TWI324163B - Process for making high molecular weight isobutylene polymers - Google Patents

Description

15 Ministry of Economic Affairs, Central Bureau of Standards, Staff Consumer Cooperatives, Printing and Invention Description (Integrated:: The cationic polymerization of the high molecular weight isobutylene polymer, the cationic polymerization of hydrocarbons is known in the art. Cationic polymerization is achieved using a catalyst system comprising (0 Lewis acid, (9) a tertiary triad containing halogen, vinegar, hydrazine, acid or alcohol group, and optionally (iii) electron supply Somatic molecules, such as ethyl acetate. This catalyst system has been used in the so-called "live" and "non-live" carbocation polymerization of olefins. ... with halogens and/or alkyl Lewis Catalyst systems based on acids (such as tri-carbitride and titanium tetrachloride) use various combinations of the above components and typically have similar processing characteristics. For so-called ••••••••••••••••••••••••• The concentration, which is more than 16 to 4 times the concentration of the initiator, is 100% conversion (based on a polymerization degree equal to 89 Å) in 30 minutes at -75 < t to -80 °C. The so-called "live" Examples of systems are described in U.S. Patent No. 4,929,683, issued to U.S. Patent No. 4, the entire disclosure of which is incorporated herein by reference. And an organic acid, an organic ester or an organic ether is used in combination to form a cationic polymerization initiator, which also produces a complex counter anion. Obviously, the composite counter anion does not help or cause proton removal. In the "polymerization system", the high molecular weight polyisobutylene is actually only used at low temperatures (-60 to -100 ° C), and in each initiator molecule more than one catalyst - 3 paper scales apply to the Chinese national standard (CNS) > A4 specification (210X297 mm)

10 15 Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed under the concentration of molecular catalysts. In fact, many of these applications have been applied to certain narrow temperature regions and concentration distributions. Catalytic systems can only be used in recent years, using compatible non-coordinating anions, based transition metal compounds (also referred to in this art). The type of Park Catalyst System has been developed. See the published European Patent Application No. 0,277,003; the published European Patent Application 〇277, 〇〇4; US Patent 5,198,401; and the published international patent application Case w〇92/00333. It is also known to use ionized compounds that do not contain active protons. 'For example, one of the following: the published European patent application 426, 426, 637Α; and the published European patent application No. 0,573,403. US 5,448,001 discloses a carbocation process for polymerizing isobutylene using a catalyst system comprising, for example, a metal alkadiene catalyst and borane. WO 00/04061 discloses a cationic polymerization process which is based on Under the 'atmospheric pressure, it is carried out in the presence of a catalyst system such as Cp*TiMe3 ("initiator") and B (C6 Fs ^ (,, activator "). Cations and "non-coordinating anions" (NCA). With this catalyst system, polymers with the desired molecular weight properties can be produced at higher temperatures and at higher temperatures than by conventional means. Produced, thus reducing the capital and operating costs of the equipment from which the polymer is made. The wide range of NCAs disclosed in WO 00/〇4〇61, including the deletion 4

(Please read the note on the back and fill out this page.) This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm). 1324163 V. Description of invention (3 10 15 Ministry of Economic Affairs Intellectual Property Office staff consumption Co-ops print and bismuth compounds, including borate and bridged diboron species. The polymerization of isobutylene with a small amount of isoprene to produce butyl rubber presents a unique battle. Clearly, as in this technique In this case, the polymerization is highly exothermic, so the reaction mixture must be cooled to about .95 ° C in a large-scale production facility, although in the art of the development of a new reactor design and / or This requirement is maintained by the advancement of the novel touch system. Furthermore, the copolymer thus produced has a significantly lower molecular weight than the homopolymer produced under similar conditions, which is the case This is because isoprene is present in the monomer feed and will cause chain termination due to B_H removal. It is generally expected to be able to be at relatively high temperatures (when compared to the method of the art 2) and Environmentally friendly article The high molecular weight isobutylene polymer ', and especially the isobutylene copolymer, is obtained in high yield. This has not been reported yet. The invention is disclosed in the large number of NCAs disclosed in WO〇〇/0406i, which has the following The NCA type of structure: [M'-Z-M"]d * where Μ and M" may be the same or different, and each has the formula: wherein M is a metal or a metalloid; and Ql to Qn are independent Bridging or unbridged hydride groups, dialkyl guanamine groups, alkoxides and aryl oxide groups, hydrocarbyl groups (please read the back of this note before refilling this page) — — — — — — — ^ -----— — II --II--------II —______ __ 90. 11. 2,000 -5-

V. INSTRUCTIONS (4) Substituted hydrocarbyl group, tooth hydrocarbyl group and substituted tooth hydrocarbyl group and hydrocarbyl group and tobacco group-substituted organic metal group, with the proviso that no more than one of Qi to Qn may be a dentate group And Z is a core-bonded bridge species selected from the group consisting of OR_, SR'SeR'NR2'PR2-5, AsR2·, SWV, F_, (Τ, Βγ· and Γ, wherein R is selected from the group consisting of hydrogen, Cl_c4 Tertiary base, Ci_C4 anthracenyl, C5-c4 aryl, 'a derivative of its south substitution and its heteroatom-substituted derivative' and η is an integer greater than or equal to 1. We have seen that caution has been found The selection of such a subset of 10 bridged NCA ethnic groups disclosed in w〇〇〇/〇4〇61 allows for the preparation of a catalyst system with surprising advantages over the systems disclosed therein. a bridged compound wherein M is selected from the group consisting of B, A1, Ga, and In, which can be prepared by adding a predetermined amount of a third component ("co-initiator to a suitable activator) The catalyst system 15 is obtained, which allows for the creation of a novel catalyst system that allows for preparation compared to WOOO/ Those disclosed in iMOH have even higher molecular weight isobutylene polymers. Furthermore, such polymers are produced in very high yields. Suitable co-initiators include alcohols, mercaptans, carboxylic acids, thioacids, etc. Such a system not only produces a polymer with a high molecular weight and a distribution with a narrow molecular weight of 20, but also causes a large monomer conversion rate. This polymerization reaction is carried out under subatmospheric pressure, and has another advantage. , ^ can be carried out at a higher temperature than previously considered to be feasible. Furthermore, this reaction can be carried out in a more environmentally friendly solvent than this technique. -6 - _ This paper scale applies to the standard (CNS) A4 size (210 X 297 mm) ------- 90. 11. 2,000 (Please read the note on the back of the M and then fill out this page) # -------订--- ------Line _ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 丄 4163 A7 ------ - _B7 V. Invention Description (5) Invention Details Therefore, the method of the present invention is directed to the polymerization of isobutylene Reaction. As indicated above, the process of the invention is particularly advantageous for the polymerization of butyl rubber The term "butyl rubber" as used throughout this patent specification is intended to mean that by making the major portion, for example about 7 〇 to " 5 parts by weight, usually 85 to 99. 5 parts by weight of the isomonoolefin, such as isobutylene and a minor portion, for example from about 3 Torr to 5 parts by weight, usually from 丨5 to 〇5 parts by weight of the olefin, such as a conjugated diene A polymer prepared by reacting, for example, isoprene or butadiene (100 parts by weight of each of the reacted monomers). The isoolefin is generally a q to C8 compound such as isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-royl-2-butene and 4-methylpentene. A preferred monomer mixture for the manufacture of butyl rubber, including isobutylene and isoprene. Optionally, another olefinic triol, such as styrene, cardiomethylstyrene, p-methylstyrene, styrene, pentadiene, etc., may be incorporated into the butyl rubber polymer. See, for example, any of the following: U.S. Patent 2,631,984; U.S. Patent 5,162,445; and U.S. Patent 5,886,106. Printed by the Ministry of Economic Affairs, Central Bureau of Standards, Staff Consumer Cooperatives (please read the notes on the back and fill out this page). The method of the present invention comprises using a cationic polymerization system comprising a 2〇 initiator and an activator, the activator being combined The middle is a reactive cation, and an activator is a compatible non-coordinating anion. Non-limiting examples of initiators useful in the practice of the present invention are disclosed in the published PCT application WO 00/04061. For the sake of clarity, the chemical formula presented below depicts the catalyst composition as 1324163 A7 B7 5. The invention description (6) becomes the "ion" state. Of course, those skilled in the art will immediately understand many of these ingredients, such as The situation depicted is unsettled and therefore derived from a neutral form of stability. For example, the following species:

Me 5 Cp2Zr+ typically does not exist alone in this state. Rather, it is formed by reacting Cp2ZrMe2 with another compound which will extract the Me group. This description of the ingredients in the form of "ion" is for illustrative purposes only and should not be construed as limiting in any way. 10 The following reference is a statement of neutral stability, and the synthesis of a cyclopentadienyl transition metal composition with NCA: published international patent application WO 92/00333; published European patent application 0,129,368A; Published European Patent Application No. 0,551,277A; 15 Published European Patent Application No. 0,520,732A; Published European Patent Application No. 277,003A; Published European Patent Application No. 0,277,004A; Published European Patent Application 0,426,637A ; Printed by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back and fill out this page). The published European patent application 0,573,403A; 20 The published European patent application 0,520,732A; European Patent Application 0,495,375 A. U.S. Patent 5,017,714; U.S. Patent 5,055,438; U.S. Patent 5,153,157; and -8- This paper scale applies to Chinese National Standards (CNS> A4 Specification (210X297 mm) 1324163 A7 B7 V. Invention Description (7) US Patent 5,198,401. A description of a compound capable of producing an ionic species on the spot can be found in any of the published European patent applications 0,500,944 A and 0,570,982 A. The metal alkadienyl ruthenium compound is reacted before or simultaneously with the addition of the activated anionic compound. The neutral form of the substituted carbocation, and its synthesis, are described in U.S. Patent No. 4,910,321, U.S. Patent No. 4,929,683, and issued European Patent Application 0,341,012 A. In general, such carbocations are neutral in the form of 10, typically represented by the formula: I I2 J I3 15 wherein R1, R2 and R3 are a plurality of substituted or unsubstituted alkane Base or aromatic group or a combination thereof, printed by the Ministry of Economic Affairs, the central sample bureau employee consumption cooperative (please read the back Note: Please fill in this page again) η is the number of initiator molecules, and preferably is greater than or equal to 1, and more preferably between 1 and 30, and 20 X is a functional group, Lewis acid will be on it. To a change, a carbocation initiation site is created. This group is typically a halogen, ester, ether, alcohol or acid group, depending on the Lewis acid used. About the stable form of the substituted (silylium) For a discussion of its synthesis, see FA Cotton, G. Wilkinson, Advanced Inorganic Chemistry, John Wiley & Sons, -9- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 >< 297 mm) 1324163 A7 B7 V. Invention Description (8) (Please read the notes on the back and fill out this page)

New York 1980. Similarly, for the stable forms of cationic tin, antimony and lead compositions, and their synthesis, see the Dictionary of Organometallic Compounds, Chapman and Hall, New York 1984. The initiator is selected from a variety of cation and cation sources. Some of the more preferred types are: (A) cyclopentadienyl transition metal complexes and their derivatives; (B) substituted carbocations; (C) substituted banknotes; (D) groups capable of generating protons' , as further described below; and 10 (E) cationic composition of antimony, tin or lead. With reference to the species (A), the preferred cyclopentadienyl metal derivative may be selected from the group consisting of compounds which are mono-, di- or para-rings selected from transition metals of Groups 4, 5 or 6 of the Periodic Table of the Elements. Pentadienyl derivatives. Preferred compositions include a mono-cyclopentadienyl (mono-Cp) or bis-cyclopentadienyl (bis-Cp) Group 4 transition metal group of 15, especially zirconium, titanium and/or yttrium composition 6 The good cyclopentadienyl derivative is a transition metal complex selected from the group consisting of: (A-Cp) M+ X1

(A-Cp)M L (CpR) Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperative Print 20 Where (C^HS-y-xSx)/ \ (A,)y\, / •^(z-l-y)

Μ—X

(C5H5-y-XSx) V R"/, X This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1324163 A7 B7 15 Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperatives Printed V. Inventions (9 (A_Cp) is either (Cp) (Cp*) or Cp_A, _Cp*; (d) or a different cyclopentyl ring, (iv) to 5 substituted diterpene * taken - (4) independently selected from the group consisting of hydrocarbon groups, It is obtained by taking an organic di-halogenated halohydrocarbyl group, a substituted halohydrocarbyl group, or a hydrocarbyl group; a metal-like, self-replacement-substituted metal, a disubstituted boron, and a Bernie's deaminin (^ gamma (tetra), substituted a chalcogen or halogen group, or CP^CP* is a cyclopentadienyl ring in which any two adjacent s groups are joined to form c4w2Gm to form a fresh or read and polycyclic cyclopentane a cation-based ligand; R f is a substituent on one of the cyclopentadienyl groups, which also binds to a metal atom; A' is a bridging group, which group can be used to limit 邙 and 邙* rings or c5H5y·XSX) and the rotation of the JR'(zM.y) group; Μ is a transition metal of Group 4, 5 or 6; y is 〇 or 1; (C5H5-y-xSx) is a cyclopentadienyl ring, Be captive 5 s groups are substituted; X is 0 to 5; JR(ziy) is a hetero atom ligand, where j is a group 15 element with a coordination number of three' or a steroid with a coordination number of 2 The element, preferably nitrogen, phosphorus, oxygen or sulfur; R" is a hydrocarbon group; X and X1 are independently a hydride group, a hydrocarbon group, a substituted hydrocarbon group, a halogen hydrocarbon group, a substituted tooth hydrocarbon group, and a hydrocarbon group-to-tooth hydrocarbon group. _Substitute organic gold-11 - (please read the notes on the back and fill out this page) Λ / ? 3 \ - - [ r - * V. Description of invention (1〇A7 B7 10 genus, substituted a pnictogen group or a substituted chalcogen group; and a dilute, diolefin or arylene ligand, or a neutral Lewis base. It can be used in a cationic polymerization catalyst system. Other cyclopentadienyl compounds are described in the following: European Patent Application No. 0,551,277 A; U.S. Patent No. 5,055,438; U.S. Patent No. 5,278,119; U.S. Patent No. 5, I98, 40, and U.S. Patent No. 5,096,867. (Β), a group of preferred reactive cations includes a rabbit IW ionic compound having the formula: (阅读Read the notes on the back and fill out this page.) 15 R1 R2-C-R3

