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1. 发明专利

JPH1053647A POLYMERIZATION OF CYCLIC ETHER 失效
公开(公告)号：JPH1053647A
公开(公告)日：1998-02-24
申请号：JP11951997
申请日：1997-05-09
申请人： MITSUBISHI CHEM CORP
发明人： SETOYAMA TORU , KAHATA YOSHIO , KOBAYASHI MITSUHARU
IPC分类号： C08G65/20 , C08G65/26
摘要： PROBLEM TO BE SOLVED: To provide a method for industrially advantageously polymerizing a cyclic ether, capable of suppressing deterioration of a polymerization catalyst with the passage of time by carrying out ring opening polymerization while reducing water content concentration in a polymerization reaction system. SOLUTION: When (A) a cyclic ether (preferably tetrahydrofuran) is subjected to ring opening polymerization reaction in the presence of (B) a carboxylic acid anhydride (preferably acetic anhydride) by using (C) a solid acid catalyst to provide a polymer in which a part or all of ends of a polymer is esterified, the polymerization reaction is carried out while keeping concentration of water in the reaction system to =0.001mmol/g ion exchange acid amount and the component C and not substantially having polymerization activity to the component A is preferably used as the hydrolysis catalyst.

2. 发明专利

JP2001302786A METHOD FOR POLYMERIZING CYCLIC ETHER 失效
公开(公告)号：JP2001302786A
公开(公告)日：2001-10-31
申请号：JP2000125539
申请日：2000-04-26
申请人： MITSUBISHI CHEM CORP
发明人： KAHATA YOSHIO
IPC分类号： C08G65/28
摘要： PROBLEM TO BE SOLVED: To provide a method for manufacturing a polyoxyalkylene polyol containing only a little amount of a high molecular-weight polymer and having a narrow molecular weight distribution represented by Mw/Mn. SOLUTION: A cyclic ether is subjected to liquid-phase polymerization in the presence of a solid acid catalyst and water and/or a polyhydric alcohol at a temperature higher than the boiling point of the ether.

3. 发明专利

JPH10158386A POLYMERIZATION OF CYCLIC ETHER 失效
公开(公告)号：JPH10158386A
公开(公告)日：1998-06-16
申请号：JP31985896
申请日：1996-11-29
申请人： MITSUBISHI CHEM CORP
发明人： SETOYAMA TORU , KAHATA YOSHIO , KOBAYASHI MITSUHARU
IPC分类号： C07C67/24 , C08G65/20 , C08G65/32 , C08G65/332
摘要： PROBLEM TO BE SOLVED: To industrially advantageously subject a cyclic ether to a ring-opening polymerization to obtain a polyalkylene glycol ester having a low molecular weight and a narrow molecular weight distribution with slight deterioration of a catalyst by performing the ring-opening polymerization in the presence of a protonic acid dissolved, in the reaction system. SOLUTION: (A) A cyclic ether is subjected to a ring-opening polymerization by using (B) a solid acidic polymerization catalyst (e.g. a catalyst obtained by baking an oxide of Ge, Sn, Al, Cu, W, Zr, Y, Si, etc., at 600-1,100 deg.C) in the presence of (C) a carboxylic acid anhydride. In the reaction, (D) a protonic acid such as a carboxylic acid (concretely acetic acid, etc.) in an amount satisfying a molar ratio to the component C of (1/16) to (1/30,000) is dissolved to be present in the reaction system. By the process, it is considered that the component D is predominantly adsorbed to the component B more than to water and the lowering of the polymerization activity can be prevented even in the presence of several 100ppm of water.

4. 发明专利

JPH07228684A PRODUCTION OF POLYOXYALKYELNE GLYCOL AND NEW METALLOALUMINOSILICATE 失效
公开(公告)号：JPH07228684A
公开(公告)日：1995-08-29
申请号：JP4413494
申请日：1994-03-15
申请人： MITSUBISHI CHEM CORP
发明人： HATANO MASAKATSU , NAKANISHI AKIO , KAHATA YOSHIO , KOBAYASHI MITSUHARU , SHIRATO MASAYUKI , TAKEO HIROSHI
IPC分类号： C08G65/20 , C08G65/02
摘要： PURPOSE:To provide a method for producing PTMG industrially and extremely advantageously, capable of obtaining especially middle molecular weight PTMG having a narrow molecular weight distribution of PTMG in high yield, readily recovering a catalyst in a batch reaction form and easily regenerating the catalyst in a circulation reaction method. CONSTITUTION:In a method for producing a polyoxyalkyelne glycol by ringopening polymerization of a cyclic ether, the characteristic of the method is to use a zeolite (except ZSM-5, ZSM-11 and Nu-5) as a catalyst. Tetrahydrofuran is especially used as the cyclic ether and is subjected to ring opening polymerization to provide the objective method for producing a polytetramethylene ether glycol. A new metalloaluminosilicate has a zeolite beta skeleton and comprises aluminum and/or silicon in the skeleton which is substituted in the same shape with at least one kind of metal selected from chromium, boron, lead, tin, copper, indium, cobalt, nickel, zinc, vanadium, molybdenum, arsenic, antimony, manganese, germanium, silver, lanthanide, cadmium, magnesium, cerium and phosphorus.

