JPS6043354B2 - 1-alkynol-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,2]octane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel compound, 1-alkyl-4-hydroxymethyl-2, which is useful as a polymerizable monomer.
6. This relates to 7-trioxabicyclo[2.2.2]octane (hereinafter referred to as compound [1]), and this compound is represented by the following formula [1].
H2−OH)3+/ ＼ ■[℃H2−℃−℃H2−碩χ−1 ＼ / In the above formula [2], R is a methyl group, an ethyl group, 1゛
1 ``Reno rl' is filled with Y, w,, O*.

／ ＼ H (Hr℃－－℃H2－碩℃－R[Month ＼／’ CH2-◇ (R represents a lower alkyl group here.

) Compound [1] is pentaerythritol and trialkyl orthoanlate represented by the following formula [2] (hereinafter compound [
2) is produced by the dealcoholization reaction.

R-C+O-R')3 [2] (R' here represents an alkyl group.

Further, R is the same lower alkyl group as in formula [1]. ) This reaction is shown below. C-(
-O-R') 3-1→ -t 3R-'----[)H Regarding the method for producing compound [2], see S.

M, McElvainandJ, walterNels
on, Journal of American Chemi
calSOciety. 64. l825-1827 (1
942) etc. Formulas [1] and [2]
R. Both sR'' are preferably lower alkyl groups having about 1 to 4 carbon atoms.

This is because the larger the alkyl group, the higher the boiling point of the compound, making isolation and purification by distillation more difficult. The novel compound [1] of the present invention can be obtained by dissolving pentaerythritol and compound [2] in a suitable solvent such as di-2-octyl phthalate or di-n-butyl phthalate. Manufactured by dealcoholization in the presence of an acid or the like. The degree of progress of the reaction can be determined not only by measuring the amount of alcohol distilled out, but also by analyzing the reaction solution using, for example, liquid chromatography. The reaction ratio of compound [2] and pentaerythritol may be equimolar or an excess of either of them, and the reaction is generally carried out under heating in an inert gas atmosphere such as nitrogen gas at a ratio of 100 molar
It is appropriate to carry out the reaction at a temperature of about 140°C.

Compound [1] can be separated from the reaction product liquid by vacuum distillation or recrystallization depending on its physical properties. Some of the bicycloorthoesters to which the compound [1] according to the present invention belongs are described by ROderick A. Barrle
s. GeraldDOyleandJOsephAOH
Offman. JOumaIOfCrgaNicChe
mistry. 27.9O-93 (1962), etc., but the presence or absence of polymerizability is unknown, and nothing is known about compound [1].

Moreover, the present invention has obtained the unexpected finding that compound [1] undergoes ring-opening step polymerization. It is believed that the polymerization of compound [1] proceeds by the following mechanism.

Cationic polymerization mechanism: In compound [1], the bicycloorthoester ring opens as shown in the above reaction formula, and an ether bond is formed to give a polymer.

As shown in Table 1 below, conventional cationic polymerizable monomers exhibit extremely large volumetric shrinkage during polymerization.

If the volumetric shrinkage during polymerization is large, for example, when used as a molding material, dimensional accuracy may be poor, when used as a casting material, the fill material may be strained due to shrinkage, or adhesion to the mold may be affected. There are problems such as the generation of force and gaps.

In addition, when used as a paint, the adhesion to the painted plate may deteriorate due to internal strain, causing warping. When used as an adhesive, internal strain may cause problems such as reduced adhesive strength, warping, and deformation. . On the other hand, when determining the volume change when compound [1] according to the present invention is cationically polymerized, for example, 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,2 ] Octane has a volumetric expansion rate of approximately 1.5%, and 1-methyl-4-hydroxymethyl-2●6●7-trioxabicyclo[2.2.2]octane has a volumetric expansion rate of 9%. Surprisingly, a volume expansion coefficient was observed. The known compound of the formula below, which is closest to compound [1], does not show any volume expansion during cationic polymerization, and in contrast, the fact that compound [1] expands in volume during polymerization as described above is truly unexpected. It is. The volumetric expansion rate (%) is [1
−(specific gravity of compound/specific gravity of polymer obtained from compound)]×
100, and the volumetric expansion rate (%) is [(specific gravity of compound/
The specific gravity of the polymer obtained from the compound is expressed as )-1]×100.

As mentioned above, the compound [1] of the present invention can be easily produced and has the advantage of expanding in volume upon polymerization.

Therefore, the compound [1] of the present invention can be used in molding materials, composite materials,
It is an extremely useful compound used in adhesives, casting materials, paints, etc. As a cationic polymerization catalyst during polymerization, for example, aromatic diazonium salts such as φ-1 = N-PF5, φ-1 = N-BF, etc.: Aromatic halonium salts such as φ-1-φ・BF'4: φ-width + (Aromatic onium salt of Group Va element of the periodic table such as H2 one person one φ. BF4-;
Examples include aromatic onium salts of elements of group Ⅰa of the periodic table.

