the cationic complex to form a neutral product. WCA anions are relatively inert in that they are non-oxidizing, non-reducing and non-nucleophilic.
[79] Anionic hydrocarbyl ligands are any hydrocarbyl ligands that have a negative charge when removed from the metal center M in a closed shell electron shape.
[80] The neutral electron donor is any ligand that has a neutral charge when removed from the metal center M in a closed shell electron shape.
[81] Unstable neutral electron donor ligands are any ligands that do not bind strongly to metal center M and are easily replaced and have a neutral charge when removed from a closed shell electron shaped metal center.
[82] In the cationic complex, M represents a Group 10 transition metal selected from nickel, palladium, or platinum. In another embodiment, M is nickel or palladium.
[83] Representative anionic hydrocarbyl containing ligands as defined under R ¹⁸ are linear and branched C ₁ -C ₂₀ alkyl, C ₅ -C ₁₀ cycloalkyl, linear and branched C ₂ -C ₂₀ alkenyl, C ₆ -C ₁₅ cycloalkenyl, allyl ligand, or a standard form thereof, C ₆ -C ₃₀ aryl, C ₆ -C ₃₀ heteroatom containing aryl, and C ₇ -C ₃₀ aralkyl, each such group being one embodiment Linear or branched C ₁ -C ₅ alkyl, linear or branched C ₁ -C ₅ haloalkyl, linear or branched C ₂ -C ₅ alkenyl and haloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus, And hydrocarbyl and / or heteroatom substituents selected from linear or branched C ₁ -C ₅ alkyl, linear or branched C ₁ -C ₅ haloalkyl, and phenyl unsubstituted or substituted with halogen. do can, R ¹⁸ is also formula ^{R 19 C (O) O,} R 19 0C (O) CHC (O) R 19, R 19 C (O) S, R l9 C (S) O, R 19 C ( S) Anionic hydrocarbyl containing a ligand of S, R ¹⁹ 0, R ¹⁹ ₂ N, wherein R ¹⁹ is the same as R ¹⁸ defined above.
[84] The cycloalkyl, and cycloalkenyl ligands can be monocyclic or polycyclic. The aryl ligand can be a single ring (such as phenyl) or a fused ring system (such as naphthyl). In addition, any of cycloalkyl, cycloalkenyl and aryl groups can be taken together to form a fused ring system. Each of the monocyclic, polycyclic and aryl ring systems described above is hydrogen, linear and branched C ₁ -C ₅ alkyl, linear and branched C ₁ -C ₅ haloalkyl, linear and branched C ₁ -C ₅ alkoxy Mono- or polysubstituted, substituted with a substituent independently selected from halogen, C ₅ -C ₁₀ cycloalkyl, C ₆ -C ₁₅ cycloalkenyl, and C ₆ -C ₃₀ aryl, selected from chlorine, fluorine, iodine and bromine It may not be.
[85] As also described in WO 00/20472, R ¹⁸ may represent a hydrocarbyl ligand containing end groups that are coordinated to the Group 10 metals. The terminal coordinating group containing a hydrocarbyl ligand is represented by the formula -C _{d '} H _2d' X, where d 'represents the number of carbon atoms in the hydrocarbyl backbone and is an integer from 3 to 10, X Denotes an alkenyl or heteroatom containing moiety that is coordinated to the Group 10 metal center. The ligand forms a metallacycle or a heteroatom containing metallacycle with the Group 10 metal.
[86] Representative neutral electron donor ligands to which L ′ belongs are amines, pyridine organophosphorus containing compounds and arsine and stibine of the formula:
[87] E (R ²⁰ ) ₃
[88] Wherein E is arsenic or antimony and R ²⁰ is independently hydrogen, linear and branched C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, linear and branched C ₁ -C ₁₀ alkoxy, allyl, linear And branched C ₂ -C ₁₀ alkenyl, C ₆ -C ₁₂ aryl, C ₆ -C ₁₂ aryloxy, C ₆ -C ₁₂ arylsulphides (such as PhS), C ₇ -C ₁₈ aralkyl, cyclic ethers And thioethers, tri (linear and branched C ₁ -C ₁₀ alkyl) silyl, tri (C ₆ -C ₁₂ aryl) silyl, tri (linear and branched C ₁ -C ₁₀ alkoxy) silyl, triaryloxysilyl, Tri (linear and branched C ₁ -C ₁₀ alkyl) siloxy, and tri (C ₆ -C ₁₂ aryl) siloxy, each of these substituents being linear or branched C ₁ -C ₅ alkyl, linear or It may or may not be substituted with branched C ₁ -C ₅ haloalkyl, C ₁ -C ₅ alkoxy, halogen and combinations thereof. Representative alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl. It is not limited to these. Representative cycloalkyl groups include, but are not limited to, cyclopentyl and cyclohexyl. Representative alkoxy groups include, but are not limited to, methoxy, ethoxy and isopropoxy. Representative cyclic ether and cyclic thioether groups include, but are not limited to, furyl and thienyl, respectively. Representative aryl groups include, but are not limited to, phenyl, o -tolyl, and naphthyl. Representative aralkyl groups include, but are not limited to, benzyl and phenylethyl (ie, —CH ₂ CH ₂ PH). Representative silyl groups include, but are not limited to, triphenylsilyl, trimethylsilyl, and triethylsilyl. As in the above general definition, each such group may or may not be substituted with linear or branched C ₁ -C ₅ alkyl, linear or branched C ₁ -C ₅ haloalkyl, and halogen.
[89] Representative pyridines include lutidine (including 2,3-; 2,4-; 2,5-; 2,6-; 3,4-; and 3,5-substituted), picoline (2-, 3 -, Or 4-substituted), 2,6-di- t -butylpyridine, and 2,4-di- t -butylpyridine.
[90] Representative arsines include triphenylarcin, triethylarcin, and triethoxysilylarcin.
[91] Representative stybins include triphenylstibin and trithiophenylstibin.
[92] Suitable amine ligands can be selected from amines of the formula N (R ²¹ ) ₃ , wherein R ²¹ is independently hydrogen, linear and branched C ₁ -C ₂₀ alkyl, linear and branched C ₁ -C ₂₀ haloalkyl, Substituted and unsubstituted C ₃ -C ₂₀ cycloalkyl, substituted and unsubstituted C ₆ -C ₁₈ aryl, and substituted and unsubstituted C ₇ -C ₁₈ aralkyl. When substituted, cycloalkyl, aryl and aralkyl groups may be mono- or polysubstituted, where the substituents are hydrogen, linear and branched C ₁ -C ₁₂ alkyl, linear and branched C ₁ -C ₅ haloalkyl, linear And branched C ₁ -C ₅ alkoxy, C ₆ -C ₁₂ aryl, and halogen selected from chlorine, bromine and fluorine. Representative amines include ethylamine, triethylamine, diisopropylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl-4- t -butylaniline, N, N-dimethyl-4- t- Octylaniline, and N, N-dimethyl-4-hexadecylaniline, but are not limited to these.
[93] Organophosphorus containing ligands include phosphine, phosphite, phosphonite, phosphinite and phosphorus containing compounds of the formula:
[94] P (R ²⁰ ) _g [X '(R ²⁰ ) _h ] _3-g
[95] Wherein X 'is oxygen, nitrogen, or silicon, R ²⁰ is as defined above, each R ²⁰ substituent is independent of each other, g is 0, 1, 2 or 3, and h is 1, 2 or 3, except that when X 'is a silicon atom, h is 3, when X' is an oxygen atom, h is 1, and when X 'is a nitrogen atom, h is 2. When g is 0 and X 'is oxygen, two or three of R ²⁰ together with the oxygen atom to which they are attached form a cyclic moiety. When g is 3, two of R ²⁰ together with the phosphorus atom to which they are attached represent a phosphacycle of the formula:
[96]
[97] Wherein R ²⁰ is as defined above and h 'is an integer from 4 to 11.
[98] Organophosphorus compounds may also include bidentate phosphine ligands of the formula: and are also contemplated herein:
[99]
[100] Wherein R ²⁰ is as defined above and i is 0, 1, 2, or 3.
[101] Representative phosphine ligands include, but are not limited to, the following: trimethylphosphine, triethylphosphine, tricyclopropylphosphine, tricyclopentylphosphine, tri-n-propylphosphine, tri-iso Propylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, tri-i-butylphosphine, tri-t-butylphosphine, tricyclopentylphosphine, triallylphosphine, tricyclo Hexylphosphine, triphenylphosphine, trinaphthylphosphine, tri-p-tolylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tribenzylphosphine, tri (p-trifluoro Romethylphenyl) phosphine, tris (trifluoromethyl) phosphine, tri (p-fluorophenyl) phosphine, tri (p-trifluoromethylphenyl) phosphine, allyldiphenylphosphine, benzyldiphenylphosphine , Bis (2-furyl) phosphine, bis (4-methoxyphenyl) phenylphosphine, bis (4-methylphenyl) phosphine, bis (3,5-bis (triple) Oromethyl) phenyl) phosphine, t-butylbis (trimethylsilyl) phosphine, t-butyldiphenylphosphine, cyclohexyldiphenylphosphine, diallylphenylphosphine, dibenzylphosphine, dibutylphenylphosphine , Dibutylphosphine, di-t-butylphosphine, dicyclohexylphosphine, diethylphenylphosphine, di-i-butylphosphine, dimethylphenylphosphine, dimethyl (trimethylsilyl) phosphine, diphenylphosph Pin, diphenylpropylphosphine, diphenyl (p-tolyl) phosphine, diphenyl (trimethylsilyl) phosphine, diphenylvinylphosphine, divinylphenylphosphine, ethyldiphenylphosphine, (2-methoxy Phenyl) methylphenylphosphine, tri-n-octylphosphine, tris (3,5-bis (trifluoromethyl) phenyl) phosphine, tris (3-chlorophenyl) phosphine, tris (4-chlorophenyl) force Pin, tris (2,6-dimethoxyphenyl) phosphine, tris (3-fluorophenyl) phosphine, tris (2-furyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (3- Methoxyphenyl) phosphine, Tris (4-methoxyphenyl) phosphine, tris (3-methoxypropyl) phosphine, tris (2-thienyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tris (trimethylsilyl Phosphine, isopropyldiphenylphosphine, dicyclohexylphenylphosphine, (+)-neomentyldiphenylphosphine, tribenzylphosphine, diphenyl (2-methoxyphenyl) phosphine, diphenyl (penta) Fluorophenyl) phosphine, bis (pentafluorophenyl) phenylphosphine, and tris (pentafluorophenyl) phosphine.
[102] Typical bidentate phosphine ligands include (R)-(+)-2,2'-bis (diphenylphosphino) -1,1'-binafyl, bis (dicyclohexylphosphino) methane, bis ( Dicyclohexylphosphino) ethane; Bis (diphenylphosphino) methane; Bis (diphenylphosphino) ethane, although not limited thereto.
[103] In addition, the phosphine ligand may be selected from phosphine compounds that are water soluble and thus impart solubility in the aqueous medium to the resulting catalyst. Selected phosphines of this type include, but are not limited to, the following: carboxylic acid substituted phosphines, such as 4- (diphenylphosphine) benzoic acid, and 2- (diphenylphosphine) benzoic acid, 2 -(Dicyclohexylphosphino) ethanesulfonic acid sodium, 4,4'- (phenylphosphineidene) bis (benzene sulfonic acid) dipotassium salt, 3,3 ', 3' '-phosphinidine tris (benzene sulfonic acid) Trisodium salt, 4- (dicyclohexylphosphino) -1,1-dimethylpiperidinium chloride, 4- (dicyclohexylphosphino) -1,1-dimethylpiperidinium iodide, 4 of phosphine Secondary amine-functionalized salts such as 2- (dicyclohexylphosphino) -N, N, N-trimethylethanealuminum chloride, 2,2 '-(cyclohexylphosphinene) bis [N, N, N- Trimethylethanealuminum dichloride, 2,2 '-(cyclohexylphosphinidene) bis (N, N, N-trimethylethanealuminum) diiodide, and 2- (dicyclohexylphosphino) -N, N N-trimethylethane aluminum Odoid.
[104] Examples of phosphite ligands include, but are not limited to, the following: trimethylphosphite, diethylphenylphosphite, triethylphosphite, tris (2,4-di-t-butylphenyl) phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, tri-secondary butyl phosphite, triisobutyl phosphite, tri-t-butyl phosphite, dicyclohexyl phosphite, Tricyclohexylphosphite, triphenylphosphite, tri-p-tolylphosphite, tris (p-trifluoromethylphenyl) phosphite, benzyldiethylphosphite, and tribenzylphosphite.
[105] Examples of phosphinite ligands include, but are not limited to, methyl diphenylphosphinite, ethyl diphenylphosphinite, isopropyl diphenylphosphinite, and phenyl diphenylphosphinite.
[106] Examples of phosphonite ligands include, but are not limited to, diphenyl phenylphosphonite, dimethyl phenylphosphonite, diethyl methylphosphonite, diisopropyl phenylphosphonite, and diethyl phenylphosphonite Do not.
[107] Representative labile neutral electron donor ligands (L '') are dienes including reaction diluents, reaction monomers, DMF, DMSO, C ₄ -C ₁₀ aliphatic and C ₄ -C ₁₀ cycloaliphatic dienes (typical dienes include butadiene, 1, 6-hexadiene, and cyclooctadiene (COD)), water, chlorinated alkanes, alcohols, ethers, ketones, nitriles, arenes, phosphine oxides, organic carbonates and esters.
[108] Representative chlorinated alkanes include, but are not limited to, dichloromethane, 1,2-dichloroethane, and carbon tetrachloride.
[109] Suitable alcohol ligands can be selected from alcohols of formula R ²² OH, wherein R ²² is linear and branched C ₁ -C ₂₀ alkyl, linear and branched C ₁ -C ₂₀ haloalkyl, substituted and unsubstituted C ₃ -C ₂₀ cycloalkyl, substituted and unsubstituted C ₆ -C ₁₈ aryl, and substituted and unsubstituted C ₆ -C ₁₈ aralkyl. When substituted, cycloalkyl, aryl and aralkyl groups may be mono- or polysubstituted, wherein the substituents are independently hydrogen, linear and branched C ₁ -C ₁₂ alkyl, linear and branched C ₁ -C ₅ haloalkyl , Linear and branched C ₁ -C ₅ alkoxy, C ₆ -C ₁₂ aryl, and halogen selected from chlorine, bromine and fluorine. Representative alcohols include methanol, ethanol, n-propanol, isopropanol, butanol, hexanol, t-butanol, neopentanol, phenol, 2,6-di-i-propylphenol, 4-t-octylphenol, 5-nor Bornen-2-methanol and dodecanol, but are not limited to these.
[110] Suitable ether ligands and thioether ligands can be selected from ethers and thioethers of formulas (R ²³ -OR ²³ ) and (R ²³ -SR ²³ ), respectively, wherein R ²³ is independently linear and branched C ₁ -C ₁₀ alkyl groups, linear and branched C ₁ -C ₂₀ haloalkyl, substituted and unsubstituted C ₃ -C ₂₀ cycloalkyl, linear and branched C ₁ -C ₂₀ alkoxy, substituted and unsubstituted C ₆ -C ₁₈ aryl, and substituted and unsubstituted C ₆ -C ₁₈ aralkyl. When substituted, cycloalkyl, aryl and aralkyl groups may be mono- or polysubstituted, wherein the substituents are independently hydrogen, linear and branched C ₁ -C ₁₂ alkyl, linear and branched C ₁ -C ₅ haloalkyl Cyclic ethers or cyclic thioethers, selected from linear and branched C ₁ -C ₅ alkoxy, C ₆ -C ₁₂ aryl, and halogen selected from chlorine, bromine and fluorine with the oxygen or sulfur atoms to which they are attached To form. Representative ethers include dimethyl ether, dibutyl ether, methyl-t-butyl ether, di-i-propyl ether, diethyl ether, dioctyl ether, 1,4-dimethoxyethane, THF, 1,4-dioxane and Tetrahydrothiophenes, but are not limited to these.
[111] Suitable ketone ligands are represented by ketones of the formula R ²⁴ C (O) R ²⁴ , wherein R ²⁴ is independently linear and branched C ₁ -C ₂₀ alkyl, linear and branched C ₁ -C ₂₀ haloalkyl, substituted And unsubstituted C ₃ -C ₂₀ cycloalkyl, substituted and unsubstituted C ₆ -C ₁₈ aryl, and substituted and unsubstituted C ₆ -C ₁₈ aralkyl. When substituted, cycloalkyl, aryl and aralkyl groups may be mono- or polysubstituted, wherein the substituents are independently hydrogen, linear and branched C ₁ -C ₁₂ alkyl, linear and branched C ₁ -C ₅ haloalkyl , Linear and branched C ₁ -C ₅ alkoxy, C ₆ -C ₁₂ aryl, and halogen selected from chlorine, bromine and fluorine. Representative ketones include, but are not limited to, methyl ethyl ketone, cyclohexanone, and benzophenone.
[112] The nitrile ligand can be represented by the formula R ²⁵ CN, wherein R ²⁵ is hydrogen, linear and branched C ₁ -C ₂₀ alkyl, linear and branched C ₁ -C ₂₀ haloalkyl, substituted and unsubstituted C ₃ -C ₂₀ cycloalkyl, substituted and unsubstituted C ₆ -C ₁₈ aryl, and substituted and unsubstituted C ₆ -C ₁₈ aralkyl. When substituted, cycloalkyl, aryl and aralkyl groups may be mono- or polysubstituted, wherein the substituents are independently hydrogen, linear and branched C ₁ -C ₁₂ alkyl, linear and branched C ₁ -C ₅ haloalkyl , Linear and branched C ₁ -C ₅ alkoxy, C ₆ -C ₁₂ aryl, and halogen selected from chlorine, bromine and fluorine. Representative nitriles include, but are not limited to, acetonitrile, propyronitrile, benzonitrile, benzyl cyanide, and 5-norbornene-2-carbonitrile.
[113] The arene ligands may be selected from substituted and unsubstituted C ₆ -C ₁₂ arenes containing mono or polysubstitutes, wherein the substituents are independently hydrogen, linear and branched C ₁ -C ₁₂ alkyl, Linear and branched C ₁ -C ₅ haloalkyl, linear and branched C ₁ -C ₅ alkoxy, C ₆ -C ₁₂ aryl, and halogen selected from chlorine, bromine and fluorine. Representative arenes include toluene, benzene, o- , m- , and p -xylene, mesitylene, fluorobenzene, o -difluorobenzene, p -difluorobenzene, chlorobenzene, pentafluorobenze, o- Dichlorobenzene, and hexafluorobenzene, but are not limited to these.
[114] Suitable trialkyl and triaryl phosphine oxide ligands can be represented by phosphine oxides of the formula P (O) (R ²⁶ ) ₃ , wherein R ²⁶ is independently linear and branched C ₁ -C ₂₀ alkyl, linear and Branched C ₁ -C ₂₀ haloalkyl, substituted and unsubstituted C ₃ -C ₂₀ cycloalkyl, linear and branched C ₁ -C ₂₀ alkoxy, linear and branched C ₁ -C ₂₀ haloalkoxy, substituted and Unsubstituted C ₆ -C ₁₈ aryl and substituted and unsubstituted C ₆ -C ₁₈ aralkyl. When substituted, cycloalkyl, aryl and aralkyl groups may be mono- or polysubstituted, wherein the substituents are independently hydrogen, linear and branched C ₁ -C ₁₂ alkyl, linear and branched C ₁ -C ₅ haloalkyl , Linear and branched C ₁ -C ₅ alkoxy, C ₆ -C ₁₂ aryl, and halogen selected from chlorine, bromine and fluorine. Representative phosphine oxides include, but are not limited to, triphenylphosphine oxide, tributylphosphine oxide, trioctylphosphine oxide, tributylphosphate, and tris (2-ethylhexyl) phosphate.
[115] Representative carbonates include, but are not limited to, ethylene carbonate and propylene carbonate.
[116] Representative esters include, but are not limited to, ethyl acetate and i -amyl acetate.
[117] Description of the WCA
[118] The weakly coordinating counteranionic complex [WCA] of formula (III) may be selected from borate and aluminate, boratobenzene anion, carborane and halocarboran anion.
[119] Borate and aluminate weakly coordinating counter anions are represented by the following formulas (IV) and (V):
[120] [M '(R ²⁷ ) (R ²⁸ ) (R ²⁹ ) (R ³⁰ )] IV
[121] [M '(OR ³¹ ) (OR ³² ) (OR ³³ ) (OR ³⁴ )] V
[122] M 'in formula (IV) is boron or aluminum, and R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are independently fluorine, linear and branched C ₁ -C ₁₀ alkyl, linear and branched C ₁ -C ₁₀ Alkoxy, linear and branched C ₃ -C ₅ haloalkenyl, linear and branched C ₃ -C ₁₂ trialkylsiloxy, C ₁₈ -C ₃₆ triarylsiloxy, substituted and unsubstituted C ₆ -C ₃₀ Aryl, and substituted and unsubstituted C ₆ -C ₃₀ aryloxy groups, wherein R ²⁷ to R ³⁰ may not all represent alkoxy or aryloxy groups at the same time. When substituted, the aryl group may be mono- or polysubstituted, wherein the substituents are independently linear and branched C ₁ -C ₅ alkyl, linear and branched C ₁ -C ₅ haloalkyl, linear and branched C _1- Selected from C ₅ alkoxy, linear and branched C ₁ -C ₅ haloalkoxy, linear and branched C ₁ -C ₁₂ trialkylsilyl, C ₆ -C ₁₈ triarylsilyl, and halogen selected from chlorine, bromine, and fluorine do. In another embodiment, halogen is fluorine.
[123] Representative borate anions belonging to formula (IV) include, but are not limited to, the following: tetrakis (pentafluorophenyl) borate, tetrakis (3,5-bis (trifluoromethyl) phenyl) borate , Tetrakis (2-fluorophenyl) borate, tetrakis (3-fluorophenyl) borate, tetrakis (4-fluorophenyl) borate, tetrakis (3,5-difluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5,6-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, Methyltris (perfluorophenyl) borate, ethyltris (perfluorophenyl) borate, phenyltris (perfluorophenyl) borate, tetrakis (1,2,2-trifluoroethyleneyl) borate, tetrakis ( 4-tri- i -propylsilyltetrafluorophenyl) borate, tetrakis (4 -Dimethyl-tert-butylsilyltetrafluorophenyl) borate, (triphenylsiloxy) tris (pentafluorophenyl) borate, (octyloxy) tris (pentafluorophenyl) borate, tetrakis [3,5- Bis [1-methoxy-2,2,2-trifluoro-1- (trifluoromethyl) ethyl] phenyl] borate, tetrakis [3- [1-methoxy-2,2,2-trifluoro Rho-1- (trifluoromethyl) ethyl] -5- (trifluoromethyl) phenyl] borate, and tetrakis [3- [2,2,2-trifluoro-1- (2,2,2 -Trifluoroethoxy) -l- (trifluoromethyl) ethyl] -5- (trifluoromethyl) phenyl] borate.
[124] Representative aluminate anions belonging to formula (IV) include tetrakis (pentafluorophenyl) aluminate, tris (perfluorobiphenyl) fluoroaluminate, (octyloxy) tris (pentafluorophenyl) aluminate, tetra Kis (3,5-bis (trifluoromethyl) phenyl) aluminates, and methyltris (pentafluorophenyl) aluminates are, but are not limited to these.
[125] In formula (V), M 'is boron or aluminum, and R ³¹ , R ³² , R ³³ and R ³⁴ are independently linear and branched C ₁ -C ₁₀ alkyl, linear and branched C ₁ -C ₁₀ haloalkyl , C ₂ -C ₁₀ haloalkenyl, substituted and unsubstituted C ₆ -C ₃₀ aryl, and substituted and unsubstituted C ₇ -C ₃₀ aralkyl groups, provided that at least three of R ³¹ to R ³⁴ Should contain halogen-containing substituents. When substituted, aryl and aralkyl groups may be mono- or polysubstituted, wherein the substituents are independently linear and branched C ₁ -C ₅ alkyl, linear and branched C ₁ -C ₅ haloalkyl, linear and branched C ₁ -C ₅ alkoxy, linear and branched C ₁ -C ₁₀ haloalkoxy, and halogen selected from chlorine, bromine, and fluorine. In another embodiment the halogen is fluorine. The groups OR ³¹ and OR ³² may be taken together to form a chelating substituent represented by -OR ³⁵ -O-, wherein the oxygen atom is bonded to M 'and R ³⁵ is substituted and unsubstituted C ₆ -C Divalent group selected from ₃₀ aryl and substituted and unsubstituted C ₇ -C ₃₀ aralkyl. In one embodiment, the oxygen atom is bonded to the aromatic ring at the ortho or meta position either directly or through an alkyl group. When substituted, aryl and aralkyl groups may be mono- or polysubstituted, wherein the substituents are independently linear and branched C ₁ -C ₅ alkyl, linear and branched C ₁ -C ₅ haloalkyl, linear and branched C ₁ -C ₅ alkoxy, linear and branched C ₁ -C ₁₀ haloalkoxy, and halogen selected from chlorine, bromine, and fluorine. In another embodiment, halogen is fluorine. Representative structures of the divalent R ³⁵ group are disclosed in WO 00/20472, which is incorporated herein by reference.
[126] Representative borate and aluminate anions belonging to formula (IV) include, but are not limited to the following: [B (OC (CF ₃ ) ₃ ) ₄ ] ^- , [B (OC (CF ₃ ) ₂ ( CH ₃ )) ₄ ] ^- , [B (OC (CF ₃ ) ₂ H) ₄ ] ^- , [B (OC (CF ₃ ) (CH ₃ ) H) ₄ ] ^- , [Al (OC (CF ₃ ) ₂ ) Ph) ₄ ] ^- , [B (OCH ₂ (CF ₃ ) ₂ ) ₄ ] ^- , [Al (OC (CF ₃ ) ₂ C ₆ H ₄ CH ₃ ) ₄ ] ^- , [Al (OC (CF ₃ ) ₃ ) ₄ ] ^- , [Al (OC (CF ₃ ) (CH ₃ ) H) ₄ ] ^- , [Al (OC (CF ₃ ) ₂ H) ₄ ] ^- , [Al (OC (CF ₃ ) ₂ C ₆ H ₄ -4- i -Pr) ₄ ] ^- , [Al (OC (CF ₃ ) ₂ C ₆ H ₄ -4- t -butyl) ₄ ] ^- , [Al (OC (CF ₃ ) ₂ C ₆ H _4- 4-SiMe ₃ ) ₄ ] ^- , [Al (OC (CF ₃ ) ₂ C ₆ H ₄ -4-Si- i -Pr ₃ ) ₄ ] ^- , [Al (OC (CF ₃ ) ₂ C ₆ H _2- 2,6- (CF ₃ ) ₂ -4-Si- i- Pr ₃ ) ₄ ] ^- , [Al (OC (CF ₃ ) ₂ C ₆ H ₃ -3,5- (CF ₃ ) ₂ ) ₄ ] ^- _{, [Al (OC (CF 3} ) 2 C 6 H 2 -2,4,6- (CF 3) 3) 4] - , and _{[Al (OC (CF 3)} 2 C 6 F 5) 4] -.
[127] Boratobenzene anions useful as weakly coordinating counter anions can be represented by the formula (VI):
[128]
[129] Wherein R ³⁶ is selected from fluorine, fluorinated hydrocarbyl, perfluorocarbyl, and fluorinated ethers and perfluorinated ethers. In another embodiment, the fluorinated hydrocarbyl and perfluorocarbyl groups contain six carbon atoms and can be linear or branched, cyclic, or aromatic. Fluorinated hydrocarbyl and perfluorocarbyl groups include fluorinated and perfluorinated linear and branched C ₁ -C ₂₄ alkyl, fluorinated and perfluorinated C ₃ -C ₂₄ cycloalkyl, fluorinated and perfluorinated C ₂ -C ₂₄ alkenyl, fluorinated and perfluorinated C ₃ -C ₂₄ cycloalkenyl, fluorinated and perfluorinated C ₆ -C ₂₄ aryl, and fluorinated and perfluorinated C ₇ -C ₂₄ aralkyl There are, but are not limited to these. Fluorinated and perfluorocarbyl ether substituents are represented by the formula-(CH ₂ ) _m OR ³⁸ , or-(CF ₂ ) _m OR ³⁸ , respectively, wherein R ³⁸ is fluorinated or perfluoro as defined above Carbyl group, m is an integer of 0-5. It should be noted that when m is zero, the oxygen atom of the ether moiety is directly bonded to the boron atom in the boratobenzene ring.
[130] In one embodiment, the R ³⁶ groups are for example trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, pentafluorophenyl and bis (3,5-trifluoromethyl) phenyl Electron attracting groups by nature, such as fluorinated and perfluorinated hydrocarbyl groups selected from.
[131] R ³⁷ independently represents a hydrogen, halogen, perfluorocarbyl and silylperfluorocarbyl group, wherein the perfluorocarbyl and silylperfluorocarbyl are as defined above. In one embodiment, the halogen group is selected from chlorine, fluorine. In another embodiment, halogen is fluorine. When R ³⁷ is halogen, perfluorocarbyl, and / or silylperfluorocarbyl, the group (s) are in one embodiment in the ortho or para position relative to the boron atom in the boratobenzene ring. In another embodiment, when R ³⁷ is halogen, perfluorocarbyl, and / or silylperfluorocarbyl, the group (s) are in para position relative to the boron atom of the boratobenzene ring.
[132] Representative boratobenzene anions include [1,4-dihydro-4-methyl-1- (pentafluorophenyl)]-2-borate, 4- (1,1-dimethyl) -1,2-dihydro -1- (pentafluorophenyl) -2-borate, 1-fluoro-1,2-dihydro-4- (pentafluorophenyl) -2-borate, and 1- [3,5-bis (tri Fluoromethyl) phenyl] -1,2-dihydro-4- (pentafluorophenyl) -2-borate, but are not limited to these.
[133] Not things weakly coordinated as a counter anion useful carborane (carborane) and halo carborane is the anion of the following, but limited _{to: CB 11 (CH 3) l2} -, CB 11 H 12 -, 1-C ^{_{2 H 5 CB 11 H 11 -}} , 1-Ph 3 SiCB 11 H ll -, 1-CF 3 CB 11 H 11 -, 12-BrCB 11 H 11 -, 12-BrCB 11 H 11 -, 7,12-Br ^{_{2 CB 11 H 10 -, 12}} -ClCB 11 H 11 -, 7,12-Cl 2 CB 11 H 10 -, 1-H-CB 11 F 11 -, 1-CH 3 -CB 11 F 11 -, 1- ^{_{CF 3 -CB 11 -F 11 -,}} 12-CB 11 H 11 F -, 7,12-CB 11 H 11 F 2 -, 7,9,12-CB 11 H 11 F 3 -, CB 11 H 6 Br _{^{6 -, 6-CB 9 H}} 9 F -, 6,8- CB 9 H 8 F 2 -, 6,7,8-CB 9 H 7 F 3 -, 6,7,8,9-CB 9 H 6 _{^{F 4 -, 2,6,7,8,9-CB 9}} H 5 F 5 -, CB 9 H 5 Br 5 -, CB 11 H 6 Cl 6 -, CB 11 H 6 F 6 -, CB 11 H 6 _{^{F 6 -, CB 11 H 6}} I 6 -, CB 11 H 6 Br 6 -, 6,7,9,10,11,12-CB 11 H 6 F 6 -, 2,6,7,8,9, _{10-CB 9 H 5 F 5} -, 1-H-CB 9 F 9 -, 12-CB 11 H 11 (C 6 H 5) -, 1-C 6 F 5 -CB 11 H 5 Br 6 -, CB _{^{11 Me 12 -, CB 11 (}} CF 3) 12 -, Co (B 9 C 2 H 11) 2 -, CB 11 (C _{^{H 3) 12 -, CB 11}} (C 4 H 9) 12 -, CB 11 (C 6 H l3) 12 -, Co (C 2 B 9 H 11) 2 -, Co (Br 3 C 2 B 9 H 8 ) ₂ ^- and dodecahydro-1-carbadodecarborate.
[134] Leaving machine
[135] A 'represents an anionic leaving group that can be easily replaced by a weakly coordinating anion provided by the WCA salt. Leaving groups form salts with cations on the WCA salts. Leaving group A 'is halogen (ie Br, Cl, I and F), nitrate, triflate (trifluoromethanesulfonate), trilimide (bistrifluoromethanesulfonimide), trifluoroacetate , _{^{tosylate, AlBr 4 -, AlF 4 -}} , AlCl 4 -, AlF 3 O 3 SCF 3 -, AsCl 6 -, SbCl 6 -, SbF 6 -, PF 6 -, BF 4 -, Cl0 4 -, HSO 4 ^- , Carboxylate, acetate, acetylacetonate, carbonate, aluminate, and borate.
[136] A more detailed description of leaving groups can be found in WO 00/20472, the teachings of leaving groups being incorporated herein by reference.
[137] The catalyst of formula (III) can be prepared as a preformed single component catalyst in a solvent or in situ by mixing the catalyst precursor component in the desired monomer to be polymerized.
[138] The catalyst of formula (III) can be prepared by mixing the catalyst precursor in a suitable solvent, running the reaction under suitable temperature conditions, and separating the catalyst product. In another embodiment, the Group 10 metal precursor-catalyst is mixed with a Group 15 electron donor compound and / or a labile neutral electron donor compound, and a salt of a weakly coordinating anion, in a suitable solvent and represented by Formula (III) above A preformed catalyst composite is obtained. In another embodiment, a Group 10 metal pro-catalyst containing a Group 15 electron donor ligand is mixed with a salt of a weakly coordinating anion in a suitable solvent to obtain a preformed catalyst complex.
[139] The catalyst preparation reaction is carried out in a solvent which is inert under the reaction conditions. Examples of suitable solvents for the catalyst preparation reaction include alkanes and cycloalkane solvents such as pentane, hexane, heptane, and cyclohexane; Halogenated alkanes solvents such as dichloromethane, chloroform, carbon tetrachloride, ethylchloride, 1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane; Ethers such as THF and diethyl ether; Aromatic solvents such as benzene, xylene, toluene, mesitylene, chlorobenzene, and o -dichlorobenzene; And halocarbon solvents such as Freon ^R 112; And mixtures thereof, but is not limited thereto. In one embodiment, the solvent is, for example, benzene, fluorobenzene, o -difluorobenzene, p -difluorobenzene, pentafluorobenzene, hexafluorobenzene, o -dichlorobenzene, chlorobenzene, Toluene, o- , m- and p -xylene, mesitylene, cyclohexane, THF, and dichloromethane.
[140] Suitable temperature ranges for carrying out the reaction are from about -80 ° C to about 150 ° C. In another embodiment, the temperature range for carrying out the reaction is from about -40 ° C to about 100 ° C. In another embodiment, the temperature range for carrying out the reaction is from about 0 ° C to about 65 ° C. In another embodiment, the temperature range for carrying out the reaction is from about 10 ° C to about 40 ° C. The pressure is not critical but may depend on the boiling point of the solvent used. That is, the pressure is sufficient to keep the solvent in a liquid state. The reaction time is also not critical and can be from several minutes to 48 hours. In one embodiment, the reaction is carried out under an inert atmosphere such as nitrogen or argon.
[141] The reaction is carried out by dissolving the procatalyst in a suitable solvent, mixing the salt of the desired weakly coordinating anion with the appropriate ligand (s) with the dissolved procatalyst and optionally heating the solution until the reaction is complete. . The preformed single component catalyst may be separated or used directly by adding a certain amount of the preformed catalyst in solution form to the polymerization reaction medium. Separation of the product can be accomplished by standard procedures, for example by evaporating the solvent, washing the solid with an appropriate solvent and then recrystallizing the desired product. The molar ratio of the catalyst components used in the preparation of the preformed single component catalyst of the present invention is based on the metal contained in the pro-catalyst component. In one embodiment, the molar ratio of pro-catalyst / Group 15 electron donor component / WCA salt is 1: 1-10: 1-100. In another embodiment, the molar ratio of pro-catalyst / Group 15 electron donor component / WCA salt is 1: 1-5: 1-20. In another embodiment, the molar ratio of pro-catalyst / Group 15 electron donor component / WCA salt is 1: 1-2: 1-5. In embodiments of the invention wherein the procatalyst is linked to a Group 15 electron donor ligand and / or an unstable neutral electron donor ligand, the molar ratio of procatalyst molar ratio (based on metal content) to WCA salt is 1: 1-100. to be. In another embodiment, this ratio is 1: 1-20. In another embodiment, this ratio is 1: 1-5.
[142] Embodiments of hydrocarbyl-free catalysts containing ligands can be synthesized by reacting the pro-catalyst of formula [M (A ') ₂ ] with the desired ligand and WCA salt according to the following scheme:
[143] [M (A ') ₂ ] + xL' + 2 [WCA] salts □ [M (L ') _x ] [WCA] ₂ + 2A' salts
[144] Wherein x is 1 or 2 and M and L 'are as defined above.
[145] Examples of pro-catalyst compounds are palladium (II) bis (acetylacetonate), palladium (acetate) ₂ , Pd (NO ₃ ) ₂ , PdCl ₂ , PdBr ₂ , and PdI ₂ .
[146] The schematic equations are presented for illustrative purposes only and other exemplary equations can be found in WO / 0020472. Although these equations are described in equilibrium form, it should be appreciated that excess reaction components can be used without departing from the spirit of the invention. For example, excess L ', L' ', A' or WCA salt containing components can be used in the process of the invention as long as the process is not adversely affected.
[147] In one embodiment, the molar ratio of Group 10 metal / Group 15 electron donor compound / lightly coordinating anion source / organometal compound is 1: 1-10: 1-100: 2-200. In another embodiment, the molar ratio of Group 10 metal / Group 15 electron donor compound / weakly coordinated anion source / organometal compound is 1: 1-5: 1-40: 4-100. In another embodiment, the molar ratio of Group 10 metal / Group 15 electron donor compound / lightly coordinating anion source / organometallic compound is 1: 1-2: 2-20: 5-50. In embodiments where the Group 10 metal ion source is an adduct containing a Group 15 metal donor compound, there is no need to use a Group 15 electron donor compound further. In this embodiment, the molar ratio of the Group 10 metal / Group 15 electron donor compound / weakly coordinated anion source / organometal compound is 1: 0: 2-20: 5-50.
[148] The optimum temperature for the present invention depends on a number of variables, primarily the choice of catalyst and the choice of reaction diluent. Thus, for any given polymerization reaction, the optimum temperature will be determined experimentally taking these variables into account.
[149] Generally, the polymerization reaction is carried out in any suitable solvent in the temperature range of about 0 ° C. to about 140 ° C., or 20 ° C. to about 130 ° C., or about 25 ° C. to about 125 ° C., in the presence of any of the catalysts of the invention. Can be. In another embodiment, the reaction is carried out at a temperature in the range of about 70 ° C. to about 130 ° C. in any suitable solvent. In another embodiment, the reaction is carried out at a temperature in the range of about 15 ° C. to about 45 ° C. in any suitable solvent.
