JPH03181516A - Production of alkyl-delta-valerolactone-based polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject polymer, excellent in thermal stability and useful as plasticizers, etc., by reacting respective specific hydroxyl group- containing polymer with cyclic ether in the presence of an acidic catalyst. CONSTITUTION:(A) A hydroxyl group-containing polymer expressed by formula I [R<1> is 1-18C m-functional hydrocarbon; Y is 2-6C alkylene and >=40mol% thereof is 5-6C alkyltetramethylene; m is 1-3; the average value of n is (1/m) to 87/m)] is reacted with (B) a cyclic ether expressed by formula II (R<2> is 2-4C alkylene; R<3> is H; R<4> is OH or lower alkoxyl or R<3> and R<4> together form single bond) preferably in a molar amount of equimolar amount to 200 times [based on OH in the component (A)] in the presence of an acidic catalyst (e.g. sulfuric acid in an amount of preferably 0.1-10wt.% based on the reaction mixture solution) to afford the objective polymer expressed by formula III.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a novel alkyl-δ-valerolactone polymer and a method for producing the same, and more specifically, the present invention relates to a novel alkyl-δ-valerolactone polymer and a method for producing the same. R2 represents an alkylene group having 2 to 4 carbon atoms, Y represents an alkylene group having 2 to 6 carbon atoms, and 40 moles or more of Y is present in the molecule. is an alkyltetramethylene group having 5 or 6 carbon atoms, m represents an integer of 1 to 3, and n
The average value of is a number of 1/m to 877m) It relates to an alkyl-δ-valerolactone polymer represented by the following and a method for producing the same.

Since the alkyl-δ-valerolactone polymer of the present invention is a liquid polymer having high thermal stability, it is useful as a pre-plasticizing material 11 for resins such as polysalt f-hibinyl.

[Conventional technology]

β-
A liquid β-methyl-δ-valerolactone polyester having a hydroxyl group at the end obtained by ring-opening polymerization reaction of a monomer containing at least 50 moles of methyl-δ-noclerolactone and an organic carbodiimide compound such as dicyclohexylcarbodiimide. The composition is useful as a plasticizer for resins such as polyvinyl chloride because the disadvantage that the polyester originally has is that it is susceptible to thermal depolymerization. is known (see Japanese Unexamined Patent Publication No. 63-225653).

[Problem to be solved by the invention]

According to the studies of the present inventors, it has been found that a liquid alkyl-δ-valerolactone polyester having a hydroxyl group at its terminal, such as the β-methyl-δ-valerolactone polyester having a hydroxyl group at its terminal, and an organic carbodiimide compound It has been found that when this composition is used as a plasticizer for resin, the resin may become cloudy due to the organic carbodiimide compound, and the resin may also exhibit skin irritation. Therefore, alkyl- with a hydroxyl group at the end
It would be extremely desirable if a derivative of δ-valerolactone polyester with improved thermal stability could be obtained since it would provide a plasticizer that is free from the above-mentioned drawbacks caused by organic carposide compounds.

DieMakro
Molecule Chemie) Volume 82, No. 4
1 to 52 (1965), δ-valerolactone-based polyester diol, which is a ring-opening polymer of δ-valerolactone produced using ethylene glycol as an initiator, is heated to reflux in acetic anhydride. It has been reported that the hydroxyl groups at both ends of the δ-valerolactone-based polyester diol were acetylated by reacting with δ-valerolactone-based polyester diol. It has been reported that, unlike polyester diols, it is less susceptible to depolymerization due to heat. When the present inventors attempted to acetylate the terminal hydroxyl group of an alkyl-δ-valerolactone polyester having a hydroxyl group at the terminal according to the acetylation method described above, the reaction occurred as shown in Reference Example 1 below. It has been found that it is difficult to produce an acetylated product with a desired molecular weight with good reproducibility because depolymerization occurs under these conditions.

Therefore, one of the objects of the present invention is to provide a liquid derivative that can be produced from an alkyl-δ-valerolactone polyester having a hydroxyl group at the terminal without depolymerization and has high thermal stability. It's about doing. Another object of the present invention is to provide a method for producing a liquid derivative from an alkyl-δ-valerolactone polyester having a terminal hydroxyl group in thermal stability without depolymerization. It is in.

[Means to solve the problem]

According to the present invention, the above object is achieved by providing an alkyl-δ-valerolactone polymer represented by -Momon (I), and -Momon (in the formula, 11, Y, m
and n are as defined above) in the presence of an acidic catalyst. An alkyl-δ-valerolactone system represented by the general formula (1), which is reacted with a cyclic ether represented by: This is accomplished by providing a method for producing a polymer.

