JP2010174241A - Method for producing polyether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyether having a (meth)acryloyloxy group, by which almost no homopolymerized product of (meth)acryloyloxy groups is generated. <P>SOLUTION: The method for producing the polyether (C) that is represented by general formula (2) and has a double bond concentration ranging from 3.0-8.0 mmol/g and a number-average molecular weight ranging from 300-5,000 is characterized by reacting a polyether (A) represented by general formula (1) with (meth)acrylic acid in the presence of a strong basic catalyst (B) having an amidine backbone within the molecule. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a polyether. More specifically, a method for producing a polyether obtained by reacting an epihalohydrin addition reaction product of a dihydric or tetrahydric alcohol with (meth) acrylic acid (meaning acrylic acid and / or methacrylic acid, the same shall apply hereinafter). About.

  Polyethers having an ethylenically unsaturated bond group are used as active energy ray-curable resin compositions in the fields of electronic materials, electrical products, automobiles, and the like. In particular, a transfer method (coating a curable resin on a substrate sheet having releasability and peeling the substrate sheet to transfer the design on the substrate sheet to the surface of the molded product, followed by irradiation with active energy rays. When used as a curable resin in a method for producing a cured product, the cured product has excellent wear resistance, strength, elongation, and the like.

  As a method for producing a polyether having an ethylenically unsaturated bond group, it has an ethylenically unsaturated bond group in the presence of a compound having a phenol structure in which both two ortho positions are substituted with a t-butyl group. A method of copolymerizing an oxirane compound and an oxirane compound not containing an ethylenically unsaturated bond group has been proposed (Patent Document 1).

  However, the method of Patent Document 1 has a problem in that a polymerization reaction between ethylenically unsaturated bond groups occurs, and thus a target polyether having an ethylenically unsaturated bond group cannot be obtained with high purity.

JP 2006-28425 A

  The present invention is a method for producing a polyether having a (meth) acryloyloxy group (meaning that it is an acryloyloxy group and / or a methacryloyloxy group; the same shall apply hereinafter), wherein (meth) acryloyloxy groups are It is an object of the present invention to provide a method for producing a polyether having a (meth) acryloyloxy group that hardly produces a polymerized polymer.

式中、Ｒ¹は炭素数１〜２２の２〜４価アルコールからすべての水酸基を除いた残基、ｎ₁及びｎ₂はそれぞれ独立に０〜２０の数であり、１≦ｎ₁＋ｎ₂≦２０を満たす、ｍは２〜４の数、Ｘはハロゲン原子、ｎ₁とｎ₂で表される繰り返し構造はランダム状の付加形式である。

式中、Ｒ¹、Ｘ及びｍは、一般式（１）におけるＲ¹、Ｘ及びｍと同様の基、原子又は数、Ｒ²は水素原子又はメチル基、ｋ₁、ｋ₂、ｋ₃及びｋ₄はそれぞれ独立に０〜２０の数であり、１≦ｋ₁＋ｋ₂＋ｋ₃＋ｋ₄≦２０を満たす、ｋ₁＋ｋ₂は一般式（１）におけるｎ₁と等しく、ｋ₃＋ｋ₄は一般式（１）におけるｎ₂と等しく、ｍは２〜４の数、ｋ₁、ｋ₂、ｋ₃及びｋ₄で表されるそれぞれの繰り返し構造はランダム状の付加形式である。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, in the present invention, the polyether (A) represented by the general formula (1) and (meth) acrylic acid are reacted in the presence of a strongly basic catalyst (B) having an amidine skeleton in the molecule. A method for producing a polyether (C) represented by the general formula (2), having a double bond concentration of 3.0 to 8.0 mmol / g and a number average molecular weight of 300 to 5,000 It is.

In the formula, R ¹ is a residue obtained by removing all hydroxyl groups from a divalent to tetravalent alcohol having 1 to 22 carbon atoms, n ₁ and n ₂ are each independently a number of 0 to 20, and 1 ≦ n ₁ + n ₂ ≦ 20, m is a number from 2 to 4, X is a halogen atom, and the repeating structure represented by n ₁ and n ₂ is a random additional form.

