JPH0149373B2 - - Google Patents

Description

Detailed Description of the Invention The present invention relates to bicyclo compounds having two or more 2,6,7-trioxabicyclo[2,2,2]octane groups in the molecule and two or more carboxylic acid halogen groups in the molecule. This is a method for ring-opening polymerization of a bicyclo compound, in which a bicyclo compound is reacted with an acid halide. Conventionally, several types of bicyclo compounds have been investigated for use as stabilizers for vinyl chloride resins, herbicides, and the like. Recently, ring-opening isomerization polymerization of this type of compound using a cationic polymerization catalyst has been investigated, and a unique phenomenon in which the volume change accompanying polymerization is extremely small has been reported. It is attracting attention for its use in adhesives and adhesives. (Journal of Polymer Science:
Polymer Letters Edition (J.Polym.Sci.;
(Polym.Lett.Ed.), 18 , 457-459 (1980)) It is necessary to ring-open the bicyclo compound when it is applied to polymerization-curable materials such as molding materials, casting materials, and adhesives. Gender arises. As a ring-opening method for bicyclo compounds, methods using phenol, organic polybasic acids, organic polybasic acid anhydrides, and carboxylic acid type polyesters (Japanese Unexamined Patent Publication No. 1983-1989-1) are used.
109534 and Japanese Unexamined Patent Publication No. 134113/1983) are known. However, with phenols, organic polybasic acids, organic polybasic acid anhydrides, and carboxylic acid type polyesters, the rate of ring opening of bicyclo compounds is slow, even in the presence of reaction accelerators such as boron trifluoride or tertiary amines. However, the disadvantage was that the ring-opening reaction had to be carried out at a high temperature of 150 to 180°C. Therefore, the present inventors have aimed to establish a technique for ring-opening polymerization of bicyclo compounds under milder conditions. As a result, acid halides having two or more carboxylic acid halogen groups (hereinafter also simply referred to as acid halogen groups) have 2,6,7-trioxabicyclo[2,2,2]octane groups in their molecules. The present inventors have discovered that bicyclo compounds having two or more molecules can be efficiently ring-opened and polymerized by a ring-opening polyaddition mechanism, and have completed the present invention. That is, the present invention relates to bicyclo compounds having two or more 2,6,7-trioxabicyclo[2,2,2]octane groups in the molecule and acid halides having two or more carboxylic acid halogen groups in the molecule. and,
The 2,6,7-trioxabicyclo[2,2,
2] A method for ring-opening polymerization of bicyclo compounds, characterized in that the reaction is carried out so that 0.5 to 2 equivalents of carboxylic acid halogen groups are present relative to octane groups. The most important feature of the present invention is the use of an acid halogen compound having two or more acid halogen groups in the molecule. Therefore, the bicyclo compound used in the present invention is 2,6,7-trioxabicyclo[2,2,
2] Any compound having two or more octane groups in its molecule can be used without particular limitation. Generally known bicyclo compounds having a 2,6,7-trioxabicyclo[2,2,2]octane group have the formula: It is also known that this bicyclo compound expands in volume upon polymerization. The acid halogen group used in the present invention is 2,6,7
-Trioxabicyclo[2,2,2] Since an addition reaction proceeds with the octane group, if you want to obtain a ring-opening polymer of a bicyclo compound, 2,6,7-trioxabicyclo[2,2,2] It is necessary that two or more octane groups and two or more acid halogen groups each exist in the molecule. Typical bicyclo compounds that are generally particularly preferably used include compounds represented by the following general formula. [Formula] [Formula] However, the meanings of the symbols in the above general formula are as follows. m = integer greater than or equal to 2 R ₁ = hydrogen atom; alkyl group (preferably an alkyl group having 1 to 18 carbon atoms); cyclopentyl,
Cycloalkyl groups such as cyclohexyl and cycloheptyl; benzyl, phenylethyl,
Aralkyl groups such as phenylpropyl and phenylisopropyl; phenyl, biphenyl,
Aryl groups such as xenyl and naphthyl; alkaryl groups such as tolyl, xylyl, ethyl phenyl, propiophenyl, isopropiophenyl and butylphenyl; hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxyoctadecyl (preferably 1 to 18 carbon atoms) (hydroxyalkyl group); acetyloxymethyl, propionyloxymethyl, (1-propionyloxy)ethyl,
Saturated and unsaturated group-substituted carbonyloxyalkyl groups such as acryloyloxymethyl, methacryloyloxymethyl and (1-methacryloyloxynoethyl groups; saturated and unsaturated group-substituted benzyloxyalkyl groups such as vinylbenzyloxymethyl groups; N-ethyl N-substituted carbamoyloxyalkyl groups such as carbamoyloxymethyl and N-phenylcarbamoyloxymethyl groups; alkenyl groups such as vinyl, α-methylvinyl, β-methylvinyl, α-ethylvinyl, propenyl, octadecenyl; chloromethyl, bromomethyl, Trichloromethyl, trifluoromethyl and (1
- halogenated alkyl groups such as ethyl (bromo). R ₂ = _hydrogen atom; alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups, alkaryl groups, hydroxyalkyl groups, saturated and unsaturated group-substituted carbonyloxyalkyl groups, saturated and Unsaturated group-substituted benzyloxyalkyl group, N-substituted carbamoyloxyalkyl group, halogenated alkyl group; Nitrogen-containing organic groups such as nitro group, dimethylamino group and amino group; Sulfur-containing group such as P-toluenesulfonyloxymethyl group Organic group; alkyloxycarbonyl group such as methoxycarbonyl and ethoxycarbonyl. R _3A = Aryl group such as phenylene group R _3B and R ₅ = Polyvalent isocyanate compound or a reaction product of this and a polyhydroxy compound, and a urethane compound having a plurality of isocyanate groups, excluding at least m isocyanates. group (hereinafter referred to as X); a group obtained by removing at least m epoxy groups from a polyepoxy compound (hereinafter referred to as Y); a group obtained by removing at least m acid halogen groups from a polyvalent organic acid halide; (hereinafter referred to as Z). R′=organic group represented by the following general formulas (7), (8), and (9). ―NHCOOR ₉ ― (7) ―CH(OH)CH ₂ OR ₉ ― (8) ―COOR ₉ ― (9) [Here, R ₉ represents an alkylene group or an alkylidene group, preferably a group having 1 to 18 carbon atoms. It is the basis. ] R ₄ and R ₈ = hydrogen atom; the same alkyl group, aralkyl group, cycloalkyl group, aryl group or alkaryl group as shown for R ₁ above. Incidentally, here, the m R ₄ 's are the same or different groups. R ₆ and R ₇ = hydrogen atom; alkyl group, aralkyl group or aryl group as shown for R ₁ above. Incidentally, here, the m R ₆ 's are the same or different groups. = Polymer structural unit in which the unsaturated bond of an ethylenically unsaturated compound is cleaved. = A polymer structural unit in which the unsaturated bonds of the unsaturated