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
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable

Definitions

• the present invention relates to a ⁇ -methyl- ⁇ -valerolactone polymer.
• Patent Document 1 discloses a biodegradable cord containing a lactic acid-based polymer, a biodegradable aliphatic polyester other than the lactic acid-based polymer, and a lubricant. It is described that the biodegradable string is biodegradable and can be continuously bound with a current binding machine.
• Patent Document 2 discloses a biodegradable plastic or sheet comprising a polylactic acid polymer and a biodegradable aliphatic polyester. It is described that the biodegradable plastic or sheet has excellent impact resistance.
• Patent Document 3 discloses, as a biodegradable aliphatic polyester, a heat-stable and liquid alkyl- ⁇ -valerolactone-based polyester.
• Patent Documents 1 and 2 describe that an aliphatic polyester obtained by ring-opening polymerization of cyclic lactones can be used as a biodegradable aliphatic polyester. However, there is no detailed disclosure of the molecular weight, viscosity, specific structure, etc. of the aliphatic polyester.
• Reference Example 1 of Patent Document 3 discloses a polymer in which the terminal of poly( ⁇ -methyl- ⁇ -valerolactone)diol is modified. However, the above polymer has a problem that depolymerization occurs during terminal modification, resulting in a decrease in molecular weight.
• the present invention provides a ⁇ -methyl- ⁇ -valerolactone polymer having high viscosity.
• 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 ⁇ -methyl- ⁇ -valerolactone polymer represented by the following general formula (I) and having a number average molecular weight of 2,000 or more and 100,000 or less.
• R 1 is 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, a One hydrogen atom bonded to a terminal carbon atom in an aryl group, an arylalkyl group having 7 to 12 carbon atoms, or a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the following formula (X).
• One hydrogen atom bonded to at least one terminal carbon atom of an 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) Indicates an oxygen atom-containing hydrocarbon group.
• formula (X) Indicates an oxygen atom-containing hydrocarbon group.
• 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, or 7 to 12 carbon atoms. represents an arylalkyl group of n is an integer from 8 to 1,000 and m is an integer from 8 to 1,000. When two or more R 2 and m are present, they may be the same or different from each other.
• R 1 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, or 7 carbon atoms.
• R 1 is an oxygen atom in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 10 carbon atoms is substituted with a group represented by the above formula (X)
• X The ⁇ -methyl- ⁇ -valerolactone-based polymer according to [1] above, which contains a hydrocarbon group.
• R 2 is a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. -Methyl- ⁇ -valerolactone polymer.
• a ⁇ -methyl- ⁇ -valerolactone polymer having high viscosity can be provided.
• the ⁇ -methyl- ⁇ -valerolactone-based polymer of the present embodiment is represented by the general formula (I) and has a number average molecular weight of 2,000 or more and 100,000 or less, so that it can exhibit high viscosity. can.
• the ⁇ -methyl- ⁇ -valerolactone-based polymer of the present embodiment (hereinafter sometimes simply referred to as “polymer”) is a polymer obtained by ring-opening polymerization of ⁇ -methyl- ⁇ -valerolactone. At least one hydroxyl group at the end of the molecule is modified with another functional group, so that a polymer can be obtained in which a decrease in thermal decomposition is suppressed.
• the raw material of the polymer is ⁇ -methyl- ⁇ -valerolactone, it is considered to have good biodegradability.
• the polymer of this embodiment can be expected to be used as a material for a pressure-sensitive adhesive having good adhesiveness because of its high viscosity.
• the polymer of the present embodiment has a high viscosity, for example, by forming a resin composition with other resins, it is considered that the strength and the like are improved as compared with other resins. It can also be expected to be used as a drug.
• ⁇ -methyl- ⁇ -valerolactone polymer The polymer of this embodiment is represented by the following general formula (I).
• R 1 is 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, a It represents an aryl group or an arylalkyl group having 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.
• Linear alkyl groups having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl.
• n-nonyl group n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group and the like.
