JPH01265094A - Novel phosphorus-containing unsaturated compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R$1 is H or methyl; R2 and R3 are formula II (n is 1-3 or 5; Cl may be substituted at any position) and either of R2 and R3 may be H; however, must not simultaneously be H; m is 0 or 1; A is 1-50C hydrocarbon residue in which the backbone or branched chain is alkoxy(carbonyl), acid amide, hydroxy, ether, halogen- or 1-4C lower alkyl-substituted aryl, halogen- or 1-4C lower alkyl-substituted arylene or alkylene which is substituted or unsubstituted by the above-mentioned aryl or halogen]. EXAMPLE:Bis(2-chlorophenyl) phosphorochloridate. USE:A flame retardant, antistatic agent, antifouling agent, biological repellent, antifungal agent and herbicide. PREPARATION:POCl3 is reacted with a halogen-substituted phenol in the presence of MgCl2 and then 2-hydroxyethyl acrylate, etc., in the presence of a tertiary amine in an organic solvent.

Description

[Detailed Description of the Invention] [Industrial Application Field] The compound of the present invention is a novel phosphorus-containing unsaturated compound having flame retardancy, antistatic property, antifouling property, biorepellent property, antifungal property, herbicidal property, etc. It concerns compounds.

For example, in recent years, many synthetic resins used in the fields of electricity, electronics, automobile parts, etc. are required to be flame retardant, and the compound of the present invention can be used as a vinyl comonomer for these synthetic resins. It can provide extremely good flame retardancy.

In addition, the compound of the present invention has antistatic properties, repellency to living things,
It is used in applications such as paints and synthetic resins that require antifungal properties, and can also be used in fields such as herbicides.

[Conventional technology]

Acrylate monomers or methacrylate monomers containing phosphorus for the purpose of imparting flame retardancy and antistatic properties have already been known;
No. 1588) Most of these compounds are acid phosphates, alkyl or aryl phosphates with phosphoric acid groups, and acrylate monomers or methacrylates containing phosphorus are esterified with aryl groups substituted with chlorine atoms such as the compounds of the present invention. The monomers and their oligomers are not disclosed at all.

[Problem to be solved by the invention]

The present inventors have developed a novel phosphorus-containing unsaturated compound having an aryl group substituted with a chlorine atom in order to improve performance such as flame retardancy, which was insufficient with the conventional acid phosphate, alkyl or aryl phosphate monomers. The present invention has been completed through development, and the compound of the present invention can simultaneously impart properties such as antistatic properties, antifouling properties, biorepellent properties, and antifungal properties to paints, resins, etc. It was also found that it has excellent properties such as herbicidal properties.

In other words, the compound of the present invention provides flame retardant, antistatic, antifouling, biorepellent, and antistatic properties to paints, resins, etc., because conventional acrylate or methacrylate monomers containing phosphorus are insufficient. The object of the present invention is to provide a novel phosphorus-containing unsaturated compound that dramatically improves mold and herbicidal properties.

[Means to solve the problem]

The present invention provides a novel phosphorus-containing unsaturated compound represented by the following formula -1.

"Here, in formula (I), R1 is a hydrogen atom or a methyl group, RHR3 is the same or 'A
0C” (n is l, 2, 8 or 5? C1
may be substituted at any position), and one of & and R may be a hydrogen atom, but must not be a hydrogen atom at the same time. m is 0 or l. When m is 0, it gives a phosphonate, and when m is 1, it gives a phosphate. A is a linear or branched C8-C5° hydrocarbon residue whose main chain or branch is an alkoxy group, an alkoxycarbonyl group, an acid amide group, a hydroxy group, an ether group, a halogen, or a C+ "" Cs lower alkyl substituted aryl group, halogen or Ct "" Cs
The lower alkyl-substituted arylene group or A is a linear or branched C8-CSO halogen-substituted or unsubstituted alkylene group. A in the above general formula CI) is as shown in Table 1 below, and examples include those having the following structures.

CH2-CH2CH2-CHz CH-90CHs CHtCHtOCCFbCHzCHsCHsCPb
-CH1CH! 0CHz-1 -CHfCH,OCNH-+CH2←NHCC)T2-
.

CHzCHCHzOCCH2CHtCOCHz-1 The compound of the invention can be synthesized in good yield by the methods t1+, +21 described below or other known methods.

(Organic bath medium A) (A-class amine) R-Cut = O-001!' Here, R1 and A are the same as above. By reacting the 710-gen substituted phenol, a highly pure f phosphoric acid diester can be easily obtained.

In this case, potassium chloride, magnesium chloride, aluminum chloride,
Use titanium tetrachloride, etc.

Particularly preferred are potassium chloride and magnesium chloride. +1
Examples of compound (a) in 1 include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 8-chloro-2-hydroxypropyl acrylate, 3-chloro-2- Hydroxypropyl methacrylate, 8-phenoxy-2-hydroxypropyl acrylate, 8-7 dynoxy 2-hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glyconyl acrylate, polypropylene glycol methacrylate, caprolactone-modified 2-hydroxyethyl acrylate or Examples include caprolactone-modified 2-hydroxyethyl methacrylate.

These (compound a) and the above-mentioned phosphoric acid diester are
The compound of the present invention can be obtained in high purity by reacting in the presence of a tertiary amine, which is a dehydrochlorination agent, at a temperature of 0 to 50°C, preferably 20 to 80°C. Examples of the tertiary amine include dimethylaniline, triethylamine, tributylamine, and pyridine.

The reaction is usually carried out in an organic solvent, and in that case, examples of the organic solvent include hydrocarbon solvents such as benzene, toluene and xylene, and ester solvents such as ethyl acetate and butyl acetate. However, alcoholic solvents such as ethanol and butanol that react with the above-mentioned phosphoric acid diesters are not suitable. is also manufactured. That is, (compound b) is heated in an organic solvent in the presence of a tertiary amine at -20°C to +50°C, preferably at 0S
This method involves reacting with acrylic acid chloride or methacrylic acid chloride at 10°C. The organic solvent and tertiary amine here are the same as in [1].

[Example 1] Synthesis of intermediate I C bis(2-chlorophenyl)phosphorochloridate] 168.99 (1, Imol) of phosphorus oxychloride was placed in nine reactors equipped with a stirrer, a thermometer, a condenser, and a temperature control device. , 2-
Chlorophenol 282. y y (2,20 mol
) and 1.69 y of magnesium chloride, and the temperature was gradually raised to 80°C.Then, while gradually raising the temperature from 80°C to 150°C, the dehydrochloric acid reaction was carried out at about 8 o'clock.
Then, while maintaining the temperature at 150° C., the reaction thread was depressurized to s OwH9 to completely remove the hydrochloric acid from the vermilion ink and obtain an intermediate 1.871.5 y as a colorless feeding liquid.

Synthesis of target product 1 [bis(2-chlorophenyl)-2-methacryloyloxyethyl phosphate] 182.6 y (1,2 mol) of 2-hydroxyethyl methacrylate
), triethylamine toe, t p (1,05 mo
l) and toluene 646.57 to the reactor, then the above intermediate 1.887.59! (summer mol) was gradually added to the reaction solution while maintaining the temperature of the reaction solution at 20 to 80°C, and after the addition, the reaction was continued for 2 hours while maintaining the reaction solution at 40 to 50°C.

Next, in order to remove triethylamine hydrochloride produced as a by-product during the reaction, the reaction solution was repeatedly washed with cold water, and toluene was distilled off under reduced pressure to obtain the desired product, 1.4 tg, sy (yield: 9
7.1%).

This material has the following physical properties.

Appearance: Yellow-brown transparent liquid LC purity: 98.7chi (LCC purity liquid-liquid chromatography purity elemental analysis value calculated value: C50,144H8,97% p7.184
R16,44% measured value; CSo, 81%H8,8
9chi p7.12% C116.58% The measured value agrees well with the calculated value, indicating that it is a novel phosphorus-containing unsaturated compound of the present invention.

[Example 2] Synthesis of target product 2 [bis(2-chlorophenyl)caprolactone-modified 2-methacryloyloxyethyl phosphate] Compound 246 having the following structure, which is a condensate of 1 mol of 2-hydroxyethyl methacrylate and I mol of bis-caprolactone. ny (t, otmol), triethylamine 106.1 y (1,05 mol) and toluene 8
17.5 y was charged, and intermediate 1* of Example 1 was added to this.
387.51 (Imol) was converted into the target substance 1 of Example 1.
Under the same conditions as the synthesis of target compound 2, 587.5 y
(Yield 98.2 cm) was obtained. This material has the following physical properties.

Appearance: Reddish brown transparent liquid Elemental analysis calculated value: C52,86% H4,99S P5.6
81 R13,00% measurement value: C5B, 014 H
5.12% ps, 59% C112, 89% From the above, the calculated values were in good agreement with the measured values, and it was found that this is a novel phosphorus-containing unsaturated compound of the present invention.

[Example 3] Synthesis of Intermediate 2 [bis(2,4,6-)lichlorophenyl)phosphorochloridate] In place of 2-chlorophenol 282.7y in Example 1, 2,4,6-dolichloro Phenol 484.5 y (
The reaction was carried out in the same manner as in the synthesis of Intermediate 1 in Example 1, except that 2.2 mol) of Intermediate 2.524 was used as a white solid.
．． Obtained 2y.

Target 3 [bis(2,4,6-)lichlorophenyl)-
101.6 p (1.05 mol) of 2-methacryloyloxyethylphosphatecotriethylamine and 284.59 p of toluene were charged, and 569 p.p. of toluene was added in place of Intermediate 10 in advance. Ofi! The above intermediates 2 and 4
A solution containing 75.5y (Imol) was added under the same conditions as in Example 10 for the synthesis of Target 1, and the reaction was completed. Then, the same post-processing was performed to obtain the target object 3.550.2.
y (yield os, y%) was obtained. This material has the following physical properties.

Appearance: White solid LC purity: SS, S elemental analysis calculated value: C88, Go [2,10% p5.44
Chi OI! 87.89chi Measurement value: 8g, 12% [
2,361% p 5.40chi C187,12chi The measured value was in good agreement with the calculated value, and it was found that this is a novel phosphorus-containing unsaturated compound of the present invention.

[Example 4] The following structural formula (denoted by Q).

Bis(2,4-dichlorophenyl)-2-hydroxyethyloxymethylphosphonate 446 y (r mo
l), triethylamine 04.0 y (1,011 m
ol) and toluene 7719 were charged into a reactor, and then methacrylic acid chloride s06.6 f/ (1,02 mol), which had been cooled in advance to 10°C or lower, was gradually added.
The reaction solution was added to the reaction solution while maintaining the temperature at 0 to 10°C.

After the addition, the reaction was continued for about 2 hours while slowly raising the temperature and maintaining the reaction solution at 40 to 50°C.

Then, after repeatedly washing the reaction solution with cold water, toluene was distilled off under reduced pressure to obtain a novel phosphorus-containing unsaturated compound (d) 478. Oy (yield 93%) was obtained. This material has the following physical properties.

Appearance: Yellow transparent liquid LC purity: 99.2% Calculated elemental analysis value: C44, 19% H8, 88% p 6.02%
Cl 27.58ch Measured value: C44.54% l(8
,80% p 5.97% QI! The measured value of 27.51% was in good agreement with the calculated value and was found to be a novel phosphorus-containing unsaturated compound of the present invention.

Based on the synthesis method of target product 1 in Example 1, in place of 2-hydroxyethyl methacrylate, unsaturated alcohol with the following structure and intermediate 1 (Example 1) or intermediate 2 (
The structure and physical properties of the target product obtained by reacting Example 3) are described in the second column.

Example 5 (8-phenoxy-2-hydroxyglobyl acrylate) Example 6? 1゛o cpbct (8-chloro-2-hydroxypropyl methacrylate) Example 7 [Example 8] Based on the synthesis method of [Example 4], bis(2,4-dichlorophenyl)-2-hydroxyethyl, oxymethyl Example 1 shows the structure and physical properties of the target product obtained by reacting bis(4-chlorophenyl)-2-hydroxyethyloxymethylphosphonate represented by the following structural formula (e) with methacrylic acid chloride instead of the phosphonate. - 7 are summarized in the second article.

-Q ( [Effects of the Invention] Due to the characteristics of the chemical structure, the compound of the present invention can be copolymerized with other monomers or prepolymers to form a copolymer, and is a highly flame retardant for paints, resins, etc. It has remarkable effects as an antistatic agent, antifouling agent, biorepellent, antifungal agent, and herbicide.

Procedural amendment (voluntary) 1. Indication of the case Patent Application No. 92801 of 1988 2. Name of the invention New phosphorus-containing unsaturated compound 3. Person making the amendment Relationship to the case Patent applicant 4. Agent 〒550 6 , In the description of the amendment (page 111, line 4 to page 2, line 5, scope of claims, as attached) (2) In line 6 from the bottom of page 2, "system conomer" is corrected to "system monomer" (3) On the 4th line from the bottom of page 2, "the present invention" is corrected to "also the present invention" (4) On the 2nd line of page 3, "conventional" is corrected to "conventionally," (6) on the 5th line of page 3, "there is (6)
1st line from the bottom of page 4 r (n is I, 2.8 or 5.)
(7) On the last line of page 4, “may be substituted” is corrected to “may be substituted” (8) On page 5, line 10, after “arylene group”, “substituted with” Insert ``(9) 6th line 10th r (n*'v2tL5) J to r(n=112t3t5
) Correction to J 0O) Correction to page 6, line 11 (11) 'Correction to page 2, line 1 - Move "Example" to "first line" in table 1, page 8.

(l(1) same, line 8 in the table 0 phrases in the table on page 9 Move "Example" to "first line".

(Forward to page 10, in the table) Move "Example" to "first line".

(17) In the table on page 11 Move "Example" to "first line".

QQ Same, 3rd and 4th rows in the table Correct r　CH,J to r　CH3J (Volume 1, same, line 6 in the table) Inside page table rmJ's 4111! Insert lK “0” r21) Same, same Move "Example" to "3rd line" by K.

Kan, same, line 6, p. 13, line 2, corrected "for phosphorus" to "for phosphorus," (Foundation) same, 1
Line 0 was corrected to "Hydroxyethyl Jtr Hydroxyethyl" 4. Line 8 from the bottom of page 15, "Implemented, then" was corrected to "Implemented. Then," Page 16, line 5 r (1-2 mol) J (1,02 mol)
Corrected to J - same, the last line "I understand." was changed to "I found out." In the second line from the bottom of page 17, "The calculated value is the measured value" was changed to "The measured value is the calculated value." Correction 4: Page 18, line 1, “(Example 3)” was corrected to “(Example 3)” - Page 18, 14
Correct line ``instead of'' to ``instead of,'' (31)
Page 19, line 8, change “Measurement value: 3g, 12%” to “Measurement value: C38,12
(32) On the first line from the bottom of page 19, “physical properties” was corrected to “physical property value” (31) On the sixth line of page 21, “rEO ethylene oxide” was corrected to “rEO=ethylene oxide” (34) On the bottom of page 21 From line 8 to line 9, "ethyl, oxy" is corrected to "ethyloxy" (85) Page 21 end line "O Correction (36) 22 Jj 2nd fi-t"J Example 4, Bw
A middle HOCHt CHt OCHt P HOC
H2CHt OCH2F-(87) Page 23, line 5~
Line 6, “Repellent” was corrected to “Repellent” (3g) (Added) Page 19, Lines 7 to 8, “Represented by the structural formula 〇.

Bis(2,4-)J [Corrected to bis(2,4-)j shown by structural formula 〇 Scope of claims general formula A novel phosphorus-containing unsaturated compound represented by

[Here, R8 in formula (I) is a hydrogen atom or a methyl group, and R,, R, may be substituted at the same or the same position. ), and any one of R, , R, may be a hydrogen atom, but must not be a hydrogen atom at the same time. m is O
Or l. A is linear or branched CI""'C5
0 hydrocarbon residue whose main chain or C branch is an alkoxy group, an alkoxycarbonyl group, an acid amide group, a hydroxy group, an ether group, a halogen or a C1 to C4 lower alkyl substituted aryl group, a halogen or CI" is substituted with a C4 lower alkyl-substituted arylene group, or A is a linear or branched C0-C3 halogen-substituted or unsubstituted alkylene group." Procedural amendment (Spontaneous) June 80, 1988 1. Display of the case 1988 Patent Application No. 92801 2. Name of the invention New phosphorus-containing unsaturated compound 3. Person making the amendment Relationship to the case Patent applicant name Director President Kozo Kitamura 4, Agent 〒550 6. In the statement of contents of the amendment (1) page 9 line 8 Hj CH.

(Page 211G, 2nd line r = t ~ 7 r = door (3) 2nd page 6th line from the bottom (procedural amendment submitted on June 3, 1988, 2nd page y6) t2
Re-correction of section i) Pressure of “system comonomer” to “thread comonomer” 14t 1
Middle line of page 1 (Re-correction of paragraph Q1 on page 4 of the procedural amendment submitted on June 8, 1988) Procedural amendment (voluntary) July 77, 1988 / 1 BA I JΔ Commissioner of the Japan Patent Office Yoshi 1 ) Moon Tsuyoshi 1, Indication of the case 1986 Patent Application No. 92801 2, Title of the invention New phosphorus-containing unsaturated compound 3, Person making the amendment Relationship with the case Patent applicant 4, Agent 〒550 6, Amendment In the contents statement of

Claims (1)

[Claims] A novel phosphorus-containing unsaturated compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I). "Here, in formula (I), R_1 is a hydrogen atom or a methyl group, R_2 and R_3 are the same or different ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (n is 1
, 2, 3 or 5, Cl may be substituted at any position. ), and either one of R_2 and R_3 may be a hydrogen atom, but must not be hydrogen atoms at the same time. m is 0 or 1. A is linear or branched C_1 to C_
5_0 hydrocarbon residue whose main chain or branch is an alkoxy group, an alkoxycarbonyl group, an acid amide group, a hydroxy group, an ether group, a halogen or a C_1 to C_4 lower alkyl substituted aryl group, a halogen or a C_1 to C_4
The lower alkyl-substituted arylene group of_4 or A is a linear or branched alkylene group of C_1 to C_5_0 substituted with halogen or unsubstituted. ”