group-substituted carbonyloxyalkyl group and benzyloxyalkyl group are cleaved as specific examples for R ₁ above. =A polymer structural unit in which an unsaturated bond of an unsaturated group-substituted carbonyloxyalkyl group, a benzyloxyalkyl group, and an alkenyl group is cleaved, as specific examples of which are given with respect to R ₁ above. α and β = mole fraction of polymer constitutional units and/or and. Most of the bicyclo compounds exemplified above are known and can be produced by various methods. For example, in the compound represented by general formula (1), R ₁ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkaryl group, a halogenated alkyl group, or an alkenyl group, and R ₂ is hydrogen Atom, alkyl group, cycloalkyl group, aralkyl group, aryl group, alkaryl group, hydroxyalkyl group, saturated and unsaturated group-substituted carbonyloxyalkyl group, saturated and unsaturated group-substituted benzyloxyalkyl group, N-substituted carbamoyloxy Regarding compounds that are an alkyl group, a nitrogen-containing organic group, a halogenated alkyl group, a sulfur-containing organic group, or an alkyloxycarbonyl group, see Macromolecules, 15 , 11-17 (1982),
Journal of Polymer Science: Polymer Letters Edition
Science: Polymer Letters Edition), 18 , 457
~459 (1980), Journal of Organic Chemistry,
46, 886-891 (1981), Polymer Preprints, Japan, 31 , 506
(1982) Journal of Polymer Science: Polymer Letters Edition
Polymer Science: Polymer Letters Edition)
18, 771-773 (1980), Polymer Journal, 14 , 485-488 (1982), Polymer Journal, 13 , 715-
718 (1981), Macromolecules, 15 , 217-223 (1982), etc. As an example, it can be produced by a dealcoholization reaction between a trialkyl orthoester represented by the following formula (13) and a trimethylol compound represented by the following formula (14). (However, R′ ₁ and R′ ₂ represent the above-mentioned groups, and R ₁₀
represents an alkyl group. ) This reaction is shown below. Furthermore, in the compound represented by general formula (1), R ₁ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkaryl group, a hydroxyalkyl group, a saturated or unsaturated group-substituted carbonyloxyalkyl group , saturated and unsaturated group-substituted benzyloxyalkyl groups, or halogenated alkyl groups, and for bicyclo compounds in which R ₂ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or an alkaryl group, Oborganic Chemistry (Journal
of Organic Chemistry, 27 , 90-93 (1962), Journal of Medical Chemistry
of Medicinal Chemistry), 13 , 1212-1215
(1970), Dutch Patent 6412636, and Polymer Preprints, 32 , 545
(1983) and others. For example, it can be produced by a dehydration reaction between a carboxylic acid represented by the following formula (15) and a trimethylol compound represented by the following formula (14'). R″ ₁ ―COOH (15) (However, R″ ₁ and R″ ₂ represent the above-mentioned groups.) This reaction is illustrated as follows. Among the compounds represented by general formula (1), R ₁ is N
- Bicyclo compounds that are substituted carbamoyloxyalkyl groups are selected from bicyclo compounds where R ₁ is a hydroxyalkyl group and monoisocyanate compounds represented by the following formula (16), Polymer Journal, 13 , 715~ 718
(1981) by a urethanization reaction. R ₁₁ —NCO (16) (However, R ₁₁ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or an alkaryl group.) This reaction is illustrated as follows. (However, R ₉ represents an alkylene group or an alkylidene group, preferably a group having 1 to 18 carbon atoms.) Furthermore, in the bicyclo compound represented by general formula (1), R ₁ is a hydrogen atom or an alkyl group. Or, it is an aralkyl group, and R ₂ is a hydroxymethyl group or
A bicyclo compound having a saturated carbonyloxymethyl group can also be produced by a direct esterification reaction of pentaerythritol represented by the following formula (17) and a monocarboxylic acid represented by the following formula (15'). R ₁ -COOH (15') (However, R ₁ represents a hydrogen atom, an alkyl group, or an aralkyl group.) The charging composition ratio of pentaerythritol and monocarboxylic acid is such that the latter is 0.5 to 5 times the molar equivalent of the former. , preferably 0.8 to 3 times the molar equivalent. This reaction is expressed as follows. This reaction is generally carried out in the presence of an acidic catalyst such as P-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, etc. in an amount of 0.05 to 5% by weight of the starting reactants. The esterification reaction can be carried out in the presence or absence of a solvent. Any solvent can be used as long as it is inert to the reaction raw materials, reaction products, and catalyst, but it is more preferable to use a solvent that can form an azeotrope with the water produced by the reaction. For example, aromatic hydrocarbons such as benzene, toluene, and xylene are preferably used. After the esterification reaction is completed, the solvent, if used, is removed from the reaction solution, and the reactants are then slowly distilled under reduced pressure. Since a bicyclo compound is produced from the ester during distillation, adjustment of the internal temperature and degree of pressure reduction and the shape of the distillation column may be considered in order to appropriate the production rate and distillation rate of the bicyclo compound during distillation. The bicyclo compound separated in this way is often a mixture of the following two types of bicyclo compounds. [Formula] [Formula] However, by appropriately selecting the charging composition ratio of pentaerythritol and monocarboxylic acid, only one type can be selectively produced. For example, pentaerythritol: propionic acid = 1:2.5
(mol ratio), 1-ethyl-4-propionyloxymethyl-2,6,7-
Trioxabicyclo[2,2,2]octane is produced in pure form. Also, by treating the above mixed product with an alkali such as sodium methoxide,
1-R ₁ -4-hydroxymethyl-2,6,7
- Trioxabicyclo[2,2,2]octane is produced in pure form. Next, the compound represented by general formula (2) is itself a novel compound. The properties and typical manufacturing method of this new compound are as follows. The aryl group represented by R _3A in the general formula (2) is not particularly limited and may be any known aromatic nucleus, but aromatic nuclei such as benzene, naphthalene, phenanthrene, anthracene, biphenyl, etc. are usually suitable. . As shown in the general formula (2), the bicyclo compound is a compound having two or more 2,6,7-trioxabicyclo[2,2,2]octane groups in the aromatic nucleus, and among them, there are many isomers are possible. However, due to steric hindrance, it may be difficult to produce bicyclo compounds with the following bonding states. For example, 2,6,7-trioxabicyclo[2,2,2]octane groups exist in ortho positions on the aromatic nucleus, or the 9 and 10 positions of anthracene, and the 4 and 5 positions of phenanthrene. These include things that exist in each location. Further, the aryl group may contain a substituent. Generally, the substituent may be one that is inert during the production of the bicyclo compound, and typical examples thereof include an alkyl group, a nitro group, a halogen, and the like. Furthermore, the number of m in the general formula (2) varies depending on the type of aryl group, and is not particularly limited as long as it can be bonded, but generally 2 to 5 is the number that can be bonded most easily. The bicyclo compound can be confirmed to be the compound by the following measurements. (1) Measurement of infrared absorption spectrum (IR) 2,6,7-trioxabicyclo[2,2,
