JP3328382B2 - Phosphorus-containing compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a contact and a manufacturing method thereof phosphorus-containing compounds that can be used in the additives used in blended with an aqueous paint or an aqueous ink or the like, 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], it was studied, and have found a 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]

Embedded image The “group in which the alicyclic epoxy group portion of the polyvalent carboxylic acid having an unsaturated alicyclic epoxy group is phosphoric esterified” in the present invention specifically corresponds to the following partial structural formula [5]. I do.

[0009] The present invention relates to phosphorus-containing <br/> compound characterized in that compounds of the general formula [1] has the following structural formula [3].

[0010]

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[0011] The present invention is related <br/> the phosphorus-containing compound having the structural formula [4] the compound of the general formula [1].

[0012]

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[0013] The present invention is related <br/> the phosphorus-containing compound having the structural formula [6] the compound of the general formula [1].

[0014]

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The present invention also relates to an epoxy compound represented by the following formulas [7] to [10] and -OP (= O) (O
H) A process for producing a phosphorus-containing compound of any of the above formulas [1], [3], [4] and [6], characterized by reacting with a compound containing _two groups.

[0016]

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[0017]

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[0018]

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[0019]

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Further, the present invention relates to the above-mentioned production method, wherein -O
A compound having P (＝ O) (OH) ₂ is orthophosphoric acid,
Alternatively, the present invention relates to a manufacturing method characterized by being a monoester thereof. Hereinafter, the present invention will be described in detail.

The epoxy which is one of the starting material components of the compound [1] of the first invention is an epoxy compound of the above compounds [7], [8], [9] and [10].

In the compound [7], R represents 1 to 3 carbon atoms.
It is an alkyl or alkenyl group of 0, may be alicyclic or linear, and may have a double bond.
Specific examples of the compound represented by the general formula [1] include the following compounds.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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However, in each of the above compounds, R ¹ is the following [24], Z is the following [25], Z ¹ is the following [26], A
Shows the structure of the following [27].

[0035]

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The above Y ¹ is the following [28], and A ² is the following [2]
9], and n represents an integer of 0 to 20.

[0037]

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These compounds can be obtained by an esterification reaction of the corresponding carboxylic acid and / or acid anhydride with 3-cyclohexenemethanol or a modified lactone thereof.

An epoxidized ester of a polybasic acid and tetrahydrobenzyl alcohol can be used.

[0040]

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[0041] As the raw material is the epoxy compound Li emissions containing compounds of the present invention, more specifically to the example JP-A 4-69360 Patent Publication (Japanese Patent Application No. Hei 2-182124) and Japanese Patent Laid-Open 4-36263 discloses And the epoxy compounds described in (1). These epoxy compounds have an epoxy group on the ring, and can be basically obtained by epoxidizing a double bond with a peracid. Product names are Eporide GT300 and Eporide GT30
1. Epolide GT302, Epolide GT400, Epolide GT401, Epolide GT403, Celloxide 2081, Celloxide 2083, Celloxide 2.
085 and the like.

The epoxy is characterized by being epoxidized with a peracid, being chlorine-free, not having an aromatic or double bond, and capable of being modified in a form in which the amount of ε-caprolactone is arbitrarily changed. Is mentioned. Therefore, there is an advantage that any epoxy equivalent, softness and adhesive epoxy compound can be selected. In addition, since it does not contain ionic components such as double engagement and chlorine, it is possible to impart high weather resistance and stability to the paint.

As the reactant as the phosphorus compound, there is a monoester of orthophosphoric acid. Examples of suitable monoesters of phosphoric acid include monobutyl phosphate, monoamyl phosphate,
There are monononyl phosphate, monocetyl phosphate, monophenyl phosphate, and monobenzyl phosphate. 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 included. The reason is that it is industrially available. Various condensed forms of phosphoric acid equivalents,
For example, a polymerized partial anhydride or ester of phosphoric acid, pyrophosphoric acid, triphosphoric acid and the like can be used.

In the reaction between phosphoric acid or its equivalent and 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 about 0.1 mole based on moles of phosphorus per mole of epoxy groups.
5 to about 4, preferably about 1 to about 2. When the number of moles of phosphorus is less than 0.5, the compound itself is unstable, and
If the ratio exceeds, it is difficult to control the reaction, so that both are not preferred.

The reaction temperature may be from about 25 ° C. to about 150 ° C., preferably from about 50 ° C. to about 100 ° C. When the reaction temperature is lower than 25 ° C., the reaction is slow.
If the temperature is higher than 50 ° C., it is difficult to control the reaction.

This reaction can be carried out usually in the presence of 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, hydrocarbon solvents such as hexane, heptane and cyclohexane, diethyl ether, tetrahydrofuran, dioxane, Examples thereof include ether compounds such as propylene glycol monopropyl ether, esters such as ethyl acetate, isopropyl acetate and butyl diglycol acetate, and solvents containing no active hydrogen such as halogen solvents.

The amount of the inert solvent used is 0.1 to 20 times, preferably 0.5 to 2 times the epoxy resin.
If the amount used is less than 0.1 times, the substrate concentration is high, and it is difficult to control the reaction. Conversely, if the amount exceeds 20 times, it is uneconomical to use it for paints, and neither is preferred.

In carrying out the reaction, the order of charging is not limited, but preferably, the epoxy compound is added dropwise to phosphoric acid and the temperature is raised to the above-mentioned temperature.

The end point of the reaction can be confirmed, for example, by measuring oxirane oxygen by titration. The compound obtained by this reaction can be directly used 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.

[0050]

The present invention will be described below in more detail with reference to examples. In the following, NMR is “GXS270WB”
And IR is JA SCO FT / IR-5300,
GPC is "HPLC LC-6A SY" manufactured by Shimadzu Corporation.
STEM "(column: polystyrene column, solvent: TH
F) was used.

[Example 1] A mixture of 40.0 g of Eporide GT403 and 40 g of propylene glycol monopropyl ether as a raw material epoxy resin was mixed with phosphoric acid * 1.
A mixture of 8.5 g and 26.0 g of propylene glycol monopropyl ether was added dropwise over about 1 hour.
The reaction rose to about 90 ° C. The temperature rose due to heat generation, but was kept constant at about 90 ° C. for about 2 hours after the heat generation was completed. After cooling, the oxirane oxygen concentration of the crude reaction solution was measured and found to be 0. From this, it is considered that the epoxy group is almost reacted. The acid value was 191.

The epoxy resin [Ia] was Eporide GT403 (manufactured by Daicel Chemical Industries, Ltd.).
The epoxy equivalent is 280, the viscosity is 700 cp / 70 ° C., the water content is 0.05%, and the acid value is 0.2. The phosphoric acid used was obtained by adding 40 g of phosphorus pentoxide to 100 g of 85% phosphoric acid.

Raw material epoxy resin and obtained phosphorus content
Spectral data was measured for each compound . FIG. 5 is an NMR chart of the raw material epoxy resin, FIG. 6 is a GPC chart, and FIG. 7 is an IR chart. Fig. 8 shows the phosphorus content
A NMR chart of compound, Figure 9 is a chart of the IR of the phosphorus-containing compound <br/>. Fig. 22 shows the phosphorus content
It is a GPC chart of a compound , MW = 21903, MN
= 2077, MW / MN = 10.55.

Example 2 A mixture of 40 g of celloxide 2083 (manufactured by Daicel Chemical Industries) and 40 g of propylene glycol monopropyl ether as a raw material epoxy resin was added to a mixture of 18.48 g of phosphoric acid * and 40 g of propylene glycol monopropyl ether for about 1 hour. It dripped over. The reaction rose to about 90 ° C. Although the temperature rises due to the heat generation, it was heated to 90 ° C. for about 2 hours after the heat generation was completed. After cooling, the oxirane concentration of the crude reaction solution was measured and found to be 0. From this, it is considered that the epoxy has almost reacted. The acid value was 183.

Celloxide 2083 has an epoxy equivalent of 35.
0, viscosity 150 (cp / 45 ° C.), moisture 0.05%, specific gravity (20/20 ° C.) 1.13.

Raw material epoxy resin and obtained phosphorus content
Spectral data was measured for each compound . FIG. 16 is an NMR chart of the raw material epoxy resin, and FIG. 17 is a GPC chart.
8 is likewise chart of IR, Figure 19 is a phosphorus-containing
A NMR chart of the compound, FIG -20 phosphorus-containing reduction
A GPC chart of the compound, FIG -21 phosphorus-containing reduction
It is an IR chart of a compound .

[Examples 3 to 8] The reaction was carried out in the same manner as in Example 1 by using the raw material epoxy compounds having the properties shown in Table 1 in the same manner as in Example 1 to obtain phosphorus.
The contained compound was obtained. Table 1 shows their properties.

[0058]

[Table 1]

FIG. 10 is an NMR chart of the raw epoxy resin used in Example 4, FIG. 11 is a GPC chart, and FIG. 12 is an IR chart. Figure 13 is a NMR chart of <br/> phosphorus-containing compounds of the embodiment, Figure 14 is also phosphorous-containing reduction
FIG. 15 is a GPC chart of the compound , and FIG.
It is an IR chart of a contained compound .

Example 9 The sample prepared in Example 1 was subjected to a rotary evaporator at 80 to 100.degree.
Low boiling components were distilled off at 5 mmHg for 2 hours. When the infrared spectrum was measured, the spectrum of the raw material epoxy was changed from FIG. 1 to FIG. 1014cm
⁻¹ , absorption derived from PO was recognized, and 780-820 was observed.
The peak attributable to epoxy at cm ^-1 disappeared. The absorption derived from P-O was observed at 1010 cm ^-1, a peak considered to be derived from appearing epoxy 800-940Cm ^-1 disappeared. In the H-NMR, the proton (δppm 3.0-3.4) at the base of the epoxy group shown in FIG.
It is shifted to a low magnetic field of 3-3.6, and it can be seen that the epoxy ring is open.

The results of Examples 2 to 8 are similarly shown in Tables.
2

[0062]

[Table 2]

From these, it is considered that the following structure is a compound of the main component.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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Hereinafter, representative spectral data will be attached as drawings.

[0073]

Compared with type phosphorus-containing compound obtained in [Effect present invention conventionally known, in particular exerts a pigment, a specific effect on the metal charge as a dispersant, an extremely high effect. 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 chart of a raw material epoxy compound used in Example 1.

FIG. 2 is an IR chart of the phosphorus- containing compound of Example 1.

FIG. 3 shows H ¹ − of the raw material epoxy compound used in Example 1.
It is an NMR chart.

FIG. 4 is an H ¹ -NMR chart of the phosphorus- containing compound of Example 1.

FIG. 5 is an NMR chart of a raw material epoxy resin of Example 1.

FIG. 6 is a GPC chart of a raw material epoxy resin of Example 1.

FIG. 7 is an IR chart of a raw material epoxy resin of Example 1.

FIG. 8 is an NMR chart of the phosphorus- containing compound of Example 1.

FIG. 9 is an IR chart of the phosphorus- containing compound of Example 1.

FIG. 10 shows NM of a raw material epoxy compound used in Example 4.
It is an R chart.

FIG. 11: GP of raw material epoxy compound used in Example 4
It is a C chart.

FIG. 12 IR of raw material epoxy compound used in Example 4
It is a chart.

FIG. 13 is an NMR chart of the phosphorus- containing compound of Example 4.

FIG. 14 is a GPC chart of the phosphorus- containing compound of Example 4.

FIG. 15 is an IR chart of the phosphorus- containing compound of Example 4.

FIG. 16 shows NM of a raw material epoxy compound used in Example 2.
It is an R chart.

FIG. 17: GP of raw material epoxy compound used in Example 2
It is a C chart.

FIG. 18 IR of raw material epoxy compound used in Example 2
It is a chart.

FIG. 19 is an NMR chart of the phosphorus- containing compound of Example 2.

FIG. 20 is a GPC chart of the phosphorus- containing compound of Example 2.

FIG. 21 is an IR chart of the phosphorus- containing compound of Example 2.

FIG. 22 is a GPC chart of the phosphorus- containing compound of Example 1.

Continuation of the front page (72) Inventor Takashi Yamamoto 3-6-8 Kutaro-cho, Chuo-ku, Osaka-shi, Osaka Inside Toyo Aluminum Co., Ltd. (72) Inventor ▲ Taka ▼▼ 3-chome, Kutaro-cho, Chuo-ku, Osaka-shi, Osaka No. 8 Toyo Aluminum Co., Ltd. (56) References JP-A-2-209997 (JP, A) JP-A-4-149289 (JP, A) JP-A-59-227923 (JP, A) JP-A-56 -100822 (JP, A) U.S. Pat. No. 3,346,667 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 9/09 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A phosphorus-containing compound represented by the following general formula [1] . Embedded image 2. The phosphorus-containing compound according to claim 1, wherein the compound of the general formula [1] has the following structural formula [3] . Embedded image 3. The phosphorus-containing compound according to claim 1, wherein the compound of the general formula [1] has the following structural formula [4] . Embedded image 4. A phosphorus-containing compound wherein the compound of the general formula [1] has the following structural formula [6] . Embedded image 5. The following formulas [7], [8] and [9]Or
Any of the epoxy compounds represented by [10] and the molecule
-OP (= O) (OH)_TwoWith a compound containing a group
The method according to any one of claims 1 to 4, wherein
Listed phosphorus-containing compoundsThingManufacturing method. Embedded imageEmbedded imageEmbedded imageEmbedded image 6. The method for producing a phosphorus-containing compound according to claim 5, wherein the compound having —OP (＝ O) (OH) ₂ is orthophosphoric acid or a monoester thereof. .