JPH0625394A - Production of crosslinked polymer - Google Patents

Abstract

PURPOSE:To obtain a crosslinked polymer good in heat resistance by facilitating the regulation of the activity of the metathesis polymerization catalyst, by using dicyclopentadiene and/or tricyclopentadiene and a specific norbornene- based compound as raw materials. CONSTITUTION:This crosslinked polymer can be obtained by ring opening-bulk polymerization of a mixture of (A) 20-80wt.% of dicyclopentadiene and/or tricyclopentadiene with (B) 20-80wt.% of a compound of the formula (A and B are each H or 1-10C hydrocarbon; X and Y are each H or monovalent organic group, at least one of them is H or a polar group other than hydrocarbon group; (m) is 1 or 2) in the presence of a metathesis polymerization catalytic system pref. at 35-200 deg.C. The compound of the formula is pref. 8-methyl-8- methoxycarbonyltetracyclo[4.4.0.1<2.5>1<7.10>]-3-dodecene. This catalytic system is pref. composed of a catalytic component such as tungsten hexachloride and an activating component such as trioctylaluminum.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a crosslinked polymer of a norbornene compound. More specifically, it relates to a method for producing a crosslinked polymer obtained by subjecting a norbornene compound containing a norbornene compound having a specific polar group as an essential component to bulk ring-opening polymerization using a metathesis polymerization catalyst.

[0002]

2. Description of the Related Art A reaction molding method is known in which a norbornene compound such as dicyclopentadiene or tricyclopentadiene is subjected to bulk ring-opening polymerization in a mold with a metathesis catalyst to obtain a crosslinked polymer molded product. By the way, the metathesis polymerization catalyst used in the above reaction molding method is generally active as a catalyst by a combination of a transition metal salt catalyst such as tungsten, molybdenum, rhenium, and tantalum and organic aluminum or organic tin for activating it. Expressed. The above method for producing a crosslinked polymer takes advantage of this point to dissolve both components of the catalyst and the activator in separately-divided norbornene-based compounds, and rapidly mix both to effect metathesis. It is devised so that polymerization is initiated, polymerization molding proceeds, and molded products are obtained all at once. However, the metathesis polymerization catalyst has a very high activity, and the reaction rate immediately after mixing both components is too fast even if the above-mentioned measures are taken, so that crosslinking is started before it is sufficiently poured into the mold. In many cases, moldings could not be obtained.

It is known to add a Lewis base to a catalyst system as a method of controlling the activity of such a metathesis polymerization catalyst and obtaining a good molded product. (JP-A-63-234
No. 021). However, when such a Lewis base is added in order to adjust the activity of the metathesis polymerization catalyst, there is a problem that the Lewis base remains in the molded product, which lowers the physical properties of the molded product or generates a volatile component. It was In order to solve these problems, a method of adding a Lewis base-containing metathesis-reactive monomer such as nadic acid diester has been proposed. (JP-A-63-234020) However,
The use of nadic acid diester has a drawback that the heat resistance of the obtained molded article is lowered.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a crosslinked polymer which enables the activity of such a metathesis polymerization catalyst to be adjusted and which does not lower the heat resistance of a molded article.

[0005]

That is, the present invention is as follows.
A mixture of (A) 20 to 80% by weight of dicyclopentadiene and / or tricyclopentadiene and (B) 20 to 80% by weight of a compound represented by the following general formula (1) is agglomerated in the presence of a metathesis polymerization catalyst system. The present invention provides a method for producing a crosslinked polymer, which is characterized by carrying out ring polymerization. General formula (1)

[Chemical 2] (In the formula, A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom or a monovalent organic group, and at least one of X and Y is a hydrogen atom and a hydrocarbon group. Is a group having a polarity other than, and m is 1 or 2.)

The dicyclopentadiene used as the component (A) of the present invention is obtained as one of the main components in the C5 cut produced as a by-product during ethylene production by naphtha cracking, but it is a substance that inhibits metathesis polymerization, such as direct reaction. High purity is not particularly required as long as chain olefins, water, alcohols, phenols, carbonyl compounds, thiol compounds, carboxylic acids, etc. are not contained, and generally 95% or more of purity is sufficient. Also, tricyclopentadiene, which is also used as the component (A), can be easily produced by heating cyclopentadiene and / or dicyclopentadiene, but this is also a substance that inhibits metathesis polymerization, such as water or alcohol. High purity is not particularly required as long as it does not contain compounds, phenols, carbonyl compounds, thiol compounds, carboxylic acids, etc., and can be used if the content of the compound having no norbornene ring is 5% by weight or less.

