JPH01278529A - Ring-opening of heterocyclic compound and polymerization thereof - Google Patents

Abstract

PURPOSE:To obtain a ring-opened monomer useful as an intermediate capable of efficiently providing a monodisperse polymer or a raw material of an anti- foaming agent and so on in a high yield under mild conditions by reacting a heterocyclic compound with a specified reaction initiator in the presence of a specified catalyst to cleave the ring. CONSTITUTION:A reaction initiator of the formula X4-nMeRn [X is halogen, alkoxy, etc.; Me is Si, Sn, etc.; R is (oxygen or nitrogen substituted)hydrocarbon residue; n is 0-3] is reacted with a heterocyclic compound (pref. epsilon-caprolactone, etc.) in the presence of a catalyst selected from a Lewis acid catalyst, a cation catalyst, an anion catalyst, a Lewis acid/anion cocatalyst and a cation/anion cocatalyst to cleave the ring of the above mentioned heterocyclic compound. The reaction initiator is preferably (CH3)3SiOCH3, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> 13= The present invention relates to a ring-opening method and a polymerization method of a heterocyclic compound.

<Prior art and its disadvantages> Conventionally, in order to polymerize cyclic monomers, protonic acids such as sulfuric acid and phosphoric acid, Lewis acids such as boron fluoride, aluminum chloride, and zinc iodide, or BF30 (C2H5
)2. The reaction is carried out using a cationic catalyst such as (C6H,) or CBF4, without a solvent or in a solvent, while adjusting the reaction temperature.

However, in the polymers obtained by the conventional polymerization method, chain transfer reactions of growing cations tend to occur during polymerization, making it difficult to obtain high molecular weight polymers, and furthermore, the polymerization reaction must be carried out at extremely low temperatures. There is a drawback.

In addition, the obtained polymer has a wide molecular weight distribution, with uneven molecular weights ranging from low molecular weight regions to high molecular weight regions, so it has the disadvantage that it is difficult to obtain high performance and highly functional polymers with uniform molecular weights. be.

Furthermore, as a method for obtaining stable polymers with uniform molecular weight, in 1983 Du Pont's Q
, IJ, 1ilebster et al., α,
An anionic polymerization method has been proposed in which a β-unsaturated unsaturated nylbonyl compound luenol ether is subjected to Michael addition.

However, there is a method in which a heterocyclic compound is subjected to a ring-opening addition reaction with an organosilicon compound, an organotin compound, or an organogermanium compound as a reaction initiator to obtain a heptamer having a polyfunctional group, and in polymerizing the monomers. At present, there is no known polymerization method that can control the molecular weight of a polymer from 1 to 1.

<Problems to be Solved by the Invention> The purpose of the present invention is to develop ring-opening monomers that can be used as raw materials for polymer modifiers and antifoaming agents, or as intermediates for efficiently obtaining monodisperse polymers. The object of the present invention is to provide a method for ring-opening a heterocyclic compound, which can be obtained in high yield under mild conditions.

Another object of the present invention is that when polymerizing a heterocyclic compound,
The object of the present invention is to provide a method for polymerizing a heterocyclic compound in which the molecular weight of the polymer can be controlled as desired.

<Means for Solving the Problems> According to the present invention, in the presence of a catalyst selected from the group consisting of a Lewis acid catalyst, a cation catalyst, an anion catalyst, a Lewis acid/anion cocatalyst, and a cation/anion cocatalyst, the following General formula % formula % (in the formula, or halogen atom, alkoxy group, acyloxy group, ketoximate group, aminooxy group, amide group,
Mercapto group, acid amide group, acetal group, cyano group,
represents an ester group or a phosphate group, Me represents a silicon atom, a tin atom or a germanium atom, R represents the same or different hydrocarbon residue, oxygen-substituted hydrocarbon residue or nitrogen-substituted hydrocarbon residue, and D represents Indicates an integer from 0 to 3. Provided is a ring-opening method for a heterocyclic compound, which comprises reacting a reaction initiator represented by () with a heterocyclic compound to cleave the heterocyclic compound to obtain a ring-opening monomer. .

Further, according to the present invention, the heterocyclic compound is reacted with a reaction initiator represented by the general formula in the presence of the catalyst to cleave and polymerize the heterocyclic compound. A method of polymerizing a compound of formula is provided.

