JPH0613605B2 - Polyalkylene oxides containing unsaturated groups at the ends of the molecule and having a narrow molecular weight distribution - Google Patents

Description

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

[Problems to be Solved by Prior Art and Invention] Polyoxypropylene having an unsaturated group at both ends of a molecular chain is already known. This polymer uses polyoxypropylene glycol obtained by ordinary anionic polymerization in which caustic potash is contacted as a starting material, and reacts the hydroxyl group of the glycol with sodium metal to form an alkoxide group, and then an unsaturated group such as allyl chloride. It can be obtained by reacting with a contained active halogen compound. However, in the usual anionic polymerization of propylene oxide by KOH contact, the number average molecular weight is increased because the growing end undergoes a chain transfer reaction with the propylene oxide monomer.
It is difficult to produce more than 3,000 polyoxypropylene glycols. Therefore, a special method is required to produce polyoxypropylene having a number average molecular weight of 3,000 or more and unsaturated groups at both ends. As the method, the hydroxyl group of polyoxypropylene glycol is reacted with sodium metal to form an alkoxide group, which is then reacted with a polyvalent halogen compound such as methylene chloride to increase the molecular weight, and then the unsaturated group-containing activity. For example, a method of reacting with a halogen compound to obtain polyoxypropylene having an unsaturated group at both ends is performed.
However, in these existing methods, it is not only difficult to accurately obtain a polymer having a target molecular weight, but also the chain extension reaction by the polyvalent halogen compound occurs non-uniformly, so the molecular weight distribution of the obtained polymer is There is also the problem that it will become wider.

[Means for Solving Problems] The present inventors have already been able to carry out a living polymerization method of propylene oxide by using a complex catalyst obtained by reacting an organoaluminum compound with a porphyrin compound. Moreover, it has been clarified that it is possible to synthesize a polymer having an arbitrary molecular weight with a narrow molecular weight distribution. The inventors of the present invention can easily apply polyoxypropylene having an unsaturated group at the molecular end and a narrow molecular weight distribution of 4,000 or more and a relatively high molecular weight to a polyoxypropylene having an arbitrary molecular weight by applying this new complex catalyst successfully. As a result of various investigations on the possibility that it can be synthesized, the present inventors have found that it can be synthesized successfully and reached the present invention.

That is, in the present invention, the main chain is essentially of formula (1): (In the formula, R ¹ is a hydrogen atom or a same or different group selected from monovalent organic compounds having 1 to 6 carbon atoms) and 70% or more of the terminal groups are represented by the formula ( 2): (In the formula, R ² is a divalent organic group having 1 to 8 carbon atoms, a is 0 or 1, and R ³ is a hydrogen atom or a methyl group) is an unsaturated group and has a number average molecular weight of 4,000. It relates to a polyalkylene oxide having a molecular weight distribution Mw / Mn of 1.5 or less in the range of ˜20,000.

The polyalkylene oxide represented by the present invention can be obtained by polymerizing an alkylene oxide by using an aluminum porphyrin complex (I) represented by the formula (3) obtained by reacting an organoaluminum compound and a porphyrin compound as a catalyst. be able to.

(In the formula, X is a group selected from a halogen atom, a hydrogen atom and an alkyl group having 4 or less carbon atoms.) The aluminum porphyrin complex (I) has the formula (4): (In the formula, R ⁵ is a group selected from a hydrogen atom and a monovalent hydrocarbon group having 10 or less carbon atoms, and R ⁴ is the same or different 1 selected from a hydrogen atom and an alkyl group having 4 or less carbon atoms.
It can be obtained by reacting a porphyrin compound represented by a valent group) with an organoaluminum compound. Specific examples of the porphyrin compound include tetramethyltetraethylporphyrin, octaethylporphyrin, and tetraphenylporphyrin, and the formula (3)
In particular, tetraphenylporphyrin in which R ⁵ is a phenyl group and R ⁴ is a hydrogen atom is particularly preferable. Examples of the organic aluminum compound include dialkylaluminum halides having an alkyl group having 4 or less carbon atoms such as diethylaluminum chloride and diethylaluminum bromide; carbon numbers such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum. Trialkylaluminums having an alkyl group of 4 or less; alkylaluminum hydrides containing an alkyl group having a carbon number of 4 or less and a hydrogen atom such as diethylaluminum hydride and diisobutylaluminum hydride can be effectively used. Aluminum porphyrin complex (I) is prepared by adding about an equimolar amount of an organoaluminum compound to a porphyrin compound in the presence of a solvent under an atmosphere of an inert gas such as nitrogen. Hydrocarbons such as benzene, toluene and xylene as the solvent;
Halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane can be used.

