TWI336335B - Method of preparing phosphonium compound for cyclic olefin polymerization - Google Patents

Description

21510pif.d〇c IX. Invention Description: The second main article, U, was filed on July 26, 2005, and the Korean Patent Application for the Korean Intellectual Property Office was filed with the Korean Patent Applicant, and it was released to South Korea on July 25, 2005. The priority of the Korean Patent Application No. -2006-0069534, which is hereby incorporated by reference, is incorporated herein by reference. TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for preparing a (4-) touch-and-chemical (four) method, and in particular, a catalyst system for the polymerization of a cyclamate-based polar functional cyclamate as a co-catalyst. . [Prior Art], the hydrocarbon polymer is a hydrocarbon-forming monomer such as norbornene. The polymerization is higher than that of the conventional hydrocarbon-based polymer, and the transparency is high, the heat resistance is good, the ml property is good, and the birefringence and hygroscopicity are extremely low. Therefore, it is widely used in f-membrane materials such as CD, DVD, or P0F_fibers, capacitors (4) and electronic materials or low-dielectric tilting (four), low-absorption syringes (syringes) for medical or blister packaging (biister packagings) )Wait. Usually used as a polymer for information or electronic materials, which must be between a metal such as a hole, a fossilized stone, a nitride, an oxidized, a copper, a sulphur, a gold, a silver, a turn, a chin, a nickel, or a chrome. Has enough adhesion. Therefore, the viscosity of the metal and the electronic, optical, chemical, and physical properties of the norbornene-based polymer are adjusted, and the polar s-mercapto group is added to the borneol thin monomer. However, the incorporation of polar functional groups in the norbornene-based monomer reduces the activity of the catalyst and requires an excess of catalyst. For example, U.S. Patent No. 5,705,503 discloses a method of polymerizing a norbornene-based monomer having a polar functional meaning using ((Allyl)PdCl) 2 /AgSbF6 catalyst complex. However, since an excessive amount of catalyst (1/100 to 1/250 of ##) is used, an excessive amount of the catalyst remains in the most polymer obtained. Therefore, the polymer will decay due to thermal oxidation and its transparency will be lower. Furthermore, the polymerization of the esterified borneol oxime monomer is carried out in the presence of a cationic catalyst [Pd(CH3CN)4][BF4]2, the yield of the polymerization reaction is low and only the exo isomer can be selectively polymerized. [Sen, A. and Lai, T.-W. J,, "Journal of the American Chemical Society (Am. Chem_Soc.), 1981, No. 103, pp. 4627-4629]. When the borneol borneol is subjected to polymerization, an excessive amount of catalyst (about 1/100 to 1/400 of the monomer) is required, and therefore, after the polymerization reaction, the residual catalyst is very difficult to remove. It is reported in the report that the use of a co-catalyst in the polymerization of a cyclic hydrocarbon can enhance the activity of the catalyst. A compound which forms a strong sigma bond with a metal, such as a natural phosphine compound or an ammonium compound, can be used for For common catalysts. For example, Sen et al. [Organometallics 2001, No. 20, pp. 2802-2812] reported [(1,5-cyclooctadiene)(CH3)Pd(Cl)] as a catalyst. And the polymerization of phosphine (PPh3) and [Na]+[B(3,5-(CF3)2C6H3)4]- as a cocatalyst esterified borneol, requiring the use of an excess of catalyst (about monomeric 1/ 400) to produce a polymer having a molecular weight of 6,500 (yield: 40% or less). U.S. Patent No. 6,455,650 discloses a catalyst complex [(R')zM(L')x(L&quot;)y]b A method of polymerizing a norbornene 2151〇pjfd〇c precursor having a functional group in the presence of [WCA]d. The catalyst is made of a phosphine-containing and hydrocarbon-based (e.g., a propyl group): a ligand. The yield of a polar functional group (e.g., a few groups) of borneol dilute t monomer is very low (5%). Therefore, the method disclosed in U.S. Patent No. 6,455,650 is not suitable for the production of a polar functional group (e.g., a few groups). The polymer was prepared in accordance with the methods disclosed in U.S. Patent Nos. 5,46, M19, pp. 69 7%, 5,912, 3 and 3, and 6,031, 〇 58. The catalyst system for polymerizing a cyclic hydrocarbon monomer having a polar functional group contains various co-contacts. (10) The problem of low activity of the catalyst caused by bribery is still present. In WO 2005/019277, Korea Patent application No. 2〇〇4_〇〇52612 and 2_·(Κ)743_ suggest that the Wei compound is suitable for use as the above-mentioned co-catalyst, Yes, it does not disclose a method for efficiently preparing scale compounds. Therefore, it is necessary to develop a method which can be easily and in high yield to prepare scale compounds, so that the scale compound can be used for a cyclic hydrocarbon monomer having a polar functional group. The polymerization reaction is used as a co-catalyst for a catalyst system. [Invention] The present invention provides a preparation method of a scaly compound used as a co-catalyst in a catalyst system for producing a cyclic hydrocarbon. According to the object of the present invention, there is provided a process for producing a ruthenium compound represented by the following formula, which is a reaction of a scaly compound represented by the following formula 2 with a salt compound of the following formula 3: &lt;Formula 1&gt; (Ri )-P(R2)a(R2,)b[Z(R3)d]c] [Ani] 21510pif.doc where: a, b and c represent the integers from 〇 to 3 and a+b+c= 3; Z is oxygen 1, sulfur, broken or gas; when Z is oxygen or sulfur, d is 1; when Z is nitrogen, d is 2; and when Z is 矽, d is 3; R! is wind , alkyl or aryl; R2, R2' and R3 represent hydrogen, respectively; unsubstituted or substituted straight or branched C2 alkyl, alkoxy, alkene substituted by a hydrocarbon, halogen or C^ohaloyl a group such as allyl or ethylene; unsubstituted or C:3·! 2 cycloalkyl substituted by a hydrocarbon, halogen or c12 hydrazine; unsubstituted or halogenated or halogenated or Ci 2 Alkyl-substituted C6-4G aryl; unsubstituted or C7·15 aralkyl substituted by a hydrocarbon, il or Cwo haloalkyl; unsubstituted or substituted by a hydrocarbon, ii or C^o haloalkyl Base; three (straight or branched i◦ alkyl) decyl; two (straight or branched Cl-IG alkoxy) decyl; three (C3_1 2 cycloalkyl)nonanyl 'its t (: 3_12 cyclodecyl fragment is unsubstituted or substituted by a hydrocarbon, _ or Ci 2 〇l group; tri-U aryl) residue, wherein c ". aryl ^ a segment, unsubstituted or substituted by a hydrocarbon, a halogen or a hydrazine; a tris(6) = oxime &amp; base 'the C64() oxy group # is unsubstituted or substituted by t H or '- group; (straight or branched C1 i. silk) soil 'di(C3-12 cyclodextyl) oxalate, wherein C3-12 cycloalkyl 2 is substituted or replaced by a hydrocarbon, halogen or CU2Q ugly group; Or a sulphate, wherein the C(tetra) aryl moiety is unsubstituted or substituted by a hydrocarbon, a conventional or ci-2〇ii alkyl group, and 21510 pif.doc [Ani] is a borate, an aluminate, [ SbF6]-, [PF6]-, [AsF6]-, perfluoroacetate ([CF3C02]-), perfluoropropionate ([C2F5C02]-), perfluorobutyrate ([CF3CF2CF2C02]-), Chlorate ([C104]-), p-toluenesulfonate ([p-CH3C6H4S03]-), [S03CF3]-, boratabenzene, or unsubstituted or substituted by i] <Formula 2>

