JPS6122086A - Spiro-orthoester compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R<1> is H, R<2> is group shown by the formula II or formula III (n is >=1); R<1> and R<2> are bonded to form group shown by the formula IV]. EXAMPLE:A compound shown by the formula V. USE:A casting and molding material, matrix for composite material, adhesive, and coating compound. Having no volume shrinkage during setting, low viscosity, improved workability, and providing a non-rigid cured material at normal temperature. PREPARATION:For example, 3-methyl-6-pentanolide is reacted with an epoxy compound such as glycidyl ether of bisphenol A, etc. by the use of a catalyst such as p-toluenesulfonic acid, etc. in a solvent such as toluene, etc. at 0-25 deg.C.

Description

[Detailed description of the invention] (a) Purpose of the invention [Field of industrial application] The present invention relates to a new polymerizable compound useful as a casting or molding material, a matrix for composite materials, an adhesive, a paint, etc. be.

[Conventional technology]

Various monomers have been synthesized as the above-mentioned polymerizable compounds and have been widely used industrially, but most of the monomers undergo volumetric contraction during the polymerization reaction.

For example, even epoxy resins with relatively low yields exhibit volume shrinkage of about 2 to 6% during polymerization. For this reason, molding, casting,
During painting, adhesion, etc., problems such as distortion, gaps, deformation, peeling, and reduction in adhesive strength occur.

On the other hand, spiroorthoester compounds synthesized so far, such as bisphenol A diglycidyl ether and ε-
Spiroorthoester synthesized from caprolactone has a fairly high viscosity and is difficult to work with during molding and casting, and when it is hardened with a hardening agent such as methylhexahydrophthalic anhydride, the resulting The cured product has a high Shore hardness and a Tg much higher than room temperature.

[Problem that the invention seeks to solve]

The present invention aims to provide a novel spiro-orthoester compound that exhibits substantially no volumetric shrinkage during curing, has low viscosity, is highly workable during use, and provides a cured product that is soft at room temperature. .

(B) Structure of the Invention [Means for Solving Problems] The compound according to the present invention is a spiro'orthoester (its structure The formula is as shown below rAJO (hereinafter referred to as compound "A"), R is a hydrogen atom, and R is a group [2]
is a spiroorthoester (its structural formula is rBJ below)
O, hereinafter referred to as compound rBJ), and spiroorthoester, which is a divalent group [3] formed by R and R together (its structural formula is as shown in "C" below, and is as follows: (referred to as compound "C").

AJ In the above formula t) ζ, 1 dollar of bamboo / 1 dollar of food / 1 man-hour (-ro).

"C" [Method for producing spiroorthoester] The above spiroorthoester can be produced by reacting 3-methyl-6-pentanolide, which is a lactone, with an epoxy compound. More specifically, an epoxy compound selected from glycidyl ether of bisphenol A or novolac phenol and 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and 3-methyl-6- An example is a method of reacting with pentanolide. For example, compound r
The reaction formula for producing AJ is as follows.

11-------+ Compound rAJ The above reaction is generally carried out using a catalyst such as a Lewis acid such as boron trifluoride/ether complex, an acid catalyst such as p-toluenesulfonic acid or sulfuric acid, and an acid catalyst such as methylene chloride or toluene. It is carried out in a solvent such as or without a solvent. The reaction temperature is generally -10 to 60°C, particularly preferably 0 to 25°C. Further, the equivalent ratio of the charged equivalents for the reaction (the number of epoxy equivalents of 3-methyl-6-pentanolide/epoxy compound) is suitably from 0.1 to 50, particularly preferably from 0.5 to 10. Next, there is no particular restriction on the amount of solvent used, but it is generally preferably 0 to 40 times the total weight of the charged 3-methyl-6-pentanolide and epoxy compound.

A desirable production method is to charge a predetermined amount of 3-methyl-6-pentanolide and a solvent 1 to 15 times its weight (weight ratio; the same applies hereinafter) into a reactor, maintain the liquid temperature at a predetermined temperature, and 0.05~ for the epoxy compound to be charged
One example is a method in which an epoxy compound solution to which 1 equivalent % of catalyst is added and diluted to about 15 times with a solvent is gradually dropped into the epoxy compound/catalyst solution. The progress of the reaction can be easily determined by analyzing the reaction solution using liquid chromatography or by measuring the epoxy groups in the reaction solution by titration.

