JPH09176152A - Polymerization of cyclic carbonate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively obtain a cyclic carbonate polymer exhibiting the expansion of the volume on polymerization, excellent in dimensional stability and adhesivity, and useful as a molding material, etc., by polymerizing a specific cyclic carbonate compound in an amine-based anion ring-opening polymerization initiator. SOLUTION: A cyclic carbonate compound of formula I [(x), (y) are each 0-3; R1 , R2 are each a <=15C alkyl, an aromatic group such as phenyl or naphthyl, allyl) or formula II or III (R3 , R4 are each a cyclic compound group) is polymerized in the presence of an amine-based anion ring-opening polymerization initiator such as 1,8-diazabicyclo [9146/28}5,4,0] undec-7-ene, 4- dimethylaminopyridine or triethylene diamine preferably in an amount of 0.1-5mol.% (based on the compound of formula I, II or III) at a temperature of 50-180 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerization method characterized in that a cyclic carbonate compound represented by a specific general formula is polymerized using an amine-based anionic ring-opening polymerization initiator. The cyclic carbonate compound in the present invention is
It is useful as a raw material for molding materials, composite materials, casting materials, sealing materials, paints, adhesives, etc., which exhibit volume expansion during polymerization and are required to have dimensional accuracy and adhesion.

[0002]

2. Description of the Related Art It is well known that vinyl monomers such as styrene and methyl methacrylate generally undergo large shrinkage during polymerization. Further, when a thermosetting resin such as an epoxy resin, a phenol resin, or an unsaturated polyester resin is cured, volume contraction occurs. These shrinkages have a large effect on the physical properties of the cured product, and cause various problems such as the occurrence of voids, cracks, poor appearance, etc., or a decrease in adhesive strength.Therefore, in the fields of casting materials, sealing materials, adhesive materials, etc. It is a big problem. If a material exhibiting non-shrinkage during polymerization can be obtained, improvement in dimensional accuracy, precise molding by reducing warpage, distortion, and peeling, and improvement in material strength and adhesion by reducing internal stress can be expected. In order to solve the above problems, it has been reported that the cyclic carbonate compound increases its volume during ring-opening polymerization, and attention has been paid to its application to the above-mentioned various applications. For example, Lewis acid cationic polymerization initiators such as methyl trifluoromethanesulfonate and boron trifluoride ether complex and alkoxides such as sodium methoxide and n-butyllithium, and alkyllithiums such as sec-butyllithium as anionic polymerization initiators It is known that it undergoes ring-opening polymerization and exhibits volume expansion (Macromolecules, Vol. 24,
No. 15,4229-4235 (1991), Proceedings of the 65th Annual Meeting of the Chemical Society of Japan, 271 (1993), Proceedings of the 43rd Annual Meeting of the Society of Polymer Science, 294 (1994)).

[0003]

The ring-opening polymerization of a cyclic carbonate compound using a Lewis acid-based cationic polymerization initiator involves the use of a Lewis acid which is a strong acid such as methyl trifluoromethanesulfonate or a boron trifluoride etherate complex. Handling at the time of polymerization was difficult, and the workability was poor due to the large influence of moisture. Furthermore, the presence of an acid component causes problems such as corrosion of the metal, and cannot be used for electronic materials. Also, alkoxides such as sodium methoxide and n-butyllithium,
In the ring-opening polymerization method of a cyclic carbonate compound by anionic polymerization using an alkyl lithium-based initiator such as sec-butyl lithium, the activity of the initiator is reduced by moisture, the influence on the ring-opening polymerization is remarkably large, and sodium ion,
Since ionic impurities such as lithium ions are present, they cannot be used for electronic materials, and have not found industrially useful uses.

[0004]

In order to solve the above problems, the present inventors have developed a method for ring-opening polymerization of a cyclic carbonate compound with an industrially easy initiator. The present inventors have completed the present invention by discovering that the cyclic carbonate compound described above undergoes ring-opening polymerization with an amine-based anionic polymerization initiator and exhibits volume expansion.