• Examples of branched alkyl groups having 3 to 20 carbon atoms include isopropyl group, 1-methylpropyl group, 2-methylpropyl group, t-butyl group, 1,1-dimethylpropyl group and 2,2-dimethylpropyl group.
• 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.
• linear alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-propenyl, n-butenyl (e.g., 2-butenyl and 3-butenyl), n-pentenyl (e.g., 3 -pentenyl group and 4-pentenyl group), n-hexenyl group (e.g., 1-hexenyl group and 5-hexenyl group), n-heptenyl group (e.g., 1-heptenyl group and 1,3-heptadienyl group), n- Octenyl group (e.g., 7-octenyl group and 2,7-octadienyl group), n-nonenyl group (e.g., 3-nonenyl group and 3,6-nonadienyl group), n-decenyl group (e.g., 1,3-decadienyl group) and 1,3,5-dec
• Examples of branched alkenyl groups having 3 to 20 carbon atoms include isopropenyl, 1-methylpropenyl, 2-methylpropenyl, t-butenyl, 1,1-dimethylpropenyl and 2,2-dimethylpropenyl.
• 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 a linear alkyl group having 1 to 20 carbon atoms and 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 an oxygen atom-containing hydrocarbon group substituted with the represented group or a branched alkyl group having 3 to 20 carbon atoms is represented by the following formula (X) represents an oxygen atom-containing hydrocarbon group substituted with a group.
• the bond indicated by * binds to a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms.
• R 2 in the above formula (X) has the same meaning as R 2 described later.
• the straight-chain alkyl group having 1 to 20 carbon atoms that bonds to the above formula (X) the groups exemplified as the "linear alkyl group having 1 to 20 carbon atoms” can be similarly exemplified.
• the linear alkyl group having 1 to 20 carbon atoms that bonds to the above formula (X) is preferably a linear alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms. group, more preferably a straight-chain alkyl group having 2 to 10 carbon atoms, and even more preferably a straight-chain alkyl group having 2 to 5 carbon atoms.
• the branched alkyl group having 3 to 20 carbon atoms that bonds to the above formula (X) can be similarly exemplified as the above-mentioned "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 number of repetitions and is an integer of 8 to 1,000, preferably 8 to 800, more preferably 10 to 500, still more preferably 10 to 300, and may be 10 to 100, 10 ⁇ 80, or 10-60. If m is an integer less than 8, the viscosity of the polymer may decrease. Moreover, when m is an integer exceeding 1,000, there is a possibility that the handleability and productivity of the resin may be deteriorated.
• 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 1 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, from the viewpoint that the polymer has a desired molecular weight and can easily obtain a high viscosity.
• One hydrogen atom bonded to a terminal carbon atom in an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or a linear alkyl group having 1 to 20 carbon atoms is represented by the above formula (X).
• One hydrogen atom bonded to at least one terminal carbon atom of an oxygen atom-containing hydrocarbon group substituted with a group or a branched alkyl group having 3 to 20 carbon atoms is represented by the above formula (X) It is preferably an oxygen atom-containing hydrocarbon group substituted with a group.
• 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
• 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 can be exemplified in the same manner as the above-mentioned "linear or branched alkyl group having 1 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 can be similarly exemplified as the above-mentioned "linear or branched alkenyl group having 2 to 20 carbon atoms".
• 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 can be similarly exemplified as the above-mentioned "aryl group having 6 to 12 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 can be similarly exemplified by the groups exemplified as the "arylalkyl group having 7 to 12 carbon atoms”.
• the arylalkyl group having 7 to 12 carbon atoms represented by R 2 is preferably a phenylmethyl group.
• R 2 is preferably a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, from the viewpoint that the polymer has a desired molecular weight and a high viscosity is easily obtained. .
• n represents the average repetition number and is an integer of 8 to 1,000, preferably 8 to 800, more preferably 10 to 600, still more preferably 10 to 500, still more preferably 10 to 300. If n is an integer less than 8, the viscosity of the polymer may become low. Moreover, when n is an integer exceeding 1,000, there is a possibility that the handleability and productivity as a resin may be inferior.
