JPS6078993A - Organic phosphorus compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula [X is H, or carboxyl; X' is H, methyl, or carboxyl (when X is not carboxyl); Y is methylene, ethylene, or branched propylene; Y' is 1-4C alkylene; R is 1-22C hydrocarbon; R' is methyl, or ethyl; a-e are 0, or 1; a+b=0, or 1; b+c=0, 1, or 2; a+c=0, or 1; 0<=p<=20; 0<=q<=50, 0<=r<=5; l is 1-3; m and n are 0, 1, or 2; l+m+n=3; with the provido that Y must be 2-hydroxypropylene when X and X' are not carboxyl]. EXAMPLE:3-Allyloxy-2-hydroxypropyl hypophosphite. USE:A reactive surface active agent, an emulsion polymerization agent for plastic, etc. PREPARATION:For example, an acidic phosphorus compound (e.g., phosphorous acid, etc.) is reacted with a glycidyl compound (e.g., allyl glycidyl ether, etc.) in a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel organic phosphorus compounds, more specifically, P-
The present invention relates to a phosphorus compound characterized in that a group having at least one terminal double bond and an alcoholic OH group or a COOH group is connected via an O bond.

There are many compounds with P-0 bonds, so-called phosphoric acid esters, which are industrially useful. It is known as an anionic surfactant type partial ester (having an acid residue) which is used as an emulsifier or a dispersant. However, there are only a few phosphate ester surfactants that have unsaturated bonds, such as oleyl alcohol, which have internal double bonds as raw materials for hydrophobic groups; Most of the compounds containing a bond are known, and even more so, those having a terminal double bond and an alcoholic OH group or a C0OH group at the same time, such as the organophosphorus compound of the present invention, have not been known at all.

As a result of extensive research, the present inventor has determined that the maximum amount of acidic P in phosphorus compounds
Either 1 to 3 moles of one or more compounds having a terminal double bond and a glycidyl group (hereinafter referred to as a specified glycidyl compound) are reacted by selecting preparation conditions that allow all of the -OH groups to react. ■t One of the phosphorus compounds having at least one glycidyl substituent (hereinafter referred to as the specified glycidyl-substituted phosphorus compound)
A monocarboxylic acid having a terminal double bond (hereinafter referred to as a predetermined unsaturated monocarboxylic acid) is prepared by selecting charging conditions such that all of the glycidyl groups in a given tucuricidyl-substituted phosphorus compound can react with each mole of the species or two or more species. (referred to as a carboxylic acid) or a dicarboxylic acid having a terminal double bond (hereinafter referred to as a predetermined unsaturated dicarboxylic acid) or 1-124411 or more (n) to a minimum of hydroxyalkyl substituents. To the maximum extent possible, all the alcoholic OH groups in the predetermined hydroxyalkyl-substituted phosphorus compound can react with 1 mole of 1a or 2 or more of the compound (hereinafter referred to as the predetermined hydroxyalkyl-substituted phosphorus compound) having at least one Either one or more of the specified unsaturated dicarboxylic acids or their anhydrides or reacted with 3 moles of hydroxyalkyl monoesters of the specified unsaturated dicarboxylic acids by selecting the appropriate charging conditions (1 M of one or more of the hydroxyalkyl monoesters of the specified unsaturated dicarboxylic acids) 3 moles or a combination of 2 moles and 1 mole of one or more types of monohydric alcohol or its alkylene oxide adduct (hereinafter referred to as a predetermined hydroxy compound), phosphorus pentoxide or oxychloride. React with 1 mole of phosphorus,
or fvl 1 m or 2 or more 1-2 moles of a hydroxyalkyl monoester of a specified unsaturated dicarboxylic acid, or 1 mole and 1 or 2 moles of a specified hydroxy compound.
Phosphorus oxychloride 1 for combination with 1 mole or more of species
After reacting 1 to 2 moles of water, the following general formula I (where X is hydrogen or a carboxyl group, K is hydrogen, a methyl group, or only when X is not a carboxyl group) Carboxyl group and 4%1
．． Y is a methylene group, an ethylene group, a branched propylene group, a branched butylene group, or a 2-hydroxypropylene group y/
represents an alkylene group having 1-4 carbon atoms, R represents a hydrocarbon group having 1-22 carbon atoms, and R' represents a methyl group or an ethyl group, respectively;
a, b, c, d and e are each 0 or 1-il, and a+b is 0 or 1. b+c is oll or 2, a+c
ViO or 1, and P, g and r are O≦P≦20.
04t450, 0, 4r≦5, t is 1, 2 or 3
, ride, l or 2, n is an integer of 0, l or 2, and represents 4+m+n-3, and in the relationship between x, x' and Y, when neither X nor X' is a carboxyl group, Y is 2 - and a droxypropylene group. ) We have arrived at the invention of obtaining a novel organic phosphorus compound shown in (1).