Rl, R2 and R3 are independently oxime, or a linear group, with the proviso that there are only two in Rl HR3:; ' is 'two || Preferably, none of RhR2W is Η. ! 1丨, r2&r3 preferably are independently Cl to C20 aromatic or aliphatic groups. Non-limiting examples of suitable aromatic groups may be selected from the group consisting of phenyl, indolyl, di-f-phenyl and biphenyl. Non-limiting examples of suitable aliphatic groups may be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, decyl, dodecyl, 3-methyl -pentyl and 3,55.trimethylhexyl. Sub-technical or cyclic aromatic or fat-In nn II I- I · I___ -12- This paper scale applies to China National Standard (CNS) A4 specification (21〇χ297 公公1324163 A7 __ B7 V. Invention Description (11) Reference type (C), the preferred reactive cation of the group, including the substituted cationic compound: t formula R1 R2—Si—R3 5 + wherein the Ministry of Economic Affairs, the central sample, the employee consumption cooperative, prints R, R and R are 'independently hydrogen, or a linear, branched or cyclic aromatic or aliphatic group' with the proviso that only one of R丨 and R4r3 may be hydrogen. Preferably, it is R1, R2 and R3. R1, R2 and ¥ are preferably independently C1 to C2〇 aromatic or aliphatic groups. Ri, R2 and R3 are more preferably independently (: 丨 to 匸8 alkyl. Can be used Non-limiting examples of aromatic groups may be selected from the group consisting of phenyl, tolyl, xylyl, and biphenyl. Non-limiting examples of aliphatic groups may be used, which may be selected from the group consisting of methyl, ethyl, Propyl, butyl, pentyl, hexyl, octyl, decyl, decyl, dodecyl, 3-15 decylpentyl and 3'5,5·trimethylhexyl. A group of excellent reactivity Instead of the banknote cation, it may be selected from the group consisting of trimethyl ketone, triethyl ketone and benzyl dimethyl meth. This cation can be made by exchanging the hydrogen group of RlR2R3Si_H with NCA such as Ph3 C+B(pfp)4 - 'generating such as R〗 R2R3 SiB (pf^ composition 'which is obtained in a suitable solvent. 2〇 reference species (D), the source of this cation can be a composition with a non-coordinating anion or containing a non-coordinating anion When combined, any compound that will produce protons. Protons can be derived from the reaction of a stable carbocationic salt containing a non-coordinating, non-nucleophilic anion with a water 'alcohol or phenol to produce protons and their corresponding by-products. In the reaction of carbocation salt with protonated additive, ______13- paper-scale (CNS) from the threat (210; <297 reading) - A7 ' __________ B7 V, invention description (彳2) and its敎Reaction ratio (4), a relatively fast situation, such reaction σ is preferred other proton-producing reactants, including mercaptans, acids, etc. Similar chemical action can be obtained by banknote type catalyst. In the real example, you want low scores. The amount of the polymerization product may be such that an aliphatic or aromatic alcohol may be added to inhibit the polymerization. Another method for producing a proton includes, preferably, the metal of the j- or group 2 metal cation is H, and is preferably combined with water. It is in the presence of a Lewis, non-f-organic organic solution I, which does not interfere with the polymerization reaction. The moist solvent is defined as a hydrocarbon solvent that is partially or completely saturated with water. It has been found that when Louis 10 A base, such as isobutylene, is produced together with a ruthenium or a Group 2 metal cation and water. In a preferred embodiment, the non-coordinating anion 1 is present in a "moist"solvent' so that when a Group 1 or 2 metal cation is added', an active catalyst is produced. Reference species _), another preferred source of cations are substituted erroneous, tin 15 or lead cations. Preferred non-limiting examples of such cations include those of the lower right formula: 〃 R1 皮 2 - Μ R3 + 2 〇 wherein R1, ^2 and R3 are independently hydrogen' or linear, branched or cyclic An aromatic or aliphatic group, and M is ruthenium, tin or lead, with the proviso that only one of R1, R2 and R3 may be hydrogen. Preferably, none of R1 and hR3 is H R R and R 3 is preferably independently a C1 to C20 aromatic or aliphatic group. .I—II -I · (Please read the notes on the back and fill out this page) Order the Ministry of Economic Affairs, the Central Bureau of the Bureau, the staff, the consumer cooperation, the printing press - 14 - 1324163 A7 B7 V. Invention Description (13 10 15 Central Economic Department A standard office employee consortium print may use non-limiting examples of aromatic groups, which may be selected from the group consisting of phenyl, phenyl, xylyl, and biphenyl. Non-limiting examples of aliphatic groups may be used. It may be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, decyl, dodecyl, 3-methylpentyl and 3,55 trimethylhexyl. The NCA component of the catalyst system is via the following activator compound (R]R2R3)M wherein Μ is B, Al, Ga or In; R, R and R3 are independently selected from bridged or unbridged dentate groups , a metal alkyl group substituted with a dialkyl guanamine group, an alkoxide and an aryl oxide group, a hydrocarbon group and a substituted hydrocarbon group, a functional hydrocarbon group and a substituted functional hydrocarbon group, and a hydrocarbon group and a halogen hydrocarbon group, Provided that no more than one such R group can be a dentate group; reacted with a "coinitiator" The co-initiator is an alcohol, a thiol, a retinoic acid, a thiocarboxylic acid or the like. Preferably, the co-initiator is one having at least 8 carbon atoms, such as decyl alcohol, stearyl alcohol and octadecanoic acid. Preferably, the fluorinated compound, such as hexafluoropropanol, hexafluoro-2-phenyl-2-propanol, and heptadecafluorodecyl alcohol, is in the preferred embodiment, the touch is the same or The different aromatic or substituted aromatic hydrocarbon groups contain from about 6 to about 2G carbon atoms and can be retarded, and the bridged groups are linked to each other; and the Han 3 series is selected from the group consisting of hydride groups, hydrocarbons and substituted Hydrocarbyl, Toothyl and Substituted Tooth Hydrocarbyl, Nicotinyl and Functional Group-Substituted Organic Metal Groups, Double Substituted Berniecomets ^ (Please read the back of the note before you fill out this page) Order -15 - Description of the invention (14 group substituted chalcogen group and dentate group. (C6 = 圭, in particular, and R1, one is 盥ϋ丨ίΐ is bound by any particular theory, salty The activator compound and the initiator system form a bridge species of the following formula: [(RiR2R3)M]2-/(zZ]· where 10 15 the central standard of the Ministry of Economy Bureau employees' consumption cooperatives are printed together (please read the notes on the back and fill out this page). Z indicates the group formed by taking the acidic proton from the co-initiator (for example, if the co-initiator is alcohol (Roi), then 2 represents an alkoxy group (〇R). Each mole activator employs at least about 〇.〇1 molar co-initiator, and the maximum amount of co-initiator used is about 丨mol per mole of activator. The ratio of the co-initiator to the boron compound is more preferably in the range of from about 0.1:1 to about 1:1, more preferably in the range of from about 0.25:1 to about 1:1, and still more preferably In the range of about 0.5: 1 to about 1: . Preferably, about 0,5 moles of co-initiator is employed per mole of activator, as this is the theoretical amount of co-initiator required to convert all of the initially present activators to bridged two-collar species. The process of the invention is carried out under subatmospheric pressure. The pressure at which the process of the invention is carried out is preferably less than about 10 kPa, more preferably less than about 90 kPa, still more preferably in the range of from about 0:00001 to about 50 kPa, and more preferably in the range of about 10,000 kPa. In the range of from 1 to about 40 kPa, more preferably in the range of from about 1 to about 3 kPa, and most preferably in the range of from about 0,0001 to about 15 kPa. The process of the present invention can be carried out at a temperature above about -8 (TC, preferably at a temperature in the range of from about _80 ° C to about 25 ° C, more preferably from about -4 Torr. (: to about 25 °). At the temperature of the C range, it is better at about -301 to about 25. (: The temperature at the range is more than -16. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). 15 Central Economic Department Standards Bureau staff consumption cooperation Du printing 1324163 V. Invention description (15 good system in the range of about -2 ° ° C to about 2yc range of pit temperature. Degree T 'the best system revealed in about ^ to about The co-initiator is used to prepare the isobutylene polymer and the ancient one is "unexpectedly superior black", the polymer thus produced has a local molecular weight, even higher than that disclosed in W〇〇_. In the case of a rare copolymer, it is more realistic. Usually the introduction of a second monomer (such as isoprene (IP)) causes the copolymer to have a molecular weight much lower than that produced under the same conditions. But this is not the case - although the molecular weight of the isobutylene copolymer is still lower than the homogenous content produced under the same conditions The reduction in the amount of knives is surprisingly lower than expected. Furthermore, these polymerizations are extremely fast and the yield is extremely high, with 1% of the monomer conversion being homopolymerized. A similar conversion is seen in the copolymerization of polar solvents. The yield in toluene is higher in the presence of a co-initiator, especially in the presence of fluorinated alcohols. The following examples are given with reference to the following examples, which are provided for purposes of illustration only and are not intended to limit the scope of the invention. All examples of glassware are dried by heating at 12 ° C for at least 12 hours prior to assembly. The nitrogen is purified by continuously passing over the heated BASF catalyst and the molecular sieve. The di-methane is refluxed over calcium hydride and dried under nitrogen, and the toluene is refluxed over sodium-dibenzophenone under nitrogen. Purified, and both solvents are just distilled, and then thawed by a refrigerated pump before use. When necessary, the solvent is stored on activated molecular sieves under nitrogen. -17 This paper scale applies to China Associate (CNS) A4 size (210X297 mm) (Please read the back issues of the note and then fill in this page)

1324163 A7 ____B7_ V. INSTRUCTIONS (16) Diene monomer isoprene (ip) is passed through a column to remove p-tert-butyl catechol to n-BuLi before use. (16M solution in hexane) was titrated and purified by steaming the crane under vacuum. It was then stored at _3 ° C in a nitrogen-filled dry box. 5 Isobutylene (IB) is purified by passing through two molecular sieve columns and condensed into scaled fingers that are immersed in liquid nitrogen. The IB was reconstituted, the volume (~8 to 24 ml) was recorded and then re-frozen by immersion in a liquid nitrogen bath. The system was evacuated to 10.3 Torr, the IB fingers were separated, and the system was set. Under the nitrogen atmosphere. 10 successively added Cp*TiMe3 (Cp*= 7;5-pentamethylcyclopentadienyl; Me = methyl; usually 11 mg '〇.〇5 mmol; recrystallized from pentane), with BO ^F5)"usually a solution of a mixture of 25 mg '0_05 millimolar; sublimed) with octadecyl alcohol (usually 13 mg, 0. 〇 5 mmol; sublimation) in 5 ml of solvent, and Freezing in liquid nitrogen yields an initiator to monomer ratio of about 15 to about 1500. Prior to the addition, the initiator and IB solutions were brought to the desired temperature (using a cooling bath of about 30 C). In some cases, before the ro condensation, it will be equivalent to ~Μ莫耳% Ministry of Economic Affairs Central Bureau of Standards staff consumption cooperative printing (please read the back of the note before filling this page) -. The amount is added to the ^ finger, which is achieved in a nitrogen-filled dry box. ', 20 is usually a solution of the olefin and initiator system, stirring under static vacuum for a long time and at a predetermined temperature (so-called "static vacuum" means that the system is sealed at this time, and the pressure is basically In order to leave a vapor pressure at the reaction temperature with the solvent. When dihalomethane is used as the solvent, a large amount of the polymer substance usually starts to precipitate after about 2 minutes. When toluene is used as a solvent, it forms a sticky -18-

1324163 A7 B7 V. INSTRUCTIONS (17) Thick solution and keep stirring. After about one hour, the reaction was terminated by precipitation into sterol (greater than 1 liter). The precipitated material was dissolved in hexane, and the solvent was evaporated under reduced pressure. The solid white polymer thus obtained was dried to constant weight. (Please read the notes on the back and fill out this page.) Department of Economics, Central Bureau of Standards, Staff Consumer Cooperatives Print -19- This paper scale applies to China National Standard (CNS) A4 specification (2丨0X297 mm) 1324163 A7 B7 V. Description of the invention (18) The Central Bureau of Standards of the Ministry of Economic Affairs, the employee consumption cooperative,

K) Η-» Η-» Ο ν〇00 σ\ OJ (〇Example Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*HfMe3 Cp*ZrMe3 Cp*TiMe3 Cp*HfMe3 Cp* ZrMe3 Cp*TiMe3 Initiator B(C6F5)3 Activator Octadecaic acid Heptafluorodecyl alcohol Heptafluorodecyl octadecyl octadecyl alcohol 1 1 1 1 1 Co-initiator K) Κ) Η-» ι Η-ι ι—^ I—^ H-» Activator: Co-initiator Benzene (15) CH2C12(15) Toluene (15) CH2C12(15) Toluene (15) CH2C12(15)I Benzene (15) Toluene (15) Toluene (15) CH2C12(15) CH2C12(10) CH2C12(15) Solvent (ml) 〇to Ό v〇Ln U) v〇bo to )—* Η-» to l/l Ό l/ϊ >-t LO H-» SO Ia 1 IB (ml) U) 0〇οο LTk οο t—» o K> LA o K> 1/1 to K) ON o H-» o ^赛^ Π5 w嗛582710 858600 529320 518710 1129000 708350 227000 431540 1 510600 1 341550 | 157300 504230 Mw (g/mole) η-» to K) Ο bo Η-» v〇K) u> Η-» <1 ίΟ k> to to MWD Bandit Umbrella BLM (please read the notes on the back and fill out this page)

This paper standard is the common Chinese national standard (CNS > A4 specification (210X297 mm) 1324163 A7 B7 V. Invention description (19) Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperative Printing K) OO h—* 5; H-» 1 -^ H-* U) X ga U) and g 〇> U) * HS 〇) * H § J? * H 1: j? * * H 1' J? * 2 J? and s J? ou蹙= = W *n uT" Π1 逵rV hired + cV 骤4 - > 联+ > 碌+ > k + > + > A 礴+ > A ++ > Micro UU 逢 ί —* I—* )—* N) H-» K) l—l K) h-* Calling: η-* H-& — I—* — Η— -s 5 n ffi (〇 1—« Ο a U) Q o 〇ffi UJ 苕-3⁄4 舛Η-» Lh S—✓ -s Hk -δ /^s Lh -a Lh Ο ffi ro B /—s Lfi 'w^ U) K) Ln ►—* K) to Η-» to t—Λ K) — N) 〇to o H-* l〇o 槲a Half bO h—* o H-* o ►—* o U) Os bo h— AU) Private U\ o A match w嗍K>u> U) as o U) LO 〇00 oo u> go -0 L/i U) o 〇\ 〇> o »—* Ui t—* μ- * u> so Lh sv〇〇00 K) o , 茗-H N>Os> 〇bo K) bo bs h * Os § 1 (Please read the note on the back and fill out this page) ♦I. This paper scale applies to Chinese national standards (CNS > A4 specification (210X297 mm) 1324163 A7 B7 Explicit description issued by the Ministry of Economic Affairs Central Bureau of Standards Staff Consumer Cooperative Printing

U) K) OJ Η-» to 00 to K) L/\ to Example Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp*HfMe3 Cp* TiMe3 Initiator B(C6F5)3 I Activator·+ rV p( Ψ wall heptafluorononol heptafluorononanol heptafluorononanol + rV • Qiqiu heptafluorononanol heptafluorodecyl alcohol seventeen Fluoranol 1 co-initiator t-k H—k ί—* t—* ί—* t—kh—ι activator: co-initiator H-» Η-» H-* benzene (15) benzene ( 15) CH2C12(15) CH2C12(15) CH2C12(15) CH2C12(15) CH2C12(15) CH2C12(15) Benzene (15) CH2C12(15) CH2C12(15) Solvent H-* ι—* Η-» Ο u> o U) Ο ο 〇s H-* W h-* IP (mg) H-* Lh H-* ί/ϊ 1—* U) H-* U) Η-* U) U) Ο H- » o H-* N) »—* N) U\ 1—* U> o to Ln IB (ml) K) U) K) v〇K) g Ο ΟΟ Κ) v〇OJ Η-» ov〇ood \ cr 166400 205288 405080 396470 583600 300270 370300 735400 168700 157290 289500 Mw (g/mole) H-* Os N) I-» ts) κ> U) Ν) 4^ N) Os H-* <1 Ιλ Lk ) Η-» bo MWD (please Read the back of the precautions to fill out this page)

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1324163 21

/V Ming Ming Ming Fa 5 Ministry of Economic Affairs Central Bureau of Standards Bureau staff consumption cooperatives

U) oo U) U) On U) U) U) Example Cp*HfMe3 Cp*HfMe3 I Cp*HfMe3 Cp*HfMe3 Cp*TiMe3 j Cp*TiMe3 Cp*TiMe3 [Cp*TiMe3 Cp*TiMe3 Cp*TiMe3 Cp* TiMe3 initiator 1 1_ - B(C6F5)3 Activator octadecyl hexa-2-phenyl _ propan-2-ol hexafluoro-propan-2-ol octadecyl octadecyl alcohol-thiol octagonal - Mercaptan octadecyl alcohol-thiol octopus·-thiol octadecanoic acid octadecyl alcohol co-initiator 1_ — — h—* H-* I—* Η-» j—» to activator: Initiator H-* Η-» H-* N-* |CH2Cl2(l5)] CH2Cl2(l5) CH2Cl2(l5) CH2Cl2(l5) CH3 Cl(50) CH3 Cl(50) CH3 Cl(40) CH2Cl2(l5 CH2C12(15) CH2C12(15) Toluene (15) Solvent ι-^ KJ\ μ—* i—to Η-» u> o 230 230 240 to U) Η-» Ui 00 23⁄4 & 13.0 13.0 13.0 13.0 V —4 K) to to M3 13.0 ON Ό Ln S gs oo o K) o — o bo H-* o Conversion rate (%) “423240 376380 232750 3H650 443560 366560 615560 386550 342280 494700 324380 Mw (g/m) N ) 〇\ bs K) bs oo K) MWD _ 2 ( ? This paper scale applies to Chinese national standards (CNS > A4 specifications) 210X297 mm) (Please read the back of the precautions to fill out this page)