2] The presence of hydrogen on the octane group and the aryl group can be confirmed. The absorption band derived from the former is 1200-950 cm
Several bands appear in ^-1 , and the absorption band originating from the latter is from 900 to
Several sharp lines appear at 650cm ^-1 . (2) ¹ H—nuclear magnetic resonance absorption spectrum ( ¹ H—
NMR) measurement In deuterated dimethyl sulfoxide and deuterated chloroform solvent, 2, 6,
A singlet absorption peak derived from the six methylene hydrogens in the 7-trioxabicyclo[2,2,2]octane group appears. Further, an absorption peak derived from hydrogen on the aryl group appears at the position of δ (ppm) = 6.5 to 9. Furthermore, the difference in the type of R ₄ in the general formula (2) can be determined by observing and analyzing the position and multiplicity of absorption peaks derived from hydrogen in R ₄ and the relative ratio of absorption peak areas. Measure the areas of the three types of absorption peaks as described above,
When the ratio is calculated, the value corresponds to the ratio of the number of hydrogens bonded to each group. (3) Mass spectrometry (MS) Molecular weight can be confirmed by using the electron impact method (abbreviated as EI method) and field desorption method (abbreviated as FD method) as means of mass spectrometry. When the molecular weight of the compound is M, a molecular ion peak is observed at the M ⁺ position, or a pseudomolecular ion peak is observed at the (M±1) ⁺ position. (4) Elemental analysis This can be confirmed by comparing the analysis results of carbon and hydrogen with the theoretical values calculated from general formula (2). The bicyclo compound can be confirmed by the various measuring methods described above. The bicyclo compound is a white crystalline solid at room temperature, and has different physical properties depending on the substitution position. For example, when comparing the case where two 2,6,7-trioxabicyclo[2,2,2]octanes are in the meta position and the case where they are in the para position of the benzene nucleus, the para isomer is larger than the meta isomer. It has poor solubility and only dissolves in small amounts in solvents such as methylene chloride, chloroform, and dimethyl sulfoxide, but the meta form not only dissolves easily in these solvents, but also
It is also soluble in solvents such as benzene, toluene, xylene, acetone and tetrahydrofuran. Furthermore, while meta-isomers have a melting point, para-isomers decompose at a certain temperature when heated. Furthermore, different physical properties such as solubility are exhibited depending on the type of R ₄ in the general formula (2). Differences in these properties can be very easily confirmed by ordinary confirmation means depending on the above-mentioned types. The method for producing the bicyclo compound represented by the general formula (2) is not particularly limited, and any method may be employed. One of the industrially suitable methods
A specific example is as follows. That is, an orthoester of an aromatic polycarboxylic acid represented by the following formula (18), (However, R ₁₀ , R′ ₁₀ and R″ ₁₀ are the same or different alkyl groups.) Trimethylol compound represented by the following formula (19) By reacting with, the bicyclo compound represented by the general formula (2) is produced. The compound represented by the formula (18) is a known compound, and is described in Journal of Organic Chemisty, 27 ,
3098-3102 (1962), etc. The reaction proceeds by a dealcoholization reaction as shown in the reaction formula below, and a bicyclo compound represented by the general formula (2) is produced. Although the above dealcoholization reaction proceeds without the use of a catalyst, a catalyst is usually used to speed up the reaction rate. As the catalyst, any known catalyst used in dealcoholization reactions may be used without any restriction. For example, an organic compound having a sulfonic acid group such as p-toluenesulfonic acid, sulfobutyric acid, sulfopropionic acid, or sulfuric acid is used as the catalyst. Catalyst amount is 0.01~10wt% preferably 0.1~5wt
It is preferably used within the range of %. It is generally preferred that the reaction is carried out in an inert solvent such as an aromatic hydrocarbon, aliphatic hydrocarbon, or halogenated hydrocarbon. It is preferable that the above reaction proceeds while removing the alcohol produced by the reaction by evaporation, and therefore the above solvent preferably has a boiling point higher than that of the alcohol produced by the reaction. Further, the conditions for the reaction can be selected from reduced pressure to increased pressure, and the reaction temperature can be selected from a range of 80 to 200°C as necessary. The bicyclo compound represented by the general formula (2) produced in the above reaction is isolated as a solid by removing the solvent, and if necessary, it can be isolated from xylene, toluene, benzene, methylene chloride or a methylene chloride-benzene mixed solvent. It is best to separate and purify it by recrystallizing it. Among the compounds represented by general formula (3), R _3B is X,
Compounds in which R' is represented by general formula (7) and general formula (4)
In the compound represented by, R ₅ is X and R′ is the general formula (7)
Regarding the compound represented by, Polymer Journal, 14 , 927-930 (1982)
It is manufactured by the method described in et al. One example is a polyvalent isocyanate compound represented by the following formula (20), and a compound (21) in which R ₁ or R ₂ is a monohydroxyalkyl group among the compounds represented by the general formula (1), or (22) is produced by urethanization reaction. X'(-NCO) _n ' (20) [However, X' is a group obtained by removing (m'-m) isocyanate groups from X explained in R _3B and R ₅ , and m' is a group of m or more is an integer. ] However, R ₄ , R ₆ and R ₉ are the same groups as described above. ) This reaction will look like this: Among the compounds represented by general formula (3), R _3B is Y,
Compounds in which R' is represented by general formula (8) and general formula (4)
In the compound represented by R ₅ is Y and R′ is the general formula (8)
Regarding the compound represented by, polyepoxy compounds having two or more epoxy groups in one molecule represented by the following general formula (10) and monohydroxyalkyl groups represented by the above general formulas (21) and (22) are used. It is produced by a method of reacting a bicyclo compound having the following. [However, Y' is Y as explained in R _3B and R ₅ above.