Here, the predetermined acidic phosphorus compound which is one of the raw materials for the organic phosphorus compound of the present invention includes, for example, orthophosphoric acid, phosphorous acid, hypophosphorous acid, m-alcohol moddiester of orthophosphoric acid, and Diesters, moddiesters and diesters of alkylene oxide adducts of m alcohols of orthophosphoric acid,
Examples include monohydric alcohol heptadiesters of phosphorous acid and monoesters of alkylene oxide adducts of m-alcohols of phosphorous acid.
Examples of the glycidyl-substituted phosphorus compounds include vinyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate, and glycidyl memethacrylate. diglycidyl ester of -
Orthophosphoric acid triester containing a residue of an alkylene oxide adduct of a -hydric alcohol and a glycidyl group at the same time, a normal/acid triester containing a residue of an alkylene oxide adduct of a -hydric alcohol and a glycidyl group at the same time, a -hydric alcohol residue and a glycidyl group at the same time Examples include phosphite diesters containing phosphorous acid diesters, and phosphorous acid diesters containing both a residue of an alkynone oxide-attached jJO form of a -hydric alcohol and a glycidyl group.

In addition, examples of the predetermined unsaturated monocarboxylic acids include acrylic acid and methacrylic acid; examples of the predetermined unsaturated dicarboxylic acids include maleic acid and itaconic acid; and furthermore, the predetermined hydroxyalkyl-substituted phosphorus compounds include For example, tri(2-hydroxyethyl) orthophosphate, tri(2-hydroxypropyl) orthophosphate, tri(2-hydroxybutyl) orthophosphate, di(2-hydroxyethyl) orthophosphate, iE diphosphate (2-hydroxypropyl),
Di(2-hydroxybutyl) orthophosphate, mono(2-hydroxybutyl) orthophosphate
2-hydroxyethyl), mono(2-hydroxypropyl) orthophosphate, mono(2-hydroxybutyl) orthophosphate,
Di(2-hydroxyethyl) sulfite, di(2-hydroxyethyl) sulfite
-hydroxypropyl), di(2-hydroxybutyl) sulfite, mono(2-hydroxyethyl) phosphite, mono(2-hydroxypropyl) phosphite, mono(2-hydroxybutyl) phosphite, 1 mol or 2 mol ethylene oxide adduct of m alcohol modiesters or diesters of orthophosphoric acid, 1 mol or 2 mol ethylene oxide adduct of m alcohol modiesters or diesters of orthophosphoric acid, m of orthophosphoric acid 1 mol or 2 mol butylene oxide adduct of m alcohol modiesters or diesters, 1 mol or Vi 2 mol ethylene oxide adduct of m alcohol modiesters or diesters of orthophosphoric acid, m orthophosphoric acid alkylene oxide adducts, 1 mol or 2 mol gloprene oxide adduct of alkylene oxide adduct of m alcohols, 1 mol or 2 mol gloprene oxide adduct of m diester or diester of alkylene oxide adduct of m alcohols, 1 mol or 2 mol of butylene oxide adduct of m diester or diester of alkylene oxide adduct of m alcohols of orthophosphoric acid. Adduct, 1 mole ethylene oxide adduct of m alcohol monoester of phosphorous acid, l mole propylene oxide adduct of m alcohol monoester of phosphorous acid, 1 mole butylene of 11 alcohol monoester of phosphorous acid Oxide adduct, 1 mole ethylene oxide adduct of monoester of alkylene oxide adduct of monohydric alcohol of phosphorous acid, monoester of alkylene oxide adduct of monohydric alcohol of phosphorous acid (p1
molar propylene oxide adduct, a 1 molar butylene oxide adduct of a monoester of an alkylene oxide adduct of a monohydric alcohol of phosphorous acid, a 1 molar or 2 molar formaldehyde adduct of m alcohol modiesters or diesters of orthophosphoric acid, 1 of the moddiester or hashiester of the alkylene oxide adduct of monohydric alcohol of orthophosphoric acid
Molar or 2 molar formaldehyde adduct, m of phosphoric acid
Examples of the predetermined hydroxy compound include 1 mol formaldehyde adduct of 1 mol of alcohol monoester and 1 mol formaldehyde adduct of 9-alkylene oxide-attached monoester of phosphorous acid monohydric alcohol. , methyl alcohol, ethyl alcohol, furobyl alcohol, isopropyl alcohol, methyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, tenyl alcohol, dotesyl alcohol, isopropyl alcohol, tetratercyl alcohol, hexatecyl alcohol Examples include alcohol, ophtateryl alcohol, hexyl alcohol, and their ethylene oxide, propylene oxide, butylene oxide, formaldehyde adducts or coadducts. In that case, the coadduct may be a random type in which identical alkylene chains are not consecutive.

Phosphorus Next, to explain in detail the method for producing an organic acid phosphorus compound of the present invention, the reaction between a predetermined acidic phosphorus compound and a predetermined glycidyl compound is carried out under normal pressure at 30-250°C, preferably at 50-1
It is carried out by bringing the two into contact at 50°C, but in this case, the use of a diluting solvent that does not participate in the reaction, such as hexane, heptane, dioxane, L2-dimethoxyethane, ethylene dichloride, carbon tetrachloride, etc., speeds up the completion of the reaction. . The reaction between a predetermined glycidyl-substituted phosphorus compound and a predetermined unsaturated monocarboxylic acid or a predetermined unsaturated dicarboxylic acid can also be easily carried out by bringing the two into contact with each other at 30-250°C, preferably 50-150°C, under normal pressure. carried out, in this case mo,
Use of diluent solvents without active hydrogen, such as hexane, heptane, dioxane, ethylene dichloride, carbon tetrachloride, etc., accelerates the reaction.