Furthermore, according to the present invention, in the presence of the catalyst, the heterocyclic compound and the reaction initiator represented by the general formula are reacted,
In the polymer obtained by cleaving and polymerizing a heterocyclic compound,
Furthermore, there is provided a method for polymerizing a heterocyclic compound, which comprises reacting the heterocyclic compound with the same or different heterocyclic compound in the presence of the catalyst to cleave and polymerize the heterocyclic compound. .

The present invention will be explained in more detail below.

In the ring-opening method of the present invention, a ring-opened monomer can be obtained by cleaving a heterocyclic compound by using a specific reaction initiator in the presence of a specific catalyst. The specific catalyst is a catalyst selected from the group consisting of a Lewis acid catalyst, a cation catalyst, an anion catalyst, a Lewis acid/anion cocatalyst, and a cation/anion cocatalyst, and specifically, ZnI2 as a Lewis acid catalyst. ．． ZnCl2. ZnF2゜Al
Cl3,5nC1□, etc., as a cation catalyst (CH3)
3S10S○2CF3. (C,H5)3CB F,.

B F 30 (C2Hs) 2, etc., as anionic catalysts, ((CH3)2N)3S S j F, (CH3
)3+ KHF21(CH3CH2CH2)3N F
, [(CH3)2N)3S HF2゜((c H3)
, N]3S CN, etc. can be preferably mentioned. Furthermore, when the Lewis acid catalyst or cationic catalyst is used, a cationic polymerization inhibitor such as triethylamine or pyridine may be used in combination.

The amount of the catalyst used is 0 per mole of the heterocyclic compound.
．． It is preferably 01 to 100 mol%, especially ],
It is desirable that it be 10 mol%.

At this time, if the amount of the catalyst is less than 0.01 mol%,
This is not preferable because the reaction rate decreases due to deactivation of the catalyst and the yield of the reaction product decreases, and if it exceeds 100 mol %, it is uneconomical in terms of cost.

The reaction initiator used in the present invention can be represented by the following general formula:
Mercapto group, acid amide group, acetal group, cyano group,
represents an ester group or a phosphate group, Me represents a silicon atom, a tin atom or a germanium atom, R represents the same or different hydrocarbon residue, oxygen-substituted hydrocarbon residue or nitrogen-substituted hydrocarbon residue, and n represents Indicates an integer from 0 to 3. If the number of carbon atoms in R increases, steric hindrance of the substituent will occur and the reactivity of the reaction initiator will decrease, so the number of carbon atoms is]. ~
A range of 12 is most preferred. Examples of the reaction initiator include (CH,)3S ]○CH3, (C4H8)3S n
0cH3゜(CH3)+l S I N (C2H5)
2(CH3) 3 S i C], (CH
3) 38 j (OCI-L)z+CH3S i,
(OCH3)3. S j (OCH3)4゜(CHl)3
Sco-0-CH2-CF,H,.

Preferred examples include (CH3)3SiOCOCI (32, etc.).The amount of the reaction initiator to be used is equal to or more than the equivalent molar amount to the heterocyclic compound to be ring-opened, and an excess amount may be added. It is preferable that the moles are equivalent in terms of cos I.

Examples of polycyclic compounds that can be ring-opened in the present invention include cyclic esters such as β-propiolactone, E-caprolactone, and tetramethyl glycolide; β-thiolpropiolactone, F-thiol Cyclic thiol lactones such as caprolactone; lactams such as β-propiolactam and E-caprolactam; cyclic ethers such as propylene oxide, cyclohexene oxide, and 3,3-bis(chloromethyl)oxetane; cyclic sulfides such as ethylene sulfide; Methyl-2-oxazoline, 2.4-. 4. Cyclic iminoethers such as 6-tetramethyl-2-oxazine; 3-phenyl-1,
3-oxazolidine-2-thione, 3-phenyl-1,
Cyclic urethane such as 3-oxazolidin-2-one; 2-
Phosphorus-containing cyclic monomers such as phenyl-]-53,2-dioxaphosphorine, 2-phenyl-1゜3.2-dithiaphosphorane, etc. 1,6,8.13-Te1
Herathio[6°6]1~spiroorthocarboner such as lyzocane~;]--phenyl-4-ethyl1~bicycloorthoester such as lioxabicyclo(2,2,2)octane;1,4. Spirool 1-ester such as 6-1-dioxa(4,,6)undecane; 1,3.6-1-
Cyclic formals such as dioxacyclooctane and 1,3-dioxolane; cyclic acetals such as 2-benzyl-1,3-oxepane; cyclic thioformals such as 1,3-dithiacyclopentane; cyclic amines such as aziridine and conidine ;To cyclic carbonate such as ethylene carbonate 1;2
Preferred examples include cyclic imides such as -azabicyclo[3,2,2)nonan-3-one; and cyclic ureas such as N,N'-ethylene urea.