A group obtained by removing (m'-m) epoxy groups, where m' is an integer greater than or equal to m. ] This reaction is shown below. Among the compounds represented by general formula (3), R _3B is Z,
Among the compounds in which R′ is represented by general formula (9) and the compound represented by general formula (4), the compound in which R ₅ is Z and R′ is represented by general formula (9) is itself a novel compound. It is. The properties and typical manufacturing method of this new compound are as follows. That is, the new compound has the following formulas (9') and (12')
It is expressed as (However, Z, R ₄ , R ₄ , R ₉ and m are as described above. This bicyclo compound can be confirmed to be the compound by the following measurements. 1. Infrared absorption spectrum (IR) Measurement of 2,6,7-trioxabicyclo[2,2,
2] The presence of an octane group and an ester bond [formula] can be confirmed. The absorption band derived from the former is 1100 ~
Several bands appear at 900 cm ^-1 , and the absorption band originating from the latter is
One strongly appears between 1700 and 1800 cm ^-1 . 2 ¹ H—Nuclear magnetic resonance absorption spectrum ( ¹ H—
Measurement of 2,6,7-trioxabicyclo[2,2,
2] A singlet peak derived from six methylene hydrogens in the octane group appears. 3 Mass spectrometry Molecular weight can be confirmed by using electron impact method (EI method) and field desorption method (FD method) as mass spectrometry. If the molecular weight of the compound is M, m/e
There is a molecular ion peak at the position of =M ⁺ or (M
±1) A quasi-molecular ion peak is observed at the ⁺ position. 4 Elemental Analysis This can be confirmed by comparing the analysis results of carbon and hydrogen with the theoretical values calculated from the above general formulas (9') and (12'). The bicyclo compound can be confirmed by the various measuring methods described above. The bicyclo compound includes carbon tetrachloride, acetone,
It is soluble in hexane, benzene, tetrahydrofuran, dioxane, chloroform, and methylene chloride, but in the general formulas (9') and (12'), Z, R ₄ ,
Different solubility is shown depending on the difference in R ₆ and R ₉ . Any method can be used to produce the bicyclo compounds represented by the general formulas (9') and (12'), but specific industrially advantageous methods are as follows. That is, from a bicyclo compound having a monohydroxyalkyl group represented by general formulas (21) and (22) and a polycarboxylic acid chloride represented by the following general formula (23), [However, Z' is a group obtained by removing (m'-m) acid chloride groups from Z explained in R _3B and R ₅ , and m' is an integer of m or more. ] Bicyclo compounds represented by general formulas (9') and (12') are produced by carrying out a dehydrochlorination reaction in the presence of a base such as triethylamine or pyridine. Examples of the polyhydric carboxylic acid chloride represented by the general formula (23) include sebacoyl chloride, adipoyl chloride, succinyl chloride, itaconyl chloride, glutaryl chloride, fumaryl chloride, malonyl chloride,
Oxalyl chloride, phthaloyl chloride,
Isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetricarboxylic acid chloride, trans-3,6-endomethylene-
1,2,3,6-tetrahydrophthalic acid chloride and trans-1,2-cyclobutanedicarboxylic acid chloride are preferably used. The dehydrochlorination reaction is carried out in an inert solvent in the presence of a base such as triethylamine or pyridine. The composition ratio of the raw materials is 2,
It is preferable to use the 6,7-trioxabicyclo[2,2,2]octane group and the acyl chloride group in equimolar amounts, or, if necessary, in a range of 0.8 to 1.2 times the equivalent of one of them. As the inert solvent, carbon tetrachloride, dioxane, tetrahydrofuran, methylene chloride, chloroform, benzene, etc. are used, and it is preferable to use them in an amount of 2 to 10 times the volume of the reaction substrate. Further, triethylamine and pyridine are preferably used in an equivalent amount of 1 to 5 times, preferably 1 to 3 times, relative to the acyl chloride group. Although the reaction can be carried out at any temperature from ice cooling to the boiling point of the solvent, it is generally preferable to carry out the reaction at a temperature in the range of room temperature to 100°C. The degree of progress of the reaction can be examined by various methods, but generally it can be confirmed by thin layer chromatography using an appropriate solvent. After the above reaction, the reaction solution is overconcentrated to produce bicyclo compounds represented by the general formulas (9') and (12'). Furthermore, if necessary, extraction and purification using hexane, heptane, ether, etc., and decolorization treatment using activated carbon can be carried out. The bicyclo compounds represented by the general formulas (5) and (6) are described in Polymer Journal,
14, 485-488 (1982), Journal of Polymer Science: Polymer Letters Edition.
Letters Edition), 18 , 771-773 (1983) and Japanese Patent Application Laid-open No. 58-61109. That is, among the compounds represented by the general formula (1), R ₁ or R ₂ is a bicyclo compound having a radically polymerizable unsaturated group, or a bicyclo compound produced by radical polymerization of this with another ethylenically unsaturated compound. be done. For example, in the compound represented by general formula (1), R ₁
The compound represented by the general formula (6) is produced by carrying out bulk polymerization of a bicyclo compound in which is an ethenyl group using, for example, ditertiary butyl peroxide as a radical initiator. This reaction is shown below. Furthermore, in the compound represented by general formula (1), R ₂ is
The compound represented by the general formula (5) is produced by radical copolymerization of a bicyclo compound having an unsaturated group-substituted carbonyloxyalkyl group as shown in the reaction formula below and methyl methacrylate according to a conventional method. Ru. Furthermore, as a method for producing bicyclo compounds represented by the general formulas (5) and (6), production is performed by a polymer reaction in which a polymer having a functional group is reacted with a bicyclo compound having a functional group that is reactive with the functional group. be done. For example, a homopolymer of styrene having a chloromethyl group or a copolymer of such styrene with other ethylenically unsaturated compounds can be produced using a dechlorination reaction to form a bicyclomolecule represented by the following formula (24) or (25). The above general formulas (5) and (6) can be obtained by subjecting the compound to a polymer reaction according to a conventional method for the reaction.