The compound represented by the general formula (1) used as the component (B) of the present invention is, for example, JP-A-1-132.
The same as those of the general formula (I) described in No. 626 can be mentioned. In the compound represented by the general formula (1), as the group having polarity, the crosslinked polymer obtained has a high glass transition temperature and a low hygroscopicity, and is represented by the formula- (C
H ₂ ) nCOOR ¹ is preferred, and this group is 1
It is preferable that the number is 1 per molecule since the hygroscopicity of the obtained crosslinked polymer is low. Moreover, the formula - (CH ₂₎ n
Of the groups represented by COOR ¹ , the smaller the value of n, the higher the glass transition temperature of the obtained crosslinked polymer, which is preferable. Usually, n = 0 is preferable for the synthesis of the monomer. It is preferable in that good properties can be obtained in the obtained crosslinked polymer. R ¹ is a hydrocarbon group having 1 to 20 carbon atoms. As the number of carbon atoms increases, the hygroscopicity of the crosslinked polymer decreases, but the glass transition temperature and thermal stability decrease, so From the viewpoint of balance with the glass transition temperature, R ¹ is a chain hydrocarbon group having 1 to 4 carbon atoms,
Alternatively, it is preferably a cyclic hydrocarbon group having 5 to 7 carbon atoms.

Further, the ^one having a carbon atom bonded to-(CH ₂ ) _n COOR ¹ substituted with a hydrocarbon group having 1 to 10 carbon atoms, particularly a methyl group, has a glass transition temperature of the obtained crosslinked polymer. It is preferable because it lowers hygroscopicity without lowering, and specifically, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0} ] -3-
Dodecene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8-methyl-8-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8-methoxycarbonylcyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-cyclohexyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-phenoxycarbonyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-dodecene, 9-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene and the like can be mentioned.

The compound represented by the general formula (1) can be generally produced by a Diels-Alder reaction between cyclopentadiene and / or dicyclopentadiene and an unsaturated compound having a polar group. At this time, tricyclopentadiene is often produced as a by-product at the same time, but in some cases, the compound represented by the general formula (1) and tricyclopentadiene and further dicyclopentadiene are not particularly separated but used for the present invention as they are mixed. It can also be used as a raw material compound. For example, as the compound represented by the general formula (1), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . When ^1,7,10 ] -3-dodecene is used, this compound can be prepared by heating dicyclopentadiene and methyl methacrylate, but 8-methyl-8-methoxycarbonyltetracyclo [4.4.0] is used. 1 ^2,5 . 1 ^7,10] -3-cyclopentadiene to dodecene and byproduct requires a relatively precise distillation to its boiling point is completely separated closer, but like this case, the tricyclopentadiene 8- Methyl-8
-Methoxycarbonyltetracyclo [4.4.0.1
^2,5 . It is economically very preferable to use a mixture of 1 ^7,10 ] -3-dodecene.

Further, in the present invention, in addition to the above-mentioned components (A) and (B), other metathesis-polymerizable monomers may be used together within the range not impairing the object of the present invention.
Such compounds generally include compounds having one or more metathesis-polymerizable cycloalkene groups, and those having a norbornene type structure are particularly preferable. Specific examples thereof include dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, and bicyclo [2.2.1] hept-2.
-Ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Examples include -3-dodecene and tetracyclopentadiene. In the present invention, the proportion of the component (A) used is 20 to 80% by weight of the mixture. If the amount of the component (A) used is less than 20% by weight, a sufficiently crosslinked polymer cannot be obtained. On the other hand, the component (B) is essential for controlling the bulk polymerization rate, and the amount used is 20 to 80% by weight.
If the proportion of the component (B) used is less than 20% by weight, the bulk polymerization is too fast to achieve the object of the present invention. vice versa,
If the amount of the component (B) used exceeds 80% by weight, a sufficiently crosslinked polymer cannot be obtained.

