WO2007052697A1 - Polyalkylene ether glycol et son procede de fabrication - Google Patents

Polyalkylene ether glycol et son procede de fabrication Download PDF

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Publication number
WO2007052697A1
WO2007052697A1 PCT/JP2006/321854 JP2006321854W WO2007052697A1 WO 2007052697 A1 WO2007052697 A1 WO 2007052697A1 JP 2006321854 W JP2006321854 W JP 2006321854W WO 2007052697 A1 WO2007052697 A1 WO 2007052697A1
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ether glycol
reaction
polyalkylene ether
propanediol
group
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PCT/JP2006/321854
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English (en)
Japanese (ja)
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Mitsuharu Kobayashi
Masaki Takai
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Mitsubishi Chemical Corporation
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Publication of WO2007052697A1 publication Critical patent/WO2007052697A1/fr

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    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups

Definitions

  • the present invention relates to a polyalkylene ether glycol and a method for producing the same.
  • the polyalkylene ether glycol of the present invention comprises a homopolymer or copolymer of 1,3 propanediol.
  • Polyether polyols are polyols that have a wide range of uses, including raw materials for soft segments such as elastic fibers, thermoplastic elastomers, and thermosetting elastomers.
  • polyalkylene ether glycols such as polyethylene glycol, poly (1,2-propanediol) (commonly referred to as polypropylene glycol), and polytetramethylene ether alcohol are known.
  • poly (1,2-propanediol) commonly referred to as polypropylene glycol
  • polytetramethylene ether alcohol are known.
  • poly (1,2-propanediol) commonly referred to as polypropylene glycol
  • polytetramethylene ether alcohol polytetramethylene ether alcohol
  • 2-propanediol is widely used because it is liquid at room temperature, easy to handle and inexpensive.
  • poly (1, 2 propanediol) usually has a terminal hydroxyl group mainly of a secondary hydroxyl group, it is less reactive than other polyols having a terminal hydroxyl group.
  • polyether polyols since it has a methyl group in the side chain, physical properties such as strength may be inferior to those of other linear polyols, and polyether polyols with better physical properties are desired depending on the application. Therefore, in recent years, polytrimethylene ether glycol has attracted attention as a polyether polyol having only a primary hydroxyl group and a low melting point.
  • a polycondensation catalyst is used, and 1, 3 propanediol, an oligomer of 1,3 propanediol having a degree of polymerization of 2 to 9, a prepolymer or a mixture thereof Force A method involving the polycondensation of selected 1,3 propanediol raw materials to form polytrimethylene ether glycol at less than 1 atm, with a number average molecular weight greater than 1,500, unsaturated less than 20 meqZkg Polytrimethylene ether glycol (specifically, polytrimethylene ether glycol having a number average molecular weight of 2,360 and an unsaturation of 12.5 meqZkg). Further, a copolymer of polytrimethylene ether glycol is also mentioned (for example, see Patent Document 1).
  • poly 2-methyl 1,3-propylene ether glycol has been proposed as an analog of polytrimethylene ether glycol, and a number average molecular weight of 515 has been obtained by ring-opening polymerization of 3-methyloxetane. Force The amount of unsaturated end groups is well documented (see, for example, Patent Document 2).
  • Patent Document 1 US Patent Application Publication No. 2002Z0007043 (Japanese translations of PCT publication No. 20003-517071)
  • Patent Document 2 JP-A-58-126828
  • the present invention has been made in view of the above circumstances, and the object thereof is a novel polyalkylene ether glycol improved so as to exhibit a sufficient reaction rate when used as a polyol raw material, and a process for producing the same. Is to provide. Means for solving the problem
  • the present inventor has conducted extensive studies considering that polytrimethylene ether glycol (or a copolymer thereof) is used as a raw material for polyols in the production of various polymers having a wide range of intrinsic viscosities (IV). As a result, the following new findings were obtained. That is, the reaction rate during the production of the polymer is critically deteriorated depending on the amount of unsaturated end groups per unit weight, and the amount of unsaturated end groups having such a critical significance is the number average molecular weight. It depends on.
  • the above-described reaction treatment is performed within a necessary range in consideration of the number average molecular weight.
  • the physical properties of the polyalkylene ether glycol obtained by the above production reaction are not impaired at all.
  • the present invention has been completed based on the above findings, and the first gist thereof is a polyalkylene ether glycol having a repeating unit force represented by the following chemical formula (I) or the following chemical formula: the content of the repeating unit represented by the formula (I) is a polyalkylene ether glycol is 50 mole 0/0 or more, per unit weight of the unsaturated end group amount Y (meq / g) satisfies the following formula (1) It exists in the polyalkylene ether glycol characterized by satisfy
  • the content of the repeating unit represented by the formula (I) is a polyalkylene ether glycol is 50 mole 0/0 or more, per unit weight of the unsaturated end group amount Y (meq / g) satisfies the following formula (1) It exists in the polyalkylene ether glycol characterized by satisfy
  • the second gist of the present invention is 1,3-propanediol, having a polymerization degree of 2-9
  • the above alkylene diol raw material ( ⁇ ) is subjected to a dehydration condensation reaction, and the resulting polyalkylene ether glycol is treated in the presence of a metal selected from the group of groups 4 to 12 of the periodic table or a catalyst containing the compound.
  • a metal selected from the group of groups 4 to 12 of the periodic table or a catalyst containing the compound.
  • FIG. 1 Graph showing the relationship between the reaction rate (vs. rate) and the amount of terminal aryl groups per unit weight.
  • FIG. 2 1 H— before and after the aryl end reduction reaction described in Example 1 NMR chart
  • FIG. 3 is a graph showing the relationship between reaction rate (vs. rate) and the amount of terminal allyl groups per unit weight.
  • the polytrimethylene ether glycol of the present invention includes two types, one of which is a polyalkylene ether glycol (polytrimethylene ether glycol) having a repeating unit force represented by the chemical formula (I).
  • a polyalkylene ether glycol polytrimethylene ether glycol having a repeating unit force represented by the chemical formula (I).
