US20010047073A1 - Process for the preparation of polycarbonate diols with a high molecular weight - Google Patents
Process for the preparation of polycarbonate diols with a high molecular weight Download PDFInfo
- Publication number
- US20010047073A1 US20010047073A1 US09/797,593 US79759301A US2001047073A1 US 20010047073 A1 US20010047073 A1 US 20010047073A1 US 79759301 A US79759301 A US 79759301A US 2001047073 A1 US2001047073 A1 US 2001047073A1
- Authority
- US
- United States
- Prior art keywords
- process according
- ranging
- carbonate
- diol
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
Definitions
- the present invention relates to a process for the preparation of polycarbonate diols (PCD) with a high molecular weight comprising two subsequent reaction steps wherein in the first step PCD with a molecular weight ranging from 500 to 2000, is synthesized and in the second step the molecular weight of the PCD is increased to the desired value.
- PCD polycarbonate diols
- Polycarbonate diols are a group of oligomeric polyols which are used in the synthesis of prepolymers with an isocyanate functionality useful in the production of thermoelastomeric polyurethanes which are used for the preparation of paints, adhesives and seals.
- PCD with a high molecular weight i.e. higher than 2000
- PCD with a high molecular weight can be used in formulations for the production of polyurethane adhesives of the reactive hot-melt type (HMR moisture curing), as well as in polymerization processes in emulsion, as for example in the production of synthetic leather, where they increase the coagulation rate of the polyurethane obtained with a consequent improvement in the tear strength.
- a second method is based on the use of aromatic carbonates (U.S. Pat. No. 3,544,524) whose considerable reactivity allows the transesterification reaction to be carried out without catalysts. This process produces PCD with a high molecular weight and with a correct hydroxyl functionality.
- Another method comprises the use of phosgene (U.S. Pat. No. 4,533,729), a toxic chemical reagent which can be synthesized and used only in appropriate industrial areas.
- phosgene U.S. Pat. No. 4,533,729
- the high acidity moreover, jeopardizes the quality of the PCD obtained, necessitating the use of acid receptors to control it.
- an objective of the present invention relates to a process for the production of polycarbonate diols with a molecular weight higher than 2000 having general formula (I)
- n is an integer or decimal ranging from 5 to 40 and R′ is a bivalent alkylene radical deriving from a diol by the loss of two hydroxyls, said process comprising:
- n′ is an integer or decimal ⁇ n and ranging from 2 to 20 and R′ has the meaning defined above, by reacting an alkyl carbonate having formula (III)
- R′ is a C 1 -C 4 alkyl radical with a linear or branched chain, with an aliphatic diol having formula (IV)
- R′ has the meaning defined above, in the presence of a transesterification catalyst, eliminating the alcohol from the reaction mixture;
- the diol (IV) and the carbonate (III) are used in a molar ratio ranging from 2/1 to 1.05/1, preferably from 1.2/1 to 1.07/1.
- R′ is selected from:
- d is a number which can vary from 2 to 4, x can vary from 1 to 25 and R can be H and/or CH 3 .
- R′ radicals are those deriving from the following dials: 1,6-hexanediol (HD), 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,5-pentanediol, 1,4-bis(hydroxymethyl-cyclohexane), diethyleneglycol (DEG), triethylene glycol (TEG), polyethyleneglycol (PEG/Mn 200-400), dipropylene glycol (DPG), poly-propylene glycol (PPG/Mn 200-400), polytetramethyleneglycol (PTMEG/Mn 250), the dial deriving from the condensation of caprolactone with 1,6-hexanediol. 1,6-hexanediol is preferred.
- R radicals are those deriving from the following carbonates: dimethyl carbonate (DMDC), diethyl carbonate (DEC), dipropyl carbonate (dnpc), diisopropyl carbonate (dipc), dibutylcarbonate (dnbc), diisobutylcarbonate (dibc). Dimethyl carbonate is preferred.
- Transesterification catalysts suitable for the purpose generally consist of organometallic compounds based on metals of group IV B in the tetravalent state such as titanium, zirconium and tin. Compounds of titanium and tin are preferred.
- titanium compounds are tetra alcoholates of ethyl, propyl, isopropyl, butyl, iso-octyl and phenyl.
- tin compounds are dibutyl tin di-laurate, dibutyl tin octoate and tin oxalate.
- the quantity of catalyst used referring to the metal which forms the active center, generally ranges from 1 to 1000 mg/kg of diol, preferably from 5 to 100 mg/kg.