• the number average molecular weight of the polymer is 2,000 or more and 100,000 or less. If the polymer average molecular weight is less than 2,000, the viscosity may become low. If the average molecular weight of the polymer exceeds 100,000, the handleability and productivity during molding may deteriorate.
• the number average molecular weight of the polymer is preferably 2,500 or more, more preferably 3,000 or more. Also, the number average molecular weight of the polymer is preferably 80,000 or less, more preferably 50,000 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.
• the weight average molecular weight of the polymer is preferably 3,000 or more and 200,000 or less. If the weight average molecular weight is 3,000 or more, it is easy to develop good viscosity. If the weight-average molecular weight is 200,000 or less, it tends to be excellent in handleability and productivity during molding.
• the weight average molecular weight of the polymer is more preferably 3,700 or more, and still more preferably 4,500 or more. Also, the weight average molecular weight of the polymer is more preferably 160,000 or less, still more preferably 125,000 or less, and more preferably 100,000 or less. All "weight average molecular weights" described in this specification are weight average molecular weights in terms of standard polystyrene obtained by gel permeation chromatography (GPC) measurement. A detailed measurement method can follow the method described in Examples.
• viscosity is the viscosity of a polymer measured with an E-type viscometer.
• the measurement temperature can be optimized according to the molecular weight and the like.
• high viscosity means that the viscosity at 80°C measured with an E-type viscometer is 400 mPa ⁇ s or more.
• the preferred viscosity range varies depending on the application of the polymer, it is preferably 400 mPa s or more at 80° C. from the viewpoint of sufficiently exhibiting functions such as substrate retention, strength, and adhesiveness. It is more preferably 1,000 mPa ⁇ s or more at °C.
• the upper limit of the viscosity of the polymer is not limited as long as it is measured with an E-type viscometer.
• an E-type viscometer for example, when the molecular weight of the polymer exceeds around 25,000, the viscosity is too high and measurement becomes difficult even if the measurement temperature is increased.
• the polymers of this embodiment are characterized by high viscosities and can even reach the measurement limits mentioned above.
• the polymer has a viscosity of 400 to 150,000 mPa ⁇ s at 80° C., so that it can be expected to be used as a material for a pressure-sensitive adhesive having good adhesiveness.
• the polymer has a viscosity of 400 to 150,000 mPa ⁇ s at 80° C., it can be expected to be used as a modifier for other resins.
• the measurement temperature can be set according to the molecular weight and the like.
• the polymer preferably has a viscosity of, for example, 3,500 to 150,000 mPa ⁇ s, more preferably 4,000 to 150,000 mPa ⁇ s at 30°C.
• the polymer preferably has a viscosity of, for example, 650 to 150,000 mPa ⁇ s at 60° C., more preferably 800 to 150,000 mPa ⁇ s.
• the polymer of the present embodiment can be obtained by adding a terminal modifier to a reaction solution obtained by reacting ⁇ -methyl- ⁇ -valerolactone, an alcohol compound or water, and a basic catalyst to perform a terminal modification reaction (hereinafter referred to as , 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 ring-opening polymerization reaction and the terminal modification reaction are performed in one pot, so the above production method can be said to be a simplified process.
• the polymer of the present embodiment is not produced by being limited to the production method described above.
• Reference Example 1 of Patent Document 3 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. Since 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.
• a high-molecular-weight polymer can be obtained by the above-described production method without lowering the molecular weight 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.
• 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.
• the alcohol compound may be a monohydric alcohol or a polyhydric alcohol such as a dihydric alcohol and a trihydric alcohol.
• Water that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained. For example, tap water, distilled water, ion-exchanged water, industrial water, deionized water, etc. can be used.
• Base catalysts that can be used in the present embodiment include metal catalysts such as alkali metals and alkali metal compounds, organic base compounds, and the like.
• the basic catalyst may be used alone or in combination of two or more.
