JPH0244313B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a new compound, which has the following general formula [1]
2-hydroxymethyl-1,4,6-
Trioxaspiro[4,m]alkane (here, m represents an integer of 4 to 6) More specifically, 2-hydroxymethyl-1,4,6-trioxaspiro[4,4]nonane, 2 -Hydroxymethyl-1,4,6-trioxaspiro[4,5]decane and 2-hydroxymethyl-1,4,6-trioxaspiro[4,6]undecane, comprising: These compounds (hereinafter collectively referred to as compounds [1]) are useful, for example, as raw materials for the synthesis of polymerizable monomers and spiro-orthoester group-containing compounds. (Here, m represents an integer of 4 to 6.) Compound [1] can be produced by an addition reaction between lactones selected from γ-butyrolactone, δ-valerolactone, and ε-caprolactone and glycidol. , this reaction is as follows. (Here, m represents an integer of 4 to 6.) When producing compound [1], the reaction is carried out with an excess of lactone of preferably 1 mol or more, more preferably 1.2 to 5 mol, of lactone per 1 mol of glycidol. It is suitable to use BF ₃ OEt ₂ , SnCl ₄ , TiCl ₄ , etc. as a catalyst in a solvent such as methylene chloride or tetrahydrofuran.
The reaction is carried out using a Lewis acid such as _FeCl3 . There is no particular restriction on the reaction temperature, but it is preferably carried out at 0°C to 60°C. As an example of a desirable production method, lactones and a solvent in an amount of 1 to 10 times the weight of the lactones are charged into a reactor, and while maintaining the liquid temperature at a predetermined temperature,
0.03 for solvents usually consisting of lactones and solvents
There is a method in which ~3% by weight (0.05~10% by weight for lactones) of catalyst is added, and then glycidol is added dropwise either alone or as a solution with a solvent up to about 5 times the weight. The degree of progress of the reaction can be easily determined by analyzing the reaction solution using, for example, a gas chromatograph or a liquid chromatograph, and when the reaction is completed, an alkali is added after the reaction to neutralize the acid catalyst. Separation and acquisition of compound [1] from the reaction solution is performed, for example, as follows. After the reaction is cooled with ice water, an alkaline aqueous solution such as a dilute aqueous sodium hydroxide solution is added thereto, stirred and mixed, and then separated into an aqueous layer and an organic layer. After repeating the above operation until the amount of unreacted lactone in the organic layer becomes almost zero, the organic layer is washed with water, and then the organic layer is dehydrated with magnesium sulfate. Next, the solvent is distilled off, and the residue is distilled under reduced pressure to obtain compound [1]. Regarding the cationic polymerization of spiro-orthoester compounds, please refer to the Journal of Macromolecular Science and Chemistry.
Macromolecular Science, Chemistry), A9(5),
849-865 (1975), the compound [1] of the present invention is similarly cationically polymerized to give a polymer. The cationic polymerization of the compound [1] of the present invention is carried out by a generally well-known method, that is, by using, for example, ultraviolet rays, infrared rays, heat, or microwaves in the presence of a cationic polymerization initiator. As a cationic polymerization catalyst in the case of ultraviolet irradiation,
For example, aromatic diazonium salts such as φ-N ⁺ ≡N·PE ₆ ^- and φ-N ⁺ ≡N·BF ₄ ^- ; aromatic halonium salts such as φ-I-φ·BF ₄ ^- ; Aromatic onium salts of Group Va elements of the periodic table, such as;

Periodic table number of [formula] etc. Aromatic onium salt of group a element;

