JP3172079B2 - Method for producing propenyl ether compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing a propenyl ether compound which is crosslinked and cured by cationic polymerization.

[0002]

2. Description of the Related Art Propenyl ether compounds are industrially very useful compounds which are crosslinked and cured at high speed by cationic polymerization. As a method for producing a propenyl ether compound, a production method is known in which an allyl ether compound is converted to a propenyl ether compound by a rearrangement reaction. As a catalyst in this case, an alkaline catalyst such as potassium hydroxide, a ruthenium-based transition metal Catalysts are known. (JV Crivello and KDJ
o, J. et al. Polym. Sci. Polym. Chem.
Ed. , 31, 1473 (1993) etc.)

[0003]

However, the above manufacturing method is
When an alkaline catalyst is used, it is necessary to use a large amount of an aprotic polar solvent such as dimethyl sulfoxide (DMSO) in order to make the reaction in a homogeneous system. During the reaction, DMSO reacts with the alkaline catalyst. It cannot be used as an industrial production method, for example, it is decomposed to give dimethyl sulfide, and the purification requires a large amount of labor such as distillation. In addition, even when a ruthenium-based transition metal catalyst is used, no industrially effective method has been proposed as a purification method, purification requires distillation, and practically both are used as industrial production. It was impossible to produce a high-boiling propenyl ether compound which was impossible and difficult to distill.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on an industrial method for producing a propenyl ether compound which cannot be distilled, and as a result, have reached the present invention. That is, the present invention provides a method for producing a propenyl ether compound by rearranging an allyl ether compound (A), wherein a hydroxide of an alkali metal and / or an alkaline earth metal (B) is used as a catalyst and a polyoxyalkylene chain is used as a reaction solvent. A process for producing a propenyl ether compound, characterized by using the compound (C).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The allyl ether compound (A) of the present invention is a compound containing at least one allyl ether group in a molecule.
A method obtained by ring-opening addition of an alkylene oxide (first method)
Method) and a method (second method) obtained by reacting an alcohol with a halogenated allyl compound.

The alkylene oxide in the first method includes, for example, ethylene oxide, propylene oxide,
Examples thereof include 1,2- or 1,4-butylene oxide and styrene oxide, and a polyalkylene oxide having an allyl ether group at one end can be obtained.

[0007] The allyl halide compound in the second method includes allyl chloride and allyl bromide, and the alcohols include aliphatic alcohols (methanol, butanol, allyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, glycerin). , Trimethylolpropane, etc.), sugars (pentaerythritol, sorbitol, sucrose, etc.), aliphatic higher alcohols (lauryl alcohol, stearyl alcohol, etc.), phenols (phenol, nonylphenol,
Bisphenol A) and their alkylene oxide adducts, and an allyl ether compound having 1 to 8 functional groups can be obtained.

[0008] Of these, the first method and
It is a polyoxyalkylene polyallyl ether obtained by using an alkylene oxide adduct of the second method as alcohols. The higher the alkylene oxide content in the allyl ether compound skeleton, the higher the efficiency of the catalyst (B), the smaller the amount of the reaction solvent (C) used, and the easier the purification after the reaction.

The catalyst (B) includes alkali metal hydroxides (such as sodium hydroxide, potassium hydroxide and cesium hydroxide), alkaline earth metal hydroxides (such as calcium hydroxide and magnesium hydroxide), and alkali metal hydroxides. Carbonates (sodium carbonate, potassium carbonate, etc.) and alkaline earth metal carbonates (calcium carbonate, magnesium carbonate, etc.). Of these, alkali metal hydroxides which are highly basic and have a high catalytic effect, alkaline earths Preference metal hydroxides are preferred, and alkali metal hydroxides are more preferred.

The amount of the catalyst (B) used is usually 0.1 to 30% by weight, preferably 1 to 30% by weight based on the weight of (A).
It is. If it is less than 0.1, the translocation reaction takes a long time,
Exceeding the weight percentage is not only wasteful, but also takes time to remove and treat the catalyst. When (A) is a polyoxyalkylene polyallyl ether (a), the amount of (B) used is such that the weight ratio of the oxyalkylene chain in (a) to (B) is from 100: 1 to 100: 30. .