[150] In one embodiment of the present invention, the reaction using the disclosed catalyst is carried out in an organic solvent that does not adversely interfere with the catalyst system and is a solvent for the monomers. Examples of organic solvents include aliphatic (nonpolar) hydrocarbons such as pentane, hexane, heptane, octane and decane; Alicyclic hydrocarbons such as cyclopentane and cyclohexane; Aromatic hydrocarbons such as benzene, chlorobenzene, o-dichlorobenzene, toluene, methoxybenzene and xylene; Ethers such as methyl-t-butyl ether and anisole; Halogenated (polar) hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 2-chloropropane, 1- Chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane.
[151] The choice of reaction solvent is based on a number of factors, including the choice of catalyst and whether it is desirable to proceed with the polymerization reaction as a slurry or solution process. Those skilled in the art will appreciate that the above-mentioned monomer combinations may be polymerized in consideration of a number of factors including, but not limited to, the exact nature of the monomers to be polymerized, the catalyst used for the polymerization, and the temperature and / or pressure at which the polymerization is carried out. It will be easy to determine which solvent is suitable for use in the process.
[152] The molar ratio of total monomers to Group 8, 9 or 10 transition metals in the catalyst represented by formula (III) is from about 2: 1 to about 100,000: 1, or from about 5: 1 to about 20,000: 1, or about 100: 1 to about 10,000: 1, or about 10: 1 to about 2,000: 1. In another embodiment, the molar ratio of total monomers to Group 8, 9, or 10 metals is from about 2: 1 to about 1000: 1, or from about 5: 1 to about 500: 1, or from about 10: 1 to about 250: It may be in the range of 1.
[153] The polymers obtained by the process of the present invention are prepared in the range of about 500 to about 1,000,000, or about 2,000 to about 700,000, or about 3,000 to about 100,000, or about 3,000 to about 50,000 molecular weight (Mn).
[154] The molecular weight can be adjusted by varying the ratio of catalyst to monomer. In addition, low molecular weight polymers and oligomers may be formed in the range of about 500 to about 500,000 by carrying out the polymerization reaction in the presence of a chain transfer agent. Macromonomers or oligomers containing from about 4 to about 50 repeat units can be prepared in the presence of a CTA (chain transfer agent) selected from compounds with terminal olefinic double bonds between adjacent carbon atoms, wherein among adjacent carbon atoms At least one hydrogen atom is attached. CTA excludes styrene (non-styrene), vinyl ether (non-vinyl ether) and conjugated dienes. Non-styreneic non-vinyl ethers mean that compounds having the following structure are excluded from the chain transfer agent of the present invention:
[155] CH ₂ = C (A) (R or H), and
[156] CH ₂ = CH-OR
[157] Wherein A is an aromatic substituent and R is hydrocarbyl.
[158] In one embodiment the CTA compound of the invention is represented by the formula:
[159] CH ₂ = C (R ¹⁶ ) (R ¹⁷ )
[160] Wherein R ¹⁶ and R ¹⁷ are independently hydrogen, branched or unbranched (C ₁ -C ₄₀ ) alkyl, branched or unbranched (C ₂ -C ₄₀ ) alkenyl, or halogen.
[161] In one embodiment, the CTA used in the present invention is an α-olefin having 2 to 10 carbon atoms (eg ethylene, propylene, 4-methyl-1-pentene, 1-hexene, 1-decene, 1, 7-octadiene, and 1,6-octadiene, or isobutylene).
[162] C ₃ to C ₁₂ cyclic olefins (such as cyclopentene) are also useful as CTAs.
[163] CTA may be used in an amount of about 0.10 mol% to 50 mol% or more relative to the moles of the total NB-type monomers. In one embodiment, CTA is used in the range of 0.10 to 10 mol%. In another embodiment, CTA is used in the range of 0.1 to 5.0 mol%. As discussed above, depending on catalyst type and sensitivity, CTA efficiency and desired end group, the concentration of CTA can be 50 mole percent effect (based on the total NB-functional monomer), such as 60 to 80 mole percent. have. Higher concentrations of CTA (eg, greater than 100 mole%) may be necessary to achieve low molecular weight embodiments of the present invention, such as oligomer and macromonomer applications. Except for chain transfer, the process of the present invention provides a method by which the terminal α-olefin end groups can be located at the ends of the polymer chain.
[164] The polymers of the invention prepared in the presence of the CTA of the invention have a molecular weight (Mn) in the range of about 500 to about 500,000, or about 2,000 to about 300,000, or sometimes about 5,000 to about 200,000.
[165] Polymers prepared in the presence of catalysts and / or CTAs of the present invention contain unsaturation at one or both terminal ends of the polymer chain. The position of the terminal unsaturation contained in the polymer chain depends on the type of chain transfer agent used in the polymerization reaction. When used with the transition metal catalyst used to polymerize polycyclic olefin monomers herein, the chain transfer agent is attached only as a terminating end group on each polycyclic polymer chain. The chain transfer agent is not copolymerized into the backbone of the polymer. Terminating end groups are meant that the end groups at one or more of the one or more terminating ends of the polycyclic polymer chain contain end groups derived from the chain transfer agent used in the polymerization reaction. Briefly described, the terminal unsaturated polymers prepared in the presence of a chain transfer agent can be represented by the following formula:
[166] PNB-CTA
[167] Wherein PNB represents a polycyclic polymer chain comprising one or more repeating units selected from the formulas (I ') and (II') set forth above, and CTA represents a chain transfer agent moiety covalently attached to the terminal of the PNB backbone. For example, when an α-olefin such as ethylene is used as the chain transfer agent, the terminal group unsaturation in the polymer backbone can be expressed as follows:
[168] PNB-CH ₂ = CH ₂
[169] When longer chain α-olefins such as 1-hexene are used as chain transfer agent, the polymer backbone can be schematically represented as follows:
[170] PNB-CH ₂ = CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₃
[171] It is noted that for longer chain α-olefin chain transfer agents (C ₃ or higher), the double bonds in the chain transfer agent can be rearranged to another position in the carbon chain to produce various unsaturated isomers. For example, the double bond in the above schematic formula for the attached hexenyl moiety may be rearranged between carbon atoms 2 and 3, between carbon atoms 3 and 4, and between carbon atoms 4 and 5 Wherein carbon 1 is located proximal to the PNB chain and carbon 6 is located distal to the PNB chain.
[172] This end group unsaturation increases the optical density of the polymer, which is detrimental to lithographic imaging. As discussed herein, the terminal unsaturation contained in the attached chain transfer moiety may result in post-functionalization of the olefin end group, for example by epoxidation, hydrogenation, hydroformylation, hydrosylation and / or cyclopropaneation. Can be removed. Treatment of the terminal unsaturated end groups with the post-functionalizer of the present invention yields a polycyclic polymer with hydrogenated, hydroformylated, hydrosylated and epoxidized end groups. The post-functionalizer is added across the double bond contained in the terminal unsaturated end group attached to the terminating end of the polycyclic polymer. Terminal unsaturation treatment of polycycloolefins is disclosed in US Pat. No. 6,294,616, which is incorporated herein in its entirety.
[173] In one embodiment of the invention, terminal unsaturation present at the terminal end of the polymer backbone can be hydrogenated in the presence of hydrogen and a hydrogenation catalyst. Any homogeneous or heterogeneous hydrogenation catalyst can be used as long as it does not deleteriously affect the polymer backbone. Examples of suitable hydrogenation catalysts include H ₂ PtCl ₄ (chloroplatinic acid), RuHCl (Ph ₃ ) ₃ , RhCl (Ph ₃ ) ₃ (Wilkinson's catalyst) and Ir (1,5-cyclooctadiene) (P (cyclo Hexyl) ₃ ) (pyridine)] PF ₆ (Crabtree catalyst). It is also contemplated that the palladium metal containing catalyst represented by formula (III) herein may be used as a hydrogenation catalyst in the presence of hydrogen. The catalyst is used in an amount of about 0.01% to about 2.5% w / w based on the polymer, and in another embodiment about 1.9% based on the polymer. The polymer is separated from the reaction medium after the polymerization reaction and then hydrogenated in the presence of hydrogen and a hydrogenation catalyst in a suitable solvent (eg toluene, benzene, tetrahydrofuran, methylene chloride). Hydrogen is used on the reaction medium at a pressure of 1 to 500 psi in one embodiment of the invention and at a pressure of 50 to 90 psi in another embodiment. In one embodiment of the invention, the polymer is hydrogenated at a temperature of about 22 to 100 ° C., and in another embodiment is hydrogenated at a temperature of 70 to 75 ° C. The hydrogenation reaction is carried out for about 10 to about 72 hours in one embodiment of the invention and for 10 to about 15 hours in another embodiment. Double bonds in the terminating olefin end groups are hydrogenated to produce hydrogenated end groups on one or both terminating ends of the polycyclic polymer.
[174] In another embodiment, terminal unsaturation present at the terminal end of the polymer backbone can be hydrosylated in the presence of a hydrosilylation catalyst and a silane post-functionalizer. Any homogeneous or heterogeneous hydrosilylation catalyst can be used so long as it does not adversely affect the polymer backbone. Examples of suitable hydrosilylation catalysts include H ₂ PtCl ₄ (chloroplatinic acid), RhCl (Ph ₃ ) ₃ (Wilkinson catalyst) and [Ir (1,5-cyclooctadiene) (P (cyclohexyl) ₃ ) (pyridine) ] PF ₆ (crabtree catalyst). Examples of silane post-functionalizers include (C ₁ -C ₁₀ ) trialkyl silanes (eg, triethylsilane, tri (n-propylsilane) and pentamethyldisiloxane) Hydrosylation catalysts in one embodiment of the invention From about 0.01 to about 2.5 w / w% based on the polymer, and in another embodiment at about 25 w / w The hydrosylating agent is from about 1 to 20 molar equivalents or from 2.0 to 39 w / w In amounts of% (based on the polymer) The polymer is separated from the reaction medium after the polymerization reaction and then after the hydrogenation catalyst and silane in a suitable solvent (eg toluene, benzene, tetrahydrofuran, methylene chloride) In the presence of a functionalizing agent The polymer is reacted at a temperature of about 22 to 100 ° C. in one embodiment of the invention and at a temperature of about 60 to 65 ° C. in another embodiment. In one embodiment, the range of about 10 to about 240 hours In another embodiment, the reaction time may range from about 10 to about 15 hours The double bond in the terminating olefin end group is hydrosylated to form one of the polycyclic polymers. Hydrosylated end groups are produced on either or both ends.
[175] In another embodiment, terminal unsaturation present at the terminal end of the polymer backbone can be epoxidized in the presence of a peracid post-functionalizer. In one embodiment of the invention, the peracid is a mixture of glacial acetic acid and hydrogen peroxide in a ratio of about 5: 1 to about 1: 5 (% by volume). In another embodiment, the ratio of acetic acid to hydrogen peroxide is 1: 1. The polymer is separated from the reaction medium after the polymerization reaction and dissolved at a concentration of about 5 to 30% by weight (polymer in the solvent) in a suitable solvent (eg toluene). The ratio of polymer solution to peracid acid is in one embodiment about 5: 1 to about 1: 1 and in another embodiment of the invention about 2: 1 to about 1: 1. The acid treated polymer solution is heated to about 50 to about 100 ° C. in one embodiment of the invention and to about 80 to about 90 ° C. in another embodiment. The reaction may be carried out for about 0.5 to 5 hours in one embodiment of the invention, and for about 1 hour in another embodiment. Double bonds in the terminating olefin end groups are epoxidized to produce oxirane end groups on the end portions of the polycyclic polymer. It should be noted that the oxirane ring can be ring-opened to produce hydroxy derivatives of the oxirane moiety.
[176] Again, it should be appreciated that for longer chain terminating groups (eg, hexenyl groups as discussed above), there are many unsaturated isomers depending on the degree of rearrangement of the double bond. Thus, the epoxidation reaction can occur across many different carbon atoms depending on where the double bond is located.
[177] Catalyst Preparation Examples
[178] Catalyst A:
[179] Palladium (II) acetate (0.20 g, 0.89 mmol) is dissolved in methylene chloride (3 ml) and cooled to -35 ° C. Tri-i-propylphosphine (0.29 g, 1.8 mmol) is dissolved in cyclohexane (7 ml) and cooled to -35 ° C. This solution is then slowly added to the palladium solution. The color of the palladium solution changes from red to yellow-orange. The solution is then concentrated and placed in a freezer at -35 ° C. Finally yellow crystals are formed which can be separated and dried in vacuo. Yield 0.35 g (72%).
[180] Data: ¹ H NMR (C ₆ D ₆ ): 2.08 (br septet, 6H), 2.00 (s, 6H), 1. 32 (q, 36H) ppm; And ³¹ P NMR (C ₆ D ₆ ): 32.8 (s) ppm. Analysis of C ₂₂ H ₄₈ 0 ₄ P ₂ Pd, yield: C, 48.07; H, 8.63. Calculations are as follows: C, 48.48; H, 8.81. Suitable crystals were analyzed by X-ray diffraction. The results of this analysis are shown in FIG. Based on the above, it can be determined that Catalyst A comprises trans-bis (tri- i -propylphosphine) palladium diacetate.
[181] Catalyst B:
[182] Palladium (II) acetate (0.20 g, 0.89 mmol) and solid tricyclohexylphosphine (0.50 g, 1.8 mmol) are added together and then dissolved in methylene chloride (3 ml). As a result, a yellow solution is obtained and a yellow solid begins to precipitate. The solution is then stored overnight in a freezer at -35 ° C. The yellow solid is then collected by filtration, washed with cyclohexane (3 × 10 ml) and dried in vacuo. Yield 0.5 g (72%).
[183] Data: ¹ H NMR (C ₆ D ₆ ): 2.20 (br d, 14H), 2.13 (s, 6H), 2.00 (br s, 8H), 1.81 (br s, 26H), 1.62 (s, 8H), 1.23 (s, 10 H) ppm; And ³¹ P NMR (C ₆ D ₆ ): 22.9 (s) ppm. Analysis of C ₄₀ H ₇₂ 0 ₄ P ₂ Pd, yield: C, 61.14; H, 8.66. Calculations are as follows: C, 61.17; H, 9.24. Based on the above, it can be determined that the catalyst B comprises trans-bis (cyclohexylphosphine) palladium diacetate.
[184] Catalyst C:
[185] Palladium (II) acetate (1.00 g, 4.46 mmol) is dissolved in methylene chloride and i -propyldiphenylphosphine (2.03 g, 8.92 mmol) is dissolved in a 50:50 mixture of methylene chloride and pentane. After cooling both solutions to −35 ° C., the phosphine solution is added to the palladium solution. The mixture is stirred at -35 ° C for 3 h. Orange solution appears with yellow insoluble matter dispersed in it. Pour out the solvent. The solid is washed with pentane and vacuum dried. Yield is 2.03 g.
[186] Data: ¹ H NMR (CD ₂ Cl ₂ ): 7.71 (m, 8H), 7.45 (m, 12H), 2.75 (m, 2H), 1.36 (s, 6H), 1.13 (d of t, 12H), ³¹ P NMR (CD ₂ Cl ₂ ): 26.9 (s) ppm. Analytical data is consistent with the formation of bis ( i -propyldiphenylphosphine) palladium diacetate.
[187] Catalyst D:
[188] Palladium (II) acetate (0.500 g, 2.23 mmol) is mixed with diethyl ether and methylene chloride and cooled to -35 ° C. To this solution is added 1.06 g of tricyclopentylphosphine (4.45 mmol) in hexane (4 ml). As a result, the solution turned yellow and stored at -35 ° C for 3 days. The solution is then filtered and the solvent is removed in vacuo to yield a yellow powder. Yield is 1.05 g (68%).
[189] Data: ¹ H NMR (toluene-d ₈ ): 1.98 (br s), 1.89 (s), 1.69 (br s), 1.46 (br s) ppm; And ³¹ P NMR (toluene-d ₈ ): 23.4 (s) ppm.
[190] Catalyst E:
[191] Palladium (II) acetate (0.500 g, 2.23 mmol) and tribenzylphosphine (1.36 g, 4.46 mmol) are mixed under nitrogen in about 10 ml of methylene chloride. As a result, a yellow solution is obtained, which is filtered. Then about 20 ml of pentane are added and the mixture is cooled to -35 ° C. As a result, yellow crystals are obtained. The solvent is poured off from the crystals and it is dried in vacuo. The yield is 0.70 g (38%).
[192] Data: ¹ H NMR (CDCl ₃ ): 7.41 (m, 12H), 7.26 (m, 18H), 3.08 (s, 12H), 1.52 (s, 6H) ppm; And ³¹ P NMR (CDC1 ₃ ): 15.6 (s) ppm.
[193] Catalyst F:
[194] Palladium (II) acetate (0.500 g, 2.23 mmol) and cyclohexyldiphenylphosphine (1.19 g, 4.45 mmol) are dissolved in about 3 ml of methylene chloride, respectively. The two solutions are combined at -30 ° C and shaken vigorously. As a result, a light yellow solid precipitates out of solution. The solvent is poured off and the yellow solid is washed with pentane. The yield is 1.70 g.
[195] Data: ¹ H NMR (CD ₂ Cl ₃ ): 7.67 (m, 8H), 7.42 (m, 12H), 2.43 (t, 2H), 2. 11 (d, 4H), 1.67 (d, 4H), 1.59 (d, 2H), 1.39 (s, 6H), 1.28 (m, 4H), 0.94 (m, 6H) ppm; And ³¹ P NMR (CD ₂ Cl ₃ ): 23.3 (s) ppm.
[196] Catalyst G:
[197] Palladium (II) acetate (1.00 g, 4.46 mmol) is dissolved in methylene chloride and di- i -propylphenylphosphine (1.73 g, 8.90 mmol) is dissolved in methylene: pentane (50:50). The two solutions are combined at -35 ° C and stirred. A red solution formed, which was filtered and the layers separated with pentane. After 18 hours, yellow crystals formed, which were separated, washed with pentane and dried in vacuo. Yield was 1.20 g (44%).
[198] Data: ¹ H NMR (CD ₂ Cl ₃ ): 7.73 (m, 4H), 7.40 (m, 6H), 2.38 (m, 4H), 1.38 (d of d, 12H), 1.33 (s, 6H), 1.18 (d of d, 12H) ppm. ³¹ P NMR (CD ₂ Cl ₃ ): 29.5 (s) ppm.
[199] Catalyst H:
[200] Palladium (II) acetate (0.50 g, 0.0022 mol) is dissolved in methylene chloride. Tree - i - butyl phosphine (0.90 g, 0.0045 mol) and dissolved in hexane. Both solutions are cooled to -35 ° C. The phosphine solution is then added to the palladium solution at −35 ° C., and the mixture is kept at −35 ° C. for 2 hours and then allowed to warm to room temperature. The solution is then filtered to give a bright orange solution. Then all solvents are removed in vacuo. The resulting orange powder is dissolved in pentane and concentrated to about 5 ml. A yellow solid is formed. The solution is poured off and the solid is dried in vacuo. Yield 0.57 g (39%).
[201] Data: ¹ H NMR (CD ₂ Cl ₃ ): 2.27 (m, 6H), 2.01 (s, 6H), 1.59 (m, 12H), 1.16 (d, 36H). ³¹ P NMR (CD ₂ Cl ₃ ): 5.6 (s) ppm.
[202] Catalyst I:
[203] Palladium (II) acetate (0.50 g, 0.0022 mol) is dissolved in methylene chloride. Di-t-butylmethoxyphosphine (0.78 g, 0.0045 mol) is dissolved in pentane. Both solutions are cooled to -35 ° C. Then, a phosphine solution is added to the palladium solution at -35 ° C, and the solution is stored at -35 ° C to form yellow crystals. Yield 0.80 g (62%).
[204] Data: ¹ H NMR (CD ₂ Cl ₃ ): 3.86 (s, 6H), 1.77 (s, 6H), 1.37 (s, 24H). ³¹ P NMR (CD ₂ Cl ₃ ): 142.6 (s) ppm.
[205] Catalyst J:
[206] Palladium (II) acetate (0.50 g, 0.0022 mol) is dissolved in methylene chloride (3.5 ml). Dicyclohexylmethoxyphosphine (1.02 g, 0.00446 mol) is dissolved in pentane (10 ml). Both solutions are cooled to -35 ° C. The phosphine solution is then added to the palladium solution at -35 ° C and the solution stored at -35 ° C for 18 hours. Then 30 ml of pentane are added to the mixture. After 64 hours, yellow crystals are formed. Yield is 1.10 g (73%).
[207] Data: ¹ H NMR (CD ₂ Cl ₃ ): 3.85 (virtual triplet, 6H), 2.08 (m, 2H), 1.95 (m, 4H), 1.84 (s, 6H), 1.82 (m, 4H), 1.71 ( s, 2H), 1.65 (m, 2H), 1.48 (m, 2H), 1.25 (m, 6H). ³¹ P NMR (CD ₂ Cl ₃ ): 129.1 (s) ppm.
[208] Polymerization Examples
[209] The above description is made of catalytic trans-bis (tri- i -propylphosphine) palladium diacetate (also known as Pd (acetate) ₂ (tri-iso-propylphosphine) ₂ ); Trans-bis (cyclohexylphosphine) palladium diacetate; Trans-bis ( i -propyldiphenyl-phosphine) palladium diacetate; Trans-bis (tricyclohexyl-phosphine) palladium diacetate (also known as Pd (acetate) ₂ (tricyclohexyl-phosphine) ₂ ); Trans-bis (tribenzylphosphine) palladium diacetate; And trans-bis (cyclohexyldiphenylphosphine) palladium diacetate, but other catalysts as discussed above, such as (η ⁶ -toluene) Ni (C ₆ F ₅ ) _2, are also disclosed herein. Belongs to the category of.
[210] When used, suitable cocatalysts for the above-mentioned palladium catalysts are salts of weakly coordinating anions, lithium tetrakis (pentafluorophenyl) borate.2.5 Et ₂ O (etherate), sodium tetrakis (bis- 3,5-trifluoromethylphenyl) borate, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are, but are not limited to these.
[211] The following polymerization reaction examples illustrate only a few embodiments that fall within the scope of the invention. That is, the following examples illustrate the polymerization of one or more monomers according to the invention using one of the catalyst systems presented above. It should be noted that the present invention is not limited to the following examples. Rather, the following examples are merely representative examples of the polymerization reaction process disclosed by the present invention.
[212] Example 1:
[213] First, α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (12.0 g, 43.8 mmol) and 1-hexene (0.92 g, 10.9 mmol, moles of monomer 20 mole%) is weighed and combined in a glass vial. 18 ml of anisole is added to this solution. 0.0069 g of trans-bis (tricyclohexylphosphine) palladium diacetate (0.0088 mmol, catalyst B) and 0.035 g of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in 10 ml of anisole ( 0.44 mmol) of stock solution is prepared. 1 ml portion of this solution is added to the monomer / 1-hexene solution mentioned above. This mixture is then heated at 120 ° C. for 91 hours. The polymer is then precipitated by pouring the reaction mixture into hexane. The precipitated polymer is filtered and dried at 90 ° C. in a vacuum oven. Conversion rate is measured by weight. The molecular weight of the polymer is determined by GPC method in THF using poly (styrene) as standard. See Table 1 for the results.
[214] Examples 2 to 6:
[215] Examples 2-6 are essentially the same as in Example 1, except that the mole% of 1-hexene varies as indicated in Table 1 below. The results obtained from Examples 2 to 6 are also described in detail in Table 1.
[216] Table 1
[217] Monopolymerization of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol ExampleMol% of 1-hexene% ConversionMwMnMw / Mn One208439,5628,5904.61 2308523,9295,9294.04 3408616,2514,6073.53 4508311,6513,8373.04 555809,4293,4512.73 660708,5493,7712.27
[218] The results obtained from Examples 1 to 6 show that these examples show 1-hexene for homopolymers of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol It is proved that the molecular weight decreases with increasing concentration of.
[219] Example 7:
[220] First, t-butyl ester of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol (7.68 g, 28.0 mmol), 5-norbornene carboxylic acid (2.33 g, 12.0 mmol) and 1-hexene (0.84 g, 10 mmol, 20 mol% based on moles of monomer) are weighed and combined in a glass vial. 18 ml of anisole is added to this solution. Subsequently, 0.0031 g of trans-bis (tricyclohexylphosphine) palladium diacetate (0.040 mmol, catalyst B) and 0.17 g of lithium tetrakis (pentafluorophenyl) borate in each 5 ml of anisole 2.5 ethe Prepare a stock solution of rate (0.20 mmol). A 1 ml aliquot of each solution is added to the monomer / 1-hexene solution. This mixture is heated at 95 ° C for 23 h. The polymer is then precipitated by pouring the reaction mixture into hexane. The precipitated polymer is then filtered and dried in a vacuum oven at 70 ° C. Conversion rate is measured by weight. The molecular weight of the polymer is measured by GPC method in THF using poly (styrene) as standard. See Table 2 for the results.
[221] Examples 8-10:
[222] Examples 8 to 10 are essentially the same as in Example 7, provided that the mole% of 1-hexene varies as indicated in Table 2 below. The results obtained from Examples 8-10 are also detailed in Table 2.
[223] TABLE 2
[224] Copolymerization of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol with t-butyl ester (acid decomposable comonomer) of 5-norbornene carboxylic acid ExampleMol% of 1-hexenetransform %MwMnMw / Mn 7206137,20013,2002.81 8306028,60011,7002.44 9406018,9008,5002.21 10505914,4007,0002.06
[225] From the results obtained in Examples 7 to 10, these examples show that α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol and 5-norbornene carboxyl The copolymer of t-butyl ester of acid demonstrates that the molecular weight decreases with increasing concentration of 1-hexene.
[226] Example 11:
[227] First, α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (1.37 g, 5.00 mmol) and cyclopentene (0.036 g, 0.53 mmol, moles of monomer 10 mole%) as standard, are weighed and combined in glass vials. This solution is then diluted with sufficient anisole to bring the monomer concentration to 2M. 100 μl aliquots of a 0.002 M stock solution of palladium bis (tricyclopentylphosphine) di (acetate) (catalyst B) in anisole and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in anisole 100 μl of a 0.01 M stock solution is added to the monomer solution. This mixture is then heated at 125 ° C. for 18 hours. The polymer is then precipitated by pouring the reaction mixture into pentane. The precipitated polymer is filtered and dried in a vacuum oven. Conversion rate is measured by weight. The molecular weight of the polymer is measured by GPC method in THF using poly (styrene) as standard. See Table 3 below for the results.
[228] Examples 12 and 13:
[229] The examples are essentially the same as in Example 11, except that the mole% of cyclopentene varies as indicated in Table 3 below. The results obtained from Examples 12 and 13 are also detailed in Table 3.
[230] TABLE 3
[231] Polymerization of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol ExampleMole% of cyclopentene% ConversionMwMnMw / Mn 11106644,5009,9004.49 12206520,1006,7702.97 13404712,1005,5602.14
[232] From the results obtained from Examples 11 to 13, these examples show that cyclopentene in the case of a homopolymer of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol It proves that the molecular weight decreases with increasing concentration.
[233] Example 14:
[234] First, α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol (100 g, 365 mmol) and 1-hexene (37.5 g, 450 mmol, moles of monomer 55 mole%) on the basis of the weights and combine in a glass vial. Then, 0.0057 g of palladium bis (tricyclohexylphosphine) di (acetate) (0.0073 mmol, catalyst B) and 0.029 g of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.037 mmol) Was added to the solution. The mixture is diluted with a sufficient amount of anisole to bring the monomer solution to 2.5 M and then heated at 120 ° C. for 64 hours. The polymer is then precipitated by pouring the reaction mixture into hexane. The precipitated polymer is filtered and dried in a vacuum oven at 70 ° C. Next, the polymer is redissolved in 250 ml of methylene chloride. This solution is added to heptane to precipitate the polymer. The resulting solid is filtered and dried in a vacuum oven at 75 ° C. The polymer is then redissolved in 150 ml of MeOH and heated at 60 ° C. for 12 hours. This solution is then filtered by passing through a 5 micron, 1 micron, 0.45 micron, 0.22 micron, and 0.1 micron filter in turn. The polymer is then precipitated by adding a sufficient amount of water to the polymer / MeOH solution to give a 75:25 mixture of water and ethanol. The isolated yield is 60 g (60%). The molecular weight of the polymer is determined by the GPC method in THF using poly (styrene) as standard: Mw = 10,500; Mn = 5130. ¹ H NMR (CDCl ₃ / DMSO-d ₆ ) spectra of the polymer show that the resonance between about 5.3 and 4.9 ppm is consistent with the olefin end group.
[235] Preparative SEC (Size Emission Chromatography) and Plgel , Guard (5 μ, 50 × 4.6 mm) + Mixed-E (3 μ, 300 × 4.6 mm column set) using the low molecular weight portion of this polymer as THF as the mobile phase Fractionation and analysis by MALDI-TOF MS (matrix assisted laser desorption time-of-flight mass spectrometry, Bruker Reflex III instrument, reflectron and linear mode, positive ion spectra). The interpretation of the MALDI-TOF MS results is consistent with the formation of polymers having hexenyl end groups.
[236] In view of the above results, Example 14 is an α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene- prepared using a palladium catalyst in the presence of 1-hexene as chain transfer agent. It is demonstrated that the homopolymer of 2-ethanol attached an end group at one end of the polymer chain.
[237] Example 15:
[238] First, α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (25 g, 91 mmol) and cyclopentene (2.7 g, 39 mmol, moles of monomer 30 mole%) as standard, are weighed and combined in a glass vial. Dilute this solution with a sufficient amount of anisole to bring the monomer concentration to 1.5 M. 500 μl of anisole stock solution of Catalyst C (0.005 g in 2 ml of anisole) and 0.0073 g of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.0091 mmol) in anisole It is added to the monomer solution. This mixture is then heated at 80 ° C. for 18 hours. Next, the polymer is precipitated by pouring the reaction mixture into hexane. The precipitated polymer is then filtered and dried in a vacuum oven. The yield is 14.1 g (56%). The molecular weight of the polymer is determined by the GPC method in THF using poly (styrene) as standard: Mw = 18,000; Mn = 8,900. ¹ H NMR (DMSO-d ₆ ) spectrum of the polymer showed broad resonance at about 5.7 ppm, which is consistent with the cyclopentenyl end group.
[239] In view of the above results, Example 15 describes cyclopentene by performing a polymerization reaction of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol in the presence of cyclopentene. It is demonstrated that homopolymers containing short term are obtained.
[240] Example 16:
[241] First, magnetic stirring is attached to the pressure reactor and deoxygenated. To this reactor was added a, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (5.00 g, 18.2 mmol) followed by a sufficient amount of anisole to give a total of 12 ml Obtain a solution. This solution was sparged with nitrogen for 20-30 minutes. To this solution is added 0.36 μmol of catalyst B (0.72 ml of 0.0005 M solution in anisole) followed by 1.8 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in about 1 ml of anisole. do. The reactor is then heated at 60 ° C., pressurized to 5 psig with ethylene and then evacuated. This is repeated several times (eg 3-7 times). Finally, the reaction mixture is left under stirring (at least 12 hours) overnight under 5 psig ethylene. Then, the reaction mixture is poured into pentane. The precipitated polymer is filtered and dried in a vacuum oven. The yield is 0.7 g. The filtrate is allowed to evaporate in a vacuum oven over several days to yield 2.0 g of polymer. The overall conversion rate is 54%.
[242] The molecular weight of the polymer is determined by the GPC method in THF using poly (styrene) as standard. The pentane insoluble fraction has Mw of 6,300 and Mn of 4,300. The pentane soluble fraction has a Mw of 2,160 and a Mn of 1,760. Both fractions showed resonance in the olefin region of their 1H NMR spectrum, which is consistent with the vinyl end groups attached to the polymer chain: Δ5.86 (br s, 1H), 5.00 (br s, 2H). The two fractions of MALDI-TOF MS (matrix assisted laser desorption time-of-flight mass spectrometry, Bruker Reflex III instrument, reflectron and linear mode, negative ion spectra) are consistent with the presence of vinyl terminated polymers.
[243] In view of the above results, Example 16 shows a low molecular weight, vinyl terminated by carrying out the polymerization of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol under ethylene pressure. It demonstrates that a homopolymer is obtained.
[244] Examples 17a to 17e:
[245] About 10 g of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol is weighed and placed in a glass vial equipped with a stir bar. Appropriate amount of (η ⁶ -toluene) Ni (C ₆ F ₅ ) ₂ is mixed with the monomer in 40 ml of a 75:25 toluene: ethyl acetate mixture. See Table 4 below for the molar ratio of monomer to nickel catalyst in each of Examples 17a-17e.
[246] The polymerization of each example is carried out at room temperature (about 25 ° C.) for 16 hours. The polymer thus produced is precipitated with heptane, filtered and then dried. The polymer is then dissolved in 100 g of MeOH and shaken with 25 g of Amberlite IRC-718 ion-exchange resin beads for 5 hours. Each sample is then filtered separately and the filtrate is shaken with 25 g of fresh Amberlite IRC-718 ion-exchange resin beads. Each sample is then filtered and the filtrate is added dropwise to water. The precipitated polymer from each example is filtered and dried at 45 ° C. See Table 4 below for details and results of Examples 17a-17e.
[247] Table 4
[248] Polymerization of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol ExampleMonomer to catalyst molar ratio% ConversionMwMnMw / Mn 17a5: 15623,9006,8203.51 17b6.7: 16427,90011,2002.49 17c10: 17028,10013,0002.16 17d30: 16339,80020,9001.90 17e40: 17245,30025,2001.80
[249] In view of the results obtained from Examples 17a to 17e, these examples illustrate the α, α-bis (trifluoro) prepared using a ratio of monomer to nickel catalyst (η ⁶ -toluene) Ni (C ₆ F ₅ ) ₂ . It demonstrates that it controls the molecular weight of the methyl) bicyclo [2.2.1] hept-5-ene-2-ethanol homopolymer.
[250] Optical density measurement of various polymers:
[251] The optical density (OD) of the polymer according to the invention is measured by the following method. A 15 wt% solution of the desired polymer is formed using propylene glycol methylether acetate (PGMEA). The solution is dispensed on 1 inch quartz wafer and spun for 15 seconds at 500 rpm and 60 seconds at 2000 rpm. The wafer is then baked at 110 ° C. for 60 seconds.