A dicarbonyl complex compound of an element of group a-a of the periodic table, such as [Formula] may be used. In addition, other combined cationic polymerization catalysts include, for example, Lewis acids such as BF ₃ , FeCl ₃ , SnCl ₄ , SbF ₃ , TiCl ₄ ; Lewis acids such as BF ₃ OEt ₂ , BF ₃ -aniline complexes, and O, S , N, etc.; oxonium salts, diazonium salts, and carbonium salts of Lewis acids; halogen compounds, mixed halogen compounds, and perhalogen acid derivatives. The amount of catalyst used is generally 0.001 to 10% by weight, preferably 0.1 to 5% by weight, based on the monomer to be polymerized. Although there are no particular restrictions regarding the polymerization temperature, it is usually carried out at room temperature to 200°C. When using a solvent during polymerization, it is desirable to choose a compound that does not react with the growing cation and reduce its activity. Suitable solvents for use include aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride, 1,1-dichloroethane, and others. Further, the functional group (OH group) of the compound [1] of the present invention
Using this, various compounds containing spiro-orthoester groups can be synthesized by nucleophilic reactions. An example of such a compound is a monomer having a radical polymer group represented by the following general formula [2] (hereinafter referred to as compound [2]). (Here, R represents a water atom or a methyl group, and m represents an integer of 4 to 6.) Compound [2] is a compound [1] and acrylic acid chloride or methacrylic acid chloride (hereinafter referred to as (meth)acrylic acid chloride). The reaction formula is as follows. (Here, R and m have the same meaning as in general formula [2].)
In the above reaction, for example, compound [1] is dehydrochlorinated by dropping (meth)acrylic acid chloride in a suitable solvent in the presence of an organic basic substance such as triethylamine. The above compound [2] is a useful compound that can introduce a spiro-orthoester group into a polymer by using a (meth)acryloyl group alone or by radical polymerization with an ethylenically unsaturated compound. . Another example is a urethane compound represented by the following general formula [3] (hereinafter referred to as compound [3]) containing a spiro-orthoester group by reacting compound [1] with an isocyanate compound. (Here, Q represents an isocyanate or urethane compound residue, m represents an integer of 4 to 6, and n represents an integer of 1 or more.) The following () or ( ) There is a method. () Urethane-forming reaction between an isocyanate compound and compound [1]. () Urethanization reaction of the following compounds (A), (B) and (C). (A) at least one polyisocyanate compound having at least two isocyanate groups;
seed. (B) At least one polyhydroxy compound having at least two hydroxyl groups. (C) At least one type of spiroorthoester represented by the general formula [1]. Isocyanate compounds that can be used in () and () above include aliphatic and aromatic monoisocyanates, aliphatic, alicyclic and aromatic polyisocyanates having two or more isocyanate groups in the molecule, and others. Examples of polyhydroxy compounds having two or more hydroxyl groups that are raw materials include polyhydric alcohols, polyester polyols, polyether polyols, and polymer polyols. Specific examples of these compounds include monoisocyanates as described in JP-A-56-167688 No. 2.
Isocyanates and polyhydroxy compounds having two or more isocyanate groups in the molecule, which are described from line 13 in the lower left column of the page to line 6 in the lower right column of the same page, are disclosed in JP-A No. 57-21417 No. 5. These are the compounds described in the third line from the bottom of the upper left column of the page to the fourth line from the bottom of the upper right column of page 6, and any of these may be used. An example of a method for producing a spiro-orthoester having a urethane group by subjecting the compounds (A), (B) and (C) in () above to a urethanization reaction is as follows: A typical method is a two-step reaction. In the production method, in the first step, a partially urethanized product having an isocyanate group at the terminal and/or side chain is produced by a urethanization reaction between a polyisocyanate compound and a polyhydroxy compound. At this time, the isocyanate group of the polyisocyanate compound is approximately 1 equivalent of hydroxyl group contained in the polyhydroxy compound.
It is preferable to carry out the reaction at a ratio of 1.1 equivalents or more, and by changing this equivalent ratio, the molecular weight of the final product composition can be adjusted. If the isocyanate group is used in a ratio lower than about 1.1 equivalents per equivalent of hydroxyl group, the molecular weight of the final product composition may become significantly large, resulting in increased viscosity or insufficient curability. In addition, by increasing the equivalent ratio of isocyanate groups to hydroxyl groups, in the final product composition, a compound represented by the following compound [4] in which the isocyanate group of a partially urethanized polyisocyanate compound is urethanized with compound [1] [4]) can be increased. Y(-NH-COO-X)f [4] (where X is

