JPS626569B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polymerizable, particularly radically polymerizable, composition containing a spiroorthoester having an unsaturated bond (hereinafter simply referred to as spiroorthoester). As a result of various studies on the chemical properties of spiro-orthoesters, the present inventors found that spiro-orthoesters represented by the following formula [1] (hereinafter referred to as compound [1]) can be produced by radical polymerization.
It was discovered that it undergoes radical ring-opening copolymerization with ethylenically unsaturated compounds. (Here, n is 3, 4 or 5) Compound [1] is produced by dehydrohalogenation reaction of spiroorthoester represented by the following formula [2] (hereinafter referred to as compound [2]) . (where n is 3, 4 or 5, X is Cl,
Compound [2] is already known [indicates a halogen atom such as Br, I, etc.]
44-28111, Japanese Patent Publication No. 44-7949), by reacting it with an alkali such as sodium alkoxide in a suitable solvent such as dimethylformamide, pyridine, etc. to dehydrohalogenate it. Compound [1] is synthesized.
The reaction proceeds at room temperature, but if necessary,
It is also possible to lower or increase the reaction temperature. The degree of progress of the reaction can be easily determined by analyzing the reaction solution using, for example, liquid chromatography. Compound [1] can be separated and obtained from the reaction solution by, for example, pouring the reaction solution into water, separating the organic layer and the aqueous layer, and then performing an extraction operation on the aqueous layer with an organic solvent such as ether, chloroform, or benzene. The extract layer and the organic layer are combined, dehydrated and dried, and the solvent is distilled off.
This can be done by distilling the residue under reduced pressure. Regarding the cationic polymerization of spiro-orthoesters to which the compound [1] according to the present invention belongs, Journal of Macromolecular Science,
Chemistry (Journal of Macromolecular)
Science, Chemistry), A9(5), 849-865
(1975) etc., the present inventors
We have come to the unexpected finding that compound [1] not only undergoes cationic polymerization but also undergoes radical ring-opening copolymerization with ethylenically unsaturated compounds. Until now, nothing has been known about the radical copolymerizability of spiroorthoesters. The radical ring-opening copolymerizability of spiroorthocarbonates, which have a somewhat similar chemical structure to spiroorthoesters, has been reported in the Journal of Polymer Science and Polymer Chemistry Edition.
Science, Polymer Chemistry Edition), 13,
2525-2530 (1975), etc., but the synthesis method for spiroorthocarbonates is complicated and requires the use of harmful _CS2 with a low boiling point and expensive raw materials, making it difficult to manufacture. Not, but
It also has the disadvantage that the target product is expensive. However, the compound [1] constituting the composition of the present invention is synthesized from a generally commercially available inexpensive epihalohydrin and a compound [2] synthesized from γ-butyrolactone, δ-valerolactone, or ε-caprolactone. It has the advantage of being easily synthesized by a simple reaction of hydrogen halide. Furthermore, compound [1] also has the feature of extremely small volumetric shrinkage during polymerization. Compound [1] undergoes radical copolymerization with an ethylenically unsaturated compound by radical polymerization means, and at this time, the double bond of the methylene group in compound [1] disappears, ring opening of the spiroester ring occurs, and an ester bond is formed. is generated. Conventional radically polymerizable monomers or oligomers undergo extremely large volumetric contraction during polymerization, as shown in Table 1 below.

[Table] If the volumetric shrinkage during polymerization is large, for example, when used as a molding material, dimensional accuracy may be lost, when used as a casting material, the filled item may be distorted due to shrinkage, or it may be difficult to adhere to the mold. There are problems such as a decrease in force and the creation of gaps. In addition, when used as a paint, internal strain may cause a decrease in adhesion to the painted plate and warping, and when used as an adhesive, internal strain may cause problems such as a decrease in adhesive strength, warping, and deformation. . On the other hand, when compound [1] of the present invention is subjected to radical polymerization alone, the volumetric shrinkage rate of 2-methylene-1,4,6-trioxaspiro[4,4]nonane is approximately 9.6%. and 2-
Methylene-1,4,6-trioxaspiro [4,
6] Undecane is about 6.0%, which is very small compared to general radically polymerizable vinyl monomers. Here, the volume shrinkage rate (%) is expressed as [1-(specific gravity of monomer/specific gravity of polymer)]×100. Since the composition of the present invention contains the compound [1] which has a small volumetric shrinkage during polymerization as a copolymerization component, it has a lower volume shrinkage during polymerization than a composition containing only an ethylenically unsaturated compound as a polymerizable component. It has the characteristic of having a small volumetric shrinkage rate. Therefore, the composition of the present invention is extremely useful for use in molding materials, composite materials, adhesives, casting materials, paints, and the like. The ethylenically unsaturated compound that can constitute the composition of the present invention is one or more compounds selected from (meth)acrylate compounds and styrene compounds, such as methyl methacrylate, ethyl acrylate, There are β-hydroxyethyl methacrylate, butyl acrylate, hexyl acrylate, lauryl methacrylate, phenyl acrylate, styrene, α-methylstyrene, hydroxystyrene, monochlorostyrene, etc., as well as those described in JP-A-52-12125. Oligoester (meth)acrylates such as (a) poly(meth)acrylates of polyhydric alcohols and polyalkylene glycols, (b) polyhydric alcohols in the form of di- to pentahydric polyhydric alcohols with alkylene oxide added. Polyacrylate, (c) Poly(meth)acryloyloxyalkyl phosphate, (d) Polyester poly(meth)acrylate, (e) Epoxy poly(meth)acrylate, (f) Polyurethane poly(meth)acrylate, (g) Polyamide poly(meth)acrylate, (h) Polysiloxane poly(meth)acrylate, (i) Vinyl-based or diene-based low polymer having (meth)acryloyloxy groups in side chains and/or ends, (j) The above Examples include modified products of oligoester (meth)acrylates described in (a) to (i). Among these ethylenically unsaturated compounds, it is preferable to use those whose volumetric shrinkage during polymerization is larger than that of the spiro-orthoester. Regarding the polymerization means of the composition according to the present invention, it is possible to perform polymerization by conventional radical polymerization means such as ultraviolet rays, infrared rays, heat, electron beams, or microwaves. In ultraviolet radical polymerization, a photoinitiator is usually used. Preferred photoinitiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Examples include benzoin isobutyl ether, benzoin octyl ether, benzyl, diacetyl, methylanthraquinone, acetophenone, benzophenone, dithiocarbamate, α-chloromethylnaphthalene, and anthracene. Further, in polymerization using infrared rays, heat, or microwaves, any radical initiator can be used as long as it can generate radicals by decomposition. For example, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, etc. can be used. In addition, polymerization caused by ionizing radiation such as electron beams
It is usually carried out in a non-catalytic system. The amount when using a catalyst is 0.01 depending on the purpose
The content is preferably in the range of ~10wt%, preferably 0.1~5wt%. Radical polymerization proceeds even at room temperature when irradiated with ultraviolet rays or ionizing radiation, but in other cases it proceeds smoothly under heating or heating conditions. Reference example 1 2-methylene-1,4,6-trioxaspiro[4,6]undecane production: Mix 43 g of sodium methoxide with 150 ml of dehydrated dimethylformamide, cool the liquid temperature to 10°C, and stir. While passing nitrogen gas underneath, 80.8 g of 2-chloromethyl-1,4,6-trioxaspiro[4,6]undecane was added dropwise over about 90 minutes. After that, stirring was continued for about 6 hours at room temperature, and then the reaction solution was poured into water from Step 1, and the aqueous layer and organic layer were separated. Next, the operation of adding 100 ml of ether to the aqueous layer for extraction was repeated three times, and each ether layer was combined with the organic layer, dehydrated with magnesium sulfate, and then the ether was evaporated. The evaporation residue was further distilled under reduced pressure to obtain 50 g of compound [1]. 2-methylene-1・4・
The yield of 6-trioxaspiro[4.6]undecane was 75%, and its physical properties are as follows. Γ elemental analysis (%): Actual value...C: 26.5, H: 8.1 Calculated value as _C9H14O3 ( _theoretical value)...C: 63.5, H: _8.2 Γ Specific gravity: 1.091/25℃ Γ Boiling point: 87-89℃/7mmHg Γ Infrared absorption spectrum: 960, 1070, 1120cm-1 (C-O-C), 1690
cm-1 (C=C) Γ nuclear magnetic resonance spectrum [in CDCl ₃ ]: δ (PPM); 4.5 (2H), 4.2 (2H), 3.9
(2H), 2.15 (2H), 1.65 (6H) Reference example 2 Production of 2-methylene-1,4,6-trioxaspiro[4,4]nonane: Add 300 ml of dehydrated dimethylformamide to 86 g of sodium methoxide. , while cooling to about 10°C and passing nitrogen gas, 2-chloromethyl-
1,4,6-trioxaspiro[4,4]nonane
141g was dropped. Thereafter, stirring was continued, the temperature was gradually returned to room temperature, and the reaction was continued for about 5 hours. The reaction solution was poured into 1.5 ml of distilled water, and the aqueous layer and organic layer were separated. Next, the operation of adding 200 ml of ether to the aqueous layer for extraction was repeated four times, and each ether layer was combined with the organic layer, dehydrated with magnesium sulfate overnight, and then the solvent was evaporated. By distilling the evaporation residue under reduced pressure, 53 g (yield 47%) of 2-methylene-1.
4,6-trioxaspiro[4,4]nonane was obtained. The physical properties of this product are as follows. Γ Specific gravity (25℃): 1.131 Γ Boiling point: 87-89℃/22mmHg Γ Infrared absorption spectrum: 1690cm ^-1 (C=C),
930, 1060, 1120 cm ^-1 (C-O-C) Γ nuclear magnetic resonance absorption spectrum [in CDCl ₃ ]: δ (PPM); 4.5 (2H), 4.1 (2H), 3.9
(2H), 2.05 (4H) Example 1 0.05 mole of 2-methylene-1,4,6-trioxaspiro[4,4]nonane and 0.05 mole of styrene were dissolved in chlorobenzene, and di-tert-
Add 3 mol% of butyl peroxide to the polymerizable components, and heat to 44°C at 120°C in a sealed tube.
Allowed time to react. The reaction solution was poured into methanol to separate the polymer, which was further purified twice to remove the homopolymer, and then dried under reduced pressure. As a result, a white powdery polymer was obtained with a yield of 46%. It was done. In the obtained polymer, ester absorption at 1740 cm ^-1 was observed by infrared absorption spectrum measurement. According to nuclear magnetic resonance spectroscopy, the copolymerization ratio in this polymer was 87 mol% of styrene and 13 mol% of 2-methylene-1,4,6-trioxaspiro[4.4]nonane. Example 2 0.05 mole of 2-methylene-1,4,6-trioxaspiro[4,6]undecane and 0.05 mole of styrene were dissolved in chlorobenzene, and di-
Tert-butyl peroxide was added in an amount of 3 mol % based on the polymerizable components, and the mixture was reacted in a sealed tube at 120°C for 44 hours. The reaction solution was poured into methanol to separate the polymer, which was further purified twice to remove the homopolymer, and then dried under reduced pressure. As a result, a white powdery polymer was obtained with a yield of 43%. Ta. In the obtained polymer, ester absorption at 1740 cm ^-1 was observed by infrared absorption spectrum measurement. According to nuclear magnetic resonance spectroscopy, the copolymerization ratio in this polymer was 89 mol% of styrene and 11 mol% of 2-methylene-1,4,6-trioxaspiro[4.6]undecane. . Examples 3 to 7 2-methylene-1,4,6-trioxaspiro[4,4]nonane (abbreviated as compound [1]-) or 2-methylene-1,4,6-trioxaspiro[4, 6] Undecane (abbreviated as compound [1]-)
Then, an ethylenically unsaturated compound was mixed at a ratio of 50:50 (weight ratio), 3 wt% of di-tert-butyl peroxide was added as a polymerization catalyst, and the mixture was mixed in a sealed tube.
The reaction was carried out at 120°C for 26 hours, and the results shown in the table below were obtained.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A spiro-orthoester having an unsaturated compound represented by the following formula [1], and one or more ethylenic compounds selected from (meth)acrylic acid ester compounds and styrene compounds. A polymerizable composition comprising an unsaturated compound. In the above formula [1], n is an integer of 3 to 5.