The m-valent hydrocarbon group having 1 to 18 carbon atoms represented by 1%' in the general formula (1) and -Momonya (II) has 1 to 18 carbon atoms.
It is roughly divided into 18 monovalent hydrocarbon groups, C1-18 divalent hydrocarbon groups, and C1-18 trivalent hydrocarbon groups. As a monovalent hydrocarbon group having 1 to 18 carbon atoms,
Methyl group, ethyl group, propyl group, inpropyl group, butyl group, inbutyl group, 5ea-butyl group, te
rt-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, tesyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
Examples include alkyl groups such as a pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group; alkenyl groups such as 2,7-octagenyl group; cycloalkyl groups such as cyclohexyl group; and aralkyl groups such as benzyl group. Examples of divalent hydrocarbon groups having 1 to 18 carbon atoms include ethylene group, trimethylene group, propylene group, tetramethylene group, and 2-methyltrimethylene us2. Alkylene groups such as z-dimethyltrimethylene group, hexamethylene group, 3-methylpentamethylene group, 2-methyloctamethylene group, nonamethylene group; 1,2-cyclohexylene group, 1.3-cyclohexylene tssx, 4- Cycloalkanediyl group such as cyclohexylene group; phenylethylene group, O-xylene-α, α-diyl group, m-
xylene-α, α-diyl group, p-xylene-α, α-
Examples include arylalkanediyl groups such as diyl groups. 1 to 18 trivalent hydrocarbon groups per gram of charcoal
．． 2.3-Probanto'JiH2- (2) Which alkanetriyl group is exemplified.

- The alkylene group having 2 to 4 carbon atoms represented by R2 in Mon'ena (1) and - Mon'ena (III) includes ethylene group, trimethylene group, propylene group, ■-methyltrimethylene group, 2-methyltrimethylene group. group, tetramethylene group, etc.

Examples of the alkylene group having 2 to 6 carbon atoms represented by Y in general formula (1) and -Momonena (II) include ethylene group, 1.1-
) methylene group, tetramethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 2-
Examples include ethyltetramethylene group and pentamethylene group. - The molecule of the alkyl-δ-valerolactone polymer represented by the parentheses ([) or the hydroxyl group-containing polymer represented by the general formula (II) contains mxn Y on average. The number of alkylene groups having 2 to 6 carbon atoms represented by Y is not limited to one type, and two or more types may be used. It is required to be an alkyltetramethylene group having 5 or 6 carbon atoms, such as a 2-methyltetramethylene group, a 1-methyltetramethylene group, or a 2-ethyltetramethylene group. - In a polymer corresponding to a case where the proportion of alkyltetramethylene groups having 5 or 6 carbon atoms in the alkylene group having 2 to 6 carbon atoms represented by Y in the pattern hole (I) is less than 40 moles; , the crystallinity may become high and the ability to plasticize the resin may become insufficient.

In addition, - In the pattern hole (1), Y is 2 or more types of carbon number 2 ~
Two or more structural units represented by the formula % (in the formula, Y is as defined above) contained in the molecule of the alkyl-δ-valerolactone polymer, which is the alkylene group of 6. The arrangement is not particularly limited and may be in the form of random copolymerization or in the form of block copolymerization.

-The average value of n in the hole (1) and -the hole (11):
1/m to 87/mQ), preferably 8/m to 44/n. - In the case of heavy tetramers corresponding to the case where the average value of n is smaller than 17 m in Monna (1), it is inappropriate to use as a plasticizer the resin that is leached from the blended southern resin. On the other hand, a polymer corresponding to the case where the average value of n in the general formula (1) is greater than 87/m has insufficient ability to plasticize the fat. In addition, the average value of On in -Momona (I) and -Momona (II) and the proportion of alkyltetramethylene groups in Y are -#!, respectively.
j, 1H-N for the alkyl-δ-valerolactone polymer case represented by formula CI) or the hydroxyl group-containing polymer represented by general formula U)? This is a value determined based on quantitative analysis of hydrogen atoms in viR measurement.

Among the alkyl-δ-valerolactone polymers represented by -Momona (1), -Momona (where Bl, R, 2 and m are as defined above, and Do" has 2 to 5 carbon atoms. represents a linear alkylene group,
The average value of J21 is a positive number, the average value of 1 phantom is a number greater than or equal to 0, and the average value of phantom and the average value of 12 are such that the sum of the average value of 11 and the average value of 12 is 1/ m~877
β-methyl-δ-valero (a number that satisfies the relationship that the number m is the number of m and the relationship that the ratio of the phantom average value to the sum of the average value of 21 and the average value of 22 is 40 moles or more) Lactone-based polymers, especially β-methyl-δ-valerolactone-based polymers represented by the general formula b (wherein Th R'S R21m and n are as defined above), have a high resistance to resin even under low temperature conditions. It is preferable because it exhibits particularly excellent plasticizing ability.

- Examples of the β-methyl-δ-valerolactone polymer represented by the pattern (1') include β-methyl-δ-valerolactone polymers represented by the following general formula. .