  • the content of the repeating unit of represented by the formula (I) is a polyalkylene ether glycol is 50 mole 0/0 or more (a copolymer of Poritorimechire emissions ether glycol).
  • the polyalkylene ether glycol of the present invention is characterized in that the unsaturated terminal group amount Y (meqZg) per unit weight satisfies the condition of the above formula (1).
  • the meqZg representing the amount of unsaturated end groups Y in the present invention is an index representing how many unsaturated end groups are present per unit weight of polytrimethylene ether glycol.
  • the mathematical formula (1) means that the unsaturated terminal group amount Y increases with a certain ratio (slope) with respect to the number average molecular weight X. According to the research by the present inventors, this proportionality expression becomes clear for the first time that the unsaturated end group Y and the number average molecular weight X are in a proportional relationship, and the relationship between X and Y can be expressed by a linear equation. It became possible. Specifically, a linear equation can be derived by the following method.
  • the critical point of the unsaturated end group amount Y at which the reaction rate changes rapidly decreases is clarified, and polytrimethylene ether glycol showing such a critical point (the vertical axis represents the unsaturated end group amount Y and the horizontal axis). Is the number average molecular weight X). Looking at the trend of this plot, the amount of unsaturated end groups Y increases in proportion to the number average molecular weight X. Therefore, it is possible to calculate the slope and intercept of the linear formula from the plotted points and derive a specific mathematical formula. Specifically, it is as shown in FIG.
  • Fig. 1 was obtained when the polyester-acid reaction was performed using polytrimethylene ether glycol (number average molecular weight 2133) having different unsaturated terminal group amount Y (meqZg) per unit weight as a raw material.
  • Unsaturated end group amount Critical points are recognized at about 0.005 (meqZg) and about 0.009 (meqZg), respectively. In other words, the rate of the polyester-ion reaction decreases rapidly depending on the amount of unsaturated end groups per unit weight, particularly 0.009 (meqZg). Similarly, there is a critical point for the number average molecular weight of 3138.
  • the slope and intercept were calculated from the molecular weight X of polytrimethylene ether glycol and the unsaturated end group amount Y (meqZg) at each critical point in each example. Furthermore, since the same effect was proved with the unsaturated terminal group amount Y (meqZg) in the range below the specific formula, the specific range of the formula (1) was derived.
  • the polytrimethylene monoterdaricol in the present invention is one in which the amount of unsaturated end groups Y (meq / g) is extremely reduced. In particular, the amount of unsaturated end groups Y (meqZg) satisfies the above formula (1).
  • polytrimethylene ether glycol when used as a raw material, the polymerization rate of the elastomer can be remarkably improved and the physical properties can be remarkably improved.
  • the object of the present invention can be achieved by using polytrimethylene ether glycol satisfying the range of the formula (1).
  • the unsaturated end group amount Y (meqZg) per unit weight preferably satisfies the following formula (2), and more preferably satisfies the following formula (3). .
  • the unsaturated terminal group in the present invention is typically a terminal aryl group, but is not limited to a terminal aryl group.
  • unsaturated terminal groups other than terminal aryl groups are typically a terminal aryl group, but is not limited to a terminal aryl group.
  • a terminal propyl group When combined, a terminal propyl group may be detected as a terminal other than the hydroxyl group.
  • the terminal propyl group is very small compared to the terminal aryl group, and the reaction conditions. It is possible to reduce to below the detection limit of NMR by selecting the matter.
  • the number average molecular weight X is usually 250 to 10,000, preferably 800 to 5,000, more preferably 1,300 to 4,000, particularly preferably 1,800 to 3,500. is there. If the number average molecular weight X is too large, the viscosity will be too high and handling will be difficult, the reactivity will be low and the elastomer manufacturing process will tend to take too much time, and if it is too small, There is a tendency that characteristics such as elasticity and softness as an elastomer are not fully exhibited.
  • the molecular weight distribution (weight average molecular weight Z number average molecular weight) is usually 1 to 4, preferably 1 to 2.5, and the Hazen color number is usually 200 or less, preferably 100 or less, more preferably 50 or less, particularly preferably. Is 30 or less, most preferably 20 or less.
  • the type of repeating unit other than the repeating unit represented by the chemical formula (I) is not limited as long as it is a unit derived from alkylene ether glycol.
  • a unit derived from 2-methyl-1,3-propanediol or 2,2-dimethyl-1,3-propanediol is particularly preferred.
  • the proportion of the repeating unit represented by the chemical formula (I) is preferably 70 mol% or more, more preferably 80 mol% or more, and the upper limit is usually 99 mol%.
  • Examples of the method for producing the polyalkylene ether glycol of the present invention include methods by dehydration condensation of alkylene diol, ring-opening polymerization of cyclic ether, and reaction between alcohol and cyclic ether.
  • JP-A-59-189120 and JP-A-2 Reference can be made to the descriptions in Japanese Patent No. 248426 and Japanese Patent Laid-Open No. 2003-147073.
  • a method by dehydration condensation of an alkylene diol described later is particularly recommended.
  • the production method of the present invention includes two steps of a production reaction of a polyalkylene ether glycol and a treatment for reducing unsaturated end groups of the polymer obtained by the production reaction. These two steps may be performed simultaneously.
  • the raw material is selected from the group consisting of 1,3 propanediol, oligomers of 1,3 propanediol having a degree of polymerization of 2 to 9, prepolymers, or mixtures thereof.
  • Puropanjioru material (a), or, the one, the content of 3-propanediol starting material to use alkylene diol starting material is 50 mol 0/0 or (B).
  • a copolymer of polytrimethylene ether glycol is obtained from the alkylene diol raw material (B).
  • Examples of copolymer components include ethylene glycol, 2-methyl-1,3 propanediol, 2,2 dimethyl-1,3 propanediol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, 1,7
  • An alkylene ether glycol having two primary hydroxyl groups such as heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 decanediol, 1,4-cyclohexanedimethanol can be suitably used.
  • trifunctional or higher functional glycols such as trimethylolethane, trimethylolpropane and pentaerythritol, or oligomers of these glycols can be used in combination.