• the alkali metal compound include organic alkali metal compounds, alkali metal hydroxide compounds, and alkali metal hydride compounds. Among them, organic lithium compounds such as butyllithium are preferred.
• organic base compounds include amine compounds having an amidine skeleton or a guanidine skeleton.
• Metal catalysts such as organomagnesium compounds and organozinc compounds can also be used as basic catalysts.
• a base catalyst in an amount of 0.005 to 1.5 molar equivalents relative to the hydroxyl group of the alcohol compound.
• a basic catalyst it is preferable to add 0.005 to 3.0 molar equivalents of a basic catalyst 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. In the reaction step, it is preferable to add 5 to 1,500 molar equivalents of ⁇ -methyl- ⁇ -valerolactone to the hydroxyl groups of the alcohol compound. When water is used, it is preferable to add 5 to 1,500 molar equivalents of ⁇ -methyl- ⁇ -valerolactone to water.
• 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. 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 arylalkyl groups having 7 to 12 carbon atoms. Acid anhydrides and acid halides having at least one group selected from the group consisting of groups can be used. The "branched alkyl group” has 3 to 20 carbon atoms, and the "branched alkenyl group” has 3 to 20 carbon atoms.
• 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.
• water it is preferable to add 1.0 to 20.0 molar equivalents of the terminal modifier 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.
• the 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 for reacting ⁇ -methyl- ⁇ -valerolactone, the alcohol compound or water, and the base catalyst may be usually 20 to 100° C., and the reaction time is usually 1 minute to 24 hours. is.
• the reaction temperature for performing the terminal modification reaction is usually 20 to 80° C., and 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. For example, the reaction mixture after the reaction step can be washed with a reaction solvent and water, concentrated, and purified by a method commonly used for separation and purification of organic compounds, such as distillation.
• Applications of the polymer of this embodiment include, for example, pressure-sensitive adhesives, adhesives, and resin modifiers.
• resins to be modified include biomass resins, biodegradable resins, and general-purpose thermoplastic resins.
• biomass resin or biodegradable resin examples include polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), Polyglycolic acid (PGA), polyethylene furanoate (PEF), polyhydroxyalkanoate (PHA) [e.g., polyhydroxybutyrate (PHB), polyhydroxybutyrate valerate (PHBV), 3-hydroxybutyrate-3-hydroxy hexanoic acid copolymer polyester, etc.], cellulose acetate (CA), and starch polyester (Mater-Bi (registered trademark)).
• PLA polylactic acid
• PCL polycaprolactone
• PBS polybutylene succinate
• PBSA polybutylene succinate adipate
• PBAT polybutylene adipate terephthalate
• PFA polyglycolic acid
• PEF polyethylene furanoate
• thermoplastic resins examples include thermoplastic resins and thermoplastic elastomers having suitable processing temperatures of about 200° C. or less.
• thermoplastic resin examples include polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), ethylene vinyl acetate copolymer (EVA), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), Polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene terephthalate succinate (PETS).
• PMMA polymethyl methacrylate
• PVA polyvinyl alcohol
• EVA ethylene vinyl acetate copolymer
• PE polyethylene
• PP polypropylene
• PVC polyvinyl chloride
• PS Polystyrene
• ABS acrylonitrile-butadiene-styrene copolymer
• PC polycarbonate
• PET poly
• thermoplastic elastomer examples include olefin-based, styrene-based, ester-based, urethane-based, acrylic-based, vinyl chloride-based, amide-based, and fluorine-based thermoplastic elastomers. Specific examples include polyester elastomer (TPC) and thermoplastic polyurethane (TPU). Further, as the general-purpose thermoplastic resin, a thermoplastic resin having high heat resistance to temperatures exceeding about 200° C. (also referred to as “high heat-resistant resin”) can be mentioned.
• the high heat-resistant resin examples include polyamide (PA), polyacetal (POM), fluororesin [e.g., polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP)], polycyclohexylene dimethylene terephthalate (PCT), polymethylpentene (PMP), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT).
• the resin to be modified using the polymer of this embodiment is not limited to the above biomass resin, biodegradable resin and general-purpose thermoplastic resin.