The metathesis polymerization catalyst system used in the present invention comprises a catalyst component and an activating component. As the catalyst component, compounds such as tungsten, molybdenum, rhenium and tantalum, particularly halogen salts, oxyhalogen salts and alkoxides thereof are preferable, and compounds such as tungsten and molybdenum can be preferably mentioned.
As such a tungsten compound, tungsten halide, tungsten oxyhalide, tungsten alkoxide and the like are preferable, and specifically, tungsten hexachloride, tungsten oxytetrachloride, tungsten dioxydichloride, pentamethoxytungsten and the like are preferable. Further, an organic ammonium salt of tungstic acid, such as tridecyl ammonium tungstate or trioctyl ammonium tungstate, can be used. Further, it is also preferable to modify a tungsten compound such as tungsten hexachloride with phenols or alcohols before use. In the present invention, the catalyst component does not have to be one type, and two or more types may be used in combination.

On the other hand, the activating component in the metathesis polymerization catalyst is preferably an organometallic compound centered on an alkylated product of a metal of Groups I to III of the Periodic Table, particularly an alkylaluminum compound or an alkylaluminum halide. The hydrides of the metals listed above can also be used. Specific examples thereof include trialkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum; dialkylaluminum halides such as diethylaluminum chloride, diethylaluminum bromide, dipropylaluminium chloride, diisobutylaluminum chloride and dioctylaluminium iodide. Examples thereof include alkylaluminum sesquihalides such as ethylaluminum sesquichloride and isobutylaluminum sesquichloride; alkylaluminum dihalides such as ethylaluminum dichloride and isobutylaluminum dichloride; or mixtures thereof. Of these, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum, which are particularly highly active catalysts, are preferable, and trioctylaluminum is more preferable.

Further, as the activating component, an alkyl compound or hydride of tin can be used. Examples of these include HSnR ¹ R ² R ³ [wherein R ¹ , R ² and R ³ may each be hydrogen, or an optionally substituted alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group having 3 to 7 carbon atoms which may be optionally substituted, or a phenyl group which may be optionally substituted]. Among these tin compounds, the formula HSnR ¹ R ² R ³ [wherein R ¹ , R ² and R ³ are each an alkyl group or a phenyl group having 1 to 10, especially 1 to 4 carbon atoms] The compound represented by the formula] is preferable, and specifically, tripropyltin hydride, tripentyltin hydride, tributyltin hydride, methyldicyclohexyltin hydride, cyclopentyldimethyltin hydride, trioctyltin hydride, hydrogen Triphenyl tin hydride, phenyl dimethyl tin hydride and the like, especially tributyl tin hydride and the like can be mentioned.

Furthermore, hydrides of silicon can be used as the activating component. As an example of these, HSi
R ¹ R ² R ³ [In the formula, R ¹ , R ² and R ³ may each be hydrogen, or an optionally substituted alkyl group having 1 to 20 carbon atoms, and 3 to 7 carbon atoms. Of the optionally substituted cycloalkyl group, or the optionally substituted phenyl group]. Of these silicon compounds, the formula HSiR ¹ R ² R ³
A silicon compound represented by the formula: [wherein at least two R ¹ , R ² and R ³ are alkyl groups or phenyl groups] is preferable, and specifically, dibutylsilane, triethylsilane, trihexylsilane, dipropylsilane. , Dipentylsilane, diphenylsilane, dicyclohexylsilane, dicyclopentylsilane, dioctylsilane and the like.

These activating components may be used alone or as a mixture of plural compounds. In the present invention, the catalyst component and the activating component are each separately described in (A) above.
The solution in which the catalyst component and / or the component (B) are dissolved and the catalyst component is dissolved (hereinafter referred to as "solution 1") and the activation component is dissolved (hereinafter referred to as "solution 2") are mixed until the initiation of polymerization. It is preferable to store without. Here, if the catalyst component is dissolved only in the component (A), cationic polymerization may occur. Therefore, the catalyst component may be dissolved in only the component (B) to prepare the solution 1, or first, the catalyst component may be dissolved in the component (B). From (A)
Solution 1 is preferably prepared by adding the ingredients. In addition,
In dissolving the catalyst component, the catalyst component may be dissolved or suspended in a small amount of an inert solvent such as benzene, toluene, xylene and the like in advance. In the present invention, basically by mixing the solution 1 and the solution 2,
Although a good crosslinked polymer can be stably obtained at a wide polymerization initiation temperature, a Lewis base or a chelating agent can be added to the solution 1 or the solution 2 to further control the polymerization rate. Such additives include acetylacetone, acetoacetic acid esters, tetrahydrofuran, benzonitrile,
Examples thereof include nadic acid diester. When an additive is used, it is used in an amount of 0.5 to 20 mol, preferably 1 to 5 mol, per 1 mol of the catalyst metal such as tungsten. The amount of the metathesis polymerization catalyst used varies depending on the types of the catalyst component and the activating component. For example, when a tungsten compound is used as the catalyst component, the ratio of the tungsten compound to the norbornene-based compound is 1000 to 15,000 on a molar basis. 1 (norbornene compound: tungsten compound), preferably 1500 to 10
000: 1, more preferably 2000-5000: 1. When alkylaluminum is used as an activating component, it is 1 to 100: 1 (alkylaluminum: tungsten) on a molar basis, preferably 1.5 to.
It is in the range of 50: 1, more preferably 2 to 30: 1.
The polymerization is usually carried out at 20 ° C to 250 ° C, but 35 to 2
The range of 00 ° C is preferred.