[252] Optical absorbance is measured at 193 nm using a Cary 400 Scan UV-Vis spectrometer. The thickness of the film is then measured using a TENCOR profilometer after scoring the film. The optical density of the film is then calculated by dividing the absorbance by the thickness (microns).
[253] Optical density for many different polymers containing α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol is measured as a function of molecular weight (Mw). FIG. 3 shows optical density (OD) (absorbance / micron) of homopolymers prepared using palladium bis (tricyclophosphine) di (acetate) and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate Plot of vs. Mw is shown. 4 shows a plot of optical density (OD) (absorbance / micron) vs. Mw of homopolymers prepared using (η ⁶ -toluene) Ni (C ₆ F ₅ ) ₂ as a function of Mw. In both cases, the optical density increases as Mw decreases.
[254] Example 18 (including post-treatment):
[255] First, α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (160 g, 584 mmol) and 1-hexene (49.1 g, 585 mmol, moles of monomer 50 mol%) is weighed and combined in glass vials. To this was added 0.0092 g of palladium bis (tricyclohexylphosphine) di (acetate) (0.012 mmol, catalyst B) and 0.047 g of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.058 mmol). Add. The mixture is diluted with a sufficient amount of anisole so that the monomer solution is 2.5 M. This mixture is then heated at 120 ° C. for 66 hours. The polymer is then precipitated by pouring the reaction mixture into hexane. The precipitated polymer is filtered and dried in a vacuum oven at 75 ° C. The polymer is then redissolved in 200 ml of toluene. This solution is added to hexane to precipitate the polymer. The solid is filtered off and dried in a 75 ° C. vacuum oven. The polymer is redissolved again in 200 ml of methanol and heated at 60 ° C. for 12 hours. The solution is filtered by passing through a 5 micron, 1 micron, 0.45 micron, 0.22 micron, and 0.1 micron filter, after which the polymer is precipitated in water, filtered and dried in a vacuum oven at 100 ° C. The separated yield is 106 g (66%). The molecular weight of the polymer is determined by GPC method in THF using poly (styrene) as standard: Mw = 28,300; Mn = 11,300. The ¹ H NMR (CDCl ₃ / DMSO-d ₆ ) spectrum of the polymer showed a resonance between about 5.3 and 4.9 ppm, which is consistent with the olefin end group.
[256] A portion of the polymer is then reacted with acetic acid and hydrogen peroxide to form epoxides and ring-opened epoxide end groups. Specifically, about 94 g of the polymer is dissolved in 310 g of toluene. To this solution is added about 250 ml of glacial acetic acid and 125 ml of 15% hydrogen peroxide. This mixture is heated at 90 ° C. for 1.5 h. Then the mixture is cooled to room temperature. The upper organic layer is separated from the aqueous layer and washed with deionized water to remove any residual acid.
[257] In the next step, the polymer is precipitated from the organic layer using heptane. The precipitated polymer is filtered off and dried under vacuum at 65 ° C. 75.7 g of polymer are separated.
[258] ¹ H NMR (CDCl ₃ / DMSO-d ₆ ) spectra of the polymer showed no resonance between about 5.3 and 4.9 ppm, consistent with the absence of olefin groups.
[259] The low molecular weight portion of this polymer is fractionated by preparative SEC and analyzed by MALDI-TOF MS (matrix assisted laser desorption time-of-flight mass spectrometry, Bruker Reflex III instrument, reflectron and linear mode, positive ion spectrum) do. The interpretation of these results is the formation of polymers with epoxidized hexenyl end groups as the main component and the formation of polymers with end groups derived from the ring-opening reaction of epoxide end groups with acetic acid to form adjacent acetate alcohol functional groups as secondary components. Matches The same fractions are analyzed by negative ion MALDI-TOF MS. In addition, the spectra obtained from the experiments are in good agreement with the presence of epoxidized hexenyl end groups on the polymer chain.
[260] In view of the above results, Example 18 is α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2 prepared using 1-hexene and palladium catalyst as chain transfer agent. It is demonstrated that homopolymers of ethanol contain hexenyl end groups that can react with acetic acid and hydrogen peroxide to form epoxide and ring-opened epoxide end groups.
[261] Example 19 (Post-treatment of the Polymer of Example 15)
[262] A vinyl terminated homopolymer of about 0.6 g of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol is dissolved in 1.8 g of toluene. To this solution add 1 ml of glacial acetic acid and 1 ml of 15% hydrogen peroxide. This mixture is heated at 80 ° C. for 1 hour. After allowing the aqueous layer and the organic layer to separate, the aqueous layer is removed. The organic layer is washed three times with 2 ml of deionized water. After each wash, the aqueous layer is removed. The resulting organic layer is then poured into heptane (about 20 ml) and the resulting polymer is filtered and dried in a vacuum oven at 65 ° C. ¹ H NMR analysis of the polymer shows that the strength of vinyl resonance is substantially reduced. The MALDI-TOF MS (Negative Ion Spectrum) of the polymer forms the epoxidized vinyl terminated homopolymer of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol Matches
[263] In view of the above results, Example 19 was prepared using palladium bis (tricyclophosphine) di (acetate) and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate with ethylene as chain transfer agent Working the vinyl terminated homopolymer of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol with a mixture of acetic acid and hydrogen peroxide Prove the formation.
[264] Example 20 (Post-treatment Example):
[265] 93 g of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol homopolymer containing 1.4 ppm of Pd (discussed in any of Examples 1-6) Prepared according to the prepared method) in 309 g of toluene. To this solution is added 250 ml of glacial acetic acid and 125 ml of 15% hydrogen peroxide. This mixture is then heated at 90 ° C. for one hour. The mixture is left to cool to room temperature. The upper organic layer is separated from the aqueous layer and washed with deionized water to remove any remaining acid. Then, heptane is used to precipitate the polymer from the organic layer. The precipitated polymer is filtered off and dried under vacuum at 65 ° C. 75.7 g of polymer are separated. Pd levels in the treated polymers were determined to be below 0.20 ppm, the detection limit of the analytical method used. Palladium levels are detected using inductively coupled plasma-optical emission spectroscopy after degradation of the polymer sample into reverse aqua regia in a closed vessel microwave system.
[266] FIG. 5 shows the OD of a homopolymer of a series of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol treated with acetic acid and hydrogen peroxide according to the above procedure. It shows that it has a substantially lower OD than this untreated homopolymer. In addition, FIG. 5 shows that unexpectedly low molecular weight polymers also exhibit low optical densities after workup following the process of Example 20.
[267] Post-treatment of the polymer composition prepared according to the invention according to the process of Example 20 or other post-treatment examples also reduces the residual amount of catalyst (including metals) present in the polymer product.
[268] Example 21 (Saturation of terminal group using hydrogenation):
[269] 0.0097 of about 3 g of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol homopolymer prepared using Pd catalyst in the presence of 1-hexene as chain transfer agent With g of (tricyclohexylphosphine) (1,5-cyclooctadiene) (pyridine) iridium (I) hexafluorophosphate was dissolved in methylene chloride and placed under 90 psig hydrogen. After 5 days, 0.0084 g of additional iridinium complex was added and the reaction mixture was left one more day under 90 psig hydrogen. Then, 0.0078 g of additional iridinium complex is added and the mixture is stirred under 90 psig hydrogen for an additional 5 days. The reaction solvent is removed on a rotary evaporator. The remaining solid is dissolved in methanol and then precipitated in water. The polymer is collected by filtration and dried overnight in a vacuum oven. Yield 2.2 g. The molecular weight of the polymer is determined by GPC method in THF using poly (styrene) as standard: Mw = 10,800; Mn = 4,740. Analysis of the ¹ H NMR spectrum of the polymer before and after hydrogenation shows that the olefin end groups are 75% hydrogenated after being treated according to the above method. The optical density of the polymer at 193 nm after being treated according to this example is determined to be 0.23 absorbance units / micron. This indicates that the optical density decreased by more than 33% compared to the non-hydrogenated polymer of the same molecular weight (the optical density of the non-hydrogenated polymer of the same molecular weight was 0.31).
[270] Example 21 is a single of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol prepared using Pd catalyst in the presence of 1-hexene as chain transfer agent. Hydrogenation of the olefin end groups attached to the polymer proves to produce a polymer with lower optical density at 193 nm.
[271] Example 22:
[272] Α, α-bis (trifluoromethyl) bicyclo prepared using palladium bis (tricyclophosphine) di (acetate), catalyst B and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate A homopolymer of [2.2.1] hept-5-ene-2-ethanol (eg, a homopolymer prepared according to Examples 1-6 above) is dissolved in CDCl ₃ and DMSO-d ₆ . ¹ H NMR spectra were recorded on a Bruker 500 MHz instrument.
[273] The same process is repeated for polymers prepared using (η ⁶ -toluene) Ni (C ₆ H ₅ ) ₂ (eg, homopolymers prepared according to Examples 17a-17e).
[274] 6 shows that the ¹ H NMR spectrum is distributed from about 4.5 ppm to 7.0 ppm. The resonance higher than 6 ppm is the hydroxyl of the CH ₂ C (CF ₃ ) ₂ OH pendant group on α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol It is due to protons. Smaller but broader resonances between about 4.6 and 6 ppm are due to the olefin end groups of the polymer. Note that after peracetic acid treatment, this olefin end group resonance was substantially reduced in both polymers prepared using palladium and nickel catalysts. This is consistent with those end groups modified with saturated epoxides or adjacent acetate alcohol end groups.
[275] Therefore, Example 22 demonstrates that post-treatment of polycyclic polymers prepared using both palladium catalysts or nickel catalysts substantially reduces the presence of olefin end groups on the polymer.
[276] Example 23:
[277] First, t-butyl ester of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol (26.9 g, 98.2 mmol), 5-norbornene carboxylic acid (8.16 g, 42.1 mmol) and 1-hexene (21.9 g, 261 mmol, 65 mol% based on moles of monomer), and lithium tetrakis (pentafluorophenyl) borate2.5 etherate (0.122 g, 0.140 mmol) is weighed and combined in a glass vial. The volume of the mixture is made 70 ml by addition of anisole. A stock solution of 0.0314 g of palladium bis (tricyclohexylphosphine) di (acetate) (0.0400 mmol, Catalyst B) is then prepared in 4 ml of anisole. A 2.8 ml aliquot from this solution is added to the monomer and 1-hexene mixture and the mixture is heated at 95 ° C. for 32 hours. The reaction mixture is then cooled and diluted with 20 ml of toluene. The polymer is then precipitated by pouring the reaction mixture into heptane (˜1000 ml). The precipitated polymer is filtered and dried. The conversion rate is 23.6 g (67%).
[278] The polymer is then dissolved in 140 ml of toluene and 5 ml of THF. To this solution, 50 ml of acetic acid, 25 ml of hydrogen peroxide (30% in water) and 25 ml of deionized water are added. The mixture is stirred at about 85 ° C. for 1 hour. The mixture is cooled and the organic layer is separated and washed four times with deionized water. Precipitate the polymer in heptane.
[279] The molecular weight of the polymer is determined by GPC method in THF using poly (styrene) as standard: Mw = 9,750, Mn = 5,150, Mw / Mn = 1.89. ¹³ C NMR analysis in DMSO-d ₆ showed that the copolymer was 60% α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol and 40% 5 Shows that it consists of t-butyl ester of norbornene carboxylic acid. There is no evidence of deprotection of acid decomposable monomers.
[280] Therefore, the process of Example 23 demonstrates that the process of polymerization according to the invention and the peracetic acid treatment after polymerization do not result in substantial deprotection of the acid degradable pendant groups.
[281] Example 24:
[282] First, α-α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol (121.2 g, 0.442 mol), t-butyl ester of 5-norbornene carboxylic acid (28.6 g, 0.147 mol) and 1-hexene (29.7 g, 0.354 mol, 38 mol% based on moles of monomer), and lithium tetrakis (pentafluorophenyl) borate2.5 etherate (0.05 in anisole 12 ml M solution, 0.0006 mol) is weighed and combined in a glass vial. Anisole (390 ml) is then added to the reaction mixture. To this reaction mixture is added a palladium bis (tricyclohexylphosphine) di (acetate) solution (15 ml of 0.0092 M solution in anisole, catalyst B). This mixture is then heated at 95 ° C. for 20 hours. The reaction mixture is then cooled and added dropwise to 4 fold volume heptane. The precipitate is then filtered off and dried under vacuum at 45 ° C. The yield is 72.3 g (48%).
[283] Next, the polymer is dissolved in MeOH and heated at 60 ° C. overnight. The solution is then cooled and then passed through 0.45 micron, 0.22 micron and 0.1 micron filters in turn. Precipitate by adding water to the polymer. The polymer is filtered and dried overnight under vacuum at 60 ° C.
[284] About 20 g of polymer is dissolved in toluene (140 g). To this solution is added hydrogen peroxide (25 g, 30% by weight) and glacial acetic acid (50 g) diluted in water (25 g). This biphasic mixture is stirred and heated at 85 ° C. for one hour. The mixture is cooled and the organic layer is separated and washed three times with water. The organic layer is added dropwise to heptane to precipitate the polymer. The polymer is filtered and dried under vacuum.
[285] The molecular weight of the polymer is determined by GPC method in THF using poly (styrene) as standard: Mw = 30,200, Mn = 15,100, Mw / Mn = 2.00. Analysis of ¹³ C NMR in DMSO-d ₆ showed that the copolymer contained 38% of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol and 38% of It is shown that it consists of t-butyl ester of 5-norbornene carboxylic acid. There is no evidence of deprotection of acid decomposable monomers.
[286] Prior to the peracetic acid treatment, the polymer contained 161 ppm of palladium and the optical density at 193 nm was determined to be 0.27 absorbance units / micron. After the peracetic acid treatment, the polymer contained 27 ppm of palladium and the optical density at 193 nm was 0.12 absorbance units / micron. The level of palladium in the polymer is measured using the method discussed in Example 20 above.
[287] 6 is a copolymer of t-butyl ester of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol and 5-norbornene carboxylic acid (about 70:30 molar composition) confirms that the peracetic acid treatment lowers the optical density across the broad molecular weight range at 193 nm. Therefore, the catalyst system of the present invention and the peracetic acid treatment after the polymerization of the present invention do not substantially result in the deprotection of any acid degradable pendant groups that may be present in the polymers produced according to the present invention. Example 24 also shows that peracetic acid treatment results in less residual palladium and lower optical density at 193 nm.
[288] Example 25:
[289] First, t-butyl ester of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol (13.6 g, 50 mmol) and 5-norbornene carboxylic acid (9.7 g, 50 mmol, 20 mol% based on monomer) is weighed and combined in a glass vial. 96 ml of toluene is added to this solution. To the mixture is added a solution of 0.97 g of (η ⁶ -toluene) Ni (C ₆ F ₅ ) ₂ in 8.73 g of toluene. This mixture is then stirred at room temperature for 4 hours. Residual monomers present in the untreated polymer produced by the reaction are measured by gas chromatography and nickel levels are measured by inductively coupled plasma-optical emission spectroscopy (ICP-OES).
[290] The solution is then stirred for 24 hours while treating a portion of the polymer solution (10 g) with 15 g of IRC-718 ion exchange resin. The solution is filtered and the solution is stirred for 18 hours while the filtrate is treated with 5 g of Amberlite 15 ion exchange resin. The polymer is precipitated by pouring the reaction mixture into heptane. The precipitated polymer is filtered and dried overnight in a vacuum oven at 65 ° C. The optical density of the ion exchanged and precipitated polymer is measured as follows. 20% by weight of a solution of polymer in propylene glycol methylether acetate (PGMEA) is dispensed onto a 1 inch quartz wafer through a 0.2 micron Teflon syringe filter and spun for 10 seconds at 50 rpm and 60 seconds at 2000 rpm. The wafer is then baked at 130 ° C. for 60 seconds.
[291] Optical absorbance is measured at 193 nm using a Cary 400 Scan UV-Vis spectrometer. The thickness of the film is then measured using a TENCOR profilometer after scoring the film. The optical density of the film is then calculated by dividing the absorbance by the thickness (microns).
[292] The remainder of the untreated polymer is treated as follows. To about 50 g of polymer solution, about 25 g of glacial acetic acid and 25 g of 30% hydrogen peroxide are added. This mixture is heated at 90 ° C. for 2 hours. Then the mixture is cooled to room temperature. The upper organic layer is separated from the aqueous layer. This extraction procedure is repeated for 1 hour at 60 ° C. using 25 g glacial acetic acid, 25 g deionized water and 12.5 g tetrahydrofuran, and then any residual acid is removed with water. The residual monomer in the peracetic acid treated polymer is measured by GC. The polymer is precipitated by pouring the reaction mixture into methanol. The precipitated polymer is then filtered and dried in a vacuum oven at 70 ° C. The optical density of the peracetic acid treated and precipitated polymer is measured as described above. Residual nickel in the peracetic acid treated and precipitated polymer is measured via ICP-OES. See Table 5 below for the results.
[293] As can be seen in Table 5, the data show that the peracetic acid treated polymer contains much lower concentration of residual monomer, lower concentration of residual nickel and shows lower optical density at 193 nm.
[294] The data also shows that treatment with peracetic acid does not deprotect acid decomposable groups. The two compositions of the ion exchange resin treated and peracetic acid treated polymers are essentially identical as measured by ¹³ C NMR. The ion exchange resin-treated polymer is 43 mol% of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol and 57 mol% of 5-norbornene carbohydrates. T-butyl ester of acid. The peracetic acid treated polymer comprises 45 mol% of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol and 55 mol% of 5-norbornene carboxylic acid. T-butyl ester is contained.
[295] Table 5
[296] processResidual monomer (% by weight based on solid polymer)Residual Nickel (ppm based on solid polymer)Optical density at 193 nm (absorbance / micron)MwMnComposition ( ¹³ C NMR) Untreated14.15,030---------------- Ion exchange and precipitation----380.22729,79017,90043:57 Peracetic acid treatmentLess than 0.01-------------------- Peracetic Acid Treatment and Precipitation----Less than 10.19230,00018,90045:55
[297] In view of the above data, this example demonstrates that peracetic acid treatment results in a substantial reduction in optical density, residual metal and residual monomer.
[298] Example 26:
[299] First, α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (1.37 g, 5.0 mmol) and 0.04 g of cyclopentene (0.56 mol) were weighed, Combine in glass vials with enough anisole to bring the monomer solution to 1.5 M. In another vial, 100 μl of anisole solution (4 ml) containing 0.0022 g of allylpalladium (trinaphthylphosphine) triflate and 0.0174 g of lithium tetrakis (pentafluorophenyl) borate2.5 etherate Mix 100 μl of anisole solution (4 ml) containing. This mixture is added to the monomer solution and heated at 80 ° C. for 18 hours. The polymer is precipitated by pouring the solution into heptane, which is then filtered and vacuum dried at 70 ° C. The yield is 0.67 g (49% conversion). The molecular weight of the polymer is determined by GPC method in THF using poly (styrene) as standard: Mw = 90,600, Mn = 38,000, Mw / Mn = 2.38.
[300] This example produces a homopolymer of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol with narrow polydispersity.
[301] Example 27:
[302] First, α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (1.37 g, 5.0 mmol) and 0.15 g of cyclopentene (2.1 mol) were weighed, Combine in glass vials with enough anisole to bring the monomer solution to 1.5 M. In a separate vial, 100 μl of anisole solution containing 0.0017 g of catalyst E (2 ml) and 100 μl of anisole containing 0.0080 g of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate Prepare solution (2 ml). These mixtures are added to the monomer solution and heated at 80 ° C. for 18 hours. The resulting solution is poured into 300 ml of heptane to precipitate the polymer, then filtered and vacuum dried at 70 ° C. Yield 0.60 g (44%).
[303] The molecular weight of the polymer is determined by GPC method in THF using poly (styrene) as standard: Mw = 108,000, Mn = 45,800, Mw / Mn = 2.35.
[304] This example demonstrates that monopolymerization of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol using catalyst E has monomodal polydispersity. Demonstrates producing a polymer.
[305] Example 28:
[306] First, α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (1.37 g, 5.0 mmol) and 0.15 g of cyclopentene (2.1 mol) were weighed, Combine the monomer solution with enough anisole to reach 1.5 M. In a separate vial, 100 μl of anisole solution (2 ml) containing 0.0015 g of catalyst F and 100 μl of anisole containing 0.0080 g of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate Prepare the solution (2 ml). These mixtures are added to the monomer solution and heated at 80 ° C. for 18 hours. The resulting solution is poured into 300 ml of heptane to precipitate the polymer, then filtered and dried under vacuum at 70 ° C. Yield 1.01 g (74%).
[307] The molecular weight of the polymer is determined by GPC method in THF using poly (styrene) as standard: Mw = 53,400, Mn = 20,300, Mw / Mn = 2.63.
[308] In general, the catalyst system of the present invention enables the polymerization of one or more of these monomers at relatively low catalyst concentrations, while allowing for control of the molecular weight to a relatively high degree.
[309] In addition, due to the reduced optical absorbance at 157 nm and 193 nm by the fluorinated polycyclic polymers prepared according to the invention, these polymers are used as photoresists in 193 nm or 157 nm original UV lithography processes. It provides an ideal composition. Without wishing to be bound by any theory, it is believed that fluorinated polymers are ideally suited for this lithography process due to the reduced optical absorbance.
[310] Example 29:
[311] Vinyl terminated homopolymer of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (1.50 g, 0.49 mmol), [(tricyclohexylphosphine) ( 1,5-cyclooctadiene) (pyridine) iridium] PF ₆ (21 mg, 0.026 mmol), and toluene (35 ml) are combined in a Buchi pressure reactor and stirred until dissolved. The reactor is sealed and filled with H ₂ gas (85 psi) and then heated to 65 ° C. for 15 hours. The reactor contents are then filtered through Whatman 42 filter paper and the solvent is evaporated under reduced pressure. The resulting yellow substance is dissolved in acetone (25 ml) with H ₂ O ₂ (about 0.25 ml, 30% w / w). The solution is heated to 56 ° C. for 30 minutes and filtered to remove solids. Smopex ^R 110 a fibrous ion exchange medium (Johnson Matthey) (10 mg) is added and the solution is stirred for 30 minutes. After filtration through 0.20 μm PTFE filter discs (Osmonics), acetone is evaporated under reduced pressure to give a colorless white solid. This material is dissolved in toluene (30 ml), washed with H ₂ O (3 × 20 ml) and precipitated by dropwise addition to heptane (150 ml). The product was isolated by filtration and dried in vacuo (70 ° C., 12 h) to give a white amorphous solid (1.1 g, 73%).
[312] Example 30:
[313] Vinyl terminated homopolymer of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-en-2-ethanol (1.5 g, 0.49 mmol), Et ₃ SiH (0.31 ml, 2.0 mmol ), H ₂ PtCl ₆ .6H ₂ O (10 mg, 0.024 mmol) and toluene (35 ml) are combined in 100 ml serum cap vials. The vial is sealed and heated to 65 ° C. for 10 hours. The reddish black solution is filtered through a 0.20 μm PTFE filter disc (Osmonics) and the solvent is evaporated under reduced pressure. The beige product is dissolved in acetone (30 ml) with H ₂ O ₂ (about 0.25 ml, 30% w / w) and the solution is heated to 56 ° C. for 30 minutes. After removing the solid by filtration through Whatman 42 filter paper, the Smopex Add 110 (Johnson Matthey) (10 mg) and stir the solution for 30 minutes. The mixture is filtered through a 0.20 μm PTFE filter disc (Osmonics) and the acetone is evaporated under reduced pressure to give a colorless white solid. The resulting material is dissolved in toluene (30 ml), washed with H ₂ O (3 × 20 ml) and then added dropwise to heptane (150 ml) to settle. The product was isolated by filtration and dried in vacuo (70 ° C., 12 h) to give a white amorphous solid (1.3 g, 87%).
[314] Example 31:
[315] 80 of t-butyl ester (1.5 g, 0.19 mmol) of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol and 5-norbornene carboxylic acid : 20 vinyl terminated copolymer, [(tricyclohexylphosphine) (1,5-cyclooctadiene) (pyridine) iridium] PF ₆ (31 mg, 0.039 mmol), and toluene (35 ml) in a Buchi pressure reactor Combine at and stir until dissolved. The reactor is sealed and filled with H ₂ gas (85 psi) and then heated to 65 ° C. for 15 hours. The solvent is evaporated under reduced pressure and the resulting yellow substance is dissolved in acetone (25 ml) with H ₂ O ₂ (about 0.25 ml, 30% w / w). After heating the solution to 56 ° C. for 30 minutes, the solution is filtered through Whatman 42 filter paper to remove solids. Smopex 110 (Johnson Matthey) (10 mg) is added and the solution is stirred for 30 minutes. The mixture is filtered through a 0.20 μm PTFE filter disc (Osmonics) and the solvent is evaporated under reduced pressure to give a colorless white solid. The resulting solid is dissolved in toluene (30 ml), washed with H ₂ O (3 × 20 ml) and precipitated by dropwise addition to heptane (150 ml). The product was isolated by filtration and dried in vacuo (70 ° C., 12 h) to give a white amorphous solid (0.97 g, 64%).
[316] Example 32:
[317] 80:20 vinyl terminated copolymer of t-butylester of α, α-bis (trifluoromethyl) bicyclo [2.2.1] hept-5-ene-2-ethanol and 5-norbornene carboxylic acid (1.4 g, 0.18 mmol), Et ₃ SiH (0.12 ml, 0.73 mmol), H ₂ PtCl ₆ .6H ₂ O (10 mg, 0.024 mmol) and toluene (35 ml) are combined in 100 ml serum cap vials. The vial is sealed and heated to 65 ° C. for 10 hours. The yellow solution is reddish black. After filtration through Whatman 42 filter paper, the solvent is evaporated under reduced pressure. The resulting beige product is dissolved in acetone (30 ml) with H ₂ O ₂ (about 0.25 ml, 30% w / w) and the solution is heated to 56 ° C. for 30 minutes. After removing the solid by filtration through Whatman 42 filter paper, the Smopex Add 110 (Johnson Matthey) (10 mg) and stir the solution for 30 minutes. The mixture is filtered through a 0.20 μm PTFE filter disc (Osmonics) and the acetone is evaporated under reduced pressure to give a colorless white solid. The resulting material is dissolved in toluene (30 ml), washed with H ₂ O (3 × 20 ml) and precipitated by dropwise addition to heptane (150 ml). The product was isolated by filtration and dried in vacuo (70 ° C., 12 h) to give a white amorphous solid (1.32 g, 88%).
[318] Table 6
[319] Exampletransform% ^A conversion rateMw ^b before treatmentMw ^b after treatmentOD ^c before treatmentOD ^c after treatment 29Hydrogenation> 97`` 307640060.450.07 30Hydrogenation67307637780.450.22 31Hydrogenation> 97765577420.350.11 32Hydrogenation63765580470.350.27
[320] ^a % conversion was obtained by incorporation of the polymer ¹ H NMR spectrum (Δ 4.5-6.0 ppm) before and after the post-conversion conversion and represents the consumption rate of unsaturation at the polymer end by hydrogen or hydrosilane.
[321] ^b Molecular weight was obtained by GPC.
[322] ^c Optical density (OD) was measured at 193 nm (absorbance / micron).
[323] After treatment:
[324] As can be seen in the above examples, the present invention also relates to a process for working up a reaction mixture produced by the polymerization reactions disclosed herein. Such post-treatment may include reducing the optical density of the polymer product; It offers many advantages, such as a reduction in the amount of residual metal and / or catalyst present in the polymer product, and this treatment does not generally deprotect any acid degradable pendant groups that may optionally be present in the polymer product.
[325] For example, the molecular weight of the homopolymer or copolymer produced according to the invention can be further controlled by the use of linear or branched C ₂ to C ₂₀ olefin compounds (eg 1-hexene). The use of such compounds to control the molecular weight of the polymers prepared according to the invention is also advantageous in that the above-mentioned olefin compounds, when present, reduce the amount of acid-decomposable groups that are cut off from the monomers during the polymerization reaction. .
[326] As discussed above, the present invention also provides a method of reducing the optical density of olefin-terminated group-containing fluorinated polymers prepared according to the present invention. For example, post-polymerization reactions that can be used to reduce the optical density of such fluorinated polymers made in accordance with the present invention include epoxidation, hydrogenation, hydroformylation, hydrosylation, cyclopropane (both hydrocarbons). Cyclopropanyl and fluorinated cyclopropanyl groups), but are not limited to these.
[327] Polymer compositions prepared according to the present invention, when subjected to peracid post-treatment (eg, persulfonic acid, perchromic acid, peracetic acid, etc.), achieve one or more of the following reductions: (1) optical density of the polymer (in one case, If present, by decreasing the amount of olefin end groups); (2) removal of residual catalyst and, if present, cocatalyst; And (3) removal of residual monomers (possibly by epoxidation and extraction). Surprisingly, the peracid workup of the polymer does not cleave the acid decomposable groups from the polymer backbone.
[328] Molecular Weight Control:
[329] As noted above, the present invention also enables molecular weight control of the polymers produced according to the present invention through the use of CTA (eg 1-hexene or cyclopentene).
[330] Removal of metals and monomers:
[331] As discussed above, the present invention allows the removal of residual metals as well as residual monomers through post-treatment with peracid.
[332] Another post treatment to reduce the optical density of the polycyclic polymer :
[333] As noted above, the present invention is not limited to the peracid treatment as a post-polymerization treatment for lowering the optical density of the polymer. Another post-polymerization treatment that may be considered is any chemical reaction that converts olefin end groups into less absorbing species at both 157 nm and 193 nm. Such reactions include, but are not limited to, epoxidation, hydrogenation, hydroformylation, hydrosilylation, cyclopropane (which forms hydrocarbon cyclopropanyl and fluorinated cyclopropanyl groups).
[334] Fluorinated Acid Degradable Monomer :
[335] Using a fluorinated acid decomposable monomer can further lower the optical density of the polymer product of the present invention.
[336] Methods of using photoresist compositions prepared in accordance with the present invention are known in the art (see US Pat. Nos. 6,136,499 and 6,232,417; these patents describe methods of using polymeric photoresist compositions in lithography). For reference).
[337] While the present invention has been presented and described with reference to certain particular preferred embodiments or embodiments, it will be apparent that equivalent changes or modifications may be made by those skilled in the art in accordance with the interpretation and understanding of the present specification and the accompanying drawings. In particular, with respect to the various functions (components, assemblies, devices, compositions, etc.) performed by the above-described integers, the terms used to describe such integers (including "means") are to be described unless otherwise stated. Although intended to correspond to any integer that performs (ie, is functionally equivalent) a special function of an integer, it is not structurally equivalent to the disclosed structure that performs the function in the illustrated embodiment or embodiments of the present invention. In addition, while certain features of the invention have been described above with reference to only one of several illustrated embodiments, such features may be combined with one or more other features of other embodiments where it may be desirable and advantageous for any given or particular application.