• thermogravimetric analysis (5% weight loss temperature)] Using thermogravimetric analysis (product name: TGA/DSC1, manufactured by Mettler Toledo), under a nitrogen atmosphere (flow rate: 100 mL/min), when the temperature was raised from 50°C to 500°C at a rate of 10°C/min. , the temperature at which the weight was reduced by 5% was measured.
• V notch processing (remaining width 8 mm, tip radius 0.25 mm) was performed on the center of the long side to prepare a notched strip test piece.
• (3) Impact resistance test The notched strip test piece prepared is stored at 23 ° C. and 49% humidity for 24 hours or more, and a Charpy impact resistance tester ("DG-CB" manufactured by Toyo Seiki Seisakusho Co., Ltd.) is used. , 23° C., 49% humidity, impact strength measured with a hammer load of 2 J was evaluated. The average value of 10 measurements was adopted.
• Example 1 A 4-necked glass flask with an internal volume of 500 mL was purged with nitrogen, 7.9 g (90 mmol) of isoamyl alcohol and 231 g (2,025 mmol) of ⁇ -methyl- ⁇ -valerolactone were charged, and the temperature was raised to 60°C. . 0.84 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 2 A 4-necked glass flask with an internal volume of 500 mL was purged with nitrogen, 1.6 g (18.2 mmol) of isoamyl alcohol and 231 g (2,025 mmol) of ⁇ -methyl- ⁇ -valerolactone were added and the temperature was raised to 60°C. I warmed up. 0.35 mL of n-butyl lithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyl lithium 1.6 M hexane solution
• Example 3 A four-necked glass flask with an internal volume of 1,000 mL was purged with nitrogen, and 1.6 g (18.2 mmol) of isoamyl alcohol and 623 g (5,460 mmol) of ⁇ -methyl- ⁇ -valerolactone were added to 60°C. The temperature was raised to 0.34 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 4 A four-necked glass flask with an internal volume of 1,000 mL was purged with nitrogen, and 0.9 g (10 mmol) of isoamyl alcohol and 627 g (5,500 mmol) of ⁇ -methyl- ⁇ -valerolactone were added and the temperature was raised to 60°C. I warmed up. 0.41 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 5 A 4-necked glass flask with an internal volume of 3,000 mL was purged with nitrogen, 0.9 g (10 mmol) of isoamyl alcohol and 913 g (8,000 mmol) of ⁇ -methyl- ⁇ -valerolactone were added, and the temperature was raised to 60°C. I warmed up. 0.45 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 6 A four-necked glass flask with an internal volume of 500 mL was purged with nitrogen, 5.6 g (90 mmol) of ethylene glycol and 231 g (2025 mmol) of ⁇ -methyl- ⁇ -valerolactone were added, and the temperature was raised to 60°C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 7 A four-necked glass flask with an internal volume of 500 mL was purged with nitrogen, 5.6 g (90 mmol) of ethylene glycol and 231 g (2025 mmol) of ⁇ -methyl- ⁇ -valerolactone were added, and the temperature was raised to 60°C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 8 A four-necked glass flask with an internal volume of 500 mL was purged with nitrogen, 5.6 g (90 mmol) of ethylene glycol and 231 g (2025 mmol) of ⁇ -methyl- ⁇ -valerolactone were added, and the temperature was raised to 60°C. 0.84 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 9 A 4-necked glass flask with an internal volume of 500 mL was purged with nitrogen, 8.1 g (90 mmol) of 1,4-butanediol and 231 g (2025 mmol) of ⁇ -methyl- ⁇ -valerolactone were added and the temperature was raised to 60°C. I warmed up. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 10 A glass four-necked flask with an internal volume of 500 mL was purged with nitrogen, 14.4 g (90 mmol) of 1,9-nonanediol and 231 g (2025 mmol) of ⁇ -methyl- ⁇ -valerolactone were added and the temperature was raised to 60°C. I warmed up. 0.80 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 11 A four-necked glass flask with an internal volume of 500 mL was purged with nitrogen, 21.8 g (90 mmol) of cetanol and 231 g (2025 mmol) of ⁇ -methyl- ⁇ -valerolactone were added, and the temperature was raised to 60°C. 0.84 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• Example 12 A four-necked glass flask having an internal volume of 500 mL was purged with nitrogen, 14.2 g (90 mmol) of decanol and 231 g (2025 mmol) of ⁇ -methyl- ⁇ -valerolactone were added, and the temperature was raised to 60°C. 0.80 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 13 A four-necked glass flask with an internal volume of 1,000 mL was purged with nitrogen, 5.6 g (90 mmol) of ethylene glycol and 639 g (5598 mmol) of ⁇ -methyl- ⁇ -valerolactone were charged, and the temperature was raised to 60°C. . 