In the group represented by the formula: Y represents a partially urethanized polyisocyanate residue, f represents an integer corresponding to the valence of the polyisocyanate compound, and m represents an integer of 4 to 6. ) This compound [4] has two or more spiro-orthoester groups, and since it is a polyfunctional polymerizable compound, it increases the degree of cross-linking when curing the final product composition. useful for. In the urethanization reaction, in order to avoid a rapid temperature rise due to heat generation, a polyhydroxy compound is added to the polyisocyanate compound in portions as necessary.
Alternatively, the temperature may be controlled by dripping. Next, in the second step, compound [1] is reacted and bonded to the terminal and/or side chain isocyanate groups of the partially urethanized product obtained in the first step. Note that some partially urethanized products of this type are commercially available, and such commercial products can also be used in the present invention. The ratio of adding compound [1] to this partially urethanized product is generally such that the number of equivalents of residual isocyanate groups in the partially urethanized product is equal to the number of equivalents of hydroxyl groups in compound [1]. Depending on the purpose, the proportion of compound [1] can be increased to an equivalent number or more. In the urethanization reaction, in order to avoid rapid temperature rise due to heat generation, compound [1] is added to the partially urethanized product.
Proceed while controlling the temperature by adding in portions or dropwise. In general, conventional cationic polymerizable monomers undergo very large volume shrinkage during polymerization, such as 23% ethylene oxide, 17% propylene oxide, 9% styrene oxide, 12% epichlorohydrin, etc. If the actual shrinkage during polymerization is large, for example, when used as a molding material, dimensional accuracy may not be achieved, when used as a casting material, the injected material may be subject to distortion due to shrinkage, or the adhesive strength with the mold may be affected. There are problems such as deterioration and 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, warpage, and deformation. . In the compound [1] of the present invention, the polymer of compound [2] derived from compound [1], and the compound [3] produced from compound [1], the spiro-orthoester group is cationically ring-opened. It polymerizes, and its volumetric shrinkage during polymerization is extremely small. Therefore, the compound [1] of the present invention and various compounds derived from the compound [1] are extremely useful compounds that can be used in molding materials, composite materials, adhesives, casting materials, paints, etc. Next, the present invention will be specifically explained with reference to Examples and Reference Examples. Example 1 215.2 g (2.5 mol) of γ-butyrolactone and 1000 ml of methylene chloride were placed in a 4-necked 2 flask equipped with a stirrer, condenser, thermometer, and dropping funnel.
and add 74.1 g of glycidol (1 g) to the dropping funnel.
mol) and 150 ml of methylene chloride were charged. After cooling the pot solution to 10° C. with ice water, 1.5 ml of BF ₃ and OEt ₂ were added. The glycidol solution was added dropwise to the pot solution over about 1.5 hours while stirring. After the addition, the mixture was further stirred for 5 hours. During the reaction, the pot liquid was cooled with water and heated for about 10 minutes.
It was kept at ℃. Next, 3 ml of triethylamine was added to deactivate the catalyst. Next, the reaction solution was cooled with ice water, and while stirring, 1000 ml of a 10% NaOH aqueous solution was gradually added. After the addition was completed, the mixture was stirred for 30 minutes, and then the alkali aqueous solution layer and the organic layer were separated. This organic layer
Washed with 500ml of water. Next, after dehydrating with magnesium sulfate, the solvent was removed. After adding 0.2 g of tri(n-octyl)amine to the residue, it was distilled under reduced pressure, and at a boiling point of 83°C/0.7 mmHg, 2-hydroxymethyl-1,4,6-trioxaspiro[4,4]nonane 11.9 g (yield 7.4%). Its physical property values are as follows. Γ boiling point: 83℃/0.7mmHg Γ specific gravity: 1.196 (25℃) ΓIR (infrared absorption spectrum): 3450cm ^-1 (O-H),
1334cm ^-1 , 1247cm ^-1 , 1132cm ^-1 , 1042cm ^-1 ,
954cm ^-1 ΓNMR (Nuclear Magnetic Resonance Spectrum) (in CDCl ₃ ); δ (ppm); 3.4-4.6 (7H, _3CH2 -O, CH-
O), 1.8 to 2.3 (4H, C-CH ₂ -CH ₂ ) Example 2 285 g (2.5 mol) of ε-caprolactone, 1000 ml of methylene chloride, and 0.7 ml of triethylamine were charged into the same flask as in Example 1, and the mixture was poured into a dropping funnel. Glycidol 74.1g (1 mol) and methylene chloride
I prepared 150ml. After cooling the pot liquid to ice water at 10℃,
1.5 ml of BF ₃ OEt ₂ was added. The glycidol solution was added dropwise to the pot over about 2 hours while stirring the solution. The mixture was further stirred for 5 hours. During the reaction, the pot liquid was cooled with water and maintained at about 10°C. Next, 3 ml of triethylamine was added to deactivate the catalyst. Next, 1000 ml of a 10% NaOH aqueous solution was gradually added to the reaction solution while cooling it with ice water, and after stirring for 30 minutes, the alkali aqueous solution and the organic layer were separated. After washing this organic layer with 500 ml of water and separating it by centrifugation twice,
Dehydrated with magnesium sulfate. Next, 0.2 g of tri(n-octyl)amine was added, the solvent was removed, and the boiling point was 95℃/
At 0.7 mmHg, 2-hydroxymethyl-1,
4,6-trioxaspiro[4,6]undecane
13.3g (yield 7.1%) was obtained. Its physical property values are as follows. Γ Boiling point: 95℃/0.7mmHg Γ Specific gravity: 1.161/25℃ ΓIR: 3450cm ^-1 (O-H), 1240cm ^-1 , 1133cm ^-1 ,
1072 cm ^-1 _, 1037 cm ^-1 , 960 cm ^-1 Γ NMR (in CDCl ₃ ); δ (ppm); 3.4-4.5 (7H, _3CH2 -O, CH-O)
1.9~2.1 (2H,