Subsequently, the reaction between the predetermined hydroxyalkyl-substituted phosphorus compound and the predetermined unsaturated dicarboxylic acid is carried out by heating and dehydrating at 50-300°C, preferably 100-200°C under reduced pressure or normal pressure. Introducing a gas that does not participate in the reaction, such as carbon dioxide residue, or using an azeotropic solvent such as benzene, toluene, or xylene makes it easier to complete the reaction. Further, the reaction between the predetermined hydroxyalkyl+-converted phosphorus compound and the anhydride of the predetermined unsaturated dicarboxylic acid is carried out under normal pressure at 30-200°C, preferably at 100-150°C.
This can be easily carried out by bringing the two into contact at a temperature of 0.degree. C. In this case as well, a diluting solvent that does not contain active hydrogen, such as hexane, heptane, dioxane, ethylene dichloride, or carbon tetrachloride, may be used.

Further, the reaction between a hydroxyalkyl monoester of a predetermined unsaturated dicarboxylic acid or a combination thereof with a predetermined hydroxy compound and phosphorus pentoxide or phosphorus oxychloride is carried out at 20-150°C under reduced pressure or normal pressure, preferably at 5o-too°C. This is done by bringing the two into full contact with each other, and in this case too, introducing gases that do not participate in the reaction, such as N, gas, carbon dioxide, etc., or introducing gases such as benzene, toluene, xylene, hexane, heptane, dioxane, ethylene dichloride, carbon tetrachloride, etc. The use of diluent solvents without active hydrogen speeds the reaction to completion.

In addition, among the organic phosphorus compounds of the present invention, in particular those having 8 carbon atoms
-22 hydrocarbon group? Those with one or two groups exhibit excellent performance as reactive surfactants, and S
Various rubbers such as BR, NBR, 2-chlorobutadiene, acrylic esters, methacrylic esters, vinyl esters of various carboxylic acids, olefins, vinyl chloride,
In addition to acting specifically as an emulsion polymerization agent or suspension polymerization agent for plastics such as vinylidene chloride and styrene, it also functions as a permanent antistatic agent for internal or external use on these rubbers, plastics, nylon, tetron, acrylonitrile fibers, etc. have. The organophosphorus compounds of the present invention as such and their polymerized grooves can serve as mold release agents in some cases and adhesives in others. Further, it is expected to be useful as an O/W type or W2O type emulsifier for various organic substances, and at the same time to have good performance as a dispersant for inorganic substances such as gold or its oxides.

Furthermore, in addition to acting as an oiliness improver for water-soluble hydraulic oils and a lubricant for water-insoluble hydraulic oils, it is also thought to have functions as an anti-fouling agent and a scale remover.

Examples are shown below.

Example 1 The following i-1 was added to a five-tube flask equipped with a stirrer, a thermometer, a dropping device, a gas inlet tube, and an adapter for connecting to a measuring tube.
[1] Add 66# (1 mol) of phosphoric acid and 600II of dipropyl ether to make a fractional liquid, and then dissolve allyl niblicidyl ether 1141J (1 mol) t- at 70-80°C.
The dropwise addition took 2 hours. Next, the internal temperature was raised to 90°C, and after reacting for 4 hours at 90-100°C and 2-4 K4/ca, the pressure was returned to normal pressure, and while passing through N2 gas,
2 hours at the same temperature? In total, 600 g of dipropyl ether was recovered, and later, colorless and transparent 3-allyloxy-2-hydroxybrovir=71 ibophosphite was obtained.

Elemental analysis value C, H, 80, P Iodine value calculation value part I
C40,00H727PI3.20 141.1 (Theoretical (straight 140.9) Experimental value (Hani) C40,Q8 H7
28PI3.19 1R spectrum)NoCtc 165
0cyn-' 1) o-H3345cm' Example 2 Phosphite 82P (1 mol) was added to the same apparatus as in Example 1.
After heating and melting at 80°C, vinyl-glycidyl-ether 100.11 (1 mol) was added dropwise over 4 hours, and the reaction was continued for 2 hours at the same temperature to form a colorless and transparent monomer. (3-vinyloxy-2-hydroxypropyl)-phosphite was obtained.

Elemental analysis value C, H1!0. P Calculated iodine value (%)
CVL97 H6,09PI3.00 138.9
(Theoretical value ta9.4) Experimental value (qbI C346
H6, 11PI3.03 IR Susuitor V'Csc
16550A"JO-" 3345 cy+' Example 3 Into the same apparatus as in Example 1, 370.49 k of an equimolar mixture of mono(methoxyethyl)-phosphate and di(methoxyethyl)-phosphate was charged, and the temperature was raised to 60°C. After that, 3 sta, p (a mol) of glycidyl acrylate was added dropwise over 5 hours, and the reaction was continued for another hour at the same temperature.
An equimolar mixture of -acryloyloxy-2-hydroxypropyl)-phosphate and di(methoxyethyl)hamono(3-acryloyloxy-2-hydroxypropyl) I11 phosphate was obtained.

