JPH10273527A - Cyclic carbonate and polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a news oligonorbornene having a cyclic carbonate structures as the side chains and excellent in heat resistance and to provide a polymer obtd. from the same. SOLUTION: An oligonorbornene represented by formula I (wherein n is 1-10; and x and y are each 0-3), comprising n repeating units, and having cyclic carbonate structures as the side chains is provided, and a polymer represented by formula II (wherein n is 1-10; m is 1-100; and x and y are each 0-3), comprising n repeating units, and having m repeating units of another type is also provided. The compd. represented by formula I is produced by mixing and thermally reacting a norbornene cyclic carbonate with an initiator (e.g. di-t-butyl peroxide) in an org. solvent (e.g. domethylformamide). The polymer represented by formula II is produced by mixing and thermally reacting the compd. represented by formula I with a polymn. initiator (e.g. sodium methoxide) in an amt. of 0.01-15 wt.% thereof in an org. solvent (e.g. toluene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oligonorbornene having a cyclic carbonate structure in a side chain and a polymer. The oligonorbornene and polymer having a cyclic carbonate structure in the side chain according to the present invention show volume expansion during polymerization, and are required to have dimensional accuracy, adhesion, heat resistance, etc., molding materials, composite materials, casting materials, sealing. It is useful as a raw material for materials, paints and adhesives.

[0002]

2. Description of the Related Art It is well known that vinyl monomers such as styrene and methyl methacrylate generally undergo large shrinkage during polymerization. Further, when a thermosetting resin such as an epoxy resin, a phenol resin, or an unsaturated polyester resin is cured, volume contraction occurs. These shrinkages have a large effect on the physical properties of the cured product, and cause various problems such as the occurrence of voids, cracks, poor appearance, etc., or a decrease in adhesive strength.Therefore, in the fields of casting materials, sealing materials, adhesive materials, etc. It is a big problem. If a material that does not exhibit shrinkage during polymerization can be obtained, improvement in dimensional accuracy, precise molding by reducing warpage, distortion, and peeling, and improvement in material strength and adhesive strength by reducing internal stress can be expected.

[0003] In order to solve the above problems, for example, inorganic fillers such as silica, calcium carbonate, and alumina are added to reduce curing shrinkage. However, the addition of such an inorganic filler is effective in improving the strength, but increases the viscosity of the resin composition, thereby deteriorating workability. Further, there is a problem that the adhesive property of the resin composition is lowered, causing peeling, cracking, and the like at the adhesive interface. Attempts have also been made to add a resin compatible with the epoxy resin to the epoxy resin, thereby preventing volume shrinkage (Japanese Patent Publication No. 58-57423). Is often not preferred.

On the other hand, it has been reported that a cyclic carbonate compound increases its volume during ring-opening polymerization, and its application to the above-mentioned various applications has attracted attention. For example, Lewis acid cationic polymerization initiators such as methyl trifluoromethanesulfonate and boron trifluoride ether complex, and alkoxides such as sodium methoxide, n-butyllithium, sec.
It is known that ring-opening polymerization of an alkyllithium such as -butyllithium as an anionic polymerization initiator causes volume expansion (Macromolecules, Vo)
l.24, No.15, 4229-4235 (1991), Proceedings of the 65th Annual Meeting of the Chemical Society of Japan, 271 (1993), Proceedings of the 43rd Annual Meeting of the Society of Polymer Science, 294 (1994) ).

[0005] Norbornene cyclic carbonate represented by the chemical formula (3), which is one of cyclic carbonates, has a larger volume expansion during polymerization than other cyclic carbonates. Norbornene cyclic carbonate hardly causes a side reaction such as an attack reaction of the terminal growing species on the polymer chain, so that a high molecular weight polymer can be easily obtained. Furthermore, it shows relatively high heat resistance to other cyclic carbonates than the skeleton of norbornene, and is attracting attention as an interesting compound.

[0006]

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[0007]

However, as shown in chemical formula (4), norbornene cyclic carbonate can be heated to 150 to 300 ° C. by retro Diels-Alder.
It reacts and decomposes into cyclic carbonate having cyclopentadiene and exomethylene. This decomposition also occurs in the polymer as shown in the chemical formula (5), and there is a problem with the material used at a high temperature of 150 ° C. or higher, and it has not been applied to a material requiring heat resistance. .

[0008]

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[0009]

Embedded image (The repeating unit 1 is an integer from 1 to 100)

[0010]

Accordingly, the present inventors have developed compounds and polymers which have improved heat resistance and expand in volume upon curing, and as a result, newly synthesized cyclic carbonates shown below, The inventors have found that ring-opening polymerization is carried out by an anionic polymerization initiator and, after curing, the heat resistance is improved as compared with the norbornene cyclic carbonate polymer, thereby completing the present invention. That is, the present invention is an oligonorbornene having a cyclic carbonate structure in a side chain having a repeating unit of n represented by the chemical formula (1) and a polymer having a repeating unit of n and m represented by the formula (2).

[0011]

Embedded image (Repeating unit n is an integer from 1 to 10) (where x and y are integers from 0 to 3)

[0012]

Embedded image (Repeating unit n is an integer from 1 to 10) (Repeating unit m is an integer from 1 to 100) (where x and y are integers from 0 to 3)

As the method for producing the cyclic carbonate compound used in the present invention, those obtained by a known method (Proceedings of the 39th Annual Meeting of the Society of Polymer Science, p. 284 (1990)) can be used. Examples of the initiator used in the present invention include Lewis acid cationic polymerization initiators such as methyl trifluoromethanesulfonate and boron trifluoride ether complex, and alkoxides such as sodium methoxide, n-butyllithium, and sec-butyl. An alkyl initiator such as lithium or an amine initiator such as 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) is used as an anionic polymerization initiator. The anionic initiator is used in an amount of 0.01 to 15% by weight, preferably 0.1 to 5% by weight, based on the cyclic carbonate compound represented by the chemical formula (1). 0.01
When the amount is less than% by weight, polymerization proceeds, but a long time is required, which is not preferable. On the other hand, if the concentration exceeds 10% by weight, a low molecular weight compound is easily generated, which is not preferable.
The conditions for the polymerization reaction vary depending on the type and amount of the curing accelerator, but are in the range of 10 to 180 ° C, preferably 30 to 160 ° C.

The reaction solvent used includes, for example, ethers such as dioxane and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloroethylene and methylene chloride, acetone and methyl ethyl ketone. Ketones, cellosolves such as methyl cellosolve, ethyl cellosolve,
Examples include dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and the like. After reaching the desired degree of polymerization, the polymer obtained is isolated and purified by known methods. Further, the polymerization may be carried out under a bulk condition at a temperature higher than the melting temperature of the oligonorbornene having a cyclic carbonate structure in the side chain.

[0015]

The present invention will be specifically described below based on examples and comparative examples. In addition, the physical property value was measured by the following method. ^{The 1} H-NMR spectrum was measured using a model JSX-400 manufactured by JEOL Ltd., and the infrared absorption spectrum was measured using a model FT / IR-3 manufactured by JASCO Corporation. The number average molecular weight was measured using a GPC-8000 system measuring device manufactured by Tosoh Corporation, and calculated in terms of polystyrene. The density was measured in an aqueous solution of potassium bromide or calcium bromide at 25 ° C. using a density gradient tube method specific gravity measurement device A manufactured by Shibayama Scientific Instruments Co., Ltd. While measuring the specific gravity of the obtained resin composition at 25 ° C., the resin composition was polymerized, and the volume expansion coefficient was determined from the difference in specific gravity before and after the polymerization. The 10% weight loss temperature is determined by the thermogravimetric method (T
In G), the weight loss was measured when heating from room temperature to 800 ° C. at a rate of 10 ° C./min.

The method for producing oligonorbornene having a cyclic carbonate structure in the side chain is as follows: using norbornene cyclic carbonate (153.0 g, 1.252 mol) and di-t-butyl peroxide (DTBP, 3,8 g) as an initiator, Stirring was carried out in DMF (2.0 M) at 120 ° C. for 20 hours. The polymerization mixture is reprecipitated in n-hexane / ethanol (volume ratio: 1.5: 1.0) to have a cyclic carbonate structure in a side chain having a number average molecular weight of 620 and a molecular weight distribution of 1.2 in a yield of 60%. Oligonorbornene (50
g) was obtained. When the ¹ H-NMR spectrum of the product was observed, 4H, δ was found at δ = 4.06 to 4.24 ppm.
A peak of 11H was observed at 0.88 to 2.35 ppm. Observation of the IR spectrum of the product showed that
957, 1750, 1182, 1125, 1107 cm
^A peak was observed at ^-1 . From this result, it was identified that the product was oligonorbornene having a cyclic carbonate structure in the side chain.

Example 1 1.8 g of oligonorbornene having a cyclic carbonate structure in the side chain represented by the chemical formula (6) and 0.016 g (3 mol%) of sodium methoxide used in the present invention were previously charged with a stirrer. The polymer was separated, purified, filtered, filtered and charged in a toluene solvent at a concentration of 3.3 ml, stirred at 100 ° C. for 1 hour, and precipitated in 500 ml of an acetic acid / methylene chloride mixed solvent. The solid was recovered to obtain 1.6 g. From the IR measurement, the peak of methylene in the cyclic carbonate was shifted from 1182 to 1258 cm ⁻¹ , confirming that the polymer had a ring-opening polymerized structure. Further, the ring opening ratio of the product was 70%. The measured density of the polymer was 1.242, and the volume calculated from the monomer density of 1.301 expanded 4.7%. The 10% weight loss temperature of the polymer was 287 ° C.

[0018]

Embedded image (M is an integer from 1 to 4)

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the initiator was sec-butyl lithium 0.0065 g, the reaction solvent was toluene 5 ml, and the reaction temperature was 30 ° C. 1.5 g of a white solid was obtained. The ring opening ratio of the product by IR was 72%.
The volume of the polymer relative to the monomer expanded 4.5%. The 10% weight loss temperature of the polymer was 280 ° C.

Example 3 In Example 1, the initiator DB was used.
Polymerization was carried out in the same manner as in Example 1 except that 0.06 g of U, 3.3 ml of the reaction solvent DMAc, and the reaction temperature were set to 120 ° C., to obtain 1.3 g of a white solid. The ring opening ratio of the product by IR was 80%. The volume of the polymer relative to the monomer expanded 4.8%. The 10% weight loss temperature of the polymer was 285 ° C.

Example 4 In Example 1, the initiator was sodium methoxide 0.018 g, and the reaction solvent was DMF5.
Polymerization was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 120 ° C. to obtain 1.6 g of a white solid. The ring opening rate of the product by IR was 83%. The volume of the polymer relative to the monomer expanded by 5.8%. The 10% weight loss temperature of the polymer was 290 ° C.

Example 5 The initiator DB in Example 1
U 0.04 g, reaction solvent DMF 3.3 ml, reaction temperature 1
Polymerization was carried out in the same manner as in Example 1 except that the temperature was 60 ° C.,
1.3 g of a white solid was obtained. The ring opening rate of the product by IR was 72%. The volume of the polymer relative to the monomer expanded 4.3%. The 10% weight loss temperature of the polymer was 281 ° C.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that 1.8 g of norbornene cyclic carbonate was used in place of 1.8 g of oligonorbornene having a cyclic carbonate structure in the side chain. 1.3 g of a white solid was obtained. The product has a number average molecular weight of 5200
Met. The density of the polymer was measured to be 1.2
3, and the volume calculated from the monomer density of 1.33 expanded 8.1%. The 10% weight loss temperature of the polymer was 262 ° C.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that 0.016 g of sodium methoxide was replaced with 0.0065 g of sec-butyllithium and the reaction temperature was 30 ° C. White solid 1.
5 g were obtained. The number average molecular weight of the product was 4,800. The 10% weight loss temperature of the polymer was 250 ° C. The volume expanded 7.0%.

Comparative Example 3 Polymerization was carried out in the same manner as in Example 1 except that 0.05 g of DBU was used instead of 0.016 g of sodium methoxide, and that the reaction solvent was 3.3 ml of DMAc. 1.5g
I got The number average molecular weight of the product was 4,800.
The 10% weight loss temperature of the polymer was 250 ° C.
The volume expanded 6.5%.

[Comparative Example 4] In Comparative Example 1, 0.012 g of sodium methoxide was used.
l, Polymerization was carried out in the same manner as in Example 1 except that the reaction temperature was 150 ° C, and 1.3 g of a white solid was obtained. The number average molecular weight of the product was 6000. The 10% weight loss temperature of the polymer was 245 ° C. The volume is 6.
Swelled 8%.

Comparative Example 5 In Comparative Example 1, the initiator was D
BU 0.5 g, reaction solvent DMF 4 ml, reaction temperature 13
Polymerization was carried out in the same manner as in Example 1 except that the temperature was changed to 0 ° C.
1.5 g of a white solid was obtained. The number average molecular weight of the product was 6,200. The 10% weight loss temperature of the polymer was 252 ° C. The volume expanded 6.0%.

[0028]

According to the present invention, oligonorbornene having a cyclic carbonate structure in the side chain and its polymer expand in volume after polymerization and exhibit excellent adhesiveness and thermal properties. Therefore, it is useful for applications of industrial materials such as casting materials, sealing materials, and adhesive materials.

Claims (2)

[Claims] An oligonorbornene having a cyclic carbonate structure in a side chain having n repeating units represented by the chemical formula (1). Embedded image (Repeating unit n is an integer from 1 to 10) (where x and y are integers from 0 to 3) 2. A polymer having n and m repeating units represented by the chemical formula (2). Embedded image (Repeating unit n is an integer from 1 to 10) (Repeating unit m is an integer from 1 to 100) (where x and y are integers from 0 to 3)