To separate and obtain the target compound from the reaction solution, first add a basic substance such as triethylamine to the reaction solution to deactivate the catalyst, and then directly remove the solvent to form 3-methyl-6-pentanolide, or use alkali treatment. 3-methyl-6
- by removing the pentanolide followed by desolvation.

[Curing of spiro orthoester]

Compound "A", compound "B", and compound r of the present invention
CJ has a spiro-orthoester group in the molecule,
In addition to suitable curing agents such as succinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, which are commonly used as curing agents for epoxy compounds, and polybasic acids derived from these, - It can be easily cured using basic acids, oxycarboxylic acids, phenolic compounds, and Lewis acid compounds including boron trifluoride and its derivatives, generally by heating.

For example, Example 1 described below. As shown in , the volume shrinkage rate of compound "A" during curing (using boron difluoride) is 0.4%, which is extremely small compared to general epoxy resins.

[Examples and comparative examples]

Example 1 In a four-loop flask equipped with a stirrer, condenser, thermometer and dropping funnel, 50 ml of methylene chloride and 3-
Methyl-6-pentanolide 14.29g (0,125
After cooling the mixture to 10°C with ice water, 31 μj! of boron trifluoride/ether complex was added. (0,2
5 meq) was added.

To this solution, 4.32 g (0,0
A mixed solution of 250 grams per M) and 30 ml of methylene chloride was added dropwise over 1 hour, and after the dropwise addition was completed, the solution was added for another 4 hours.
The reaction was carried out at 0°C. Then add 70μ of triethylamine!
In addition, the reaction is stopped by deactivating the catalyst,
Next, in order to remove excess 3-methyl-6-pentanolide, this reaction solution was mixed with 10% aqueous sodium hydroxide solution.
5 g and stirred vigorously for one hour.

Next, after separating the organic layer by centrifugation, this
4N was washed three times with water, dehydrated with anhydrous magnesium sulfate, and then the solvent was removed to obtain compound rAJ in an amount of 5.72 g and a yield of 80%. ,.

The product is a pale yellow viscous liquid with a spiro-orthoester equivalent weight of 286 g/eq. Other physical property values are as follows.

This compound "A" (specific gravity i1.155) is easily polymerized by boron trifluoride/ether complex to give a pale yellow transparent cured product (specific gravity: 1.160), and compound rA
From the specific gravity value of J and its cured product, the volumetric shrinkage rate during curing is 0.
．． It was found to be 4%. Note that the specific gravity was measured at 20°C.

◎Infrared absorption (hereinafter abbreviated as IR) spectrum:
(See Figure 1) (NaC1) 1070 c'm
-'(C-0-C) ◎Nuclear magnetic resonance (hereinafter abbreviated as NMR) spectrum;
(See Figure 2) (CDC13) "8" δ (ppm) Proton 0.8-1. 1, d (611) 1.1
~2. ．． 4 b, c (6H) 3, 3 ~ 4
．． 8 a (14I-I) 6.5 ~ 7.2
Aromatic nucleus (8H) Example 2゜As an epoxy compound, epoxy equivalent: 190 g/eq
Using bisphenol A diglycidyl ether (trade name: Epicote 828, manufactured by Yuka Shell Epoxy Co., Ltd.), Example 1. A spiro-orthoester (hereinafter referred to as compound r'A''J) was synthesized in a yield of 91% in the same manner as above.

The product was a pale yellow viscous liquid with a spiro-orthoester equivalent weight of 305 g/eq.

Example 3 As an epoxy compound, a cresol novolak type epoxy compound (n) having about 6 cresol units (n) was used as an epoxy compound.
Manufactured by Tobu Kasei Co., Ltd. Product name: Evo 1--) YDCN
-22ON) 5.1.5g (0,0250 gram equivalent) was used, and the same operation as in Example 1 was performed except for that, to obtain compound "B". The yield of product was 6.22 g, giving a yield of 91%.

The product was a pale yellow powder with a spiro-orthoester equivalent weight of 290 g/eq. Other physical properties of this product are as follows.