(In the formula, B5 represents an alkyl group having 1 to 18 carbon atoms such as a methyl group, ethyl group, propyl group, or octadecyl group,
The average value of nl is a number from 1 to 87) (in the formula.

R5 and nl are as defined above) (wherein R
6 represents an alkylene group having 2 to 10 carbon atoms such as ethylene group, trimethylene group, propylene group, tetramethylene group, 3-methylpentamethylene group, hexamethylene group, nonamethylene group, 2-methyloctamethylene group, and B2 The average value is a number from 0.5 to 43.5 (wherein R6 and B2 are as defined above) (wherein R7 is 1.2.3 monopropanetriyl group, in the formula represents an alkantriyl group having 3 to 1 o carbon atoms such as the group shown, and the average value of B3 is 1/3 to 29 (in the formula, R and B3 are as defined above) (in the formula, R7
and B3 are as defined above) Examples of the hydroxyl group-containing polymer represented by the general formula (II) used as a raw material in the production method according to the present invention include a group of hydroxyl group-containing polymers represented by the following general formula. be able to.

(wherein R5 and nl are as defined above) (
(In the formula, B6 and B2 are as defined above) (In the formula, R? and B3 are as defined above.) The general formula (I
Examples of the lower alkoxyl group that R4 in [I] may represent include a methoxy group, a nidoxy group, a propoxy group, an inpropoxy group, a butoxy group, and the like. - Monka (I)
The cyclic ether represented by II) is a hydroxyl group-containing cyclic ether represented by -Momona (wherein B2 is as defined above), -Momona (% formula %) (wherein H and 2 are as defined above). They are broadly classified into lower alkoxyl group-containing cyclic ethers represented by the formula (wherein R2 is as defined above) and unsaturated cyclic ethers represented by the general formula (wherein R2 is as defined above). - Monka (I[[-1)
Examples of the hydroxyl group-containing cyclic ethers include tetrahydro-4-methyl-2H-bilan-2-ol, tetrahydro-2H-bilan-2-ol, and tetrahydrofuran-2-ol; ) The lower alkoxyl group-containing cyclic ether is tetrahydro2-methoxy-4-methyl-2H-bilane.

Tetrahydro-2-nitoxy-4-methyl-2H-bilane, Tetrahydro-2-globoxy-4-methyl-2H
-2-lower alkoxyte 1-lahydro- such as bilane
4-Methyl-2H-bilane; Tetrahydro-2-methoxy-2H-bilane, Tetrahydro-2-ethoxy-2H
2-Lower alkoxy-tetrahydro-2H-bilane such as -bilane, tetrahydro-2-globoxy 2H-bilane; Examples include 2-lower alkoxy-tetrahydrofuran such as 2-methoxytetrahydrofuran, 2-ethoxytetrahydrofuran, and 2-propoxytetrahydrofuran. be done. In addition, examples of the unsaturated cyclic ether represented by Monana (III-3) include 3,4-dihydro-4-methyl-2H-bilane, 3,4-dihydro-2H-bilane, 2,3-dihydrofuran, etc. is exemplified. −Monka (
In order to obtain the alkyl-δ-valerolactone-based polymer represented by 1) with high purity, the entire amount of the hydroxyl group-containing polymer represented by (II) is consumed in the reaction, thereby eliminating any unused material in the reaction system. It is desirable that the hydroxyl group-containing polymer not be left in the reaction. From this slowness, it is found that the cyclic ether represented by Monekana (III) is contained in an amount equal to or equal to 200 moles of the hydroxyl group contained in the hydroxyl group-containing polymer represented by the general formula (n).
It is preferable to use the amount in a double molar range. - When using the unsaturated cyclic ether represented by Monka (1-3), the unsaturated cyclic ether is used in equimolar to 1,
It is preferable to use it in an amount in the range of 3 molar.

- When a hydroxyl group-containing cyclic ether represented by general formula (III-1) is used as the cyclic ether represented by Monka (III), water is produced as the reaction progresses, and -
As a cyclic ether represented by Monka (III), the general formula (
When a lower alkoxyl group-containing cyclic ether represented by Ill-2) is used, a lower alcohol is produced as the reaction progresses. In these cases, the reaction is carried out while removing the water casing or lower alcohol produced during the reaction from the reaction system, using a hydroxyl group-containing cyclic ether represented by -Monken (nl-1) or a general formula The lower alkoxyl group-containing cyclic ether represented by (■-2) is equimolar to 1 molar to the hydroxyl group-containing polymer represented by the general formula (n).
．． This is desirable because the conversion rate to the alkyl-δ-valerolactone polymer represented by the general formula (1) can be increased even when it is used in a relatively small amount in the range of 3 times the mole! Yes. Examples of methods for removing the produced water or lower alcohol from the reaction system during the reaction include a method in which the water or lower alcohol is distilled out of the reaction system as an azeotrope with the organic solvent or the organic solvent described below. It will be done. In addition, during the reaction, water or lower alcohol that produces a hydroxyl group-containing cyclic ether represented by -Momonena (Ill-1) or a lower alkoxyl group-containing cyclic ether represented by general formula (III-2) is removed during the reaction. In order to increase the conversion rate to the alkyl-δ-valerolactone-based polymer represented by -Monkana (1), these cyclic ethers may be used in a reaction method represented by general formula (n). It is preferable to use it in an amount ranging from 40 to 150 times the mole of the hydroxyl group-containing polymer.