A bicyclo compound represented by is produced. Specific examples of ethylenically unsaturated compounds that can constitute units in the bicyclo compounds represented by general formulas (5) and (6) include vinyl acetate, acrylonitrile, methyl methacrylate, chloromethylstyrene, or styrene alone. Or you can cite a combination of these. α and β, which are the molar fractions of units and/or units, can take any value β≠0. The bicyclo compound explained above is ring-opened by the acid halide mentioned later. The acid halide used in the present invention can be used without particular limitation as long as it has two or more carboxylic acid halogen groups in the molecule. Specific examples of these acid halides are as follows. (A) Oxalyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride, azeroyl chloride, sebacoyl chloride, malonyl chloride, oxalyl bromide, trans-3,6-endomethylene-1,2,3, Polyvalent carboxylic acid halides having no double bond or aromatic nucleus at the α position, such as 6-tetrahydrophthaloyl chloride and trans-1,2-cyclobutanedicarboxylic acid chloride. (B) A double bond or aroma at the alpha position such as fumaryl chloride, isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride, itaconyl chloride, trimellitic acid chloride, 1,3,5-benzenetricarboxylic acid chloride, etc. Polyvalent carboxylic acid halide with a nucleus. Generally, the acid halides mentioned above tend to be unstable and difficult to handle if the bicyclo compound has a high ring opening rate. For example, acid bromide has a higher ring opening rate than acid chloride, but acid chloride is more stable and easier to handle. In addition, a double bond at the α position,
Acid halide without aromatic nucleus or nitrogen atom, α
Acid halides with a double bond or aromatic nucleus in the position,
The ring opening rate of bicyclo compounds decreases in the order of acid halides having a nitrogen atom at the α-position, but conversely, the stability increases. Among acid halides, bicyclo compounds which have a high ring opening rate but are unstable are preferably used by dissolving them in a solvent, as described below, in order to improve stability. When a solvent or the like is not used, an acid halide having a double bond or an aromatic nucleus at the α-position, which has a relatively high ring-opening rate and good stability, is preferably used. The method for mixing the bicyclo compound and the acid halide compound is not particularly limited, and any known method may be employed.
Examples of suitable mixing methods are as follows. When the bicyclo compound and acid halide are in liquid form, this method involves mixing them as they are. When at least one of the substances is solid and has a unique melting point, a method of mixing the two by heating above that temperature and melting the two. When one is liquid and the other is solid, a method of mixing the two by dissolving the solid substance in the liquid substance. When one is liquid or liquefies above a specific temperature and the other cannot be liquefied, a method in which the solid is dispersed in the liquid and mixed in a non-uniform system. If both are solids, a method is to mix them together in a solid state by grinding, kneading, etc. A method of mixing solids and liquids in a dissolved state using an appropriate solvent. The solvent used above is preferably a solvent inert to bicyclo compounds and acid halides. Generally, an appropriate solvent is selected depending on the use of the ring-opened product of the bicyclo compound of the present invention with an acid halide. For example, low boiling point substances such as ethyl ether, acetone, chloroform, methylene chloride, carbon tetrachloride, heptane, hexane, pentane, octane, cyclohexane, shikunpentane, benzene, toluene, xylene, ethyl benzoate, tetrahydrofuran, dioxane, ethyl acetate, etc. Inert solvent and styrene, methyl methacrylate, methyl acrylate, vinyl acetate,
Polymerizable monomers such as acrylonitrile, ethylene glycol dimethacrylate, etc. are generally used. Although the acid halides mentioned above are unstable, they can be made to exist stably by using a solvent. Therefore, a method using a solvent is a preferred method because it allows easy handling of the acid halide. In the ring-opening polymerization method of the present invention, the blending ratio of the bicyclo compound and the acid halide can be selected as appropriate depending on the ring-opening polymerization reaction conditions, the use of the ring-opening polymerization reaction product, the types of additives, etc. ,In general,
2,6,7-trioxabicyclo[2,2,2]
The acid halogen group is used in an amount of 0.5 to 2 times, preferably 0.7 to 1.3 times, relative to the octane group. The method for ring-opening polymerization of bicyclo compounds of the present invention can be carried out in any manner depending on the use of the ring-opening polymerization reaction product. For example, when used as an adhesive, it can be applied to an adherend surface and the adherends brought into contact with each other. When used as a molding material, it can be poured into a mold. The optimum conditions for conducting the ring-opening polymerization reaction vary depending on the type of bicyclo compound and acid halide used, but it is usually 0°C to 250°C, preferably 15°C.
The reaction may be carried out for several minutes to several hours at a temperature of 150°C to 150°C. The ring-opening polymerization method of the present invention can also be carried out when the following substances are simultaneously present in addition to the bicyclo compound and the acid halide. (1) Epoxy compounds, spiro-orthoester compounds, lactones,
A cyclic compound that can be copolymerized with bicyclo compounds such as acid anhydrides and cyclic ethers. (2) Fillers for composite materials such as glass fiber, carbon fiber, quartz powder, aluminum powder, spherical alumina, spherical silica, polymethyl methacrylate, polyvinyl chloride, polyethylene, and polypropylene. The mechanism of the ring-opening polymerization reaction of bicyclo compounds with acid halides is not yet clear, but for example, when using carboxylic acid chlorides, the results of infrared absorption spectra and nuclear magnetic resonance absorption spectra indicate that the ring-opening reaction occurs according to the following reaction. It is thought that it undergoes ring isomerization. When the bicyclo compound is subjected to ring-opening isomerization using an organic polybasic acid, an organic polybasic acid anhydride, phenol, etc. based on a conventional method, the reaction rate is extremely low, as shown in the comparative example described below. In this case, the addition of accelerators is essential. For example, 1,4-diethyl-
2,6,7-trioxabicyclo[2,2,2]
Octane with acetic acid, n-caprylic acid, o-ethoxybenzoic acid, ethyl salicylate, acetic anhydride, and
Using 4-methylhexahydrophthalic anhydride
When the reaction was carried out at 150℃ for 4 hours, the ring opening reaction rates in each case were 46, 22, 17, 2, 0 and 0%.