  • 2-methyl-1,3 propanediol or 2,2 dimethyl-1,3 propanediol is preferred.
  • the content of 1,3 propanediol raw material is preferably 70 mol% or more, more preferably 80 mol% or more, and the upper limit is usually 99 mol%. It is. If the amount of 1,3 propanediol is too small, the softness and thermal stability of the polymer that can obtain the copolymer power of polytrimethylene ether glycol tends to deteriorate.
  • the oligomers, prepolymers and the like in the 1,3-propanediol raw material (A) are prepared by the method described in the above-mentioned US Patent Application Publication No. 2002 0007043 (Japanese Patent Publication No. 20003-517071). I can do it. In other words, in the present invention, the dehydration condensation reaction can be performed in multiple stages as in the above prior art.
  • the dehydration condensation reaction can be performed according to a known method, and may be either a batch system or a continuous system.
  • a raw material and a catalyst an acid and a metal compound selected from the group consisting of Group 4 and Group 13
  • a reactor may be charged into a reactor and reacted under stirring.
  • the raw material and the catalyst are continuously supplied from one end of a reaction apparatus in which a large number of stirring tanks are connected in series or a flow-type reaction apparatus, and the inside of the apparatus is moved in a piston flow or a manner close to this.
  • a method of continuously extracting the reaction solution from the other end can be used.
  • the reaction temperature is usually 120 to 250. C, preferably 140-200. C, more preferably 155-175 ° C. If the reaction temperature is too high, the amount of terminal unsaturated groups tends to increase, and the polymer tends to be colored easily. If it is too low, a sufficient polymerization reaction rate tends to be not obtained.
  • the reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
  • the reaction pressure is arbitrary as long as the reaction system is maintained in a liquid phase, and usually atmospheric pressure conditions are employed. If desired, the reaction may be carried out under reduced pressure or an inert gas may be circulated through the reaction system in order to promote elimination of water produced by the reaction from the reaction system.
  • the reaction time varies depending on the amount of catalyst used, the reaction temperature, the yield and physical properties of the produced polymer, and is usually 0.5 to 50 hours, preferably 1 to 20 hours.
  • the reaction is usually carried out without a solvent, but a solvent can be used if desired.
  • the solvent may be appropriately selected from organic solvents used for usual organic synthesis reactions.
  • Separation and recovery of the produced polymer from the reaction system can be performed by a conventional method.
  • an acid acting as a heterogeneous catalyst is used as the catalyst, first, the acid suspended in the reaction solution is removed by filtration or centrifugation. Next, the low-boiling oligomers and organic bases are removed by distillation or extraction with water to obtain the target polymer.
  • an acid that acts as a homogeneous catalyst first add water to the reaction solution to form a polymer layer, acid, organic A water layer containing a base and an oligomer is separated.
  • the polymer since a part of the polymer forms an acid and an ester used as a catalyst, after adding water to the reaction solution, it is heated to hydrolyze the ester to make a force layer. At this time, an organic solvent having an affinity for both the polymer and water can be used together with water. If the polymer is highly viscous and the operability of the layer separation is not good, it is preferable to use an organic solvent that has an affinity for the polymer and can easily separate the polymer by distillation. The polymer phase obtained by layering is distilled to distill off the remaining water and organic solvent to obtain the desired polymer. If acid remains in the polymer phase obtained by phase separation, it can be washed with water or an aqueous alkaline solution or treated with a base such as calcium hydroxide or calcium to remove the acid. And then subject to force distillation.
  • a base such as calcium hydroxide or calcium
  • the storage temperature is usually ⁇ 20 to 70 ° C., preferably 0 to 50 ° C., more preferably 10 to 40 ° C. If the storage temperature is too high, decomposition and coloring of the polymer may be accelerated, and if it is too low, a large force device is required, which is preferable.
  • the number average molecular weight X of the polymer obtained by the dehydration condensation reaction can be adjusted by the type of catalyst used, the amount of catalyst, the polymerization temperature, and the polymerization reaction time, and the ranges thereof are as described above.
  • a catalyst containing at least one metal or a compound thereof selected from group 4 to 12 in the periodic table is also selected. It is important to treat the polymer obtained in the presence of.
  • a hydrogen donor for example, formic acid, for example, a polyether (specifically, a polyether containing an oxypropylene unit from which propylene oxide is also derived)
  • a method of treating with a hydrocracking catalyst JP-A-4-227926
  • a method of contacting with an isomerization catalyst then separating the isomerization catalyst, and contacting with an acid catalyst
  • the method for reducing unsaturated end groups is not a method directly related to polytrimethylene ether glycol and its copolymer, but has the following problems. That is, in the case of the above-mentioned method, a part of the terminal hydroxyl group is formed by the hydrogen donor. Because of the high possibility of tellurization, even if it is applied to polytrimethylene ether glycol and its copolymer, even if the unsaturated group at the terminal is reduced, another non-reactive terminal is generated. In the case of the latter method, the process is complicated, and it is not efficient and economical.
  • the reduction of unsaturated end groups of polytrimethylene ether glycol and its copolymer found by the present inventors is at least a group force of groups 4 to 12 of the periodic table is also selected. Since it is carried out in the presence of a catalyst containing one metal or its compound and does not require a hydrogen donor, it avoids the above problems and efficiently and economically reduces the amount of unsaturated end groups. It can be reduced to.
  • Metals for which the group force of the periodic table group 4 to 12 is also selected include, for example, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganone, rhenium, iron, ruthenium, osmium, Examples include cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, and mercury.
  • a preferred metal is a metal selected from Group 6: L 1 group, and specific examples thereof include chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, Examples include rhodium, iridium, nickel, iron ⁇ radium, platinum, copper, silver, and gold.
  • a more preferable metal is a metal having a group strength of 8 to: LO group selected, and specific examples thereof include iron, ruthenium, osmium, connort, rhodium, iridium, nickel, no ⁇ radium, and platinum. It is done. Particularly preferred metals are rhodium, palladium, ruthenium or platinum, and palladium is most suitable from the viewpoint of availability and price.