The hydroxyl group-containing polymer represented by the general formula (II) and the general formula (
Examples of acidic catalysts to be present in the reaction system in the reaction with the cyclic ether shown in 1) include: 1) Mineral acids such as sulfuric acid and phosphoric acid; halogenated compounds such as calcium chloride and zinc chloride [: p-)luenesulfonic acid, benzoic acid; Examples include organic acids such as acids and cation exchange resins; inorganic solid acids such as activated clay, acidic clay, and cinnabar earth; among them, activated clay is preferred.

The amount of these acidic catalysts used is not particularly limited, but when the reaction is carried out in a stirred tank, the reaction with the cyclic ether shown in the reaction mixture is preferably carried out at 10-150°C,
It is preferably carried out at a temperature in the range of 20 to 100°C.

Although the reaction according to the production method of the present invention can be carried out in the absence of a solvent, the reaction can also be carried out in the presence of an organic solvent that does not adversely affect the reaction. Specific examples of such organic solvents include hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, and dichloroethane; diethyl ether, dibutyl ether, and tetrahydrofuran. , ethers such as dioxane; and ketones such as acetone and methyl ethyl ketone.

In particular, when carrying out the reaction using a hydroxyl group-containing cyclic ether represented by Monekana (III-1) or a lower alkoxyl group-containing cyclic ether represented by the general formula Cm-2>, water generated during the reaction Alternatively, in order to facilitate the distillation of the lower alcohol out of the reaction system, it is recommended to include an organic solvent in the reaction system that forms an azeotrope with water or lower alcohols such as hydrocarbons as in the above specific examples. It's so desirable.

The vessel reactor used in the reaction according to the production method of the present invention is not particularly limited. Examples of such a reaction apparatus include a stirred tank type reaction apparatus and a fixed bed type reaction apparatus.

After the reaction is completed, the acidic catalyst is removed from the resulting reaction mixture by neutralization or filtration, if necessary.

Further, after washing with water as necessary, unreacted cyclic ether and solvent are distilled off using an evaporator such as a falling film evaporator, a centrifugal evaporator, or a stirred film evaporator. Alkyl-δ- indicated by the hole (I)
Valerolactone polymer can be separated and obtained.

The hydroxyl group-containing polymer represented by the general formula (n), which is a raw material in the production method of the present invention, is disclosed in, for example, JP-A No. 60-5502.
According to the method described in Publication No. 6 and Japanese Patent Application Laid-Open No. 63-225623, −Monhole R1+oH)m(N
) (wherein Bl and m are as defined above) using the alcohol shown as an initiator, with the general formula (wherein 72 represents an alkyltetramethylene group having 5 or 6 carbon atoms) The alkyl-δ-valerolactone shown in the formula (V-1) is subjected to ring-opening polymerization, or
δ-valerolactone general formula (in the formula, y3 has 2 to 6 carbon atoms, excluding the alkyltetramethylene group having 5 or 6 carbon atoms)
It can be obtained by ring-opening copolymerization with a lactone represented by (representing an alkylene group) at a molar ratio of 40 or more to less than 60.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. In addition,
In the following examples and reference examples, the average molecular weight of a polymer is a value determined based on quantitative analysis of hydrogen atoms in L H-NMR measurement of the polymer.

Example 1 In a four-loaf flask with a content of 500 d, equipped with a thermometer, a stirrer, a dropping funnel and a liquid-liquid separator with a condenser, the average value of s kl and 2 is each 9. ) Poly(β-methyl-δ-valerolactone)
Diol (average molecular t: 2100) 100 F was dissolved in toluene 10 (IJ), and the resulting solution was added with activated clay 2
Added 2. Tetrahydro-4-methyl-2H-pyran-2 was added while refluxing the toluene in the solution under heating and stirring.
A toluene solution prepared by dissolving -ol 13.9F in toluene 5Qd was added dropwise over 3 hours. During the dropping, water produced was removed from the reaction system using a liquid-liquid separator. The reaction was continued for an additional hour from the time when no water generation was observed (total reaction time 24 hours). After the reaction was completed, activated clay was removed from the resulting reaction mixture by filtration, and most of the toluene was distilled off from the filtrate using a rotary evaporator. Toluene and unreacted tetrahydro-4-methyl-2a-pyran-2-ol were removed from the obtained residue using a stirred film evaporator (evaporator dimensions: 60 mm (inner diameter) x 200 mm).
■(height)) by complete distillation under reduced pressure of 5w5Hf at 150°C.
A liquid β-methyl-δ-valerolactone polymer (average molecular weight: 2300) represented by 105H was obtained (yield:
96 yen).

