JP3328383B2 - Phosphorus-containing compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to relates to a phosphorus-containing compound used as a dispersant for metal compounds such as water-based paints and water-based inks, such as body painting of automobiles.

[0002]

2. Description of the Related Art As a treating agent added to a water-based paint, there is known a treating agent disclosed in JP-A-1-190765. This relates to the technology of using a phosphorylated acrylic polymer as an aluminum gassing inhibitor.

The acrylic polymer used here is (meth) acrylic acid containing glycidyl epoxy,
It is characterized by reacting this epoxy with a phosphoric acid compound. However, if an excessive amount of alcohol or carboxylic acid is added as an acrylic monomer component to be used, the resin itself becomes unstable. At the same time, the epoxy concentration itself has its own limit, and it is industrially difficult to obtain a high-concentration epoxy-containing acrylic. Therefore, a sufficient gas generation suppressing effect cannot be expected, and at the same time, it is difficult to obtain a balance in terms of weather resistance and adhesion.

[0004] On the other hand, Japanese Patent Application Laid-Open No. 61-47771 discloses that a compound obtained by reacting a compound having an epoxy with phosphoric acid is useful as a gas generation inhibitor from aluminum. The epoxy used here is mainly an aromatic glycidyl such as bisphenol A diglycidyl.

[0005] However, conventionally known glycidyl epoxy uses epichlorohydrin as a raw material, so that residual chlorine remains in the product. Therefore, when mixed with aluminum or the like, the metal may be adversely affected, which is not preferable. On the other hand, for those having an aromatic structure,
It is unstable to light or oxygen and has difficulty in weather resistance.

[0006]

In order to solve this problem [0005], was examined and Tsu reached a finding novel phosphorus-containing compounds having excellent functions.

[0007]

Means for Solving the Problems That is, the present invention relates to phosphorus-containing compound represented by the following general formula [1].

[0008]

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Further, the present invention is characterized in that a compound represented by the following general formula [7] is reacted with a compound having a —OP (ＯO) (OH) ₂ group in the molecule. the method for producing a phosphorus-containing compound represented by [1].
Hereinafter, the present invention will be described in detail.

[0010]

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The epoxy, which is one of the starting material components of the phosphorus-containing compound [1] of the first invention, includes:
An epoxy compound represented by the general formula [7].

[0012] n ₁ ~n _i in the general formula [1] is an integer of 0 or 1 to 30. The sum is 1 to 100, but if the sum is 100 or more, it becomes a resin having a high melting point and is difficult to handle, so that it is not practically usable.
i is an integer from 1 to 100, and a hydroxyl group, a carboxyl group, an amino group,
Or represents the number of -SH groups.

It is essential that at least one group represented by the formula [4] or [5] among the substituent X of A in the general formula [1] is contained, but the more this group is, the more it is. preferable. In particular, the smaller the group represented by the formula [6], the better. That is, in the present invention, the substituent X is mainly a group represented by the formula [4] or [5].

In the novel phosphorus-containing compound represented by the general formula [1] of the present invention, R ¹ represents a hydroxyl group,
Group, an amino group, or a residue of a compound containing at least one -SH group . Hydroxyl group, carbo group used in the present invention
Compounds having a xyl group, an amino group, or a -SH group include alcohols, phenols, carboxylic acids,
Examples include amines, thiols, hydroxyl-terminated polymers, and polymers containing hydroxyl groups. Alcohols are monovalent, divalent, trivalent or higher, for example,
Methanol, ethanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol, triglycerol, etc. .

In addition, neopentyl glycol, neopentyl glycol ester of hydroxyhivalic acid, dipentaerythritol, 1,4-cyclohexanedimethanol, trimethylpentaneddiol, 1,3,5- Tris (2-hydroxyethyl) cyanuric acid, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, and the like can also be used.

Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone,
Hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4-dihydroxybenzophenone, bisphenol S, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, phenol Resin and cresol novolak resin.

The hydroxyl-terminated polymer used in the present invention includes polyethylene glycol and polypropylene glycol.
Polyether methylene glycol, polybutylene glycol, polycyclohexene glycol, polyvinylcyclohexene glycol, etc.
And hydroxyl-terminated polyester, hydroxyl-terminated polybutadiene, hydroxyl-terminated polycaprolactone, polycarbonate todiol and the like.

An acrylic copolymer having a hydroxyl group may be used in place of the hydroxyl group-terminated polymer.

The carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane diacid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, and isophthalic acid. Acid and terephthalic acid. Further, compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid, are also included.

The amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine,
Octylamine, dodecylamine, 4,4-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, ethanol
Luamine and the like.

As thiols, methyl mercaptan,
Mercaptos such as ethyl mercaptan, propyl mercaptan and phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol esters of mercaptopropionic acid, for example, ethylene glycol-dimercaptopropionate, trimethylolpropane trimercaptopropionate, pentaerythritol- Lupentamercaptopropionic acid and the like.

Furthermore, a hydroxyl group, a carboxyl group,
Examples of the compound having an amino group or -SH group include polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, starch, cellulose, cellulose acetate, cellulose
Acetate butyrate, hydroxyethyl cellulose
And acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol, polytetramethylene glycol, and the like.

Also, a hydroxyl group, a carboxyl group, an amino
Group or a compound having a -SH group, rather it may also have an unsaturated double bond in its backbone, and specific examples include allyl alcohol, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, 3 -Cyclohexenemethanol, tetrahydrophthalic acid and the like.

These hydroxyl, carboxyl, amino
Any compound having a group or a -SH group can be used, and two or more kinds thereof may be mixed.

In order to produce a novel phosphorus-containing compound represented by the general formula [1] of the present invention, first, at least one of a hydroxyl group, a carboxyl group, an amino group, and-
A polyether resin, that is, a polycyclohexane polymer having a vinyl group side chain is obtained by ring-opening polymerization of 4-vinylcycloxene-1-oxide using a compound having an SH group as an initiator.

Then, the vinyl group side chain is epoxidized with an oxidizing agent such as peracid to produce an epoxy compound having an epoxy group as a side chain.

4-vinylcycloxene-1-oxide can be obtained by partially epoxidizing 4-vinylcyclohexene obtained by the dimerization reaction of butadiene with peracetic acid or the like.

4-vinylcycloxene-1-oxide is
Including hydroxyl group, carboxyl group, amino group or -SH group
When polymerizing in the presence of an organic compound, it is preferable to use a catalyst. Examples of the catalyst include amine acids such as methylamine, ethylamine, propylamine, and piperazine; organic bases such as pyridines and imidazoles; organic acids such as formic acid, acetic acid and propionic acid; organic acids such as sulfuric acid and hydrochloric acid; sodium methylate; Alcoholates of alkali metals, alkalis such as KOH and NaOH, BF ₃ , ZnC
Examples thereof include Lewis acids such as l ₂ , AlCl ₃ and SnCl _{4 and} complexes thereof, and organometallic compounds such as triethylaluminum and diethylzinc. These catalysts can be used in the range of 0.01 to 10%, preferably 0.1 to 5%, based on the starting materials.

The temperature of the polyetherification reaction is -70 to 20
0 ° C, preferably -30 ° C to 100 ° C. The reaction can also be performed using a solvent. Hydroxyl,
Those having a ruboxyl group, an amino group, or a -SH group cannot be used. That is, acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone, aromatic solvents such as benzene, toluene and xylene, ethers, aliphatic hydrocarbons, esters and the like can be used.

The polycyclohexene oxide polymer having a vinyl group side chain synthesized in this manner is epoxidized with an epoxidizing agent, and used in the general formula [7] used in the present invention.
Is produced.

As the epoxidizing agent, peracids and hydroperoxides can be used. As the peracids, formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like can be used. Of these, peracetic acid is particularly preferable because it is industrially available at low cost and has high stability. As the hydroperoxides, hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like can be used.

At the time of epoxidation, a catalyst can be used if necessary. For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as nitric acid can be used as a catalyst. In the case of hydroperoxide, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. .

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the apparatus and the physical properties of the raw materials. Depending on the conditions of the epoxidation reaction, at the same time as the epoxidation of the olefin bond, the olefin bond reacts with the substituent of the following formula [9] in the raw material, the generated substituent of the following formula [8], and the epoxidizing agent, thereby being modified. Substituents are generated and included in the target compound.

[0034]

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The ratio of the substituent and the modified substituent and the modified substituent in the target compound is determined by the type of the epoxidizing agent, the molar ratio of the epoxidizing agent olefin bond, and the reaction conditions. When the epoxidizing agent is peracetic acid, the modified substituent has a structure represented by the following formula [10], and is generated from the generated epoxy group and acetic acid by-produced. The target compound can be extracted from the crude reaction solution by ordinary chemical engineering means such as concentration.

[0036]

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Next, the phosphorylation reaction of the obtained epoxy compound will be described. Examples of the phosphorus compound include a monoester of orthophosphoric acid. Phosphoric acids useful herein include hydrated phosphoric acid to pure phosphoric acid, ie, about 70% to
About 100% phosphoric acid, preferably about 85% phosphoric acid is used. The reason is that it is industrially available. If it is less than 70%, the content of water is undesirably too large. Various condensed forms of phosphoric acid equivalents may be used, for example, polymeric anhydrides or esters of phosphoric acid, pyrophosphoric acid, triphosphoric acid, and the like.

In the reaction of phosphoric acid or its equivalent with an epoxy compound, the ratio of the reactants can be selected in all or any ratio. Typically, the molar ratio of phosphoric acid to epoxy compound used herein is 0.5 based on the number of moles of phosphorus per mole of epoxy group.
-4, preferably 1-2. 0.5 mole of phosphorus
When the amount is less than 4, the phosphorus compound itself is unstable. On the contrary, when the amount exceeds 4, the residual phosphoric acid increases.

The temperature of the phosphorylation reaction is from 25 ° C. to 150 ° C.
C., preferably a reaction temperature between 50.degree. When the reaction temperature is lower than 25 ° C., the reaction is slow. On the contrary, when the reaction temperature is higher than 150 ° C., it becomes difficult to control the reaction.

This reaction can be usually carried out in an inert solvent. Examples of the solvent used include aromatic solvents such as benzene, toluene and xylene; ketone solvents such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone and isophorone; , Heptane, hydrocarbon solvents such as cyclohexane, diethyl ether, tetrahydrofuran, dioxane, ether compounds such as propylene glycol monopropyl ether, ethyl acetate, isopropyl acetate, esters such as butyl diglycol acetate,
Hydroxyl groups such as halogen solvents , carboxyl groups, amino groups,
Or a solvent having no -SH group . The amount of the inert solvent used is 0.1 to 20 with respect to the epoxy compound.
Times, preferably 0.2 to 5 times. If the amount used is less than 0.1, the substrate concentration is high, and it is difficult to control the reaction,
Conversely, if it exceeds 20, it becomes uneconomical when used as a paint, and neither is preferred.

In carrying out the reaction, the order of charging is not limited, but it is preferable to add an epoxy compound (solid to high-viscosity solution after dissolving in the above-mentioned solvent) to phosphoric acid. After charging the starting materials, the temperature is raised to the above-mentioned temperature. The end point of the reaction can be confirmed, for example, by measuring the oxirane concentration by titration. By the phosphorylation reaction of the epoxy group, the group of the formula [7] is changed into a structure as shown in the formulas [11] and [12].

[0042]

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The compound obtained by this reaction can be used as it is for applications such as aqueous paints. Isolation can also be carried out by washing with water and distilling low-boiling components under reduced pressure, or distilling low-boiling components as they are. In order to obtain a higher purity, recrystallization using an insoluble solvent is also possible.

[0044]

The present invention will be described below in more detail with reference to examples. In the following, IR is JA SCO FT / I
R-5300 was used.

Example 1 Alicyclic epoxy compound EHPE3150 manufactured by Daicel Chemical Industries, Ltd. [for example, an epoxy resin disclosed in JP-A-60-166675]
35.7 g are dissolved in 35.7 g of methyl ethyl ketone and then propylene glycol monopropyl ether.
8 g was added to make a uniform solution.

24.7 gr of phosphoric acid was placed in a 500 ml flask.
And the solution prepared above was added dropwise over about 1 hour.
The temperature was kept constant so as to reach 90 ° C. for about 2 hours after the end of the heat generation. After cooling, the oxirane concentration of the reaction crude liquid was measured to be 0, and the acid value was 145. Spectrum data was measured for each of the obtained phosphorus compounds.

Example 2 The sample prepared in Example 1 was heated at 80-100 ° C. using a rotary evaporator.
Low boilers were distilled off at 2 to 5 mmHg for 2 hours. When the IR spectrum was measured, the spectrum of the raw material epoxy changed from FIG. 1 to FIG. NMR is manufactured by JEOL ^{(Ltd.) JNM-GX270 (6.34T, 13} C67.
8MH _Z) was used. The conditions are as follows. Measurement method: CP-MAS, contact time: 1.0ms, pulse waiting time: 5S, spinning: 4.75KH _Z.

[Example 3] On the other hand, NMR was analyzed and studied. Since this compound was hardly soluble in deuterated chloroform and the like, it was compared with a solid C ¹³ -NMR chart (FIG. 4). . Carbon in the raw material epoxy is found at around 46 ppm and around 56 ppm. In FIG. 3, it can be seen that the peak has disappeared and the epoxy group has disappeared. 6
0 to 90 ppm is the absorption of carbon bonded to oxygen, which is considered to have shifted into this.

[0049]

The phosphorus- containing compound obtained by the present invention exerts a specific action as a dispersant, particularly on pigments and metal materials, as compared with the conventionally known types, and an extremely high effect can be obtained. An excellent flame retardant effect can be obtained by adding it to a general resin.

[Brief description of the drawings]

FIG. 1 is an IR spectrum chart of a raw material epoxy [EHPE3150].

FIG. 2 Phosphorus content of raw material epoxy [EHPE3150]
3 is an IR spectrum chart of the compound .

FIG. 3 is a C ¹³ -NMR spectrum chart of a phosphorus- containing compound .

FIG. 4 C ¹³ -N of raw material epoxy [EHPE3150]
It is an MR spectrum chart.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Yamamoto 3-6-8 Kutaro-cho, Chuo-ku, Osaka-shi, Osaka Toyo Aluminum Co., Ltd. (72) Inventor ▲ Takashi ▼ Kutaro-cho, Chuo-ku, Osaka-shi, Osaka JP-A-6-256823 (JP, A) JP-A-1-190765 (JP, A) JP-A-3-203975 (JP, A) Kaihei 2-290890 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 9/09 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A phosphorus-containing compound represented by the following general formula [1] . Embedded image 2. The method according to claim 1, wherein a phosphorus-containing compound represented by the following general formula [7] is reacted with a compound having a —OP (＝ O) (OH) ₂ group in the molecule. A method for producing the phosphorus-containing compound according to the above. Embedded image 3. The phosphorus-containing compound according to claim 2, wherein the compound containing a —OP (＝ O) (OH) ₂ group in the molecule is either orthophosphoric acid or a monoester of orthophosphoric acid. Method of manufacturing a product .