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 14 A four-necked glass flask with an internal volume of 2,000 mL was purged with nitrogen, 5.6 g (90 mmol) of ethylene glycol and 1072 g (9396 mmol) of ⁇ -methyl- ⁇ -valerolactone were added, and the temperature was raised to 60°C. . 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 15 A 4-necked glass flask with an internal volume of 500 mL was purged with nitrogen, and 12.1 g (90 mmol) of trimethylolpropane and 231 g (2025 mmol) of ⁇ -methyl- ⁇ -valerolactone were charged. and the temperature was raised to 60°C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• Example 16 A four-necked glass flask with an internal volume of 2,000 mL was purged with nitrogen, 12.1 g (90 mmol) of trimethylolpropane and 1064 g (9324 mmol) of ⁇ -methyl- ⁇ -valerolactone were added, and the temperature was raised to 60°C. bottom. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 60° C. for 60 minutes.
• n-butyllithium 1.6 M hexane solution
• 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.
• the obtained polymer is represented by the above general formula (Ib), and R 1 , R 2 , n and m are as shown in Table 1.
• the resulting reaction solution containing the polymer was extracted with toluene and water and purified by a thin film evaporator to obtain 135 g (0.04 mmol) of the polymer.
• the obtained polymer is represented by the following structural formula (II), where n and m are as 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. After putting 1500 mL of dichloromethane as a solvent into a 3,000 mL internal volume glass 4-necked flask, the above purified ring-opening polymer, 22.7 g (270 mmol) of 3,4-dihydro-2H-pyran, and p-toluenesulfone 0.9 g (3.6 mmol) of pyridinium acid was added and stirred at 25° C. for 5 hours to obtain a reaction solution containing a polymer.
• the resulting reaction solution containing the polymer was purified by extraction with dichloromethane and water and distillation to obtain 114 g (0.06 mmol) of the polymer.
• the obtained polymer is represented by the following structural formula (III), where n and m are as shown in Table 1.
• Table 1 shows the results of the various physical property measurements and evaluations described above for the polymers obtained in Examples and Comparative Examples. For reference, Table 1 shows the impact resistance of the polylactic acid alone.
• the polymers obtained in Examples have higher viscosities than the polymers obtained in Comparative Examples. Further, from thermogravimetric analysis, the polymers obtained in Examples are considered to be polymers with suppressed thermal decomposition. From the comparison between Examples 1 to 16 and Comparative Example 2, it can be seen that the structure of the polymer of this embodiment significantly improved the thermal stability. Further, it can be seen that the impact strength in Examples 1-16 is superior to the impact strength in polylactic acid alone and Comparative Examples 1-4. In particular, from the comparison between Example 1 and Comparative Example 4, the comparison between Example 6 and Comparative Example 1, and the comparison between Example 6 and Comparative Example 3, resins using the polymers obtained in Examples It can be seen that the composition has much better impact strength. Therefore, it can be seen that the polymer of this embodiment can improve the strength of polylactic acid and is useful as a modifier.
• the polymer of this embodiment has a high viscosity. Therefore, it is useful for various applications where high viscosity is required.
• Polymers of this embodiment can be used, for example, as adhesives, adhesives and modifiers.

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