Norbornenyl group-containing compound and method for producing the same

Abstract

To provide a compound that is obtained by an inexpensive and simple method and has a polycyclic hydrocarbon skeleton and a norbornenyl group, which is a group having an aliphatic unsaturated bond capable of undergoing a hydrosilylation addition reaction.SOLUTION: The present invention provides a norbornenyl group-containing compound represented by general formula (1): X(-Z-R1)n (1) (where, X represents an n-valent organic group that includes a cyclic structure and does not contain a silicon atom, each R1 independently represents an allyl group or a norbornenyl methyl group, provided that at least one R1 represents a norbornenyl methyl group, Z represents a single bond, -O-, or -C(=O)O-, and n represents a number of 2 to 4).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a compound having a norbornenyl group and a method for producing the same.

Background Art

[0002] An organically modified silicone resin composition having a polycyclic hydrocarbon skeleton such as a norbornane skeleton in the main chain has high heat resistance and high transparency of a silicone resin (dimethyl silicone resin), and high hardness, high toughness, and high gas barrier properties of an organic resin such as a polyolefin resin or a polyethylene terephthalate resin. It is a hybrid resin having both properties (Patent Document 1).

[0003] As a method for introducing such a norbornane skeleton into the main chain skeleton, a norbornene derivative substituted with a vinyl group such as vinyl norbornene and a compound having a plurality of hydrosilyl groups such as bis(dimethylsilyl)benzene are hydrosilylated in the presence of a platinum group metal catalyst. A method of reacting with a polysiloxane component using a prepolymer obtained by the reaction is generally used. However, in such a method, when producing the prepolymer, it is necessary to use a norbornene monomer having a vinyl group introduced therein and an expensive platinum group metal catalyst, which causes a problem of high production cost.

[0004] On the other hand, as a method for introducing a polycyclic hydrocarbon group as a substituent of a silane compound or a polysiloxane compound, a method of converting a vinyl group to a norbornenyl group by subjecting a silane compound or a polysiloxane compound having a vinyl group to a Diels-Alder addition reaction with cyclopentadiene has been proposed (Patent Document 2).

[0005] In any of the above methods, the obtained structure is limited to a unit in which a norbornane skeleton (or a norbornenyl group) is bonded to a silicon atom, and there is room for improvement in terms of the degree of freedom of molecular design.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention has been made in view of the above circumstances, and an object thereof is to provide a compound having a norbornenyl group which is a polycyclic hydrocarbon skeleton and a group having an aliphatic unsaturated bond capable of hydrosilylation reaction, and which can be obtained by an inexpensive and simple method.

Means for Solving the Problems

[0008] In order to solve the above problems, the present invention provides a norbornenyl group-containing compound represented by the following general formula (1). X(-Z-R 1 ) n (1) (In the formula, X is an n-valent organic group containing a cyclic structure and not containing a silicon atom, R 1 are each independently an allyl group or a norbornenylmethyl group, provided that at least one of R 1 is a norbornenylmethyl group, Z is a single bond, -O- or -C(=O)O-, and n is a number from 2 to 4.)

[0009] Since the norbornenyl group-containing compound of the present invention has a polycyclic hydrocarbon skeleton and an aliphatic unsaturated bond, it is capable of a hydrosilylation reaction with an organohydrogenpolysiloxane, and by introducing it into a silicone resin skeleton, properties such as high hardness, high toughness, and high gas barrier properties can be imparted.

[0010] The norbornenyl group-containing compound of the present invention is preferably, for example, one represented by the following formula (2).

Chemical Formula

[0011] Moreover, the norbornenyl group-containing compound of the present invention is preferably represented by the following formula (3). [Chemical formula] (In the formula, R 1 is an allyl group or a norbornenylmethyl group, and R 3 is a hydrogen atom, an allyl group or a norbornenylmethyl group.)

[0012] Furthermore, the norbornenyl group-containing compound of the present invention is preferably represented by the following formula (4). [Chemical formula] (In the formula, R 1 is an allyl group or a norbornenylmethyl group.)

[0013] Such a norbornenyl group-containing compound can be produced by an inexpensive and simple method.

[0014] Moreover, the present invention provides a method for producing a norbornenyl group-containing compound represented by the above formula (1), which comprises mixing a compound represented by the following general formula (5) and dicyclopentadiene, heating the mixture, and reacting cyclopentadiene generated by thermal decomposition of dicyclopentadiene with the compound represented by the following general formula (5). X(-Z-R 4 ) n (5) (In the formula, X is an n-valent organic group containing a cyclic structure and not containing a silicon atom, R 4 is an allyl group, Z is a single bond, -O- or -C(=O)O-, and n is a number from 2 to 4.)