  • the form of the metal or metal compound is particularly limited as long as it has a function as a catalyst for reducing unsaturated end groups of polytrimethylene ether glycol and its copolymer (also referred to as a metal catalyst in the present invention). However, it can usually be used in the form of an alloy with one or more other metals, in the form of a salt, or in the form of a coordination compound. Further, a metal and a compound containing Z or metal can be supported on a carrier. Examples of the carrier include activated carbon, alumina, silica, zeolite, clay, activated clay and the like.
  • a compound containing a metal in the II-valent state is selected as a catalyst at the time of addition to the reaction system. It is also possible.
  • the loading amount when a metal and Z or a compound containing metal are supported on the carrier is not particularly limited, but is usually 0.1 to 50% by weight, preferably 0.5 to 20% by weight, more preferably, based on the carrier. 1 to 10% by weight.
  • embodiments of the metal catalyst include finely divided metal palladium, supported metal palladium catalyst, for example, palladium on carbon, palladium on alumina, palladium on silica, and the like.
  • the catalyst should be added separately and the complex formed as a salt.
  • the catalyst is used in an amount sufficient to increase the rate of reduction of unsaturated end groups so that it can be measured.
  • the catalyst concentration is preferably such that the reaction proceeds to the desired ratio in a time that is practical in industrialization, for example, usually 24 hours or less, preferably 10 hours or less, more preferably 5 hours or less!
  • the amount used is appropriately selected according to the type of the catalyst, but is based on the dry base relative to the weight of polytrimethylene ether glycol and its copolymer.
  • the proportion of the metal catalyst (excluding the support) is usually from 0.0001 to LO weight%, preferably from 0.001 to 1 weight%, more preferably from 0.005 to 0.25 weight%.
  • the metal catalyst may be a complex catalyst or a metal salt such as tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, palladium (II) chloride, palladium (II) bis (triphenylphosphine).
  • a metal salt such as tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, palladium (II) chloride, palladium (II) bis (triphenylphosphine).
  • the amount used is appropriately selected according to the type of polytrimethylene ether glycol and its It is usually 0.001 to 10% by weight, preferably 0.001 to 5% by weight, more preferably 0.005 to 1% by weight, based on the weight of the copolymer.
  • polyalkylene about 0.5 weight relative to ether glycol 0/0, preferably 1 by weight%, more preferably It is preferred that a 10% by weight excess) of water be present in the reaction system.
  • the amount of water in practical treatment is usually 1 to 50 parts by weight, preferably 5 to 30 parts by weight, and more preferably 10 to 20 parts by weight with respect to 100 parts by weight of the polyalkylene ether glycol.
  • the upper limit of the desaturation temperature is selected as a range force of a temperature lower than the decomposition temperature (T) of the polyalkylene ether glycol, and is usually T-20 ° C, preferably T-120 ° C, more preferably T 200 ° C temperature is adopted.
  • the lower limit of the desaturation temperature is usually 25 ° C, preferably 50 ° C.
  • the decomposition temperature is the temperature measured by DSC.
  • the specific upper limit of the temperature is usually 200 ° C., preferably 150 ° C., more preferably 120 ° C., and particularly preferably 110 ° C.
  • the desaturation treatment may be performed in the presence of a solvent.
  • the solvent include methanol, ethanol, propanol, butanol, water, tetrahydrofuran, toluene, and acetone.
  • the amount of the solvent is not particularly limited, but the upper limit is usually 10 times by weight, preferably 2 times by weight with respect to the polyalkylene ether glycol.
  • the desaturation treatment may be either a batch type or a continuous type. Examples of the continuous method include a method in which a raw material such as polyalkylene ether glycol Z water Z solvent is continuously supplied to a column type reactor filled with a metal catalyst.
  • the catalyst for the desaturation treatment can be recycled after separation from the reaction solution after the reaction.
  • a separation method in the case of a batch type, for example, a method of separating the catalyst by filtration, centrifugation or the like can be mentioned. It may also be effective to wash the catalyst used with a suitable solvent.
  • the washing solvent include methanol, ethanol, propanol, butanol, tetrahydrofuran, ethyl ether, propyl ether, butynoether, water, ethyl acetate, 1,3 propanediol, toluene, acetone and the like.
  • the activity of the catalyst can be recovered to some extent by washing at an appropriate temperature using these solvents.
  • the reduction rate of the terminal unsaturated groups of the polyalkylene ether glycol by the above desaturation treatment is usually 20% or more, preferably 50% or more, and more preferably 75% or more. Then, a polyalkylene ether glycol satisfying the formula (1) defined in the present invention is obtained.
  • a method for producing a polyether ester copolymer using the polyalkylene ether glycol of the present invention as a raw material for example, a conventional method for producing a copolyester can be employed. Specifically, in the presence of a catalyst, a diester compound of an aromatic dicarboxylic acid, an excess amount of aliphatic and Z or cycloaliphatic diol and the polyalkylene ether glycol of the present invention are subjected to a transesterification reaction, and subsequently obtained.
  • an aromatic dicarboxylic acid and an aliphatic and Z or alicyclic diol and the polyalkylene ether glycol of the present invention are esterified, followed by A method in which the obtained reaction product is polycondensed under reduced pressure, a short-chain polyester (for example, polybutylene terephthalate) is prepared in advance, and another aromatic dicarboxylic acid and the polyalkylene ether glycol of the present invention are added to the polycondensation.
  • a short-chain polyester for example, polybutylene terephthalate
  • another aromatic dicarboxylic acid and the polyalkylene ether glycol of the present invention are added to the polycondensation.
  • a method of transesterifying by adding another copolymer polyester using a twin screw extruder or the like may be employed.
  • tetraalkyl titanate typified by tetra (isopropoxy) titanate, tetra (n-butoxy) titanate, tetraalkyl titanate and alkylene glycol Reaction products, partial hydrolyzates of tetraalkyl titanates, metal salts of titanium hexaalkoxides, titanium carboxylates, titanium compounds, and other mono-n-butyl monohydroxy tins
  • Monoalkyltin compounds such as oxide, mono-n-butyltin triacetate, mono-n-butyltin monooctylate, mono-n-butyltin monoacetate, di-n-butyltin oxide, di-n-butyltin diacetate, diphenol Zuoxide, diphenol tin diacete
  • dialkyl (or dialyl) tin compounds such as di-butyltin dio
  • Mg, Pb, Zr, Metal compounds such as Zn, Sb, Ge, and P are also useful.
  • These catalysts may be used in combination of two or more. In particular, when used alone, tetraalkyl titanate is preferred. When used in combination, tetraalkyl titanate and magnesium acetate are preferred. Further, the above catalyst may be added at the start of the transesterification or esterification reaction and then added again at the copolymerization reaction.
  • the amount of the catalyst to be used is generally 0.001 to 0.5% by weight, preferably 0.003 to 0.2% by weight, based on the produced polyether ester copolymer. If the amount of the catalyst used is too small, the reaction will not proceed easily and the productivity will deteriorate, and if it is too large, the resulting polyether ester copolymer will be colored or the surface appearance of the copolymer molded product will be uneven. May be evil.
  • polycarboxylic acid, polyfunctional hydroxy compound, oxyacid or the like may be copolymerized as a part of dicarboxylic acid diol.
  • the polyfunctional component acts effectively as a viscosity-increasing component, and its content in the copolymer is usually 3 mol% or less. If the polyfunctional component content exceeds 3 mol%, the resulting polyether ester copolymer may gel.
  • polyfunctional component examples include trimellitic acid, trimesic acid, pyromellitic acid, benzophenone tetracarboxylic acid, butanetetracarboxylic acid, glycerin, trimethylolpropane, pentaerythritol, and esters and acids thereof. And anhydrides.
  • reaction conditions for producing the polyetherester copolymer can be used as the reaction conditions for producing the polyetherester copolymer.
  • the reaction temperature of the transesterification reaction or esterification reaction is usually 120 to 250 ° C, preferably 140 to 240 ° C, and the reaction time is usually 1 to 5 hours.
  • the latter polycondensation reaction is usually carried out under a reduced pressure of 10 torr or less, the reaction temperature is usually 200 to 280 ° C, preferably 220 to 270 ° C, and the reaction time is usually 1 to 6 hours.
  • the polyether ester copolymer obtained as described above is maintained at a temperature equal to or higher than the melting point, and sequentially subjected to molding such as discharge from a reaction can and pelletizing.
  • the pellets obtained here may be further subjected to solid phase polymerization if necessary.
  • Liester ester copolymer has many terminal unsaturated groups and has higher solution viscosity and lower terminal carboxy group concentration compared to polyether ester copolymer produced from polyalkylene ether glycol. Have a good color tone.
  • the polyalkylene ether glycol of the present invention is also useful as a raw material for polyurethane resin.
  • Polyurethane resin is produced by a conventional method mainly from a compound having an active hydrogen group typified by a polyol and a polyisocyanate.
  • the polyalkylene monoterdaricol of the present invention can be easily introduced into a polyurethane resin by reaction with a polyisocyanate as one of active hydrogen compounds.
  • the polyalkylene ether glycol of the present invention can be used in combination with other polyols.
  • Polyols that can be used in combination include polytetramethylene ether glycol, polyethylene glycolol, polypropylene glycol, polytrimethylene ether glycol, ethylene oxide and propylene oxide or ethylene oxide and tetrahydrofuran or propylene oxide and tetrahydrofuran.
  • Polyether polyols such as copolymers; adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, superic acid, azelaic acid, Carboxylic acids such as sebacic acid, dimer acid, trimellitic acid and pyromellitic acid, their anhydrides, ester compounds, or cyclic esters such as ⁇ -force prolataton and y-valerolataton Terui ⁇ product polyester polyols obtained by the reaction; ho Sugen, methyl carbonate, Echiru include polycarbonate polyols obtained by reacting an organic carbonate and ethylene carbonate, such as carbonate phenyl.
  • Polyolefin polyols such as hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, hydroxyl group-containing chlorinated polyethylene; castor oil polyol, silk Animal and vegetable oil-based polyols such as hive mouth-in; epoxy-modified polyols obtained by addition reaction of alkanolamines such as diisopropanolamine and diethanolamine to bisphenol A type epoxy resin and novolak phenol type epoxy resin; Acrylic polyols obtained by polymerizing acrylic monomers having an alcoholic hydroxyl group such as hydroxy esters of methacrylic acid; dimer acid polyols; hydrogenated dimers A monoacid polyol etc.
  • compounds having an active hydrogen group such as a mercapto group, primary or secondary amino group, carboxyl group, silanol group can be used in combination.
  • the amount of these other polyols used is usually 50 mol% or less, preferably 20 mol% or less, as a proportion of the total polyol.
  • chain extender for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3 propanediol, 1,2 butanediol, 1,3 butane Diol, 1,4 Butanediol, 2,3 Butanediol, 3-Methyl-1,5 Pentanediol, Neopentyl Glycol, 2-Methyl-1,3 Propanediol, 2-Methyl-2 Pill 1,3 Propanediol, 2 Butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4 trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexane Diol, 2, 5 Dimethyl-2,
  • chain extenders compounds having two or more amino groups
  • fragrances such as 2, 4 1 or 2, 6-tolylenediamine, xylylenediamine, 4, 4'-diphenylmethanediamine, and the like.
  • IPDA 1-amino-3 aminomethyl-3, 5, 5 -Tri
  • a chain terminator having one active hydrogen group can be used to control the molecular weight of the polyurethane resin.
  • the chain terminator include aliphatic monoamines such as ethanol, propanol, butanol and hexanol, and aliphatic monoamines such as jetylamine having amino groups, dibutylamine, monoethanolamine and diethanolamine.
  • polyisocyanate examples include 2,4 mono- or 2,6 tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl-nomethane diisocyanate (MDI), paraffin.
  • MDI 4,4'-diphenyl-nomethane diisocyanate
  • Aromatic diisocyanates such as enylene diisocyanate, 1, 5 naphthalene diisocyanate, and tolidine diisocyanate; having aromatic rings such as a,, ⁇ ', ⁇ ' -tetramethylxylylene diisocyanate Aliphatic diisocyanate; methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, 2, 2, 4 or 2, 4, 4 trimethylhexamethylene diisocyanate, 1, 6 hexamethylene diisocyanate Aliphatic diisocyanates such as isocyanates; 1,4-cyclohexane diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI), 1 isocyanate 3 Isocyanate methyl-3,5,5 Trimethylcyclohexane (IPDI) 4,4'-dicyclohexylmethane diisocyanate, isopyridene dicyclohe
  • polyisocyanates in which a part of the NCO group of the polyisocyanate is modified to urethane, urea, burette, allophanate, carpositimide, oxazolidone, amide, imide, etc.
  • Polyisocyanates containing the body can also be used.
  • polyurethane resin made of the polyalkylene ether glycol of the present invention as a raw material for use in high-performance polyurethane elastomers such as polyurethane elastic fibers and synthetic leather, the following examples are given as combinations of raw materials.
  • the polymer of the present invention having a molecular weight of 500 to 5000 is used.
  • Alkylene ether glycol, other active hydrogen compound components ethylene diamine, propylene diamine, hexane diamine, xylylene diamine, 2-methylolene, 1,5-pentane diamine at least one compound selected, chain At least one compound selected as a group extender such as 1,4-butanediol, 1,3-propanediol as an extender, 4,4'-dimethanemethane diisocyanate or 2,4 as diisocyanate 4—or 2,6-tolylene diisocyanate.
  • a known method can be adopted as a method for producing the above-mentioned polyurethane resin.
  • a polyisocyanate component and a polyol component can be reacted in a single step, or a prepolymer is prepared in advance by reacting with a polyisocyanate component and a polyol component at a reaction equivalent ratio of 0.1 to 10.0. Then, a polyisocyanate component or an active hydrogen compound component (polyhydric alcohol, amine compound, etc.) can be added thereto and reacted.
  • the reaction may be carried out in a Balta state without using a solvent, and may be either a batch type or a continuous type.
  • an organic solvent examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane and tetrahydrofuran; hydrocarbons such as hexane and cyclohexane; Aromatic hydrocarbons such as toluene and xylene: Esters such as ethyl acetate and butyl acetate; Halogenated hydrocarbons such as chlorobenzene, tricrene, and parkrene; Dimethyl sulfoxide, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl And aprotic polar solvents such as acetamide. When producing a polyurethane urea chain-extended with diamine, dimethylformamide or dimethylacetamide is preferred from the viewpoint of solubility.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl
  • reaction equivalent ratio of the NCOZ active hydrogen group is usually 0.50 to L50, preferably 0.8 to 1.2.
  • the hard segment content in the polyurethane resin is usually a value calculated by the formula shown in “PJ Flory, Journal of the American Chemical Society, 58 ,, pages 1877-1885 (1936;)”. 2-50%.
  • the reaction temperature is usually 0 to 250 ° C. This temperature varies depending on the presence or absence of a solvent, the reactivity of raw materials used, reaction equipment, and the like.
  • the reaction may be performed while degassing under reduced pressure.
  • a catalyst, a stabilizer, etc. can also be used in the case of reaction as needed.
  • the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, and the like.
  • the stabilizer examples include 2, 6 Examples thereof include dibutyl-4-methylphenol, distearyl thiodipropionate, di'betanaphthylphenol-diamine, tri (dinoylphenol) phosphite and the like.
  • the obtained polyurethane elastomer is produced into a target product by a general molding method such as dry spinning, wet spinning, melt spinning, casting, injection molding, extrusion molding, and calendar molding.
  • the polyurethane resin using the polyalkylene ether glycol of the present invention as a raw material can be used in various applications, and exhibits excellent performance particularly when used as an elastic fiber.
  • preferred production conditions for producing a polyurethane urea resin for elastic fibers are exemplified.
  • the added amount of monool such as BuOH or hexanol is usually 500 to 5000 ppm with respect to the polyalkylene ether glycol.
  • a cooled prepolymer solution and an aliphatic diamine having a methylene chain length of 6 or less such as propandamine, ethylenediamine, 2-methinoleyl 1,5-pentanediamine, hexanediamine), or aromatic diamine (xylylenediamine, etc.)
  • chain extension by reacting with DMAc or amine solution dissolved in DMF.
  • Aliphatic diamines with too long methylene chain length When used in, the physical properties of the polyurethane elastic fiber may deteriorate.
  • the reaction is stopped by adding a DMAc or DMF solution of an aliphatic monoamine such as jetylamine, dibutylamine, monoethanolamine, or diethanolamine.
  • an aliphatic monoamine such as jetylamine, dibutylamine, monoethanolamine, or diethanolamine.
  • monoamine and diamine may be mixed in advance, and the chain extension reaction and the chain termination reaction may proceed simultaneously.
  • the chain extension reaction may be performed by adding a prepolymer solution to the diamine solution or by adding the diamine solution to the prepolymer solution. Let it react continuously.
  • An antioxidant can be added at any time during or after the production of the polyetherester copolymer or polyurethane resin.
  • the polyether ester copolymer particularly when the polyalkylene ether glycol of the present invention is exposed to a high temperature, for example, at the time of entering the copolymerization reaction, the deterioration of the acidity of the polyalkylene ether glycol of the present invention is reduced.
  • antioxidants include, for example, phosphoric acid, phosphorous acid aliphatic, aromatic or alkyl group-substituted aromatic ester; hypophosphorous acid derivative, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, poly Phosphorus compounds such as phosphonates, dialkylpentaerythritol diphosphites, dialkylbisphenol A diphosphites; phenolic derivatives such as hindered phenolic compounds; And compounds containing iodo such as acid esters; tin compounds such as tin malate and dibutyltin monooxide. Two or more of these may be used in combination.
  • the addition amount of the antioxidant is usually from 0.001 to 3 parts by weight, preferably from 0.01 to 2 parts by weight, based on 100 parts by weight of the polyetherester copolymer and polyurethane resin.
  • the amount of antioxidant added is too small, the effect of the acid-depressing agent is manifested 1, and when it is too large, the resulting polyether ester copolymer is colored or the surface appearance of the molded copolymer product is There is a case where it makes a bad habit.
  • Examples of the components include silica, talc, my strength, titanium dioxide, alumina, calcium carbonate, calcium silicate, clay, kaolin, diatomaceous earth, asbestos, barium sulfate, aluminum sulfate, calcium sulfate.
  • Foaming agents Crosslinking agents such as epoxy compounds and isocyanate compounds; Viscosity modifiers such as process oil, silicone oil and silicone resin; various conductive materials.
  • the polyalkylene ether glycol of the present invention comprises a polyester copolymer such as a thermoplastic polyether ester elastomer (TPEE), a polyether ester elastic fiber, a polyether ester film, a thermoplastic polyurethane elastomer (TPU). ), Thermosetting polyurethane elastomer (TSU), polyurethane elastic fiber, polyurethane urea fiber, synthetic leather 'artificial leather', etc., it can be suitably used as a polyol raw material for various copolymers.
  • TPEE thermoplastic polyether ester elastomer
  • TPU thermoplastic polyurethane elastomer
  • TSU Thermosetting polyurethane elastomer
  • polyurethane elastic fiber polyurethane urea fiber
  • synthetic leather 'artificial leather' synthetic leather 'artificial leather'
  • Number average molecular weight (Mn) [58 X (3.4 to 3.7 p pm methylene peak integrated value) / (3.8 p pm terminal methylene peak side integral value)] + 18
  • a reactor equipped with a nitrogen inlet and a decompression port was charged with 40.2 parts of dimethyl terephthalate, 25.0 parts of 1,4 butanediol, and 109.0 parts of polytrimethylene ether glycol (B). 107 parts (lOOppmZ polymer as Ti metal) were dissolved in 1,4-butanediol and prepared. After substituting under reduced pressure, the temperature was increased from 150 ° C to 230 ° C over 3 hours under nitrogen to conduct a transesterification reaction.
  • Table 2 shows the polymerization time and the relative polymerization rate of the obtained polyetherester copolymer. It was.
  • the polymerization reaction rate was expressed by the following formula by increasing the torque per unit time during stirring at 12 rpm.
  • Example 1 The polytrimethylene ether glycols ( ⁇ ) and ( ⁇ ) obtained in Example 1 were mixed at a predetermined ratio to prepare four types of polytrimethylene ether glycols having different terminal aryl group amounts per unit weight. Each polytrimethylene ether glycol was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 “5% rhodium carbon powder” (manufactured by NE Chemcat, Lot No. 317-80360, water-containing product (water content 51.46 wt. %)) was used instead 0. 206 g (0. 5 wt 0/0 as a dry product with respect to polytrimethylene ether glycol) was carried out the same reaction as in Example 1.
  • the concentration of the terminal aryl group of the obtained polytrimethylene ether teraricol was below the detection limit of NMR.
  • the concentration of the terminal 1 probe group was below the detection limit of NMR.
  • Example 1 except for using 10% of activated carbon (powder, manufactured by Kanto Yigaku Co., Ltd.) instead of “5% palladium carbon powder” in the case of unsaturated end group reduction reaction, Example 1 The reaction was carried out in the same manner as above. The concentration of the terminal aryl group of the obtained polytrimethylene ether glycol was 0.0156 meqZg as measured by NMR, which was different from that before the unsaturated end group reducing reaction.
  • Example 1 when the unsaturated terminal reducing reaction, as a catalyst "2% platinum carbon powder" (NE Chemcat Co., Lot No. 117- 91360, water-containing product (water content 52.71 wt 0/0)) 12 . except for using 69 g (3 wt 0/0 as a dry product with respect to polytrimethylene ether glycol) was carried out the same reaction as in example 1.
  • the concentration of the terminal aryl group of the obtained polytrimethylene ether dialicol was 0.0049 meqZg.
  • the concentration of the terminal 1-probe group was below the detection limit of NMR.
  • a catalyst used in the unsaturated end reducing reaction was prepared in the following manner. Demineralized water was added to a palladium nitrate aqueous solution (manufactured by NE Chemcat) to prepare a palladium solution containing 1.67% by weight as palladium metal. In an eggplant-shaped flask, 60 cc of this solution and 2 Og of silica gel (“Silysia 540” manufactured by Fuji Silysia Chemical Co., Ltd.) were placed, and water was distilled off with an evaporator to support palladium on the silica gel.
  • This catalyst precursor is filled into a Pyrex (registered trademark) glass tube, dried at 150 ° C for 2 hours under a nitrogen stream, and further subjected to a reduction treatment at 400 ° C for 2 hours under a hydrogen stream. Then, the mixture was cooled to obtain 5 wt% palladium silica powder.
  • Pyrex registered trademark
  • Example 1 in the unsaturated end reducing reaction, 2.00 g of the above-mentioned "5 wt% palladium silica powder" as a catalyst (1 wt% relative to polytrimethylene ether glycol) %) was used, and the reaction was carried out in the same manner as in Example 1.
  • the concentration of the terminal aryl group of the obtained polytrimethylene monoterdaricol was 0.0035 meqZg.
  • the concentration of the terminal 1 propenyl group was below the detection limit of NMR.
  • the catalyst was filtered off with a filter equipped with a 0.2 mPTFE membrane filter.
  • the filtrate was concentrated by an evaporator and dried at 120 ° C. and 4 mmHg while nitrogen publishing.
  • the results are shown in Run 6 of Table 2. In this way, the activity of the catalyst can be restored to some extent by washing with an appropriate solvent.
  • Example 1 except that the reaction time after reaching the reaction start point (170 ° C) of the dehydration condensation reaction was changed to 17 hours, and the reflux time of hydrolysis of sulfate ester was changed to 24 hours.
  • the same operation as in Example 1 was carried out to obtain polytrimethylene ether glycol (C) having a number average molecular weight of 3138 and a terminal aryl group concentration of 0.0193 meqZg.
  • the polytrimethylene terdaricol (C) was subjected to the same unsaturated end group reduction reaction as in Example 1.
  • the concentration of the terminal aryl group of the obtained polytrimethylene ether glycol (D) was below the detection limit of NMR.
  • the concentration of the terminal 1 probe group was also below the detection limit of NMR.
  • the relative polymerization rate was determined in the same manner as in Example 1 except that polytrimethylene ether glycol (D) was used as a raw material in Example 1. The results are shown in Table 3.
  • Example 9 The polytrimethylene ether glycols (C) and (D) obtained in Example 9 were mixed at a predetermined ratio, and four types of polytrimethylene ether glycols having different terminal aryl groups per unit weight were mixed. Recall was prepared. Each polytrimethylene ether glycol was evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • FIG. 3 is a graph similar to FIG. 1 showing the relationship between the reaction rate (vs. speed) and the amount of terminal aryl groups per unit weight, and is a graph based on the results of Table 3.
  • Example 2 While supplying nitrogen with INLZmin to the same four-necked flask as in Example 1, 500 g of 1,3-propanediol was charged. To this was added 0.348 g of sodium carbonate, and 6.78 g of 95 wt% concentrated sulfuric acid was gradually added while stirring. This flask was immersed in an oil bath and heated, and the liquid temperature in the flask reached 163 ° C in about 1 hour. The time when the liquid temperature in the flask reached 163 ° C was taken as the reaction start point, and then the reaction was continued for 12 hours while maintaining the liquid temperature at 162-164 ° C. Next, after hydrolysis with sulfate ester, the same operation as in Example 1 was performed.
  • polytrimethylene ether glycol (E) having a number average molecular weight of 1125 and a terminal aryl group concentration of 0. OlOOmeqZg was obtained.
  • the concentration of the terminal 1 probe group was below the detection limit of NMR.
  • the polytrimethylene terdaricol (E) was subjected to the same unsaturated end group reduction reaction as in Example 1.
  • the concentration of the terminal aryl group of the obtained polytrimethylene ether glycol (F) was below the detection limit of NMR.
  • the concentration of the terminal 1 probe group is also N
  • the relative polymerization rate was determined in the same manner as in Example 1, except that L was used in Example 1 and polytrimethylene ether glycol (E) was used as a raw material. The results are shown in Table 4.
  • each polytrimethylene ether glycol was evaluated in the same manner as in Example 1. The results are shown in Table 4.

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  • Health & Medical Sciences (AREA)
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  • Organic Chemistry (AREA)
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Abstract

L’invention concerne un nouveau polyalkylène éther glycol amélioré de manière à présenter une vitesse de réaction satisfaisante pour une utilisation en tant que matière brute de polyol, à savoir un polyalkylène éther glycol consistant en des unités de répétition représentées par la formule chimique (I) ou comprenant au moins 50 % en mole d’unités de répétition représentées par la formule chimique (I), la teneur en extrémités insaturées par unité de poids, Y(meq/g), satisfaisant à la condition représentée par la formule (1) : [Formule chimique I] - (CH2-CH2-CH2-O)- (I) [Formule numérique 1] Y < 1,69 × 10-6X + 0,0055 (1) (dans laquelle X représente la masse moléculaire moyenne en nombre)
PCT/JP2006/321854 2005-11-02 2006-11-01 Polyalkylene ether glycol et son procede de fabrication WO2007052697A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2483328A2 (fr) * 2009-09-30 2012-08-08 E. I. Du Pont De Nemours And Company Polytriméthylène éther glycol ou ses copolymères présentant une couleur améliorée, et leurs procédés de préparation
CN106589344A (zh) * 2016-12-01 2017-04-26 浙江皇马科技股份有限公司 一种不饱和聚醚的制备方法

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JPH04506226A (ja) * 1989-06-16 1992-10-29 ザ　ダウ　ケミカル　カンパニー エラストマーのポリウレタン又はポリウレタン―ウレアポリマーの製造方法及びこれにより製造されるポリウレタン
JPH08507827A (ja) * 1993-12-09 1996-08-20 サントル・ナショナル・ドゥ・ラ・ルシェルシュ・シャンティフィク 水素化によるポリ（オキシアルキレン）系タ−ポリマー生成方法
JP2003517071A (ja) * 1999-12-17 2003-05-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリトリメチレンエーテルグリコールおよびそのコポリマーの生成
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JP2004182974A (ja) * 2002-11-22 2004-07-02 Mitsubishi Chemicals Corp ポリエーテルポリオールの製造方法
WO2006001482A1 (fr) * 2004-06-29 2006-01-05 Mitsubishi Chemical Corporation Procédé servant à produre un polyéther de polyol
WO2006121111A1 (fr) * 2005-05-13 2006-11-16 Mitsubishi Chemical Corporation Procede de fabrication de polyether polyol

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JPH04506226A (ja) * 1989-06-16 1992-10-29 ザ　ダウ　ケミカル　カンパニー エラストマーのポリウレタン又はポリウレタン―ウレアポリマーの製造方法及びこれにより製造されるポリウレタン
JPH04227926A (ja) * 1990-05-23 1992-08-18 Dow Chem Co:The ポリエーテルの不飽和を低減させるための方法およびその方法で得られた低不飽和ポリエーテル
JPH08507827A (ja) * 1993-12-09 1996-08-20 サントル・ナショナル・ドゥ・ラ・ルシェルシュ・シャンティフィク 水素化によるポリ（オキシアルキレン）系タ−ポリマー生成方法
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JP2004182974A (ja) * 2002-11-22 2004-07-02 Mitsubishi Chemicals Corp ポリエーテルポリオールの製造方法
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Publication number Priority date Publication date Assignee Title
EP2483328A2 (fr) * 2009-09-30 2012-08-08 E. I. Du Pont De Nemours And Company Polytriméthylène éther glycol ou ses copolymères présentant une couleur améliorée, et leurs procédés de préparation
EP2483328A4 (fr) * 2009-09-30 2014-09-24 Du Pont Polytriméthylène éther glycol ou ses copolymères présentant une couleur améliorée, et leurs procédés de préparation
CN106589344A (zh) * 2016-12-01 2017-04-26 浙江皇马科技股份有限公司 一种不饱和聚醚的制备方法

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