JPH0717988A - Phosphorus-containing compound and production thereof - Google Patents

Abstract

PURPOSE:To obtain the compound providing a specific action particularly on pigments and metal materials as a dispersant and having a flame-retardant effect by reacting a specific phosphorus-containing compound with a compound having a specific group in the molecule. CONSTITUTION:The compound of formula I [R, A are 1-20C alkyl, alkenyl; X is -P(=O)(OH)2; i is 1-10] is obtained by reacting (A) a compound of formula II (A' is 1-20C glycidyl group-having group) with (B) a compound having -OP =O)(OH). group 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 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 such problems, a novel organophosphorus compound having an excellent function was found.

[0007]

That is, the present invention relates to 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 [2] with a compound containing a —OP (═O) (OH) ₂ group in the molecule. The present invention relates to a method for producing a phosphorus-containing compound represented by [1].
The present invention will be described in detail below.

[0010]

[Chemical 4]

In the general formula [1], R has 1 to 2 carbon atoms.
Is an alkyl or alkenyl group of 0, and A has 1 carbon atom
~ 20 alkyl or alkenyl groups, depending on the chemical structure of the starting epoxy compound [2].
R having more than 20 carbon atoms is not preferable because it has too many saturated alkyl groups and becomes too soft as a resin. X is -P (= O) (OH) ₂ and i is 1 to
It is an integer of 10 and corresponds to the number of epoxy groups in the starting epoxy compound. When i exceeds 10, the epoxy compound is unstable and gelation is likely to occur during the addition reaction, which is not preferable.

The epoxy which is one of the starting material components of the phosphorus-containing compound represented by the general formula [1] is an epoxy compound represented by the general formula [2]. General formula [2]
In, R is an alkyl group or an alkenyl group having 1 to 20 carbon atoms, A'is a compound having a glycidyl group having 1 to 20 carbon atoms, and i is an integer of 1 to 10.

The compound represented by the general formula [2] is specifically sorbitol polyglycidyl ether, sorbitan polyglycidyl ether polyglycerol, polyglycidyl ether, pentaerythritol. Polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentylglycol diglycidyl ether, polyethylene glycol diglycidyl ether Examples thereof include compounds such as -ter, polypropylene diol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and diglycidyl adipate.

Examples of the phosphorus compound include monoesters of orthophosphoric acid. Suitable examples of phosphoric acid monoesters are monobutyl phosphate, monoamyl phosphate, monononyl phosphate, monocetyl phosphate, monophenyl phosphate, and monobenzyl phosphate. Phosphoric acid useful here includes:
From hydrated phosphoric acid to pure phosphoric acid, ie about 70%
To about 100% phosphoric acid, preferably about 85% phosphoric acid. The reason is that it is industrially easily available. When it is 70% or more, the amount of water is 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 and the like can 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 compound itself is unstable, and conversely, if the amount exceeds 4, it becomes difficult to control the reaction, which is not preferable.

As the reaction temperature, a reaction temperature of 25 ° C to 150 ° C, preferably 50 ° C to 100 ° 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 the presence of an inert solvent. As the solvent to be used, benzene, toluene, aromatic solvents such as xylene, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, ketone solvents such as isophorone, hexane, heptane, hydrocarbon solvents such as 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 that of 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. On the other hand, if it exceeds 20 times, it is uneconomical to use for paints, and therefore both are not preferable.

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

The end point of the reaction can be confirmed, for example, by measuring the oxirane oxygen by titration. 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.

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples. In addition, in the following, NMR refers to JEOL Ltd. “J
NM-EX270 "(solvent: deuterated chloroform or deuterated methanol), IR is JA SCO FT / IR-5
300, GPC is Shimadzu Corporation "HPLC LC-
6A SYSTEM "(column: polystyrene column,
Solvent: THF) was used.

Example 1 A mixture of 40 g of Epolide NT212 (diethylene glycol diglycidyl ether, epoxy equivalent 150) manufactured by Daicel Chemical Industries, Ltd. and 40 g of propylene glycol monopropyl ether was added to 28.8 g of phosphoric acid for about 1 hour. It dripped over. The reaction temperature rose to about 90 ° C. Although the temperature rises due to heat generation, the temperature was kept constant at 90 ° C. for about 2 hours after the end of heat generation. After cooling, the oxirane oxygen concentration of the reaction crude liquid was measured and found to be 3.0. From this, it is considered that the epoxy has almost reacted. Acid value is 316.0 mg /
It was KOH.

