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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment

Definitions

• the present invention relates to a method for producing a ⁇ -methyl- ⁇ -valerolactone polymer.
• Patent Document 1 discloses a heat-stable liquid alkyl- ⁇ -valerolactone polymer and a method for producing the same. As the above production method, it is described that a hydroxyl group-containing polymer represented by a specific general formula is reacted with a cyclic ether represented by a specific general formula in the presence of an acidic catalyst.
• the present invention provides a production method capable of producing a terminal-modified ⁇ -methyl- ⁇ -valerolactone polymer without causing a decrease in molecular weight.
• the present inventors have conceived the following invention and found that the problems can be solved. That is, the present invention is as follows.
• a method for producing a ⁇ -valerolactone polymer. [2] The production method according to [1] above, wherein a terminal modification reaction is performed at a reaction temperature of 20 to 80° C. after adding the terminal modifying agent. [3] The production method according to [1] or [2] above, wherein 1.0 to 20.0 molar equivalents of a terminal modifier are added to the hydroxyl groups of the alcohol compound.
• the terminal modifier includes a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and carbon
• the method for producing the ⁇ -methyl- ⁇ -valerolactone-based polymer (hereinafter sometimes simply referred to as “polymer”) of the present embodiment comprises mixing ⁇ -methyl- ⁇ -valerolactone with an alcohol compound or water. , a step of adding a terminal modifying agent to the reaction solution reacted with the base catalyst to carry out a terminal modifying reaction (hereinafter also referred to as a “reaction step”).
• the above production method is characterized by adding a terminal modifying agent directly to a reaction solution obtained by reacting ⁇ -methyl- ⁇ -valerolactone, an alcohol compound or water, and a basic catalyst.
• a terminal modifier is added to the reactor in which the ring-opening polymerization was performed without removing the ring-opening polymer once, and the terminal of the ring-opening polymer is Denaturation can be performed.
• the reaction step since the ring-opening polymerization reaction and the terminal modification reaction are performed in one pot, the above production method can be said to be a simplified process, and an improvement in productivity can be expected.
• Reference Example 1 of Patent Document 1 describes that the molecular weight is reduced by terminal modification.
• ⁇ -methyl- ⁇ -valerolactone becomes a ring-opening polymer having terminal hydroxyl groups through a ring-opening polymerization reaction. Since the ring-opening polymer has a terminal hydroxyl group in this manner, depolymerization is likely to occur.
• terminal modification of the ring-opened polymer once taken out is carried out at a relatively high temperature (about 100°C), the rate of thermal decomposition tends to increase, and the ring-opened polymer undergoes depolymerization, resulting in a decrease in molecular weight. Conceivable.
• the molecular weight does not decrease, it is possible to obtain a high-molecular-weight polymer even though the terminal is modified.
• Alcohol compound or water The alcohol compound that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained.
• An alcohol compound may be used individually by 1 type, and may use 2 or more types together.
• Alcohol compounds include, for example, linear or branched aliphatic hydrocarbon alcohols having 1 to 20 carbon atoms, alcohols of aromatic hydrocarbons having 6 to 12 carbon atoms, and alkyl aromatic hydrocarbons having 7 to 12 carbon atoms. Alcohol etc. are mentioned. These alcohol compounds may have saturated or unsaturated hydrocarbon groups. In the case of the above-mentioned "alcohol of branched aliphatic hydrocarbon", the number of carbon atoms is 3-20.
• alcohol compounds include alcohols of linear or branched aliphatic hydrocarbons having 1 to 16 carbon atoms, alcohols of aromatic hydrocarbons having 6 to 9 carbon atoms, and alkyl compounds having 7 to 10 carbon atoms.
• Aromatic hydrocarbon alcohols are preferred, linear or branched aliphatic hydrocarbon alcohols having 1 to 10 carbon atoms are more preferred, and linear or branched aliphatic hydrocarbon alcohols having 1 to 5 carbon atoms are preferred.
• the alcohol compound may be at least one selected from the group consisting of monoalcohols and polyhydric alcohols.
• alcohol compounds include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1 -tridecanol, 1-tetradecanol, 1-heptadecanol, 1-hexadecanol (cetanol), 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-icosadecanol; Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octane Diol, 1,9-nonanediol, 1,10-decane
• the water that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained.
• tap water, distilled water, ion-exchanged water, industrial water, deionized water, etc. can be used, and from the viewpoint of reaction efficiency, yield, etc., distilled water and ion-exchanged water are preferred.
• Organic lithium compounds such as methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, tert-octyllithium, n-decyllithium, phenyllithium, 2-naphthyl Lithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclopentyllithium and the like.
• alkali metal hydroxide compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide and the like.