The crosslinked polymer obtained by the present invention includes
If necessary, various additives can be added. Such additives include reinforcing materials, fillers, pigments, colorants, antioxidants, light stabilizers, flame retardants and the like. It is also possible to add an elastomer to improve the impact strength and to adjust the viscosity of the norbornene compound used for bulk polymerization. Such an additive may be dissolved in the solution 1 or the solution 2, and the third norbornene-based compound solution containing no metathesis polymerization catalyst or activator may be added. It may be prepared and mixed and cross-linked simultaneously with the solution 1 and the solution 2. Further, depending on the additive, it can be filled in the mold in advance. As the antioxidant, phenol type, amine type, phosphorus type, and sulfur type can be used. As specific examples of the phenolic antioxidant,
2,6-t-butyl-p-cresol and 2,6-t-butyl-p-methylphenol can be mentioned. As an amine-based antioxidant, N, N′-diphenyl-p-
Examples include phenylenediamine.

Examples of the reinforcing material or filler include glass fiber, mica, carbon black and the like. Also, those obtained by surface-treating these fillers with a silane coupling agent or the like can be used. The addition of an elastomer is effective in enhancing impact resistance and controlling the viscosity of the solution. Elastomers used for such purpose include styrene-butadiene copolymer, polybutadiene, polyisoprene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene block copolymer, styrene-isoprene system. Examples thereof include block copolymers. The crosslinked polymer obtained in the present invention is used for a wide range of applications, mainly for large molded articles and printed circuit boards such as members of various transportation equipment including automobiles, housings of electric and electronic devices, outer skins of constructions, etc. it can. The present invention will be described in detail below with reference to examples.
It should be noted that the embodiment is for the purpose of explanation and is not limited to this.

[0018]

【Example】

Example 1 (Preparation of Solution 1) 20 g of tungsten hexachloride was added to 70 ml of dry toluene under a nitrogen stream, and then a solution of 13 g of nonylphenol and 16 ml of toluene was added to prepare a 0.5 M tungsten-containing solvent solution. Nitrogen gas was blown into this solution overnight to remove hydrogen chloride gas produced by the reaction between tungsten hexachloride and nonylphenol, to obtain a polymerization solvent. Such a solution 1
ml and 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 50
0 ml was mixed to prepare a solution 1 having a tungsten content of 0.001M. (Preparation of Solution 2) 0.55 g of trioctylaluminum, 300 ml of dicyclopentadiene, 150 ml of tricyclopentadiene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 50 ml of ^1,7,10 ] -3-dodecene was mixed to obtain aluminum content.
A 0.003M solution 2 was prepared. (Polymerization) 10 ml of the solution 1 and 10 ml of the solution 2 were heated to a predetermined temperature and then taken out into a syringe replaced with nitrogen. The solution was extruded from the syringe at a constant speed into a glass flask equipped with a stirrer at the same time with stirring, and after rapid stirring, the stirrer was raised and a thermocouple was inserted. (Polymerization time) was measured. Further, the solidified crosslinked resin was taken out, a section was cut out, and the glass transition temperature was measured under nitrogen. The results are shown in Table 1.