[(R1)-P(R2)a(R2〇b]HX wherein, hydrazine is hydrogen; X is a halogen atom; and R!, R2, R2, a, and b are as defined above; and <Formula 3> [ C] [Ani] wherein C is an alkali metal or MgX, and [Ani] is as defined above. The preparation method of the present invention further comprises a method for preparing a cation compound of the formula 2, which is treated with an acid as shown in the following formula 4 Phosphine compound: &lt;Formula 4&gt; [(10) 抓~] R], R2, R2, a, and b are as defined above. To make the above and other objects, features and advantages of the present invention more apparent, DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the accompanying drawings. [Embodiment] The present invention will be described in detail below with reference to the accompanying drawings. 21510pif.doc The present invention provides a preparation of the following formula 1. The method for scalding a preparation includes reacting a scaly compound represented by the following formula 2 with a salt compound represented by the following formula 3: &lt;Formula 1&gt; [(Ri)-P(R2)a(R2,) b[Z(R3)d]c][Ani] where: a, b and c represent an integer from 〇 to 3 and a+b+c=3; Z is oxygen, sulfur 'broken or gas; when Z is oxygen Or sulfur, d is 1; when z is nitrogen, d is 2; And when Z is 矽, d is 3;

Ri is an anthracene, a stilbene or an aryl group; R2, Rr and R3 each represent hydrogen; a straight or branched Cwo alkyl group, alkoxy group, alkene which is unsubstituted or substituted by a hydrocarbon, a halogen or a Q-20 alkyl group; A group such as allyl or vinyl; unsubstituted or 匸3_12 cycloalkyl substituted by a hydrocarbon, halogen or Cuo haloalkyl; unsubstituted or by a hydrocarbon,! a C6-40 aryl group substituted with a halogen or a halogen atom; a C7-I5 aryl group which is unsubstituted or substituted by a hydrocarbon, a hydrazine or a halogen group; an unsubstituted or a hydrocarbon, a halogen or a Cj-20 haloalkyl group Substituted C3-2G alkynyl; tri(linear or branched CMG alkyl)decyl; tris(linear or branched alkoxy)decyl; tris(c3_I2cycloalkyl)decyl, wherein Cm cycloalkane The base moiety is unsubstituted or substituted by a hydrocarbon, _ or c^o halogen; a tri(C6-40 aryl) fluorene group wherein the C6_40 aryl moiety is unsubstituted or is a hydrocarbon, halogen or Cl-2 Substituted by a fluorenyl group; a tris(c6_40 aryloxy) fluorene group wherein the C6-40 aryloxy moiety is unsubstituted or substituted by a hydrocarbon, halogen or Ci-2 hydrazine alkyl; Branched CM 〇 alkyl) 1336335 21510pif.doc 矽 oxyalkyl; three (C3_12 cycloalkyl) decylalkyl, wherein the 〇 3-12 cycloalkyl fragment is unsubstituted or by hydrocarbon, halogen or C _2 Q _ Substituted by a ketone group; or a bis(匸6_4〇•aryl) oxirane group in which the C6-40 aryl moiety is unsubstituted or substituted by a hydrocarbon, halogen or Cuo-alkyl, and [Ani] is boric acid Salt, aluminate, [SbF6]-, [PF6]- [AsF6]-, perfluoroacetate ([CF3C02]-), perfluoropropionate ([C2F5C02]-), perfluorobutyrate ([CF3CF2CF2C〇2]-), peroxyacid salt ([C104] -), p-toluenesulfonate ([p-CH3C6H4S03]-), [S03CF3]-, boratabenzene, or unsubstituted or halogen-substituted carborax, &lt;Formula 2&gt;

[(Ri)-P(R2)a(R2')b]HX wherein 'Η is hydrogen; X is a halogen atom; and R丨, r2, R2, a, and b are as defined above; and &lt;Formula 3&gt; [C][Ani] wherein C is an alkali metal or MgX and [Ani] is as defined above. φ In more detail, in the preparation method of the compound of Formula 1, the single proton-derived compound of Formula 2 is reacted with the salt compound of Formula 3 to form a scale compound of the formula and [C][x] The product precipitated. The salt compound of the formula 3 is a salt of an [Ani] anionic compound mainly comprising an alkali metal or a Mg). The reaction of the oxime compound of the formula 2 with the salt compound of the formula 3 can be carried out in a solvent such as a hydrocarbon solvent (e.g., hexane) or a conventional organic agent (e.g., a gas smoldering, tetrachlorophosphonium, tetra Hydrogen tridentate, diethyl _, benzene, hydrazine ' 1336335 21510pif.doc = chemistry p, wherein (iv) solvent such as methylene chloride, toluene carbon or gasification of benzene 2 formula and salt compound of formula 3 The reaction can be carried out by dissolving the two compounds in a solution towel of the lyophilized solution, or in the slurry (yy) containing the solvent-insoluble component, into the compound of the formula HI During the reaction, [C][X] produced by f is a by-product. [c] is just added to the reaction solvent and is removed by filtration, so the compound obtained by the reaction

No further purification is required. The anti-lying temperature can be from 0 degrees Celsius to degrees Celsius, and more preferably room temperature. The preparation method of the present invention may further comprise a method of preparing the scaly compound of the formula 2 by treating the phosphine compound represented by the following formula 4 with an acid: &lt;Formula 4&gt; [(Ri)-P(R2)a(R2.)b ]

Ri, R2, R2, a, and b are as defined above.