Example 2 A mixture of 40 g of Epolide NT214 (diethylene glycol diglycidyl ether, epoxy equivalent 215) and 40 g of propylene glycol monopropyl ether was added dropwise to 20.0 g of phosphoric acid over about 1 hour. The reaction temperature rose to about 90 ° C. Although the temperature rises due to heat generation, a constant temperature was maintained at 90 ° C. for about 2 hours after the end of heat generation. After cooling, the oxirane oxygen concentration of the reaction crude liquid was measured and found to be 0. From this, it is considered that the epoxy has almost reacted. The acid value was 239.0.

Example 3 A mixture of 40 g of neopentyl glycol diglycidyl ether and 40 g of propylene glycol monopropyl ether as an epoxy compound was added dropwise to 26.0 g of phosphoric acid over about 1 hour. The reaction temperature rose to about 90 ° C. Although the temperature rises due to heat generation, a constant temperature was maintained 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 found to be 0. The acid value was 280.0 mg / KOH. Fig. 6 is a NMR chart of the raw material epoxy compound, and Fig. 7 is a GPC chart of the same.
38 is also an IR chart. Fig.8 is an NMR chart of the phosphoric acid adduct, and Fig.9 is G chart of the phosphoric acid adduct.
Fig. 39 is a chart of PC, and Fig. 39 is a chart of IR of a phosphoric acid compound.

Example 4 Diglycerol polyglycidyl ether (epoxy equivalent 15
5) A mixture of 40 g and 40 g of propylene glycol monopropyl ether was added dropwise to 25.3 g of phosphoric acid over about 1 hour. Others were performed similarly to Example-1. The oxirane concentration was 0 and the acid value was 275. FIG. 10 is an NMR chart of the starting epoxy compound, FIG. 11 is a GPC chart, and FIG. 12 is an IR chart. FIG. 13 is an NMR chart of the phosphoric acid adduct, and FIG. 14 is an IR chart of the phosphoric acid adduct.

Example 5 A mixture of 40 g of polyethylene glycol diglycidyl ether (epoxy equivalent 587) and 40 g of propylene glycol monopropyl ether as an epoxy compound was added dropwise to 6.8 g of phosphoric acid over about 1 hour. Others were performed similarly to Example-1. The oxirane oxygen concentration was 0 and the acid value was 90.0. Figure-15
Is an NMR chart of the raw material epoxy compound, and FIG.
6 is a GPC chart, and FIG. 17 is an IR chart. Figure 18 shows the NM of the phosphate adduct.
FIG. 19 is an R chart, FIG. 19 is a GPC chart of a phosphate adduct, and FIG. 20 is an IR chart of a phosphate adduct.

Example 6 As an epoxy compound, a mixture of 40 g of tripropylene glycol diglycidyl ether (epoxy equivalent of 198.7) and 40 g of propylene glycol monopropyl ether was added dropwise to 19.8 g of phosphoric acid over about 1 hour. Others were performed similarly to Example-1. The oxirane oxygen concentration was 0 and the acid value was 227.
Spectral data was measured for each of the obtained phosphorus compounds. Figure 21 shows the NMR of the starting epoxy compound.
FIG. 22 is an IR chart, and FIG. 23 is the same GPC chart. Fig. 24
Is an NMR chart of a phosphoric acid adduct, FIG. 25 is a GPC chart of a phosphoric acid adduct, and FIG. 26 is an IR chart of a phosphoric acid adduct.

[Example-7] The sample synthesized in Example-3 was depressurized by a rotary evaporator at 80 ° C to 100 ° C for 2 hours at 2 to 5 mHg to remove volatile matter.
Spectral data was measured. When the infrared spectrum was measured, the spectrum changed from that shown in FIG. 1 (raw material epoxy) to that shown in FIG. That is, 950 cm ^{-1 to} 1100
Absorption derived from P—O was observed at cm ⁻¹ . H ¹ -N
Regarding MR, the epoxy of Fig. 3 changed as shown in Fig. 4. As a characteristic change, δ2.6-2.8 ppm
, The peak of the epoxy group disappeared and changed to 2.05 ppm of methylene. At the same time, the absorption of protons of phosphoric acid can be found at 8.0 ppm. Regarding the molecular weight, the distribution is as shown in FIG. 5, and the number average molecular weight was 457, the weight average molecular weight was 832, and MW / MN = 1.82 (in terms of polystyrene).