In the aluminum porphyrin complex (I), when X is a hydrogen atom or an alkyl group, (a) is reacted with an organic compound having a hydroxyl group or water to convert X into an alkoxide group, a phenoxide group or a hydroxyl group. Complex compound,
(b) by reacting with an organic compound containing a carboxylic acid group,
A complex compound in which X is converted to an acyloxy group can be obtained, and such a derivative can also be effectively used as a complex catalyst.

In the present invention, for the purpose of introducing an unsaturated group to the polymer terminal (a specific example will be described later), such a derivative contains an organic compound having a hydroxyl group of (a) or a carboxylic acid group of (b). As an organic compound, (c) an active hydrogen group selected from a hydroxyl group and a carboxylic acid group and a terminal unsaturated group 1
An organic compound contained in the molecule or an organic compound containing (d) two or more groups having active hydrogen atoms such as a hydroxyl group and a carboxylic acid group in one molecule can be preferably used.

Examples of the organic compound represented by (C) include unsaturated aliphatic alcohols such as allyl alcohol, ethylene glycol monoallyl ether, 3-butenyl alcohol, and 2-hydroxyethyl acrylate; vinylphenol,
Specific examples include unsaturated phenols such as allyloxyphenol; unsaturated carboxylic acids such as acrylic acid and methacrylic acid. Examples of the organic compound represented by (d) include polyethylene alcohols such as triethylene glycol, tripropylene glycol, 2,2-bis (4-hydroxyphenyl) propane and glycerin; adipic acid,
Specific examples include polyvalent carboxylic acids such as sebacic acid. A complex obtained by reacting allyl alcohol and acrylic acid is particularly preferable.

The polyalkylene oxide in the present invention essentially has the above formula (1): (In the formula, R ¹ is the same as the above) and is a main chain having a repeating unit. R ¹ is a hydrogen atom or 1 having 1 to 6 carbon atoms
It is a group selected from valent organic groups. Specific examples of the organic group include a methyl group, an ethyl group, a chloromethyl group, and a phenyl group. These polyalkylene oxides are produced by using aluminum porphyrin complex (I) as a catalyst,
It can be obtained by polymerizing alkylene oxide,
The alkylene oxide, a fatty acid alkylene oxide having a terminal three-membered ring epoxy group such as ethylene oxide, propylene oxide, 1-butylene oxide, epichlorohydrin, etc., preferably aliphatic alkylene oxide, particularly propylene oxide or propylene oxide and ethylene oxide Is preferably used in combination.

The polyalkylene oxide in the present invention can be obtained by polymerizing the alkylene oxide using the aluminum porphyrin complex (I) in the atmosphere of an inert gas without solvent or in the presence of a solvent. Nitrogen is suitable as the inert gas, and hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane are used as the solvent. 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.

Further, as already described in the specification of the applicant's application dated February 28, 1985 (Japanese Patent Application No. 60-39663), it contains a hydroxyl group or a carboxyl group atom together with the aluminum porphyrin complex (I). It is also possible to coexist and polymerize an organic compound having an active hydrogen atom such as a compound. In this case, there is an advantage that a polymer having a narrow molecular weight distribution can be obtained although the amount of the aluminum porphyrin complex used can be reduced. Examples of the organic compound having an active hydrogen atom include those mentioned above.
The compound (a), (b), (c) or (D) can be used, and the compound (c) or (d) is preferable for the convenience of introducing an unsaturated group at the polymer terminal. Therefore, allyl alcohol and acrylic acid are particularly preferable.

