JPS63215720A - Production of functional group-terminated lactone polymer - Google Patents

Abstract

PURPOSE:To produce a double bond-terminated lactone polymer readily in good yields, by reacting a lactone polymer obtained by the ring-opening polymerization of a lactone by using an anionic initiator with a specified acid halide. CONSTITUTION:A lactone polymer obtained by the ring-opening polymerization of a lactone (e.g., epsilon-caplolactone or beta-methyl-delta-valerolactone) by using an anionic initiator (e.g., a mixture of a metal or an organometallic compound such as sodium or butyllithium with an active hydrogen compound such as ethylene glycol) is reacted with a compound of the formula (wherein X is a halogen, and R<1>, R<2> and R<3> are each H, a lower alkyl or an aryl) [e.g., (meth)acryloyl chloride]. In this way, a double bond-terminated polymer can be produced readily in high yields.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel method for producing a polymer obtained by ring-opening polymerization of lactone and having a double bond at its terminal.

[Conventional technology]

In recent years, oligomers having functional groups at their terminals, so-called teleclick oligomers, have been developed for use in block copolymers such as polycrethane. In addition, oligomers such as acrylics with double bonds at the ends, so-called polyester acrylates, are beginning to be used in paints, adhesives, binders for magnetic tapes, etc. as radiation-curable resin compositions when combined with polymerizable monomers. . It is thought that the scope of their use will further expand in the future.

Polyester acrylates are known to have various compositions, and the properties and physical properties of the cured product can be selected from a wide range.They are inexpensive and have physical properties comparable to those of urethane-modified acrylate resins. It is considered promising because of the

On the other hand, in the ring-opening polymerization of lactones, etc., a method for obtaining a polymer with terminal hydroxyl groups is to use a mixture of a metal such as sodium or an organometallic compound such as butyllithium and a compound having active hydrogen such as glycol as an initiator. is already known (%Kokusho 40-23917, In
industrial and engineeringC
hemistry, Product Re5earc
h Development Volume 13 No. 3 1974 1
(pp. 93-197, JP-A-55-104315, JP-A-60-55026), these methods use metals or organometallic compounds as catalysts, and the terminal groups formed are only hydroxyl groups or carboxyl groups. there were.

Conventionally, oligomers having double bonds at the terminals have been produced by dehydration condensation of oligomers having terminal hydroxyl groups and compounds having double bonds such as acrylic acid, or by polyesters made from glycol and dicarboxylic acid as raw materials, From the beginning, a method has been used in which a compound having a heavy bond is subjected to a dehydration condensation reaction with a glycol and a dicarboxylic acid.

[Problem that the invention seeks to solve]

However, in the case of oligomers or polymers obtained by ring-opening polymerization of lactones, the latter method is impossible in principle;
The former method also has problems such as dissociation and changes in molecular weight distribution during the dehydration reaction, and an industrially sufficient production method has not been obtained. Therefore, although excellent performance is expected, there are problems with the manufacturing technology, and it is used industrially, and improvements in the manufacturing method have been desired.

An object of the present invention is to provide a novel method for producing a lactone polymer having a double bond at its terminal, which is simple and has a high yield.

[Means to solve the problem]

According to the present invention, the above object is achieved by reacting a compound represented by the following general formula [■] with a lactone-based polymer obtained by ring-opening polymerization of lactone using an anionic initiator. (Here, X is Rogen,
R1, R2 and Ha each represent hydrogen, a lower alkyl group or an aryl group. ) The anionic initiator used in the present invention is a mixture of a metal or an organometallic compound and a compound having active hydrogen. As the metal, for example, an alkali metal such as sodium or potassium is used, and as the organometallic compound, an organic alkali metal such as butyllithium is used. There are many compounds with active hydrogen, but specifically, when producing a final polymer with a double bond at one end, monofunctional alcohols such as methanol, ethanol, gropanol, and butanol are used. , When producing products with double bonds at both ends, ethylene glycol, propylene glycol, butanediol, 1,5-bentanediol, 3-methyl-1,5-pene, tanediol, 1,6-hexanediol, Glycols such as 2-methyl-1,8-octanediol and 1,9-nonanediol are used, and polyfunctional alcohols such as glycerin, trimethylolpropane and pentaerythritol are used when producing trifunctional or higher functional glycols. It is preferable that the compound having active hydrogen does not include water removal in the reaction, and it is desirable that the compound is dehydrated and dried before the reaction.