权利要求:
Claims (21)
[1" claim-type="Currently amended] A polycyclic addition polymer containing a hydrogenated end group, a hydrosylated end group, or a hydroformylated end group at one or both terminal ends.
[2" claim-type="Currently amended] The polymer of claim 1 comprising repeat units selected from one or more of the repeat units represented by the formula:

Wherein R ¹ to R ⁴ are independently hydrogen, linear or branched (C ₁ -C ₃₀ ) alkyl, linear or branched (C ₁ -C ₂₄ ) halohydrocarbyl, linear or branched (C _2- C ₃₀ ) olefin,-(CH ₂ ) _n -C (O) OR ^* ,-(CH ₂ ) _n -C (O) OR,-(CH ₂ ) _n -OR,-(CH ₂ ) _n -OC ( O) R,-(CH ₂ ) _n -C (O) R,-(CH ₂ ) _n -OC (O) OR,-(CH ₂ ) _n -C (R) ₂ -CH (R) (C ( O) OR ^** ),-(CH ₂ ) _n- (CR ₂ ) _n -CH (R) (C (O) OR ^** ),-(CH ₂ ) _n -C (OR ^*** )-( CF ₃ ) ₂ ,-(CR ' ₂ ) _n -OR- and-(CH ₂ ) _n -C (R) ₂ -CH (C (O) OR ^** ) ₂ , where R is hydrogen, linear or Branched (C ₁ -C ₁₀ ) alkyl, — (CH ₂ ) _s —OH, R ′ represents hydrogen or halogen, R ^* represents an acid decomposable moiety, and R ^** independently represents R or R ^* R ^*** represents -CH ₂ OR, -C (O) OR or -C (O) R, n is an integer from 0 to 10; m is an integer from 0 to 5 and s is an integer from 1 to 10; Z represents oxygen, sulfur, -NR ''-, or-(CR '' ₂ ) _p- , wherein R '' is hydrogen and p is 1 or 2; R ⁵ to R ⁸ are independently hydrogen, linear or Branched (C ₁ -C ₃₀ ) alkyl, linear or branched (C ₂ -C ₃₀ ) olefin,-(CH ₂ ) _n -C (O) OR ^* ,-(CH ₂ ) _n -C (O) OR ,-(CH ₂ ) _n -OR,-(CH ₂ ) _n -OC (O) R,-(CH ₂ ) _n -C (O) R,-(CH ₂ ) _n -OC (O) OR,- (CH ₂ ) _n -C (R) ₂ -CH (R) (C (O) OR ^** ),-(CH ₂ ) _n- (CR ₂ ) _n -CH (R) (C (O) OR ^{* *} ),-(CR ' ₂ ) _n -OR- and-(CH ₂ ) _n -C (R) ₂ -CH (C (O) OR ^** ) ₂ , where R is hydrogen, linear or branched (C ₁ -C ₁₀ ) alkyl, R ′ represents hydrogen or halogen, R ^* represents an acid decomposable moiety, R ^** independently represents R or R ^* , n is an integer from 0 to 10 and , m is an integer from 0 to 5, Z represents oxygen, sulfur, -NR "-or-(CR" ₂ ) _p- , where R "is hydrogen and p is 1 or 2.
[3" claim-type="Currently amended] The polymer of claim 2 wherein Z is methylene.
[4" claim-type="Currently amended] The halohydrocarbyl group of claim 3, wherein the halohydrocarbyl group is represented by the formula C _r X '' _{2r + 1} , wherein X '' is independently selected from fluorine, chlorine, bromine and iodine, and r is an integer from 1 to 20 Characterized by a polymer.
[5" claim-type="Currently amended] The polymer of claim 4 wherein the repeating unit is represented by the formula:

Wherein n is an integer from 0 to 10 and R ^*** is as previously defined.
[6" claim-type="Currently amended] A polycyclic addition polymer comprising polycyclic repeating units, wherein a portion of such polymer contains pendant acid decomposable groups, wherein one or more terminal ends of such polymers are epoxidized end groups, hydrogenated end groups, hydrosylated end groups Or polycyclic addition polymers containing hydroformylated end groups.
[7" claim-type="Currently amended] The polymer of claim 6 comprising repeat units selected from one or more of the repeat units represented by the formula:

Wherein R ¹ to R ⁴ are independently hydrogen, linear or branched (C ₁ -C ₃₀ ) alkyl, linear or branched (C ₁ -C ₂₄ ) halohydrocarbyl, linear or branched (C _2- C ₃₀ ) olefin,-(CH ₂ ) _n -C (O) OR ^* ,-(CH ₂ ) _n -C (O) OR,-(CH ₂ ) _n -OR,-(CH ₂ ) _n -OC ( O) R,-(CH ₂ ) _n -C (O) R,-(CH ₂ ) _n -OC (O) OR,-(CH ₂ ) _n -C (R) ₂ -CH (R) (C ( O) OR ^** ),-(CH ₂ ) _n- (CR ₂ ) _n -CH (R) (C (O) OR ^** ),-(CH ₂ ) _n -C (OR ^*** )-( CF ₃ ) ₂ ,-(CR ' ₂ ) _n -OR- and-(CH ₂ ) _n -C (R) ₂ -CH (C (O) OR ^** ) ₂ , where R is hydrogen, linear or Branched (C ₁ -C ₁₀ ) alkyl, R ′ represents hydrogen or halogen, R ^* represents an acid decomposable moiety, and R ^** independently represents R or R ^* ; R ^*** represents —CH ₂ OR, —C (O) OR or —C (O) R, and n is an integer from 0 to 10; m is an integer from 0 to 5; Z represents oxygen, sulfur, -NR ''-, or-(CR '' ₂ ) _p , wherein R '' is hydrogen and p is 1 or 2; R ⁵ to R ⁸ are independently hydrogen, linear or minute Topographic (C ₁ -C ₃₀ ) alkyl, linear or branched (C ₂ -C ₃₀ ) olefin,-(CH ₂ ) _n -C (O) OR ^* ,-(CH ₂ ) _n -C (O) OR, -(CH ₂ ) _n -OR,-(CH ₂ ) _n -OC (O) R,-(CH ₂ ) _n -C (O) R,-(CH ₂ ) _n -OC (O) OR,-( CH ₂ ) _n -C (R) ₂ -CH (R) (C (O) OR ^** ),-(CH ₂ ) _n- (CR ₂ ) _n -CH (R) (C (O) OR ^** ),-(CR ' ₂ ) _n -OR- and-(CH ₂ ) _n -C (R) ₂ -CH (C (O) OR ^** ) ₂ , where R is hydrogen, linear or branched ( C ₁ -C ₁₀ ) alkyl,-(CH ₂ ) _s -OH, R 'represents hydrogen or halogen, R ^* represents an acid decomposable moiety, R ^** independently represents R or R ^* , n is an integer from 0 to 10, m is an integer from 0 to 5, s is an integer from 1 to 10, Z represents oxygen, sulfur, -NR "-or-(CR" ₂ ) _p- , Where R "is hydrogen and p is 1 or 2, provided that R ¹ One of R ⁸ must represent an acid decomposable moiety.
[8" claim-type="Currently amended] 8. The polymer of claim 7, wherein Z is methylene.
[9" claim-type="Currently amended] The polymer of claim 8 wherein at least one of R ¹ to R ⁸ is selected from the group represented by the formula-(CH ₂ ) _n -C (O) OR ^* .
[10" claim-type="Currently amended] The compound of claim 9, wherein at least one of R ¹ to R ⁴ is a halohydrocarbyl group represented by the formula C _r X '' _{2r + 1} , wherein X '' is independently selected from fluorine, chlorine, bromine and iodine , r is an integer from 1 to 20.
[11" claim-type="Currently amended] The polymer of claim 9 wherein the repeating unit is represented by the formula:

Wherein n is an integer from 0 to 10 and R ^*** is as previously defined.
[12" claim-type="Currently amended] A method of reducing the optical density of a polymer containing a terminal group unsaturated moiety by reacting the terminal group unsaturated moiety with a postfunctionalizer selected from hydrogen, peracid, hydrosilylation agent, and hydroformylating agent.
[13" claim-type="Currently amended] 13. The method of claim 12, wherein the peracid is a mixture of glacial acetic acid and hydrogen peroxide.
[14" claim-type="Currently amended] A method of reducing the optical density, residual metal content and residual monomer content of an additive polymer comprising polycyclic repeating units containing pendant acid decomposable groups and unsaturated terminating end groups,
a) reacting the mixture comprising the polymer and the solvent with peracid for a time sufficient to epoxidize the unsaturated end groups at elevated temperature;
b) separating the epoxidized polymer from the solvent.
[15" claim-type="Currently amended] 15. The method of claim 14, wherein the peracid is a 1: 1 mixture of glacial acetic acid and hydrogen peroxide.
[16" claim-type="Currently amended] 15. The method of claim 14, wherein the mixture further comprises a fibrous ion exchange resin.
[17" claim-type="Currently amended] The method of claim 16 wherein the polymer comprises repeating units selected from one or more of the repeating units represented by the formula:

Wherein R ¹ to R ⁴ are independently hydrogen, linear or branched (C ₁ -C ₃₀ ) alkyl, linear or branched (C ₁ -C ₂₄ ) halohydrocarbyl, linear or branched (C _2- C ₃₀ ) olefin,-(CH ₂ ) _n -C (O) OR ^* ,-(CH ₂ ) _n -C (O) OR,-(CH ₂ ) _n -OR,-(CH ₂ ) _n -OC ( O) R,-(CH ₂ ) _n -C (O) R,-(CH ₂ ) _n -OC (O) OR,-(CH ₂ ) _n -C (R) ₂ -CH (R) (C ( O) OR ^** ),-(CH ₂ ) _n- (CR ₂ ) _n -CH (R) (C (O) OR ^** ),-(CH ₂ ) _n -C (OR ^*** )-( CF ₃ ) ₂ ,-(CR ' ₂ ) _n -OR- and-(CH ₂ ) _n -C (R) ₂ -CH (C (O) OR ^** ) ₂ , where R is hydrogen, linear or Branched (C ₁ -C ₁₀ ) alkyl, R ′ represents hydrogen or halogen, R ^* represents an acid decomposable moiety, and R ^** independently represents R or R ^* ; R ^*** represents —CH ₂ OR, —C (O) OR or —C (O) R, and n is an integer from 0 to 10; m is an integer from 0 to 5; Z represents oxygen, sulfur, -NR ''-, or-(CR '' ₂ ) _p , wherein R '' is hydrogen and p is 1 or 2; R ⁵ to R ⁸ are independently hydrogen, linear or minute Topographic (C ₁ -C ₃₀ ) alkyl, linear or branched (C ₂ -C ₃₀ ) olefin,-(CH ₂ ) _n -C (O) OR ^* ,-(CH ₂ ) _n -C (O) OR, -(CH ₂ ) _n -OR,-(CH ₂ ) _n -OC (O) R,-(CH ₂ ) _n -C (O) R,-(CH ₂ ) _n -OC (O) OR,-( CH ₂ ) _n -C (R) ₂ -CH (R) (C (O) OR ^** ),-(CH ₂ ) _n- (CR ₂ ) _n -CH (R) (C (O) OR ^** ),-(CR ' ₂ ) _n -OR- and-(CH ₂ ) _n -C (R) ₂ -CH (C (O) OR ^** ) ₂ , where R is hydrogen, linear or branched ( C ₁ -C ₁₀ ) alkyl, R ′ represents hydrogen or halogen, R ^* represents an acid decomposable moiety, R ^** independently represents R or R ^* , n is an integer from 0 to 10, m is an integer from 0 to 5, Z represents oxygen, sulfur, -NR "-, or-(CR" ₂ ) _p- , where R "is hydrogen, p is 1 or 2, provided that R ¹ One of R ⁸ to an acid-decomposable moiety Should be indicated.
[18" claim-type="Currently amended] 18. The method of claim 17, wherein Z is methylene.
[19" claim-type="Currently amended] ^19. The method of claim 18, wherein at least one of R ¹ to R ⁸ is selected from the group represented by the formula-(CH ₂ ) _n -C (O) OR ^* .
[20" claim-type="Currently amended] The compound of claim 19, wherein at least one of R ¹ to R ⁴ is a halohydrocarbyl group represented by the formula C _r X '' _{2r + 1} , wherein X '' is independently selected from fluorine, chlorine, bromine and iodine , r is an integer from 1 to 20.
[21" claim-type="Currently amended] 20. The method of claim 19, wherein the repeating unit is represented by the formula:

Wherein n is an integer from 0 to 10 and R ^*** is as previously defined.

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同族专利:

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公开号 | 公开日

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KR100880313B1|2009-01-28|

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CN1561355A|2005-01-05|

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JP2005511833A|2005-04-28|

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CN100413898C|2008-08-27|

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CN1789300A|2006-06-21|

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DE60218342D1|2007-04-05|

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CN1253485C|2006-04-26|

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AU2002358247A1|2003-06-23|

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WO2003050158A1|2003-06-19|

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US20060025540A1|2006-02-02|

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US20030176583A1|2003-09-18|

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US7612146B2|2009-11-03|

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HK1071385A1|2006-09-08|

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DE60218342T2|2007-10-31|

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AT354599T|2007-03-15|

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JP4389158B2|2009-12-24|

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EP1461373A1|2004-09-29|

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EP1461373B1|2007-02-21|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-12-12|Priority to US34052601P

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2001-12-12|Priority to US60/340,526

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2002-12-12|Application filed by 스미토모 베이클라이트 가부시키가이샤

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2002-12-12|Priority to PCT/IB2002/005795

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2004-07-21|Publication of KR20040065209A

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2009-01-28|Application granted

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2009-01-28|Publication of KR100880313B1

优先权:

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申请号 | 申请日 | 专利标题

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US34052601P| true| 2001-12-12|2001-12-12|

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US60/340,526|2001-12-12|

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PCT/IB2002/005795|WO2003050158A1|2001-12-12|2002-12-12|Polymeric compositions and uses therefor|