The obtained polyalkylene oxide has a molecular weight of the complex (I)
The amount of alkylene oxide to be used is almost automatically determined (when an organic compound having an active hydrogen atom is coexistent, the amount of alkylene oxide to be used relative to the total amount of complex (I) and the organic compound). As the amount of alkylene oxide used increases with respect to the complex (I), the molecular weight of the polyalkylene oxide produced also increases. When an organic compound having an active hydrogen atom coexists with the complex (I), the complex
The organic compound may be added in the range of 1-fold to 1000-fold the mole of (I), but particularly preferably in the range of 1-fold to 200-fold.

The polyalkylene oxide represented by the present invention has the formula (2): (In the formula, R ² , R ³ and a are the same as the above) and have an unsaturated group at the molecular end. R ³ is a hydrogen atom or a methyl group, and R ² is a divalent organic group having 1 to 8 carbon atoms. R ² is Preferred are divalent organic groups, and R ³ is particularly preferably a hydrogen atom. The unsaturated group represented by the formula (2) can be introduced at the terminal of the molecule by reacting with the active halogen compound represented by (e) during the polymerization of the alkylene oxide or after the completion of the polymerization. Specifically, for example, the polyalkylene oxide of the present invention can be obtained by the following method, but the method is not limited to these methods.

(B) One molecule of (c) an active hydrogen atom selected from a hydroxyl group and a carboxylic acid group and an unsaturated group, in the aluminum porphyrin complex (I) in which X is a hydrogen atom or an alkyl group. A complex catalyst obtained by reacting the active hydrogen atom of the organic compound contained therein with the X group of the complex (I) is prepared to polymerize the alkylene oxide, and then (e) one molecule of the unsaturated group and the halogen atom is prepared. The termination reaction is performed with the organic compound contained therein.

In this method, a polyalkylene oxide having a terminal unsaturated group can be obtained all at once. Specific examples of the compound represented by (c) are as described above.

Examples of the compound (e) include allyl halogen compounds such as allyl chloride, allyl bromide and allyl iodide; benzyl type halogen compounds such as vinylbenzyl chloride and allylbenzyl chloride;
Specific examples thereof include acid halogen compounds such as acrylic acid chloride, methacrylic acid chloride, vinyl benzoic acid chloride, allyl chloroformate and the like.

An example of the method (a) is shown as a reaction formula as follows.

Porphyrin aluminum complex catalyst utilizing Y, Y is a halogen atom, and n is a positive integer) (b) Polymerization of alkylene oxide is carried out in the same manner as in (a), and (f) active halogen atom in one molecule. The termination reaction is carried out with a compound containing two or more active halogens.

The residue excluding the halogen group in the compound (f) is introduced into the polyalkylene oxide main chain, and the terminal unsaturated polyalkylene oxide is obtained all at once.

Examples of the compound (f) include bis (chloromethyl) benzene, bis (bromomethyl) benzene and tris (bromomethyl)
Specific examples thereof include halogen compounds containing two or more benzyl type halogens or acid halogen type halogens such as benzene, adipic acid dichloride and phosgene.

An example of the method (b) is shown by the reaction formula as follows.

(In the formula, -R- is a divalent organic group) (C) The activity of the above-mentioned (d) hydroxyl group and carboxylic acid group with respect to the aluminum porphyrin complex (I) in which X is a hydrogen atom or an alkyl group An organic compound containing two or more hydrogen atom-containing groups in one molecule is reacted in an equivalent amount to prepare a complex catalyst, and then alkylene oxide is polymerized, and a termination reaction is carried out with the compound (e).

In this method, a polyalkylene oxide having a terminal unsaturated group can be obtained all at once.

An example of the method of (c) is shown by the reaction formula as follows.

(In the formula, -R- and Y are the same as above.) (D) The alkylene oxide is polymerized in the presence of the aluminum porphyrin complex (I) or its derivative and the compound of the above (c). In this method, a polymer having an unsaturated group at one end and a hydroxyl group at the other end can be obtained. Then, this polymer is reacted with the compound (e) in the presence of an alkaline substance to obtain a polyalkylene oxide having unsaturated groups at both ends.

An example of the production of a polymer having an unsaturated group at one end and a hydroxyl group at the other end in the method (d) is shown by the reaction formula as follows.

(In the formula, m and n are positive integers) Examples of the alkali substance include alkali metals or alkali metal compounds, organic amines, and the like, and specifically, metal sodium, potassium hydroxide, sodium hydroxide, sodium. Examples include methylate, triethylamine, pyridine and the like.

(V) The aluminum porphyrin complex can be obtained by polymerizing alkylene oxide in the presence of (I) or its derivative and the organic compound represented by (d) above to obtain a polyalkylene oxide having a hydroxyl group at the terminal. Next, this polymer is reacted with the compound (e) in the presence of an alkaline substance.

An example of the production of the hydroxyl-terminated polyalkylene oxide in the method (e) is shown by the reaction formula as follows.

(In the formula, m and n are the same as above) The methods (a) and (d) are more preferable because the amount of catalyst used and the amount of salt produced can be small.

The polyalkylene oxide having an unsaturated group at the terminal and having a number average molecular weight of 4,000 to 20,000 and a molecular weight distribution Mw / Mn of 1.5 or less, which is represented by the present invention, can be analyzed for its structure by the following method. it can. Terminal unsaturated group is ³ C-NMR, ¹ H-NMR
And IR can be used for structure determination and quantification of unsaturated group content. Number average molecular weight and molecular weight distribution Mw / Mn are GPC
Can be obtained by

The polyalkylene oxide shown in the present invention can be usefully used as a reactive liquid rubber material as it is or by converting a terminal unsaturated group into another active functional group.

Since the polymer of the present invention has a high number average molecular weight of 4,000 or more and a narrow molecular weight distribution of 1.5 or less, a rubber cured product having excellent properties such as elongation can be obtained. In particular, when the number average molecular weight is 5,000 or more and the molecular weight distribution is 1.3 or less, a rubber cured product having more excellent properties can be obtained.

[Effect of the Invention] The polyalkylene oxide of the present invention can be used for the production of liquid rubber, but has a high number average molecular weight of 4,000 or more and a narrow molecular weight distribution of 1.5 or less. It has excellent characteristics.

[Example] Reference example 1 0.28 ml of triethylaluminum and α, β, γ, δ-
Tetraphenylporphyrin 1.21g and nitrogen atmosphere,
A solution containing a complex in which R ⁴ is a hydrogen atom, R ⁵ is a phenyl group and X is an ethyl group in the aluminum porphyrin complex (I) is reacted in the presence of 40 ml of a methylene chloride solvent at room temperature. I got it. After adding 1.2 ml of allyl alcohol to this solution and reacting at room temperature, allyl alcohol remaining unreacted with the solvent was removed under reduced pressure to obtain a complex catalyst (A). This complex catalyst (A) had a structure in which R ⁴ was a hydrogen atom, R ⁵ was a phenyl group, and X was an allyloxy group in the aluminum porphyrin complex (I).