Wherein, R ^1, X and m, R ¹ in the general formula (1), the same groups as X and m, atom or number, R ² is a hydrogen atom or a methyl group, k _1, k _2, k ₃ and k ₄ is each independently a number from 0 to 20, satisfying 1 ≦ k ₁ + k ₂ + k ₃ + k ₄ ≦ 20, k ₁ + k ₂ is equal to n ₁ in the general formula (1), and k ₃ + k ₄ is It is equal to n ₂ in the general formula (1), m is a number of 2 to ₄ , and each repeating structure represented by k ₁ , k ₂ , k _3, and k ₄ is a random additional form.

  By the production method of the present invention, it is possible to produce a polyether having a (meth) acryloyloxy group that hardly produces a polymer obtained by polymerizing (meth) acryloyloxy groups.

  The polyether (A) represented by the general formula (1) in the present invention can be obtained by subjecting a divalent to tetravalent alcohol and an epihalohydrin to an addition reaction in the presence of an acidic catalyst.

R ¹ in the general formula (1) is a residue obtained by removing all hydroxyl groups from a divalent to tetravalent alcohol of 1 to 22 carbon atoms.
Examples of the residue obtained by removing all hydroxyl groups from a C1-C22 divalent to tetravalent alcohol include the following residues obtained by removing all hydroxyl groups from a divalent to tetravalent alcohol.
C2-C22 dihydric alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 2,3-butanediol, Pinacol, 1,2-cyclohexanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1,2-butanediol, 2-ethyl-2-methyl-1,2-propanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4 -Pentanediol, 1,4-cyclohexanediol, 1,7-heptanediol, 2-methyl -1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neo Pentyl glycol), 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 1,8-octanediol and 2,2,4-trimethyl- 1,2-pentanediol, etc. Trivalent alcohol having 1 to 22 carbon atoms: glycerin, 1,2,4-trihydroxybutane, 2,3,4-trihydroxypentane, 1,1,1-tris (hydroxymethyl) Ethane, 1,2,6-trihydroxyhexane, 1,2,3-trihydroxyheptane, etc. Tetravalent alcohol having 1 to 22 carbon atoms: pentaerythritol Le

  X in General formula (1) is a halogen atom, and a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

In the general formula (1), n ₁ is the number of moles of the portion added by the α-cleavage of epihalohydrin. N ₂ in the general formula (1) is the number of moles of a portion added by β-cleavage of epihalohydrin. n ₁ and n ₂ are each a number from 0 to 20, and n ₁ + n ₂ represents the number of moles of epihalohydrin added to a divalent to tetravalent alcohol, and is usually a number from 1 to 20, preferably from the viewpoint of reactivity. Is 1-15. The repeating structure represented by n ₁ and n ₂ is a random additional form.

  M in General formula (1) represents the valence of a polyhydric alcohol, and the number is 2-4.

  Examples of the epihalohydrin to be reacted with the dihydric to tetrahydric alcohol include epifluorohydrin, epichlorohydrin, epibromohydrin and epiiodohydrin.

Examples of the acidic catalyst include a Lewis acid catalyst, such as boron trifluoride, tris (pentafluorophenyl) borane, methylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), chloride. Examples include aluminum and trimethylaluminum.
The amount of the acidic catalyst used is preferably 0.005 to 3% by weight, more preferably 0.05 to 1% by weight, particularly preferably 0.1 to 0.1% by weight, based on the total weight of the divalent to tetrahydric alcohol and epihalohydrin. 0.5% by weight.