In addition, other catalysts for cationic polymerization include, for example, BF3, FeCI3, SncI4, SbCI5, Sb
Lewis acids such as F3, TiCl4; BF3OEt2, B
Lewis acids such as F3-aniline complex and 0
．． ．． S. ．． Coordination compounds with compounds having N etc.: oxonium salts, diazonium salts, carbonium salts of Lewis acids: halogen compounds, mixed halogen compounds, perhalogen acid derivatives and the like.

The amount of the catalyst used is usually preferably in the range of 0.001 to 10 wt%.

There are no particular restrictions regarding the polymerization temperature, but it is usually 30 to 200
It is carried out at ℃. Example 1 Pentaerythritol 272y (2 mol), triethyl orthopropionate 352y (2 mol), di-n-octyl phthalate 345y and P-
Toluenesulfonic acid 2y was charged, and the temperature was gradually raised from 110°C to 140°C while stirring while passing nitrogen gas.

As the temperature rises, distillation of ethanol begins; 3. The reaction was carried out for a period of time to obtain a distillate 261y containing ethanol as a main component. After neutralizing the catalyst by adding 10 Da of anhydrous potassium carbonate to the reaction solution, centrifugation was performed to remove precipitates consisting of unreacted raw material (pentaerythritol) and catalyst neutralized product.

By distilling the supernatant liquid under reduced pressure, 1-ethyl-4-hydroxymethyl-2,6,7-
trioxabicyclo(2.2.2) octane 233 da(
A yield of 67% was obtained. The physical properties of this compound are as follows.

Example 2 Triethyl orthoacetate 162 was added to the 2e flask.
y (1 mol), 136 y (1 mol) of pentaerythritol, 250 y of di-n-octyl phthalate, and 0.5 y of P-toluenesulfonic acid, and the temperature was raised to 135° C. while stirring while passing nitrogen gas.

The reaction was carried out at this temperature for 4 hours to obtain distillate 12611 whose main component was ethanol. Triethylamine 1 in the reaction solution
After neutralizing the catalyst by adding y, the mixture was allowed to stand overnight at room temperature to precipitate crystals consisting of the target product and unreacted raw material (pentaerythritol).

The precipitated crystals were separated, and the separated crystals were washed three times with cyclohexane, which is a non-solvent of the target product, to remove the reaction solvent (d-n-octyl phthalate). The washed crystals were dissolved in acetone, and acetone-insoluble matter was separated and removed. After evaporating acetone from the filtrate, it was purified three times by recrystallization using chloroform to obtain compound [1] as a white powder of 1-methyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2].・2.2] Octane 25y (yield 1
6%). The physical properties of this compound are as follows. O nuclear magnetic resonance spectrum (in deuterated acetone) O elemental analysis (%) c; Calculated value as stone J2O4 (theoretical value)
-C; 52.5sH7.6○ infrared absorption spectrum; Reference Example 1 BF3OE was added to the compound [1] of Example 1 as a polymerization catalyst.
t23 mol% was added and polymerized for 1 m at 70°C in a sealed tube.

As a result, a viscous polymer was obtained. The molecular weight of this polymer was approximately 4,000.

Further, the specific gravity was 1.186 (25°C), and the volumetric expansion rate due to polymerization calculated from this value was about 1.5%. The infrared absorption spectrum of the obtained polymer is as shown in FIG.
peaks were generated. Reference Example 2 BF3OE was added to the compound [1] of Example 2 as a polymerization catalyst.
Add 3 mol% of t2 and heat in a sealed tube at 110'C.
Polymerized for hours.

As a result, a solid polymer was obtained. Its specific gravity is 1.2
5 (25℃), and the volumetric expansion rate due to polymerization is approximately 9%.
It was hot.

[Brief explanation of the drawing]

FIG. 1 is a nuclear magnetic resonance spectrum diagram of compound [1] of Example 1, FIG. 2 is an infrared absorption spectrum diagram of compound [1] of Example 1, and FIG. 3 is a nuclear magnetic resonance spectrum diagram of compound [1] of Example 1. FIG. 4 is an infrared absorption spectrum diagram of a polymer obtained by cationically polymerizing compound [1] in Reference Example 1, and FIG. 4 is a nuclear magnetic resonance spectrum diagram of compound [1] of Example 2.

Claims (1)

[Scope of Claims] 1 1-Alkyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,
2] Octane ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [1]
(In the above formula, R represents a lower alkyl group.)