The lactone used in the present invention is not particularly limited as long as it is capable of ring-opening polymerization. A specific example of a lactone is β
-Propiolactone, γ-butyrolactone, vivalolactone, γ-valerolactone, γ-caprylolactone, δ
-valerolactone, β-methyl-δ-valerolactone,
Examples include ε-caprolactone, and these lactones may be used alone or in combination of two or more.

The present invention is characterized in that a compound represented by the general formula (11) is reacted with a lactone-based polymer obtained by ring-opening polymerization of lactone using an anionic initiator. In the compound represented by formula (1), X represents F, cJ!, Br, I, etc., and R1, R2, and R3 each represent hydrogen, a lower alkyl group,
Examples of lower alkyl groups representing aryl groups include methyl, ethyl, propyl, isopropyl, and butyl groups, and examples of aryl groups include phenyl, tolyl, xylyl, cumenyl, and the like. Examples include groups.

Specific examples of compounds represented by general formula CI) include:
Examples include acid halides such as acrylic acid chloride, methacrylic acid chloride, cinnamic acid chloride, and crotonic acid chloride.

The polyester acrylate of the present invention can be produced in the presence or absence of a solvent. In its presence, the reaction can proceed more uniformly than in its absence, but some unreacted two-chton monomer may remain. The solvent is
Dissolving the generated oligomer and having active hydrogen,
Further, any substance may be used as long as it does not react with the compound represented by the general formula (1), such as aromatic hydrocarbons such as toluene and benzene, and aliphatic and alicyclic hydrocarbons such as hexane and cyclohexane. When using a solvent, it is preferable to dehydrate it before use in the reaction.

The reaction temperature may be any temperature between -100°C and 100°C, but preferably 0°C to 30°C. When the temperature is below 0°C, the viscosity is high and it becomes difficult to mix uniformly, and when the temperature is above 30°C, unreacted lactone monomer tends to remain.

To give a specific example of the production method of the present invention, a solvent such as toluene and a compound having active hydrogen such as glycol are charged into a reactor equipped with a stirring blade, and the temperature inside the reaction tank is adjusted to 0'' to 30°C.
Keep at ℃. Further, an alkali metal such as sodium or potassium or an organometallic compound such as butyllithium is added in an amount of 1.0 to 1.1 times the number of moles of active hydrogen of a compound having active hydrogen such as glycol. If the amount of the metal and organometallic compound is too little or too much, the double bond of acrylic or the like will not quantitatively enter at the end.

Furthermore, lactones such as ε-caprolactone and β-methyl-δ-valerolactone are added dropwise at once.

The degree of polymerization of the completed polymer is approximately determined by the amount charged at this time.

Next, a compound represented by the general formula [■], such as acrylic acid chloride, is added at 1.1 to 1.2 times the number of moles of active hydrogen of the compound having active hydrogen, such as glycol.
After reacting for 5 to 1 hour, water is added to terminate the reaction. At this time, the polymer and solvent are separated. After separating this, the organic layer is washed about three times.

The solvent and trace amounts of water present in the system are distilled off under reduced pressure and heating. Thereafter, the desired lactone-based polyester acrylate having a double bond at the end is obtained by purification by molecular distillation or the like.

The compound can be identified by 1) f-NMR spectrum and infrared absorption spectrum.

The lactone-based polymer having a double bond at the end obtained by the present invention has characteristics different from conventionally known polymers having a double bond at the end such as polyester acrylate made from glycol and dicarboxylic acid as starting materials. It can be widely used as a raw material or intermediate for heat- and photo-curable paints, adhesives, photosensitizers, binders, printing inks, crosslinking agents, copolymer modifiers, etc.

The present invention will be explained in detail below with reference to Examples, but the present invention is not limited thereto.

〔Example〕

Example 1 Content 1 with stirring device, dropping funnel and gas inlet/outlet
! 3. After thoroughly purging the Tulo flask with dry nitrogen gas, immerse the flask in a 0°C path, and add 40% of toluene, which has been dehydrated and purified with sodium, to the flask.
0d, ethylene glycol 4t and butyllithium (
Prepare 10.4 mol/hex'') 13.6 m#,
Stirred for about 5 minutes.