◎IR spectrum; (See Figure 3) (KBr) 107
0 cm (C-0-C) ◎NMR spectrum; (See Figure 4) (CDCl
2) δ (ppm) Proton 0.8-1.1 0 1.1-2.0 b 3.2-4.8d 6.5-7.2 Aromatic nucleus Example 4゜As an epoxy compound, 3'', 4'-epoxycyclo-
・Xylmethyl-3,4-epoxycyclo-xylcarboxylate (trade name: Celoxide 2201, manufactured by Daicel Chemical Industries, Ltd.) 3.33 g (0,0250
Example 1. Compound rcJ was obtained by performing the same operation as above. Product yield is 4.5g
The yield was 73%.

The product was a pale yellow viscous liquid with a spiroorthoester equivalent weight of 247 g/eq. Other physical properties of this product are as follows.

◎IR spectrum: (See Figure 5) (NaC1)
1050 cm' (C-0--C) ◎NMR spectrum; (See Figure 6) (CDCl
2) δ (ppm) Proton 0.9-1
．． 1! (6H) 1.1 to 1.9 d, e, (24I-I) 3.1
~4.2 b, c (10I4) Comparative Example 1° Example 2. as an epoxy compound. Epicote 82 described
8. Except for using ε-caprolactone as the lactone,
Example 1. A spiro-orthoester (hereinafter referred to as compound rDJ) was synthesized in a yield of 87% using the same procedure as above. The product was a pale yellow viscous liquid with a spiro-orthoester equivalent weight of 360 g/eq.

Its structural formula is as follows.

(c) Example 2 of the effects of the invention. The compound "Ao" shown in Comparative Example 1. The compound rDJ shown in 2 differs only in the presence or absence of branching and the number of ring members involved, and its skeleton, including the number of constituent carbon atoms, is the same, but the physical properties of the recombined compound and the cured product obtained from it differ. , there are notable differences as follows.

First, the viscosities at 65°C of compound "Ao" and compound rDJ are 12,800 cp and 7,500 Qcp, respectively, and compound "Ao" has a considerably lower viscosity and better fluidity.

Next, the physical properties of the cured product cured using acid anhydride are as shown in the table below. T
It can be seen that the g and Shore hardness are low, while the elongation rate is high. A similar tendency can also be seen from a comparison with the case where the compound rDJ is cured with hexahydrophthalic anhydride, which is an acid anhydride whose structure is slightly different from that of methyl-xahydrophthalic anhydride.

Furthermore, the cured product obtained by curing the compound "Ao" with a boron trifluoride/ether complex was soft at room temperature, whereas the cured product obtained in the same manner from the compound rDJ was hard.

As described above in detail and specifically, 3-methyl-6
-A compound synthesized from pentanolide "AJ, compound r
BJ and compound rCJ have very small volumetric shrinkage during polymerization, and compared to spiro-orthoesters synthesized from ε-cabrolactoshi and the like that have been found so far,
It has the feature of low viscosity, and its use improves workability during molding, casting, painting, etc.

Furthermore, the cured product of spiro-orthoester alone or with an acid anhydride according to the present invention generally tends to give a soft cured product with a low Tg, and can be used in fields where conventional similar compounds are difficult to use. be able to.

Because of these features, the spiroorthoester according to the present invention is a useful substance as a new material.

[Brief explanation of drawings]

FIG. 1 shows Example 1. IR spectrum of compound rAJ obtained in )
FIG. 2 is an NMR spectrum diagram of the same compound. FIG. 3 shows Example 2. FIG. 4 is an IR spectrum diagram of the obtained compound rBJ, and FIG. 4 is an NMR spectrum diagram and a vector diagram of the same compound. FIG. 5 shows Example 3. FIG. 6 is an IR spectrum diagram of the compound rcJ obtained in FIG. 6, and FIG. 6 is an NMR spectrum diagram of the same compound.

Claims (1)

[Claims] 1. A spiroorthoester compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R^1 is a hydrogen atom and R^2 is the following [
1] or [2], or R^1
and R^2 are a divalent group represented by [3] below, formed by the combination of the two. ) [1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [2] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (n in formula [2] is a positive number of 1 or more.) [3] ▲ Mathematical formulas , chemical formulas, tables, etc.▼