,,) c=c 1647 c〆1 JQ-H3340c nail-l Example 4 In the same apparatus as in Example 1, mono(nonylphenoxypoly(9 mol) ethyleneoxyethyl)mophosphene L l-
Equimolar mixture of N51-(9 mol) ethyleneoxyethyl)-phosphate 2126
After charging 9t and raising the temperature to 75℃, glycidyl acrylate was completely charged and added dropwise, and then reacted at 80-85℃ for 5 hours to produce a yellow transparent mono(nonylphenoxy poly(9 mol) ethylene oxyethyl). )=mono(3-methacryloyloxy2-hydroxypropyl)-phosphate and di(
An equimolar mixture of nonylphenoxy poly(9 mol) ethyleneoxyethyl)-mono(3-methacryloyloxy-2-hydroxypropyl)-phosphate was obtained.

Elemental analysis value J-(C42,)l W O17P +
C! 7. Positive-04P) Iodine value V'C; c 1645
(m' uo-M 3340 can' Example 5 In the same manner as in Example 4, mono
9 mol) ethyleneoxyethyl) isophate and di(
Equimole A compound of intridecoxypoly(9 mol) ethyleneoxyethyl)-phosphate (A) Va 206611 was reacted with glycidyl methacrylate 284.29 (2 mol) to form a slightly yellow transparent liquid mono(indridecoxypoly( Equimole/1 of ethyloxyethyl)-mono(3-methacryloyloxy-2-hydroxypropyl)-phosphate was also synthesized.

Experimental level %l C57,78H9,60P 243
1 R spectrum V'C=C1645crh-')'0-)1 3340 cm' Example 6 In an apparatus similar to Example 1, mono(butoxypoly(20-
"mol) oxypropylene poly(50 mol) oxyethylene poly(5 mol) oxymethylene)-phosphe) 36
After preparing 6.8 g (0.1 mol) and 850 g of dioxane to make a homogeneous solution, vinyl-glycidyl-ether 1
0# (0.1 mol) was added and reacted at 90°C for 10 hours. Next, the temperature was raised to 120°C, and 850 g of dioxane was recovered over 3 hours at the same temperature, and later a light yellow paste of mono(butoxypoly(20 moles), oxypropylene poly(50 moles), oxyethylene poly( 5 mol) oxymethine/)-mono(3-vinyloxy-2-hydroxypropyl)-phosphate gold was obtained.

Elemental analysis value CI? 4 H34Q o8. 'p Calculated iodine value (C55, 45H9, 34Po, 82
6.71 (Theoretical Direction 674) Experimental Value (%l C55,
43H935PO180IR spectrum "y" 6
50 (ffil sio-u 3345 cv-') Example 7 As in Example 1, di(tocosyloxypoly(2)
0 mol) oxybutylene)-phosphate 183.2y
(o, x mol) After total charging and heating to 80° C., gusipoly(20 mol) oxybutylene)-mono(3-acryloyloxy-2-hydroxypropyl) phosphate was obtained.

Elemental analysis value Cl084+otep Iodine value calculation value (
%l C66, 18Hll, 01 Pi, ss tzl
Theory 1i1a, o) Experimental value (%l C66,21Hll
, 00P1.56 IR Susuitor V'C-c 164
5 (y; )ノ0. 1 3345c Example 8 In a device similar to Example 1, triglycidyl orthophosphate 26
6.2.9 (1 mol) After charging, 10% of acrylic acid 216.219 (3 mol) was added while cooling at 60°C.
The mixture was added dropwise over a period of time, and further aged at 70-80°C for 2 hours to obtain tri(3-acryloyloxy-2-hydroxypropyl)-phosphate as a slightly yellow transparent liquid.

Elemental analysis value Cl8 H2?011 P Calculated iodine value (%) C44,82H5,64P6.42 157
．． 5 (theoretical value 157.9 > experimental value (%l C44,80
H5,64P6.43 1R spectrum 1c-c 16
50 C,4 Jo-H3340cwv' Example 9 In an apparatus similar to Example 1, methyl-glycidyl-phosphite) 152.1. fl (1 mol) fully charged ryo, 60
Methacrylic acid 86.1.9 (1
mol) was added dropwise over 5 hours, and then heated to 70-80°C.
The mixture was aged for 2 hours to obtain a colorless transparent liquid methyl-3-methacryloyloxy-2-hydroxypropyl-phosphite.

