WO1995025754A1 - Procede d'isolement d'un polymere d'isobutylene - Google Patents
Procede d'isolement d'un polymere d'isobutylene Download PDFInfo
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- WO1995025754A1 WO1995025754A1 PCT/JP1995/000486 JP9500486W WO9525754A1 WO 1995025754 A1 WO1995025754 A1 WO 1995025754A1 JP 9500486 W JP9500486 W JP 9500486W WO 9525754 A1 WO9525754 A1 WO 9525754A1
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- isobutylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
Definitions
- the present invention relates to a method for isolating an isobutylene-based polymer after polymerization, and an efficient method for producing an isobutylene-based polymer having a telechelically unsaturated group. (Background technology)
- polymers having a functional group of ⁇ for example, polymers having a vinyl group on the surface are photo-curable resins, UV-curable resins, electro-curable resins, and sealing for electronics. It is useful as a raw material for sealing materials, m, modifiers, coating materials, and sealing materials.
- An isobutylene-based polymer which is a kind of functional combination, for example, having 3 in rain and a chlorine atom bonded to a carrier, is 1,4-bis-chloro-isopropyl) benzene (hereinafter simply referred to as (p-DCC).
- p-DCC 1,4-bis-chloro-isopropyl) benzene
- the use of a transfer agent, boron trichloride, as a catalyst for the cationic polymerization of isobutylene has been demonstrated by the Inifer method (U.S. Pat. No. 4,276,394).
- Lewis acids such as BC 3 , Ti C, A 1 C 1 and the like are usually used as a polymerizer.
- water is added to generate a Lewis acid and a ligand of water, thereby stopping the polymerization. The water is separated because it is dissolved in Lewis acid and ice.
- An object of the present inventors is to provide a method for separating a polymer from a polymer without using water in the case of polymerization of isobutylene or the like using a difficult Lewis acid.
- telechelic polymer as used in the present invention means a polymer having the same or ⁇ functional group that can participate in cross-linking on the thigh of the polymer.
- the present invention is constituted as follows.
- ⁇ represents a metal atom
- ⁇ represents ⁇ of 2 J3 ⁇ 4 ⁇ 6 or less
- X represents a halogen atom or a monovalent carbon atom, which may be the same or different.
- Q is the Periodic Table I a, n a, m b, or metal atoms belonging to Wa group, m is an «of 13 ⁇ 4 ⁇ 6 below.
- R represents a hydrogen atom or monovalent thanks, m is 2 or more, and m Rs may be the same or different.
- a telechelic isobutylene-based polymer is ⁇ and an adsorbent that has acid adsorption ability is used.
- the method for isolating an isobutylene-based polymer is as follows.
- the compound ⁇ (represented by the above formula ⁇ ) is added to remove HC 1 from the polymer.
- a reaction and a ligand exchange reaction are carried out to pirate a telechelic isobutylene-based polymer having an unsaturated group and to remove a component containing ⁇ in the formula (I). Single polymer method.
- R 1 represents an aromatic compound or a substituted or unsubstituted fatty acid.
- R 2 and R 3 are the same or different and each represents a hydrogen atom or a substituted or unsubstituted monovalent carbon. However, lipophilicity is not the same as elementary age, and R 2 and R 3 are not hydrogen atoms at the same time.
- X is a halogen atom, R 4 COO- group (R 4 is a hydrogen atom or, showing a ⁇ number 1-5 alkyl group) or R 5 0- group (R 5 is a hydrogen atom or Fuji Number 1 5 represents an alkyl group).
- w is an integer of 1 LL8 or less.
- the amount of GOH is represented by a small amount of GOH (G is a hydrogen atom or a monovalent carbon group).
- G is a hydrogen atom or a monovalent carbon group.
- the use of a compound as a marauder is a power, but specifically, for example, CH 3 OH, CH 3 CH 2 OH, (CH 3 ) 2 CH OH, and water of m »can be used.
- non-aqueous means that the player does not bow, and does not necessarily mean that he does not fluff water at all. If necessary, a very small amount of water may be added to facilitate the exchange of the ligands of the marauder.