In the present invention, in order to ring-open the heterocyclic compound, in the presence of the catalyst, the reaction initiator and the heterocyclic compound are mixed in the absence of a solvent or in the presence of a solvent, for example, at a reaction temperature of -9
Ring opening can be carried out by reacting in the range of 5°C to room temperature to solvent reflux temperature. Examples of the solvent include halogenated hydrocarbons such as methylene chloride and chloroform; aromatic hydrocarbons such as benzene and 1-toluene; 21-ro compounds such as 21-heromethane and nitrobenzene; amides such as dimethylformamide. Preferable examples include ester compounds such as ethyl acetate. When using the above solvent, the amount of solvent used is 10% of the heterocyclic compound.
It is desirable that the amount is 0 to 5000 parts by weight, and a larger amount can be used depending on the properties or solubility of the product. Regarding the order of charging the catalyst, reaction initiator, and heterocyclic compound, it is preferable that the reaction initiator is charged first or second.

The reaction time is usually preferably in the range of 0.5 to 24 hours, but to complete the reaction, for example, in the middle of the reaction, the reaction solution is extracted and the presence or absence of the heterocyclic compound is measured using a gas chroma 1 graph or the like. Therefore, it is possible to know easily.

The obtained product can be purified by a known purification method, specifically Kara 1.
1. It can be easily purified by separation and purification methods, distillation, etc.

Further, in the polymerization method of the present invention, the same catalyst, cationic polymerization inhibitor, reaction initiator, and heterocyclic compound as in the ring-opening method can be used, and in the presence of the catalyst, the reaction initiator and the heterocyclic compound can be used. By adjusting the mixing ratio with the compound and using the same reaction conditions as in the ring-opening method described above, the heterocyclic compound is ring-opened.
A polymer can be obtained by polymerization. The polymer used in the present invention has a wide range of meaning, including dimers, dimers, oligomers, and even high polymers.

In the present invention, a polymer having a desired molecular weight can be obtained by adjusting the blending ratio of the reaction initiator and the heterocyclic compound. That is, in the polymerization method of the present invention, the molar ratio of heterocyclic compound:reaction initiator is defined as 20:1, for example, so that the degree of polymerization n = 2.
0 polymers can be synthesized. At this time, if an equivalent mole or more of the reaction initiator is added to the heterocyclic compound,
Since no polymerization reaction takes place, the amount of initiator must be added in less than equivalent molar amounts. Furthermore, it is also possible to synthesize a random copolymer by using a mixture prepared by mixing two or more different heterocyclic compounds in advance.

Furthermore, in the polymerization method of the present invention, in the presence of the catalyst, the mixing ratio of the heterocyclic compound that is the same as or different from the heterocyclic compound is adjusted, and the step of adding and reacting it to the polymer is repeated as desired. It is also possible to obtain polymers by this method. At this time, a block copolymer with a controlled molecular weight can be obtained by using different heterocyclic compounds.

Furthermore, in the polymerization method of the present invention, it is also possible to use a ring-opening monomer obtained by opening a ring of a heterocyclic compound as an initiator.

In the present invention, in order to purify the obtained polymer, for example, a method can be used in which the polymer is reprecipitated in an organic solvent such as methanol and the precipitated polymer is purified by decantation.

<Effects of the Invention> By the ring-opening method of the heterocyclic compound of the present invention, raw materials such as polymer modifiers and antifoaming agents, or monodisperse (w/Mn-1,
, O) A ring-opening monomer that can be used as an intermediate for efficiently obtaining a polymer can be obtained even under mild reaction conditions, especially at room temperature.

Furthermore, by the method for polymerizing a heterocyclic compound of the present invention, it is possible to easily polymerize a polymer whose molecular weight is adjusted, and furthermore, the obtained polymer has a monodisperse molecular weight distribution (Mw/Mn
= 1.0), so it has excellent heat resistance, mechanical strength, etc., and by appropriately selecting the heterocyclic compound,
A wide variety of polymers can be produced, including polyethers, polyesters, polycarbonates, polyether carbonates, polyamides, polyurethanes, or random copolymers and block copolymers thereof. Furthermore, the polymerization method of the present invention allows polymerization under mild conditions, particularly at room temperature, and therefore does not require special equipment, is advantageous in terms of cost, and can be used industrially.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