The results of 'H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisilane) Solvent (CDCl5) 60.7 s ~ 1.10 (m, 6 oH) 1.2
4-2.50 (m, 100H) 3.10-4.30 (m, 44H) 4.62-4.
72 (m, 2H) After heating the obtained β-methyl-δ-valerolactone polymer at 200°C for 0.5 hour in a glass sealed tube, the amount of β-methyl-δ-valerolactone generated and β - When the molecular weight change of the methyl-δ-valerolactone polymer was investigated, the amount of β-methyl-δ-valerolactone generated was rumored to be only 0.4 weight per weight of the polymer. Almost no change in the average molecular weight was observed based on quantitative analysis of hydrogen atoms in 1H-NMR measurement.

Example 2 Tetrahydro-2H-bilan-2 instead of tetrahydro-4-methyl-2H-pyran-2-ol 13.9F
1 formula (wherein skl and 2 are as defined above) by carrying out the reaction and treatment of the reaction mixture in the same manner as in Example 1 except that -ol 12.3P is used.
1,042 liquid β-methyl-δ-valerolactone polymers (average molecular weight: 23oo) represented by (yield: 95%) were obtained.

The results of 'H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisilane) Solvent (CDC13) δo, ss ~t, io (m, 54H) 1.22 ~ 2
．． 52 (m, 102H) 3.13-4.26 (m,
44H) 4.42-4.63 (m, 2H) After heating the obtained β-methyl-δ-valerolactone polymer at 200°C for 0.5 hour in a glass sealed tube, β-methyl-δ- Amount of valerolactone produced, β-methyl-δ
- When we investigated the molecular weight change of the valerolactone polymer, we found that the amount of β-methyl-δ-valerolactone generated was only 0.4 times the amount of the polymer! 'H of the polymer
- Almost no change in average molecular weight was observed based on quantitative analysis of hydrogen atoms in -NMR measurements.

Example 3 Reaction and treatment of reaction mixture as in Example 1 except that tetrahydrofuran-2-ol 11.5F is used in place of tetrahydro-4-methyl-2H-pyran-2-ol 13.99. By performing 1 formula (in the formula, b kl and 2 are as defined above)
103y of a liquid β-methyl-δ-valerolactone polymer (average molecular weight: 2300) represented by (yield: 94 excellent) was obtained.

The results of LH-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisilane) Solvent (CDC13) 60.83~1.10 (m, 54 H) 1.20~
2.50 (m, 98H) 3.05-4.26 (m, 44H) 4.93-5.
12 (m, 2H) The obtained β-methyl-δ-valerolactone polymer was heated at 200°C for 0.5 hour in a glass sealed tube, and then
- Amount of methyl-δ-valerolactone generated When the molecular weight change of the β-methyl-δ-valerolactone polymer was investigated, the amount of β-methyl-δ-valerolactone generated was only 0.0% compared to the polymer. Furthermore, almost no change in the average molecular weight was observed based on quantitative analysis of hydrogen atoms in H-NMR measurement of the polymer.

Reference example 1 Contents 5001L equipped with thermometer, stirrer and cooler
Poly(β-methyl-δ-valerolactone) diol of the formula (wherein kl and 2 are υ as defined above) (average molecular weight: 21o
O) 9. Add acetic anhydride to 10o7. l'i9F was added. 10
The mixture was heated to 0°C and stirred for 4 hours. After the reaction was completed, toluene and acetic acid were distilled off from the resulting reaction mixture using a rotary evaporator. From the obtained residue, β-methyl-δ-valerolactone produced by decomposition,
By completely distilling it off under a reduced pressure of 150°C and 5mH7 using a stirred model evaporator similar to that used in Example 1, the formula % formula % (wherein the average value of ``1'' and ``2'') A liquid β-methyl-δ-valerolactone polymer (average molecular i: 1700) represented by 81F was obtained.

Reference Example 2 Poly(β-methyl-δ-valerolactone)′) represented by the formula (wherein kl and ni2 are as defined above)
20% of all (average molecular weight: 2100) in a glass sealed tube.
After heating at 0°C for 0.5 hours, the amount of β-methyl-δ-valerolactone generated and the change in the molecular weight of the β-methyl-δ-valerolactone polymer were investigated. The amount of lactone generated is 7. ○
It was a heavy fly, and the average molecular weight of the polymer had decreased to 1,900.