The reaction solvent (C) used in the present invention
Is a polyoxyalkylene chain-containing compound, which can be easily obtained by adding an alkylene oxide to an active hydrogen-containing compound. Examples of the active hydrogen-containing compound include aliphatic alcohols (methanol,
Butanol, allyl alcohol, ethylene glycol,
Diethylene glycol, propylene glycol, glycerin, trimethylolpropane, etc.), sugars (pentaerythritol, sorbitol, sucrose, etc.), aliphatic higher alcohols (lauryl alcohol, stearyl alcohol, etc.), phenols (phenol, nonylphenol, bisphenol A, etc.), Amines (ethylenediamine, diethylenetriamine, tripropanolamine,
Piperazine, tolylenediamine, bisaminodiphenylmethane, etc.), fatty acids, aromatic carboxylic acids, water, and ammonia. Examples of the alkylene oxide include ethylene oxide and propylene oxide (hereinafter referred to as E, respectively).
O, PO), 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, styrene oxide and the like, and combinations thereof. Preferred among these are ethylene oxide and a combination of ethylene oxide and propylene oxide, which has high solubility for the catalyst. The addition form of the alkylene oxide is not particularly limited, and known addition forms such as block addition and random addition can be used.

The number average molecular weight of (C) can be arbitrarily selected, but is usually from 62 to 40,000, preferably from 62 to 10,000. If it exceeds 40,000, the viscosity of the reaction system increases, and handling becomes difficult.

In the present invention, the amount of the reaction solvent (C) used is such that the weight ratio of the oxyalkylene chain in (C) or (C) and (A) to the catalyst (B) is usually 100: 1. ~ 1
00: 100, preferably 100: 2 to 100: 80
It is. When the weight ratio of the oxyalkylene chain in (C) or (C) and (A) to (B) is less than 100: 1, the solubility of the alkali catalyst in the system becomes small, and the rearrangement reaction takes a long time, If the ratio exceeds 100: 100, the yield is not only wasteful but also the yield of the desired propenyl ether compound.

As the reaction conditions for the rearrangement reaction in the present invention, known methods can be applied.
It can be set arbitrarily within the range of 200 ° C.

Since the reaction vessel used in the production uses an alkaline substance as a catalyst, it is not preferable to use a reaction vessel which is easily corroded by alkali such as glass. A metal, especially a stainless steel reaction vessel is preferred.

The catalyst after the rearrangement reaction can be directly extracted with water, neutralized with an acid (mineral acids, carboxylic acids, etc.) and then extracted with water, neutralized with an acid and dehydrated to form a neutralized salt. Known methods, such as a method of filtration and an ion adsorption treatment method using an ion exchange resin, can be used, but the propenyl ether compound is easily subjected to a hydrolysis reaction under acidic conditions,
Since acid neutralization easily causes hydrolysis, a method of neutralizing with water as it is or an ion adsorption treatment method is preferable.

The propenyl ether compound obtained according to the present invention is a very useful compound which crosslinks and cures at high speed by cationic polymerization, and industrially, a photocationic initiator (triphenylsulfonium hexafluoroantimonate, triphenyl Sulfonium phosphate, etc.) and cross-linking and curing by irradiating ultraviolet rays. Coating materials such as photoresist materials, printing ink materials, optical fibers, optical disks, woodwork, paper, metal, etc., photosensitive printing plates, adhesives, etc. Can be widely used.

[0018]

EXAMPLES The present invention will be specifically described below by way of synthesis examples and examples, but the present invention is not limited to these examples. Parts and% represent parts by weight and% by weight, respectively.

Synthesis Example 1: Synthesis of polyethylene glycol diallyl ether In a 500 ml SUS autoclave, 300 g (1 mol) of macrogol PEG-300 (polyethylene glycol having a number average molecular weight of 300: manufactured by Sanyo Chemical Industries, Ltd.) was added. 84 g (1.5 mol) of potassium are added,
Allyl chloride (115 g, 1.5 mol) was gradually added dropwise at 80 ° C. over 1 hour, and reacted for 5 hours. Thereafter, 200 g of water was added, and excess potassium hydroxide and generated salts were separated and removed. Unreacted allyl chloride and water were removed from the organic layer at 50 ° C. under a pressure of 100 mmHg to obtain 325 g (yield 86%) of polyethylene glycol diallyl ether.

Synthesis Example 2: Synthesis of Polypropylene Glycol Monoallyl Ether Into a 500 ml SUS autoclave, 58 g (1 mol) of allyl alcohol and 0.5 g of potassium hydroxide were charged, and 232 g of propylene oxide was poured from a pressure dropping funnel.
(4 mol) at 110 ° C. over 2 hours, and further 3
Aged for hours. After cooling the system to 80 ° C., 10 g of water and 10 g of acid clay were added and mixed for 30 minutes, and the acid clay adsorbed with allium hydroxide was filtered off, and 100 m at 50 ° C.
Water was removed under a pressure of mHg to obtain 258 g (89% yield) of polypropylene glycol monoallyl ether.

Synthesis Example 3: Synthesis of trimethylolpropane triallyl ether In a 1000 ml SUS autoclave, 134 g (1 mol) of trimethylolpropane and 160 g (4 mol) of sodium hydroxide were charged, and 345 g of allyl chloride was charged.
(4.5 mol) was gradually added dropwise at 80 ° C. over 2 hours,
The reaction was performed for 5 hours. Thereafter, 500 g of water was added, and excess sodium hydroxide and generated salts were separated and removed. Unreacted allyl chloride and water were removed from the organic layer at a pressure of 100 mmHg at 50 ° C. to obtain 198 g of trimethylolpropane triallyl ether (77% yield).

Example 1: Synthesis of polyethylene glycol dipropenyl ether (1) In a 500 ml SUS autoclave, 300 g of polyethylene glycol diallyl ether, 50 g of potassium hydroxide as a catalyst, and PEG-300 as a reaction solvent.
80 g (weight ratio of oxyalkylene chain to catalyst = 10
0:16) and subjected to a rearrangement reaction at 140 ° C. for 4 hours. Thereafter, 200 g of water was added, and excess alkali was washed with water to remove liquid. 80 ° C, 10m
Dehydration was performed under reduced pressure of mHg to obtain 276 g (yield 92%) of slightly yellow transparent polyethylene glycol dipropenyl ether. By H-NMR, 99% or more of the allyl ether group was rearranged to a propenyl ether group, and it was confirmed that the desired product was obtained.

Example 2: Synthesis of polyethylene glycol dipropenyl ether (2) In a 500 ml SUS autoclave, 300 g of polyethylene glycol diallyl ether and 30 g of potassium hydroxide as a catalyst were charged, and (weight of oxyalkylene chain and catalyst). (Ratio = 100: 13) Rearrangement reaction was performed at 140 ° C. for 4 hours. Thereafter, 200 g of water was added, and excess alkali was washed with water to remove liquid. The washed product is 80
Dehydration was performed at 10 ° C. and a reduced pressure of 10 mmHg to obtain 276 g (yield 92%) of slightly yellow and transparent polyethylene glycol dipropenyl ether. By H-NMR, 99% or more of the allyl ether group was rearranged to a propenyl ether group, and it was confirmed that the desired product was obtained.

Example 3 Synthesis of Polyethylene Glycol Dipropenyl Ether (3) The reaction solvent used in Example 1 was Newpol PE-68.
(A number average molecular weight of about 9,9 obtained by adding ethylene oxide to polypropylene glycol having a number average molecular weight of 1,800.
000 polyethylene polypropylene glycol: manufactured by Sanyo Chemical Industries, Ltd.), except that 50 g (weight ratio of oxyalkylene chain to catalyst = 100: 18) was used. 252 g (84% yield) of dipropenyl ether was obtained. By H-NMR, 99% or more of the allyl ether group was rearranged to a propenyl ether group, and it was confirmed that the desired product was obtained.

Example 4 Synthesis of Polypropylene Glycol Monopropenyl Ether In a 1000 ml SUS autoclave, 400 g of polypropylene glycol monopropenyl ether, 100 g of sodium hydroxide as a catalyst, and 100 g of PEG-300 as a reaction solvent (with an oxyalkylene chain). (Weight ratio with the catalyst = 100: 24), and a rearrangement reaction was performed at 160 ° C. for 3 hours. Thereafter, 300 g of water was added, and excess alkali was washed with water to remove liquid. The water-washed product was dehydrated at 80 ° C. under a reduced pressure of 50 mmHg to give a slightly yellow transparent polypropylene glycol monopropenyl ether 374.
g (94% yield). By H-NMR, 99% or more of the allyl ether group was rearranged to a propenyl ether group, and it was confirmed that the desired product was obtained.

Example 5: Synthesis of trimethylolpropane tripropenyl ether In a 500 ml SUS autoclave, 250 g of trimethylolpropane triallyl ether, 40 g of sodium hydroxide as a catalyst, and PEG-3 as a reaction solvent.
100 (weight ratio of oxyalkylene chain to catalyst = 100: 40) was charged, and a rearrangement reaction was performed at 130 ° C. for 4 hours. Thereafter, 300 g of water was added, and excess alkali was washed with water to remove liquid. 80 ° C, 3
After dehydration under reduced pressure of 0 mmHg, 220 g of a slightly yellow transparent polyethylene glycol dipropenyl ether (yield 88
%). According to H-NMR, allyl ether group was 99
% Or more, and it was confirmed that the desired product was obtained.

Comparative Example 1 In a 500 ml SUS autoclave, 300 g of trimethylolpropane triallyl ether, 50 g of potassium hydroxide as a catalyst, and 1 g of DMSO as a reaction solvent.
50 g was charged and a rearrangement reaction was performed at 140 ° C. for 2 hours. Thereafter, 300 g of water was added, and excess alkali and DMSO were washed with water to isolate trimethylolpropane tripropenyl ether. However, a brown component presumed to be derived from a decomposition product of DMSO could not be removed. 80 ° C, 50m
HN of brown product obtained by dehydration under reduced pressure of mHg
From MR, it was found that trimethylolpropane tripropenyl ether was the main component, but was considerably poor in purity.

Comparative Example 2 A reaction was carried out in the same manner as in Example 5 except that no reaction solvent was used. The rate of rearrangement reaction was measured by H-NMR of the product, and was found to be as low as 22%.

[0029]

According to the present invention, there is provided a method for producing a propenyl ether compound which is cross-linked and cured by cationic polymerization. According to the present invention, the conventional production method is difficult to purify and cannot be produced. , A high-boiling propenyl ether compound can be easily produced.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI // C07B 61/00 300 C07B 61/00 300 C07C 41/16 C07C 41/16 (56) References JP-A-9-143234 ( JP, A) Journal of Polymer Science Part A Polymer Chemistry 31 (6), p1473-82 (1993) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 41/32 C07C 43/15 C07C 43 / 178 C08F 2/46 B01J 23/02 C07B 61/00 300 C07C 41/16 C08G 65/329 C08F 299/00 C08F 16/20

Claims (5)

(57) [Claims] 1. A method for producing a propenyl ether compound by rearranging an allyl ether compound (A),
A method for producing a propenyl ether compound, comprising using a hydroxide (B) of an alkali metal and / or an alkaline earth metal as a catalyst and a compound (C) containing a polyoxyalkylene chain as a reaction solvent. 2. The content of (B) is based on the weight of (A).
The production method according to claim 1, wherein the content is 0.1 to 30% by weight. 3. The method according to claim 1, wherein (A) is a polyoxyalkylene polyallyl ether. 4. The weight ratio of (C) or the oxyalkylene chain in (C) and (A) to (B) is from 100: 1 to 10:
The method according to any one of claims 1 to 3, wherein the ratio is 0:30. 5. The method according to claim 1, wherein
Photo cation initiation to the resulting propenyl ether compound
Crosslinking agent by adding UV light and irradiating UV light
Way.