- the reaction is carried out at a temperature ranging from 150 to 200° C. and under boiling conditions at the operating pressure, the alcohol R—OH co-produced by the transesterification being removed as it is formed.
- Temperatures lower than the first limit indicated can be used but are not advantageous as the reaction rate is too low, whereas temperatures higher than the second limit favour secondary reactions such as the formation of ether bridges by the decarboxylation of the carbonate bridges in the polymeric chain, or, in relation to the structure of the monomeric diol, the elimination of cyclic ethers deriving from the same monomeric diol.
- the pressure at which the reaction is carried out depends on the vapor pressure of the reaction mixture at the temperature indicated for the reaction and, in any case, is such as to allow the removal by boiling of the alcohol co-produced by the transesterification.
- DMC is used, the methanol is removed in the form of an azeotropic mixture with the carbonate itself.
- an additional quantity of DMC equal to that removed by distillation with the methanol, is added to the quantity of DMC put into the reaction with the purpose of reacting with the diol.
- the pressure adopted when DMC is used generally ranges from 1 to 5 bars.
- the reaction is carried out for such times as to effect the complete conversion of the dialkyl carbonate and generally ranging from 1 to 12 hours.
- the transesterification reaction can be carried out batchwise or in semi-continuous, i.e. by progressively feeding the dialkyl carbonate to the reactor under regime conditions, as it is used up by the reaction. This operating procedure allows the reaction to be carried out at a lower pressure than that required by the operation effected batchwise.
- This second phase of step a) is carried out within a period of time ranging from 1 to 20 hours, preferably from 3 to 10 hours.
- PCD (II) is obtained with a hydroxide functionality equal to 2 and whose molecular weight is a function of the diol/di-alkyl carbonate ratio used.
- the reaction can be carried out in a reactor equipped with a rectification column for the removal of the ROH alcohol co-produced.
- a rectification column for the removal of the ROH alcohol co-produced.
- n>n′ and c ⁇ a; R′ has the meaning defined above and Ar is an aromatic radical selected from those deriving from the following carbonates: diphenylcarbonate (DPC), dinitrophenylcarbonate and dichlorophenylcarbonate. Diphenyl carbonate is preferred.
- a molar ratio between PCD (II) and diaryl carbonate ranging from 1.1/1 and 6/1 is used, at a temperature ranging from 120 to 150° C., preferably from 130 to 140° C.
- the reaction is carried out batchwise by feeding the aryl carbonate to the PCD (II) mass pre-charged into the reactor maintained under stirring and then brought to the pre-selected temperature conditions.
- the operating pressure is not particularly critical, as boiling conditions are not adopted and is preferably atmospheric pressure.
- reaction times are such as to obtain the complete conversion of the aryl carbonate and, however, generally range from 1 to 10 hours, typically from 2 to 4 hours.
- the transesterification is completed in a period of time ranging from 1 to 20 hours, preferably from 3 to 10 hours, to obtain PCD (I) with a hydroxide functionality equal to 2 and whose molecular weight, which is in relation to the PCD(II)/aryl carbonate ratio used, is higher than 2000, generally ranging from 2500 to 5000.
- the process of the present invention allows PCD (I) to be obtained with a high molecular weight optimizing the space yield of the reactor and economy of the transesterification process.
- the flask is heated to an internal temperature of 190° C. at atmospheric pressure and 1372 g (15.24 moles) of dimethyl carbonate are then gradually fed through the drip funnel.
- a total aliquot of DMC is fed which is such as to make the reaction mixture, maintained at 190° C., boil, the column being kept at total reflux until the temperature at the head of the column is equal to 65° C., corresponding to that of the azeotropic mixture of methanol/DMC (70/30 by weight) at atmospheric pressure.
- the final part of the reaction is carried out by progressively reducing the pressure to 25 mbars and maintaining the synthesis temperature at 195° C. In this way the transformation of the residual alkylcarbonic terminations is completed, by stripping the methanol generated from the reaction mixture.
- 2000 g of PCD are obtained with a number average molecular weight Mn equal to 1000.
- step A) The equipment used in step A) is used, excluding the rectification column and directly connecting the reaction flask to a condenser conditioned at 42° C.
- step A) The mixture coming from step A) is cooled to 135° C. and, maintaining it under stirring at atmospheric pressure, 283 g (1.32 moles) of diphenylcarbonate (DPC) melted at 81° C. are fed. The resulting mixture is kept under these conditions for at least 2 hours to obtain the complete conversion of the DPC. The phenol formed is then removed, by slowly reducing the pressure of the system to a minimum value of 25 mbars.