Example 4 In a reactor similar to that used in Example 1, the formula (wherein
The average value of k3 is 8) Poly(β-methyl-δ-valerolactone) monool (average molecular ffi: 94o) toor is dissolved in 100d of hexane, and 2f of acid clay is added to the resulting solution. Ta. While heating and stirring the hexane in the solution to reflux, a hexane solution prepared by dissolving 13.9 F of tetrahydro-4-methyl-2H-bilan-2-ol in 5 QmJ of hexane was added dropwise over 4 hours. During the dropping, water produced was removed from the reaction system using a liquid-liquid separator. The reaction was continued for an additional hour from the time when no water generation was observed (total reaction time: 5 hours). After the reaction was completed, acid clay was removed from the resulting reaction mixture by filtration, and most of the hexane was distilled off from the filtrate using a rotary evaporator. Hexane and unreacted tetrahydro-4-methyl-2H-bilan-2-ol were extracted from the obtained residue in Example 1.
150 using a stirred film evaporator similar to that used in
1 by complete distillation under reduced pressure of 5 H2 at
1002 liquid β-methyl-δ-valerolactone polymers (average molecular weight: 1000) represented by the formula (wherein k3 is as defined above) were obtained (yield: 94).

The results of H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisilane) Solvent (CDCa) δ0.88-1.10 (m, 27H) 1.22-2
．． 52 (m, 45H) 3.13-4.26 (m,
21H) 4.42-4.63 (m, IH) After heating the obtained β-methyl-δ-valerolactone polymer at 200°C for 0.5 hour in a glass sealed tube, β-methyl-δ -Amount of valerolactone generated and β-methyl-
When the molecular weight change of the δ-valerolactone polymer was investigated, it was found that the amount of β-methyl-δ-valerolactone generated was only 0.5 times higher than that of the polymer.
Almost no change in the average molecular weight was observed based on quantitative analysis of hydrogen atoms in H-NMR measurements.

Example 5 In a reactor similar to that used in Example 1, poly(β-methyl-δ -valerolactone) triol (average molecule: il: 2200) 100V was dissolved in benzene 10Qd, and the resulting solution was dissolved in sulfonic acid (H
+) type cation exchange resin (Amperlis manufactured by Rohm and Haas, USA)
(Amberlyst) 15:] 1.5 F
added. While stirring the resulting mixture at room temperature,
．． 4-dihydro-2H-bilane 9.9? Wobenzen 50
A solution of pensene dissolved in d was added dropwise over 0.5 hours. After the dropwise addition was completed, the reaction was continued for an additional 3.5 hours (total reaction time: 4 hours). After the reaction was completed, the cation exchange resin was removed from the resulting reaction mixture by filtration, and the resulting benzene solution was washed three times with 50 d each of distilled water. Most of the benzene is distilled off from this water-washed benzene solution using a rotary evaporator.1. Ta. From the resulting residue, benzene and unreacted 3,4-dihydro-2H-bilane were completely evaporated under reduced pressure of 150° Cs 5 tm Hp using a stirred model evaporator similar to that used in Example 1. A liquid β-methyl-δ-valerolactone polymer (average molecular weight: 2400) represented by the formula (wherein s k4s k5 and 6 are as defined above) was obtained by distilling off 105F. (Yield:
95 Yu).

The results of H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

1 standard (hexamethyldisilane) Solvent (CDC13) δ0.79-1.16 (m, 57H) 1.30-2
．． 56 (m, 110H) 3.10~4.30 (m
, 48H) 4.44-4.66 (m, 3H) After heating the obtained β-methyl-δ-valerolactone polymer at 200°C for 0.5 hour in a glass sealed tube, β-methyl-δ -Amount of valerolactone generated and β-methyl-δ
- When the molecular weight change of the valerolactone-based polymer was investigated, it was found that the amount of β-methyl-δ-valerolactone generated was only 0.6 tit higher than that of the cased polymer.
Almost no change in average molecular weight was observed based on quantitative analysis of hydrogen atoms in H-NMR measurement.

Example 6 In a three-bottle flask with a content of 500 d, equipped with a thermometer, a stirrer and a condenser, the formula (where s kl and 2 are as defined above) was prepared.
Poly(β-methyl-δ-valerolactone) diol (average molecular weight: ztoo)xoor and 3,4
-dihydro-2H-bilane 10.4F to toluene 100%
It was dissolved in 1 Lt. 0.5 ft L of the obtained toluene solution Kp-h toluenesulfonic acid was added and stirred at room temperature for 4 hours. After the reaction was completed, the resulting reaction mixture was washed three times with 100 d of distilled water each time. From the obtained toluene solution, unreacted 3,4-dihydro-2H-bilane and toluene were removed using a rotary evaporator, and then a stirred film evaporator similar to that used in Example 1 (150°C, under reduced pressure of 5 mHr). ) by complete distillation.

A liquid β-methyl-δ-valerolactone polymer (average molecular weight: 2300) represented by the formula (wherein kl and ni2 are as defined above) was mixed with 1o3? (Yield: 9
4%). The results of IH-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer show that the β-methyl-δ-valerolactone polymer obtained in Example 2 is
The analysis results were the same as for the δ-valerolactone polymer.