Elemental analysis value C8H,,06P Calculated iodine value (Chil
C40,33H6,35P 13.00 106.4
(Silver AP) Experimental value (%l C40,31H6,34P
13. OOIR suite V'C=c], 645,,
, -+ JO-H3345crn" Example 10 In the same apparatus as in Example 1, methoxypoly(20
mol) Oxypropylene poly(50 mol) Oxyethylene poly(5 mol) Oxymethylene nidocosyl fricidyl-phosphate 399.1 g (0.1 mol) and acrylic acid 7.2 F (0.1 mol) Total charge , reacted at 90-100°C for 5 hours under the flow of N2 gas to form white wax-like methoxypoly(20 mol), oxypropylene poly(50 mol), oxyethylene poly(5 mol), oxymethylene poly(3-mol) Acryloyloxy-2-hydroxyglobil phosphate was obtained.

Elemental analysis value Cl94H38T o, □P Iodine value experimental value (%l C57,33H9,62P0.74 1R
Spectrum lct 1648 (7-'v'o- + 43345 cyI-' , it took 3 hours at the same temperature to produce methacrylic acid 8.
6.1N (1 mol) was added dropwise and further aged for 2 hours to obtain dilauryl-3-methacryloyloxy-2-hydroxypropyl-phosphate as a slightly yellow transparent liquid.

Elemental analysis value C194H38□082P Iodine value calculation l1lf (%l' C57,35H9,60Po,7
6' 6.24 (Theoretical value 625) Experimental value (%l C5
7,33H9,62Po,74 1R spectrum WC=
'1648 Cm-l 5. ) o・u 3345C I Example 11 485.6 g (1 mol) of dilauryl-glycidyl range phosphate was charged into the same apparatus as in Example 1, and after raising the temperature to 90°C, it was heated at the same temperature for 3 hours. Then, 86.1 N (1 mol) of methacrylic acid was added dropwise to the mixture, and the mixture was further aged for 2 hours to obtain dilauryl-3-methacryloyloxy-2-hydroxybrovir phosphate as a slightly yellow transparent liquid.

Elemental analysis value C,, H o, p Iodine value theory 1 direct calculation value (@C65, 12H9, 87P5.42 44.
4 (44,4) Experimental value (C65,09H9,86
P5.40 IR suite X) C=c 1645 c
η9 Vlo-s 3345 Cl11-' Example 12 Octylphenoxy poly(8
mole) oxyethylene=glycidyl-phosphite 67
After charging 8.89 (1 mol) and raising the temperature to 80°C,
Acrylic acid 724F (1 mol) was obtained at the same temperature for 2 hours.
was added dropwise and further aged for 5 hours to form a colorless transparent liquid octylphenoxypoly(8 mol) oxyethylene-3.
-Acryloyloxy-2-hydroxypropyl-phosphitera obtained.

Elemental analysis value C38H63014P Iodine value experimental value (
@C57,59H8,4S P4.11 1R spectrum Jc=c 1647 Cl11-' QO-g 3345 c weight-1 Example 13 In an apparatus similar to Example 1, di(oleyl poly(8 mol)
(oxyethylene)-glycidyl-phosphate 1307
．． 7.9 (1 mol) was charged, the temperature was raised to 90°C, and the temperature was set.
86.1y (1 mol) of methacrylic acid was added dropwise over 1 hour at the same temperature, and further aged for 3 hours to form a yellow transparent liquid di(oleylpoly(8 mol)oxyethylene)-3.
-methacryloyloxy-2-hydroxyprohydrophosphate)'iJ.

Elemental analysis value C,,H,. o2sp iodine value calculation value (
%i C61,18H10,20PL, Zl 54.5
(Rijimi1') 54.6 Experimental value (@ C61, 16HI0.19PZ, 20 I
C1645c+η1 Jo-I'+3345 crn-' Example 14 Example 14 Into the same apparatus as in Example 1, add as much as ophtateryl (50 mol) oxyethylene-diglycidyl-phosphate) 266
．． 5F (0.1 mol) i was dissolved in 200 g of 1.2-dimethoxyethane and heated to 80 t; then 17.2 # (0.2 mol) of methacrylic acid was added and the mixture was heated at the same temperature for 4 hours. Made it react. Then, 59 m-th decyl poly(50 mol)oxyethylene poly(3-methacryloyloxy-2-hydroxypropyl)-phosphate was obtained.

Elemental analysis value C8°H2°0. . P Calculated iodine value (
%l C55,8? ' H9, 2θP1.09 17.
9 (Desired) Experimental value (%i C3a86H9,2IP1
．． 07 1R spectrum c=c 1650 (H-l)o-I+3340 Cwl Example 15 In an apparatus similar to Example 1, maleic acid 11.6 #(0
, 1 mol) in 150# acetone, and then dioctyl-glycidyl-
37.9 # (0.1 mol) t" of phosphate was added and reacted for 3 hours. Then, the internal temperature was raised to 60°C,
N gas is introduced to distill the acetone of 509 out of the system, and a slightly yellow liquid dioctyl-3-maleoyloxy-
2-Hydroxypropyl functional phosphate was obtained.