More specifically, the scaly compound of the formula 2 can be prepared by reacting a phosphine compound of the formula 4 with a protonic acid. The protonic acid described herein is a provider that can act as H+, such as Ηα, HBr, HI, HF or HPF6. The protic acid is specifically defined, and it may be any of the acids conventionally used. The reaction between the phosphine compound of the formula 4 and the protonic acid can be carried out in a solvent such as a hydrocarbon (e.g., hexane) or a proton oxime compound of the formula 2 &gt; Therefore, the obtained proton squamous compound of the formula 2 can be purified without further purification. The reaction temperature may be from Celsius to 1 degree, preferably room temperature. 21510pif.doc The bismuth borate or aluminate of '[Ani] in the hydrazine compound represented by Formula 1 may be an anion represented by the following Formula 1A or 1B: &lt;Formula 1A&gt; [M'(R4)4] &lt; Formula 1B&gt; [M'(OR4)4] wherein Μ' is boron or aluminum; R4 is hydrogen; unsubstituted or linear or branched CK2 substituted by hydrocarbon, dentate or haloalkyl ( Alkenyl or alkenyl; unsubstituted or by hydrocarbon, halogen or C]-2〇 _ ;): a radically substituted straight bond or a branched Cm cycloalkyl; unsubstituted or by a hydrocarbon, _ or Ci2 〇 _ burnt-substituted C6_4 〇 aryl, by a direct bond or branched c, 2 〇 dialkyl oxyalkyl substituted or linear or branched cu_48 three burning base ^ An oxygen atomic group, or a C7-15 aromatic alkyl group which is unsubstituted or substituted with a hydrocarbon, _ _ or Cuo _ alkyl group. // // Stone Factory/1 7|;&gt; 々乂口 J 7本 |. Addition polymerization of the monomer of the ring. The medium containing the cocatalyst compound formed by the preparation method of the present invention has good thermal stability and chemical stability, and therefore, deterioration due to the polar functional group of the monomer can be prevented. Therefore, the yield of the polymer of = = is high, and the amount of the catalyst relative to the monomer is reduced, so that it is not necessary to remove the residual catalyst. It can be = a co-catalyst compound prepared by the method of the present invention. It is used as a pre-catalyst (formula 5), a metal compound, and a scale as a co-catalyst. The catalyst pair 1336335 2I5I0pif.doc has high stability to monomers containing polar functional groups. In contrast to the conventional use of ammonium sulphate as a co-catalyst, such a co-catalyst can stabilize the catalyst system with a town and can avoid the degradation of the catalyst due to the polar functional groups of the polar monomer. <Formula 5>

(R5)x(R6)yM wherein Μ is a metal of group X; X and y are 〇 to 2; and Rs and R6 respectively represent hydrogen; halogen; linear or branched alkyl, 匸6-2〇 An aromatic group, a C7_2〇 aromatic alkyl group or a C2-2G alkynyl group; a linear, cyclic or branched building of a group of atoms or functional groups consisting of a hetero atom (such as Si, Ge, S, 0 or N), an alkyl group, an alkenyl group and an alkynyl group, Cwo ^ Aromatic group, Cuo alkoxy group, Daiky group, amine group, c7 2 () aromatic alkyl group or C2 2 decynyl group; unsubstituted or substituted by hydrocarbon or linear or branched Q-20 il alkyl, Cuo halide Alkenyl, c3-20 _alkynyl or c6_40 _aryl. More specifically, the catalyst system used in the process for preparing a cyclic hydrocarbon polymer having a polar functional group of the present invention comprises a co-catalyst prepared by the method of the present invention, which comprises the steps of: preparing a catalyst mixture, The catalyst comprising a group X metal prior to formula 5 and a co-catalyst comprising a scaly compound of the formula ;; and the presence of the aforementioned catalyst mixture at a temperature of 8 (^ to 150 ° C, having at least - Addition polymerization of a cyclopental solution of a polar functional group. ΐίΤ: The catalyst system of the cocatalyst prepared by the method of the month is thermally stable, and does not thermally decompose above 8 G Celsius, therefore, ~ Under the action of the polar functional group hindering the cyclic hydrocarbon monomer and the rider catalyst = 14 1336335 21510pif.doc. Therefore, the active site of the catalyst can be formed or activated, so the high molecular weight formed has at least The cyclic hydrocarbon polymer of a polar functional group has a high yield. If the temperature of the polymerization reaction exceeds 150 degrees Celsius, the activity of the catalyst component is lowered due to thermal decomposition of the catalyst component, which makes it difficult to prepare a high score. A cyclic hydrocarbon polymer having at least one polar functional group. The monomer used in the process for preparing a cyclic hydrocarbon polymer containing at least one polar functional group may be a norbornene-based monomer having at least one polar functional group. The cyclobornene monomer or the norbornene derivative refers to a monomer containing at least one of the norbornene (bicyclo[2.2.1]hept-2-ene) units. The cyclic hydrocarbon addition polymer containing a polar functional group may Is a homogeneous polymer prepared by the addition polymerization of a norbornene monomer having at least one polar functional group in the presence of the above catalyst mixture; or it may be a copolymer or The terpolymer is prepared by adding different norbornene monomers having different polar functional groups by addition polymerization; or alternatively, it may be a co-polymer or a terpolymer, and the preparation method thereof The norbornene-based monomer having a polar functional group and the norbornene-based monomer having no polar functional group are formed by addition polymerization. The norbornene-based monomer having a polar functional group may be It is a compound of formula 6: &lt; Formula 6 &gt;