It was hot. In addition to the above compounds, alcohols such as trichloroethanol, aldehydes such as salicylaldehyde, organic esters such as triethyl phosphite, methyl benzoate, and diethyl malonate, and amines such as triethanolamine and trimethylene diamine , isocyanates such as tolylene diisocyanate, nitriles such as acetonitrile, halogen compounds such as hexachlorocyclopentadiene, organometallic compounds such as tetrabutoxytitanate, and epichlorohydrin, tetrahydrofuran, thiophene, tetrahydropyran, ε
- When a 3- to 7-membered ring organic compound such as caprolactone was used, ring opening of the bicyclo compound hardly proceeded. On the other hand, when using oxalyl chloride, which is an acid halide, at room temperature, 2
A surprisingly high reaction rate of 100% was demonstrated in an hour. The ring-opening method of the present invention is characterized in that when at least one of the bicyclo compound and the acid halide is polyfunctional, a cured product can be obtained after the ring-opening reaction, and the volume shrinkage accompanying curing is extremely small. It also has For example, a bicyclo compound produced from sebacoyl chloride and 1(-1-hydroxyethyl)-4-ethyl-2,6,7-trioxabicyclo[2,2,2]octane (bicyclo compound [26] described below)
After mixing equimolar amounts of and adipoyl chloride,
The cured product obtained by ring opening at 100°C for 2 hours had a volumetric shrinkage of 0.2%. Also, adipoyl chloride and 1-hydroxymethyl-4-ethyl-
2,6,7-trioxabicyclo[2,2,2]
A bicyclo compound produced from octane (bicyclo compound [27] described below) and 1,3,5-benzenetricarboxylic acid chloride were combined into [acid chloride group]/[2,6,7-trioxabicyclo[2,
After mixing at a ratio of 2,2 [octane group] = 0.82,
The cured product obtained by ring opening at 150℃ for 3 hours is
The volume shrinkage was 0.8%, and the surface hardness was 0.16 Kg/mm ² as measured by a micro Brinell hardness tester. Here, the volumetric shrinkage rate (%) is expressed as [1-(specific gravity of mixture before ring-opening reaction/specific gravity of product after ring-opening reaction)]×100. As mentioned above, the ring-opening method of the present invention is characterized in that the ring-opening polymerization reaction proceeds without the addition of a promoter, and is more gentle than the conventional ring-opening method for bicyclo compounds. It has the advantage that ring-opening polymerization can be carried out in a shorter time under the following conditions. Furthermore, by selecting the type of bicyclo compound and acid halide, it is possible to obtain a cured product without volumetric shrinkage. Therefore, the ring-opening polymerization method of the present invention is an extremely effective ring-opening polymerization method that can be used in various fields of casting materials, molding materials, composite materials, adhesives, and coatings. EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, Production Examples, and Comparative Examples, but the present invention is not limited to these Examples. Production example 1 2.04 g (0.007/mol) of trimethyl orthoisophthalate, 1.91 g (0.0143 mol) of trimethylolpropane, 0.03 g of P-toluenesulfonic acid, and 20 g of xylene were placed in a 50 c.c. eggplant-shaped flask. Attach a branched fractionating head, a thermometer, a cooling tube, and a receiver, and gradually raise the temperature of the reaction solution to 100-120°C while stirring.
heated to ℃. As the temperature rose, methanol began to distill out, and after about 10 minutes, about 1.7 cc of distillate containing methanol as the main component was obtained. After that, the reaction solution was air-cooled,
After cooling, 0.05 g of triethylamine was added to neutralize the acid. Next, the product was recrystallized and isolated from the reaction solution to obtain 1.84 g of white needle-like crystals. The yield was 72%. The physical properties of the white crystalline solid thus obtained were as follows. (1) Melting point 149-152℃ (2) Infrared absorption spectrum 1120, 1095, 1005 and 995cm ^-1
[Formula] 910, 805, 720 and 700 cm ^-1 (δ _CH , [Formula] Out of plane) (3) ¹ H-Nuclear magnetic resonance spectrum Measurement solvent: Deuterium chloroform Standard: Tetramethylsilane [Table] (4) Mass Analysis EI method m/e=362 (M ⁺ ) (5) Elemental analysis [Table] The following bicyclo compound [23] was produced by the above method. Production Example 2 2.0 g (0.0070 mol) of trimethyl orthoisophthalate, 1.68 g (0.00140 mol) of trimethylolethane, 0.03 g of p-toluenesulfonic acid, and 20 g of xylene were put into a 50 c.c. eggplant-shaped flask, and then added with branches. Attach a fractionator head, thermometer, cooling tube, and receiver, and gradually raise the temperature of the reaction solution to 100 to 120℃ while stirring.
heated to. As the temperature rose, the reaction solution became cloudy and methanol began to distill out. After reacting for about 10 minutes, 1.7 cc of a distillate containing methanol as a main component was obtained.
The reaction was then air cooled, and after cooling, triethylamine
0.05 g was added to neutralize the p-toluenesulfonic acid and stirring was stopped. The reaction solution was then filtered to obtain a white precipitate. This was recrystallized from methylene chloride to obtain 1.67 g of a white crystalline solid. The yield is
It was 72%. The physical properties of the white crystalline solid thus obtained were as follows. (1) Melting point 250-251℃ (2) Infrared absorption spectrum 1120, 1100, 1000 and 980cm ^-1
[Formula] 895, 885, 805, 730 and 700 mm ^-1 (δ _CH , [Formula] Out of plane) (3) ¹ H-Nuclear magnetic resonance absorption spectrum Measurement solvent: Deuterium chloroform Standard: Tetramethylsilane [Table] ( 4) Mass spectrometry EI method m/e = 334 (M ⁺ ) (5) Elemental analysis [Table] By the above method, the following bicyclo compound [24]
was manufactured. Production example 3 formula, Bicyclo compound [8] 18.8g
(0.1 mol), pyridine 8.69 g (0.11 mol), and carbon tetrachloride 50 cc. were placed in a 300 cc. two-necked flask equipped with a dropping funnel and a nitrogen introduction tube. After purging the inside of the flask with nitrogen, add 9.15 g of adipoyl chloride from the dropping funnel while stirring magnetically.
(0.05 mol) and carbon tetrachloride was added dropwise over about an hour. After the dropwise addition was completed, the mixture was stirred at 70°C all day and night. Thereafter, the solvent was removed from the solution using an evaporator. Next, the residue was extracted with hexane, and this extract was concentrated to obtain a colorless and transparent viscous liquid. The yield was 78%. Various measurements of the viscous liquid thus obtained were as follows. (1) Viscosity 1341 poise (23℃) (2) Infrared absorption spectrum 1740cm ^-1 (ν _c=0 ) 1105, 1025, 1000 and 950
cm ^-1 [Formula] (3) ¹ H-Nuclear Magnetic Resonance Absorption Spectrum Measurement solvent: Deuterium chloroform Standard: Tetramethylsilane [Table] (4) Elemental analysis [Table] The following bicyclo compound [25] was prepared by the above method. Manufactured. Production Example 4 18.8g (0.10mol) of the same bicyclo compound [8] used in Production Example 3, 8.69g of pyridine
(0.11 mol) and 50 c.c. of carbon tetrachloride were placed in a 300 c.c. two-necked flask equipped with a dropping funnel and a nitrogen introduction tube. After replacing the inside of the flask with nitrogen, add sebacoyl chloride from the dropping funnel while stirring magnetically.
11.96 g (0.05 mol) was added dropwise over about 1 hour.
After the dropwise addition was completed, the mixture was stirred at 70°C all day and night. Thereafter, the solvent was removed from the solution using an evaporator. Next, the residue was dissolved in carbon tetrachloride, and activated carbon was added to this solution and stirred for about 2 hours. Thereafter, the filtered solution was concentrated using an evaporator to obtain 19.52 g of a colorless and transparent viscous liquid. The yield was 72%.
Various measurements of the viscous liquid thus obtained were as follows. (1) Viscosity 164 poise (23℃) (2) Infrared absorption spectrum 1730cm ^-1 (ν _c=0 ) 1100, 1020, 1000 and 950
cm ^-1 [Formula] (3) ¹ H-Nuclear Magnetic Resonance Spectrum Measurement solvent: Deuterium chloroform Standard: Tetramethylsilane [Table] (4) Elemental analysis [Table] The following bicyclo compound [26] was produced by the above method. did. Production Example 5 The bicyclo compounds shown in Table 1 were produced according to the methods of Production Examples 3 and 4. [Table] [Table] Production Example 6 8.4 g (0.05 mol) of hexamethylene diisocyanate, formula Bicyclo compound [19] 17.2g
(0.1 mol), 0.7 g of dibutyltin dilaurate, and 70 ml of toluene were stirred at 70° C. for 6 hours. After the reaction, toluene was distilled off under reduced pressure, and the residue was recrystallized from an ethyl acetate-n-hexane system to obtain the following bicyclo compound [31].
The yield was 15 g, and the yield was 58%. Production Example 7 The following bicyclo compound was produced according to the method of Production Example-6. [Table] Production example 8 formula, 1.06g of bicyclo compound [15] shown by
45.2 mg of tertiary butyl peroxide was placed in an ampoule, and then nitrogen gas was bubbled through it for 5 minutes. Thereafter, the ampoule was degassed using a vacuum pump while being cooled in dry ice. After degassing, the ampoule was sealed. The sealed ampoule was heated in a 120°C oil bath for 24 hours. After the reaction, the ampoule was broken, about 2 c.c. of dichloromethane was added to dissolve the contents, and then precipitated into hexane. The precipitate was filtered and dried. The polymer thus obtained was the following bicyclo compound [35]. The yield was 0.69g, and the yield was 62.4%. Manufacturing example 9 formula 1 g of the bicyclo compound [12], 4 g of dimethylformamide, and 6.8 mg of azobisisobutyronitrile were placed in a test tube, and then nitrogen was bubbled through it for 5 minutes. Thereafter, the test tube was tightly stoppered, and the reaction was then carried out in a 70°C oil bath for 1 hour. After the reaction, the contents were precipitated into methanol, filtered,
By drying, 0.59 g of a white powder polymer was obtained. The polymer thus obtained was the following bicyclo compound [36]. Production example 10 types Bicyclo compound [22] 2.42g, methyl methacrylate 1.00g, dimethylformamide 5g
and 32.8 mg of azobisisobutyronitrile were placed in an ampoule, and then nitrogen gas was bubbled through the ampoule for 5 minutes. Thereafter, the ampoule was degassed using a vacuum pump while being cooled in dry ice. After degassing, the ampoule was sealed. The ampoule was then heated in a 70°C oil bath for 15 hours. Thereafter, the ampoule was broken and 5 c.c. of methylene chloride was added to the contents, and the contents were precipitated into a tetrahydrofuran-hexane mixed solution. After filtering and drying, about 2 g of a white polymer was obtained. The polymer thus obtained was subjected to elemental analysis and
NMR measurement confirmed that it was a bicyclo compound [37] with the structure shown below. Production Example 11 4.25 g of the same bicyclo compound [15] used in Production Example 8, 1.33 g of acrylonitrile, and di-
0.21 g of tertiary butyl peroxide was placed in an ampoule. After bubbling nitrogen gas for 5 minutes, the ampoule was degassed while being cooled in dry ice. After degassing, the ampoule was sealed. The ampoule was then heated in a 70°C oil bath for 24 hours.
After the reaction, the ampoule was broken and 5 c.c. of methylene chloride was added, mixed and dissolved with the contents, and then precipitated in hexane. The precipitate was filtered and dried to obtain 2.1 g of a white powdery polymer. The thus obtained polymer was confirmed to be a bicyclo compound [38] with the following structure by elemental analysis and NMR measurement. Comparative Examples 1 to 8 A bicyclo compound represented by the formula [Formula] was placed in an ampoule with a volume and weight of 5 c.c., and then an acid halide as shown in Table 2 was added to 2,6,7-trioxabicyclo[2,
2,2] The octane group and the acid halogen group were taken in equal equivalent weight. Next, the ampoule was sealed, and a ring-opening reaction was carried out under the conditions shown in Table 2. After the reaction, the ampoule was broken, the contents were taken into a sample tube for nuclear magnetic resonance spectroscopy measurement, and a nuclear magnetic resonance absorption spectrum was measured using deuterated chloroform as a solvent and tetramethylsilane as a standard. The ring opening rate is determined by a sharp singlet of 3.8 to 4.2 ppm based on the six methylene protons in the 2,6,7-trioxabicyclo[2,2,2]octane group on the nuclear magnetic resonance spectrum. It was determined from the rate of decrease in the integral value. The results were as shown in Table 2. [Table] [Table] Examples 1 to 9 The bicyclo compounds produced in Production Examples 1 to 5 were placed in an ampoule with a capacity of 5 c.c., and then the acid halides shown in Table 3 were mixed with 2,6 , 7-trioxabicyclo[2,2,2]octane group and acid halogen group were taken in equivalent amounts. Next, the ampoule was sealed, and a ring-opening polymerization reaction was carried out under the conditions shown in Table 3. After the reaction, the ampoule was broken, the contents were taken out, and the infrared absorption spectrum was observed. The degree of ring opening is 2, on the infrared absorption spectrum.