Elemental analysis value CゎH, 0゜P Calculated iodine value (C
55,85H&76 P6.2651.0 (Theoretical value 5
L3) Experimental value (%l C3a83 H&76P6.25
1B Spectrum SoC=Cl645cmI1cso1710ζ1-arJs In an apparatus similar to Example 1, itaconic acid 13.0p (
Next, 25011 pe/zene was injected and heated to 70°C to dissolve 2yB itaconic acid, and then tocosyl poly(20 moA/)oxypropylene-glycidyl-phosphite 160 .8g (o, 1 mole)
was added and reacted for 5 hours. Next, the internal temperature was 80℃
250.9% of benzene was distilled out at 80-85°C for 2 hours by introducing Nt scum into a pale yellow paste of tocosyl poly(20 mol) oxopropylene.
3-itaconoyloxy-2-hydroxypropyl phosphite was obtained.

Elemental analysis value coo noise 0. ．． p Calculated iodine value (%)
C6Z18H10,26P1.78 14.6 (theoretical value 14.6) Experimental value (%lc6!16H10,24P17
6 IEL Space Jl/S) Cric 1648c → )/1CeO1710cm" (3CI4) Example 17 Di(2-hydroxyethyl) was added to the same apparatus as Example 1.
-Phosphite l? o# (1 mol>k), heated to 90°C, and then heated at the same temperature for 5 hours to form maleic anhydride 1
9e, 1 g (2 mol) was added slowly.

Then, the internal temperature was raised to 5°C and ripened at the same temperature for 2 hours to synthesize white wax-like di(maleoyloxymethyl)-phosphite.

Elemental analysis value C1tH15011P Iodine value calculation value (%
l C39,35) 14.13 P8.46 13&5
(Theoretical value 138.6 Experimental value (%l C39,33H4
, 13P & 44 IR Suittle-1/1 (sc 16
45 cdi1 Example 18 In an apparatus similar to Example 1, di(methoxypoly(20 mol) oxybutylene) class hydroxymethyl phosphate aoz4y (o, t mol) and malei/acid 11.6p (
o, 1 mol) and 5001 toluene, 105
After 4 hours at -110°C, 1.8 # of water was distilled out of the system. Then, the internal temperature was lowered to 1-80℃, and 50-
5001 of toluene was recovered under a reduced pressure of H,9 to obtain di(methoxypoly(20 mol)oxybutylene)-maleoyloxymethyl-phosphate as a pale yellow liquid.

Elemental analysis value C11ff H2S2O8P Iodine value 1
c=c 1645 ('1+1' Into the same apparatus as in Example 1, docosoloxypterouge (
2-hydroxybutyl) l=1 phosphate 311.5
g (0,5 mol) and itaconic acid 65.1.9 (0,
5 mol) and boron trifluoride-ether) 0.15 J'
The mixture was heated at 190-200°C for 8 hours under the flow of nitrogen gas, and 18 g of water was distilled out of the system. Hydroxybutyl-phosphate was obtained.

Elemental analysis value '4oHyaQ6P Iodine value calculation value (chil
C6a73 Hlo, 29 P4.22 34.4
(Theoretical value 345) Experimental value (%) C6λ71 Hlo, 2
? P4.20 1 R spectrum) no c=c 164
7(v;I soC=o, 1710(,,-+ (a-)) Example 20 In the same apparatus as in Example 1, octylpoly(20 mol)oxypropyleneoxymethyldi(2-hydroxyethyl)!phosphate was added. Prepare 889.4g (1 mol),
After heating to 100°C, it took 4 hours to convert maleic anhydride 19
6.1 g (2 moles) was added to the awns and aged at the same temperature for 3 hours to obtain a colorless liquid octyl poly(20 moles).
Oxypropyleneoxymethyl Nawate di(2-maleoyloxyethyl)miphosphate was obtained.

Elemental analysis value C61HII8018 P Iodine value calculation value (%) C67,49Hlo, 49 P2S546.7
(Theoretical value 46.8) Experimental value C%l C67,46Hlo
, 50 P 13 I LX vector JC-c 164
7 (, J Example 21 Into the same apparatus as in Example 1, 564.5.9 (3 mol) of mono(2-hydroxybutyl) maleate was charged, and 70
After raising the temperature to ℃, phosphorus pentoxide 142II (1
t - 5 hours, and further aged for 3 hours to form a yellow paste of mono(2-maleoyloxybutyl)-phosphate and di(2-maleoyloxybutyl) phosphate. A molar mixture was obtained.

Experimental value (Aya C40, 79H5, 14P8.79 IR
Susuitor VC=c 1645 (f1゛l Into the same apparatus as in Example 1, 564.1 (3 mol) of mono(2-hydroxypropyl) itaconate and 100,100 O of 1,2-dimethoxyethane were charged, and then heated to 70°C. Then, at the same temperature, 142 g (1 mol) of phosphorus pentoxide was added over a period of 5 hours, and then, at the same temperature, 14219 phosphorus pentoxide (1 mol Hr) was added over a period of 5 hours. Aged.Continued, 50+l11
10009 of 12-dimethoxyethane was distilled out under reduced pressure of
-itaconoyloxybutyl)-phosphate and di(2
An equimolar mixture of -itaconoyloxybutyl)-phosphate was obtained.