15 1336335 21510pjf.doc wherein m is an integer from 0 to 4' and r7, r, 7, r, 7, and R, &quot; at least one of which is a polar functional group and the other is a non-polar functional group. R7, R, 7, R"7 and R&quot; '7 can be used to form a saturated or unsaturated C4-12 ring group or a C6.24 benzene ring. The non-polar functional group is hydrogen; halogen; straight chain or minute Alkyl, i-alkyl, alkenyl, alkenyl; linear or branched C3 c alkynyl or haloalkyn; unsubstituted or alkyl, alkenyl, alkynyl, ii, li alkyl a linear or branched C 12 alkyl group substituted with a haloalkenyl group or an i-alkynyl group; unsubstituted or substituted by an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a haloalkyl group, a aryl group or an alkynyl group Substituted % of the base; or a substituted or substituted aryl 7-!5 aromatic alkyl group substituted by a deuterium, a dilute radical, a fast radical, a pyrolyzed group, a _thinyl group or a _fast radical. The polar functional group is a non-hydrocarbyl polar functional group comprising at least one of oxygen, nitrogen, phosphorus, sulfur, antimony and boron, the non-hydrocarbyl polar functional group being selected from the group consisting of: -R OR, -OR9, -C(0) 0R9, _R8c(〇)〇R9, _〇c(〇)〇r 9, -R80C(0)0R9, _C(0)R9, _r8c(〇)r9, _〇c(〇)r9, -R 0C(0)R9, -(R80)k-〇R9, _(〇R8 k 〇R9, _c(〇)_〇c(〇)r9, φ -RC(0)-0-C(0)R9 ' -SR9 ^ .r8sr9 x _ssr8 . -R8SSR9 ' -S(=0)R9 ' -R8S(=0)R9 λ -R8C(=S)R9 ' -R8C(=S)SR9 ' -R S03R, -S03R9, _R8N=〇s, _N=C=S, _NC〇, R8_NC〇, - CN, -R8CN, -NNC(=S)R9, R8Nnc(=s)r9, _N〇2, _R8N〇2, p(r9)2, -r8p(r9)2, -p(=0)(r9) 2, R8p (= 〇) (R9) 2, 16 1336335 21510pif.doc R12 R12 R12 R12

-C(0)N

-R11C(0)N

-R11N

R 13 , R13 R13 , 12 R· , r13

R 12 0C(0)N: —叚11〇. (.)〆

O -SR12 II O G -RU[:RII o 12

Q

Q 〇l: R12 — Rn〇|

;R 12

O

O 0 -oloRII 0 u ——RU〇l OR12

O /R12 X2 OR12 —RUBX R13 'R13 \r« OR12

R12 O , OR13 -N—C—R13 R12 O R12 O R12 〇HRrnN—C—R13 ——N—C—OR13—RllN—c—〇R13 〇R14 OR12 八R14-RUC—V ii2 NR13 O R12 O II I II 13 —C—N—C—R13

O R12 O -RUC-N-C-R13 OR12

HllP: OR12 OR12

OR13 〇 OR12 V OR13 -OP; Seven 11. 〆 \〇R13 OR13 ° OR124, P OR12, 〇R13

OR 13 —ΟΪ , 0R13 17 1336335 21510pif.doc

R 12

OR 12 OR12

RiiSj^Ri3—Si—OR13 —R11Si —OR13 OR' OR1

R 12 OR12

R 12

OR 12 -0-R11Si—R13 -0-R11Si—OR13 —R110-R11Si—R13 —R11-0-R11Si—OR13 R·

OII

R 12

OR14 OII OR12 R_

OII OR·

R 12

C—O—R11Si—R13 —c—〇—Rl1Si—OR13 ——R11-C—〇-R11Si—R 13 R1 0 OR12 OR1 R12 R1 OR12 -R11 C 0—R11 Si—OR13 —0-R1 b- R11 Si—R13 —0-R11-0 -R11Si—OR13 OR1 R1 0,1 Jl

R 12

0II

OR OR14 12

一〇—R11C—0—R11Si———R13 一〇—R11-c—0—R11 Si—OR 13

-R 11

0II R1

R 12

o—R11-c—〇-R11Si—R 13

oII

〇R14 OR 12 R11-0—R11-C—0-R11Si- R'

R 12

OR 12 OR OR14 R12 13 -R11 -0 -R110 -R11 Si-R13 -R11 0 -R11 0 -R11 Si-OR13 -R11 N -R11 Si — R13 R1 OR1

H R1 OR12 0 Rl 2 〇 —R11 N-R11Sii~OR13 —R11-C-N-R11Si—R13 —R11-C-N-R11 Si—OR13

OR 12 0R, H OR12R12 R' OR*

0 II H2 , —C 0 C CH-C-N R11Si-R H2 \rU

R 12 13 or12r12 I H2 c o c cH-c-r o or12r12

R 12 -R11C 0 C2CH-C-N R11 Si—R13 H2 OR12 OR OR or12r12 —R11&lt;1 0-C2CH-C-N R11 Si—OR13 0 12

R 12 R1 »12

R cr 7 R' 11 N-R1^R11Si—R13 cr

H2 R 12

OR OR' 12 H2+ R' -R11N-R1i!l R11Si —OR 'OR14 13 18 1336335 21510pif.doc wherein R8' and R11 represent a straight or branched Ci 2 nonenyl, haloalkenyl, or aene Or a haloalkenylene group; a linear or branched C3 2 fluorenylene or haloalkenyl group; unsubstituted or alkyl, alkenyl, alkynyl, yl, haloalkyl, alkenyl Or i-alkynyl-substituted c:3·]2-cycloalkene; unsubstituted or C64 fluorinated aryl group substituted by alkyl, alkenyl, alkynyl, infraumyl, #alkyl, haloalkenyl or alkynyl Or a C7_15 adenine group which is unsubstituted or substituted by an alkyl group, an alkenyl group, an alkynyl group, a hydrazino group, a haloalkyl group, an alkenyl group or a quaternary alkynyl group; 乂R9', R12', R13' and R14, respectively Derivative of hydrogen; halogen; linear or cleavage C j _2 〇 alkyl, dentate, alkenyl or alkenyl; linear or branched C3-2 anthracene or alkynyl; unsubstituted or alkane Alkyl, alkenyl, alkynyl, dentate, dentate, ialkenyl or iynyl substituted c3_12 cycloalkyl; unsubstituted or quaternary, alkenyl, alkynyl, halo, haloalkyl, _ Alkenyl or ynkynyl substituted 〇6-4〇 aryl; unsubstituted or alkane An alkenyl group, an alkynyl group, a hydrazino group, a hydrazino group, a haloalkenyl group or a haloalkynyl group substituted with a c7-15 arylalkyl group; an alkoxy group; a dentate oxy group; a carbonyl group or a carbonyl group; The integer. In the method of preparing a cyclic hydrocarbon polymer having a polar functional group, the molar ratio between the co-catalyst and the catalyst containing the group x excess metal may be 0.5-1 Torr to 1. If the molar ratio between the co-catalyst and the pre-catalyst is less than 0.5, the rigid catalyst may have only a slight activation. On the other hand, if the molar ratio of the co-catalyst to the pre-catalyst is greater than 10, the symmetry is weakened by the scale of the metal of the pre-catalyst, and the interaction between the double bond of the catalyst and the monomer is weakened. The catalytically active cationic species produces specific steric hindrance and is too stable, resulting in a decrease in the yield and molecular weight of the product. 19 21510 pif.doc In a process for preparing a cyclic hydrocarbon polymer containing a polar functional group, the catalyst mixture can be supported on a particulate carrier (micr〇particle SUpp〇rt). The particulate carrier may be alumina, titansite, alumina/chromium, alumina/chromite/titanium, alumina/minglite, aluminum phosphate colloid, decaneized alumina, hydrogel, montmorillonite (montmonllonite) ) or Buddha stone. The catalyst mixture carried on the particulate carrier can adjust the molecular weight distribution of the polymer in accordance with the polymer specific application to the apparent density of the k liter polymer. The catalyst mixture can be introduced directly into the solid phase without the use of solvents. Alternatively, the precursor catalyst and the co-catalyst may be mixed in a solvent phase to prepare a tongue-forming catalyst solution, or two solvents prepared by dissolving a precursor catalyst and a co-catalyst in a cereal solution. The catalyst solution is used in the polymerization reaction. The solvent for the soluble, precatalyst and cocatalyst may be di-methane, dichloroethane, methyl, benzene, or a mixture thereof. The content of the organic solvent used for the polymerization reaction may be the total weight of the monomer solution = (1 〇〇〇 里 )) to the parts by weight, preferably % to 4 〇〇 and : part] if the content of the organic solvent is less than 50 parts by weight is difficult to stir, and the viscosity is too high to cause the monomer to fail to react, resulting in an excessively low yield. If the solvent is excessive, the viscosity of the reaction solution is too low and it is difficult to commercialize. On the other hand, if the content of the organic solvent exceeds 8 parts by weight, the reaction rate is low, which leads to a decrease in the yield of the product and a decrease in the molecular weight. ~ It is a gold compound composed of a compound and a copolymer. The molar ratio of the touch zone of the touch zone to the monomer solution monomer is ^2,500 to ι/2 〇〇, 〇〇〇, preferably θ 1/5 _ to face 〇. That is, even with the catalyst system of the 1336335 21510 pif. doc catalyst system, a cyclic hydrocarbon polymer having at least one &apos;polar functional group, particularly a borneol thin polymer, can be obtained in high yield. A norbornene-addition polymer containing at least one polar functional group prepared by a method for producing a cyclic hydrocarbon polymer containing at least one polar functional group may include 0.1 to 99.9 mol% of norbornene containing at least one polar functional group Is a monomer. The norbornene-based monomer having at least one polar functional group may be a mixture of an endo isomer and an exo isomer, and the mixing ratio of the isomer and the exo isomer is not limited. . A method for preparing a cyclic hydrocarbon polymer containing a polar functional group can be carried out by a conventional method for preparing a borneol-based polymer. The preparation method comprises the steps of: mixing a borneol-based monomer and a catalyst in a solvent to polymerize the formed mixture. According to the above process, a cyclic hydrocarbon polymer containing a polar functional group having a high yield of at least 40% and a high molecular weight and having a weight average molecular weight (Mw) of 100,000 or more can be obtained. When a cyclic hydrocarbon polymer containing a polar functional group is used as an optical film, its Mw can be adjusted to 100,000 to 1,000,000. The functional group-containing norbornene-based polymer prepared according to the above method is transparent; has good adhesion to metals or polymers having different polar functional groups; and has a low dielectric constant and is suitable for isolating electronic components; Has good thermal stability and strength. Further, the functional group-containing borneol-based polymer has adhesiveness to an electric substrate in the absence of a coupling agent; and it also has good adhesion to a metal substrate such as copper, silver or gold. Further, optical properties of a norbornene-based polymer containing a functional group 21 1336335 21510 pif.doc This can be used as a protective film material for a polarizing plate. Further, the borneol thin polymer containing a functional group can be used as a material for an electronic component such as an integrated circuit, a printed circuit board or a multi-wafer module. In the same year, the general morphological unit (c〇nf〇rmati〇nai has one or two stable rotation states. Therefore, the cyclic hydrocarbon can have a stretched shape. ^^(10) "Polyyleneamine" is a rigid, stupid ring. Compared with a simple cyclic hydrocarbon polymer, the introduction of a polar cyclic b group into a cyclic hydrocarbon polymer having such an extended form can increase the intermolecular Φ. X interaction. Therefore, 'the stacking between molecules is directional, so the cyclic hydrocarbon polymer can have optical and electrical anisotropy (anis〇tiOpy). Thereafter, it will be combined with the following working examples. The invention is described in detail. The following working examples are for illustrative purposes and are not intended to limit the invention. In the working example of =, all operations suitable for treating compounds in air or water are performed using standard Schlenk techniques or The NMR spectrum was measured by a 6 〇〇 spectrometer. The molecular weight and molecular weight distribution of the polymer was based on a colloidal gas permeation chromatography (GPC) system (water). ) and standard polystyrene samples were measured. Prior to the use of the solution, the hydrazine and diethyl ether were purified by distillation with potassium/dibenzophenone; the dichloromethane was purified by CaH2 distillation and the chlorination was stupid. Example 1 t Preparation (CAPHCl (Cy) 3P (2. 〇 2 g, 7. 2 mmol, Cy = cyclohexane) was added to a 250 ml Schlenk flask and added with diethyl ether (5 ml). Then 'at room temperature, anhydrous HC1 (14.4 ml,! 〇M was added to the flask in 22 1336335 21510 pif.doc ether) and the reaction was carried out for about 20 minutes. The obtained white sink was filtered through a glass filter funnel and washed three times with diethyl ether (80 ml), then at room temperature. Remove the residual solvent in a vacuum environment' (CyhPHCl (86%, 1.95 g). W-NMR (600MHz, CD2C12): δ7.02 to 6.23 (d, 1H, JH-p = 470 Hz), 2.56 ~ 1·30 (m, 33H) ; 13C-NMR (600MHz, CD2C12) : δ28.9 (d), 28.5 (d), 26.8 (d), 25.6 (s) ; 31P-NMR (600MHz, CD2C12) : δ 22.98 (d, Jp-h=470 Hz) Example 2 Preparation (η-Βΐ^ΡΗα Add (n-Bu)3P (2.0 g, 10.0 mmol, n-Bu = n-butyl) to 250 ml In the Schlenk flask 'and add diethyl ether (1 house) ). Then, at room temperature, anhydrous HC1 (20.0 mL, 1.0M in ether) was added to the flask and the reaction for about 20 minutes. The obtained white sink was filtered through a glass filter funnel and washed three times with diethyl ether (80 ml). After that, the residual solvent was removed in a vacuum at room temperature to give (n-Bu)3PHCl (90%, 2.15 grams). Example 3 In a dry box, (Cy)3PHCl (0.56 g, 1.75 mmol) prepared in Example 1 and [Li][B(C6F5)4] (1.0 g, M6 mmol) were added to Schlenk, respectively. A flask (capacity 1 cc) was added to dioxane (20 mL) in a Schlenk flask at 23 1336335 21510 pif.doc. Then, a (Cy)3PHCl solution was added dropwise to the [Li][B(C6F5)4] solution at room temperature. After 1 hour, the unreacted reactant was filtered through a glass filter funnel, and the solvent was removed in vacuo to give [(Cy)3PH][B(C6F5)4] (90%, 1.26 g). 'H-NMR (600MHz, CD2C12): 55.32-4.65 (d, 1H, JH-P=440 Hz), 2_43~1.33 (m, 33H); nC-NMR (600MHz, CD2C12): δ149_7, 148.; , 139.7, 139.2, 138.1, 138.0, 137.8, 136.2, 125.1, 124.9, 29.0, 28.8, 26.7 (d), 25.4 (s); 31P-NMR (600MHz, CD2C12): 31.14 (d, Jp.h=440 Hz 19F-NMR (600MHz, CD2C12): -130.90, -16.51, -163.37. A gas smelting solution was used to obtain a gentleman's crystal suitable for X-ray diffraction analysis. The molecular structure of the χ ray crystal is shown in Figure 1. Referring to Fig. 1, there is a non-bonded j-interaction between the atom of the [(Cy), pH] and the gas atom of [B(C6F5)4]. σ Example 4