- DPC diphenylcarbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
- The present invention relates to a process for the preparation of polycarbonate diols (PCD) with a high molecular weight comprising two subsequent reaction steps wherein in the first step PCD with a molecular weight ranging from 500 to 2000, is synthesized and in the second step the molecular weight of the PCD is increased to the desired value.
- Polycarbonate diols are a group of oligomeric polyols which are used in the synthesis of prepolymers with an isocyanate functionality useful in the production of thermoelastomeric polyurethanes which are used for the preparation of paints, adhesives and seals.
- In particular, PCD with a high molecular weight, i.e. higher than 2000, can be used in formulations for the production of polyurethane adhesives of the reactive hot-melt type (HMR moisture curing), as well as in polymerization processes in emulsion, as for example in the production of synthetic leather, where they increase the coagulation rate of the polyurethane obtained with a consequent improvement in the tear strength.
- The preparation of polycarbonate diols by the carbonylation of an aliphatic glycol with a carbonylating agent, optionally in the presence of suitable catalysts, is known in the art.
- For example patents U.S. Pat. No. 2,789,964 and U.S. Pat. No. 3,000,849 describe the use of alkyl carbonates as carbonylating agents. Operating according to these processes, however, it is difficult to obtain PCD with a correct hydroxyl functionality. The problem is particularly significant in the case of the synthesis of PCD with a high molecular weight, for example higher than 2000 (referring to the number average).
- A second method is based on the use of aromatic carbonates (U.S. Pat. No. 3,544,524) whose considerable reactivity allows the transesterification reaction to be carried out without catalysts. This process produces PCD with a high molecular weight and with a correct hydroxyl functionality.
- The high molecular mass of the aromatic carbonate used as carbonylating agent, however, reduces the space yield of reactors and implies the production of a stream of phenol distillate whose entity makes the process of little economic interest.
- Another method comprises the use of phosgene (U.S. Pat. No. 4,533,729), a toxic chemical reagent which can be synthesized and used only in appropriate industrial areas. The high acidity, moreover, jeopardizes the quality of the PCD obtained, necessitating the use of acid receptors to control it.
- A simple and economic process has now been found for the preparation of polycarbonate diols with a high molecular weight and with a correct hydroxyl functionality which overcomes the drawbacks of the known art described above.
- In accordance with this, an objective of the present invention relates to a process for the production of polycarbonate diols with a molecular weight higher than 2000 having general formula (I)
- HO—R′—[OCOOR′]n—OH (I)
- wherein: n is an integer or decimal ranging from 5 to 40 and R′ is a bivalent alkylene radical deriving from a diol by the loss of two hydroxyls, said process comprising:
- (a) a first reaction step wherein a polycarbonate diol is prepared with a molecular weight ranging from 500 to 2000, having general formula (II)
- HO—R′—[OCOOR′]n—OH (II)
- wherein n′ is an integer or decimal <n and ranging from 2 to 20 and R′ has the meaning defined above, by reacting an alkyl carbonate having formula (III)
- RO—CO—OR (III)
- wherein R′ is a C1-C4 alkyl radical with a linear or branched chain, with an aliphatic diol having formula (IV)
- HO—R′—OH (IV)
- wherein R′ has the meaning defined above, in the presence of a transesterification catalyst, eliminating the alcohol from the reaction mixture; and
- (b) a second step wherein the mixture containing the compound having formula (II) obtained in the first step is reacted with an aryl carbonate ArO—CO—OAr (V).
- Step a
- In this step the diol (IV) and the carbonate (III) are reacted, in the presence of a transesterification catalyst, according to the following scheme (i)
- n′RO—CO—OR+(n′+1) HO—R′—OH
- HO—R′—[OCOOR′]n′—OH+2n′R—OH (i)
- wherein R, R′ and n′ have the meaning defined above.
- The diol (IV) and the carbonate (III) are used in a molar ratio ranging from 2/1 to 1.05/1, preferably from 1.2/1 to 1.07/1.
- In the compounds have formula (I), R′ is selected from:
- 1. linear or branched alkylene radicals or cycloalkylene radicals containing from 3 to 14 carbon atoms; said radicals may optionally have one or more substituents which do not interfere with the transesterification reaction.
- 2. bivalent radicals deriving from polyether dials having formula (V):
- HO—[(CHR)d—O]x—H (V)
- wherein: d is a number which can vary from 2 to 4, x can vary from 1 to 25 and R can be H and/or CH3.
