JPH072838B2 - Process for producing polyalkylene oxide containing unsaturated group at molecular end - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyalkylene oxide containing an unsaturated group at the molecular end and having a narrow molecular weight distribution.

The polyalkylene oxide having an unsaturated group at the molecular terminal can be used alone as a rubber material after curing, or can be used as a crosslinkable modifier blended with other polymer. Further, the unsaturated group at the terminal of the molecule can be converted into another more active functional group and used as a telechelic liquid rubber in various applications.

[Prior arts and problems to be solved by the invention] As a method of introducing an unsaturated group into both ends of a molecular chain, a hydroxyl group of polyoxypropylene glycol obtained by usual anionic polymerization is converted into caustic alkali (KOH, NaOH). , Sodium methoxide or metallic sodium to form an alkoxide terminal, and then react with an unsaturated group-containing active halogen compound such as allyl chloride to obtain a polypropylene oxide having an unsaturated group terminal. In the usual anionic polymerization of propylene oxide with KOH catalyst, it is difficult to produce polyoxypropylene glycol having a molecular weight of 3,000 or more because the growing end undergoes a chain transfer reaction to the propylene oxide monomer, and the molecular weight distribution is broadened. I also have problems.

Therefore, in order to obtain a polymer having a molecular weight of 3,000 or more, an unsaturated group-terminated polypropylene oxide produced using this as a raw material must also undergo a molecular chain extension reaction by reacting the hydroxyl groups of polyoxypropylene glycol. However, there is a problem that it is difficult to obtain a polymer having a narrow molecular weight distribution.

[Means for Solving Problems] The present inventors have already used a complex catalyst obtained by reacting an organoaluminum compound with porphyrin,
It has been found that living polymerization of propylene oxide can be carried out, and that it is possible to synthesize a polymer having an arbitrary molecular weight with a narrow molecular weight distribution.

The present inventors thought that if this new complex catalyst was applied successfully, it would be possible to easily synthesize polypropylene oxide containing an unsaturated group at the molecular end and having a narrow molecular weight distribution at any molecular weight. The inventors have found that the desired polymer can be obtained by selecting a special complex catalyst to polymerize propion oxide, and then terminating the reaction with a special halogen compound, and arrived at the present invention.

That is, the present invention relates to an aluminum porphyrin complex obtained by reacting an organoaluminum compound and a porphyrin compound with (a) an active hydrogen atom selected from a hydroxyl group and a carboxylic acid group and an unsaturated group in one molecule. The alkylene oxide is polymerized by using a complex catalyst obtained by reacting an active hydrogen-containing organic compound, and then (c) an organic compound containing an unsaturated group and an active halogen atom in one molecule, and (d) an activity. The present invention relates to a method for producing a polyalkylene oxide having an unsaturated group at the molecular end, which comprises reacting an active halogen-containing compound selected from organic compounds containing two or more halogen atoms in one molecule.

In addition, the present invention relates to an aluminum porphyrin complex obtained by reacting an organoaluminum compound and a porphyrin compound with (b) an activity containing two or more active hydrogen atoms selected from a hydroxyl group and a carboxylic acid group in one molecule. The alkylene oxide is polymerized using a complex catalyst obtained by reacting a hydrogen-containing organic compound, and then (c) an active halogen-containing compound containing an unsaturated group and an active halogen atom in one molecule is reacted. The present invention relates to a method for producing a polyalkylene oxide containing an unsaturated group at a characteristic molecular end.

[Operations and Examples] Alkylene oxides applicable to the present invention include aliphatic alkylene oxides having a terminal three-membered ring epoxy group such as ethylene oxide, propylene oxide, 1-butylene oxide, epichlorohydridone, and styrene oxide. Among the aromatic alkylene oxides having a three-membered ring epoxy group, aliphatic alkylene oxides are preferable, and propylene oxide is particularly preferable.

The organoaluminum compound used in the present invention is
Trialkylaluminums having an alkyl group having 4 or less carbon atoms such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, etc., and an alkyl group having 4 or less carbon atoms such as diethylaluminum hydride, diisobutylaluminum hydride and the like. Although alkylaluminum hydrides containing a hydrogen atom can be effectively used, trialkylaluminums are preferable, and triethylaluminum is particularly preferable.

The porphyrin compound used in the present invention has the formula (1): (In the formula, R ² is a group selected from a hydrogen atom and a monovalent hydrocarbon having 10 or less carbon atoms, and R ¹ is the same or different monovalent group selected from a hydrogen atom and an alkyl group having 4 or less carbon atoms. Is indicated). Specific examples thereof include tetramethyltetraethylporphyrin, octaethylporphyrin, and tetraphenylporphyrin, and tetraphenylporphyrin in which R ¹ is a hydrogen atom and R ² is a phenyl group in formula (1) is particularly preferable.

The aluminum porphyrin complex (I) obtained by the reaction of an organoaluminum compound and a porphyrin compound is obtained by adding about an equimolar amount of an organoaluminum compound to a porphyrin compound in the presence of a solvent in an atmosphere of an inert gas such as nitrogen. Is prepared. As the solvent, for example, hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane can be used. The aluminum porphyrin complex thus obtained has the formula (2): when triethylaluminum is used as the organoaluminum compound and tetraphenylporphyrin is used as the porphyrin compound. Is estimated as.

In the present invention, the aluminum porphyrin complex,
(A) An organic compound containing an active hydrogen atom and an unsaturated atom selected from a hydroxyl group and a carboxylic acid group in one molecule, and (b) an active hydrogen atom selected from a hydroxyl group and a carboxylic acid group in one molecule. An active hydrogen compound selected from two or more organic compounds is reacted to prepare a complex catalyst (II) for alkylene oxide polymerization. Examples of the compound (a) include unsaturated aliphatic alcohols such as allyl alcohol, ethylene glycol monoallyl ether, 3-butenyl alcohol, and 2-hydroxyethyl acrylate,
Specific examples thereof include unsaturated phenols such as vinylphenol and allyloxyphenol; and unsaturated carboxylic acids such as acrylic acid and methacrylic acid.
Examples of the compound (b) include polyethylene alcohols such as triethylene glycol, tripropylene glycol, 2,2-bis (4-hydroxyphenyl) propane and glycerin;
Specific examples include polyvalent carboxylic acids such as adipic acid and sebacic acid. The compound (a) is preferable, and allyl alcohol and acrylic acid are particularly preferable.

The complex catalyst (II) obtained by reacting the aluminum porphyrin complex with the active hydrogen-containing compound is prepared by mixing the aluminum porphyrin complex and the active hydrogen atom so that the amounts are almost equimolar. As the complex catalyst thus obtained, when the one having the formula (2) is used as the aluminum porphyrin complex and allyl alcohol or acrylic acid is used as the active hydrogen-containing compound, the compound having the formula (3): (Wherein, in the case of the alcohol R ³ is -OCH ₂ CH = CH _2, if R ₃ Acrylic acid Is proposed as.

In the present invention, the alkylene oxide is polymerized using the complex catalyst (II) in the atmosphere of an inert gas, without solvent or in the presence of a solvent. Nitrogen is preferable as the inert gas, and as the solvent, hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform,
Halogenated hydrocarbons such as dichloroethane are used. The amount of the solvent used can be arbitrarily selected, and although the polymerization proceeds sufficiently at room temperature, it is also possible to carry out heating polymerization. The molecular weight of the obtained polyalkylene oxide is determined almost automatically as the amount of alkylene oxide used with respect to the complex catalyst (II) increases. When the amount of alkylene oxide used is increased with respect to the complex catalyst (II), the molecular weight of the polyalkylene oxide produced also increases. The amount of alkylene oxide used can be arbitrarily selected, but is usually 10 times mol based on the catalyst (II).
It is in the range of 1000 times the mole. Particularly, the range of 50-fold to 500-fold mole is preferable.

After the alkylene oxide is polymerized using the complex catalyst (II), (c) an organic compound containing a terminal unsaturated group and an active halogen atom in one molecule, and (d) an active halogen atom in the molecule of 2 A polyalkylene oxide having an unsaturated group at the molecular end can be produced by reacting an active halogen-containing compound selected from organic compounds containing at least one of these. However, when the complex catalyst (II) is prepared using the active hydrogen-containing organic compound (b), only the compound (c) can be used. Examples of the compound (c) include allyl halides such as allyl chloride, allyl bromide and allyl iodide; benzyl type halogen compounds such as vinylbenzyl chloride and allylbenzyl chloride; acrylic acid chloride, methacrylic acid chloride, Specific examples thereof include acid halogen compounds such as vinyl benzoyl chloride and allyl chloroformate. Examples of the compound (d) include bis (chloromethyl) benzene, bis (bromomethyl) benzene, tris (bromomethyl) benzene, adipic acid dichloride, halogens containing two or more benzylic halogens or acid halogenic halogens such as phosgene. The compound may be specifically exemplified. Preferably (c)
The halogen compound of (1) is particularly preferable, and an allyl halogen compound and acrylic acid chloride are particularly preferable. When the compound (c) is used, it may be reacted in an equimolar amount or more with respect to the complex catalyst (II). When the compound of (d) is used, it may be reacted with the complex catalyst (II) under the condition that the active halogen groups in (d) are almost equimolar.

In the present invention, a polyalkylene oxide having an unsaturated group at its molecular end can be specifically obtained by, for example, the following method.

(A) The compound of (a) is reacted with the aluminum porphyrin complex (I) to prepare the complex catalyst (II), the alkylene oxide is polymerized, and then the termination reaction is carried out with the compound of (c).

(B) After the alkylene oxide is polymerized in the same manner as in (a), the termination reaction is carried out with the compound (d).

(C) The aluminum porphyrin complex (I) is reacted with the compound (b) to prepare the complex catalyst (II), and the alkylene oxide is polymerized, and then the termination reaction is carried out with the compound (c).

The method (a) is preferable because a polymer having a target molecular weight can be obtained with a small amount of catalyst.

The alkylene oxide polymer having an unsaturated group at the molecular end and having a narrow molecular weight distribution obtained in the present invention can be used as an adhesive, a paint, a rubber material, etc. by curing with an electron beam or ultraviolet ray. It can also be blended with other polymers and used as a crosslinkable modifier. Further, the unsaturated group at the terminal of the molecule can be converted into another more active functional group, and can be used in various applications as a telechelic liquid rubber.

[Effect of the Invention] According to the method of the present invention, a high molecular weight polyalkylene oxide having an unsaturated group at the terminal can be obtained by a simple method, and a polymer having a narrow molecular weight can be obtained.

The method of the present invention will be described below with reference to Reference Examples and Examples, but the present invention is not limited to such Examples.

Reference Example 1 0.28 ml of triethylaluminum and 1.21 g of α, β, γ, δ-tetraphenylporphyrin were reacted at room temperature in the presence of a methylene chloride solvent of 40 ml under a nitrogen atmosphere, and the structure of the formula (2) was estimated. A methylene chloride solution containing an aluminum porphyrin complex having After 1.2 ml of allyl alcohol was added to this solution and reacted at room temperature, the solvent and unreacted allyl alcohol were removed under reduced pressure to obtain a complex catalyst (A). The complex catalyst (A) in the formula (3) had a structure wherein R ³ is assumed is -OCH ₂ CH = CH _2.

Reference Example 2 A complex catalyst (B) was obtained in the same manner as in Reference Example 1 except that 0.14 ml of acrylic acid was used instead of allyl alcohol.
In this complex catalyst (B), in the formula (3), R ³ is Had a structure presumed to be

Example 1 1.21 g of the complex catalyst (A) obtained in Reference Example 1 was placed in a nitrogen-purged glass eggplant-shaped flask, and then 10 ml of methylene chloride and 2.2 g of propylene oxide were added under a nitrogen atmosphere, and the mixture was magnetic. Polymerization was carried out at room temperature for 2 days while stirring with a stirrer. After completion of the polymerization, unreacted propylene oxide and methylene chloride were removed under reduced pressure and the polymerization rate was measured to be 100%. Next, allyl bromide 2
After adding 0 ml and reacting at 70 ° C. for 32 hours, excess allyl bromide was removed under reduced pressure. Subsequently, hexane was added, the porphyrin complex was filtered off, and hexane was removed from the filtrate under reduced pressure to obtain 2.1 g of polypropylene oxide. The results of measuring the molecular weight and molecular weight distribution of this polypropylene oxide by GPC are shown in Table 1.

Moreover, the analysis of the terminal groups of the polypropylene oxide ¹³
Performed by C-NMR and IR.

When propylene oxide is polymerized with aluminum porphyrin complex and purified as it is in the presence of water, It is known that polypropylene oxide having a terminal hydroxyl group structure can be obtained. ^{In the 13} C-NMR spectrum, the resonance absorption of this carbon with a hydroxyl group is in the vicinity of 66.5 ppm, but in the polypropylene oxide obtained in this example, this resonance absorption of 66.5 ppm was not observed. .

Further, in the IR spectrum, the characteristic absorption of the hydroxyl group is usually around 3500 cm ^-1 , but this absorption was not observed in the polypropylene oxide of this example. From these results,
It can be concluded that there are almost no hydroxyl groups at the ends of the obtained polypropylene oxide. On the other hand, in the polypropylene oxide of this example, The resonance absorption of ¹³ C-NMR corresponding to (a) carbon is 115 to 11
6 ppm, (b) carbon 133-134 ppm, (c) carbon 70
Observed at ~ 72ppm. The resonance absorption of carbon of the methyl group of the main chain in polypropylene oxide was ¹³ C-NMR at 17.3 ppm, but from the ratio of the integral ratio of this methyl group and allyloxy unsaturated group, all unsaturated groups at both ends were The estimated molecular weight calculated assuming that it was introduced was obtained. Since this estimated molecular weight and the number average molecular weight determined by GPC were in good agreement, it was concluded that the polypropylene oxide obtained in this example had allyloxy unsaturated groups at both ends.

Example 2 Polymerization, reaction and analysis were carried out in the same manner as in Example 1 using the complex catalyst (A). Table 1 shows the polymerization and reaction conditions, and the results of GPC and NMR analysis. NMR
Was performed by ¹ H-NMR.

Of polypropylene oxide In ¹ H-NMR, the terminal group is (a) a proton attached to carbon is δ
At 5.0 to 5.3 ppm, (b) protons attached to carbon are δ 5.7 to 5.
At 9 ppm, a proton attached to carbon (c) was observed as resonance absorption at δ3.9 to 4.1 ppm. The resonance absorption of the main chain methyl group in polypropylene oxide is δ1.0-1.1 ppm,
The content of the terminal unsaturated group was calculated from the ratio of the integral ratio of the methyl group and the proton on the carbon (a) of the allyloxy group. When calculated based on the number average molecular weight of 8190 determined by GPC, it was estimated that about 78% of both ends were allyloxy unsaturated groups.

Example 3 Similar to Example 1 except that the complex catalyst (B) obtained in Reference Example 2 was used in place of the complex catalyst (A), and acrylic acid chloride was used in place of allyl bromide after polymerization. Polymerization, reaction and analysis were carried out. Table 1 shows the polymerization and reaction conditions and the analysis results.

The terminal functional group analysis was performed by ¹³ C-NMR and IR. It was obtained because the characteristic absorption of the hydroxyl group around 3500 cm ^-1 was not observed in the IR spectrum and the resonance absorption around 66.5 ppm of the carbon with the hydroxyl group was not observed in the ¹³ C-NMR spectrum. It can be concluded that there were almost no hydroxyl groups at the ends of polypropylene oxide. on the other hand, The resonance absorption of ¹³ C-NMR corresponding to (a) carbon is about 130-
At 132 ppm, (b) carbon was observed at about 128 to 130 ppm, and (c) carbon was observed at about 165 to 166 ppm.
Absorption of ester 5 cm ^-1, the absorption of unsaturated groups 1620～1640Cm ^-1 was observed, it can be said that had the acryloyloxy groups at the molecular terminal. Further, the estimated molecular weight calculated on the assumption that all unsaturated groups were introduced at both ends was obtained by the ratio of the integral ratio of the main chain methyl group and acryloyloxy unsaturated group in polypropylene oxide. Since the estimated molecular weight and the number average molecular weight determined by GPC were in good agreement, it was concluded that the polypropylene oxide obtained in this example had an acryloyloxy unsaturated group at both ends.

Claims (14)

[Claims] 1. An aluminum porphyrin complex obtained by reacting an organoaluminum compound and a porphyrin compound, wherein (a) an active hydrogen atom selected from a hydroxyl group and a carboxylic acid group and an unsaturated group are contained in one molecule. The alkylene oxide is polymerized by using a complex catalyst obtained by reacting an active hydrogen-containing organic compound, and then (c) an organic compound containing an unsaturated group and an active halogen atom in one molecule, and (d) an activity. A process for producing a polyalkylene oxide having an unsaturated group at the molecular end, which comprises reacting an active halogen-containing compound selected from organic compounds containing two or more halogen atoms in one molecule. 2. The method according to claim 1, wherein the porphyrin compound is tetraphenylporphyrin. 3. The method according to claim 1, wherein the alkylene oxide is propylene oxide. 4. The production method according to claim 1, wherein the active hydrogen-containing organic compound is allyl alcohol or acrylic acid. 5. The production method according to claim 1, wherein the active halogen-containing compound is an allyl halogen compound or acrylic acid chloride. 6. The production method according to claim 1, wherein the polyalkylene oxide having an unsaturated group at the terminal of the molecule is polypropylene oxide having an allyloxy group at the terminal. 7. The method according to claim 1, wherein the polyalkylene oxide having an unsaturated group at the terminal of the molecule is polypropylene oxide having an acryloyloxy group at the terminal. 8. An aluminum porphyrin complex obtained by reacting an organoaluminum compound with a porphyrin compound, wherein (b) active hydrogen containing two or more active hydrogen atoms selected from a hydroxyl group and a carboxylic acid group in one molecule. Polymerization of an alkylene oxide is carried out using a complex catalyst obtained by reacting an organic compound containing a compound, and then (c) an active halogen-containing compound containing an unsaturated group and an active halogen atom in one molecule is reacted. And a method for producing a polyalkylene oxide containing an unsaturated group at the molecular end. 9. The method according to claim 8, wherein the porphyrin compound is tetraphenylporphyrin. 10. The production method according to claim 8, wherein the alkylene oxide is propylene oxide. 11. The production method according to claim 8, wherein the active hydrogen-containing organic compound is allyl alcohol or acrylic acid. 12. The method according to claim 8, wherein the active halogen-containing compound is an allyl halogen compound or acrylic acid chloride. 13. The method according to claim 8, wherein the polyalkylene oxide having an unsaturated group at the terminal of the molecule is polypropylene oxide having an allyloxy group at the terminal. 14. The production method according to claim 8, wherein the polyalkylene oxide having an unsaturated group at the terminal of the molecule is polypropylene oxide having an acryloyloxy group at the terminal.