JP2003286338A - Polymerizable compound, urethane (meth)acrylate and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable compound having an oxyalkylene group which has a low CPR and is suited in the urethane reaction, and a urethane (meth)acrylate which excels in stability and handling properties. <P>SOLUTION: The polymerizable compound contains ≥10 ppm 2,6-t-butyl-4- methylphenol, has a CPR of ≤30 and a pH of 4.5-7, and is represented by formula (1): XO(AO)<SB>n</SB>H (wherein X is an acryloyl group or a methacryloyl group; AO is a 2-4C oxyalkylene group; and n is 2-100). The urethane (meth)acrylate is obtained by reacting the polymerizable compound with a polyisocyanate compound. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerizable compound having an oxyalkylene group having a low CPR, a method for producing the same,
The present invention relates to a urethane (meth) acrylate which is a reaction product of the polymerizable compound and a polyisocyanate compound, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, many photocurable resin compositions have been developed for use in paints, adhesives, letterpress materials, optical fiber coating materials, stereolithography materials and the like. Such a photocurable resin composition is composed of a photocurable oligomer, a photopolymerizable monomer, a photopolymerization initiator, a sensitizer, and other additives, does not contain a volatile solvent, and has a specific wavelength of light. The resin is cured by the irradiation of to obtain a cured product having excellent flexibility and adhesiveness. The photocurable oligomer used for such a purpose contains one or more (meth) acryloyl groups which are photocurable functional groups in the molecule. Among them, urethane (meth) acrylate obtained by the reaction of a polyol and a polyisocyanate compound has a cured product whose toughness, hardness, chemical resistance, flexibility, adhesion, light resistance,
It is used in a wide range of fields because of its excellent low-temperature characteristics. The urethane (meth) acrylate composed of a polyol and a polyisocyanate compound can be easily changed in molecular design by changing the raw material, and the performance can be easily changed particularly depending on the type of the polyol used. Examples of the polyol used for such purpose include polyoxyalkylene polyol, polyester polyol, polycaprolactone polyol, and polycarbonate polyol. Among these, polyoxyalkylene polyol is widely known as a polyol having a low viscosity and excellent workability. In the reaction between the polyoxyalkylene polyol and the polyisocyanate compound, in addition to the components as designed, the by-products such as high-molecular components and low-molecular components are also contained, so the molecular weight of the urethane (meth) acrylate finally obtained. Varies widely.

On the other hand, polyalkylene glycol (meth) acrylate having a structure in which one end of the polyoxyalkylene molecule is a (meth) acryloyl group and the other end is a hydroxyl group, the molecular weight is controlled by the reaction with a polyisocyanate compound. It is possible to provide a urethane (meth) acrylate which has been prepared. Since this polyalkylene glycol (meth) acrylate is easy to change the molecular design such as the molecular weight and composition of the polyoxyalkylene portion, it is possible to obtain the one having performance suitable for the purpose.
Polyalkylene glycol (meth), which is a substrate for urethane (meth) acrylate having such controlled molecular weight
The acrylate can be obtained by ring-opening polymerization of an alkylene oxide according to a method of cationic polymerization using a Lewis acid catalyst, which uses a low-molecular weight (meth) acrylate derivative as a substrate. it can. However, in this method, the temperature is not controlled when the raw materials are charged, and there is a possibility that polymerization of the (meth) acryloyl group at the molecular end or addition reaction of the (meth) acryloyl group and the hydroxyl group may occur before the alkylene oxide ring-opening polymerization reaction. Becomes higher. In addition, as a purification method, dehydration is performed after neutralization. However, since the neutralization salt becomes very fine, a large amount of the neutralization salt remains in the product, which tends to increase the CPR. During the urethane (meth) acrylate reaction in the next step, there is a high possibility that the reaction temperature will rapidly rise and the viscosity of the reaction solution will increase. Japanese Examined Japanese Patent Publication 52-304
According to Japanese Patent Publication No. 89 and Japanese Patent Publication No. 53-15493,
Although purification with an adsorbent has also been performed, the amount of adsorbent added to the catalyst is too small to perform sufficient purification, resulting in poor stability of the polyalkylene glycol (meth) acrylate, and the polyisocyanate compound. There is a high possibility that deterioration of reactivity with will occur.

[0004]

DISCLOSURE OF THE INVENTION The present invention uses the CP defined in JIS K1557 6.8 as an index of the content of alkali metal in a polyalkylene glycol derivative.
Focusing on R, a polymerizable compound having a low CPR and having an oxyalkylene group suitable for a urethane reaction, and a urethane (meth) which is a reaction product of the polymerizable compound having excellent stability and handleability and a polyisocyanate compound. An object of the present invention is to provide an acrylate, a method for producing the polymerizable compound, which can easily obtain a highly purified product, and a method for producing a urethane (meth) acrylate, which is a reaction product of the polymerizable compound and a polyisocyanate compound. And

[0005]