[0015] According to the manufacturing method of the present invention, a norbornenyl group-containing compound can be manufactured by an inexpensive and simple method.

Advantages of the Invention

[0016] As described above, for the norbornenyl group-containing compound of the present invention, it can be manufactured by an inexpensive and simple method, and by a hydrosilylation reaction with an organohydropolysiloxane, properties such as high hardness, high toughness, and high gas barrier properties can be imparted to a silicone resin.

Brief Description of the Drawings

[0017]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Modes for Carrying Out the Invention

[0018] As described above, there has been a demand for the development of a norbornenyl group-containing compound obtained by an inexpensive and simple method.

[0019] As a result of intensive studies on the above problems, the present inventors have found that a norbornenyl group-containing compound can be synthesized in one step by reacting a compound having an organic group containing a cyclic structure and not containing a silicon atom and an allyl group with cyclopentadiene generated by thermal decomposition of dicyclopentadiene, and have completed the present invention.

[0020] That is, the present invention is a norbornenyl group-containing compound represented by the following general formula (1). X(-Z-R 1 ) n (1) (In the formula, X is an n-valent organic group containing a cyclic structure and not containing a silicon atom, R 1 is, independently of each other, an allyl group or a norbornenylmethyl group, provided that one or more of R 1 are norbornenylmethyl groups, Z is a single bond, -O- or -C(=O)O-, and n is a number from 2 to 4.)

[0021] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0022] [Norbornenyl group-containing compound] The norbornenyl group-containing compound of the present invention is a compound represented by the following general formula (1). X(-Z-R 1 ) n (1) (In the formula, X is an n-valent organic group containing a cyclic structure and not containing a silicon atom, R 1 is, independently of each other, an allyl group or a norbornenylmethyl group, provided that one or more of R 1 are norbornenylmethyl groups, Z is a single bond, -O- or -C(=O)O-, and n is a number from 2 to 4.)

[0023] The organic group containing a cyclic structure and not containing a silicon atom of X may have a heterocyclic structure containing a nitrogen atom, a sulfur atom, an oxygen atom, etc., and may contain a carbonyl bond, an amide bond, a urethane bond, a urea bond, etc. Specific examples of such structures include a benzene ring, an isocyanuric ring, an isopropylidene diphenol structure, etc.

[0024] It is known that norbornenyl group-containing compounds generally have structural isomers as shown below, and the present invention may be in either the cis configuration (exo form) or the trans configuration (endo form). [Chemical formula]

[0025] The norbornenyl group-containing compound of the present invention is preferably represented by any one of the following formula (2), formula (3), or formula (4). [Chemical formula] (In the formula, R 1 is an allyl group or a norbornenylmethyl group, and R 2 are each independently a hydrogen atom, an allyloxycarbonyl group, or a norbornenylmethyloxycarbonyl group.)

[0026] [Chemical formula] (In the formula, R 1 is an allyl group or a norbornenylmethyl group, and R 3 is a hydrogen atom, an allyl group, or a norbornenylmethyl group.)

[0027] [Chemical formula] (In the formula, R 1 is an allyl group or a norbornenylmethyl group.)

[0028] [Method for producing norbornenyl group-containing compound] The norbornenyl group-containing compound of the present invention can be produced, for example, by subjecting an organic compound having two or more allyl groups in one molecule, represented by the following general formula (5), and cyclopentadiene to a Diels-Alder addition reaction. X(-Z-R 4 ) n (5) (In the formula, X is an n-valent organic group containing a cyclic structure and not containing a silicon atom, R 4 is an allyl group, Z is a single bond, -O-, or -C(=O)O-, and n is a number from 2 to 4.)

[0029] Specific examples of the compound represented by the general formula (5) include diallyl phthalate, triallyl trimellitate, tetraallyl pyromellitate, diallyl isocyanurate, triallyl isocyanurate, 2,2-bis[4-(2-propenyloxy)phenyl]propane (bisphenol A diallyl ether), and the like.

[0030] Cyclopentadiene can be easily obtained by thermally decomposing dicyclopentadiene, which is generally a dimer stable at room temperature, generally at around 160°C.

