JPS629579B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing oligo(meth)acrylate. For more details, see (meta)
The present invention relates to a method for stably producing oligo(meth)acrylate from acrylic acid, polybasic carboxylic acid anhydride, and alkylene oxide.
In this specification, the term (meth)acrylic acid is used as a general term for acrylic acid and/or methacrylic acid, and also refers to acrylic acid and/or methacrylic acid, polybasic carboxylic acid anhydrides, and alkylene oxides. The term oligo(meth)acrylate will be used as a general term for ester oligomers having an acrylic ester group and/or a methacrylic ester group produced by the reaction. Oligo(meth)acrylate is usually 70-150℃
It is produced by a method in which (meth)acrylic acid, a polybasic carboxylic acid anhydride, and an alkylene oxide are reacted in the presence of a catalyst and a radical polymerization inhibitor at a temperature range of . However, since (meth)acrylic acid and oligo(meth)acrylates produced by reaction have high radical polymerizability, troubles such as abnormal thickening or gelation of the entire system during the manufacturing reaction are likely to occur. Such troubles are particularly likely to occur when using commonly used iron-based reaction equipment or raw materials stored in iron-based containers, and become a major problem in the production of oligo(meth)acrylates. ing. On the other hand, in order to prevent troubles during this type of production reaction, if the amount of a normal polymerization inhibitor such as hydroquinone is increased,
A new problem arises in that the obtained oligo(meth)acrylate has significantly poor curing reactivity when used. In view of the current situation, the present inventors have discovered that the entire system may become abnormally thick during the reaction when producing oligo(meth)acrylate from (meth)acrylic acid, polybasic carboxylic acid anhydride, and alkylene oxide. As a result of intensive research into ways to prevent troubles such as gelation, the inventors discovered that the above troubles could be prevented by coexisting a specific compound with chelate-forming ability in the reaction system, leading to the completion of the present invention. . Therefore, the object of the present invention is to provide (meth)acrylic acid,
It is an object of the present invention to provide a method for stably producing oligo(meth)acrylate from polybasic carboxylic acid anhydride and alkylene oxide without causing troubles such as abnormal thickening and gelation. That is, the method for producing oligo(meth)acrylate of the present invention comprises (meth)acrylic acid (A), polybasic carboxylic acid anhydride (B), and alkylene oxide (C).
70 in the presence of a catalyst and a radical polymerization inhibitor
Oligo(meth) reacted at a temperature range of ~150℃
In the method for producing acrylates, o-nitrosophenols, nitrosonaphthols, carboxypyridines, 8-hydroxyquinolines, carboxyquinolines, hydroxynaphthyridines, amino acids, aminopolycarboxylic acids, polyaminopolycarboxylic acids and 2,2 It is characterized in that one or more compounds (D) having chelate-forming ability selected from '-bipyridine are allowed to coexist in the reaction system. The (meth)acrylic acid used in the present invention is acrylic acid and/or methacrylic acid as described above. Commercially available acrylic acid and methacrylic acid can be used. Polybasic carboxylic anhydride (B) refers to a compound containing at least one carboxylic anhydride group in one molecule, such as phthalic acid, succinic acid, maleic acid, tetrahydrophthalic acid, hexahydrophthalic acid, , 6-endomethylenetetrahydrophthalic acid, 3,6-endomethylenehexahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, alkenylsuccinic acid,
Anhydrides of dicarboxylic acids such as 3,6-endodichloromethylenetetrachlorophthalic acid, tetrabromophthalic acid, and tetrachlorophthalic acid, or anhydrides of trivalent or higher carboxylic acids such as trimellitic acid, pyromellitic acid, butyltetracarboxylic acid, etc. I can name things. Alkylene oxide (C) refers to a compound having at least one epoxy group in one molecule, such as ethylene oxide, propylene oxide,
Examples include styrene oxide, cyclohexylene oxide, phenyl glycidyl ether, allyl glycidyl ether, methacrylic acid glycidyl ester, acrylic acid glycidyl ester, acetic acid glycidyl ester, epichlorohydrin, epibromhydrin, tribromophenyl glycidyl ether, etc. . Moreover, instead of some of these compounds, compounds having two or more epoxy groups in one molecule (for example, compounds collectively referred to as so-called epoxy resins) can be used as a modifier. The usage ratios of (meth)acrylic acid (A), polybasic carboxylic anhydride (B), and alkylene oxide (C) vary depending on the intended use of the oligo(meth)acrylate. Although not particularly limited, the very general ratio of use is 0.5 to 15 moles of polybasic carboxylic acid anhydride (B) and alkylene oxide to 1 mole of (meth)acrylic acid (A).
(C) 1 to 20 moles. As the catalyst used for reacting (meth)acrylic acid (A), polybasic carboxylic acid anhydride (B), and alkylene oxide (C), those commonly used in the technical field can be used. . Such catalysts include, for example, metal hydroxides such as potassium hydroxide and lithium hydroxide; metal halides such as lithium chloride, potassium bromide, tin chloride, potassium chloride, lithium bromide, zinc chloride, and zirconium chloride. Class: ethanolamine, laurylamine, aniline, dibutylamine, morpholine, piperidine, diphenylamine, triethylamine, dimethylaniline, triethylenediamine, pyridine, diethylamine hydrochloride, dimethylamine acetate, trimethylamine hydrochloride, tetramethylammonium bromide, trimethylbenzyl Amines such as ammonium chloride, their inorganic and organic acid salts, and quaternary ammonium salts; amides such as N,N-dimethylformamide; alkali metal salts of organic acids such as potassium acetate and sodium phthalate; benzenephosphon Acids, phosphonic acids and phosphonium salts such as triphenylmethylphosphonium iodide; sulfonic acids and sulfonium salts such as para-toluenesulfonic acid and triphenylsulfonium chloride; Lewis acid type compounds such as boron trifluoride, etc. One type or two or more types of these compounds can be used. Among these, compounds selected from the group consisting of amines, their inorganic acid salts, organic acid salts, and quaternary ammonium salts can be used as particularly advantageous catalysts because they cause fewer side reactions. The amount of such a catalyst used is usually in the range of 0.0001 to 5 parts by weight, based on 100 parts by weight of the total amount of (meth)acrylic acid (A), polybasic carboxylic acid anhydride (B), and alkylene oxide (C). is the amount of the ratio of In the reaction of (meth)acrylic acid (A), polybasic carboxylic acid anhydride (B), and alkylene oxide (C), a radical polymerization inhibitor is used together with the above-mentioned catalyst. A radical polymerization inhibitor is usually added to acrylic acid (A) to prevent it from polymerizing during storage, so polybasic carboxylic acid anhydride (B) and alkylene oxide (C)
It is also possible to carry out the reaction without adding a radical polymerization inhibitor again during the reaction. However, it can be further added and used if necessary. Such radical polymerization inhibitors include:
For example, quinones such as p-benzoquinone, naphthoquinone, paratoluquinone, 2,5-diphenyl-p-benzoquinone, 2,6-dichloroquinone; hydroquinone, p-t-butylhydroquinone, toluhydroquinone, catechol, p-t-butylcatechol , polyhydric phenols such as tetrachlorohydroquinone, pyrogallol, and hydroquinone monomethyl ether, and their alkyl ethers; phenols such as di-t-butyl p-cresol and phenol; copper salts such as copper naphthenate and copper chloride; picrylic acid , dinitrophenol, trinitrotoluene, and the like, and one or more of these compounds can be used. The amount of such radical polymerization inhibitor to be used, including the amount of radical polymerization inhibitor used in (meth)acrylic acid (A), polybasic carboxylic acid anhydride, etc. The total amount of compound (B) and alkylene oxide (C) is
The amount is usually in the range of 0.0001 to 0.5 parts by weight per 100 parts by weight. In the present invention, the reaction of (meth)acrylic acid (A), polybasic carboxylic acid anhydride (B) and alkylene oxide (C) is carried out within a temperature range of 70 to 150°C. When the reaction temperature is higher than this range, the reaction system tends to gel, and when it is lower than this range, the reaction takes a long time, both of which are unfavorable. When reacting (meth)acrylic acid (A), polybasic carboxylic acid anhydride (B), and alkylene oxide (C), these three components can be reacted simultaneously, or (meth) After reacting acrylic acid (A) and a part of alkylene oxide (C) in advance as a first stage reaction, polybasic carboxylic acid anhydride (B) and alkylene oxide (C) are further reacted as a second stage reaction.
The reaction may be carried out by adding the remainder of the reaction mixture, or furthermore, this latter stage reaction may be further divided into several stages and the reactions may be carried out sequentially. The compound (D) having chelate-forming ability used in the present invention includes one or more compounds selected from various compounds represented by the compounds shown below and 2,2'-bipyridine. It consists of a compound. In other words, the various compounds include O-nitrosophenols such as o-nitrosophenol, 4-methyl-O-nitrosophenol, and 5-t-butyl-O-nitrosophenol; 2-nitroso-1-naphthol, 5-methyl -2-nitroso-1-naphthol, 1-nitroso-2-naphthol, 6-t-butyl-1-nitroso-2-naphthol, 3,6-di(sodium sulfo)-1-nitroso-2-naphthol (nitroso-2-naphthol) Nitrosonaphthols such as R salt); 2-carboxypyridine,
2,6-dicarboxypyridine, 4-methyl-2
- Carboxypyridines such as carboxypyridine, 2,3-dicarboxypyridine, 2,4-dicarboxypyridine; 8-hydroxyquinoline, 2
-Methyl-8-hydroxyquinoline, 4-methyl-8-hydroxyquinoline, 5-methyl-8-hydroxyquinoline, 7-methyl-8-hydroxyquinoline, 8-hydroxyquinoline-5-sulfonic acid, 7-iodo-8 -Hydroxyquinoline-5
-8-hydroxyquinolines such as sulfonic acid; 2
- Carboxyquinolines such as carboxyquinoline, 8-carboxyquinoline, 5-methyl-2-carboxyquinoline; 4-hydroxy-1,5-
Hydroxynaphthyridines such as naphthyridine, 8-hydroxy-1,6-naphthyridine, 8-hydroxy-1,7-naphthyridine, 5-ethyl-8-hydroxy-1,7-naphthyridine; glycine, N-methylglycine, alanine, β-alanine, α-aminobutyric acid, cysteine, threonine,
Hydroxyproline, glycylglycine, N,N
-Amino acids such as dimethylglycine; iminodiacetic acid, iminodipropionic acid, N-methyliminodiacetic acid, N-(3,3-dimethylbutyl)iminodiacetic acid, N-phenyliminodiacetic acid, N-(2-hydroxyethyl)iminodiacetic acid, N-(2-mercaptoethyl)iminodiacetic acid, N-(2-hydroxyethyl)iminodipropionic acid, N-(3-
hydroxypropyl)iminodipropionic acid, N
-(2-hydroxycyclohexyl)iminodiacetic acid, N-(2-methoxyethyl)iminodiacetic acid,
N-(2-hydroxybenzyl)iminodiacetic acid,
N-(3-carboxyphenyl)iminodiacetic acid,
N-(carbamoylmethyl)iminodiacetic acid, N-
(2-aminoethyl)iminodiacetic acid, N-(2-
aminoethyl)iminodipropionic acid, nitrilotriacetic acid, N-carboxymethyliminodipropionic acid, nitrilotripropionic acid, N-(2-
Aminopolycarboxylic acids such as carboxyethyl)iminodiacetic acid and N-(2-methyl-2-carboxyethyl)iminodiacetic acid; -ethylenediaminediacetic acid, N,N'-ethylenediaminedipropionic acid, N,N'-di(2 -Hydroxyethyl)ethylenediaminediacetic acid, N-n-butylethylenediaminetriacetic acid, N-cyclohexylethylenediaminetripropionic acid, N-(2-hydroxycyclohexyl)ethylenediaminetriacetic acid, N
-(2-hydroxyethyl)ethylenediaminetriacetic acid, N-benzylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, N,N'-di(2-carboxyethyl)ethylenediaminediacetic acid, N,
N'-di(1-carboxyethyl)ethylenediaminediacetic acid, 1,2-propylenediaminetetraacetic acid, trimethylenediaminetetraacetic acid, tetramethylenediaminetetraacetic acid, pentamethylenediaminetetraacetic acid, octamethylenediaminetetraacetic acid, octamethylenediamine Tetrapropionic acid, N,N'-(2-carboxyethyl)octamethylenediamine diacetic acid, 1,2-cyclopentanediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, 1,2-cyclohexanediaminetetrapropionic acid, 1,3-cyclohexanediaminetetraacetic acid, 1,4-cyclohexanediaminetetrapropionic acid, 1,3,5-
triaminocyclohexanehexaacetic acid, 2-hydroxytrimethylenediaminetetraacetic acid, 2,
2'-ethyl ether diamine tetraacetic acid, 2,
2'ethylthioether diamine tetraacetic acid, bis(ethyl iminodiacetate) methylamine, diethylenetriaminepentaacetic acid, diethylenetriaminepentapropionic acid, 2-(2-iminodiacetic acid ethoxy)-2'-iminodiacetic acid-ethyl ether,
Trimethylenetetraminehexaacetic acid, triethylenetetraminehexapropionic acid, N,N′-dimethyltriethylenetetramine-N″,N″,N
, N-tetraacetic acid, N,N'-dimethyltriethylenetetramine-N'',N'', N,N-tetrapropionic acid, and metal salts, metal complexes, or ammonium salts thereof. Also, metal salts of these compounds,
Metal complexes or ammonium salts can also be used. The metals that form such metal salts and metal complexes include lithium, sodium,
Examples include potassium, magnesium, calcium, barium, lead, gallium, manganese, cobalt, nickel, copper, zinc, zirconium, cadmium, lanthanum, cerium, and gadolinium. In the present invention, one or more of these compounds are used as the compound (D) having chelate-forming ability, and the amount of the compound (D) having chelate-forming ability is ) acrylic acid
0.0001 based on the total amount of (A), polybasic carboxylic acid anhydride (B) and alkylene oxide (C) as 100 parts by weight
Preferably, the amount is in proportions of parts by weight or more. If the amount used is less than this, the excellent effects of the present invention will not be fully exhibited, which is not preferable. The upper limit of the amount of the compound (D) having chelate-forming ability to be used is not particularly limited, but usually (meth)acrylic acid (A), polybasic carboxylic acid anhydride (B), and alkylene oxide (C). A ratio of 2 parts or less per 100 parts of the total amount is enough to exhibit its effect. The compound (D) having chelate-forming ability may be added to the reaction system before the reaction starts, or when the reaction is carried out without the compound (D), the reaction starts from the start of the reaction. The period until the system becomes abnormally thickened or gels (hereinafter referred to as
This is called the viscosity-generating group. ) is also fine. The period during which viscosity increase occurs varies depending on the type and amount of catalyst and radical polymerization inhibitor used, and reaction conditions such as reaction temperature, so it is difficult to specify it uniformly. However, the period during which thickening occurs for each reaction system with specified reaction conditions can be easily determined by repeating simple experiments. Therefore, for example, suppose that when the reaction is carried out under certain reaction conditions in the absence of the compound (D) having chelate-forming ability, the reaction system becomes abnormally thickened or gelled 5 hours after the start of the reaction. Under the same conditions, a compound with chelate-forming ability is added to the reaction system before the reaction starts or within 5 hours from the start of the reaction.
By adding (D), oligo(meta) can be stabilized.
Acrylates can be produced. The oligo(meth)acrylate thus obtained according to the present invention can be used for various purposes in the same manner as conventionally known oligo(meth)acrylates. For example, the obtained oligo(meth)acrylate can be used as paint resin, FRP molding resin, casting resin, etc. with or without addition of a polymerizable monomer as necessary. . It can also be used as a thermosetting polyurethane by reacting with a polyfunctional isocyanate compound. Based on the present invention, it is possible to stably produce oligo(meth)acrylates with such a wide range of uses without causing problems such as abnormal thickening or gelation during the production reaction, and this invention is useful in this technical field. This will make a huge contribution. Although it is not theoretically clear why the method of the present invention exhibits such excellent effects in preventing gelation during the production of oligo(meth)acrylates, it is difficult to explain why the method of the present invention exhibits such excellent effects in preventing gelation during the production of oligo(meth)acrylates. The effect of preventing gelation is surprising when compared with the case where the compound (D) is not present or when a compound having a chelate-forming ability other than the compound (D) is present. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to these Examples. In the examples, "parts" represent "parts by weight" unless otherwise specified, and the numbers in parentheses after "parts" represent molar ratios. Example 1 Total condenser, thermometer, gas introduction pipe,
860 parts (1) of methacrylic acid and maleic anhydride were placed in 10 reactors made of stainless steel (SUS 304) equipped with a heating device, a cooling device, a stirring device and a raw material inlet.
1,960 parts (2) of phthalic anhydride, 1,480 parts (1) of phthalic anhydride, 0.72 parts of hydroquinone, 22 parts of triethylamine, and 0.7 parts of ethylenediaminetetraacetic acid were added, and the temperature was raised to 100°C while introducing air. Next, the inside of the reaction system is 100
After introducing 2900 parts (5) of propylene oxide over 5 hours while maintaining the temperature at ~115°C, the reaction was continued for an additional 4 hours to obtain oligomethacrylate with an acid value of 8. The viscosity of the resin liquid obtained by mixing 70 parts of oligomethacrylate and 30 parts of styrene at 25°C is
It was 3.7 poise. Comparative Example 1 When an attempt was made to produce oligomethacrylate in the same manner as in Example 1 except that ethylenediaminetetraacetic acid was not used, the viscosity of the reaction system began to increase approximately 30 minutes after the end of the introduction of propylene oxide. After about 70 minutes, stirring became difficult, so the reaction was stopped. Example 2 In Example 1, ethylenediaminetetraacetic acid was not added to the reaction system from the start of the reaction, but instead, it was added to the reaction system 15 minutes after the end of propylene oxide introduction, but in the same manner as in Example 1. An oligomethacrylate having an acid value of 9 was obtained. The viscosity of the resin liquid obtained by mixing 70 parts of this oligomethacrylate and 30 parts of styrene was 4.0 poise at 25°C. Example 3 In a reactor similar to Example 1, 216 parts of acrylic acid was added.
(1), phthalic anhydride 1776 parts (4), hydroquinone 0.8
After adding 40 parts of triethylamine and 40 parts of triethylamine, the temperature was raised to 100°C while introducing air, and then 870 parts of propylene oxide (5) was introduced over 3 hours. Next, 1176 parts (4) of maleic anhydride, 0.8 parts of ethylenediaminetetraacetic acid and 3300 parts of styrene were added to the reaction system, and then 870 parts (5) of propylene oxide was added to the reaction system.
The acid value was
11. A styrene solution of oligoacrylate with a viscosity of 2.4 poise at 25°C was obtained. Comparative Example 2 In Example 3, an attempt was made to produce oligoacrylate in the same manner as in Example 3 except that ethylenediaminetetraacetic acid was not used, but from the start of the reaction
After 5.5 hours, the viscosity of the reaction system began to increase, and after another 15 minutes, the viscosity reached 20 poise or more, so the reaction was stopped. Example 4 The following experiment was conducted using a four-necked flask similar to that used in Example 1, except that all parts in contact with the liquid were made of glass. 86 parts (1) of methacrylic acid (containing 200 ppm of hydroquinone), 2.0 parts of triethylbenzylammonium chloride, and 0.08 parts of cyclohexanediaminetetraacetic acid, which had been stored in a stainless steel (SUS 304) drum for about 6 months, were added, and air was removed. The temperature was raised to 100°C while the mixture was being introduced, and then 58 parts (1) of propylene oxide was introduced over a period of 2 hours. Next, 222 parts (1.5) of phthalic anhydride was added, and then 44 parts (1) of ethylene oxide were introduced over a period of 2 hours, and the reaction was continued for 2 hours to obtain an oligomethacrylate having an acid value of 53. The viscosity of the resin liquid obtained by mixing 70 parts of oligomethacrylate and 30 parts of styrene is 25°C.
So, it was 1.3 poise. Comparative Example 3 Oligomethacrylate with an acid value of 49 was obtained in the same manner as in Example 4 except that cyclohexanediaminetetraacetic acid was not used, and 70 parts of this oligomethacrylate and 30 parts of styrene were mixed. The resulting resin liquid had a high viscosity of 60 poise at 25°C. Examples 5 to 19 Example 1 except that 0.7 part of ethylenediaminetetraacetic acid was replaced with a compound (D) having various chelate-forming abilities listed in Table 1.
Each oligo(meth)acrylate was produced in the same manner as above. The type and amount of compound (D) having chelate-forming ability, the acid value of each oligo(meth)acrylate obtained, and the resin liquid obtained by mixing 70 parts of each oligo(meth)acrylate and 30 parts of styrene. The respective viscosities are shown in Table 1.

【table】

【table】

Claims (1)

[Claims] 1. (Meth)acrylic acid (A), polybasic carboxylic anhydride (B) and alkylene oxide (C) in the presence of a catalyst and a radical polymerization inhibitor at a temperature range of 70 to 150°C. o-nitrosophenols, nitrosonaphthols, carboxypyridines, 8-hydroxyquinolines, carboxyquinolines, hydroxynaphthyridines, amino acids, aminopolycarboxylic acids, , polyaminopolycarboxylic acids, and 2,2′-bipyridine, and one or more compounds having chelate-forming ability (D) are allowed to coexist in the reaction system. Production method. 2 The compound (D) having chelate-forming ability is added in an amount of 0.0001 parts by weight or more based on the total amount of (meth)acrylic acid (A), polybasic carboxylic acid anhydride (B) and alkylene oxide (C) being 100 parts by weight. A method for producing oligo(meth)acrylates according to claim 1, wherein the oligo(meth)acrylates are used in proportionate amounts.