Total X (if%l c4o, 80 H5, 14P 8.7
7 107.6 R1? ) Experimental value (Aya C40,80H
5,12Pa76 1R spectrum 7c=c 1645
, -Wl-1 In the same apparatus as in Example 1, mono(2-hydroxyethyl) maleate 320.2.9 (2 mol) and poly(50 mol) oxyethylene monododecyl ether 238 &
After charging 919 (1 mol) and raising the temperature to 60°C,
Phosphorus oxychloride 153.4E (1 mol) at -65℃
It took some time to drip. The apparatus is then evacuated and 50
-150-1O0 for 8 hours to remove by-product hydrogen chloride from the system, and then white waxy mono(dodecylpoly(50 mol)oxyethylene 1-di(2-maleoyloxyethyl)-phosphate) I got it.

Elemental analysis value Cl24H2+100ff2 P Iodine value theory 1 direct calculation value (correspondence) C54,09H8,75P1.13 1
8.4 ()18.4 Experimental value (%l C54,08Ha74p1.1a IR
,
After charging 30 ON'jH of dimethoxyethane, it was heated to 60°C, and then phosphorus oxychloride 153°C was added at 60-65°C.
41 (x mol) was added dropwise over a period of 4 hours, and hydrogen chloride as a by-product was removed from the system over a period of 4 hours while nitrogen gas was introduced into the system. Next, 5 (llllIll
After distilling 300 g of 1,2-dimethoxyethane under reduced pressure of H# for 2 hours, 36 J+ (2 mol) of water was added, and newly produced hydrogen chloride was distilled under a nitrogen stream. The residue was removed from the system to obtain slightly yellow waxy mono(2-itaconoyloxybutyl)-phosphate.

Elemental analysis value CoHhOgP Iodine value calculation (direct (%l)
C3B, 30 H5, 36Plo, 98 89.6
(Mechanical, *1 shift 89.9) Experimental value (%l C38,32H
5,3SP10.97 1R spectrum tag 0go c 16
47Cura-1 On the surface of the same apparatus as in Example 1, 34 & 3 # (2 mol) mono(2-hydroxypropyl) maleate toshioxane 50019'i was sorted, and after heating to 60°C, 60-7
Phosphorus oxychloride 153.4P (1 mol) was added dropwise over a period of 4 hours at 0°C, and the reaction was further carried out for 5 hours under a nitrogen stream to remove by-product hydrogen chloride from the system.

Next, 1 si (t mol) of water was added, and newly generated hydrogen chloride was removed from the entire system, and then TO-80■11.9
500 g of geogysanate gold was distilled out over a period of 3 hours under reduced pressure, yielding a yellow paste of di(2-maleoyloxypropyl) phosphate.

Elemental analysis value Cl4HI90□, P Iodine value calculation value (%
l C40,98H4,67P7.55 1219 (
Theoretical value 123.7) Experimental value part I C40,96H4,6
6P7.55 IR SUITRUSHIC-C-1645C- CISC1705cJ (δcIl+) Example 26 Same as Example 1! 11, monohydroxymethyl itaconate 160.1 F (1 mol) and 2-ethylhexyl alcohol 130.2. fl (1 mol) total charge, 6
After heating to 0℃, phosphorus oxychloride 153.4 at the same temperature
．． 90 mol) was added dropwise over a period of 3 hours, and the reaction was further carried out for 6 hours under a nitrogen stream to remove by-product hydrogen chloride from the system.

Next, 1811 (1 mol) of water was added to remove newly generated hydrogen chloride from the system, and a slightly yellow paste-like 2-
Ethyl helicyl 2-itaconoyloxymethyl deprived phosphate was obtained.

Elemental analysis value C14 electron o, p Iodine value calculation value f%l C47,72H7,15P8.79 7
1.8 (Theoretical value 720) Experimental value (@C47,69H
7,15P8.78 1R spectrum t=c 164
5cm-' Patent applicant: Toho Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. General formula I (However, X is hydrogen or a carboxyl group, K is hydrogen, a methyl group or a carboxyl group only when X is not a carboxyl group, Y is a methylene group, ethylene group, a branched propylene group, a branched butylene group, or a 2-hydroxypropylene group, Y is an alkylene group having 1 to 4 carbon atoms, R is a hydrocarbon group having 1 to 22 carbon atoms, and ``represents a methyl group or an ethyl group, respectively. represents, a%b, c, d and eri are each 0 or ril, and 8+b is 0 or 1.b+c is 0, l or 2, a+'e is 0 or 1, Pst and r are 0
<P<20, o<t<so, O≦r 45, t is 1.2 or 3, m is 0, l or 2, n is an integer of 0.1 or 2, and t+m+n-3 , and X%X
In the relationship between ' and Y, when neither X nor K is a carboxyl group, Y must be a 2-hydroxypropylene group. ) Organophosphorus compounds shown in 2 The compound represented by general formula I is mono(nonylphenoxypoly(9 mol) ethyleneoxyethyl)=mono(3-
The organic phosphorus compound according to claim 1, which is methacryloyloxy-2-hydroxypropyl)-phosphate. The organic compound according to claim 1, wherein the compound represented by the general formula Phosphorus compound. A compound represented by the general formula 1.
-methacryloyloxy-2-hydroxypropyl)-
The organic phosphorus compound according to claim 1, which is a phosphate. 5. The compound represented by the general formula 1 is di(isotritechoxypoly(9 mol) ethyleneoxyethyl)-mono(3-
The organic phosphorus compound according to claim 1, which is methacryloyloxy-2-hydroxypropyl)-phosphate. 6. Phosphorus compound having at least 1 P -OH group t1M (
For 1 mole of two or more types of 1 ijl (hereinafter referred to as the predetermined acidic phosphorus compound), the terminal terminal is selected by selecting preparation conditions that will allow maximum reaction of all the P-OH groups in the predetermined acidic phosphorus compound. NMI of a compound having both a heavy bond and a glycidyl group (hereinafter referred to as a specified glycidyl compound)
Or, react 2 or more 1-3 moles, or,
lal of a phosphorus compound/rostrum having at least one glycidyl substituent (hereinafter referred to as a specified glycidyl-substituted phosphorus compound)
Alternatively, monocarboxylic acids having a terminal double bond (hereinafter referred to as a specified unsaturated monocarboxylic acid) are selected by selecting preparation conditions such that all the glycidyl groups in a specified glycidyl-substituted phosphorus compound can react to the maximum extent possible for 1 mole of two or more types. carboxylic acid)
Or react one or more dicarboxylic acids (hereinafter referred to as predetermined unsaturated dicarboxylic acids) with 1 to 3 moles of dicarboxylic acids having double bonds, or a hydroxyalkyl substituent? The alcoholic OH group in the predetermined hydroxyalkyl-substituted phosphorus compound to the maximum extent is Either one or two or more 1 to 3 moles of the specified unsaturated dicarboxylic acid or its anhydride are reacted by preparing the preparation conditions such that all of the components can be reacted, or the hydroxyalkyl monomer of the specified unsaturated dicarboxylic acid is prepared. For a combination of 3 moles of one or more esters, or 2 moles and 1 mole of lal or two or more of monohydric alcohols or their alkylene oxide adducts (hereinafter referred to as predetermined hydroxy compounds). , 1 mole of phosphorus pentoxide or phosphorus oxychloride, or 1 mole or more of 1 to 2 moles of hydroxyalkyl monoester of a given unsaturated dicarboxylic acid, or 1 mole and 1 mole of hydroxyalkyl monoester of a given unsaturated dicarboxylic acid; 1 mole of phosphorus oxychloride reacts with 1 mole of one or more compounds? ci, and a general formula I characterized in that 1 to 2 moles of water are reacted in total (however, X is hydrogen or a carboxyl group, K is hydrogen, a methyl group, or a carboxyl group only when X is not a carboxyl group) , Y is a methylene group, ethylene group, branched propylene group, branched butylene group or 2-hydroxypropylene group, Y is an alkylene group having 1-4 carbon atoms, R is a hydrocarbon group having 1-22 carbon atoms, R' represents a methyl group or an ethyl group, and a, bXc, d and e are each 0 or 1
And, a+b is 0 or l, b+c is 0.1 or 2,
a+C is 0 and 1, and P1? and r is 0≦P<2
0, O, (y-, (50, Ol;;, r 45, t is 1.2 or 3, m is 0, l is 2, n is an integer of 0.1 or 2, and t+m+n -3'e expression, and
X1! and Y, when neither X nor X' is a carboxyl group, Y must be a 2-hydroxypropylene group. ) A method for producing an organic phosphorus compound shown in 7: Reacting 2 moles of glycidyl methacrylate with a mixture of 1 mole of mono(nonylphenoxypoly(9 moles) ethyleneoxyethyl)-phosphate and 1 mole of di(nonylphenoxypoly(9 moles) ethyleneoxyethyl)-phosphate. Mono(nonylphenoxy poly(9)
mol)ethyleneoxyethyl)-mono(3-methacryloyloxy-2-hydroxypropyl)-phosphate and di(nonylphenoxypoly(9 mol)ethyleneoxyethyl)-mono(3-methacryloyloxy-2-hydroxypropyl)-phosphate The method for producing an organic phosphorus compound according to claim 6, wherein an equimolar mixture of the organic phosphorus compound and the organic phosphorus compound is obtained. 8. Mono(indoritekoxypoly(9 mol) ethyleneoxyethyl)...52 mol of glycidyl methacrylate for a mixture of 1 mol of phosphate and 1 mol of di(indoritekoxypoly(9 mol) ethyleneoxyethyl)-phosphate After complete reaction, mono(indoritecoxypoly(
9 mol) ethyleneoxyethyl) 2-mono(3-methacryloyloxy-2-hydroxypropyl)-phosphate and di(isotrite(9 mol) ethyleneoxyethyl) mono(3-methacryloyloxy-2)
7. The method for producing an organic phosphorus compound according to claim 6, wherein an equimolar mixture of -hydroxypropyl)-phosphate is obtained.