Evaluation was made from the degree of decrease in several absorption lines between 1200 and 900 cm ^-1 based on the 6,7-trioxabicyclo[2,2,2]octane group. For example, for the bicyclo compound produced in Production Example-1, 1120, 1095,
Evaluation was made from absorption at 1005 and 995 cm ^-1 . As a result, reaction products as listed in Table 3 were obtained, and
In all cases, it was confirmed that the absorption based on each bicyclo compound in the infrared absorption spectrum disappeared. From this, it was found that the ring opening rate of the bicyclo compound reached almost 100%. [Table] Examples 10 to 15 The bicyclo compounds produced in Production Examples 3 and 4 were placed in an ampoule with a capacity of 5 c.c., and then the acid halides shown in Table 4 were mixed with 2,6,7- The trioxabicyclo[2,2,2]octane group and the acid halogen group were taken in equivalent amounts. Next, the ampoule was sealed, and a ring-opening reaction was carried out under the conditions shown in Table 5. After the reaction, the ampoule was broken, the contents were taken out, and the infrared absorption spectrum and specific gravity were measured. The specific gravity was measured for the mixture before the reaction by the pycnometer method, and for the product after the reaction by the floatation method using an aqueous potassium carbonate solution. The volumetric shrinkage rate was determined from these two measured values of specific gravity using the following formula. [1-(specific gravity of mixture before ring-opening reaction/specific gravity of product after ring-opening reaction) × 100 As a result of observation of infrared absorption spectrum, each of 2,6,7-trioxabicyclo[2,2, 2]
Absorption based on octane group, that is, in the case of bicyclo compound [25], 1105, 1025, 1000 and 950
cm ^-1 In the case of bicyclo compound [26], 1100, 1020,
It was confirmed that the absorption at 1000 and 950 cm ^-1 had disappeared. This revealed that the ring opening rate of the bicyclo compound reached almost 100%. The properties of the product after the reaction and the results of the volume change after the reaction are also listed in Table 4. [Table] Example 16 In a test tube with a capacity of 20 c.c., 5.93 g of the bicyclo compound [27] produced in Production Example-5 and 1.88 g of 1,3,5-benzenetricarboxylic acid chloride were placed. Next, the mixture was heated to the melting point of the bicyclo compound [27], and both were uniformly mixed. Next, the test tube is tightly capped,
It was heated in a 150°C oil bath for 3 hours. After the reaction,
The test tube was broken and the polymer was taken out. The polymer is
The infrared absorption spectrum, surface hardness, and specific gravity were measured. Here, the surface hardness was measured using a micro Brinell hardness meter, and the specific gravity was measured by the method described above. As a result, in the infrared absorption spectrum, 2,
Several absorptions between 1100 and 900 cm ^-1 based on the 6,7-trioxabicyclo[2,2,2]octane group have completely disappeared, and the surface hardness is 0.16 Kg/mm ² .
The volume change accompanying polymerization was 0.8% shrinkage. Example 17 Bicyclo compound produced in Production Example 5 [29] 5.15
g and 1.5 g of 1,3,5-benzenetricarboxylic acid chloride were placed in a test tube, polymerization was carried out in the same manner as in Example 16, and the resulting polymer was further analyzed. As a result, in the infrared absorption spectrum,
2,6,7-trioxabicyclo[2,2,2]
Several absorptions between 1100 and 900 cm ^-1 based on octane groups have completely disappeared, and the surface hardness is 0.13 Kg/
mm ² , and the volume change due to polymerization was 0.2% shrinkage. Examples 18-21 The bicyclo compounds produced in Production Examples 6 and 7 were
Take an ampoule with a capacity of 5 c.c., and then add the acid halides shown in Table 5 in an amount equal to 2,6,7-trioxabicyclo[2,2,2]octane groups and acid halogen groups. I took it so that it became. Next, the ampoule was sealed, and a ring-opening reaction was carried out under the conditions shown in Table 5. After the reaction, the ampoule was broken, the contents were taken out, and its infrared absorption spectrum was measured. The results are also listed in Table-5. The produced polymer was a pale yellow transparent rubbery solid. [Table] Comparative Examples 9 to 16 The bicyclo compounds produced in Production Examples 1 to 4 were placed in an ampoule with a capacity of 5 c.c., and then the acid halides shown in Table 6 were added to 2, 6, 7 -Acid halogen groups were added in amounts shown in Table 6 relative to trioxabicyclo[2,2,2]octane groups. Next, the ampoule was sealed, and a ring-opening polymerization reaction was carried out under the conditions shown in Table 6. After the reaction, the contents were taken into a sample tube for nuclear magnetic resonance spectrum measurement, and a nuclear magnetic resonance spectrum was measured using deuterochloroform as a solvent and tetramethylsilane as a standard. The ring opening rate is determined by the nuclear magnetic resonance spectrum of 2,6,7-trioxabicyclo[2,2,
2] Calculated from the reduction rate of the integral value of a sharp singlet of 3.8 to 4.22 ppm based on 6 methylene protons in the octane group. The results are also listed in Table 6. [Table] [Table]

Claims (1)

[Claims] 1 2,6,7-trioxabicyclo [2,2,
2] A bicyclo compound having two or more octane groups in the molecule and an acid halide having two or more carboxylic acid halogen groups in the molecule are combined into the 2,6,7-
1. A method for ring-opening polymerization of bicyclo compounds, which comprises reacting so that 0.5 to 2 equivalents of carboxylic acid halogen groups are present relative to trioxabicyclo[2,2,2]octane groups. 2. The ring-opening polymerization method according to claim 1, wherein the acid halide is a carboxylic acid halide.