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. Under a nitrogen atmosphere, 16.4 g of propylene oxide was added, and the mixture was polymerized for 2 days at room temperature with stirring with a magnetic stirrer. After that, unreacted propylene oxide was removed under reduced pressure and the polymerization rate was measured to be 86%. Subsequently, 20 ml of allyl bromide was added and reacted at 70 ° C. for 32 hours, after which 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 13.8 g of polypropylene oxide. When the molecular weight and the molecular weight distribution of this polypropylene oxide were measured by GPC, it was found that the molecular weight distribution (w / n) was 1.12, which was extremely narrow although the number average molecular weight (n) was as high as 8,190. GPC
Was measured by using a column packed with polystyrene gel (manufactured by Toyo Soda Co., Ltd.) and tetrahydrofuran as a distilling solvent at an oven temperature of 40 ° C. Further, the end group analysis of this polypropylene oxide was conducted by ¹ H-NMR. Allyloxy group The resonance absorption corresponding to (a) is about δ for protons attached to carbon.
5.0 to 05.3 ppm, (b) about 5.7 to 5 with proton attached to carbon.
It was observed at 9 ppm, and at about δ3.9-4.1 ppm due to the proton attached to (c) carbon. The resonance absorption of the proton of the main chain methyl group in polypropylene oxide was about δ1.0 to 1.1 ppm.However, the ratio of the integral ratio of this methyl group and the proton on carbon (a) of the allyloxy group showed that the terminal The content of saturated groups was calculated. GP
When calculated based on the number average molecular weight of 8,190 obtained from C, it was estimated that about 78% of both ends were allyloxy unsaturated groups. Figure 1 shows the polypropylene oxide
A chart of ¹ H-NMR spectrum is shown.

Example 2 3.0 g of the polypropylene oxide obtained in Example 1 was placed in a glass eggplant-shaped flask. Add 1 ml of 28% methanol solution of sodium methylate and stir at 80 ℃.
After heating to room temperature and removing methanol under reduced pressure, 2 ml of allyl chloride was added, and the mixture was heated at 60 ° C for 2 hours and then at 80 ° C for 2 hours.
Reacted for hours. After cooling to room temperature, hexane was added to the solution, washed with water, the hexane layer was dried over magnesium sulfate, filtered, and then heated under reduced pressure to remove hexane to obtain a polymer. The end group analysis of this polymer is IR, ¹
It was performed by 1 H-NMR and ¹³ C-NMR. ^{In 13} C-NMR spectrum, resonance absorption of carbon with hydroxyl group (usually, resonance absorption of hydroxyl group-terminated secondary carbon of polypropylene oxide is around 66.5 ppm) was not observed, and IR spectrum of 3,500 c
Since no characteristic absorption of hydroxyl group around m was observed, it can be concluded that there are almost no hydroxyl groups at the ends of this polymer. In addition, by reading the integral ratio of the methyl group in the polypropylene oxide main chain and the allyloxy unsaturated group in the ¹ H-NMR spectrum, the estimated molecular weight calculated assuming that the allyloxy unsaturated group was introduced at both ends was calculated. , 7,500. Since this molecular weight was in good agreement with the number average molecular weight determined by GPC, it can be concluded that the obtained polypropylene oxide had an ayloxy group at both ends. ¹ H-NMR of this polyprene oxide
The spectrum chart is shown in FIG.

[Brief description of drawings]

1 and 2 are ¹ H-NMR spectrum charts of the polyoxypropylenes obtained in Examples 1 and 2, respectively.

Claims (6)

[Claims] 1. The backbone is essentially of the formula (1): (In the formula, R ¹ is a hydrogen atom or a same or different group selected from monovalent organic groups having 1 to 6 carbon atoms), and 70% or more of the terminal groups are represented by the formula ( 2): (In the formula, R ² is a divalent organic group having 1 to 8 carbon atoms, a is 0 or 1, and R ³ is a hydrogen atom or a methyl group) is an unsaturated group and has a number average molecular weight of 4,000. A polyalkylene oxide having a molecular weight distribution Mw / Mn of 1.5 or less in the range of up to 20,000. 2. The polyalkylene oxide according to claim 1, wherein the polyalkylene oxide is polypropylene oxide or a propylene oxide-ethylene oxide copolymer. 3. The polyalkylene oxide according to claim 1, wherein the terminal unsaturated group is an allyloxy group. 4. The polyalkylene oxide according to claim 1, wherein the terminal unsaturated group is an acryloyloxy group. 5. The polyalkylene oxide according to claim 1, which has a molecular weight distribution Mw / Mn of 1.3 or less. 6. The polyalkylene oxide according to claim 1, having a number average molecular weight of 5,000 to 12,000.