• alkali metal hydride compounds include sodium borohydride and the like.
• organic base compounds include amine compounds having an amidine skeleton or a guanidine skeleton.
• amine compounds include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), guanidine, 1,1, 3,3-tetramethylguanidine (TMG), 1,5,7-triazabicyclo[4.4.0]decan-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[ 4.4.0] decan-5-ene (MTBD) and the like.
• DBU 1,8-diazabicyclo[5.4.0]undecene-7
• DBN 1,5-diazabicyclo[4.3.0]nonene-5
• TMG 1,1, 3,3-tetramethylguanidine
• TMD 1,5,7-triazabicyclo[4.4.0]decan-5-ene
• TBD 7-methyl-1,5,7-triazabicyclo[ 4.
• Metal catalysts such as organomagnesium compounds and organozinc compounds can also be used as basic catalysts.
• the base catalyst is preferably 0.005 to 1.5 molar equivalents, more preferably 0.007 to 1.2 molar equivalents, still more preferably 0.007, relative to the hydroxyl group of the alcohol compound. It is preferable to add up to 1.0 molar equivalents, more preferably 0.007 to 0.8 molar equivalents, and even more preferably 0.007 to 0.6 molar equivalents.
• a basic catalyst in an amount of preferably 0.005 to 3.0 molar equivalents, more preferably 0.1 to 1.5 molar equivalents, relative to water.
• ⁇ -methyl- ⁇ -valerolactone As ⁇ -methyl- ⁇ -valerolactone that can be used in this embodiment, one produced by a known method can be used. For example, it can be produced by a known method using 2-hydroxy-4-methyltetrahydropyran or the like as a raw material (JP-B-6-53691, etc.). In addition, ⁇ -methyl- ⁇ -valerolactone can be used as a commercial product, and can be used regardless of whether it is derived from petrochemicals or bio-derived.
• Terminal modifiers that can be used in this embodiment include acid anhydrides and acid halides (acid halides are also referred to as “halogenated esters”). Acid anhydrides and acid halides are not particularly limited as long as the effects of the present invention can be obtained.
• terminal modifiers include, for example, linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 12 carbon atoms, and carbon A terminal modifier having at least one group selected from the group consisting of 7 to 12 arylalkyl groups can be used.
• the terminal modifier contains at least one group selected from the group consisting of linear or branched alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 12 carbon atoms, and arylalkyl groups having 7 to 12 carbon atoms. acid anhydrides and acid halides having The "branched alkyl group” has 3 to 20 carbon atoms, and the "branched alkenyl group” has 3 to 20 carbon atoms. Among them, from the viewpoint of handleability, the terminal modifier is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, or 6 to 9 carbon atoms.
• an acid anhydride and acid halide having at least one group selected from the group consisting of an aryl group and an arylalkyl group having 7 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms They are acid anhydrides and acid halides having at least one group selected from the group consisting of groups.
• Specific acid anhydrides include acetic anhydride, oxalic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, glutaric anhydride, methacrylic anhydride, butyric anhydride, and isobutyric anhydride. , 1,8-naphthalic anhydride, trifluoroacetic anhydride, cyclohexanecarboxylic anhydride and the like.
• acid halides include acetyl chloride, propionyl chloride, butyroyl chloride, trifluoroacetyl chloride, benzoyl chloride, 2-furoyl chloride, hexanoyl chloride, phenylacetyl chloride, acetyl bromide, propionyl bromide, and bromide. benzoyl and the like.
• a terminal modifier is preferably added in an amount of 1.0 to 20.0 molar equivalents, more preferably 1.0 to 10.0 molar equivalents, still more preferably 1 to the hydroxyl group of the alcohol compound. It is preferable to add 0.0 to 8.0 molar equivalents.
• water it is preferable to add a terminal modifier in an amount of preferably 1.0 to 20.0 molar equivalents, more preferably 1.0 to 10.0 molar equivalents, relative to water.
• a co-catalyst may be added in the reaction step, if necessary.
• cocatalysts that can be used include amine compounds such as triethylamine, tributylamine, trioctylamine, imidazole, pyridine, aminopyridine and 4-dimethylaminopyridine.
• amine compounds such as triethylamine, tributylamine, trioctylamine, imidazole, pyridine, aminopyridine and 4-dimethylaminopyridine.
• a co-catalyst can be added in an amount of 0.001 to 10 molar equivalents relative to the hydroxyl group of the alcohol compound.
• water when water is used, the co-catalyst can be added in an amount of 0.001 to 10 molar equivalents relative to water.
• solvent The reaction step can be performed in the presence of a solvent inert to the ring-opening polymerization reaction.
• solvents include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane and n-pentane; aromatic hydrocarbons such as benzene, toluene and xylene.