iJiuxcy^mEBmeEsiiL is the same as the method of Example 3 but replacing [Li][B(C6F5)4] with [Na][B(C6F5)4] or [MgBr][B(C6F5)4] Cy) 3PH] array 6f5) 4]. The yield was about 9 G%, and almost *3 was the same. 24 1336335 21510pif_d〇c In the dry box, (n-Bu)3PHCl (0,42 g, i.75 mmol) prepared in Example 2 and [Li][B(C6F5)4] (1.0 g' 1.46 millimoles) were separately added to a Schlenk flask (capacity 100 ml) and a gas purge (2 ml) was added to the Schlenk flask. Then, (n-Bu)3PHCl solution was added dropwise to the [Li][B(C6F5)4] solution at room temperature. After 1 hour, the unreacted reactant was filtered through a glass filter funnel and the solvent was removed in vacuo to give [(n-Bu)3PH][B(C6F5)4] (87%, 1.12 g). Example 6 Άί% rrt-Bu^PHirBrc.F^j (t-Bu)3P (0.35 g, 1.73 mmol) was added to a 250 ml Schlenk flask, and diethyl ether (30 ml) was added to the Schlenk flask. ). Then, anhydrous HCl (1.9 ml, 1.0 M in ether) was added to the flask at room temperature, and the reaction mixture was allowed to react for about 2 Torr. Thereafter, the obtained white sink was filtered through a glass filter funnel and washed three times with diethyl ether (30 ml). Thereafter, the residual solvent was removed in a vacuum at room temperature to obtain (t-Bu)3PHCl white solid. . (t-Bu)3PHCl was added and dissolved in di-methane (1 mL). Add [Li][B(C6F5)4](l.〇7 g, 1.56 mmol) to a 1 mL mL Schlenk flask (100 mL) in a dry box and add to the Schlenk flask. Dichlorodecane (20 mL). Then, a (t_Bu)3PHCl solution was added dropwise to the [Li][B(C6F5)4] solution at room temperature. After 1 hour, the UC1 by-product was filtered through a glass filter funnel and solvent was removed in vacuo to give [(t-Bu)3PH][B(C6F5)4] (67%, L05 g). 25 1336335 2l510pif.doc 'H-NMR (600MHz, CD2C12) : 65.34-4.63 (d, 1H, JH-p=440 Hz)' 1.61 (d, 27H) ; 13C-NMR (600MHz, CD2C12): δ149·5 , 147.9, 139.6, 138.0, 137.7, 136.0, 124.4, 38_3, 30.4; 31P-NMR (600MHz, CD2C12): 63.0 (d, Jp_h=440 Hz); 19F-NMR (600MHz, CD2C12): -133.3, -163.9 , -167.8. Example 7 (Et) 3P (0.8 g ' 6.77 mmol, Et = ethyl) was placed in a 250 ml Schlenk flask, and diethyl ether (50 ml) was placed in a Schlenk flask. Then, anhydrous HCl (7.4 ml, 1.0 M in ether) was added to the flask at room temperature, and the reaction mixture was allowed to react for about 2 Torr to obtain a white precipitate. The residual solvent was removed in a vacuum at room temperature to give (Et) 3P HCl white solid. (EtLPHCl was dissolved in a gas (10 ml). [Li][B(C6F5)4] (4.41 g, 6.43 mmol) was added to a 1 ml ml Schlenk flask in a dry box. (100 ml), and dioxane (50 ml) was added to the Schlenk flask. Then, at room temperature, the (Et)3PHCl solution was added dropwise to the [Li][B(C6F5)4] solution. After 1 hour, the LiCl by-product was filtered through a glass filter, funnel, and solvent was removed in vacuo to give [(Et)3:PH][B(C6F5)4] (54%, 2.91 g). H-NMR (600MHz, CD2C12): 56.06 (m, 0.5H)' 5.30 (m, 0.5H) ' 2.28 (m, 6H) &gt; 1.40 (m5 9H) ; 13C-NMR (600MHz, CD2C12): δΐ49 .5, 147.9, 139.7, 138.0, 137.9, 137.7, 136.1, 26 1336335 21510pif.doc 124.6, 10.6 (d), 6.8 (d); 31P-NMR (600MHz, CD2C12): 26.3 (d); 19F-NMR ( 600MHz, CD2C12): -133.5, -163.7, -167.8. Example 8 Emperor borneol pinch-2-methyl citrate polymer 5- borneol dilute-2-restroxate (1 〇 ml '55.6 mmol) Add to a 250 liter Schlenk flask. Pd(〇Ac)2(〇Ac=acetate, 2.5 mg' 11 mM) And [(Cy)3PH][B(C6F5)4] (211 mg, 22 耄mol) was added to another 25 〇ml Schlenk flask and 1 liter of dichloromethane was added. Injecting the syringe The catalyst solution was added one by one to the flask containing the monomer. The reaction mixture was allowed to react at 90 ° C for 1 G hour 'and adding % ml of toluene to dissolve the polymer. The solution was added to an excess of ethanol, and the white polymer was filtered through a glass filter funnel, and dried in a vacuum at 80 ° C for 24 hours to obtain 8.4 g of 5_bornene carboxylic acid. The _% of the amount of poly = f. The Mw and Mw / Mn of this polymer are 204,000 and 2 〇 2 respectively. Example 9-15 ^ Rare-2-A cool (5_norbornene-2-methvl preparation vinegar @ §^tate) Aggregate @ Change Pd(〇Ac)2 to [(Cy)3p chat(c^] Mo Erbi (2,1,1:1, 2:3, ι,〇Ί,,〇丄·2 ' , 1:6 and 1:8) to prepare 5-amylacetate hydrate of acetic acid. 5-Ibornene-2-oxime acetate (4 ml, 24.7 mM 27 1336335 21510 pif. doc Mo) and Aben (12 liter) were added to a loo ml Schienk flask to form a monomer solution. Various molar ratios of Pd(0Ac)2 (umg' 4.9 millimoles) and [(Cy)3PH][B(C6F5)4] were dissolved in di-methane (1 ml) to form a catalyst solution. . Various catalyst solutions were added to the monomer solution, and the reaction mixture was stirred at 90 ° C for 4 hours. The polymerization was carried out in the same manner as in Example 8 and the recovery of the polymer was carried out to obtain a 5-bornene-2-methyl acetate polymer. The yield, Mw and Mw/Mn of the 5-bornetiene-2-nonyl acetate polymer are shown in Table 1 below. Table 1 Sample Pd(OAc)2 (mg) [(Cy)3PH] [B(C6F5)4](mg) Pd/B Moh ratio Yield Mw Mw/Mn [g] [%] Example 9 1.1 2.4 2 /1 1.77 43.2 333,400 2.11 Example 10 1.1 4.7 1/1 3.52 86.0 272,800 2.28 Example 12 1.1 9.5 1/2 3.83 93.4 256,300 2.49 Example 13 1.1 19.0 1/4 3.80 90.5 221,600 2.45 Example 14 1.1 28.4 1/6 3.39 82.7 194,100 2.25

