JPH07126222A - Hydroxyl-containing acrylic monomer having carbonate linkage - Google Patents

Abstract

PURPOSE:To obtain a new acrylic monomer with the OH group situated further apart from the carbon-carbon bond serving as polymerization point compared to the case with the starting material, by binding a OH-contg. group thereto through chemically stable carbonate linkage(s). CONSTITUTION:The acrylic monomer of formula I (R<1> is H or methyl; R<2>-R are each 2-8C alkylene chain; n is O or an integer of 1-6), e.g. 2-hydroxyethyl acrylate's neopentyl glycol carbonate adduct can be obtained by reaction between a hydroxyalkyl (meth)acrylate of formula II or a lactone adduct thereof and a cyclic carbonate compound of formula III in the presence of a catalyst.

Description

Detailed Description of the Invention

[0001] Acrylic polymers with a background hydroxyl in this invention are widely used as a thermosetting resin can be made to cure by means of an external crosslinking agent such as melamine resin or polyisocyanate compound. In this case, it is known that the higher the position of the hydroxyl group is from the polymer main chain composed of carbon-carbon bonds, the higher the reactivity is. One of them is a lactone adduct of hydroxyalkyl (meth) acrylate, for example, Praxel FA and FM series manufactured by Daicel Chemical Industries, Ltd. The pendant group containing a hydroxyl group in the polymer is an ester bond which is relatively easily hydrolyzed. It is bonded to the main chain through, and there is a problem that the improvement of water resistance is limited.

In the acrylic monomer of the present invention, the position of the hydroxyl group is farther from the polymer main chain than that of the hydroxyalkyl (meth) acrylate / lactone adduct, and the pendant group having the hydroxyl group is chemically stable to form a carbonate bond. To give the polymer.

DISCLOSURE OF THE INVENTION According to the present invention, an acrylic monomer having a hydroxyl group-containing group bonded by a chemically stable carbonate bond, and the hydroxyl group is located farther from the carbon-carbon bond which is a polymerization point than the starting material. Will be provided.

The monomer has the formula

[Chemical 2] (In the formula, R ¹ is a hydrogen atom or methyl, R ² , R ³ and R ⁴ are independently an alkylene chain having 2 to 8 carbon atoms, n is 0 or an integer of 1 to 6, and m is an integer of 1 to 6. There is).

The monomer also has the formula

[Chemical 3] (Wherein R ¹ , R ² , R ³ and n are the same as above), and a hydroxyalkyl (meth) acrylate or a lactone adduct thereof,

[Chemical 4] (In the formula, R ⁴ is the same as above.) The compound can be synthesized by reacting with a cyclic carbonate compound in the presence of a catalyst.

The hydroxyalkyl (meth) acrylate or the lactone adduct thereof which is a starting material includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl. It is an adduct obtained by ring-opening addition (polymerization) of a corresponding lactone using a (meth) acrylate and such a hydroxyalkyl (meth) acrylate as an initiator. Various ε-caprolactone addition (polymerization) products of hydroxyethyl (meth) acrylate are commercially available from Daicel Chemical Industries, Ltd. as Praxel FA and FM series.

The other raw material, cycloaliphatic carbonate, is a method of depolymerizing a polymer obtained by the reaction of glycol and dialkyl carbonate (JP-A-2-5).
6356), or by reacting the corresponding alkylene oxide with carbon dioxide. The cyclic carbonate has a 5-membered ring, a 6-membered ring or a 7-membered ring structure, and specific examples thereof include ethylene carbonate as a 5-membered ring, 1,3-propylene carbonate and neopentyl glycol carbonate (5,5 membered ring as a 6-membered ring. −
It can be named dimethyl-1,3-dioxan-2-one. ) And 7-membered rings include 1,4-butanediol carbonate and the like. Neopentyl glycol carbonate is preferred. The reason for this is that this compound can be synthesized from raw materials that are industrially easily available in relatively short steps, is stable under normal conditions, but is relatively mild in the presence of a catalyst under relatively mild conditions. Another reason is that a ring-opening addition reaction with the lactone adduct is carried out.

The charged amount of the cycloaliphatic carbonate with respect to the hydroxyalkyl (meth) acrylate or the lactone adduct thereof may be 1: 0.5 or more in molar ratio.
When charged in excess of 1: 1, at least part of the cyclic carbonate undergoes ring-opening addition polymerization.

Examples of the catalyst used in the present invention include organic tin compounds such as dibutyltin oxide, dibutyltin dilaurate, monobutyltrichlorotin, dibutyldichlorotin, tributyl monochloross, and hydroxybutyltin oxide, and further stannous chloride and stannic bromide. 1 stannous, stannous iodide, etc. can be used. Furthermore, phosphotungstic acid and silicotungstic acid can also be used. Also, strong acid cation exchange resins such as Amberlyst 15, hydrogen fluoride, hydrogen chloride, hydrogen bromide, sulfuric acid, p
-Toluenesulfonic acid, dodecylbenzenesulfonic acid,
Bronsted acids such as methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid and the like can be mentioned.
Also, as a Bronsted acid anion onium salt,
Onium salts of nitrogen, sulfur, phosphorus or iodine are mentioned. Below are some typical examples.

(I) Quaternary ammonium salt type compound: N,
N-dimethyl-N-benzylanilinium antimony hexafluoride N, N-diethyl-N-benzylanilinium boron tetrafluoride N, N-diethyl-N-benzylpyridinium antimony hexafluoride N, N-diethyl-N- Benzylpyridinium trifluoromethanesulfonic acid N, N-dimethyl-N- (4-methoxybenzyl) pyridinium antimony hexafluoride N, N-diethyl-N- (4-methoxybenzyl) pyridinium antimony hexafluoride N, N-diethyl- N- (4-methoxybenzyl) toludinium antimony hexafluoride N, N-dimethyl-N- (4-methoxybenzyl) toludinium antimony hexafluoride (ii) Sulfonium salt type compound: triphenylsulfonium boron tetrafluoride triphenylsulfonium Antimony hexafluoride Trifehel sulfonium arsenic hexafluoride ADEKA CP-66 (manufactured by Asahi Denka Kogyo) ADEKA CP-77 (manufactured by Asahi Denka Kogyo) Tri (4-methoxyphenyl) sulfonium hexafluoroarsenic diphenyl (4-phenylthiophenyl) sulfonium hexafluoride Arsenic Iodide (iii) Phosphonium salt type compound: Ethyltriphenylphosphonium antimony hexafluoride Tetrabutylphosphonium antimony hexafluoride (iv) Iodonium salt type compound: Diphenyliodonium hexafluoroarsenic di-4-chlorophenyliodonium hexafluoroarsenic di -4-Bromphenyl iodonium arsenic hexafluoride Di-p-tolyl iodonium arsenic hexafluoride Phenyl (4-methoxyphenyl) iodonium arsenic hexafluoride

The anionic components of the above-mentioned onium salts include, for example, acetic acid, propionic acid, octanoic acid, lauric acid, stearic acid and other aliphatic carboxylic acids, benzoic acid and other aromatic carboxylic acids, benzenesulfonic acid, toluenesulfone. An acid, an aromatic sulfonic acid such as dodecylbenzenesulfonic acid, or an onium salt substituted with an anionic component such as perchloric acid may be used.

Alkali alkali metals such as n-butyllithium and sec-butyllithium, Li- and Na
Alkali metal alcoholates such as-, K-ethylate, -butyrate, -isobutyrate, -t-butyrate and -octylate are also effective catalysts. In addition, diethylamine, triethylamine, dibutylamine, N,
Amines such as N-dimethylcyclohexylamine, dimethylbenzylamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] -7-undecene are also effective catalysts.

The amount of catalyst added is 1 ppm to 5%, preferably 5 to 5000 ppm.

When the amount of the catalyst added is less than 1 ppm, the polymerization reaction rate is extremely slow and has no practical meaning.
On the other hand, if it exceeds 5%, many side reactions due to decarboxylation or transesterification occur, which is not preferable.

The reaction temperature is generally room temperature to 150 ° C., though it depends on the kinds of starting monomers and catalysts.

The reaction is solvent-free or aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane and dichloroethane, and tetrahydrofuran. , An ether such as 1,4-dioxane, or an aprotic organic solvent such as acetonitrile, nitrobenzene, or nitromethane.

The use of a solvent has the effect of lowering the viscosity of the reaction crude liquid in the system after completion of the reaction, and makes the temperature uniform during the reaction by making the system uniform. Is. The amount of the inert solvent used is 5 to
It is 80% by weight, preferably 10 to 50% by weight.

When the amount of the solvent used is more than 80% by weight, the reaction becomes slow, which is not preferable. On the contrary, if the amount of the solvent used is less than 5% by weight, the effect of decreasing the viscosity is small.

Usually, the reaction is carried out by charging the reactor with the solvent, the acrylic monomer, the cyclic carbonate compound and the catalyst in this order, and then raising the temperature within the above-mentioned temperature range.

The end point of the addition reaction of the aliphatic cyclic carbonate is carried out by gas chromatography, and usually the time point when the concentration of the aliphatic cyclic carbonate becomes 1% or less is regarded as the end point of the reaction.

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 A 2-hydroxyethyl acrylate (2-H) was placed in a four-necked flask equipped with an air inlet tube, a thermometer, a cooling tube, and a stirring device.
EA) 1.371 g, neopentyl glycol carbonate 1.950 g, hydroquinone monomethyl ether 0.019 g as a polymerization inhibitor, and stannous chloride (SnCl ₂ ) 0.003 g as a reaction catalyst were added, and the mixture was reacted at 115 ° C. for 25 hours while passing air. Let

When the reaction was traced by ¹ H-NMR, the reaction rate of neopentyl carbonate was 69.7%. The color of the reaction product was 100 (APHA).

The GPC pattern of the obtained product was as follows: unreacted neopentyl glycol (28.789 minutes) and unreacted 2-hydroxyethyl acrylate (28.277).
Min), a 1-mole neopentyl glycol carbonate adduct of 2-hydroxyethyl acrylate (26.237
Min), 2 mol adduct (25.145 min), 3 mol adduct (24.415 min), and mixtures of more adducts.

In ¹ H-NMR, 0.938 to 1.01
The peak seen at 1 ppm is a methyl group due to ring opening of neopentyl glycol carbonate, 1.139 ppm.
The peak seen at 2 supports the methyl groups of unreacted neopentyl glycol carbonate. 3.358-3.
The peak seen at 374 ppm is the methylene group adjacent to the terminal hydroxyl group of the 2-HEA adduct, 3.819-3.
The peaks seen at 877 ppm and 4.292 to 4.343 ppm support the methylene groups of unreacted HEA.

The peak seen at 3.968 to 4.015 ppm supports the methylene group due to ring opening of neopentyl glycol carbonate, and the peak seen at 4.079 ppm supports the methylene group of unreacted neopentyl glycol carbonate.

The peaks seen at 4.389-4.411 ppm support the methylene groups of the 2-HEA adduct.
The peak seen at 5.853 to 6.574 ppm is H
It is presumed to be the acrylic group of the EA adduct and the acrylic group of unreacted 2-HEA, and it is supported that the obtained product is a product in which neopentyl glycol carbonate is ring-opened by 2-HEA.

Example 2 A reactor similar to that of Example 1 was charged with 1.950 g of 2-hydroxyethyl methacrylate (2-HEMA), 1.950 g of neopentyl glycol carbonate and 0.019 of hydroquinone monomethyl ether as a polymerization inhibitor.
g, hydroxybutyltin oxide as a reaction catalyst 0.
004 g was added, and the mixture was reacted at 115 ° C. for 27 hours while passing air.

When the reaction was traced by ¹ H-NMR, the reaction rate of neopentyl glycol carbonate was
It was 89.8%. The color of the reaction product is 120 (APH
It was A).

Example 3 In the same reactor as in Example 1, 1.371 g of 2-hydroxyethyl acrylate (2-HEA), 1.950 g of neopentyl glycol carbonate, 0.019 g of hydroquinone monomethyl ether as a polymerization inhibitor, and the reaction were carried out. 0.003 g of p-toluenesulfonic acid was added as a catalyst, and the mixture was reacted at 115 ° C. for 25 hours while passing air.
When the reaction was traced by ¹ H-NMR, the reaction rate of neopentyl glycol was 95.7%. The color of the reaction product was 100 (APHA).

Example 4 In the same reactor as in Example 1, 1.371 g of 2-hydroxyethyl acrylate (2-HEA), 1.949 g of neopentyl glycol carbonate, 0.019 g of hydroquinone monomethyl ether as a polymerization inhibitor, and the reaction were carried out. 0.003 g of sodium ethoxide was added as a catalyst, and the mixture was reacted at 115 ° C. for 25 hours while passing air.
When the reaction was traced by ¹ H-NMR, the reaction rate of neopentyl carbonate was 79.6%. The color of the reaction product was 90 (APHA).

Example 5 In the same reaction apparatus as in Example 1, 1.371 g of 2-hydroxyethyl acrylate (2-HEA), 1.949 g of neopentyl glycol carbonate, 0.019 g of hydroquinone monomethyl ether as a polymerization inhibitor, and the reaction were carried out. 0.009 g of triethylamine was added as a catalyst, and the mixture was reacted at 115 ° C. for 25 hours while passing air. Reaction
It was 62.4% when traced by ¹ H-NMR. The color of the reaction product was 120 (APHA).

Example 6 In the same reaction apparatus as in Example 1, 2.6 g of 2-hydroxyethyl methacrylate, 2.6 g of neopentyl glycol carbonate, 0.026 g of hydroquinone monomethyl ether as a polymerization inhibitor, and p-toluene as a reaction catalyst were used. Sulfonic acid.1H ₂ O (0.038 g) was added, and the mixture was heated with stirring at 40 ° C for 120 minutes while passing air. ¹ H-
From the NMR and IR spectra, it was confirmed that the product was mainly a starting material as a monomer obtained by ring-opening addition polymerization of 2 mol of neopentyl glycol carbonate.

Example 7 In the same reactor as in Example 1, 5.2 g of 2-hydroxypropyl acrylate, 5.2 g of neopentyl glycol carbonate, 0.052 g of hydroquinone monomethyl ether as a polymerization inhibitor, and p-toluene as a reaction catalyst were added. 0.076 g of sulfonic acid · 1H ₂ O was added, and the mixture was heated with stirring at 40 ° C. for 18 hours while passing air. ¹ H-N
MR and IR spectra confirmed that the product was primarily a starting material with 1 mol of neopentyl glycol carbonate ring-opening added.

Example 8 A reactor similar to that of Example 1 was charged with 2.88 g of 4-hydroxybutyl acrylate, 2.6 g of neopentyl glycol carbonate, 0.027 g of hydroquinone monomethyl ether as a polymerization inhibitor, and p-toluene as a reaction catalyst. 0.038 g of sulfonic acid · 1H ₂ O was added, and the mixture was stirred at 40 ° C. for 60 minutes while passing air. ^{From the 1} H-NMR and IR spectra, it was confirmed that the product was a monomer mainly obtained by ring-opening addition polymerization of 2 mol of neopentyl glycol carbonate.

Example 9 12.688 g of Praxel FM-1 (manufactured by Daicel Chemical Industries, Ltd.) and neopentyl glycol carbonate were placed in a four-necked flask equipped with an air inlet tube, a thermometer, a cooling tube, and a stirrer. 414 g was added, and p was added as a reaction catalyst.
- toluenesulfonic acid · IH ₂ O added 0.049 g, heated and stirred for 60 minutes at 40 ° C.. After completion of the reaction, the reaction solution was cooled and the precipitated solid was filtered off.

As for the ¹ H-NMR and IR spectra, the product was mainly obtained from 2 {[6-, in which 1 mol of neopentyl glycol carbonate was subjected to ring-opening addition to Praxel FM-1.
Support (3-hydroxy-2,2-dimethylpropyl) oxycarbonyloxy] caproyl} ethylmethacrylate.

Example 10 12.688 g of Praxel FM-1 (manufactured by Daicel Chemical Industries, Ltd.) and 3.414 g of neopentyl glycol carbonate were added to the same reaction apparatus as in Example 9, and Amberlyst 15 was used as a reaction catalyst. Add 0.049g,
The mixture was heated and stirred at 40 ° C. for 60 minutes. After completion of the reaction, the reaction solution was cooled and the precipitated solid was filtered off. The product was consistent with that of Example 9.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinya Yamada 19-17 Ikedanaka-cho, Neyagawa City, Osaka Prefecture Japan Paint Co., Ltd. (72) Inventor Takaaki Fujiwa 4-13-5 Kunami, Otake City, Hiroshima Prefecture (72) ) Inventor Hideki Matsui 4-13-5 Kuba, Otake City, Hiroshima Prefecture (72) Inventor Takeharu Tabuchi 4-4-1 Kuma, Otake City, Hiroshima Prefecture

Claims (3)

[Claims] 1. The formula: (In the formula, R ¹ is a hydrogen atom or methyl, R ² , R ³ and R ⁴ are independently an alkylene chain having 2 to 8 carbon atoms, n is 0 or an integer of 1 to 6, and m is an integer of 1 to 6. .) Acrylic monomer having. 2. n is 0 and R ⁴ is 2,2-dimethyl-
The acrylic monomer according to claim 1, which is a 1,3-propylene chain and m is an integer of 1 to 3. 3. R ³ is a 1,5-pentylene chain, n is an integer of 1 to 3, and R ⁴ is 2,2-dimethyl-1,3.
An acrylic monomer according to claim 1, which is a propylene chain and m is an integer from 1 to 3.