- the number average molecular weight (Mn) of the isobutylene-based polymer is usually from 500 to 300,000, preferably from 1,000 to 50,000. When Mn is less than 500, the excellent properties of the isoptylene-based polymer are lost, and when it is more than 300,000, the polymer becomes solid and the properties are extremely deteriorated.
- the number-average ⁇ ? (Mn) and Mw / Mn values of the isobutylene-based polymer were determined by GPC using a polystyrene gel column [Showdex «Co., Ltd. Shodex K-804 mobile phase: Kuroguchi form]. It was determined from a polystyrene equivalent value.
- the ⁇ represented by the one ⁇ formula (I) can force it to noodles without particular limitation as long as it is a known metal complex as a Lewis acid, usually, TiC 1 4, SnC 14, A1C1 3, CH 3 CH 2 AICI 2, (CH 3 CH 2 ) 2 A 1 CI, VC 15, FeCls, BF 3, etc. are not limited to these.
- Preferred Lewis acids include TiCl 4 , SnC 14, and Al Cls.
- the Lewis acid is generally used in the range of 0.1 to 100 with respect to the cationically polymerizable monomer containing isobutylene, and the preferred amount of fffl is in the range of 1 to 30% by weight. If the conversion of the Lewis acid, which is a mist, is less than 0.1 dragon%, there is a problem in that the yield of cationic polymerization is reduced, and there is no merit in converting more than 100.
- the ⁇ Equation 5 is of ⁇ / As that represented by ([pi), the periodic table i a, n a, m b, or, if the having of ⁇ !
- a metal atom belonging to IV a group especially force Ku can force it to without limitation ", typically, NaOH, KOH, L i OH , Ca (OH) 2, NaHCOa, NaOCH 3, KOCH 3, L i OCH 3, Ca (OCH 3) 2, Mg (0CH 3 ) 2 , A1 (OCH 3 ) 3 , Ti (OCH 3 ) 4 , NaOCH 2 CH 3 , KOCH 2 CH 3 , Li OCH 2 CH 3 ,
- a 1 [OCH (CH 3 ) 2 ] 3 and the like are subjected to ⁇ ffl, and preferred examples include NaOCHs, KOCH 3 , NaOH, KOH, and NaOCH 2 CH 3 . Also, in the present invention, "the formula ⁇ / represented by the formula ( ⁇ ) is usually one
- the enzymatic exchange ⁇ SJS is usually carried out at normal pressure or reduced pressure at a temperature of 100 to 150 ° C for 1 to 600 minutes.
- the method of Lewis ⁇ after ligand exchange is preferably a method by filtration of the solid of the metal complex derived from bandits, and a method of distilling off the liquid from the liquid complex. It is not particularly limited to these methods, and any method is difficult.
- the adsorbent having an acid-adsorbing ability which is used for removing a marauder, contains at least one of an active material, titanium oxide, Mg, A 1 and Si or Si as ⁇ .
- ⁇ Compounds that have the power to flip ⁇ and so on ⁇ Si have the following properties: aluminum gayate (silica-alumina), molecular sieves (zeolite), silica gel, alumina gel, activated clay, etc.
- the adsorbent having an acid-adsorbing ability is usually used in a range of 0.2 to 300 times as long as that of the compound represented by the above-mentioned formula (I), but the preferred usage is 3 to 3 times.
- the range is 100 times.
- the cationic heavy monomer containing isobutylene is not limited to a monomer consisting of only isobutylene, but includes a monomer that can co-polymerize with isobutylene, and is preferably
- Examples of the cationic heavy monomer that can be copolymerized with isobutylene include, for example, olefins, gens, vinyl ethers, aromatic vinyl compounds m, norbornenes, and vinylsilanes represented by Formulas 3 to 12 below. Among these, carbon Numerical values 3 to 12 are preferred.
- cationic heavy monomer that can be copolymerized with isobutylene, specifically, propene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, Xene, cyclohexene, vinylcyclohexane, 5-ethylidene norbornene, 5-propylidene norbornene, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinyl carbazole, methoxy styrene , Ethoxystyrene, t-butoxystyrene, hexeninoleoxystyrene, styrene, -methynolestyrene, methstyrene, dimethynolestyrene, chloromethyl ⁇ 1 / styrene, chlorostyren
- the weight of the cationic heavy monomer containing notch isobutylene is generally 1 to 10 mol Z 1, preferably 0.5 to 6 mol Z 1.