Example 16 Preparation of 5-bornene-2-carboxylate/bornene addition copolymer borneol carboxylic acid oxime monomer (16.74 g), norbornene monomer (4.44 g) and 37 ml of toluene Add to a 250 ml Schlenk flask. Add Pd(OAc)2 (4.79 house) and 28 1336335 2I510pif.doc [(Cy)3PH][B(C6F5)4] (40.4 mg) solution dissolved in dichlorohydrazine (2 ml) to the flask. Among them, the reaction mixture was stirred at 90 ° C for 1 hour. Then, an excess amount of ethanol was added to the reaction solution to obtain a white copolymer agglomerate. The precipitate was filtered through a glass filter funnel and dried in a vacuum oven at 65 ° C for 24 hours to obtain 14.86 g of a borneol-5-bornene-2-carboxylic acid decyl ester copolymer (yield: total monomer weight) 70.2%). The Mw and Mw/Mn of this polymer were 184,000 and 2.12, respectively. • Example 17 Preparation of 5-bornene-2-carboxylate/butyl norbornene addition copolymer 5-pentene-2-carboxylate-oxime monomer (14.64 g), butyl norbornene The body (6.14 g) and 37 ml of toluene were added to a 250 ml Schlenk flask. A solution of pd(acac) 2 (4.19 mg, aacac = acetamidine) and [(Cy)3PH][B(C6F5)4] (32.8 mg) dissolved in dichloromethane (2 ml) was added to the flask. The reaction mixture was stirred at 90 ° C for 10 hours. Then, an excess amount of ethanol was added to the reaction solution to obtain a white copolymer precipitate. The precipitate was filtered through a glass filter funnel and dried in a vacuum oven at 65 ° C for 24 hours to obtain 13.7 g of butylbornene-5-bornene-2-carboxylic acid oxime ester copolymer (yield: total monomer) 65.9% of the weight). The Mw and Mw/Mn of this polymer were 157,000 and 2.13, respectively. Example 18

Preparation of 5-bornene-2-methyl acetate/Dingmou; Taitene addition copolymerization Jinjie f touch: Pd(acacD 29 215IOpif.doc 5-pentene-2-nonyl acetate monomer (8.2 g ), butyl norbornene monomer (3.2 gram) and 36 ml of acetoin were added to a 250 ml Schlenk flask. Pd(〇Ac) 2 (3) dissolved in dichloromethane (2 ml) 2 mg) and a solution of [(Cy)3PH][B(C6F5)4] (27.0 mg) was added to the flask, and the reaction mixture was allowed to react at 90 ° C for 4 hours. Then, excess ethanol was added to the reaction solution. To obtain a white co-polymer precipitate. The chamber was filtered with a glass filter funnel and dried in a vacuum oven at 65 degrees Celsius for 24 hours to obtain 9.30 g of butyl borneol/carboxylic acid 5-borneol 唏_2_曱Ester polymer (yield: 81.7% by weight of the total monomer). The Mw and Mw/Mn of this polymer were 218, 300 and 3.52, respectively. Comparative Example 1 Preparation of 5-bornene-2-carboxylic acid copolymer 10 g 5- borneol-baked-2-weilic acid and 1 mg of [Pd(C6H5CN)Cl2]2 were added to the reaction flask, and the reaction mixture was allowed to react at 140 ° C for 10.5 hours to obtain 5.75 g of a polymer. The Mw of the compound was 1129. Comparative Example 2 Preparation of 5-ethylen-2-yl decyl acetate of acetic acid % Addition of 5-bornene-2-mercaptoacetate acetate (1.03 g, 3.7 mmol) In a Schlenk flask, [(Allyl)PdCl]2 (13.15 mg, 3.60XUT2 mmol) and AgSbF6 (35 mg, 1〇·1χ1〇-2 mmol) were added to another Schlenk flask and added 2 ml of gasification stupid. 30 215 丨Opif.doc The AgC1 in the catalyst solution was passed through the chamber, and the remaining catalyst solution was added dropwise to the flask containing the monomer solution at room temperature. % reaction. The yield and Mw of the obtained standard polymer were respectively gram (% and 58,848. 'I: 匕Comparative Example 3 Preparation of 5-bornene-2-methyl acetate)