1324163 Ministry of Economic Affairs, Lost Samples, Bureau of Staff, Consumer Cooperatives, Printing A7 B7 V. Inventions (22) These results support the use of the catalyst system disclosed in this paper to carry out the polymerization of isobutylene under sub-atmospheric pressure. Comparisons in the absence of a co-initiator in the presence of a co-initiator result in the formation of polymers with higher _. Similarly, these results support a total of 5 isobutene/isoprene under similar conditions. The polymerization reaction, when compared to the polymerization or copolymerization reaction of isobutylene in the absence of a co-initiator, results in the production of a copolymer having a higher Mw. The above specific embodiments of the disclosed invention are detailed in Experiments conducted under sub-atmospheric pressure. Without wishing to be bound by any particular theory, it is generally believed that 10 reactions at sub-atmospheric pressure will allow superior heat transfer to occur in the reaction medium 'thus preventing "hot spots" Or accumulate, which is known to be harmful. Therefore, 'any way that contributes to superior heat transfer (eg highly efficient cooling, improved reactor) The invention is covered by the present invention as disclosed herein. All of the publications, patents, and patent applications referred to herein are hereby incorporated by reference in their entireties in their entireties in It is expressly and individually displayed to the same extent as it is for reference in the text. (Read the first note on the back and fill out this page again}

-twenty four-

Claims (1)

2 A8 Βδ C8 D8 VI. Application for Patent Fangyuan Patent Application No. 91100912 No. 91100912 ROC Patent Appln. No.91100912 Revision of the application for patent-free Fanyuan Chinese-Annex (III) -Amended Claims in Chinese - Fncl. Year ^ month / 〇日修 (£) original (Min - submitted on December 10, 1998) Submitted on December 10, 2009) 10 15 Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives prints 20 1. A cation can be aggregated A process for the polymerization of an olefin comprising the step of polymerizing at least one cationically polymerisable olefin in the presence of a cationic polymerization catalyst system at subatmospheric pressure, the catalyst system comprising an initiator and an activator, together Forming a reaction|-generated % ion and a non-coordinating anion via a compound of the formula: (RlR2R3)M wherein: Μ is B, Al, Ga or In; Rl, R_2 and R_3 are independently substituted by halogen匸6 aryl. Prepared by reacting with a co-initiator selected from the group consisting of partially fluorinated alcohols, carboxylic acids, and mixtures thereof; wherein the activator and co-bow 1 hair styling agent —_ - the bridge of the species 'and the reactivity _ child riding the red county Yi metal complex' and the transition metal complex is Cp * M (Ci 6 yard base) 3, M is a Group 4, 5 or 6 transition metal; Cp* is (pentamethylcyclononanthylene. 2. According to the method of the scope of application of the patent item, wherein Μ is Β. 3. According to the method of the third paragraph of the patent application, wherein the co-initiator pair (R ^RUM molar ratio, is in 〇〇1. 4. According to the method of claim 3 (R1R2R3) M molar ratio, is in 〇]. To the range of the co-initiator pair to 1 : 1 range 90687B-connected 2 set • I -25 - 1324163 A8 B8 C8 D8 VI. Patent application scope 5. According to the fourth paragraph of the patent application scope, the co-initiator pair (ΙΜΙ^3) The ratio of Moer is in the range of 0.5.1 to 1:1. 6. According to the fifth paragraph of the patent application scope, the ratio of the total initiator to the molar ratio of 5 is 〇5: 卜7. According to the method of the scope of the patent application, wherein &, Κ and r are interconnected via a stability bridging group. 2 3 Rl, R2 and R3 8. According to the method of claim 2, wherein Ri and 10 are each C6F5. 9. The method of claim 4, wherein the co-initiator is a part of fluorinated alcohol. 10. According to the method of item 1, the reaction is carried out at a temperature higher than 100 C. 15 η· According to the method of claim 1G of the patent application, wherein the reaction is carried out at a temperature higher than -80 °C. Π. The method of claim 2, wherein the reaction is carried out at a temperature higher than -60 °C. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consumer Cooperatives η. The method of applying the patent range of μ, the sub-atmospheric pressure system 20 is lower than lOOkPa. M. Roots is directed to the method of claim 13, wherein the sub-atmospheric dust force is less than 1 kPa. 15. The method of claim 14, wherein the subatmospheric pressure is less than O.OlkPa. -26 - This paper size applies to China National Standard (CNS) A4 specification (21〇 X 297 public) 6. A mixture of olefins polymerized in a cationic manner according to item I of the scope of the patent application. The method of item 1 wherein the at least one may include isobutylene and isoprene The activator is via a compound of the formula: 永名, 夂万法, its encapsulated olefin, and the cation catalyst system comprises a derivative (RlR2R3)M wherein 10 Μ is B, Al, Ga or In; R1, Κ·2 and The ruler 3 is independently a halogen-substituted c6 2〇 aryl group; and is prepared by reacting with a co-initiator selected from the group consisting of a partially vaporized alcohol, a carboxylic acid, and a mixture thereof. This reaction is carried out in such a manner as to cause highly effective cooling of the reaction mixture. The activator together with the co-initiator forms a stable bridging species. This paper scale applies to the Chinese National Standard (CMS) A4 specification (210 X 297 Gong Chu 3 ~ '~~~'