- R 6 and R 7 are the same or different and represent a hydrogen atom or a monovalent carbon bk group having 1 to 20 mysteries.
- X is a halogen atom, R 4 C ⁇ group (R 4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) or R 5 ⁇ — group (RS is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) Represents).
- R 4 C ⁇ group R 4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- RS is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- B represents a substituted group of 4 to 40, and represents an unsubstituted carbon group.
- Z is a halogen atom bonded to the third atom, R 8 COO- group (R 8 represents a hydrogen atom or an alkyl group carbon number 1 5) or R 8 0- group (R 9 is a hydrogen atom or a C 1-5 Represents an anoalkyl group).
- m is 1-4 Wei. However, the present invention is not limited thereto. These compounds ⁇ ! May be used as ⁇ or 2 3 ⁇ 4Ri: may be used together.
- A which is a group having 1 to 4 aromatic rings in the formula ⁇ / represented by the formula (IV), may be formed by condensation traces or may be a non-condensed one.
- the group having an aromatic ring include benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, Ph— (CH 2 ) i-Ph (Ph is a phenyl group, 1 is 1 to 10 ⁇ ) and the like.
- These groups having an aromatic ring are ⁇ 1 to 20 and / or branched fatty acids such as a hydrogen group, a hydroxyl group, an ether group, and a vinyl group. It may be substituted with a group having a functional group.
- a compound having a functional group of Z such as a vinyl group or a silyl group can be subjected to ⁇ ffl.
- the oligomer include an oligomer of monochlorostyrene and an oligomer obtained by copolymerizing a monochlorostyrene with a monomer copolymerizable therewith.
- the "" ⁇ formula (m )) The halogen atom, R 4
- R 4 represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms
- R 5 0- group represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R 4 C OO- group or R 5 0- groups and of having other reactivity functional group ⁇ as initiator-transfer agents, ⁇ 3 ⁇ 4 to polymer functional I ⁇ It is very powerful because it can be high.
- the general formula (1) represented by the above formula (1) is usually, for example, specifically, for example,
- H 2 C CH-CH 2 CH 2 CH 2 CH 2 -X
- X is a halogen atom, R 4 CO O- group (R 4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) or R 50— group (R 5 is a hydrogen atom or a key number of 1 to 5 ) Or an alkyl group of 5)] or other monochlorostyrene oligomers, but is not limited thereto.
- R 4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R 50— group R 5 is a hydrogen atom or a key number of 1 to 5
- alkyl group of 5 or other monochlorostyrene oligomers, but is not limited thereto.
- the preferred ones among these are:
- H 2 C CH-CH 2 CH 2 CH 2 CH 2 — 0 — ⁇ -C- CI
- the amount of the compound represented by the formula ( ⁇ ) is usually in the range of 0.01 to 20% by weight of the thiothion polymerizable monomer containing isobutylene. It is in the range of 0.1 to 10fi *%.
- the isomer there are those having a donor number of 15 to 50, and known ones can be widely used.
- Preferred electrolytes include, for example, pyridines, amines, amides, and sulfoxides. The power is not limited to these.
- the electrolyte specifically, specifically, specifically, 2,6-di-tert-butylpyridine, 2-t-butynolepyridine, 2,4,6-trimethinolepyridine, 2,6-dimethyl pyridine, 2-methyl pyridine, pyridine, getylamine, trimethylamine, triethylamine, tributylamine, getylamine, N, N-dimethylaniline, N, N-dimethylformamide, N, N-dimethylase Toamide, N, N-Jetylacetamide, dimethyl sulfoxide, dimethyl ether, methyl, ethyl, trimethyl phosphate, hexamethyl phosphate triamide, etc.
- Di-t-butylpyridine, 2,6-dimethylpyridine, 2-methylpyridine, pyridine, getylamine, trimethylamine, triethylamine, N, N-dimethylformamide, N, N-dimethylacetamide, Dimethyl sulfoxide can be mentioned.
- the electric body ⁇ ⁇ is usually represented by a formula represented by the following formula (m).