Example 7 Poly(β-methyl-δ -valerolactone) diol (average molecular weight: 2100) LOOP was dissolved in tetrahydro-2-methoxy-4-methyl-2H-bilane 3507, and after adding activated clay for 2y to the resulting solution, the internal temperature was raised to 80℃. The mixture was heated and stirred for 4 hours. After completion of the reaction, the activated clay was removed from the resulting reaction mixture by filtration, methanol and most of the unreacted tetrahydro-2-methoxy-4-methyl-2H-bilanno were distilled off from the filtrate using a rotary evaporator, and the obtained Tetrahydro-2-methoxy-4-methyl-2H-bilane was completely distilled off from the resulting residue at 150°C under a reduced pressure of 5wHf using a stirring model evaporator similar to that used in the working example. By doing this, 102F was obtained (yield: 9
3%). The LH-NMR (90 MHz) analysis results for the obtained β-methyl-δ-valerolactone polymer show that the β-methyl-δ obtained in Example 1
-The analysis results were the same as those for valerolactone-based polymers.

Example 8 In a four-loaf flask with a content of 500 d equipped with a thermometer, a stirrer, a dropping funnel and a liquid-liquid separator equipped with a liquid-liquid separator with a thermometer, a stirring device, a dropping funnel and a condenser poly(β-methyl-δ-valerolactone) represented by
Diol (average molecule t: 2zoo) xoo5F was dissolved in 100d of toluene, and activated clay 2y was added to the resulting solution. Tetrahydro-4-methyl-2H-bilan-2-ol 14. While refluxing the toluene in the solution under heating and stirring, 14. A toluene solution prepared by dissolving OF in 5Qm of toluene was added dropwise over 3 hours. During the dropping, water produced was removed from the reaction system using a liquid-liquid separator. The reaction was continued for an additional 1 hour from the time when no water generation was observed (total reaction time = 4 hours). After the reaction was completed, the activated clay was removed from the resulting reaction mixture by filtration.

Most of the toluene was removed from the filtrate using a rotary evaporator. Toluene and unreacted tetrahydro-4-methyl-2H-bilan-2-ol were removed from the resulting residue at 150°C under a reduced pressure of 5wHf using a stirring model evaporator similar to that used in Example 1. By completely distilling it off at
6y was obtained (yield: 97 excellent).

The results of 1H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisilane) Solvent (CDCIs) 60.75-1.11 (m, 63H) 1.23-2
．． 51 (rn, 105H) 3.09-4.29 (m,
44H) 4.61-4.72 (m, 2H) After heating the obtained β-methyl-δ-valerolactone polymer at 200°C for 0.5 hour in a glass sealed tube, β-methyl-δ- Amount of valerolactone generated and -β-methyl-
When we investigated the molecular weight change of the δ-valerolactone polymer, we found that the amount of β-methyl-δ-valerolactone generated was only 0.5% by weight compared to the polymer, and IH-NMR measurements of the polymer revealed that Almost no change in the average molecular weight was observed based on quantitative analysis of hydrogen atoms.

Example 9 In a four-loaf flask with a content of 500 d, equipped with a thermometer, a stirrer, a dropping funnel and a liquid-liquid separator with a condenser, the formula (wherein the average value of kg and klo is 20 each) poly(β-methyl-δ-)clerolactone)
Diol (average molecular weight: 47oo) was dissolved in toluene at 300 dK, and activated clay 27 was added to the resulting solution. While refluxing the toluene in the solution under heating and stirring,
A toluene solution prepared by dissolving 6.52 grams of tetrahydro-4-methyl-2H-bilan-2-ol in 50 d of toluene was added dropwise over 3 hours. During the dropping, water produced was removed from the reaction system using a liquid-liquid separator. The reaction was continued for an additional hour from the time when no water generation was observed (total reaction time: 4 hours). After the reaction was completed, activated clay was removed from the resulting reaction mixture by filtration, and most of the toluene was distilled off from the filtrate using a rotary evaporator. Toluene and unreacted tetrahydro-4-
Methyl-2H-bilan-2-ol was heated at 150°C for 50 minutes using a stirred film evaporator similar to that used in Example 1.
By completely distilling the parrot H2 under reduced pressure, the liquid β-methyl-δ-valerolactone polymer (average molecular "ik: 490 o)" was obtained (yield: 96%).

The results of 1H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisilane) Solvent (CDC13) δ0.72-1.20 (m, 126H) 1.20-2
．． 51 (m, 224H) 3.09~4.29 (m
, 88H) 4.60 to 4.72 (m, 2H) The obtained β-methyl-δ-valerolactone polymer was heated at 200°C for 0.5 hour in a glass sealed tube, and then β-methyl- Amount of δ-valerolactone generated and β-methyl-
When we investigated the molecular weight change of the δ-valerolactone polymer, we found that the amount of β-methyl-δ-valerolactone generated was only 0.4% by weight compared to the polymer. Almost no change in the average molecular weight was observed based on quantitative analysis of hydrogen atoms in NMR measurement.