[0031] Note that cyclopentadiene obtained by thermal decomposition undergoes a relatively rapid Diels - Alder addition reaction at room temperature to return to the dimer dicyclopentadiene. Therefore, until it is mixed with a vinyl group - containing siloxane compound and reacted, it needs to be stored at a low temperature to suppress the Diels - Alder addition reaction. Therefore, when supplying cyclopentadiene, it is preferable to mix the compound represented by the general formula (5) with dicyclopentadiene, heat it, and react the cyclopentadiene generated in the reaction vessel by thermal decomposition of dicyclopentadiene with the compound represented by the general formula (5).

[0032] From the viewpoint of suppressing the reverse reaction of the Diels - Alder addition reaction (the reaction in which cyclopentadiene desorbs from the norbornyl group) and promoting the thermal decomposition of dicyclopentadiene (the supply of cyclopentadiene), the reaction temperature is preferably 100 - 250°C, more preferably in the range of 120 - 200°C.

[0033] The reaction time is not particularly limited, but in any case of reacting the compound represented by the general formula (5) with cyclopentadiene or dicyclopentadiene, it is preferably 0.5 - 50 hours, more preferably 1 - 24 hours.

[0034] In the production method of the present invention, a reaction solvent may be used. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, mesitylene, and decalin, aliphatic hydrocarbons such as decane, undecane, dodecane, and liquid paraffin, and various solvents such as ethers and alcohols.

[0035] The reaction solvent may be used alone or in combination of two or more. From the viewpoint of easy separation during purification, the boiling point of the solvent is preferably 20 °C or more different from the boiling point of the target product.

[0036] In the production method of the present invention, after completion of the reaction, preferably under reduced pressure conditions of about 10 5 ~1 Pa, by a general distillation operation, unreacted raw materials (and optionally the reaction solvent) are distilled off from the reaction mixture, and then the target norbornenyl group-containing compound is distilled off to obtain a purified high-purity (however, it becomes a mixture of isomers as described above) norbornenyl group-containing compound. Note that when the norbornenyl group-containing compound is exposed to a temperature higher than necessary, a part of it causes a reverse reaction of the Diels-Alder addition reaction and decomposes into the reaction raw materials (cyclopentadiene and allyl group-containing compound), and these may be mixed into the fraction of the target product and the purity may decrease. Therefore, it is desirable to increase the degree of vacuum as much as possible during distillation and keep the temperature in the system during distillation as low as about 250 to 0 °C. In addition, measures such as reducing the heat history applied to the target product and reducing the influence of heat during distillation can also be taken by using a special device such as a thin-film distillation device.

Examples

[0037] Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited thereto.

[0038] Note that 1 1H-NMR analysis was performed using AVANCE III (manufactured by Bruker BioSpin) with deuterated chloroform as the measurement solvent.

[0039] [Example 1] Into a 500 mL four-necked flask equipped with a coil cooler and a thermometer, 123 g (1.0 mol) of diallyl phthalate and 117.2 g (1.8 mol) of dicyclopentadiene were added, and the mixture was reacted at 160 °C for 24 hours. After the reaction, the mixture was concentrated at 130 °C and 1 kPa to obtain 194 g of a mixture (2A). Of the obtained mixture (2A) 1 From the integration ratios of peaks a and a' derived from the unsaturated bond of the norbornenyl group and peak b derived from the allyl group of diallyl phthalate in the 1H-NMR spectrum (Figure 1), R represented by the following formula (2A) 1 had a molar ratio of allyl group:norbornenylmethyl group = 8:92. [Chemical formula]

[0040] [Example 2] Into a 500 mL four-necked flask equipped with a coil cooler and a thermometer, 82.9 g (0.25 mol) of triallyl trimellitate (manufactured by Fujifilm Wako Pure Chemical Corporation, TRIAM-705) and 89.2 g (0.68 mol) of dicyclopentadiene were added, and the mixture was reacted at 160 °C for 24 hours. After the reaction, the mixture was concentrated at 130 °C and 1 kPa to obtain 112 g of a mixture (2B). Of the obtained mixture (2B) 1 From the integration ratios of peaks c and c' derived from the unsaturated bond of the norbornenyl group and peak d derived from the allyl group of triallyl trimellitate in the 1H-NMR spectrum (Figure 2), R represented by the following formula (2B) 1 had a molar ratio of allyl group:norbornenylmethyl group = 26:74. [Chemical formula]

[0041] [Example 3] Into a 500 mL four-necked flask equipped with a coil cooler and a thermometer, 103.6 g (0.25 mol) of tetraallyl pyromellitate (manufactured by Fujifilm Wako Pure Chemical Corporation, TRIAM-805) and 119.0 g (0.90 mol) of dicyclopentadiene were added, and the mixture was reacted at 160 °C for 24 hours. After the reaction, the mixture was concentrated at 130 °C and 1 kPa to obtain 142 g of a mixture (2C). Of the obtained mixture (2C) 1 From the integration ratios of peaks e and e' derived from the unsaturated bond of the norbornenyl group and peak f derived from the allyl group of tetraallyl pyromellitate in the 1H-NMR spectrum (Figure 3), R represented by the following formula (2C) 1 The molar ratio of was allyl group:norbornenylmethyl group = 23:77. [Chemical formula]

[0042] [Example 4] Into a 500 mL four-necked flask equipped with a coil cooler and a thermometer, 62.4 g (0.25 mol) of triallyl isocyanurate (manufactured by Shinryo Corporation, TAIC) and 87.9 g (0.68 mol) of dicyclopentadiene were added, and the mixture was reacted at 160 °C for 24 hours. After the reaction, the mixture was concentrated at 130 °C and 1 kPa to obtain 81 g of a mixture (3A). Of the obtained mixture (3A) 1 From the integration ratios of peaks g and g' derived from the unsaturated bond of the norbornenyl group and peak h derived from the allyl group of triallyl isocyanurate in the 1H-NMR spectrum (Figure 4), R represented by the following formula (3A) 1 The molar ratio of was allyl group:norbornenylmethyl group = 50:50. [Chemical formula]

[0043] [Example 5] 77.1 g (0.25 mol) of bisphenol A diallyl ether (manufactured by Kitakyo Chemical Co., Ltd., BPA-DAE) and 58.6 g (0.45 mol) of dicyclopentadiene were placed in a 500 mL four-necked flask equipped with a coiled tube cooler and a thermometer, and reacted at 160 °C for 24 hours. After the reaction, the mixture was concentrated at 130 °C and 1 kPa to obtain 90 g of a mixture (4A). Of the obtained mixture (4A) 1 From the integration ratios of peaks i and i' derived from the unsaturated bond of the norbornenyl group and peak j derived from the allyl group in the 1H-NMR spectrum (Figure 5), R represented by the following formula (4A) 1 had a molar ratio of allyl group:norbornenylmethyl group = 45:55. [Chemical formula]

[0044] From the above, it was found that the norbornenyl group-containing compound of the present invention can be produced by an inexpensive and simple method, and has a polycyclic hydrocarbon skeleton and an aliphatic unsaturated bond capable of hydrosilylation reaction, so that it can impart properties such as high hardness, high toughness, and high gas barrier properties to silicone resins.

[0045] Note that the present invention is not limited to the above embodiments. The above embodiments are examples, and any configuration that has a configuration substantially the same as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Claims

1. A norbornenyl group-containing compound, characterized in that it is represented by the following general formula (1). X(−Z−R １ ) ｎ (1) (In the formula, X is an n-valent organic group containing a cyclic structure and not containing a silicon atom, R １ are, independently of each other, an allyl group or a norbornenylmethyl group, provided that one or more of R １ are norbornenylmethyl groups, Z is a single bond, -O- or -C(=O)O-, and n is a number from 2 to 4.)

2. The norbornenyl group-containing compound according to Claim 1, characterized in that it is represented by the following formula (2). 【Chemical Formula 1】 (In the formula, R １ is an allyl group or a norbornenylmethyl group, and R ２ are, independently of each other, a hydrogen atom, an allyloxycarbonyl group or a norbornenylmethyloxycarbonyl group.)

3. The norbornenyl group-containing compound according to Claim 1, characterized in that it is represented by the following formula (3). 【Chemical Formula 2】 (In the formula, R １ is an allyl group or a norbornenylmethyl group, and R ３ is a hydrogen atom, an allyl group or a norbornenylmethyl group.)

4. The norbornenyl group-containing compound according to Claim 1, characterized in that it is represented by the following formula (4). 【Chemical Formula 3】 (In the formula, R １ is an allyl group or a norbornenylmethyl group.)

5. A method for producing a norbornenyl group-containing compound according to claim 1, characterized by mixing a compound represented by the following general formula (5) and dicyclopentadiene, heating, and reacting cyclopentadiene generated by thermal decomposition of dicyclopentadiene with the compound represented by the following general formula (5). X(−Z−R ４ ｎ (5) (In the formula, X is an n-valent organic group containing a cyclic structure and not containing a silicon atom, R ４ is an allyl group, Z is a single bond, —O— or —C(═O)O—, and n is a number from 2 to 4.)​

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