- the solvent is, for example, halogen! ⁇ B7_ element, fat or aromatic substance must be used; ⁇ can be used, and as the halogenated carbon element, methyl chloride, methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane are usually used.
- examples of the fatty acid or the aromatic carbon include butane, pentane, neopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene, and the like.
- Examples of the mixed solvent include methylene chloride Z hexane, 1,2-dichloroethane Z hexane, 1-chloro propane Z hexane, 1-chlorobutane Z hexane, and 1-chloro mouth pentane Z hexane. You can ⁇ ffl various combinations. In the present invention, when the polymerization is difficult, there is no particular limitation and the polymerization method can be widely applied.
- ⁇ 1 cation heavy weight containing isobutylene ⁇ Monomer ⁇ 1 chemical formula ( ⁇ ) expressed by formula ( ⁇ )
- Lewis acid body transport
- diisobutylene-containing force-ion heavy ⁇
- Add ⁇ -Lewis acid-containing sickle to Nada containing monomer In the semi-batch method of adding the Lewis acid-containing separation medium and diisobutylene-containing force-ion weight 3 ⁇ 4 and the monomer-containing sickle in a fiber-like manner, the full-length ⁇ - It is also possible to use the fiber method in which the mark is made while the material is being added, and then the mark is removed.
- the age at which dehydrogenation of ⁇ is performed, together with the spirit ligand exchange ®S represented by the formula (I), is expressed by the formula (1).
- reduction represented, in particular able force used without limitation, as is preferred NaOH, KOH, L i OH , Ca (OH) 2, NaHCOa, NaOCH 3, KOCHs, L i OCH3, Ca (OCH 3 ) 2 , NaOCH 2 CH 3 ,
- KOC (CH 3) 3, L i OC (CH 3) 3, NaOC (CH 3) 2 CH 2 CH 3, A 1 [OCH (CH 3) 2] 3 a can be force Ku mentioned.
- HC 1 Sit is usually performed at 700 mmHg or less, but is preferably performed at 20 mmHg or less, more preferably at 1 rniHg or less.
- a method of isobutylene-based polymer having a telechelic non-functional group that converts NaOCH 3 or KOC (CH 3 ) 3 at normal pressure is already known, but the speed at normal pressure is actually However, there is a problem that it takes 20 to 30 hours to separate at a temperature of 100 ° C or less. [See US Patent No. 4316973 and JP-A-1-261405.
- the present invention is not limited to the ⁇ i example.
- isobutylene-based polymer is dissolved and filtered by suction using a filter paper for Kiriyama funnel (No. 4, retained particles 1 micron), and then the volatile matter is distilled off to obtain a colorless and transparent isobutylene-based polymer. 1 g was obtained. The results of the obtained polymer are shown in Table 1.
- a liquefied gas exhaust pipe made of a pressure-resistant glass with a needle valve containing 85.5 mL of isobutylene monomer was immersed in a three-way cock, and the polymerization vessel was placed in a dry ice Z ethanol bath at 75 ° C
- the inside of the container was spotted using a vacuum pump. After opening the needle vanolev and introducing the isobutylene monomer from the liquefied gas collecting tube into the polymerization vessel, the inside of the vessel was returned to normal pressure by introducing nitrogen from one of the three-way cocks.
- Titanium oxide l.oogm was weighed into a well-equipped conical flask with a file. 91.6 g (100 mL) of a mixture of methylene chloride Zn—hexane (volume ratio 4 Z 6) and the desired water were added thereto, and the mixture was stirred for 1 hour with. No. 4 paulownia slurry He performed a bow IM with Mr. Yama ⁇ ; and measured the water woven in the filtrate with a force-feeder-moisture meter.
- the moisture in the air, the moisture previously adsorbed on the titanium oxide, and the moisture in the mixed solvent were each subjected to empty fiber, and the moisture in the filtrate was determined by measuring the moisture from the measured values. .
- the results are as shown in Table 2. If the titanium oxide has a water content of up to 1.5 times its own weight, the filtrate will not be separated.
- Table 3 shows the GPC and NMR analysis values of the obtained polyisobutylene. Also shown are the results of atomic absorption of sodium in the polymer and of titanium by the ICP method.
- Table 4 shows the results of GPC and NMR analysis of polymer 2 and the results of sodium and titanium.
- the polymerization 1 at 70 ° C was put into 300 mL of water to deactivate.
- the aqueous phase was removed by decantation, and the organic phase was washed repeatedly with 300 mL of ion exchange until the electrical conductivity of the wastewater became constant. Three washings were required. 1200 mL of wastewater containing t ⁇ mouth ⁇ ⁇ containing methylene chloride and n-hexane was used.
- Polymerization 1 was placed in a bath at 45 ° C. and heated, and methylene chloride was distilled off. During the heating, salt was found to be generated. Extensive rot: occurred in the details of a metal container (material: SUS316L). When the distilling power remained, the inside was poured into 300 mL of water, and washing was repeated three more times.
- Titanium oxide Water addition amount Water / titanium oxide ratio Water in filtrate Filtrate (mg) Ung) (mol z mol)
- the filtrate is separated into ⁇ of the aqueous phase and the organic phase.
- Mn and MwZMn are the number averages calculated by GPC in terms of polystyrene, respectively: ⁇ quantity, good * ⁇ cloth, Fn (v) is the number of vinyl groups per unit obtained by combining the results of GPC and NMR. Indicates a number.
- the stirrer chip and the adsorbent were placed in an Erlenmeyer flask, and nitrogen was replaced. After 100 mL of methylene chloride was added to disperse the adsorbent, titanium tetrachloride was added with a crane syringe and stirred at room temperature for 1 hour. 30 mL of each sickle was withdrawn and transferred to a separating funnel, and washed three times with ion exchange of the same sickle. All the waste liquids after the washing were added, and the dish was made up to 100 mL with ion exchange. The ⁇ of this wastewater was measured using a ⁇ meter using ⁇ JE in advance. The results are shown in Table 7, indicating that starvation and the ability to adsorb aluminum silicate were high.
- Adsorbent amount (g) Titanium tetrachloride amount (g) Wastewater pH
- Mn and MwZMn represent the number-average liver volume and molecular weight distribution obtained by GPC, respectively, and Fn (iso) and Fn (inn) represent the isopropenyl group and 2-methyl-1-one, respectively.
- the number of propionyl groups, DCM indicates the amount of methylene chloride in wastewater.
- Example 7 The same operation as in Example 7 was performed, except that 0.1 g, 0.5 g, and 2.6 g of aluminum were used instead of the activity, to obtain an isobutylene-based polymer. The results obtained are not shown in Table 9.
- Example 10 Using an adsorbent, the same operation as in Example 7 was performed to obtain an isoptylene-based polymer. Table 10 shows the obtained results.
- Adsorbent amount (g) Mn Mw / Mn Fn (iso) Fn (inn) DCM
- the cold methanol method shown in Table 11 is a practical simple method, and produces a mixed solvent which has the least amount of by-products and is difficult to purify because of the ability to obtain a sample. It is strongly known that the polymer end of the heavy ⁇ 3 of this system is the third substituent monochlorine bond, and that Fn (iso) and Fn (inn) in Table 11 are each 0 means that Indicates that no conversion has occurred. In the method without using the adsorbent shown in Table 10, it can be seen that the liver * ⁇ cloth becomes large at the same time as the isomerization of and the undesired side is generated.
- halide such as methylene chloride as a polymerization solvent for the isobutylene-based monomer, but do not discharge ice in which the halide is dissolved.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/704,607 US5739267A (en) | 1994-03-18 | 1995-03-17 | Process for isolation of isobutylene polymer |
CA002184999A CA2184999A1 (en) | 1994-03-18 | 1995-03-17 | Method of isolating isobutylene polymer |
DE69525615T DE69525615D1 (de) | 1994-03-18 | 1995-03-17 | Verfahren zur isolation eines isobutylenpolymers |
EP95912465A EP0752429B1 (en) | 1994-03-18 | 1995-03-17 | Method of isolating isobutylene polymer |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7288394 | 1994-03-18 | ||
JP6/72883 | 1994-03-18 | ||
JP6/179669 | 1994-07-08 | ||
JP6/179668 | 1994-07-08 | ||
JP17966994 | 1994-07-08 | ||
JP17966894 | 1994-07-08 |
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WO1995025754A1 true WO1995025754A1 (fr) | 1995-09-28 |
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PCT/JP1995/000486 WO1995025754A1 (fr) | 1994-03-18 | 1995-03-17 | Procede d'isolement d'un polymere d'isobutylene |
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US (1) | US5739267A (ja) |
EP (1) | EP0752429B1 (ja) |
CA (1) | CA2184999A1 (ja) |
DE (1) | DE69525615D1 (ja) |
WO (1) | WO1995025754A1 (ja) |
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JPS63205305A (ja) * | 1987-02-20 | 1988-08-24 | Kanegafuchi Chem Ind Co Ltd | 官能性末端を有するイソブチレン系ポリマ−の製造方法 |
JPH0420511A (ja) * | 1989-12-23 | 1992-01-24 | Basf Ag | イソブテンポリマーの精製法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2893981A (en) * | 1954-06-29 | 1959-07-07 | Exxon Research Engineering Co | Recovering olefin polymers |
US2786828A (en) * | 1955-12-27 | 1957-03-26 | Exxon Research Engineering Co | Neutralization of friedel-crafts catalyst |
US4197398A (en) * | 1974-12-04 | 1980-04-08 | Exxon Research & Engineering Co. | Process for neutralizing and deashing polypropylene |
US4342849A (en) * | 1979-09-10 | 1982-08-03 | The University Of Akron | Novel telechelic polymers and processes for the preparation thereof |
JPS59157035A (ja) * | 1983-02-28 | 1984-09-06 | Kyowa Chem Ind Co Ltd | ハロゲン含有触媒を含む有機化合物中のハロゲン成分除去方法 |
DE3336355A1 (de) * | 1983-10-06 | 1985-04-18 | Basf Ag, 6700 Ludwigshafen | Verfahren zur qualitaetsverbesserung von polymerisaten des isobutens |
US4758631A (en) * | 1986-10-16 | 1988-07-19 | Dow Corning Corporation | Method of preparing allyl-terminated polyisobutylene |
JPH0651752B2 (ja) * | 1987-02-20 | 1994-07-06 | 鐘淵化学工業株式会社 | 官能性末端を有するイソブチレン系ポリマ−の製造法 |
JP2618430B2 (ja) * | 1988-04-11 | 1997-06-11 | 鐘淵化学工業株式会社 | イソプロペニル基を有するイソブチレン系ポリマーの製法 |
JPH0759601B2 (ja) * | 1989-05-08 | 1995-06-28 | 日本ゼオン株式会社 | 重合体の製造方法 |
IT1244724B (it) * | 1991-02-11 | 1994-08-08 | Enimont Anic Srl | Procedimento per la preparazione di resine idrocarburiche incolori e prodotti da esso risultanti |
-
1995
- 1995-03-17 WO PCT/JP1995/000486 patent/WO1995025754A1/ja active IP Right Grant
- 1995-03-17 DE DE69525615T patent/DE69525615D1/de not_active Expired - Lifetime
- 1995-03-17 CA CA002184999A patent/CA2184999A1/en not_active Abandoned
- 1995-03-17 US US08/704,607 patent/US5739267A/en not_active Expired - Fee Related
- 1995-03-17 EP EP95912465A patent/EP0752429B1/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63205305A (ja) * | 1987-02-20 | 1988-08-24 | Kanegafuchi Chem Ind Co Ltd | 官能性末端を有するイソブチレン系ポリマ−の製造方法 |
JPH0420511A (ja) * | 1989-12-23 | 1992-01-24 | Basf Ag | イソブテンポリマーの精製法 |
Non-Patent Citations (1)
Title |
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See also references of EP0752429A4 * |
Also Published As
Publication number | Publication date |
---|---|
US5739267A (en) | 1998-04-14 |
CA2184999A1 (en) | 1995-09-28 |
EP0752429A1 (en) | 1997-01-08 |
EP0752429B1 (en) | 2002-02-27 |
EP0752429A4 (en) | 1998-03-18 |
DE69525615D1 (de) | 2002-04-04 |
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