Li[B(C6F5)4] was added to a 5-lens diacetate acetate (5.0 g, 30 mmol) in a Schlenk flask. [(Allyl)PdCl] 2 (0.55 house gram, 0.0015 mM) and p(Cy) 3 (mg mg, 0.0030 mmol) solution of toluene dissolved in 1 ml of toluene were added dropwise to the monomer containing In the flask of the solution, the reaction mixture was allowed to react at 65 ° C for 4 hours to obtain 0.25 g (5%) of the target polymer. τ &quot; Comparative Example 4 In the presence of Pd(OAc)2 and Methylaniline IV (Fructus sylvestris), Shipen Lienong^_catalyst system, t-prepared acetic acid 5-; A polymer was added to a 250 ml Schlenk flask with acetic acid 5-borneon -2-pylon (5 ml, 30.9 mmol) and 曱 Table 05 liter. Pd (OAcM 1.4 mg '6.2 micromoles) and dimethyl phenylamine tetrakis(pentafluorophenyl) borate (10.9 mg, 13.6 micromoles) dissolved in di-methane (1 ml) The solution was added to the flask. The reaction mixture was stirred at 9 ° C for 18 hours. Then, an excess amount of ethanol was added to the reaction solution. However, no polymer precipitated. 1336335 2I510pif.doc In accordance with the process for the preparation of scale compounds of the present invention, the yield of scale compounds which can be used as a cocatalyst for the preparation of cyclic hydrocarbon polymers is relatively high. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the X-ray crystal structure of a tricyclohexyl squarate salt of tetrakis(pentafluorophenyl)borate. [Main component symbol description] Μ

32

Claims (1)

1336335 21510pif] ί ';· stomach and stomach 9M27238 Chinese wei lj range without slash correction this ". Revision period: September 29, 1999 , the scope of application for patents: i A method for producing a scaly compound represented by the following formula 1, which comprises reacting a scaly compound represented by the following formula 2 with a salt compound represented by the following formula 3: &lt;Formula 1&gt; [(Ri)-P(R2) a(R2〇b[Z(R3)d]c][Ani] where: mad, b and c respectively represent an integer from 〇 to 3 and a+b+c=3; Z is oxygen, sulfur, ash or nitrogen; when Z is oxygen or sulfur, d is 1; when Z is nitrogen, d is 2; and when Z is 矽, d is 3; Ri is hydrogen, alkyl or Aromatic group I, Rr and R3 each represent hydrogen; a straight 'chain or branched Ci 2 alkyl group, alkoxy group, alkenyl group which is unsubstituted or substituted by a hydrocarbon, halogen or Cia i alkyl group is unsubstituted or is substituted by fe, _ Or a C3_12 ring-based group substituted with a substituent or substituted with a hydrocarbon, a halogen or a Cuo haloalkyl group; unsubstituted or substituted by a hydrocarbon, a halogen or a (^-20 haloalkyl group) C7_15 aralkyl; unsubstituted or C32Q alkynyl substituted by a hydrocarbon, _ or C12G from an alkyl; tri (straight or branched Cl-indole) alkyl) decyl; three (straight or branched Ci- K) alkoxy), a tris(Cm cycloalkyl)decyl group, wherein the C312 cycloalkyl moiety is unsubstituted or substituted by a hydrocarbon, dentate or Cl-2G-alkyl; three (c6_4〇) Aromatic group) wherein the c6 40 aryl group is unsubstituted or substituted by a hydrocarbon, halogen or C^o haloalkyl; tris(c6 4 fluorene oxy) decyl, wherein Q-4 is aromatic The oxy fragment is unsubstituted or substituted by a hydrocarbon, halogen or Ci 2 〇 haloalkyl; tri (straight or branched Ci 1Q alkyl) decyl alkyl; three (C312 33 1336335 21510 pifl is Chinese patent No. 95127238) Range without line repair Original date of revision: September 29, 1999, cyclamate base), where (: 312 cycloalkyl fragment is unsubstituted or substituted by hydrocarbon, halogen or Cuo 螽 alkyl; or three (c6-4) Anthracene aryloxyalkyl, wherein the C^o aryl moiety is unsubstituted or substituted by a hydrocarbon, halogen or Cl 2 〇 haloalkyl, and [Ani] is a borate, aluminate, [SbF6]- , [PF6]-, [AsF6]-, perfluoroacetate ([CF3C〇2]-)' all-gas propionate ([c2f5C02]-), perfluorobutyrate ([CF3CF2CF2C02]-), perchlorination Acid salt ([ci〇4]_), p-toluenesulfonate ([p-CH3C6H4S〇3]-), [S〇3CF3]-, carboxylic acid benzene, or unsubstituted or halogen-substituted carborane, <Formula 2> [(R!)-P(R2)a(R2,)b]HX wherein, hydrazine is hydrogen; X is a halogen atom; and &, r2, r2, a, and b are as defined above; And &lt;Formula 3&gt; [C][Ani] wherein 'C is an alkali metal or MgX, and [Ani] is as defined above. H 2. The method for preparing a scale compound as described in claim 1 of the patent application, further includes The compound of the formula 2 is prepared by treating the phosphine compound represented by the following formula 4 with an acid: . &lt;Formula 4&gt; [(R1)-P(R2)a(R2〇b] R!, R2, R2, a, and b are as defined above.