That is, the present invention is characterized in that the cyclic carbonate compound represented by the general formula (1) or (2) is polymerized by using an amine type anionic ring-opening polymerization initiator. Is the way

Embedded image (In the formula, x and y are integers from 0 to 3, and R ₁ and R ₂ are 1
Indicates an alkyl group containing 5 or less carbon atoms, an aromatic group such as phenyl or naphthyl, or an allyl group)

Embedded image (In the formula, x and y are integers from 0 to 3, and R ₃ and R ₄ are cyclic compounds.) Further, the polymerization of the cyclic carbonate compound in which the amine-based anionic ring-opening polymerization initiator is a cyclic amine compound. And the cyclic amine ring-opening polymerization initiator is 1,8-diazabicyclo [5,4,0] undec-7.
It is a method for polymerizing the above cyclic carbonate compounds which are -ene (hereinafter abbreviated as DBU), 4-dimethylaminopyridine and triethylenediamine.

Preferred examples of the cyclic carbonate compound in the present invention include the following compounds.

Embedded image

The cyclic carbonate compound in the present invention may be used not only as one compound but also as a mixture of two or more compounds. The cyclic carbonate compound may be produced by a known method (obtained by the 39th Annual Meeting of the Polymer Society of Japan, Proceedings pp. 284 (1990). Amine ring-opening polymerization used in the present invention. As the initiator, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, benzyldimethylamine, 2-
(Dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, triethylamine,
Examples thereof include diethylamine, ethylamine, aniline, tetramethylguanidine, alkyl tert-monoamine and the like. Particularly, as the initiator in which the amine-based ring-opening polymerization initiator is a cyclic amine compound, 2-methylimidazole, 2
-Ethyl-4-methyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 1-benzyl-2-methyl imidazole, 1-cyanoethyl-2-methyl imidazole,
2,4-diamino-6- [2-methylimidazolyl-
(1)]-Ethyl S-triazine, piperidine, N, N'-
Dimethylpiperazine, pyridine, picoline and the like. Among the cyclic amine compounds, 1,8-diazabicyclo [5,4,0] undec-7-ene, triethylenediamine and 4-dimethylaminopyridine are cyclic carbonates represented by the general formula (1) and the general formula (2). The reaction with the compound is extremely fast, and the molecular weight and yield are high.

The above-mentioned amine-based anion initiator is 0.01 to 15 mol%, preferably 0.1 to 15 mol% with respect to the cyclic carbonate compound represented by the general formula (1) or (2).
It is used within the range of 0.1 to 5 mol%. 0.01 mol%
If it is less than 1, the polymerization will proceed, but it requires a long time, which is not preferable. On the other hand, if the concentration exceeds 10 mol%, a low molecular weight product is likely to be formed, which is not preferable. The conditions of these polymerization reactions vary depending on the kind and amount of the curing accelerator, but are usually room temperature to 200 ° C., preferably 50 to 18
It is in the range of 0 ° C. The compound of the present invention, if necessary,
Additives such as fillers, dyes and pigments can be added. Examples of the filler include organic powders such as wood powder, pulp powder, various crushed textiles, crushed thermosetting resin laminates and molded products, and inorganic powders such as silica, glass, talc, alumina, calcium carbonate, and carbon; Inorganic fibers such as glass fiber, carbon fiber, and mica can be selected.

[0009]

The present invention will be specifically described below based on examples and comparative examples. ¹ H-NMR spectrum is TM
Using S as an internal standard, an EX-90 type manufactured by JEOL Ltd. was used, and an infrared absorption spectrum was measured using an FT / IR-3 type manufactured by JASCO Corporation. The number average molecular weight is
It measured using the GPC-8000 system measuring device by Tosoh Corporation, and calculated by polystyrene conversion. The density is
Shibayama Scientific Instruments Co., Ltd. Density Gradient Tube Method Specific Gravity Measuring Device Type A, potassium bromide or calcium bromide aqueous solution 25 ° C
Measured in

[Example 1] 1, represented by the chemical formula (4),
3-dioxan-2-one 1.02 g,

Embedded image DBU (0.04 g) was placed in a test tube pre-loaded with a stirrer, heated and stirred at 120 ° C. for 10 minutes, and 10 ml of methylene chloride / acetic acid was added to terminate the polymerization and dissolve the polymer to obtain 200 ml of methanol. The precipitate was reprecipitated in the solution, collected after filtration, and 0.80 g of a white solid product was obtained. The number average molecular weight of the product was 10,000. When the ¹ H-NMR spectrum of the product was measured, a methylene peak indicating ring-opening polymerization at 4.24 and 2.05 ppm was observed. When the IR spectrum of the product was observed, it was 2970, 1750, 1470, 124.
A peak was observed at 0 cm ^-1 . From these results, the product is composed of repeating units of the following chemical formula (5):
It was confirmed to be a polymer having a structure in which 1,3-dioxan-2-one was subjected to ring-opening polymerization.

Embedded image When the density of the polymer was measured, it was 1.20,
The volume expansion coefficient calculated from the monomer density of 1.25 is 4.
1%.

[Second Embodiment] In the first embodiment, 1,3-
Norbornene cyclic carbonate represented by the chemical formula (6) in place of 1.02 g of dioxan-2-one 1.
Using 80 g,

[Chemical 6] Polymerization was performed in the same manner as in Example 1 except that the reaction time was 30 minutes to obtain 1.20 g of a white solid. The number average molecular weight of the product was 8,000. The product is ¹ H-NMR
From the spectrum and IR spectrum, it was confirmed that the norbornene cyclic carbonate was a polymer having a structure obtained by ring-opening polymerization.

[Embodiment 3] DBU in Embodiment 1
Dimethylaminopyridine 0.03 g instead of 0.04 g
Polymerization was conducted in the same manner as in Example 1 except that the reaction time was 1 hour to obtain 0.75 g of a white solid.
The number average molecular weight of the product was 9000. The product was analyzed by ¹ H-NMR spectrum and IR spectrum to give 1,3-
It was confirmed that dioxan-2-one was a polymer having a structure obtained by ring-opening polymerization.

Comparative Example 1 DBU in Example 1
Methyl trifluoromethanesulfonate (0.04 g) was used instead of 0.04 g, and the reaction time was changed to 1 hour.
Polymerization was carried out in the same manner as in Example 1 to give a white solid 0.1
0 g was obtained. The number average molecular weight of the product was 500. From the ¹ H-NMR spectrum and IR spectrum, it was confirmed that the product was a polymer having a structure in which 1,3-dioxan-2-one was subjected to ring-opening polymerization.

Comparative Example 2 DBU in Comparative Example 1
Sec-Butyllithium 0.04 g instead of 0.04 g
Was used in place of 1.02 g of 1,3-dioxan-2-one, 2.10 g of norbornene cyclic carbonate was polymerized in the same manner as in Example 1 except that the reaction time was 1 hour. Got The number average molecular weight of the product was 800. From the ¹ H-NMR spectrum and IR spectrum, it was confirmed that the product was a polymer having a structure in which a norbornene cyclic carbonate was subjected to ring-opening polymerization.

[0015]

INDUSTRIAL APPLICABILITY The cyclic carbonate gives a high yield and high molecular weight polymer by the amine type anionic ring-opening polymerization initiator, and exhibits volume expansion. Therefore, it is useful for applications of industrial materials such as casting materials, sealing materials, and adhesive materials.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C07D 321/10 C07D 321/10 487/04 150 487/04 150 C08G 64/30 NPU C08G 64/30 NPU // C07D 213/74 C07D 213/74

Claims (3)

[Claims] 1. A method for polymerizing a cyclic carbonate compound, which comprises polymerizing the cyclic carbonate compound represented by the general formula (1) or (2) using an amine-based anionic ring-opening polymerization initiator. Embedded image (In the formula, x and y are integers from 0 to 3, and R ₁ and R ₂ are 1
Indicates an alkyl group containing 5 or less carbon atoms, an aromatic group such as phenyl or naphthyl, or an allyl group) (In the formula, x and y are integers from 0 to 3, and R ₃ and R ₄ are cyclic compounds.) 2. The method for polymerizing a cyclic carbonate compound according to claim 1, wherein the amine-based anionic ring-opening polymerization initiator is a cyclic amine compound. 3. A cyclic amine ring-opening polymerization initiator is 1,8-
The method for polymerizing a cyclic carbonate compound according to claim 1, which is diazabicyclo [5,4,0] undec-7-ene, 4-dimethylaminopyridine, or triethylenediamine.