- 3. bivalent radicals deriving from polyester diols having formula (VI)
- HO—[(CHR″)f—COO—(CH2)g—O]y—H (VI)
- deriving from the condensation of a lactone with a linear aliphatic dial and wherein f is a number ranging from 3 to 6, g is a number ranging from 3 to 14, y is a number ranging from 1 to 10 and R″ can be H and/or CH3.
- 4. a mixture of two or more bivalent radicals selected from those listed under points 1-3.
- Examples of R′ radicals are those deriving from the following dials: 1,6-hexanediol (HD), 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,5-pentanediol, 1,4-bis(hydroxymethyl-cyclohexane), diethyleneglycol (DEG), triethylene glycol (TEG), polyethyleneglycol (PEG/Mn 200-400), dipropylene glycol (DPG), poly-propylene glycol (PPG/Mn 200-400), polytetramethyleneglycol (PTMEG/Mn 250), the dial deriving from the condensation of caprolactone with 1,6-hexanediol. 1,6-hexanediol is preferred.
- Examples of R radicals are those deriving from the following carbonates: dimethyl carbonate (DMDC), diethyl carbonate (DEC), dipropyl carbonate (dnpc), diisopropyl carbonate (dipc), dibutylcarbonate (dnbc), diisobutylcarbonate (dibc). Dimethyl carbonate is preferred.
- Transesterification catalysts suitable for the purpose generally consist of organometallic compounds based on metals of group IV B in the tetravalent state such as titanium, zirconium and tin. Compounds of titanium and tin are preferred.
- Examples of titanium compounds are tetra alcoholates of ethyl, propyl, isopropyl, butyl, iso-octyl and phenyl.
- Examples of tin compounds are dibutyl tin di-laurate, dibutyl tin octoate and tin oxalate.
- The quantity of catalyst used, referring to the metal which forms the active center, generally ranges from 1 to 1000 mg/kg of diol, preferably from 5 to 100 mg/kg.
- The reaction is carried out at a temperature ranging from 150 to 200° C. and under boiling conditions at the operating pressure, the alcohol R—OH co-produced by the transesterification being removed as it is formed.
- Temperatures lower than the first limit indicated can be used but are not advantageous as the reaction rate is too low, whereas temperatures higher than the second limit favour secondary reactions such as the formation of ether bridges by the decarboxylation of the carbonate bridges in the polymeric chain, or, in relation to the structure of the monomeric diol, the elimination of cyclic ethers deriving from the same monomeric diol.
- Temperatures ranging from 180 to 195° C. are preferably used.
- The pressure at which the reaction is carried out depends on the vapor pressure of the reaction mixture at the temperature indicated for the reaction and, in any case, is such as to allow the removal by boiling of the alcohol co-produced by the transesterification.
- If DMC is used, the methanol is removed in the form of an azeotropic mixture with the carbonate itself. In this case, an additional quantity of DMC equal to that removed by distillation with the methanol, is added to the quantity of DMC put into the reaction with the purpose of reacting with the diol.
- The pressure adopted when DMC is used generally ranges from 1 to 5 bars.
- The reaction is carried out for such times as to effect the complete conversion of the dialkyl carbonate and generally ranging from 1 to 12 hours.
- The transesterification reaction can be carried out batchwise or in semi-continuous, i.e. by progressively feeding the dialkyl carbonate to the reactor under regime conditions, as it is used up by the reaction. This operating procedure allows the reaction to be carried out at a lower pressure than that required by the operation effected batchwise.
- Subsequently, by maintaining the synthesis temperature within the pre-selected values and progressively reducing the pressure of the system to a value ranging from 1 to 200 mbars, preferably from 10 to 100 mbars, the conversion of the residual alkylcarbonic terminations in the PCD (II) is made quantitative by their reaction with the hydroxide terminations with a consequent further release of the alcohol produced in accordance with the following reaction (ii):
- R—[OCOO—R′]s—OH+HO—R′—[OCOO—R′]t—OH
- HO—R′[OCOO-R′](s+t)—OH+R—OH
- wherein: (s+t)=n in formula (II) and R and R′ have the meaning defined above.
- This second phase of step a) is carried out within a period of time ranging from 1 to 20 hours, preferably from 3 to 10 hours. In this way PCD (II) is obtained with a hydroxide functionality equal to 2 and whose molecular weight is a function of the diol/di-alkyl carbonate ratio used.
- The reaction can be carried out in a reactor equipped with a rectification column for the removal of the ROH alcohol co-produced. During the second phase it is preferable to exclude the column and directly connect the reactor to a condenser situated downstream of the column, where there is a vacuum regulation system.
- Step b)
- The reaction mixture coming from the first step, which contains PCD (II) and the catalyst, is reacted with the aryl carbonate (V) according to the following scheme (iii):
- a HO—R′—[OCOOR′]n′—OH+b ArO—CO—OAr
- c HO—R′—[OCOOR′]n —OH+2b ArOH
- wherein: n>n′ and c<a; R′ has the meaning defined above and Ar is an aromatic radical selected from those deriving from the following carbonates: diphenylcarbonate (DPC), dinitrophenylcarbonate and dichlorophenylcarbonate. Diphenyl carbonate is preferred.
- A molar ratio between PCD (II) and diaryl carbonate ranging from 1.1/1 and 6/1 is used, at a temperature ranging from 120 to 150° C., preferably from 130 to 140° C.
- Temperatures lower than the first limit indicated are not advantageous due to a reaction rate which is too low and also to the high viscosity which the reaction mass would obtain with an increase in the molecular weight of the PCD with consequent mechanical difficulties.
- Temperatures higher than the second limit are undesired as they favor colouring of the product.
- The reaction is carried out batchwise by feeding the aryl carbonate to the PCD (II) mass pre-charged into the reactor maintained under stirring and then brought to the pre-selected temperature conditions. The operating pressure is not particularly critical, as boiling conditions are not adopted and is preferably atmospheric pressure.
- The reaction times are such as to obtain the complete conversion of the aryl carbonate and, however, generally range from 1 to 10 hours, typically from 2 to 4 hours.
- Subsequently, by maintaining the synthesis temperature and progressively reducing the pressure of the system to values ranging from 1 to 200 mbars, preferably from 10 to 100 mbars, the ArOH co-produced is removed from the reaction mixture and at the same time the conversion of the residual arylcarbonic terminations in the PCD (I) is made quantitative, by their reaction with the hydroxide terminations with the consequent release of further ArOH according to the following reaction (iv):
- Ar—[OCOO—R′]v—OH+HO—R′—[OCOO—R′]w—OH
- HO—R′—[OCOO—R′](v+w)—OH+Ar—OH
- wherein: (v+w)=n in formula (I).
- Operating under the conditions described above, the transesterification is completed in a period of time ranging from 1 to 20 hours, preferably from 3 to 10 hours, to obtain PCD (I) with a hydroxide functionality equal to 2 and whose molecular weight, which is in relation to the PCD(II)/aryl carbonate ratio used, is higher than 2000, generally ranging from 2500 to 5000.
- The process of the present invention allows PCD (I) to be obtained with a high molecular weight optimizing the space yield of the reactor and economy of the transesterification process.
- The following examples should be considered as being illustrative but non-limiting of the present invention. In the examples, a three-liter jacketed flask is used, equipped with a stirrer, drip funnel, thermometer and plate distillation column (20 nominal steps) having a sampling head in liquid phase (L/D) regulated by means of a valve temporized in order to control the reflux ratio. The heating system consists of an oil bath.
- A) 1681.5 g (14.25 moles) of 1,6-hexanediol and 119.35 mg (0.42 mmoles) of titanium tetra-isopropylate are charged in the molten state into the flask, inertized with nitrogen.
- The flask is heated to an internal temperature of 190° C. at atmospheric pressure and 1372 g (15.24 moles) of dimethyl carbonate are then gradually fed through the drip funnel.
- A total aliquot of DMC is fed which is such as to make the reaction mixture, maintained at 190° C., boil, the column being kept at total reflux until the temperature at the head of the column is equal to 65° C., corresponding to that of the azeotropic mixture of methanol/DMC (70/30 by weight) at atmospheric pressure.
- At this point the azeotropic mixture produced is removed and DMC is fed, regulating the feeding flow-rate so as to maintain the temperature of the reaction mixture and the head of the column at the respective values indicated above.
- At the end of the addition of DMC the synthesis temperature is gradually raised to 195° C., the distillation being continued until the rise in temperature at the head of the column indicates the exhaustion of methanol production.
- During this phase about 80% of the overall methanol co-produced by the transesterification (784 g) is collected. The phase requires about 6 hours for completion.
- The final part of the reaction is carried out by progressively reducing the pressure to 25 mbars and maintaining the synthesis temperature at 195° C. In this way the transformation of the residual alkylcarbonic terminations is completed, by stripping the methanol generated from the reaction mixture. 2000 g of PCD are obtained with a number average molecular weight Mn equal to 1000.
- B) The equipment used in step A) is used, excluding the rectification column and directly connecting the reaction flask to a condenser conditioned at 42° C.
- The mixture coming from step A) is cooled to 135° C. and, maintaining it under stirring at atmospheric pressure, 283 g (1.32 moles) of diphenylcarbonate (DPC) melted at 81° C. are fed. The resulting mixture is kept under these conditions for at least 2 hours to obtain the complete conversion of the DPC. The phenol formed is then removed, by slowly reducing the pressure of the system to a minimum value of 25 mbars.
- A total of 248.5 g (2.64 moles) of phenol are stripped and 2034 g (0.67 moles) of PCD are obtained with a molecular weight equal to 3000.
- 1.0 kg of PCD was therefore obtained starting from 1.64 kg of reagents.
- The direct preparation of a polycarbonate diol having a molecular weight Mn of 3000 is effected starting from 1,6-hexanediol (HD) and DPC.
- 1681.5 g (14.25 moles) of HD are fed in the molten state to the equipment described above, and are heated to the melting point of DPC (81° C).
- 2906 g (13.57 moles) of DPC in the molten state are subsequently fed. The reactor is heated to an internal temperature of 190° C. at atmospheric pressure and the mixture is left under stirring for at least 2 hours. The phenol formed is then distilled, by reducing the pressure of the system to a minimum value of 25 mbars.
- A total of 2553 g (27.17 moles) of phenol are removed and 2034 g of PCD are obtained with a molecular weight Mn equal to 3000.
- 1.0 kg of PCD was therefore obtained starting from 2.26 kg of reagents.
Claims (25)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI00A0549 | 2000-03-16 | ||
ITM12000A000549 | 2000-03-17 | ||
IT2000MI000549A IT1318397B1 (en) | 2000-03-17 | 2000-03-17 | PROCEDURE FOR THE PREPARATION OF MOLECULAR HIGH POLYCARBONATE DIOLS. |
Publications (2)
Publication Number | Publication Date |
---|---|
US20010047073A1 true US20010047073A1 (en) | 2001-11-29 |
US6384178B2 US6384178B2 (en) | 2002-05-07 |
Family
ID=11444492
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/797,593 Expired - Fee Related US6384178B2 (en) | 2000-03-16 | 2001-03-05 | Process for the preparation of polycarbonate diols with a high molecular weight |
Country Status (7)
Country | Link |
---|---|
US (1) | US6384178B2 (en) |
EP (1) | EP1134248B1 (en) |
JP (1) | JP2001261811A (en) |
AT (1) | ATE301148T1 (en) |
DE (1) | DE60112347T2 (en) |
ES (1) | ES2246262T3 (en) |
IT (1) | IT1318397B1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100233378A1 (en) * | 2007-07-19 | 2010-09-16 | Kao Corporation | Polyether polycarbonate |
US20110190471A1 (en) * | 2008-08-01 | 2011-08-04 | Masahiko Watanabe | Polycarbonate diol and polycarbonate diol copolymer |
US9447234B2 (en) | 2012-11-09 | 2016-09-20 | Lotte Chemical Corporation | High molecular weight aliphatic polycarbonate copolymer and preparation method thereof |
US9475905B2 (en) | 2013-01-18 | 2016-10-25 | Lotte Chemical Corporation | High-molecular weight aliphatic polycarbonate prepared using base catalyst |
US10316130B2 (en) | 2012-12-26 | 2019-06-11 | Mitsubishi Chemical Corporation | Polycarbonate diol and polyurethane using same |
WO2019119466A1 (en) * | 2017-12-21 | 2019-06-27 | 万华化学集团股份有限公司 | Polycarbonate polyol, synthesis method therefor and application thereof |
US20190330421A1 (en) * | 2017-01-10 | 2019-10-31 | Mitsubishi Chemical Corporation | Polycarbonate diol, polycarbonate diol-containing composition, polycarbonate diol production method, and polyurethane |
CN111479844A (en) * | 2017-12-19 | 2020-07-31 | 科思创德国股份有限公司 | Polycarbonate polyols, polyisocyanate prepolymers and polyurethane urea elastomers based thereon |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10219028A1 (en) * | 2002-04-29 | 2003-11-06 | Bayer Ag | Production and use of high molecular weight aliphatic polycarbonates |
SE531577C2 (en) * | 2006-12-04 | 2009-05-26 | Perstorp Specialty Chem Ab | Process for obtaining increased molecular weight of a polymer and use of said polymer |
WO2013076099A1 (en) | 2011-11-24 | 2013-05-30 | Bayer Intellectual Property Gmbh | Production and use of high-molecular-weight aliphatic polycarbonates |
ES2747852T3 (en) * | 2014-05-07 | 2020-03-11 | Asahi Chemical Ind | Polycarbonate / polyoxyethylene block copolymer for aqueous compositions and aqueous composition, aqueous coating composition, aqueous ink composition and aqueous tackifier composition comprising the same |
CN108430629B (en) | 2015-12-21 | 2021-11-12 | 国际壳牌研究有限公司 | Hydrogenation catalyst and process for its preparation |
EP3394149B1 (en) * | 2015-12-22 | 2019-10-30 | Shell International Research Maatschappij B.V. | Method for producing polycarbonate |
CN108473672B (en) * | 2015-12-22 | 2020-12-08 | 国际壳牌研究有限公司 | Process for preparing melt polycarbonate |
CN108473671A (en) * | 2015-12-22 | 2018-08-31 | 国际壳牌研究有限公司 | The method for preparing makrolon oligomer |
US10844297B2 (en) | 2015-12-23 | 2020-11-24 | Shell Oil Company | Residual base oil process |
US11142705B2 (en) | 2015-12-23 | 2021-10-12 | Shell Oil Company | Process for preparing a base oil having a reduced cloud point |
CN110088239B (en) | 2016-12-23 | 2022-04-05 | 国际壳牌研究有限公司 | Haze free base oil fraction derived from a fischer-tropsch feedstock |
CN110099983B (en) | 2016-12-23 | 2022-09-27 | 国际壳牌研究有限公司 | Haze free base oils with high paraffin content |
CN109107207B (en) * | 2018-07-18 | 2021-07-23 | 万华化学集团股份有限公司 | Reactive distillation device with external circulation system and application thereof |
CN113292714B (en) * | 2021-06-01 | 2023-01-31 | 山东元利科技有限公司 | Preparation method of polycarbonate diol |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1694080B1 (en) * | 1966-10-13 | 1971-09-30 | Bayer Ag | PROCESS FOR THE PRODUCTION OF CROSS-LINKED POLYURETHANES ON THE BASIS OF HYDROXYL POLYCARBON EASTERS |
DE4102174A1 (en) * | 1991-01-25 | 1992-07-30 | Basf Ag | METHOD FOR THE PRODUCTION OF CELLED POLYURETHANE ELASTOMERS USING POLYETHERCARBONATE DIOLES AS THE STARTING COMPONENT |
CN1145078A (en) * | 1994-04-08 | 1997-03-12 | 旭化成工业株式会社 | Process for producing hydroxyl-terminated polycarbonate |
IT1283314B1 (en) * | 1996-03-28 | 1998-04-16 | Enichem Spa | PROCESS FOR THE PREPARATION OF POLYCOL POLYCARBONATES |
-
2000
- 2000-03-17 IT IT2000MI000549A patent/IT1318397B1/en active
-
2001
- 2001-02-12 EP EP01103237A patent/EP1134248B1/en not_active Expired - Lifetime
- 2001-02-12 DE DE60112347T patent/DE60112347T2/en not_active Expired - Fee Related
- 2001-02-12 AT AT01103237T patent/ATE301148T1/en not_active IP Right Cessation
- 2001-02-12 ES ES01103237T patent/ES2246262T3/en not_active Expired - Lifetime
- 2001-03-05 US US09/797,593 patent/US6384178B2/en not_active Expired - Fee Related
- 2001-03-19 JP JP2001079254A patent/JP2001261811A/en active Pending
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100233378A1 (en) * | 2007-07-19 | 2010-09-16 | Kao Corporation | Polyether polycarbonate |
US8796379B2 (en) | 2007-07-19 | 2014-08-05 | Kao Corporation | Polyether polycarbonate |
US20110190471A1 (en) * | 2008-08-01 | 2011-08-04 | Masahiko Watanabe | Polycarbonate diol and polycarbonate diol copolymer |
US9447234B2 (en) | 2012-11-09 | 2016-09-20 | Lotte Chemical Corporation | High molecular weight aliphatic polycarbonate copolymer and preparation method thereof |
US10316130B2 (en) | 2012-12-26 | 2019-06-11 | Mitsubishi Chemical Corporation | Polycarbonate diol and polyurethane using same |
US11220572B2 (en) | 2012-12-26 | 2022-01-11 | Mitsubishi Chemical Corporation | Polycarbonate diol and polyurethane using same |
US9475905B2 (en) | 2013-01-18 | 2016-10-25 | Lotte Chemical Corporation | High-molecular weight aliphatic polycarbonate prepared using base catalyst |
US20190330421A1 (en) * | 2017-01-10 | 2019-10-31 | Mitsubishi Chemical Corporation | Polycarbonate diol, polycarbonate diol-containing composition, polycarbonate diol production method, and polyurethane |
US11591437B2 (en) * | 2017-01-10 | 2023-02-28 | Mitsubishi Chemical Corporation | Polycarbonate diol, polycarbonate diol-containing composition, polycarbonate diol production method, and polyurethane |
CN111479844A (en) * | 2017-12-19 | 2020-07-31 | 科思创德国股份有限公司 | Polycarbonate polyols, polyisocyanate prepolymers and polyurethane urea elastomers based thereon |
US11926701B2 (en) | 2017-12-19 | 2024-03-12 | Covestro Deutschland Ag | Polycarbonate polyols, polyisocyanate prepolymers and polyurethane and polyurethane urea elastomers based thereon |
WO2019119466A1 (en) * | 2017-12-21 | 2019-06-27 | 万华化学集团股份有限公司 | Polycarbonate polyol, synthesis method therefor and application thereof |
Also Published As
Publication number | Publication date |
---|---|
ES2246262T3 (en) | 2006-02-16 |
ITMI20000549A0 (en) | 2000-03-17 |
ATE301148T1 (en) | 2005-08-15 |
DE60112347D1 (en) | 2005-09-08 |
ITMI20000549A1 (en) | 2001-09-17 |
EP1134248A1 (en) | 2001-09-19 |
JP2001261811A (en) | 2001-09-26 |
DE60112347T2 (en) | 2006-05-24 |
US6384178B2 (en) | 2002-05-07 |
IT1318397B1 (en) | 2003-08-25 |
EP1134248B1 (en) | 2005-08-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6384178B2 (en) | Process for the preparation of polycarbonate diols with a high molecular weight | |
US7420077B2 (en) | Preparation of aliphatic oligocarbonate diols | |
US5703196A (en) | Process for producing polycarbonate having terminal hydroxyl groups | |
KR100573235B1 (en) | Process for preparation of polyisocyanate composition | |
US20060052572A1 (en) | Metal acetylacetonates as transesterification catalysts | |
US20060004176A1 (en) | Oligocarbonate polyols having terminal secondary hydroxyl groups | |
CA2466255C (en) | Ytterbium(iii) acetylacetonate as a catalyst for the preparation of aliphatic oligocarbonate polyols | |
US7317121B2 (en) | Preparation of aliphatic oligocarbonate polyols | |
JPH04239024A (en) | Production of hydroxyl-terminated polycarbonate | |
JPH03252420A (en) | Production of copolymerized polycarbonate diol | |
McCabe et al. | Synthesis of novel polyurethane polyesters using the enzyme Candida antarctica lipase B | |
JP4198940B2 (en) | Production method of polycarbonate polyol | |
JP3530706B2 (en) | Method for producing aromatic polycarbonate | |
US5053528A (en) | Novel dihydroxy compounds with ester groups and preparation thereof | |
JPH10251398A (en) | Production of polycarbonate diol | |
JP2810548B2 (en) | Preparation of polycarbonate with terminal hydroxyl group | |
JPH10231360A (en) | Production of polycarbonate diol | |
JP2680678B2 (en) | Production method of polycarbonate | |
JPH02284918A (en) | Production of aliphatic polycarbonate diol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ENICHEM S.P.A., ITALY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MIZIA, FRANK;RIVETTI, FRANCO;REEL/FRAME:011961/0689 Effective date: 20010403 |
|
AS | Assignment |
Owner name: ENICHEM S.P.A., ITALY Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE FIRST ASSIGNOR'S NAME PREVIOUSLY RECORDED ON REEL 011961 FRAME 0689;ASSIGNORS:MIZIA, FRANCO;RIVETTI, FRANCO;REEL/FRAME:012236/0248 Effective date: 20010403 |
|
CC | Certificate of correction | ||
FEPP | Fee payment procedure |
Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20100507 |