That is, the present invention is
(A) 2,6-t-butyl-4-methylphenol is contained at 10 ppm or more, CPR is 30 or less, and pH is 4.
A polymerizable compound represented by the formula (1) which is 5 to 7, XO (AO) _n H (1) (X is an acryloyl group or a methacryloyl group,
AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is 2-1.
00. (B) A urethane (meth) acrylate obtained by the reaction of the polymerizable compound of (A) with a polyisocyanate compound and (C) a Lewis acid catalyst are used, and the temperature at the time of charging the raw materials into the reaction vessel is 25 ° C. or lower. And 2,6-t-butyl-4-methylphenol is added as a polymerization inhibitor to ring-opening-polymerize an alkylene oxide in the compound represented by the formula (2), and then 20 to 80% by weight of magnesium oxide and oxidation A method for producing a polymerizable compound represented by the formula (1), which comprises adding a mixed metal oxide containing 5 to 50% by weight of aluminum in an amount 7 times by weight or more based on the amount of the Lewis acid catalyst added, and XO. (AO) _n H (1) (X is an acryloyl group or a methacryloyl group,
AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is 2-1.
00. ) XO (AO) _l H (2) (X is an acryloyl group or a methacryloyl group,
AO is an oxyalkylene group having 2 to 4 carbon atoms, and 1 is 1 to 9
9) (D) After adding an organotin compound as a catalyst to the polymerizable compound represented by the formula (1) obtained in (C) above, 3
It is a method for producing a urethane (meth) acrylate obtained by reacting a polyisocyanate compound at 0 to 80 ° C.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable compound represented by the formula (1) of the present invention has a CPR of 30 or less, preferably 15
Or less, and more preferably 5 or less. CPR is 3
If it is greater than 0, an abnormal reaction is likely to occur during the reaction with isocyanate. CPR is JIS K1557 6.8
, And can be measured according to the method described therein. The polymerizable compound represented by the formula (1) is 2,6
-T-butyl-4-methylphenol (hereinafter referred to as BHT) is 10 ppm or more, preferably 300 to 1000
contains ppm. If the BHT is less than 10 ppm, the storage stability will be poor.

The polymerizable compound represented by the formula (1) has a pH of 4.5 to 7, preferably 5 to 7. If the pH is lower than 4.5, deterioration of the polyether chain portion is likely to proceed, and if it is higher than 7, the (meth) acryloyl group portion, which is a polymerizable group, is likely to be eliminated. In addition, since the influence of water is large during the urethane reaction, the water content of the polymerizable compound represented by the formula (1) of the present invention, which is a raw material, is preferably 0.2% by weight or less, more preferably 0.1% by weight. % Or less, and more preferably 0.05% by weight or less. Formula (1) used in the present invention
In the polymerizable compound represented by, X is an acryloyl group or a methacryloyl group.

The number of carbon atoms represented by AO in the formula (1) is 2
Examples of the oxyalkylene group of to 4 include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxytetramethylene group. Further, one kind or a mixture of two or more kinds thereof may be used, and the polymerization form when two or more kinds are used may be either block-like or random-like. n has 2 to 2 carbon atoms
4 is the average number of moles of the oxyalkylene group added,
It is 100, preferably 2 to 50.

The polymerizable compound represented by the formula (1) is CP
Since R is low, it can be suitably used as a urethane raw material.
Urethane (meth) acrylate can be produced by reacting the polymerizable compound represented by the formula (1) with a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. Among them, it is preferable to use a di- or triisocyanate compound having 2 or 3 isocyanate groups because the control of the reaction is excellent.
The di- or triisocyanate compound is an aromatic, aliphatic or alicyclic isocyanate compound having two or three isocyanate groups, and known compounds used for producing polyurethane can be used. For example,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, any isomer mixture of tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, Any isomer mixture of diphenylmethane diisocyanate, toluylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, norbornene diisocyanate and the like, preferably 2,4-tolylene diisocyanate and hexamethylene It is a diisocyanate.

In the polymerizable compound represented by the formula (1) of the present invention, a Lewis acid catalyst is used, the temperature at the time of charging the raw materials into the reaction vessel is set to 25 ° C. or lower, and BHT is added as a polymerization inhibitor. After 1-99 mol of alkylene oxide is subjected to ring-opening polymerization with 1 mol of the compound represented by the formula (2), 20-80 wt% of magnesium oxide and 5-5 of aluminum oxide.
It can be obtained by adding 0% by weight of the mixed metal oxide in an amount 7 times or more the amount of the Lewis acid catalyst added and treating the mixture.

In the formula (2), X is an acryloyl group or a methacryloyl group. The oxyalkylene group having 2 to 4 carbon atoms represented by AO in the formula (2) is an oxyethylene group, an oxypropylene group, an oxybutylene group,
Examples thereof include an oxytetramethylene group, and an oxyethylene group and an oxypropylene group are preferable. Further, one kind or a mixture of two or more kinds thereof may be used, and the polymerization form when two or more kinds are used may be either block-like or random-like. 1 is the average number of moles of the oxyalkylene group having 2 to 4 carbons and is 1 to 99, preferably 1 to 4
It is 9. Specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate,
2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polybutylene glycol monoacrylate, polybutylene glycol monomethacrylate, Examples thereof include polytetramethylene glycol monoacrylate, polytetramethylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monoacrylate and polyethylene glycol-polypropylene glycol monomethacrylate. Preferably 2-hydroxyethyl acrylate, 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate.

Examples of the Lewis acid catalyst used in the present invention include tin tetrachloride, boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride di-n-butyl ether complex, boron trifluoride tetrahydrofuran complex, and trifluoride. Examples thereof include boron trifluoride compounds such as boron fluoride phenol complex and boron trifluoride acetic acid complex. Preferred are tin tetrachloride, boron trifluoride diethyl ether complex, boron trifluoride di-n-butyl ether complex and boron trifluoride tetrahydrofuran complex, and more preferred is tin tetrachloride. The addition amount of the Lewis acid catalyst is 0.01 to 10% by weight, more preferably 0.0 to 10% by weight based on the total weight of the compound represented by the formula (2) and the alkylene oxide used in the reaction.
It is in the range of 1 to 1% by weight.

As the polymerization inhibitor used in the present invention, BH
T. Unlike other phenolic polymerization inhibitors, BHT does not contribute to the oxyalkylene reaction, there is almost no loss due to the mixed metal oxide treatment, the hue after addition is colorless and transparent, and the urethane (meth) in the next step is used. ) Since it can be used as it is as a polymerization inhibitor during the acrylate reaction, there is an advantage that it is not necessary to additionally add it during the urethane reaction. The amount of BHT added is preferably in the range of 0.001 to 0.1% by weight based on the total weight of the compound represented by the formula (2) and the alkylene oxide used in the reaction. Another polymerization inhibitor may be added as a polymerization inhibitor, but if the amount added is too large, it may react with isocyanate during the urethane reaction.
pm or less is preferable. Examples of other polymerization inhibitors include hydroquinone and hydroquinone monomethyl ether.

The order of charging into the reaction vessel is usually preferably the order of the polymerizable compound represented by the formula (2), the polymerization inhibitor and the Lewis acid catalyst. The charging temperature is 25 ° C. in order to suppress the polymerization of the polymerizable compound represented by the formula (2).
It is the following. If the charging temperature exceeds 25 ° C, the viscosity in the reactor will increase with time after the addition of the Lewis acid catalyst, which is not preferable. An alkylene oxide having 2 to 4 carbon atoms is used in the reaction, and examples thereof include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. And one or two of these
A mixture of two or more kinds may be used, and a polymerization mode when two or more kinds are used may be a block type or a random type. The reaction is 25
After all the polymerizable compound represented by the formula (2), the polymerization inhibitor and the Lewis acid catalyst are charged in a reaction vessel at a temperature of not higher than 0 ° C., the reaction vessel is replaced with an inert gas such as nitrogen and the system is stirred. On the other hand, the alkylene oxide is injected under pressure at a temperature of -20 to 90 ° C, preferably 10 to 70 ° C for about 3 to 10 hours. When the reaction temperature is lower than -20 ° C, the reaction rate is very low, and when it is higher than 90 ° C, problems such as polymerization of the polymerizable group and coloring are likely to occur. In the case of a mixture of two or more alkylene oxides, when they are randomly added, they are mixed homogeneously and press-fitted little by little to react. Further, since the reactivity of tetrahydrofuran is inferior to that of other alkylene oxides, a method may be used in which the whole amount of tetrahydrofuran is charged into the reaction vessel before the reaction is started and then the alkylene oxide is injected little by little. In the case of block-wise addition, various alkylene oxides are press-fitted and reacted according to the order of addition.

As the composite metal oxide used in the method for producing a polymerizable compound of the present invention, magnesium oxide 20 to
It contains 80% by weight and 5 to 50% by weight of aluminum oxide. Preferably magnesium oxide 30-
70% by weight and 10 to 40% by weight of aluminum oxide, more preferably magnesium oxide 5
It contains 0 to 70% by weight and 25 to 40% by weight of aluminum oxide. By using the mixed metal oxide in this range, the Lewis acid catalyst, which is the reaction catalyst, is effectively removed, and it is effective in reducing the CPR of the product. The shape of the composite metal oxide is not particularly limited, but powdery one is preferable.

Commercially available composite metal oxides containing 20 to 80% by weight of magnesium oxide and 5 to 50% by weight of aluminum oxide are, for example, Kyoward 300, Kyoward 500 and Kyowa Chemical Co., Ltd. Word 1000, Kyoto Word 2000, Tomita Pharmaceutical Co., Ltd.
Manufactured by Tomix AD500 and the like. The representative compositions of the above commercial products are as follows. Kyo word 30
0 (26.4% by weight of magnesium oxide, 26.3% by weight of aluminum oxide), KYOWARD 500 (38.2% by weight of magnesium oxide, 16.1% by weight of aluminum oxide), KYOWARD 1000 (35.35% of magnesium oxide).
2% by weight, aluminum oxide 19.1% by weight), KYOWARD 2000 (magnesium oxide 59.2% by weight, aluminum oxide 33.0% by weight), Tomix AD50
0 (magnesium oxide 37.4% by weight, aluminum oxide 17.2% by weight). In the present invention, the composite metal oxide may be used alone or in combination of two or more. The amount of the composite metal oxide used is preferably 7 times by weight or more, more preferably 7 to 10 times by weight, based on the amount of the Lewis acid catalyst added. If the amount of the Lewis acid catalyst added is less than 7 times, the degree of purification is not sufficient, which is not preferable. Although the use amount is large, it does not affect the obtained product, but when the amount is 10 times or less, it is preferable to remove the complex metal oxide itself, and the yield of the polyalkylene glycol derivative is less likely to decrease.

In the treatment method using the composite metal oxide, the polymerizable compound and the composite metal oxide obtained by the reaction can be mixed or brought into contact with each other by any method, but it is preferable to bring them into contact with stirring. The order of addition is not particularly limited, but the composite metal oxide is usually added to the polymerizable compound obtained by the reaction. The treatment conditions are usually an oxygen concentration of 20 ±
Pressure of 0.133 to 6.67k while passing 5% gas
Pa (1 to 50 mmHg) for 1 to 6 hours, preferably 2
Do ~ 4 hours. If it is shorter than 1 hour, the CPR may not be sufficiently reduced, and if it is longer than 6 hours, no further effect may be observed. Processing temperature is usually 40-90
C., preferably 60 to 80.degree. If the temperature is lower than 40 ° C., the CPR is not sufficiently reduced, and unreacted alkylene oxide and other low molecular weight components remain, so that the product tends to have a slightly lowered viscosity. If the temperature is higher than 90 ° C., it may cause deterioration of the polyalkylene glycol derivative or a problem in stability of the polymerizable group. After the treatment, it is preferable to remove the complex metal oxide by a usual method such as filtration or centrifugation. The treatment with the complex metal compound is different from the method of dehydrating after neutralization,
It is possible to suppress the water content in the system to a low level, and it is possible to solve the problem that the dehydration time is usually long at a treatment temperature of 90 ° C. or lower.

The urethane (meth) acrylate of the present invention is prepared by placing a polymerizable compound represented by the formula (1) in a reaction vessel, adding a catalyst, and reacting with a polyisocyanate compound while passing a gas having an oxygen concentration of 20 ± 5%. You can do and get. In this urethane (meth) acrylate reaction system, BHT as a polymerization inhibitor is 0.001 to 0.1% by weight in the polymerizable compound represented by the formula (1).
Since it is included, it is not necessary to add it additionally.
The catalyst used here is mainly an organic tin compound, preferably tin octylate or tin laurate. The amount of the catalyst added is 0.1% of the total weight of the polymerizable compound represented by the formula (1) and the polyisocyanate compound.
It is desirable that the content is 001 to 0.1% by weight. The catalyst may be added at any time before the dropping of the polyisocyanate compound is started. The atmosphere in the reaction system has an oxygen concentration of 20 ± 5.
% Gas is preferably vented, more preferably dry air. For example, it is possible to use one dried by a condensation type air dryer or the like. If the drying is insufficient, water may be mixed in the reaction system to induce a reaction between the polyisocyanate compound and water, which may increase the viscosity of the obtained urethane (meth) acrylate. The temperature at the start of the reaction is 20 to 90 ° C., preferably 30
~ 80 ° C. If the temperature is lower than 20 ° C, a long time is required for the reaction, which may lead to a decrease in production efficiency.
If higher, polymerization reaction may occur or urethane (meta)
Acrylate may be colored.

The urethane reaction is carried out by adding a polyisocyanate compound. At this time, it is preferable to add the polyisocyanate compound dropwise. The urethane reaction is started by adding the polyisocyanate compound, and is completed by continuing the reaction as necessary after the addition is completed. The reaction time varies depending on the size and structure of the reaction vessel, but is 1 to 30 hours, preferably 1 to 20 hours. If it is shorter than 1 hour, the reaction may not be completed, and if it is longer than 30 hours, it may cause excessive heat history to urethane (meth) acrylate to cause polymerization, or it may lead to price increase due to deterioration of production efficiency. There is. The reaction temperature is usually 20 to 90 ° C, more preferably 30 to 80 ° C. If the temperature is lower than 20 ° C, a long reaction time is required, which may lead to a decrease in production efficiency. If it is higher than 90 ° C, a polymerization reaction may occur or the urethane (meth) acrylate may be colored. As a method for determining the completion of the reaction, a Fourier transform infrared absorption spectrophotometer (FT-IR) compliant with JIS K 0117 is used to measure that absorption due to an isocyanate group near 3100 cm ^-1 is no longer observed, JIS K 15
56 5.5 It confirms by the method of measuring the content of the isocyanate compound in a reaction product by the titration method based on 5.5. Regarding the latter, specifically, a method of extracting the reaction product from the reaction vessel, reacting it with di-n-butylamine, back titrating an appropriate amount of amine with hydrochloric acid, and measuring the content of the isocyanate compound in the reaction product. Is. The content of the isocyanate compound is calculated by this method, and the end point is when the content of the isocyanate compound is 0.5% by weight or less, preferably 0.1% by weight or less. The urethane (meth) acrylate produced as described above may be contaminated with foreign matter, and thus can be removed by filtration.

The urethane (meth) acrylate obtained by the production method of the present invention is a photocurable resin such as paint, adhesive, printing ink, letterpress material, stereolithography material, optical fiber coating material, electronic material and information recording material. It is very useful as a raw material, etc., and can be particularly suitably used as a fiber coating material.

[0021]

INDUSTRIAL APPLICABILITY The polymerizable compound of the present invention is a good raw material for urethanization in terms of CPR, water content, and pH, and is excellent in thermal stability, so that it can be suitably used as a urethane raw material. Further, the production method of the present invention makes it possible to produce the polymerizable compound having a high degree of purification more easily than ever before. The urethane (meth) acrylate, which is a reaction product of the polymerizable compound and the polyisocyanate compound obtained by the production method of the present invention, has excellent storage stability and handleability. Further, the production method of the present invention enables stable production of the polymerizable compound to urethane (meth) acrylate all at once.

[0022]

EXAMPLES The present invention will be described in more detail below by showing Examples and Comparative Examples of the present invention. In addition, hydroquinone monomethyl ether is represented as MQ. Example 1 A 5-liter autoclave equipped with a stirrer, a thermometer and a pressure gauge was kept at 25 ° C or lower, and 232 g (2.0 mol) of 2-hydroxyethyl acrylate, MQ.
0.468 g, 0.468 g of BHT, and 5.6 g of tin tetrachloride were added, and the system was replaced with nitrogen gas, and then 704 g (16.0 mol) of ethylene oxide was added at 1 MPa (1
The mixture was injected under pressure of 0.0 kg / cm ² ) or less and 55 ° C. or less over 4 hours, and the reaction was continued for 1 hour. Next, unreacted ethylene oxide was removed through a gas having an oxygen concentration of 20 ± 5%. After that, 40.3 g (7.2 times the amount of tin tetrachloride) of Kyoward 500 (38.2% by weight of magnesium oxide, 16.1% by weight of aluminum oxide) manufactured by Kyowa Chemical Industry Co., Ltd. was added, and the oxygen concentration was increased. While bubbling 20 ± 5% gas, it was treated under the conditions of 5 kPa and 70 ° C. for 4 hours. Next, Kyoward 500 was filtered to obtain 843 g of a polymerizable compound (polyethylene glycol (9.0) monoacrylate).

Example 2 A 5-liter autoclave equipped with a stirrer, a thermometer and a pressure gauge was kept at 25 ° C. or lower, and 260 g (2.0 mol) of 2-hydroxyethyl methacrylate, MQ.
0.263 g, BHT 0.263 g, and tin tetrachloride 4.8 g were put, and after the system was replaced with nitrogen gas, 616 g (14.0 mol) of ethylene oxide was stored at 1 MPa or less and 55 ° C. or less for 3 hours. Press-fit, then 1
The reaction continued for an hour. Next, unreacted ethylene oxide was removed while passing a gas having an oxygen concentration of 20 ± 5%. After that, Kyowaad 500 manufactured by Kyowa Chemical Industry Co., Ltd. (38.2% by weight of magnesium oxide, aluminum oxide 16.
15.0% by weight (7.3 times the amount of tin tetrachloride) was added, and the mixture was treated under conditions of 5 kPa and 70 ° C. for 3 hours while bubbling a gas having an oxygen concentration of 20 ± 5%. . Next, Kyoward 500 was filtered to obtain 797 g of a polymerizable compound (polyethylene glycol (8.0) monomethacrylate).

Example 3 A 5-liter autoclave equipped with a stirrer, a thermometer and a pressure gauge was kept at 25 ° C or lower, and 260 g (2.0 mol) of 2-hydroxypropyl acrylate, MQ.
0.47 g, BHT 0.47 g, and tin tetrachloride 6.3
After adding g and substituting the inside of the system with nitrogen gas, 684.4 g (11.8 mol) of propylene oxide was injected under pressure of 1 MPa or less and temperature of 55 ° C. or less over 6 hours, and the reaction was continued for another 2 hours. did. Next, unreacted propylene oxide was removed while passing a gas having an oxygen concentration of 20 ± 5%. After that, Kyowa Chemical 200 Kyoward 200
0 (59.2% by weight of magnesium oxide, 33.0% by weight of aluminum oxide) was added to 47.2 g (7.5 times the amount of tin tetrachloride) and 5 kPa while bubbling a gas having an oxygen concentration of 20 ± 5%. It was treated at 70 ° C. for 4 hours. Next, Kyoward 2000 was filtered to obtain 859 g of a polymerizable compound (polypropylene glycol (6.9) monoacrylate).

Example 4 A 5-liter autoclave equipped with a stirrer, a thermometer and a pressure gauge was kept at 25 ° C or lower, and 288 g (2.0 mol) of 2-hydroxypropyl methacrylate, MQ.
0.31 g, BHT 0.31 g, and tin tetrachloride 4.6
After adding g, the inside of the system was replaced with nitrogen gas, and 487.2 g (8.4 mol) of propylene oxide was injected under pressure of 1 MPa or less and temperature of 55 ° C. or less over 6 hours, and the reaction was continued for another 2 hours. did. Next, unreacted propylene oxide was removed while passing a gas having an oxygen concentration of 20 ± 5%. After that, Kyowa Chemical 200 Kyoward 200
0 (59.2% by weight of magnesium oxide, 33.0% by weight of aluminum oxide, containing no silicon dioxide).
Add 8 g (8.3 times the amount of tin tetrachloride), oxygen concentration 2
While bubbling 0 ± 5% gas, 5 kPa, 70
It was treated for 4 hours under the condition of ° C. Next, KYOWARD 200
0 was filtered to obtain 713 g of a polymerizable compound (polypropylene glycol (5.2) monomethacrylate).

Example 5 A 5-liter autoclave equipped with a stirrer, a thermometer and a pressure gauge was kept at 25 ° C or lower, and 260 g (2.0 mol) of 2-hydroxyethyl methacrylate, MQ.
0.232 g, BHT 0.232 g, and tin tetrachloride 4.1 g were put therein, and after the system was replaced with nitrogen gas, a mixture of ethylene oxide 212 g (4.8 mol) and propylene oxide 300 g (5.2 mol) was added. Pressurization was performed for 5 hours under the conditions of a pressure of 1 MPa or less and a temperature of 55 ° C. or less, and the reaction was continued for another 2 hours. Next, unreacted ethylene oxide and propylene oxide were removed while passing a gas having an oxygen concentration of 20 ± 5%. After that, Kyowa Chemical Industry Co., Ltd.
30.9 g of KYOWARD 500 (38.2% by weight of magnesium oxide, 16.1% by weight of aluminum oxide)
(7.5 times the amount of tin tetrachloride) added, oxygen concentration 20 ±
While bubbling 5% gas, it was treated at 5 kPa and 70 ° C. for 4 hours. Next, KYOWARD 500 was filtered to obtain a polymerizable compound (polyethylene glycol (3.
4) / polypropylene glycol (2.6) monomethacrylate, random binding type) (718 g) was obtained.

Comparative Example 1 Reaction was carried out under the same reaction conditions and reaction method as in Example 1 until the unreacted ethylene oxide was removed. Then 5
Add 34.1 g of a weight% sodium hydroxide aqueous solution, and add 5
It was dehydrated for 7 hours under the conditions of kPa and 70 ° C. The neutralized salt formed thereafter was filtered to obtain 835 g of a polymerizable compound (polyethylene glycol (9.0) monoacrylate). Comparative Example 2 The reaction was performed under the same reaction conditions and reaction method as in Example 2 until the unreacted ethylene oxide was removed. Then 5
Add 28.1 g of a weight% sodium hydroxide aqueous solution, and add 5
It was dehydrated for 6 hours under the conditions of kPa and 70 ° C. The neutralized salt formed thereafter was filtered to give 782 g of a polymerizable compound (polyethylene glycol (8.0) monomethacrylate).
Got

Comparative Example 3 Until the unreacted propylene oxide was removed, the reaction was carried out under the same reaction conditions and reaction method as in Example 3. afterwards,
Charge 66.1 g of a 5 wt% sodium hydroxide aqueous solution,
It was dehydrated for 6 hours under the conditions of 5 kPa and 70 ° C. The neutralized salt formed thereafter is filtered to obtain a polymerizable compound (polypropylene glycol (6.9) monoacrylate) 834.
g was obtained. Comparative Example 4 Until the unreacted propylene oxide was removed, the reaction was carried out under the same reaction conditions and reaction method as in Example 4. afterwards,
32.6 g of a 5 wt% sodium hydroxide aqueous solution was added,
It was dehydrated for 6 hours under the conditions of 5 kPa and 70 ° C. The neutralized salt formed thereafter was filtered to polymerize the polymerizable compound (polypropylene glycol (5.2) monomethacrylate) 69.
9 g was obtained.

Comparative Example 5 Until the unreacted ethylene oxide and propylene oxide were removed, the reaction was carried out under the same reaction conditions and reaction method as in Example 5. Then, 28.5 g of a 5 wt% sodium hydroxide aqueous solution was added, and the mixture was added at 6 kPa and 70 ° C.
It was dehydrated for an hour. The neutralized salt formed thereafter was filtered to obtain 690 g of a polymerizable compound (polyethylene glycol (3.4) / polypropylene glycol (2.6) monomethacrylate, random bond type). Table 1 shows the analysis results of the compounds obtained in Examples 1 to 5 and Comparative Examples 1 to 5.

[0030]

[Table 1]

* 1: Hue results of hue after storage at 100 ° C. for 2 hours. Examples 1 to 5 and Comparative Examples 1 to 5 are compared. The CPR of each of the polymerizable compounds produced according to the examples was 30 or less, which was significantly lower than the CPR of the comparative example. Furthermore, the water content was low, and the pH became more neutral. From these, the polymerizable compound of the present invention satisfies all the parameters specified in the present invention, the polymerizable compound obtained by the production method of the present invention is higher than that obtained by the conventional production method. It can be seen that a purified product is obtained.

Comparative Examples 6 to 8 The reaction was carried out under the same reaction conditions and method as in Example 1 until the unreacted ethylene oxide was removed. After that, 23.5 g, 28.0 g, and 32.5 g of Kyowaad 500 (38.2% by weight of magnesium oxide and 16.1% by weight of aluminum oxide) manufactured by Kyowa Chemical Industry Co., Ltd., respectively.
(4.2 times amount, 5.0 times amount and 5.8 times amount, respectively, with respect to tin tetrachloride), and while bubbling a gas having an oxygen concentration of 20 ± 5% under the conditions of 5 kPa and 70 ° C. It was treated for 4 hours. Next, Kyoward 500 was filtered to obtain each polymerizable compound (polyethylene glycol (9.0) monoacrylate). Table 1 shows the analysis results of the compounds obtained in Comparative Examples 6 to 8.

Analysis results and 1 for Comparative Examples 6 to 8
The results of the hue after 2 hours at 00 ° C. are shown in Table 1.
From the results of Table 1, in Comparative Examples 6 to 8 in which the amount of adsorbent added was smaller than that in Example 1, the pH was low and the CPR was slightly high because the Lewis acid as the catalyst was not sufficiently removed. Further, since the hue after storage at 100 ° C. for 2 hours is also deteriorated, it can be seen that the degree of purification is inferior.

Comparative Example 9 The reaction was carried out under the same reaction conditions and method as in Example 1 except that BHT was not added, and 830 g of the polymerizable compound of Comparative Example 9 (polyethylene glycol (9.0) monoacrylate) was added. Obtained. Comparative Example 10 The reaction was performed under the same reaction conditions and reaction method as in Example 2 except that BHT was not added, and 790 g of a polymerizable compound of Comparative Example 10 (polyethylene glycol (8.0) monomethacrylate) was obtained. The analysis results of the compounds obtained in Comparative Examples 9 to 10 are shown in Table 1, Examples 1 to 5 and Comparative Examples 9 to.
Table 2 shows the evaluation results of the storage stability of No. 10.

[0035]

[Table 2]

* 2: 50 g sample was taken in a 100 mL sample bottle and observed for liquid color and viscosity at 100 ° C. for each hour. From the results in Table 2, BHT was added at the time of reaction in Examples 1 to 1.
The polymerizable compound 5 had a slight change in liquid color even after 24 hours, but the viscosity did not increase. BHT during reaction
In Comparative Examples 9 and 10 in which was not added, the liquid color was already deteriorated and the viscosity started to increase after 10 hours, and the viscosity and the polymerization due to polymerization occurred after 24 hours. From these results, it is understood that the polymerizable compound obtained by the production method of the present invention has excellent stability.

Example 6 A 1-liter four-necked flask equipped with a stirrer and a thermometer was charged with 468 g of the polymerizable compound of Example 1 (polyethylene glycol (9.0) monoacrylate).
Add 0.2 g of tin octylate and add 84 g of hexamethylene diisocyanate (HMDI) using a dropping funnel at 70 ± 5 ° C. for 2 hours while passing a gas having an oxygen concentration of 20 ± 5%, and then for 1 hour. The reaction was continued and it was confirmed by titration that the residual isocyanate was 0.02% by weight. This was filtered to obtain 519 g of urethane diacrylate (a reaction product of polyethylene glycol (9.0) monoacrylate + HMDI + polyethylene glycol (9.0) monoacrylate).

Example 7 438 g of the polymerizable compound of Example 2 (polyethylene glycol (8.0) monomethacrylate) was placed in a 1 liter four-necked flask equipped with a stirrer and a thermometer, and tin octylate was added. 0.15g added, oxygen concentration 20 ±
Using a dropping funnel while passing 5% gas, 2,4
-87 g of tolylene diisocyanate (TDI) was added dropwise at 70 ± 5 ° C over 2 hours, and then the reaction was continued for 1 hour, and it was confirmed by titration that the residual isocyanate was 0.03% by weight. This is filtered and urethane dimethacrylate (polyethylene glycol (8.0) monomethacrylate + TDI + polyethylene glycol (8.
0) monomethacrylate reaction product) 494 g was obtained.

Example 8 472 g of the polymerizable compound of Example 3 (polypropylene glycol (6.9) monoacrylate) was placed in a 1 liter four-necked flask equipped with a stirrer and a thermometer, and tin octylate was added. Add 0.20g, oxygen concentration 20 ±
HMD using dropping funnel while passing 5% gas
After dropping I84 g at 70 ± 5 ° C. for 2 hours, the reaction was continued for 1 hour as it was, and it was confirmed by titration that the residual isocyanate was 0.05% by weight. This is filtered and urethane diacrylate (polypropylene glycol (6.
9) Monoacrylate + HMDI + Polypropylene glycol (6.9) Monoacrylate reaction product) 511 g
Got

Comparative Example 11 Example 6 except that the polymerizable compound of Comparative Example 9 (polyethylene glycol (9.0) monoacrylate) was used.
Perform the same operation as for urethane diacrylate (polyethylene glycol (9.0) monoacrylate + HMD
505 g of a reaction product of I + polyethylene glycol (9.0) monoacrylate was obtained. Comparative Example 12 The procedure of Example 6 was repeated except that the polymerizable compound of Comparative Example 10 (polyethylene glycol (8.0) monomethacrylate) was used, and urethane dimethacrylate (polyethylene glycol (8.0) monomethacrylate +
490 g of a reaction product of TDI + polyethylene glycol (8.0) monomethacrylate was obtained.

Comparative Example 13 A urethane diacrylate was prepared in the same manner as in Example 6 except that the polymerizable compound (polypropylene glycol (6.9) monoacrylate) produced in the same manner as in Example 3 except that BHT was not added. (Polypropylene glycol (6.9) monoacrylate + HMDI
+ 509 g of polypropylene glycol (6.9) monoacrylate reaction product) was obtained. Table 3 shows the analysis results of the compounds obtained in Examples 6 to 8 and Comparative Examples 11 to 13.

[0042]

[Table 3]

* 1: TDI has a benzene ring and is not measured because it causes blur in the measurement of bromine number. * 2: TPR of Example 3 and Comparative Example 3 were adjusted so that the calculated CPR values would be these values. Blending of polymerizable compound * 3: Value calculated by blending ratio of Example 3 and Comparative Example 3. From the results of Table 3, Examples 6 to 8 and Comparative Examples 11 to 13
The CPR and water content of the polymerizable compound before the reaction are almost the same in the corresponding Example and Comparative Example, respectively. Nevertheless, after reacting with isocyanates, Comparative Examples 11-1
In Comparative Example 3, the value of kinematic viscosity was increased and the bromine number was decreased by about 2 to 3 as compared with Examples 6 to 8. This is probably because the polymerizable compound caused some polymerization. Further, although the hues were also slight, Comparative Examples 11 to 13 were worse.
From the above, it is understood that the urethane (meth) acrylate obtained by the reaction of the polymerizable compound obtained by the production method of the present invention and isocyanate has excellent handleability and stability.

Comparative Example 14 152.1 g of the polymerizable compound of Example 3 (polypropylene glycol (6.9) monoacrylate) was placed in a 1-liter four-necked flask equipped with a stirrer and a thermometer.
And 93.9 g of the polymerizable compound of Comparative Example 3 (polypropylene glycol (6.9) monoacrylate) were added and well stirred to prepare a polymerizable compound having a calculated CPR of 35. Then, it was confirmed that the water content was 0.05% after dehydration treatment was performed at 5 kPa and 70 ° C. for 3 hours while cooling with a gas having an oxygen concentration of 20 ± 5%. Then, with respect to 236 g of these, the same operation as in Example 8 was carried out,
Urethane diacrylate (a reaction product of polypropylene glycol (6.9) monoacrylate + HMDI + polypropylene glycol (6.9) monoacrylate) 2
50 g was obtained.

Comparative Example 15 In a 1-liter four-necked flask equipped with a stirrer and a thermometer, 107.4 g of the polymerizable compound of Example 3 (polypropylene glycol (6.9) monoacrylate) was used.
And 138.6 g of the polymerizable compound of Comparative Example 3 (polypropylene glycol (6.9) monoacrylate) were added and well stirred to prepare a polymerizable compound having a calculated CPR of 50. Then, it was confirmed that the water content was 0.05% after dehydration treatment was performed at 5 kPa and 70 ° C. for 3 hours while cooling with a gas having an oxygen concentration of 20 ± 5%. Then, with respect to 236 g of this, the same operation as in Example 8 was carried out to obtain urethane diacrylate (a reaction product of polypropylene glycol (6.9) monoacrylate + HMDI + polypropylene glycol (6.9) monoacrylate).
246 g were obtained.

Comparative Example 16 In a one-liter four-necked flask equipped with a stirrer and a thermometer, 246 g of the polymerizable compound of Comparative Example 3 (polypropylene glycol (6.9) monoacrylate) was collected, and the oxygen concentration was 20. 5kPa while passing ± 5% gas,
After dehydration treatment at 70 ° C for 3 hours and cooling, the water content is 0.0
It was confirmed to be 5%. And 236g of this
Was carried out in the same manner as in Example 8 to obtain 230 g of urethane diacrylate (a reaction product of polypropylene glycol (6.9) monoacrylate + HMDI + polypropylene glycol (6.9) monoacrylate). Table 3 shows the analysis results of the compounds obtained in Comparative Examples 14 to 16.

From the results shown in Table 3, in Comparative Examples 15 and 16 in which the polymerizable compound having a high CPR was used, a phenomenon was observed in which the reaction temperature rapidly increased to 70 ° C. or higher in the course of the reaction. Further, as compared with Example 8, the finally obtained substance had a considerably high viscosity, the bromine number decreased as the CPR increased, and the hue slightly deteriorated. From these facts, it was suggested that when the CPR is high, a rapid reaction may occur during the urethane reaction, so that a part of the terminal polymerizable group may be polymerized. On the other hand, in Comparative Example 14, the reaction was performed using a polymerizable compound having a CPR adjusted to 35, but it was found that even in this case, both the viscosity and the bromine number were slightly worse than in Example 8. From these, it can be seen that good urethane (meth) acrylate can be obtained by using a polymerizable compound having a CPR of 30 or less.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 71/02 C08L 71/02 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Yoshifumi Kubo 8-5-3-333 F-term, Yokosuka City, Kanagawa Prefecture (reference) 4H006 AA01 AA02 AB46 AC43 AC48 BA06 BA09 BA30 BA94 BC10 BC32 BN10 BP10 KA19 4H039 CA60 CA61 CA66 CF90 4J002 CH051 EJ026 FD036 GH00 GH01 G00G00 G00 GP00 GQ GQ01 G00 GP00 GQ AA12 BA00 BB01 BB02 BD05

Claims (4)

[Claims] 1. Containing 10 ppm or more of 2,6-t-butyl-4-methylphenol, CPR of 30 or less, pH.
Is a polymerizable compound represented by the formula (1) wherein 4.5 to 7. XO (AO) _n H (1) (X is an acryloyl group or a methacryloyl group,
AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is 2-1.
00. ) 2. A urethane (meth) acrylate obtained by reacting the polymerizable compound according to claim 1 with a polyisocyanate compound. 3. A Lewis acid catalyst is used, the temperature at the time of charging the raw materials is 25 ° C. or lower, and 2,6-t-as a polymerization inhibitor.
A complex metal oxide containing 20 to 80% by weight of magnesium oxide and 5 to 50% by weight of aluminum oxide after ring-opening polymerization of an alkylene oxide with a compound represented by the formula (2) in the presence of butyl-4-methylphenol. The method for producing a polymerizable compound represented by the formula (1), characterized in that 7 times by weight or more of the Lewis acid catalyst is added for treatment. XO (AO) _n H (1) (X is an acryloyl group or a methacryloyl group,
AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is 2-1.
00. ) XO (AO) _l H (2) (X is an acryloyl group or a methacryloyl group,
AO is an oxyalkylene group having 2 to 4 carbon atoms, and 1 is 1 to 9
9) 4. The polymerizable compound represented by the formula (1) obtained in claim 3 in the presence of an organotin compound as a catalyst, 3
A method for producing a urethane (meth) acrylate, which comprises reacting a polyisocyanate compound at a temperature of 0 to 80 ° C.