Example 2 In Example 1, when the solution 2 was prepared, 400 ml of dicyclopentadiene and 100 m of tricyclopentadiene were prepared.
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . An experiment was conducted in the same manner as in Example 1 except that the experiment was conducted without using ^1,7,10 ] -3-dodecene. The results are shown in Table 1. Example 3 In Example 1, the solution 2 was prepared by adding 200 ml of dicyclopentadiene and 200 m of tricyclopentadiene.
1, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 10
The experiment was performed in the same manner as in Example 1 except that 0 ml was used. The results are shown in Table 1. Example 4 In Example 1, the preparation of Solution 1 was carried out using 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene (250 ml) and dicyclopentadiene (250 ml) were mixed. Further, solution 2 was prepared by using 250 ml of dicyclopentadiene, 200 ml of tricyclopentadiene, and 8-methyl-8-methoxycarbonyltetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ]
An experiment was performed in the same manner as in Example 1 except that 50 ml of -3-dodecene was used. The results are shown in Table 1.

Example 5 In Example 1, the preparation of solution 1 was carried out using 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
- done in dodecene 500 ml, manufactured by adjusting the solution 2 dicyclopentadiene 400 ml, tricyclopentadiene using 100 ml, 8- methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]
An experiment was conducted in the same manner as in Example 1 except that -3-dodecene was not used. The results are shown in Table 1. Example 6 In Example-1, the preparation of Solution 1 was performed using 8-methyl-8-
Methoxycarbonyltetracyclo [4.4.0.
1 ^2,5 . 200 ml of 11, ^10] -3-dodecene and 11-methyl-11-methoxycarbonylhexacyclo [6.6.
1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene and carried using 300 ml, further, dicyclopentadiene Preparation of solution 2 250 ml, tricyclopentadiene 200 ml, 8- methyl-8-methoxycarbonyltetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10 ]
An experiment was conducted in the same manner as in Example 1 except that 50 ml of -3-dodecene was used. The results are shown in Table 1.

Example 7 In Example 1, the preparation of Solution 1 was carried out by using 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
400 ml of 1 ^7,10 ] -3-dodecene and 11-methyl-
11-Methoxycarbonylhexacyclo [6.6.1.
1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene and carried using 100 ml, further, dicyclopentadiene Preparation of solution 2 250 ml, tricyclopentadiene 100 ml, 8- methyl-8-methoxycarbonyltetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene 50 ml, tetracyclopentadiene 100
The experiment was performed in the same manner as in Example 1 except that the experiment was performed using ml. The results are shown in Table 1. Comparative Example 1 In Example 1, the preparation of Solution 1 was carried out using 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene (50 ml) and dicyclopentadiene (450 ml) were mixed, and solution 2 was prepared using dicyclopentadiene (150 ml) and tricyclopentadiene (350 ml) with 8-methyl-8-methoxycarbonyl. Tetracyclo [4.4.0.1 ^2,5 . 1
^The experiment was conducted in the same manner as in Example 1 except that ^7,10 ] -3-dodecene was not used. The results are shown in Table 1.

Comparative Example 2 In Example 1, the solution 1 was prepared using 500 ml of nadic acid dimethyl ester, and the solution 2 was prepared using 300 ml of dicyclopentadiene and 150 ml of tricyclopentadiene. Methyl-8-
Methoxycarbonyltetracyclo [4.4.0.
1 ^2,5 . An experiment was conducted in the same manner as in Example 1 except that the use of [ ^17,10 ] -3-dodecene was omitted. The results are shown in Table 1.
It was shown to. Comparative Example 3 In Example 1, the preparation of solution 1 was performed by preparing 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-.
Further, 500 ml of ene was used to prepare solution 2, and 400 ml of dicyclopentadiene and 100 ml of tricyclopentadiene were used to prepare 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 ． 1
An experiment was conducted in the same manner as in Example 1 except that ^7,10 ] -3-dodecene was not used. The results are shown in Table 1.

[0023]

[Table 1]

[0024]

EFFECTS OF THE INVENTION According to the present invention, it is possible to produce a crosslinked polymer in which the activity of the metathesis polymerization catalyst can be adjusted and the heat resistance of the molded article is not lowered.

Claims (1)

[Claims] 1. A mixture of (A) 20 to 80% by weight of dicyclopentadiene and / or tricyclopentadiene and (B) 20 to 80% by weight of a compound represented by the following general formula (1) in a metathesis polymerization catalyst system. In existence,
A method for producing a crosslinked polymer, which comprises performing bulk ring-opening polymerization. General formula (1) (In the formula, A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom or a monovalent organic group, and at least one of X and Y is a hydrogen atom and a hydrocarbon group. Is a group having a polarity other than, and m is 1 or 2.)