[Formula]) 1.4-1.9 (6H, CH ₂ -CH ₂ -CH ₂ ) Γ mass spectrum (GC-MS); Parent peak; m/e = 188 Reference example 1 A cationic polymerization catalyst was added to the compound obtained in Example 1. 3 mol% of BF ₃ OEt ₂ was added thereto and heated at 80° C. for 3 hours to obtain a transparent soft polymer. IR analysis revealed that this polymer had ester absorption at 1730 cm ^-1 . The volume shrinkage rate due to polymerization was approximately 0. Reference Example 2 3 mol% of BF ₃ OEt ₂ was added as a cationic polymerization catalyst to the compound obtained in Example 2, and the mixture was heated at 80° C. for 3 hours to obtain a transparent soft polymer. An IR analysis of this polymer revealed that it had an ester absorption of 1730 cm ^-1 . Further, the volume shrinkage rate due to polymerization was approximately 0.

[Brief explanation of drawings]

Figure 1 is an IR diagram of 2-hydroxymethyl-1,4,6-trioxaspiro[4,4]nonane obtained in Example 1, Figure 2 is an NMR diagram of the same compound, and Figure 3 is an NMR diagram of the same compound. The figure shows 2-hydroxymethyl-1,4,6-trioxaspiro[4,6] obtained in Example 2.
This is an IR diagram of undecane, and Figure 4 shows the IR diagram of the same compound.
It is an NMR diagram.

Claims (1)

[Scope of Claims] 1 2-hydroxymethyl-1,4,6-trioxaspiro[4,
m] Alkane. (Here, m represents an integer from 4 to 6.)