For Examples 8 to 12, the same analysis as in Example 7 was performed.

[Example-8] The spectral data of each sample of Example-1 was measured. FIG. 27 is an NMR chart of the starting epoxy compound, FIG. 28 is an IR chart, and FIG. 29 is a GPC chart. Figure 30 shows the NMR chart of the phosphoric acid adduct.
FIG. 31 is a GPC chart of the phosphate adduct, and FIG. 32 is an IR chart of the phosphate adduct. The results of characterizing each chart of the phosphoric acid adduct are shown below. NMR (δ ppm): 8.2 (P-OH) 4H, 3.9
-4.2 (CH) 2H, 3.2-3.7 ( CH 2) 1
2H; I. R (cm ^-1 ): 3736 (OH), 2879
(Alkyl group), 1000-1020 (PO); GP
C: MW = 749, MN = 383, MW / MN = 1.9
54

[Example-9] The spectrum data of each sample of Example-2 was measured. Figure 33 is the NMR chart of the raw material epoxy compound, Figure 34 is the same IR chart, and Figure 35 is the same GPC chart.
It is FIG. 36 is a GPC chart of the phosphate adduct, and FIG. 37 is an IR chart of the phosphate adduct. The results of characterizing each chart of the phosphoric acid adduct are shown below. NMR (δ ppm): 3.9-4.2 (CH), 3.
_{2-3.7 (CH 2), 8.2 (} P-OH); I. R
(Cm ⁻¹ ): 3700 (OH), 2878 (alkyl group), 1010-1100 (P—O absorption); GPC:
MW = 740, MN = 370, MW / MN = 2.0

[Example-10] The results of characterization of each chart of the phosphoric acid adduct of Example-3 are shown below. NMR (δ ppm): 8.0 (P-OH) 4H, 3.8
-4.2 (CH) 2H, 3.8-3.4 ( CH 2) 8
_{H, 2.0 (CH 2) 4H} , 0.8 (CH 3) 6H; I.
R (cm ^-1 ): 3700 (OH), 2800 (alkyl group), 950-1100 (P-OH); GPC: MW =
832, MN = 457, MW / MN = 1.82

[Example-11] The results of characterization of each chart of the phosphoric acid adduct of Example-4 are shown below. NMR (δ ppm): 8.1 (P-OH) 6H, 3.8
-4.3 (CH) 4H, 2.9-3.7 ( CH 2) 20
H; I. R (cm ^-1 ): 3300 (P-OH), 287
0 (alkyl group), 980-1060 (P-OH)

[Example-12] The results of characterization of each chart of the phosphoric acid adduct of Example-5 are shown below. NMR (δ ppm): 8.1 (P-OH) 4H, 3.8
-4.2 (CH) 2H, 2.8-3.8 ( CH 2) 24
H; I. R (cm ^-1 ): 3366 (OH), 2878
(Alkyl group), 980-1050 (P-O absorption); G
PC: MW = 602, MN = 472, MW / MN = 1.
277

[Example-13] The results of characterization of each chart of the phosphoric acid adduct of Example-6 are shown below. NMR (δ ppm): 8.2 (P-OH) 2H, 4.2
-3.8 (CH) 4H, 3.8-3.2 ( CH 2) 14
_{H, 1.2 (CH 3) 9H} : I.R (cm -1): 2879
(Alkyl group), 1000-1100 (P-O absorption);
GPC: MW = 575, MN = 461, MW / MN =
1.248

[0036]

The phosphorus-containing compound obtained in the present invention exerts an extremely high effect as a dispersant, in particular, exerts a peculiar action on pigments and metal materials 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 chart of a raw material epoxy compound used in Example-3 (Example-7).

FIG. 2 is the phosphoric acid adduct I of Example-3 (Example-7).
It is the R chart.

FIG. 3 is a H ¹ -NMR chart of a raw material epoxy compound used in Example-3 (Example-7).

FIG. 4 H of the phosphoric acid adduct of Example-3 (Example-7)
^1- NMR chart.