Example 1O In a four-loaf flask with a content of 5ooR1, equipped with a thermometer, a stirrer, a dropping funnel and a liquid-liquid separator with a condenser, the formula: poly(β-methyl-δ-valerolactone) monool (average molecular weight: 4800) Zo.

2 was dissolved in 300 d of toluene, and activated clay 22 was added to the resulting solution. A toluene solution prepared by dissolving 3.2 f of tetrahydro-4-methyl-2H-bilan-2-ol in 50 a/ml of toluene was added dropwise over 3 hours while stirring and heating to reflux the toluene in the solution. During the dropping, water produced was removed from the reaction system using a liquid-liquid separator.

The reaction was continued for an additional hour when no water generation was observed (total reaction time: 4 hours). After the reaction was completed, activated clay was removed from the resulting reaction mixture by filtration, and most of the toluene was distilled off from the filtrate using a rotary evaporator. From the resulting residue, toluene and 5 pools of unreacted tetrahydro-4-methyl-2H-bilane were evaporated for 15 min using a stirred model evaporator similar to that used in Example 1.
By completely distilling it off under a reduced pressure of 5 mHy at 0°C, in the formula ζ, the! 972 liquid β-methyl-δ-valerolactone polymers (average molecular i1: 4900) (yield: 95
Section).

The results of 1H-NMR (90 MHz) analysis of the obtained β-methyl-δ-valerolactone polymer are shown below.

Internal standard (hexamethyldisilane) Solvent (CDC13) δ0.72-1.20 (m, 126H) 1.20-2
．． 52 (m, 237H) 3.10-4.30 (m,
54) 1) 4.59-4.71 (m, IH) Example 11 In a three-loaf flask with a content of 500 d, equipped with a thermometer, a stirrer and a condenser, the formula (where kl2, kl3, kl4 and Random copolymer of β-methyl-δ-valerolactone and ε-caprolactone (average molecular weight -7:21)
00) LOOP and 3,4-dihydro-4-methyl-
2H-Biran 12. OF was dissolved in 1OORI of toluene. 0.52 of p-1-toluenesulfonic acid was added to the obtained toluene solution, and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, the resulting reaction mixture was washed three times with 10 Qd of distilled water.

From the obtained toluene solution, unreacted 3,4-dihydro-4-methyl-2H-bilane and toluene were removed using a rotary evaporator and then a stirred abdominal evaporator (150"G*) similar to that used in Example 1. 5rxmHy (under a reduced pressure of
(as defined above) 104F of a liquid β-methyl-δ-valerolactone polymer (average molecular weight: 2300) was obtained (yield: 95 yen).

The results of analysis of the obtained β-methyl-δ-valerolactone polymer by 1H-NMR (90 MHz') are shown below.

Internal standard (tetramethylsilane) Solvent (CDC13) 60.77-1.10 (m, 33H) 1.24-2
．． 50 (m, 127H) 3.10~4.3o (m,
44H) 4.61-4.74 (m, 2H) The obtained β-methyl-δ-valerolactone polymer was heated at 200°C for 0.5 hour in a glass sealed tube, and then β-methyl-δ - When we investigated the amount of valerolactone and ε-caprolactone generated and the molecular weight change of β-methyl-δ-valerolactone polymer, we found that the amount of generated β-methyl-δ-valerolactone was slightly 0
．． 3 weight, and the generation of ε-caprolactone is 1.
I couldn't admit it. Furthermore, 1H-NM of one polymer
I (, almost no change in the average molecule 1 was observed based on quantitative analysis of hydrogen atoms in the measurement.

〔Effect of the invention〕

According to the present invention, as is clear from the above examples, a liquid alkyl-δ-valerolactone polymer represented by general formula (I) having high thermal stability is provided. - The alkyl-δ-valerolactone polymer represented by Monka (1) is produced from the corresponding hydroxyl group-containing polymer represented by general formula (II) without depolymerization.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ~4 alkylene group, Y
represents an alkylene group having 2 to 6 carbon atoms, and 40 mol% or more of Y contained in the molecule is an alkyltetramethylene group having 5 or 6 carbon atoms, m represents an integer of 1 to 3,
(The average value of n is a number from 1/m to 87/m.) An alkyl-δ-parerolactone polymer represented by: 2. The hydroxyl group-containing polymer represented by the general formula ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R^1, Y, m and n are as defined in claim 1) in the presence of an acid catalyst Below is the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^2 is as defined in claim 1, R^3 represents a hydrogen atom, and R^4 is a hydroxyl group or lower alkoxyl group. or R^3 and R^4
The method for producing an alkyl-δ-parerolactone polymer according to claim 1, characterized in that the reaction is carried out with a cyclic ether represented by: