JPH0717987A - Composition comprising phosphorus-containing compound and production thereof - Google Patents

Abstract

PURPOSE:To obtain the composition providing a specific action especially on pigments and metal materials as a dispersant and providing a flame-retardant effect by reacting a specific phosphorus-containing compound with a compound having a specified group in the molecule. CONSTITUTION:The composition comprising a phosphorus-containing compound of formula I [R<1> is the residue of an organic compound having i atoms of active hydrogen; n1, n2...ni, are 0, 1...30, their sum being 1-100; i is 1-10 which is the number of the active hydrogen atoms of R<1>; A is an oxycyclohexane skeleton of formula II having a substituent X; X is group of formula III-VI (R<2> is H, alkyl, etc.,)] is obtained by reacting (A) a phosphorus-containing compound of formula VII (A<1> is group of formula VIII) with (B) a compound containing a group of formula: -OP(=O)(OH) in the molecule (preferably orthophosphoric acid).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition comprising a phosphorus-containing compound used as a dispersant for metal compounds such as water-based paints and water-based inks for car body painting.

[0002]

2. Description of the Related Art As a treating agent to be added to an aqueous paint, one disclosed in JP-A-1-190765 is known. This relates to a technique of using a phosphated acrylic polymer as an aluminum gas generation inhibitor.

The acrylic polymer used here is (meth) acrylic 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 the acrylic monomer component used, the resin itself becomes unstable. At the same time, the epoxy concentration is also limited by itself, and it is industrially difficult to obtain a high-concentration epoxy-containing acrylic resin. 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.

On the other hand, JP-A-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 aromatic glycidyl such as bisphenol A diglycidyl.

However, the 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, it may adversely affect the metal, which is not preferable. On the other hand, for those having an aromatic structure,
It is unstable with respect to light and oxygen and has a difficulty in weather resistance.

[0006]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of studies to solve the above problems, a composition containing a novel phosphorus-containing compound having an excellent function was found.

[0007]

That is, the present invention relates to a composition comprising a phosphorus-containing compound represented by the following general formula [1].

[0008]

[Chemical 3]

Further, the present invention is characterized by reacting a compound represented by the following general formula [7] with a compound containing a —OP (═O) (OH) ₂ group in the molecule. The present invention relates to a method for producing a composition comprising a phosphorus-containing compound represented by [1]. The present invention will be described in detail below.

[0010]

[Chemical 4]

The epoxy which is one of the starting material components of the phosphorus-containing compound [1] of the first invention is
The epoxy compound described as 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 it is 100 or more, it becomes a resin having a high melting point, is difficult to handle, and cannot be practically used.
i is an integer of 1 to 100 and represents the number of active hydrogen groups of the organic compound which is the initiator used.

Of the substituents X of A in the general formula [1], it is essential that at least one group represented by the above formula [4] or [5] is contained. preferable. In particular, the smaller the number of groups represented by the above formula [6], the more preferable. That is, in the present invention, the substituent X is mainly a group represented by the above formula [4] or [5].

In the novel phosphorus-containing compound represented by the general formula [1] of the present invention, R ¹ is a compound containing at least one active hydrogen group. Examples of the compound having active hydrogen used in the present invention include alcohols, phenols, carboxylic acids, amines, thiols, hydroxyl group-terminated polymers, and hydroxyl group-containing polymers. The alcohols are monovalent, divalent, trivalent or higher, and include, for example, methanol, ethanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, Dipropylene glyco-
, Butanediol, hexanediol, glycerin,
Butanol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol
And triglycerol.

In addition, neopentyl glycol, neopentyl glycol ester of hydroxyhyvalic acid, dipentaerythritol, 1,4-cyclohexanedimethanol, trimethylpentanediol, 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 the phenols are 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, cresol novolac resin and the like.

The hydroxyl group-terminated polymer used in the present invention includes polyethylene glycol and polypropylene glycol.
Polyether polyols such as poly (tetramethylene glycol), poly (butylene glycol), poly (cyclohexene glycol) and poly (vinylcyclohexene glycol)
And hydroxyl-terminated polyesters, hydroxyl-terminated polybutadienes, hydroxyl-terminated polycaprolactones, and polycarbonate diols.

Further, an acrylic copolymer having a hydroxyl group can be used instead of the hydroxyl group-terminated polymer.

As carboxylic acids, 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, isophthalic acid. Acid, terephthalic acid, etc. Further, compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid and oxycaproic acid, can also be mentioned.

The amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine,
Octylamine, dodecylamine, 4,4-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, ethano-
Lumin, etc.

As thiols, methyl mercaptan,
Mercapto such as ethyl mercaptan, propyl mercaptan, phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol ester of mercaptopropionic acid, for example, ethylene glycol dimercaptopropionic acid ester, trimethylolpropane trimercaptopropionic acid, pentaerythritol- Examples include rupentamercaptopropionic acid and the like.

Further, other compounds having active hydrogen include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate.
, Cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin,
Polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, polytetramethylene glycol, and the like.

The compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples thereof include allyl alcohol, acrylic acid, methacrylic acid,
2-hydroxyethyl methacrylate, 3-cyclohexene methanol, tetrahydrophthalic acid and the like.

Any compound having these active hydrogens can be used, and two or more kinds thereof may be mixed.

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

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

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

When polymerizing 4-vinylcycloxene-1-oxide in the presence of active hydrogen, it is preferable to use a catalyst. As the catalyst, amine acids such as methylamine, ethylamine, propylamine and piperazine, organic bases such as pyridine and imidazole, organic acids such as formic acid, acetic acid and propionic acid, organic acids such as sulfuric acid and hydrochloric acid, sodium methylate and the like. Alkali metal alcoholates,
Alkali such as KOH, NaOH, BF ₃ , ZnCl
₂ , Lewis acids such as AlCl ₃ and SnCl ₄ or complexes thereof, and organometallic compounds such as triethylaluminum and diethylzinc can be given. These catalysts can be used in the range of 0.01 to 10%, preferably 0.1 to 5%, based on the starting material.

The temperature of the polyetherification reaction is -70 to 20.
It is 0 ° C, preferably -30 ° C to 100 ° C. The reaction can also be carried out using a solvent. A solvent having active hydrogen cannot be used. That is,
Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic solvents such as benzene, toluene and xylene, as well as ethers, aliphatic hydrocarbons and esters 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 present invention of the general formula [7].
New epoxy resin is manufactured.

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 a preferable epoxidizing agent because it is industrially available at low cost and has high stability. As the hydroperoxides, hydrogen peroxide, tert-butyl hydroperoxide, cumene peroxide and the like can be used.

A catalyst can be used if necessary in the epoxidation. 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 tert-butyl hydroperoxide. .

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the physical properties of the equipment and raw materials. Depending on the conditions of the epoxidation reaction, at the same time as the epoxidation of the olefin bond, a substituent of the following formula [9] in the raw material, a substituent of the following formula [8] to be formed, and an epoxidizing agent are reacted, and as a result, it is modified Substituents are generated and are contained in the target compound.

[0034]

[Chemical 5]

The ratio of the three substituents in the target compound to the modified substituents and the modified substituents 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 by-product acetic acid. The target compound can be taken out from the reaction crude liquid by ordinary chemical engineering means such as concentration.

[0036]

[Chemical 6]

Next, the phosphorylation reaction of the obtained epoxy compound will be described. The phosphorus compound includes a monoester of orthophosphoric acid. Phosphoric acid useful herein includes hydrated phosphoric acid to pure phosphoric acid, ie, about 70% to
About 100% phosphoric acid is used, preferably about 85% phosphoric acid. The reason is that it is industrially easily available. If it is less than 70%, the water content becomes too large, which is not preferable. Various condensed forms of phosphoric acid equivalents, such as polymeric partial anhydrides or esters of phosphoric acid, pyrophosphoric acid, triphosphoric acid, etc. may be used.

In the reaction of phosphoric acid or its equivalent with an epoxy compound, the ratio of the reactants can be selected in all or in 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 groups.
-4, preferably 1-2. 0.5 mol of phosphorus
If the amount is less than 4, the phosphorus compound itself is unstable, and conversely, if the amount exceeds 4, the residual phosphoric acid increases, which is not preferable.

The temperature of the phosphorylation reaction is 25 ° C to 150 ° C.
C., preferably a reaction temperature of 50.degree. C. to 100.degree. C. can be used. If the reaction temperature is lower than 25 ° C, the reaction is slow, while if it exceeds 150 ° C, it becomes difficult to control the reaction.

This reaction can be carried out usually in an inert solvent. As the solvent to be used, aromatic solvents such as benzene, toluene and xylene, ketone solvents such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone and isophorone, and hexane are used. , Hydrocarbon solvents such as heptane and cyclohexane, ether compounds such as diethyl ether, tetrahydrofuran, dioxane and propylene glycol monopropyl ether, esters such as ethyl acetate, isopropyl acetate and butyl diglycol acetate,
Solvents that do not have active hydrogen, such as halogen solvents, are mentioned. The amount of the inert solvent used is 0.1 to 20 times, preferably 0.2 to 5 times that of the epoxy compound. When the amount used is less than 0.1, the substrate concentration is high and it is difficult to control the reaction.
It is uneconomical and neither is preferable.

When carrying out the reaction, the order of charging is not limited, but it is preferable to add an epoxy compound (after dissolution in the above solvent in the case of solid to high viscosity) to phosphoric acid. After charging the starting materials, the temperature is raised to the above 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 above formula [7] is changed into a structure like the formulas [11] and [12].

[0042]

[Chemical 7]

The compound obtained by this reaction can be directly used for applications such as an aqueous paint. It can also be isolated by washing with water and distilling off the low-boiling component under reduced pressure, or distilling off the low-boiling component as it is. It is also possible to recrystallize using an insoluble solvent in order to obtain a higher purity product.

[0044]

EXAMPLES The present invention will be specifically described below 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. [eg, epoxy resin disclosed in JP-A-60-166675]
35.7 g of methyl ethyl ketone was dissolved in 35.7 g of propylene glycol monopropyl ether 142.
8 g was added to make a uniform solution.

Phosphoric acid 24.7 gr in a 500 ml flask
Was added, and the solution prepared above was added dropwise over about 1 hour.
The temperature was kept constant at 90 ° C. for about 2 hours after the end of heat generation. After cooling, the oxirane concentration of the reaction crude liquid was measured, and it was 0. The acid value was 145. Spectral data was measured for each of the obtained phosphorus compounds.

[Example-2] The sample produced in Example-1 was subjected to a rotary evaporator at 80-100 ° C.
The low boiling point product was distilled off at 2 to 5 mmHg for 2 hours. When the IR spectrum was measured, the raw material epoxy changed from the spectrum shown in FIG. 1 to that shown in FIG. NMR is JNM-GX270 (6.34T, ¹³ C67., Manufactured by JEOL Ltd.).
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, an analytical analysis of NMR was conducted, but since this compound is poorly soluble in deuterated chloroform and the like, it was compared with the solid C ¹³ -NMR chart (Fig. 4). . Carbon of the raw material epoxy is found around 46 ppm and around 56 ppm. In FIG. 3, it can be seen that this peak has disappeared and the epoxy group has disappeared. 6
0 to 90 ppm is the absorption of carbon bound to oxygen, and it is considered that the carbon is shifted into this.

[0049]

EFFECT OF THE INVENTION The phosphorus compound obtained in the present invention exerts an extremely high effect as a dispersant, in particular, exerts a peculiar action on a pigment and a metal material as compared with the conventionally known type. Further, an excellent flame retardant effect can be brought about by adding it to a general resin.

[Brief description of drawings]

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

FIG. 2 is an IR spectrum chart of a phosphorus oxide of a raw material epoxy [EHPE3150].

FIG. 3 is a C ¹³ -NMR spectrum chart of a phosphoric acid adduct.
It is

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takatsugu Yamamoto 3-6-8, Kutaro-cho, Chuo-ku, Osaka City, Osaka Prefecture Toyo Aluminum Co., Ltd. 3-6-8 Toyo Aluminum Co., Ltd.

Claims (3)

[Claims] 1. A composition comprising a phosphorus-containing compound represented by the following general formula [1]. [Chemical 1] 2. A phosphorus-containing compound represented by the following general formula [7] is reacted with a compound containing a —OP (═O) (OH) ₂ group in the molecule. A method for producing a composition comprising the phosphorus-containing compound as described above. [Chemical 2] 3. A composition comprising a 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. Manufacturing method.