JPS61148217A - Phosphorus-containing polyphenol compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [Q1-Q3 are H, aliphatic group, aromatic group or phosphorus-containing group expressed by formula II (R' and R'' are aliphatic group or aromatic group), provided that at lest one of Q1-Q3 is expressed by formula II; R1-R3 are H, halogen, OH, aliphatic group or aromatic group; R4 is H or 1-4C alkyl; n is a number >=0]. USE:A flame retardant for curable resins, e.g. epoxy resins or phenolic resins. PREPARATION:A phenolic compound expressed by formula III-V is reacted with an aldehyde expressed by the formula R4CHO.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel phosphorus-containing polyphenol compound and a method for producing the same.

More specifically, in the following general formula (I) 1, the present invention provides Ql
, Q2 and Q8 are the same or different and are hydrogen, an aliphatic group, an aromatic group, or a phosphorus group represented by the formula (wherein R'' and R'' are the same or different and represent an aliphatic group or an aromatic group) Represents a containing group. However, at least one of Ql, Q2 and Q8 represents the phosphorus-containing group. R1, R2 and 佽 are the same or represent an alkyl group having a prime number of 1 to 4, and n represents a number of 0 or more.] A phosphorus-containing polyphenol compound represented by
), the following general formulas (n), (m) and (TV), Q+ 1OH [wherein Ql, Q2, Q8, R1, R2 and Ra have the above-mentioned meanings] 1. At least one species is reacted with an aldehyde represented by the following general formula (V) approximately 4cHo (v) [wherein IL4 has the above-mentioned meaning], or (2) the following general formula (
vr), [wherein R1, R2, R8-R4 and n have the above meanings, Yl, Y2 and Y8 are the same or different,
Hydrogen, aliphatic group, aromatic group or formula (wherein, X represents a halogen or hydroxy group)
represents a substituted methyl group represented by

However, at least one of yt + Y2 and Y8 represents the substituted methyl group. ] Polynuclear phenols represented by the following general formula (vn), [
In the formula, R″ and R″ have the above meanings, and R5 is 1e
Represents an aliphatic group. ] A method for producing a phosphorus-containing polyphenol compound represented by the general formula (T), characterized by reacting the compound with a phosphinite represented by the formula (T).

In the above general formula, examples of aliphatic groups represented by Ql, Q2- and Q8 include cI C,s alkyl groups such as methyl, ethyl, and butyl groups, and examples of aromatic groups include substituted or unsubstituted phenyl groups. be done.

The aliphatic groups represented by R'' and R'' include methyl,
Ct 04 alkyl groups such as ethyl, butyl, and aromatic groups include unsubstituted or lower alkyl groups (methyl,
An ethyl (t)substituted phenyl group is exemplified. Among these, methyl group, phenyl group, etc. are preferred.

The halogens represented by R1, R2 and R8 are chlorine,
Bromine, etc., and aliphatic groups include Ct-ct such as methyl, ethyl, propyl, butyl, octyl, nonyl, etc.
o Examples include alkyl groups, lower alkoxy groups such as methoxy and ethoxy, lower alkenyl groups such as allyl and isopropenyl, and aralkyl groups such as benzyl, and aromatic groups include unsubstituted or lower alkyl substituted phenyl or phenoxy groups. Illustrated.

Examples of the aliphatic group represented by R5 include CI-c4 alkyl groups such as methyl, ethyl, and butyl.

The phosphorus-containing polyphenol compound represented by the general formula (I) has the general formula (TI) -(m) and (tV)
It can be produced by reacting at least one phenol compound represented by the formula (V) with an aldehyde represented by the general formula (V).

Among the phenolic compounds represented by the general formula (II), (m) or (Iv), as Qz, Q2 or Q8, phosphorus represented by the formula (wherein R'' and R'' have the above meanings) Phenol compounds having a containing group include compounds represented by the general formula (■), H (wherein R1, R2, R8 and X have the above-mentioned meanings), and phosphinites represented by the general formula (VTI). It can be obtained by reacting with. This reaction can be carried out by mixing and heating and stirring in the absence of a solvent or in the presence of a solvent if necessary. Examples of the solvent used include ethyl ether, 1-tetrahydrofuran, dioxane, benzene, toluene, xylene, acetone, ethyl methyl ketone, and methyl isobutyl ketone. The reaction temperature is 20-150°C, preferably 30-120°C.

The phenolic compounds having a phosphorus-containing group obtained in this way include (dimethylphosphinylmethyl)phenol, (diethylphosphinylmethyl)phenol,
(diphenylphosphinylmethyl)phenol, (methylphenylphosphinylmethyl)phenol (more than 0
9m.

p-isomer), 2-dimethylphosphinylmethyl-5-methoxyphenol, 3-diphenylphosphinylmethyl-6-methoxyphenol, 2-diphenylphosphinylmethyl-5-bromophenol, etc. be able to.

Examples of the phenol compound represented by the general formula (II), (m) or (TV) and having no phosphorus-containing group include phenol, resorcinol, hydroquinone, cresol,
Examples include xylenol, ethylphenol, isopropylphenol, octylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol (including o, m, and p-isomers, respectively).

Specific examples of the aldehydes represented by the general formula [v] include formaldehyde, acetaldehyde, butyraldehyde, and the like.

The reaction between at least one phenolic compound represented by the general formula (It), (m') or (TV) and the aldehyde represented by the general formula (v) can be carried out using the following as a medium for an acidic catalyst:
Acidic catalysts used in the production of ordinary novoravuk type phenolic resins can be used, specifically sulfuric acid, hydrochloric acid,
Examples include inorganic acids such as phosphoric acid, organic acids such as para-toluenesulfonic acid and oxalic acid, and metal salts such as zinc acetate, zinc chloride, and tin tetrachloride. The polycondensation reaction can be carried out in the absence of a solvent or in the presence of a solvent. Examples of the solvent include toluene, dichlorobenzene, diphenyl ether, butanol, hexanol, and cyclohexanol.

The aldehyde represented by the general formula (V) is generally used in an amount of 0.5 to 1.0 mol, preferably 0.6 to 0.95 mol, per 1 mol of all phenolic components. The acidic catalyst is generally used in an amount of Q, 001 to 2 mol, preferably 0.01 to 1 mol, based on the total phenolic components.

The reaction temperature is usually 60 to 200°C, preferably 80 to 1
50"C. The time required for the reaction varies depending on the reaction temperature and other conditions, but is usually 1 to 20 hours.

After the reaction is completed, the catalyst used is neutralized if necessary, and water, solvent, etc. are distilled off under heating to obtain the phosphorus-containing polyphenol compound (I) of the present invention.

The phosphorus-containing polyphenol compound represented by the general formula (T) can also be produced by reacting a polynuclear phenol represented by the general formula (vr) with a phosphinite represented by the general formula (VU). can.

Polynuclear phenols represented by the general formula (Vt) have the following general formulas (TX), (X), (xr), (TX
) (X) (XT) [wherein, R1,
R2 and R3 have the above meanings, Y1', Y2'
and Y8' each independently represents a screw, an aliphatic group or an aromatic group. Among the phenols represented by 1, at least one is Y1'
, using phenols in which Y2' or Ys' is hydrogen, polycondensing them with aldehydes represented by general formula (V) using an acidic catalyst, followed by methylolation or halomethylation. be able to. Specifically, 5,5'-bishydroxymethyl-2,2'-dihydroxy-3,3-dimethyldiphenylmethane, 8°8
'-bishydroxymethyl-2,2'-dihydroxy-
5,5-dimethyldiphenylmethane, 8゜8'-bishydroxymethyl-5,5'-dibromo-2,2-dihydroxydiphenylmethane, α-hydroxymethyl-ω-
Hydroxy-tris [(2-hydroxy-5-methyl-
1,3-phenylene)methylene] and the like.

Specific examples of the phosphinites represented by the general formula (vn) include methyldimethylphosphinite, ethyldimethylphosphinite, methyldiphenylphosphinite, and ethyldiphenylphosphinite.

Polynuclear phenols (vr) and phosphinites (vn)
) can be carried out by heating, for example, from 20° to 150°C, in the same manner as the reaction between the compound (vm) and phosphinites (VU) described above.

The phosphorus-containing polyphenol compound (T) of the present invention thus obtained is blended into a curable resin such as an epoxy resin, urethane resin, urea resin, melamine resin, polybismaleimide resin, alkyd resin, or ordinary phenol resin. By doing so, a curable resin composition with excellent flame retardancy can be obtained. In addition, synthetic fibers such as polyester, polyamide or polyacrylonitrile, polyolefins,
It can also be used as an additive flame retardant for synthetic resins such as polystyrene or ABS resin. Furthermore,
Modifications such as glycidyl etherification and allyl etherification can provide novel flame-retardant thermosetting resins.

The present invention will be explained below with reference to Examples.

Reference Example 1 In a reactor equipped with a thermometer, a stirrer, and a condenser, 0-
(Hydroxymethyl)phenol (99.21 kg) and tetrahydrofuran (400 kg) were charged to form a homogeneous solution. Next, 184 g of ethyl diphenylphosphinite was charged, and the mixture was reacted for 3 hours while being heated and refluxed.

The reaction solution was cooled, and the precipitated white crystals were separated in a furnace and dried to remove 0.-(diphenylphosphinylmethyl)phenol 180%. The yield was 73%, and the melting point was 179°C.

Reference Example 2 Instead of 99.2g of 0-(hydroxymethyl)phenol, 99.2g of p-(hydroxymethyl)phenol
The reaction was carried out in the same manner as in Production Example 1 except that f was used to obtain 160 g of white crystalline P-(diphenylphosphinylmethyl)phenol. The yield was 65% and the melting point was 125"C.

Reference Example 3 Ethyldiphenylphosphinite 184f Reacts in the same manner as white crystals o -(diethylphosphinylmethyl)
Phenol 144f was obtained. Yield 85%, one point 127°
It was C.

Reference Example 4 P-
Cresol 540f, 80 g of 187.7% formalin and 20 g of 86% hydrochloric acid were charged and reacted at 60 to 65°C for 4 hours. Then, the water and unreacted p in the system are heated under reduced pressure.
- After distilling off the cresol, 2,2'-dihydroxy-5,5'-dimethyldiphenylmethane 142
Obtained f. When cooled, it solidifies and its melting point is 1
The temperature was 24°C.

Then, in a similar reactor, add 1850 f of water.

40 g of 20% caustic soda aqueous solution was charged and nitrogen was blown into the flask. Next, 114f of 2,2'-dihydroxy-5,5-dimethyldiphenylmethane was charged and dissolved uniformly, and then 119f of 87.7% formalin was added. 72
After reacting at ~75°C for 2 hours, it was cooled to 30°C and carbon dioxide gas was blown into it. When the pH of the system reached 7.1, the blowing of carbon dioxide gas was stopped. The precipitated white precipitate was separated in a furnace, thoroughly washed with water, and then dried under reduced pressure at room temperature.1.
Recrystallization from 2-dichloroethane gave 8,8'-bishydroxymethyl-2,2'-dihydroxy-5,5-dimethyldiphenylmethane 118f. Melting point is 147
It was ℃.

Example 1 In a reactor equipped with a thermometer, a stirrer, and a condenser, 92.4 f of 0-(diphenylphosphinylmethyl)phenol obtained in Reference Example 1, 19 f of para-toluenesulfonic acid hydrate, and 60 g of n-butanol were added. - and 105℃
The mixture was heated and stirred to obtain a homogeneous solution. 19.5 g of 37% formalin was charged here and reacted at 100 to 110°C for 7 hours. Then, 2Of 20% caustic soda aqueous solution was added to neutralize the catalyst. After separating and removing the aqueous layer, moisture, n-butanol, etc. were removed by vacuum concentration, and the resin
I got 1. The softening point of this resin was 162°C.

Number average molecular weight Mn of this resin determined by gel permeation chromatography (polystyrene equivalent)
is 1340, and the molecular weight distribution (Mw/Mn) is 1
．． It was 4.

Table 1 shows the results of H nuclear magnetic resonance spectra measured by dissolving this resin in dimethyl sulfoxide-d6.

From the above results, it was confirmed that the obtained resin was a novola-l of 〇-(diphenylphosphinylmethyl)phenol, and the repeating unit structure was as follows.

Table 1 Example 2 Same as Example 1 except that p-(diphenylphosphinylmethyl)phenol 92.4f obtained in Reference Example 2 was used instead of 〇-(diphenylphosphinylmethyl)phenol. Resin 94.1f was obtained.

Is it worth it? : Tree 111 was a novolak of p-(diphenylphosphinylmethyl)phenol.

Example 3 Into the same reaction apparatus as in Example 1, the 0-
(diethylphosphinylmethyl)phenol 106F,
Prepare 85% hydrochloric acid 5- and n-butanol 100-,
After heating to 100°C to uniformly dissolve, 82.49% of 87% formalin was charged and reacted at 100 to 110°C for 6 hours. Next, the aqueous layer was separated and removed, and then concentrated under reduced pressure to obtain Tree I11108.6 f.

The obtained resin is 0-(diethylphosphinylmethyl)
It was the phenol Novola Tsuku.

(2B) Example 4 In the same reaction apparatus as Example 1, the 0-
(diphenylphosphinylmethyl)phenol 61.6
fI, orrifresol 21.6f, concentrated hydrochloric acid 8m7! and toluene were added, and heated and stirred to obtain a homogeneous solution.

Add 87% formalin 26f to this, and add 100 to 1
The reaction was carried out at 05°C for 10 hours. After separating and removing the aqueous layer, the mixture was concentrated under reduced pressure to obtain 86 g of resin. The obtained resin is 0-(diphenylphosphinylmethyl)phenol/
It was an orthocresol copolymerized novolak.

Example 5 In the same reaction apparatus as Reference Example 1, 3 obtained in Reference Example 4,
115.2 F of 8'-bishydroxymethyl-2°2'-dihydroxy-5,5'-dimethyldiphenylmethane and 500 F of tetrahydrofuran were charged to form a homogeneous solution. Next, 184g of ethyldiphenylphosphinite
After charging, the mixture was reacted at 67 to 70°C for 4 hours. After the reaction is complete, the reaction solution is cooled and the precipitated white crystals are separated from the furnace.
Dry. The amount of white crystals obtained was 233f.

The yield was 88.8%. The melting point of the crystals was 221°C.

The elemental analysis values of the obtained white crystals were as shown in Table 2.

Table 2 Elemental analysis values Also, as a result of field desorption mass spectrometry, it was confirmed that the molecular weight was 656. Furthermore, the H nuclear magnetic resonance spectrum measured by dissolving the crystal in CDCl2 is shown in Table 8. From the above analysis results, it was confirmed that the structure of the obtained crystal was as follows.

Table 8 (27 completed)

Claims (3)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, Q_1, Q_2 and Q_3 are the same or different, and are hydrogen, an aliphatic group, an aromatic group, or a formula ▲Mathematical formula , chemical formula, table, etc. ▼ (In the formula, R' and R'' are the same or different and represent an aliphatic group or an aromatic group.) Represents a phosphorus-containing group. However, Q_1, Q_2 and Q_3 At least one represents the phosphorus-containing group.R
_1, R_2 and R_3 are the same or different, hydrogen,
It represents a halogen, a hydroxyl group, an aliphatic group, or an aromatic group, R_4 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and n represents a number of 0 or more. ] A phosphorus-containing polyphenol compound represented by (2) The following general formulas (II), (III) and (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ Mathematical formulas, chemical formulas, tables, etc. ▼ (IV) [In the formula, Q_1, Q_2 and Q_3 are the same or different, and may be hydrogen, an aliphatic group, an aromatic group, or a formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R' and R '' are the same or different and represent an aliphatic group or an aromatic group.) However, at least one of Q_1, Q_2 and Q_3 represents the phosphorus-containing group. R_1, R_2 and R_3 are the same or different and represent hydrogen, a halogen, a hydroxyl group, an aliphatic group or an aromatic group. ] and the following general formula (V) R_4CHO(V) (wherein, R_4 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.) The following general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) Medium, Q_1, Q_2, Q_3, R_1, R_2, R
_3 and R_4 have the above meanings, and n represents a number of 0 or more. ] A method for producing a phosphorus-containing phenol compound. (3) General formula (VI) below ▲Mathematical formulas, chemical formulas, tables, etc.▼(VI) [In the formula, R_1, R_2, and R_3 are the same or different, and are hydrogen, halogen, hydroxy group, aliphatic group, or aromatic group , R_4 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and Y_1, Y_2 and Y_3 are the same or different and are hydrogen, an aliphatic group, an aromatic group or a group of the formula -CH_2X (wherein, X is a halogen or hydroxy (represents a substituted methyl group). However, at least one of Y_1, Y_2 and Y_3 represents the substituted methyl group. n represents a number of 0 or more. ] Polynuclear phenols represented by the following general formula (VII) ▲Mathematical formulas, chemical formulas, tables, etc.▼(VII) [In the formula, R' and R'' are the same or different and represent an aliphatic or aromatic group where R_5 represents an aliphatic group.] The following general formula (I) is characterized by reacting with a phosphinite represented by ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1, R_2, R_3, R_4 and n have the above meanings, and Q_1, Q_2 and Q_3 are the same or different and are hydrogen, an aliphatic group, an aromatic group or a formula▲a mathematical formula, a chemical formula, a table, etc.▼ (in the formula , R' and R'' have the above-mentioned meanings. However, at least one of Q_1, Q_2 and Q_3 represents the phosphorus-containing group. ] A method for producing a phosphorus-containing polyphenol compound.