Afterwards, the previously dehydrated and purified β-methyl-δ
-Valerolactone tzsf? [Added the lower rotary yoshi at once. Immediately, the internal temperature rose and the viscosity also rose. After 1 hour, 12.5 rxl of acrylic acid chloride was added dropwise using a syringe, and after 30 minutes, 400 ml of distilled water was added. Return the flask to room temperature and separate the liquids.

Repeat the washing operation with triple-distilled water, and then
After removing toluene and a trace amount of water using an evaporator, it is purified by molecular distillation to produce a colorless and transparent viscous liquid 140. When this liquid was analyzed using 0GPC (Kölpermeation Chromatography) K from which OF was obtained, it was found to be an Oryi H-sesame with a molecular weight of approximately 2000 and a distribution with one peak. I understand. Furthermore, in the half-NNR spectrum and infrared absorption spectrum, it was confirmed that O is a polymerized form of β-methyl-δ-valerolactone having acrylic double bonds at both ends, as shown below. Furthermore, it is shown that there is no terminal hydroxyl group at all, and in the present invention, approximately 10
It was found that it is possible to introduce a double bond at the 0% end.

IH-NMR spectrum (in deuterated chloroform solvent, TM
S standard) 5.7-6.6 ppm Acrylic proton 4.15 9pm Methylene proton 1.2
~2.4ppm methylene and methine protons 0.
85 ppm Methyl proton infrared absorption spectrum 1720 to 1730 cm-'' carbonyl group of ester bond, 1640 an-'' acrylic group, 1380 cm
-” indicates absorption derived from methyl group.

Example 2 A viscous, colorless and transparent liquid was obtained in the same manner as in Example 1, except that cinnamic acid chloride 1260- was reacted instead of acrylic acid chloride 12.5d in Example 1. This liquid was confirmed to be a polymer of β-methyl-δ-valerolactone having cinnamic acid groups at both ends by the IH-NMR spectrum and infrared absorption spectrum shown below. in solvent, TM
Sfi quasi) o, ss ppm methyl proton 1
．． 2-2.3 ppm methine and methylene protons 4.05 ppm methylene protons 7.
4 ppm phenyl proton 6.4-7・'7
ppm The proton infrared absorption spectrum of the double bond of the cinnamic acid group is 1720 cm-'', the carbonyl group of the ester bond, 16
Olefin 1600a conjugated with aromatic ring to 25an-'
Example 3 Absorption caused by an aromatic ring at n-' and a methyl group at 1380 an-' A white solid was obtained in the same manner as in 1. This solid was confirmed to be a polyester with double bonds at both ends, so-called polycaprolactone diacrylate, by the H-NMR spectrum and infrared absorption spectrum shown below. C11C11H-N vector (in deuterated chloroform solvent, TMS group iJ 1.2-2.2 ppm methylene proton 4.0 ppm methylene proton 5.7-6.6 ppm acrylic proton infrared absorption spectrum 1720-1730 cm-') Absorption derived from the acrylic group was confirmed in the carbonyl group s 1640an-'.

[Effects of the Invention] As described above, the present invention discloses a simple, quantitative, and novel method for producing lactone-based polymers having double bonds at the terminals, and thus is useful in various industries such as paints, adhesives, and photosensitizers. This manufacturing method can provide products useful for various purposes.

Claims (1)

[Claims] (1) A compound represented by the following general formula [I] is reacted with a lactone-based polymer obtained by ring-opening polymerization of lactone using an anionic initiator. A method for producing a lactone polymer essentially having a double bond at the terminal. [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, X is a halogen, and R^1, R^2, and R^3 each represent hydrogen, a lower alkyl group, or an aryl group.) (2
) The compound represented by the general formula [I] is at least one compound selected from the group consisting of acrylic acid chloride, methacrylic acid chloride, crotonic acid chloride, and cinnamic acid chloride, according to claim 1 Production method. (3) The lactone is ε-caprolactone and/or β-
Claim 1 which is methyl-δ-valerolactone
The manufacturing method according to item 1 or 2. (4) Anionic initiator is glycol and sodium,
The manufacturing method according to claim 1, 2 or 3, which is a mixture of potassium or butyllithium.