FIG. 5: G of phosphoric acid adduct of Example-3 (Example-7)
It is a PC chart.

FIG. 6 is an NM of a raw material epoxy compound used in Example-3.
It is the R chart.

FIG. 7: GP of raw material epoxy compound used in Example-3
It is a C chart.

FIG. 8 is an NMR chart of a phosphoric acid adduct of Example-3.

9 is a GPC chart of the phosphoric acid adduct of Example-3.

FIG. 10 shows N of a raw material epoxy compound used in Example-4.
It is an MR chart.

FIG. 11: G of the raw material epoxy compound used in Example-4
It is a PC chart.

FIG. 12: I of raw material epoxy compound used in Example 4
It is the R chart.

FIG. 13 is an NMR chart of a phosphoric acid adduct of Example-4.

FIG. 14 is an IR chart of the phosphoric acid adduct of Example-4.

FIG. 15 shows N of a raw material epoxy compound used in Example-5.
It is an MR chart.

FIG. 16: G of the raw material epoxy compound used in Example-5
It is a PC chart.

FIG. 17: I of raw material epoxy compound used in Example-5
It is the R chart.

FIG. 18 is an NMR chart of a phosphoric acid adduct of Example-5.

FIG. 19 is a GPC chart of the phosphoric acid adduct of Example-5.

FIG. 20 is an IR chart of the phosphoric acid adduct of Example-5.

FIG. 21 shows N of a raw material epoxy compound used in Example-6.
It is an MR chart.

FIG. 22: I of raw material epoxy compound used in Example-6
It is the R chart.

FIG. 23: G of the raw material epoxy compound used in Example-6
It is a PC chart.

FIG. 24 is an NMR chart of a phosphoric acid adduct of Example-6.

FIG. 25 is a GPC chart of the phosphoric acid adduct of Example-6.

FIG. 26 is an IR chart of the phosphoric acid adduct of Example-6.

FIG. 27 is an NMR chart of a raw material epoxy compound used in Example-1 (Example-8).

FIG. 28 is an IR chart of a raw material epoxy compound used in Example-1 (Example-8).

FIG. 29 is a GPC chart of the raw material epoxy compound used in Example-1 (Example-8).

FIG. 30 is an NMR chart of a phosphoric acid adduct of Example-1 (Example-8).

FIG. 31 is a GPC chart of the phosphoric acid adduct of Example-1 (Example-8).

FIG. 32 is an IR chart of the phosphoric acid adduct of Example-1 (Example-8).

FIG. 33 is an NMR chart of a raw material epoxy compound used in Example-2 (Example-9).

FIG. 34 is an IR chart of a raw material epoxy compound used in Example-2 (Example-9).

FIG. 35 is a GPC chart of a raw material epoxy compound used in Example-2 (Example-9).

FIG. 36 is a GPC chart of the phosphoric acid adduct of Example-2 (Example-9).

FIG. 37 is an IR chart of the phosphoric acid adduct of Example-2 (Example-9).

FIG. 38: I of raw material epoxy compound used in Example-3
It is the R chart.

FIG. 39 is an IR chart of the phosphoric acid adduct of Example-3.

Front page continuation (72) Inventor Takatsugu Yamamoto 3-6-8, Kutaro-cho, Chuo-ku, Osaka City, Osaka Prefecture Toyo Aluminum Co., Ltd. No. 8 Toyo Aluminum Co., Ltd.

Claims (4)

[Claims] 1. A phosphorus-containing compound represented by the following general formula [1]. [Chemical 1] 2. The compound represented by the general formula [1] is a phosphoric acid adduct of propylene glycol diglycidyl ether, a phosphoric acid adduct of diethylene glycol diglycidyl ether, a phosphoric acid adduct of trimethylolpropane triglycidyl ether, or penta. The compound according to claim 1, which is a phosphoric acid adduct of erythritol tetraglycidyl ether. 3. A compound represented by the following general formula [2]:
The method for producing a phosphorus-containing compound according to claim 1 or 2, which comprises reacting with a compound having a -OP (= O) (OH) ₂ group in the molecule. [Chemical 2] 4. The method for producing a phosphorus-containing compound according to claim 3, wherein the compound containing a —OP (═O) (OH) ₂ group in the molecule is orthophosphoric acid or a monoester of orthophosphoric acid.