A three-way stopcock was attached to a 20 m eggplant-shaped flask containing salmon and starch, and the system was purged with dry nitrogen to remove moisture, and then 5 ml of methylene chloride was added as a solvent into the nitrogen stream. Then, while stirring, (CH3)3S i OS○2CF3. '0.02 g
(3mo1%) and (CH3)3Sj as a reaction initiator
OCH30.3], 3 g (3 mmol) was added. Then 0.2 co-6 g of β-propiolactone
(3mmo]-) was slowly added dropwise, and at the end of the dropwise addition, the system was sealed and allowed to react at room temperature for 2 hours. During the reaction, about 10 μQ of the reaction solution in the system was sampled using a microsyringe, and the reaction solution was subjected to a gas chromagraph to determine the presence or absence of β-propiolamine. When the presence of β-propiolactone completely disappeared, the solvent was removed under reduced pressure, and the product was then separated and purified using a column. The yield of the product obtained was determined by NMR and IR.
The structure of the product was determined.

The results are shown in Table 1.

Differences - Example "/] Each" - The same procedure as in Example 1 was carried out except that the heterocyclic compound, reaction initiator, catalyst and reaction conditions shown in Table 1 were changed. The results are shown in Table 1. Further, the NMR and IR analysis results of Example]-3 are shown below.

'H-NMR (CC14,60MJ(Z)δ0,07
(S, 9H, O8iMe3)0,62-2.17(b
A pressure cock was attached to a 20 ml eggplant-shaped flask containing a stirrer chip, the inside of the system was replaced with dry nitrogen to remove moisture, and then the mixture was poured into a nitrogen stream as a solvent. 5 ml of methylene chloride was added. Then, while stirring, as a catalyst (CH3)3S i OS○2CF3.0-02 g
(0.1 mmol.) and (CH3) as a reaction initiator,
, S i OCH3゜0,01 g (0,1 mmol
) was added. Then β-propiolactone 0,
324 g (4,5 mmol) was slowly added dropwise, and at the end of the dropwise addition, the system was sealed and allowed to react at room temperature for 12 hours. During the reaction, approximately 0.1 μQ of the reaction solution in the system was sampled using a microsyringe, and the reaction solution was subjected to gas chromatography to determine the presence or absence of β-propiolamine. When the presence of β-propiolac 1- was completely eliminated, the catalyst was removed using a glass filter, and then the solvent was removed under reduced pressure. Next, the reaction solution was added dropwise to a methanol solution, and the product was purified by reprecipitation, and the solvent was removed under pressure. The yield of the obtained product was measured and analyzed by NMR and IR
The structure of the product was determined by: The results are shown in Table 2.

Examples 37 to 75 The same procedure as Example 36 was carried out except that the heterocyclic compound, reaction initiator, catalyst, and reaction conditions shown in Table 2 were changed. The structure of the product was also determined by NMR and IR analysis.

The results are shown in Table 2. Also, NMR and I of Example 37
The R analysis results are shown below.

"H-NMR (CDC13, 60MHz) δ0.83 (
S, 08I(CH3))2,65(t, J=6.
0Hz, -CI-I2-C-0-)○ I 3,45(S, -C-○CH,) 4,35(t, J=7.0Hz, -〇-CH2-)I
R1740, 1180, 1015 (7) -' (-co〇-) Arrow side LL Dan After attaching a three-way cock to a 20ml eggplant-shaped flask containing a stirrer chip and replacing the inside of the system with dry nitrogen to remove moisture. , 5 ml of methylene chloride was added as a solvent in a nitrogen stream. Then, while stirring, as a catalyst (CH3)3S i 08Ci2CF3.0.02 g
(0,1mmo], ) and as a cationic polymerization inhibitor (
C7H5)3N.

0.01 g (0.1 mmol) and (CH3)3S10 CH30.01 g (0-1
mmol) was added. Thereafter, a mixture of 0.324 g (3 mmol) of β-propiolactone and 0.397 g (3 mmol) of β-thiolpropiolactone was slowly added dropwise, and at the end of the dropwise addition, the system was sealed.
The reaction was allowed to proceed at room temperature for 24 hours. During the reaction, about 0.1 μQ of the reaction solution in the system was sampled using a microsyringe, and the reaction solution was subjected to gas chromatography to determine the presence or absence of the heterocyclic compound. When the presence of the heterocyclic compound completely disappeared, the catalyst was removed using a glass filter, and then the solvent was removed under reduced pressure.

The yield of the obtained product was measured, and the structure of the product was determined by NMR and IR, and as shown in Table 3, it was a random copolymer. The results are shown in Table 3.

Example 77 The same procedure as Example 76 was carried out except that the heterocyclic compound, reaction initiator, catalyst and reaction conditions shown in Table 3 were changed. Further, the structure of the product was determined by NMR and IR analysis, and it was found to be a random copolymer. The results are shown in Table 3.

(Left below) Broiling procedure (Attach a three-way stopcock to a 20 ml eggplant-shaped flask containing an L shadow stirrer chip, replace the system with dry nitrogen to remove moisture, and add 5 ml of methylene chloride as a solvent in a nitrogen stream. Then, with stirring, 20.32 g (0,1-mmol) of ZnI as a catalyst and (CH3), 0,01 g of Si OCH, as a reaction initiator.
(0.1 mmol) was added. Thereafter, 0.324 g (3 mmol) of β-propiolac was slowly added dropwise, and at the end of the dropwise addition, the system was sealed, and during the reaction, about 0.1 μQ of the reaction solution in the system was collected with a microsyringe, The liquid was subjected to gas chroma 1 to graph to obtain the β-
The presence or absence of propiolactone was determined a+ll. When the presence of β-propiolone is completely eliminated,
β-thiol propiolachon 0, 397 g (3
Similarly, when the presence of β-thiolpropiolamine was completely eliminated, the catalyst was removed using a glass filter, and then the solvent was removed under reduced pressure. The yield of the obtained product was measured and analyzed by NMR and IR
When the structure of the product was determined, it was found to be a block copolymer as shown in Table 4. The results are shown in Table 4.

Example 79 The same procedure as Example 78 was carried out except that the heterocyclic compound, reaction initiator, catalyst and reaction conditions shown in Table 4 were changed. The structure of the product was determined by complete NMR and IR analysis, and it was found to be a random copolymer. The results are shown in Table 4.

(Margin below)

Claims (1)

[Scope of Claims] 1) In the presence of a catalyst selected from the group consisting of a Lewis acid catalyst, a cation catalyst, an anion catalyst, a Lewis acid/anion cocatalyst, and a cation/anion cocatalyst, the following general formula X_4_-_nMeR_n (formula Among them, X is a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an aminooxy group, an amide group,
Mercapto group, acid amide group, acetal group, cyano group,
represents an ester group or a phosphate group, Me represents a silicon atom, a tin atom or a germanium atom, R represents the same or different hydrocarbon residue, oxygen-substituted hydrocarbon residue or nitrogen-substituted hydrocarbon residue, n is 0 Indicates an integer between ~3. ) A ring-opening method for a heterocyclic compound, which comprises reacting a reaction initiator represented by the following formula with a heterocyclic compound to cleave the heterocyclic compound to obtain a ring-opening monomer. 2) In the presence of a catalyst selected from the group consisting of a Lewis acid catalyst, a cation catalyst, an anion catalyst, a Lewis acid/anion cocatalyst, and a cation/anion cocatalyst, the following general formula , alkoxy group, acyloxy group, ketoximate group, aminooxy group, amide group,
Mercapto group, acid amide group, acetal group, cyano group,
represents an ester group or a phosphate group, Me represents a silicon atom, a tin atom or a germanium atom, R represents the same or different hydrocarbon residue, oxygen-substituted hydrocarbon residue or nitrogen-substituted hydrocarbon residue, n is 0 Indicates an integer between ~3. ) A method for polymerizing a heterocyclic compound, which comprises reacting a reaction initiator represented by () with a heterocyclic compound to cleave and polymerize the heterocyclic compound. 3) In the presence of a catalyst selected from the group consisting of a Lewis acid catalyst, a cation catalyst, an anion catalyst, a Lewis acid/anion cocatalyst, and a cation/anion cocatalyst, the following general formula , alkoxy group, acyloxy group, ketoximate group, aminooxy group, amide group,
Mercapto group, acid amide group, acetal group, cyano group,
represents an ester group or a phosphate group, Me represents a silicon atom, a tin atom or a germanium atom, R represents the same or different hydrocarbon residue, oxygen-substituted hydrocarbon residue or nitrogen-substituted hydrocarbon residue, n is 0 Indicates an integer between ~3. ) is reacted with a heterocyclic compound, and the heterocyclic compound is cleaved and polymerized to obtain a polymer, and in the presence of the catalyst, the same or the same as the heterocyclic compound is added. A method for polymerizing a heterocyclic compound, which comprises reacting different heterocyclic compounds to cleave and polymerize the heterocyclic compound.