• reaction temperature during the ring-opening polymerization reaction in which ⁇ -methyl- ⁇ -valerolactone, an alcohol compound or water, and a basic catalyst are reacted is usually 20 to 100°C, preferably 20°C. ⁇ 80°C, more preferably 30-80°C.
• the reaction time is usually 1 minute to 24 hours.
• the reaction temperature at which the terminal modification reaction is carried out is usually 20 to 80°C, preferably 30 to 80°C, more preferably 50 to 80°C. is.
• the terminal modification reaction can proceed under relatively mild temperature conditions.
• the reaction time is usually 1 minute to 24 hours.
• the polymer of this embodiment can be produced through the reaction steps described above. If desired, a post-treatment step may be performed to isolate the polymer produced.
• a suitable method can be adopted from known methods.
• the reaction mixture after the reaction step can be washed with a reaction solvent or water, concentrated, and purified by separation and purification.
• the separation and purification for example, methods used for separation and purification of ordinary organic compounds, such as distillation, thin film evaporation, degassing under reduced pressure, and reprecipitation, can be employed.
• the solvent used for the reprecipitation is not particularly limited as long as it is a solvent in which the polymer is insoluble.
• organic solvents examples include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, and alcohols such as methanol, ethanol, and propanol.
• aliphatic hydrocarbons such as pentane, hexane, heptane, and octane
• alcohols such as methanol, ethanol, and propanol.
• hexane and methanol are preferred, and hexane is preferred when partial dissolution of a low-molecular-weight polymer is suppressed.
• R 1 is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or It represents an aryl group of 6 to 12 or an arylalkyl group of 7 to 12 carbon atoms.
• the "branched alkyl group” has 3 to 20 carbon atoms
• the "branched alkenyl group” has 3 to 20 carbon atoms.
• the linear or branched alkyl group having 1 to 20 carbon atoms is preferably a linear or branched alkyl group having 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms, from the viewpoint of handleability.
• It is a linear or branched alkyl group, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylbutyl group, 3-methylbutyl group, n-pentyl group and 2,2-dimethylpropyl group are preferred.
• the linear or branched alkenyl group having 2 to 20 carbon atoms is preferably a linear or branched alkenyl group having 2 to 15 carbon atoms, more preferably a linear or branched alkenyl group having 3 to 10 carbon atoms, from the viewpoint of handleability. It is a linear or branched alkenyl group, more preferably a linear or branched alkenyl group having 3 to 6 carbon atoms.
• the aryl group having 6 to 12 carbon atoms includes a phenyl group, 2-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2-naphthyl group and the like.
• a phenyl group is preferred.
• Examples of arylalkyl groups having 7 to 12 carbon atoms include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, naphthylmethyl and naphthylethyl groups.
• a phenylmethyl group is preferred.
• R 1 is, as a preferred embodiment, a linear alkyl group having 1 to 20 carbon atoms in which one hydrogen atom bonded to the terminal carbon atom is represented by the following formula (X).
• One hydrogen atom bonded to at least one terminal carbon atom of a substituted oxygen atom-containing hydrocarbon group or a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (X) represents an oxygen atom-containing hydrocarbon group.
• formula (X) the bond indicated by * bonds to a straight-chain alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms.
• the branched alkyl group having 3 to 20 carbon atoms that bonds to the above formula (X) is preferably a branched alkyl group having 3 to 15 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms. , more preferably a branched alkyl group having 3 to 6 carbon atoms, and may be a branched alkyl group having 3 to 5 carbon atoms.
• one hydrogen atom bonded to all terminal carbon atoms of the branched alkyl group having 3 to 20 carbon atoms is an oxygen atom-containing hydrocarbon group substituted with the group represented by the above formula (X).
• m represents the average repeating number, preferably an integer of 8 to 1,000, more preferably 8 to 800, still more preferably 10 to 500, still more preferably 10 to 300.
• the polymer can have a relatively high molecular weight, and the effects of the present invention can be favorably exhibited.
• m is an integer of 1,000 or less, the polymer is excellent in handleability and productivity.
• R 1 when there are a plurality of groups represented by the above formula (X), these may be the same or different.
• a plurality of R 2 and m may be present. When two or more R 2 are present, they may be the same or different from each other. Moreover, when there are a plurality of m, these may be the same or different from each other.
• R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the above formula (X);
• the following structures can be specifically exemplified as the general formula (I).
• R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having Q carbon atoms is replaced with a group represented by the above formula (X)
• the above general formula (I) is represented by the following general formula (Ia).
• Q is an integer of 1-20.
• R 1 is an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X).
• the following structures can be specifically exemplified as the general formula (I).
• R 1 is an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the above carbon atoms at all terminal carbon atoms of the 2-methylpropyl group is replaced with a group represented by the above formula (X);
• the above general formula (I) is represented by the following general formula (Ic).
• R 1 is an oxygen atom-containing hydrocarbon in which one hydrogen atom bonded to the above carbon atoms at two terminal carbon atoms of a 2,2-dimethylpropyl group is substituted with a group represented by the above formula (X)
• the above general formula (I) is represented by the following general formula (Id).
• R 1 is an oxygen atom-containing hydrocarbon in which one hydrogen atom bonded to the carbon atoms at the two terminal carbon atoms of the 2,2-dimethylbutyl group is replaced with a group represented by the above formula (X).
• the above general formula (I) is represented by the following general formula (Ie).
• R 1 is an oxygen atom-containing hydrocarbon in which one hydrogen atom bonded to the above carbon atoms at all terminal carbon atoms of a 2,2-dimethylpropyl group is substituted with a group represented by the above formula (X)
• the above general formula (I) is represented by the following general formula (If).
• R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, Alternatively, it represents an arylalkyl group having 7 to 12 carbon atoms.
• the "branched alkyl group” has 3 to 20 carbon atoms, and the “branched alkenyl group” has 3 to 20 carbon atoms.
• the linear or branched alkyl group having 1 to 20 carbon atoms represented by R 2 is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, more preferably carbon A linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms.
• methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylbutyl group, n-pentyl group and 2,2-dimethylpropyl group are preferred.
• the linear or branched alkenyl group having 2 to 20 carbon atoms represented by R 2 is preferably a linear or branched alkenyl group having 2 to 15 carbon atoms, more preferably 3, from the viewpoint of handleability. It is a linear or branched alkenyl group having up to 10 carbon atoms, more preferably a linear or branched alkenyl group having 3 to 6 carbon atoms.
• the aryl group having 6 to 12 carbon atoms represented by R 2 is preferably a phenyl group.
• the arylalkyl group having 7 to 12 carbon atoms represented by R 2 is preferably a phenylmethyl group.
• the number average molecular weight of the polymer is preferably 2,000 or more and 80,000 or less. All "number average molecular weights" described herein are standard polystyrene-equivalent number average molecular weights determined by gel permeation chromatography (GPC) measurement. A detailed measurement method can follow the method described in Examples.
• Examples 2 to 12 A polymer was obtained in the same manner as in Example 1, except that the conditions were changed to those shown in Table 1.
• Example 13 to 16 In Example 1, the procedure was the same as in Example 1, except that the conditions were changed to those shown in Table 1, and the post-treatment steps were extraction with toluene and water, reprecipitation in a large amount of hexane, and purification under reduced pressure at 80°C under vacuum. to obtain a polymer.
• Example 17-18 A polymer was obtained in the same manner as in Example 1, except that the conditions were changed to those shown in Table 1.
• Examples 19 to 30 A polymer was obtained in the same manner as in Example 1, except that the conditions were changed to those shown in Table 1.
• the resulting reaction solution containing the ring-opened polymer was purified by extraction with toluene and water, reprecipitation in a large amount of hexane, and drying under reduced pressure at 80°C.
• the above purified ring-opening polymer was placed in a glass four-necked flask having an internal volume of 500 mL, 22.1 g (216 mmol) of acetic anhydride was added, and the mixture was stirred at 100°C for 6 hours to obtain a reaction solution containing the polymer. .
• the resulting reaction solution containing the polymer was purified by extraction with toluene and water and distillation to obtain 114 g (0.06 mmol) of the polymer.
• Comparative Example 2 A polymer was obtained in the same manner as in Comparative Example 1, except that the conditions in Comparative Example 1 were changed to those shown in Table 1.
• the polymers obtained in Examples 1 to 18, 24, 29 and 30 and Comparative Examples 4 and 5 are represented by the above general formula (I), and R 1 , R 2 and n are as shown in Table 2. be.
• the polymers obtained in Examples 19 to 21, 25, 26 and Comparative Examples 1 and 2 are represented by the above general formula (Ib), and R 1 , R 2 , n and m are shown in Table 2. That's right.
• the polymers obtained in Examples 22 and 23 are represented by the above general formula (Ia), and R 1 , R 2 , n and m are as shown in Table 2.
• the polymers obtained in Examples 27 and 28 and Comparative Example 6 are represented by the above general formula (Ie), and R 1 , R 2 , n and m are as shown in Table 2.

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• 2022
  • 2022-10-20 JP JP2023554748A patent/JPWO2023068347A1/ja active Pending
  • 2022-10-20 WO PCT/JP2022/039198 patent/WO2023068347A1/ja not_active Ceased
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