Specific examples of the method of adding an epihalohydrin to a dihydric to tetrahydric alcohol include the following methods.
A pressure-resistant reaction vessel equipped with a stirrer, a cooler, a thermometer, and an inert gas introduction tube is charged with a 2- to 4-hydric alcohol and an acidic catalyst, and the reaction is carried out by dropping epihalohydrin after nitrogen substitution. The reaction temperature is preferably 0 to 70 ° C, more preferably 10 to 50 ° C, and particularly preferably 20 to 40 ° C. The dropping time of epihalohydrin is usually 1 to 20 hours, and after completion of the dropping, it is preferably aged for 30 minutes at the same temperature as the reaction temperature. In the reaction, a solvent may be used if necessary. Examples of the solvent include hydrocarbon solvents (such as toluene, xylene, benzene, cyclohexane, n-hexane and n-octane), halogenated hydrocarbons (such as methylene chloride, dichloroethane and trichloroethane), and ether compounds (such as dimethyl ether and diethyl). Ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxane and the like). These may be used alone or in combination of two or more. After completion of the reaction, the acidic catalyst can be removed by a method of filtration after treating with an adsorption treating agent {“KYOWARD 1000” [manufactured by Kyowa Chemical Industry Co., Ltd.] etc.]. The amount of the adsorption treatment agent used is preferably 0.1 to 5% by weight, more preferably 0.1 to 1% by weight, and particularly preferably based on the total weight of the 2 to 4 alcohol, the acidic catalyst and the epihalohydrin. 0.1 to 0.5% by weight. After completion of the reaction, unreacted epihalohydrin and solvent can be removed under reduced pressure.

The number average molecular weight (hereinafter abbreviated as Mn) of the polyether (A) used in the present invention is usually 100 to 8,000, preferably 250 to 7,000, more preferably 400 to 5,000. It is. Mn can be measured, for example, under the following measurement conditions.
Model: HLC-8220GPC [Tosoh Corporation liquid chromatograph]
Column: TSK gel Super H4000
+ TSK gel Super H3000
+ TSK gel Super H2000
[Both made by Tosoh Corporation]
Column temperature: 40 ° C
Detector: RI (Refractive Index)
Solvent: Tetrahydrofuran flow rate: 0.6 ml / min Sample concentration: 0.25 wt%
Injection volume: 10 μl
Standard: Polystyrene [TSK STANDARD POLYSTYLE NE; manufactured by Tosoh Corporation]

  The viscosity at 30 ° C. of the polyether (A) in the present invention is preferably 300 to 20,000 mPa · s, more preferably 400 to 15,000 mPa · s, and particularly preferably 500 to 10,000 mPa · s. . The viscosity of (A) can be measured using a BL type rotational viscometer.

The polyether (C) in the present invention is a compound represented by the general formula (2), and R ¹ , X and m in the general formula (2) are R ¹ , X and The same group, atom or number as m is mentioned. R ² in the general formula (2) is a hydrogen atom or a methyl group.

In the general formula (2), k ₁ represents the number of moles added of the portion reacted with (meth) acrylic acid among the portions added by the α-cleavage of epihalohydrin to the divalent to tetravalent alcohol. k _2, of the portion of epihalohydrin to a divalent to tetravalent alcohol was added by cleavage alpha, it represents the molar number of addition of the portion that has not reacted with (meth) acrylic acid. Therefore, k ₁ + k ₂ is equal to n ₁ in the general formula (1).
K ₃ in the general formula (2) represents the number of added moles of a portion reacted with (meth) acrylic acid among the portions added by β-cleavage of epihalohydrin to a divalent to tetravalent alcohol. k ₄ represents the number of moles added of a portion that has not reacted with (meth) acrylic acid, among the portions of epihalohydrin added by α-cleavage to a dihydric to tetrahydric alcohol. Therefore, k ₃ + k ₄ is equal to n ₂ in the general formula (1).
In the general formula (2), k ₁ , k ₂ , k _3, and k ₄ are each independently a number of 0 to 20, preferably 1 to 14. k < ₁ > + k < ₂ > + k < ₃ > + k < ₄ > is a number of 1-20, Preferably it is 2-15. The repeating structure represented by k ₁ , k ₂ , k ₃ and k ₄ is a random additional form.

Examples of the strongly basic catalyst (B) having an amidine skeleton in the molecule in the present invention include compounds represented by the general formula (3). An amidine skeleton is a structure in which two nitrogen atoms are bonded to a carbon atom, one of which is bonded by a single bond (CN) and the other by a double bond (C = N). When the amidine skeleton binds to hydrogen ions (H ⁺ ) desorbed from (meth) acrylic acid, the positive charge is delocalized and stabilized on the two nitrogen and carbon atoms by electron resonance. It is much easier to accept hydrogen ions than its amine, and is strongly basic.
By reacting the polyether (A) and (meth) acrylic acid in the presence of (B), in the obtained polyether (C), (meth) acryloyloxy groups possessed by (C) are present. Little polymerized polymer is formed.

式中、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶はそれぞれ独立に水素原子又は炭素数１〜１０の脂肪族炭化水素基であり、Ｒ³とＲ⁴、Ｒ³とＲ⁵、Ｒ³とＲ⁶、Ｒ⁴とＲ⁵、及び／又はＲ⁴とＲ⁶が相互に結合して環を形成していてもよい。
炭素数１〜１０の脂肪族炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基及びデシル基等が挙げられる。

In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , and / or R ⁴ and R ⁶ may be bonded to each other to form a ring.
Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

  Specific examples of the compound represented by the general formula (3) include 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) (pKa = 12.5), 1,5-diazabicyclo [4. 3.0] Nonene-5 (DBN) (pKa = 12.7), guanidine (pKa = 12.5), 4-dimethylaminopyridine (DMAP) (pKa = 9.2), pyridine (pKa = 5.2) ) And 4-aminopyridine (pKa = 9.3). The pKa value of the strongly basic catalyst (B) is preferably 11.0 or more, more preferably 11.5 or more, and particularly preferably 12.0 or more. Since it is preferable that the pKa value has a large numerical value, no particular upper limit is specified. Among these, DBU, DBN and guanidine are preferable from the viewpoint of pKa.

Since the strongly basic catalyst (B) in the present invention acts as a hydrogen halide scavenger when the polyether (A) and (meth) acrylic acid react with each other, the polyether (A) and (meth) acrylic acid The reaction rate can be improved.
For example, when the strongly basic catalyst (B) is DBU, first, the DBU captures hydrogen ions (H ⁺ ) from the carboxyl group of (meth) acrylic acid to become DBU-H ⁺ . On the other hand, a residue obtained by removing a hydrogen ion from the carboxyl group of (meth) acrylic acid nucleophilically attacks the haloalkyl group (X—CH ₂ —) of the polyether (A), thereby eliminating the halogen atom and leaving. The halogen atom thus bonded to DBU-H ⁺ forms a salt of DBU and hydrogen halide.
Since the salt of DBU and hydrogen halide settles in the solution in a coarse granular form, it is very easy to filter. Further, by treating the salt of DBU and hydrogen halide with sodium hydroxide or potassium hydroxide, DBU can be recovered almost quantitatively, so that it can be reused.

  As the (meth) acrylic acid in the present invention, commercially available products can be used, and those dehydrated with sodium sulfate, magnesium sulfate, molecular sieves and the like may be used as necessary.

Specific examples of the method for the addition reaction of the polyether (A) and (meth) acrylic acid include the following methods.
A solvent and a strongly basic catalyst (B) are charged into a reaction vessel equipped with a stirrer, a cooler, a thermometer, an air introduction tube, and a dropping funnel. Next, a polymerization inhibitor is charged, and (meth) acrylic acid is added dropwise at 30 ° C. or lower while aerated air is aerated with stirring, and then the polyether (A) is added dropwise to react. The reaction temperature is preferably 30 to 130 ° C, more preferably 40 to 120 ° C, and particularly preferably 50 to 110 ° C. After completion of the dropwise addition of the polyether (A), aging is performed at the same temperature as the reaction temperature for 1 to 30 hours. After completion of the aging, the hydrogen halide salt of the strong basic catalyst (B) produced after cooling to room temperature is filtered, and ion-exchanged water is added to unreacted (meth) acrylic acid and the strong basic catalyst (B). Remove with water. Furthermore, the polyether (C) of the present invention can be obtained by removing the solvent from the organic layer under reduced pressure.

  Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene; linear or branched aliphatic hydrocarbons having 5 to 35 carbon atoms such as hexane, pentane, octane and decane; methylene chloride, chloroform and Chlorohydrocarbons such as carbon tetrachloride; alcohols such as methanol, ethanol and isopropyl alcohol; ethers such as dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran;

  Examples of the polymerization inhibitor include phenol compounds such as methoxyphenol and 2,6-di-t-butyl-4-methylphenol; amine compounds such as N, N′-diphenyldiaminobenzene; sulfur-containing compounds such as phenothiazine. Metal ion compounds such as copper acetate (divalent) monohydrate; and the like. The amount of the polymerization inhibitor used is preferably 0.0001 to 0.5% by weight, more preferably 0.001 to 0.3% by weight, based on the total weight of the polyether (A) and (meth) acrylic acid. %, Particularly preferably 0.01 to 0.1% by weight.

  The reaction molar ratio of the polyether (A) and (meth) acrylic acid is preferably 1.0 to 3.0 mol, more preferably 1.0 mol with respect to 1.0 mol of the haloalkyl group of the polyether (A). The amount is 1.1 to 2.0 mol, particularly preferably 1.2 to 1.5 mol.

  The molar ratio of the polyether (A) and the strongly basic catalyst (B) is preferably 0.1 to 3.0 mol, more preferably 1.0 mol, relative to 1.0 mol of the haloalkyl group of the polyether (A). Is 0.5 to 2.0 mol, particularly preferably 1.0 to 1.5 mol.

The double bond concentration of the polyether (C) is usually 3.0 to 8.0 mmol / g, preferably 3.5 to 7.5 mmol / g, more preferably 4.0 to 7.0 mmol / g. is there.
Here, the double bond concentration is the content (mmol / g) of the carbon-carbon double bond (C = C) of the (meth) acryloyl group of the polyether (C). When the double bond concentration is low, it means that a polymer obtained by polymerizing (meth) acryloyloxy groups of the polyether (C) is produced.

The double bond concentration can be measured by a titration method using an addition reaction (Michael addition) of an amine to a double bond of a (meth) acryloyl group, and a specific measurement method is as follows.
(1) About 1 g of a sample is precisely weighed and placed in an Erlenmeyer flask, and then about 10 ml of acetone is added and dissolved.
(2) Add 10 ml of morpholine standard solution [mixed morpholine and methanol at 1: 4 (volume ratio)], and then add 50 volume% acetic acid standard solution [1: 1 (volume ratio) of acetic acid and ion-exchanged water]. After adding 1.5 ml and shaking well, leave at room temperature for 15 minutes.
(3) Add 15 ml of acetonitrile and 10 ml of acetic anhydride to the Erlenmeyer flask and shake well.
(4) Titrate with a 0.5 mol / L acetic acid / methanol titration solution using a recording type automatic titrator.
(5) At the same time, the blank test [the one in which the above operations (1) to (4) are performed without adding a sample) is performed, and the double bond concentration is calculated from the following equation.
Double bond concentration (mmol / g) = f × (A−B) / 2S
However, A: Number of ml of 0.5 mol / L acetic acid / methanol titration solution required for titration of sample B: Number of ml of 0.5 mol / L acetic acid / methanol titration solution required for blank test.
f: titer of 0.5 mol / L acetic acid / methanol titration solution S: sampling amount (g)

  Mn of the polyether (C) is usually 300 to 5,000, preferably 400 to 4,000, and more preferably 500 to 3,000. In addition, Mn of (C) can be measured on the same measurement conditions as Mn of the said polyether (A).

  The viscosity of the polyether (C) at 30 ° C. is preferably 300 to 20,000 mPa · s, more preferably 400 to 15,000 mPa · s, and particularly preferably 500 to 10,000 mPa · s. The viscosity of (C) can be measured using a BL type rotational viscometer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Unless otherwise specified, “%” means “% by weight” and “parts” means “parts by weight”.

[Production Example 1]
Into a pressure-resistant reaction vessel equipped with a stirrer, a cooler, a thermometer, and an inert gas introduction tube, 76 parts (1.0 mol part) of propylene glycol and 2.2 parts of a 47% tetrahydrofuran solution of boron trifluoride are charged. Then, the system was replaced with nitrogen, and 370 parts (4.0 mole parts) of epichlorohydrin was added dropwise while adjusting the temperature to 25 to 35 ° C., followed by aging at 50 to 60 ° C. for 30 minutes. Next, unreacted epichlorohydrin was removed under reduced pressure (20 mmHg). Addition of 4.4 parts of the adsorption treatment agent “KYOWARD 1000” [manufactured by Kyowa Chemical Industry Co., Ltd.] and stirring at 95 to 105 ° C. for 1 hour, the adsorption treatment agent is filtered, and polyether (A-1) [general R1 in the formula (1) is a residue obtained by removing all hydroxyl groups from propylene glycol, and X is a chlorine atom, a compound in which n ₁ + n ₂ = 2.0 and m = 2]. Mn of (A-1) was 450, and the viscosity at 30 ° C. was 930 mPa · s.

[Production Example 2]
Polyether (A-2) [in the general formula (1), in the same manner as in Production Example 1, except that 370 parts (4.0 mole parts) of epichlorohydrin was changed to 925 parts (10 mole parts). R1 is a residue obtained by removing all hydroxyl groups from propylene glycol, and X is a chlorine atom, n ₁ + n ₂ = 5.0, and m = 2. Mn of (A-2) was 1,000, and the viscosity at 30 ° C. was 5,200 mPa · s.

[Production Example 3]
Polyether (A-3) [in the general formula (1), in the same manner as in Production Example 1 except that 370 parts (4.0 mole parts) of epichlorohydrin was changed to 3700 parts (40 mole parts). R1 is a residue obtained by removing all hydroxyl groups from propylene glycol, and X is a chlorine atom, a compound in which n ₁ + n ₂ = 20 and m = 2]. Mn of (A-3) was 3,800, and the viscosity at 30 ° C. was 15,000 mPa · s.

[Production Example 4]
Propylene glycol 76 parts (1.0 mol part) to glycerin 92 parts (1.0 mol part) and epichlorohydrin parts 370 parts (4.0 mol parts) to 555 parts (6.0 mol parts) Polyether (A-4) [R1 in the general formula (1) is a residue obtained by removing all hydroxyl groups from glycerin, X is a chlorine atom, and n ₁ + n ₂ = 2 in the same manner as Example 1 except for the change. 0.0, m = 3]. Mn of (A-4) was 650, and the viscosity at 30 ° C. was 1,300 mPa · s.

[Production Example 5]
76 parts (1.0 mole part) of propylene glycol is 136 parts (1.0 mole part) of pentaerythritol, and 370 parts (4.0 mole part) of epichlorohydrin is 555 parts (6.0 mole part). In the same manner as in Example 1, except for changing to polyether (A-5) [R1 in the general formula (1) is a residue obtained by removing all hydroxyl groups from pentaerythritol, X is a chlorine atom, n ₁ + n ₂ = 1.5 and m = 4]. Mn of (A-5) was 700, and the viscosity at 30 ° C. was 1,800 mPa · s.

[Production Example 6]
A polyether (A-6) [general formula] was obtained in the same manner as in Example 1 except that 370 parts (4.0 mole parts) of epichlorohydrin was changed to 548 parts (4.0 mole parts) of epibromohydrin. A compound in which R1 in (1) is a residue obtained by removing all hydroxyl groups from propylene glycol, and X is a bromine atom, n ₁ + n ₂ = 2.0, m = 2] was obtained. Mn of (A-6) was 630, and the viscosity at 30 ° C. was 1050 mPa · s.

[Example 1]
To a reaction vessel equipped with a stirrer, a cooler, a thermometer, an air introduction tube and a dropping funnel, 130 parts of toluene and 31.9 parts (0.21 mole part) of DBU were charged. A polymerization inhibitor, 0.014 part of phenothiazine, was added, and 18.1 parts (0.21 mole part) of methacrylic acid was slowly added dropwise at 25 to 30 ° C. with aeration of dry air through the liquid while stirring. Next, the temperature was raised to 90 ° C., and 13.4 parts (0.03 mol parts) of the polyether (A-1) obtained in Production Example 1 was added dropwise at 90 to 100 ° C. over 1 hour. Aged at 90-100 ° C. for 7 hours. After completion of the aging, the mixture was cooled to room temperature, the produced DBU hydrochloride was filtered, 150 ml of ion-exchanged water was added, and unreacted (meth) acrylic acid and DBU were removed by washing with water. Toluene in the organic layer was removed under reduced pressure (20 mmHg) at 50 ° C., and polyether (C-1) [R1 in the general formula (2) is a residue obtained by removing all hydroxyl groups from propylene glycol, R2 is a methyl group, Compound in which X is a chlorine atom, k ₁ + k ₂ + k ₃ + k ₄ = 2.0, m = 2] was obtained.

[Example 2]
13.4 parts (0.03 mole part) of polyether (A-1) is added to 30.0 parts (0.03 mole part) of polyether (A-2), and 18.1 parts (0.01 mole part) of methacrylic acid. 21 mol part) was changed to 51.6 parts (0.6 mol parts) in the same manner as in Example 1, except that polyether (C-2) [R1 in the general formula (2) A residue excluding a hydroxyl group, a compound in which R2 is a methyl group, X is a chlorine atom, k ₁ + k ₂ + k ₃ + k ₄ = 5.0, m = 2] was obtained.

[Example 3]
13.4 parts (0.03 mole part) of the polyether (A-1) is replaced with 113.3 parts (0.03 mole part) of the polyether (A-3), and 18.1 parts (0. 21 mol part) was changed to 206.4 parts (2.4 mol parts) in the same manner as in Example 1, except that polyether (C-3) [R1 in the general formula (2) Residue excluding the hydroxyl group, R2 is a methyl group, X is a chlorine atom, k ₁ + k ₂ + k ₃ + k ₄ = 20, m = 2].

[Example 4]
Except for changing 13.4 parts (0.03 mol parts) of the polyether (A-1) to 19.4 parts (0.03 mol parts) of the polyether (A-4), the same as in Example 1, Polyether (C-4) [R1 in the general formula (2) is a residue obtained by removing all hydroxyl groups from glycerin, R2 is a methyl group, X is a chlorine atom, k ₁ + k ₂ + k ₃ + k ₄ = 2.0, Compound with m = 3] was obtained.

[Example 5]
Except for changing 13.4 parts (0.03 mol) of polyether (A-1) to 20.7 parts (0.03 mol) of polyether (A-5), the same as in Example 1, Polyether (C-5) [R1 in the general formula (2) is a residue obtained by removing all hydroxyl groups from pentaerythritol, R2 is a methyl group, X is a chlorine atom, k ₁ + k ₂ + k ₃ + k ₄ = 1.5 , Compound with m = 4].

[Example 6]
Except having changed 13.4 parts (0.03 mol part) of polyether (A-1) to 18.7 parts (0.03 mol part) of polyether (A-6), the same as in Example 1, Polyether (C-6) [R1 in the general formula (2) is a residue obtained by removing all hydroxyl groups from propylene glycol, R2 is a methyl group, X is a bromine atom, k ₁ + k ₂ + k ₃ + k ₄ = 2.0 , Compound in which m = 2].

[Example 7]
Polyether (C-7) [general formula] in the same manner as in Example 1 except that 18.1 parts (0.21 mol) of methacrylic acid was changed to 15.1 parts (0.21 mol) of acrylic acid. A compound in which R1 in (2) is a residue obtained by removing all hydroxyl groups from propylene glycol, R2 is a hydrogen atom, X is a chlorine atom, k ₁ + k ₂ + k ₃ + k ₄ = 2.0, and m = 2 is obtained. It was.

[Example 8]
Polyether (A-1) 13.9 parts (0.03 mol) to polyether (A-4) 19.4 parts (0.03 mol), methacrylic acid 18.1 parts (0.21 mol) ) Was changed to 15.1 parts (0.21 mole part) of acrylic acid in the same manner as in Example 1 to obtain the product (C-8) [wherein R1 in the general formula (2) represents all hydroxyl groups from glycerin. The removed residue, R2 is a hydrogen atom, X is a chlorine atom, k ₁ + k ₂ + k ₃ + k ₄ = 2.0, m = 3 is obtained].

[Example 9]
In the same manner as in Example 1 except that 31.9 parts (0.21 mol) of DBU was changed to 26.0 parts (0.21 mol) of DBN, polyether (C-9) [in the general formula (2) A compound in which R1 is a residue obtained by removing all hydroxyl groups from propylene glycol, R2 is a methyl group, X is a chlorine atom, k ₁ + k ₂ + k ₃ + k ₄ = 2.0, and m = 2 is obtained.