5. 发明专利

JP2000327770A PRODUCTION OF POLYOXYALKYLENE GLYCOL OR ITS ESTER 失效
公开(公告)号：JP2000327770A
公开(公告)日：2000-11-28
申请号：JP14463099
申请日：1999-05-25
申请人： MITSUBISHI CHEM CORP
发明人： SETOYAMA TORU , KAHATA YOSHIO , KOBAYASHI MITSUHARU
IPC分类号： C08G65/20
摘要： PROBLEM TO BE SOLVED: To provide a method for the industrially advantageous and efficient ring-opening polymerization of a cyclic ether in the presence of a catalyst capable of conveniently being separated. SOLUTION: When producing a polyoxyalkylene glycol or its ester by the ring-opening polymerization of a cyclic ether in the presence of or in the absence of a carboxylic anhydride, the following solid acid is used as a catalyst: an oxide carrier supports a compound containing at least one element which is selected from the group consisting of group 3-14 metal or semimetal and is different from elements contained in the carrier and; the oxide carrier features containing sodium metal in a concentration of

6. 发明专利

JPH09241374A CATALYST, ITS PRODUCTION AND PROCESS FOR POLYMERIZING CYCLIC ETHER BY USING THIS CATALYST 失效
公开(公告)号：JPH09241374A
公开(公告)日：1997-09-16
申请号：JP4776396
申请日：1996-03-05
申请人： MITSUBISHI CHEM CORP
发明人： SETOYAMA TORU , KAHATA YOSHIO , KOBAYASHI MITSUHARU
IPC分类号： C08G65/10 , C08G65/02
摘要： PROBLEM TO BE SOLVED: To provide a novel catalyst which can give a low-molecular-weight (especially, a number-average molecular weight (Mn) of 700-3,000) polymer when used in producing a polyoxyalkylene glycol ether (e.g. polytetramethylene ether glycol) by polymerizing a cyclic ether (e.g. tetrahydrofuran), a process for producing the same, and a process for polymerizing a cyclic ether by using the same. SOLUTION: This catalyst is used to polymerize a cyclic ether and is prepared by impregnating a metallosilicate zeolite having an Si/M ratio of 10 or greater (wherein Si is the content of Si atoms in the metallosilicate zeolite; and M is the total amount of the intralattice metallic component except Si atoms) with an oxide of at least one element selected from among Ge, Sn, Pb, B, Al, Ga, Zn, Cd, Cu, Fe, Mn, Ni, Cr, Mo, W, Ti, Zr, Hf, Y, La, Ce, Yb, Zn and Si. Also provided are a process for producing this catalyst and a process for polymerizing a cyclic ether in the presence of a carboxylic anhydride and/or a carboxylic acid with the aid of the catalyst.

7. 发明专利

JP2001302784A METHOD FOR POLYMERIZING CYCLIC ETHER 失效
公开(公告)号：JP2001302784A
公开(公告)日：2001-10-31
申请号：JP2000125538
申请日：2000-04-26
申请人： MITSUBISHI CHEM CORP
发明人： KAHATA YOSHIO
IPC分类号： C08G65/10
摘要： PROBLEM TO BE SOLVED: To provide a method for manufacturing a polyoxyalkylene polyol having a narrow molecular weight distribution and, at the same time, a reduced content of high molecular weight substances by polymerizing a cyclic ether. SOLUTION: The cyclic ether is polymerized in the presence of a water vapor-treated zeolite catalyst and water/or a polyhydric alcohol.

8. 发明专利

JPH0994464A METHOD FOR CARRYING METAL HYDROXIDE AND/OR OXIDE ON CARRIER 失效
公开(公告)号：JPH0994464A
公开(公告)日：1997-04-08
申请号：JP25246095
申请日：1995-09-29
申请人： MITSUBISHI CHEM CORP
发明人： KUSAKA HARUHIKO , KOBAYASHI MITSUHARU , KAHATA YOSHIO , ENDOU HIROYOSHI , SETOYAMA TORU
IPC分类号： B01J37/02 , B01J37/08 , B01J37/16
摘要： PROBLEM TO BE SOLVED: To produce a compsn. having a hydroxide or oxide carried as very fine crystallite on a carrier and useful as an acid-base catalyst or catalyst carrier. SOLUTION: A metallic salt or metal alkoxide is carried on a carrier, a basic gas is brought into contact with the metallic salt or metal alkoxide in the state of a solid phase and the metallic salt or metal alkoxide is converted into its corresponding hydroxide or oxide by hydrolysis.

9. 发明专利

JPH08231706A PRODUCTION OF POLYOXYALKYLENE GLYCOL OR ITS ESTER 失效
公开(公告)号：JPH08231706A
公开(公告)日：1996-09-10
申请号：JP3681295
申请日：1995-02-24
申请人： MITSUBISHI CHEM CORP
发明人： SETOYAMA TORU , KAHATA YOSHIO , KOBAYASHI MITSUHARU , HATANO MASAKATSU
IPC分类号： C08G65/20 , C08G65/02
摘要： PURPOSE: To produce a polymer (e.g. polyoxytetramethylene glycol) having a medium molecular weight and a narrow molecular-weight distribution and useful, as an industrial material by ring-opening polymerization of tetrahydrofuran, etc. CONSTITUTION: A polyoxytetraalkylene glycol or its ester is produced by subjecting a cyclic ether to ring-opening polymerization in the presence or absence of a carboxylic acid anhydride. A solid-acid catalyst of a multiple oxide containing an element selected from elements of the group (a) and those of the group (b) is used as a catalyst of the ring opening polymerization. The elements of the group (a): Ge, Sn, Pb, B, Ga, In, Cd, Cu, Fe, Mn, Ni, Cr, Mo, Co, Ta, Hf, Y, La, Nb and Ce. The elements of the group (b): Si, Al, Zr, Ti and Zn. Since the catalyst is a solid-acid catalyst, the catalyst phase, an unreacted raw material phase and a produced polymer are easily separated from each other. Further, the catalyst can be easily regenerated. Furthermore, since the acidity of the catalyst is not extremely strong, the reaction apparatus is dispensing with the use of an expensive material.

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