[Example 10]
Polyether (C-10) [general formula (2)] in the same manner as in Example 1 except that 31.9 parts (0.21 mole part) of DBU was changed to 12.4 parts (0.21 mole part) of guanidine. In which R1 is a residue obtained by removing all hydroxyl groups from propylene glycol, R2 is a methyl group, X is a chlorine atom, k ₁ + k ₂ + k ₃ + k ₄ = 2.0, and m = 2.

[Comparative Example 1]
A polyether (C′-1) was obtained in the same manner as in Example 1 except that 31.9 parts (0.21 mole part) of DBU was changed to 21.2 parts (0.21 mole part) of triethylamine.

[Comparative Example 2]
A polyether (C′-2) was prepared in the same manner as in Example 1 except that 31.4 parts (0.21 mol) of DBU was changed to 19.1 parts (0.21 mol) of tetramethylammonium hydroxide. Obtained.

  Double bond concentration, Mn, and polyethers (C-1) to (C-10), (C′-1) and (C′-2) obtained in Examples 1 to 10 and Comparative Examples 1 and 2 The viscosity at 30 ° C. was measured by the above method. The results are shown in Table 1.

As is clear from Table 1, since the polyethers (C-1) to (C-10) obtained in Examples 1 to 10 have a high double bond concentration, the polyethers (C-1) to (C-1) to ( A polymer obtained by polymerizing (meth) acryloyloxy groups of C-10) is hardly formed.
On the other hand, (C′-1) and (C′-2) obtained in Comparative Examples 1 and 2 have a lower double bond concentration than the polyethers (C-1) to (C-10), A polymer obtained by polymerizing (meth) acryloyloxy groups of (C′-1) and (C′-2) is produced.

Since the polyether having a (meth) acryloyloxy group produced by the production method of the present invention has a high double bond concentration, it is excellent in tack-free property and stretchability before UV curing, and has high hardness after UV curing. Therefore, the active energy ray-curable resin composition can be used in the fields of electronic materials, electrical products, automobiles, and the like.
It can also be used as a curable resin in a transfer method, and can be widely used as a resin material for small precision parts, notebook computers, mobile phones and the like.

Claims (5)

Characterized in that the polyether (A) represented by the general formula (1) and (meth) acrylic acid are reacted in the presence of a strongly basic catalyst (B) having an amidine skeleton in the molecule, A method for producing a polyether (C) represented by the formula (2), having a double bond concentration of 3.0 to 8.0 mmol / g and a number average molecular weight of 300 to 5,000.

[Wherein, R ¹ is a residue obtained by removing all hydroxyl groups from a C1-C22 dihydric or tetrahydric alcohol, n ₁ and n ₂ are each independently a number of 0-20, and 1 ≦ n ₁ + n ₂ ≦ 20 is satisfied, m is a number from 2 to 4, X is a halogen atom, and the repeating structure represented by n ₁ and n ₂ is a random additional form. ]

Wherein, R ^1, X and m, R ¹ in the general formula (1), X and m the same group, atom, or a few, R ² is a hydrogen atom or a methyl _{group, k 1, k 2, k} 3 And k ₄ are each independently a number from 0 to 20, satisfying 1 ≦ k ₁ + k ₂ + k ₃ + k ₄ ≦ 20, k ₁ + k ₂ is equal to n ₁ in the general formula (1), and k ₃ + k ₄ Is equal to n ₂ in the general formula (1), m is a number of 2 to ₄ , and each repeating structure represented by k ₁ , k ₂ , k ₃ and k ₄ is a random additional form. ] The method for producing a polyether (C) according to claim 1, wherein the strongly basic catalyst (B) is a compound represented by the general formula (3).

[Wherein, R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ³ and R ⁴ , R ³ and R ⁵ , R ³ And R ⁶ , R ⁴ and R ⁵ , and / or R ⁴ and R ⁶ may be bonded to each other to form a ring. ]   The method for producing a polyether (C) according to claim 1 or 2, wherein the strongly basic catalyst (B) has a pKa value of 11.0 or more.   The method for producing a polyether (C) according to any one of claims 1 to 3, wherein the viscosity at 30 ° C is 300 to 20,000 mPa · s.   The strongly basic catalyst (B) is composed of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and guanidine. The method for producing a polyether (C) according to any one of claims 1 to 4, which is one or more selected from the group consisting of: