JPS61251692A - Mixed ether composition containing oligomer of polyfunctional phosphine oxide and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides polyether derivative mixtures of polyfunctional hydroxyalkyl phosphine oxides, namely tris-
The present invention relates to oligomer mixtures derived from his-3-hydroxyalkylphosphine oxides and methods for producing such ether derivatives.

The above polyesters can be used as flame retardants for thermoplastic and thermoset resins such as polyamide resins and polyphenylene oxide resins.

Simple low molecular weight ethers of phosphine oxides have been previously described in the literature. Monomeric ether derivatives of hydroxymethylphosphine-oxide have been produced from chloromethylphosphines and chloromethylphosphine oxides by reacting them with sodium alcoholade or sodium phenolate. This reaction is described in DE 2,258,662. G.

Polishiv also Vysokonol Soedim, 5
ect A, 15°275 (1973) K methyl
A low molecular weight polyester made from bischloromethyl phosphine oxide and bisphenol A sodium salt is described. Other monomeric ethers made from dimethyl chloromethyl phosphine oxide and sodium phenolate (formed from halogen-containing phenols and bisphenols) are described in U.S. Pat. No. 3,883,474. The latter monomeric phosphine oxide ethers are said to be useful flame retardants for polyester resins.

Chloroether is a simple monomeric ether derivative found by the reaction of phosphine oxide with sodium alcoholade, phosphor by Mayer.
US I, 245-249 (1972). The reaction between hydroxybutyl dialkyl phosphine oxide and alkylene oxides is disclosed in U.S. Pat.
, No. 267.149. However, the phosphine oxide ethers of the present invention have repeating phosphine oxide groups in the polymer and are known in the art in that the ether group (and terminal hydroxyl group) is either 2 or 3 carbon atoms removed from the phosphorus atom. It is also structurally distinguishable from many ether derivatives of phosphine oxides. These phosphine oxides are excellent flame retardants and are characterized by being more stable than other conventionally known phosphine oxides in which the residual hydroxyl group is on the a-carbon atom.

According to the present invention, the structural formula:
Y represents the same or different groups selected from hydrogen, an aliphatic group, a cycloaliphatic group, an aromatic group, a halogenated aliphatic group, a halogenated cycloaliphatic group, and a halogenated aromatic group, and R
Ifi aliphatic group, cycloaliphatic group and -(CH,)nOX
an oligomer-containing mixed ether composition useful as a flame retardant; is provided.

According to the present invention, a mixed ether composition comprising oligomers of the polyhydroxyalkyl phosphine oxide described above is prepared by heating the phosphine oxide to a temperature of about 139 to about 200° C. in the presence of an acid catalyst and removing the water produced during the etherification reaction. It is produced by separating it from the reaction mixture. Aliphatic, cycloaliphatic, and aromatic alcohols having one or more hydroxyl groups and their no-logenated derivatives can be added to the phosphine oxide to form an ether between the phosphine oxide and the added alcohol.

Certain of the novel mixed ether compositions of the present invention include hydroxyalkyl phosphine oxides and monovalent aliphatic, cycloaliphatic, aromatic, halogenated aliphatic, non-halogenated cycloaliphatic, and halogenated aromatic compounds. Produced from alcohol, structural formula: 1, where 2 is 1.2 or 3, n is 2 or 3, and Y
may be the same or different and are selected from the group consisting of hydrogen, aliphatic, cycloaliphatic, aromatic, halogenated aliphatic, halogenated aliphatic, and halogenated aromatic groups, but includes oligomers having a group selected from the group consisting of hydrogen and Y groups, which may be the same or different.

Another of the novel mixed ether compositions of the present invention is derived from bishydroxyalkyl phosphine oxides and has the structural formula: , 2 is 1.2 or 3, and n is 2 or 3
Toshikari Y includes an oligomer (representing a group selected from the group consisting of hydrogen aliphatic, cycloaliphatic, aromatic/halogenated aliphatic, halogenated cycloaliphatic, and halogenated aromatic group).

The mixed ether compositions of the present invention are excellent flame retardants and enhance the flame resistance of thermoplastic and thermoset resins. This mixed ether composition is particularly effective when added to polyamide and polyphenylene oxide resins.

Preferred mixed ether compositions made from bis-hydroxy alkyl phosphine oxides and polyfunctional alcohols have the structural formula: and cycloaliphatic groups).

The mixed ethers of the present invention are produced by thermal condensation of and-su-hydroxyalkylphosphine oxide, tris-hydroxyalkylphosphine oxide, or mixtures thereof in the presence of an acid catalyst. The preferred hydroxyalkyl phosphine oxide is tris-(
3-Hydroxypropyl) phosphine oxide, but also 2-hydroxyethyl phosphine oxide condenses to form oligomeric ethers. other 1
Polyhydric and polyhydric aliphatic, aromatic, and cycloaliphatic alcohols and their halogenated derivatives can also be added to the hydroxyalkyl phosphine oxides to form ethers of the phosphine oxide and the added alcohol.

By forming an azeotrope, an inert liquid such as xylene can be added to the reaction mixture for heating control and removal of water formed during the reaction. In the presence of xylene, the esterification reaction occurs at reflux temperature, ie, about 139-144°C. However, xylene is not a suitable additive for low boiling alcohols and polyols which are fairly soluble in xylene. Under these conditions, it is preferred to use high m (170-200 DEG C.) to remove the water produced by the etherification reaction. The progress of the reaction can be monitored by thin layer chromatography and by the amount of water removed during the reaction. When heating tris-hydroxyalkylphosphine oxides alone or with polyols having two or more hydroxyl groups, care must be taken to stop the reaction before gelatinization occurs due to cross-linking reactions. Mixed ethers result in oils of low to high viscosity that can be dissolved in water or in hydrocarbons, depending on the reactants used.

Sulfuric acid or other sulfuric acids such as methanesulfonic acid or p-)luenesulfonic acid are the catalysts of choice for this etherification reaction, although other catalysts can also be used. The amount of catalyst that can be used is 0.5-10%, preferably 1-2%, based on the mole of phosphine oxide. After the reaction, the catalyst can be left in the reaction mixture or neutralized with sodium hydroxide. Once neutralized, the sodium sulfate may be precipitated with methanol or placed in the reaction mixture.

As described above, the acid-catalyzed etherification reaction of hydroquine alkyl phosphine oxides can be carried out with or without adding other hydroxyl group-containing substances. Other alcohols and polyols that can be added to the preparation of mixed ether compositions include ethylene glycol, neopentyl glycol, pentaerythritol, chrycerin, trimethylol propane, cyfuromoneobentyl glycol, tribromoneopentyl alcohol, tecanol, cyclohexyl alcohol, Butyl selonube, butyl calpitol, linear l-alcohol, 2.
Examples include 3-dibromopropanol, phenol, tribromophenol, bisphenol A1 and tetrabromobisphenol A.

The ether/polyny chill-containing phosphine oxides described herein can be used as flame retardant additives for both thermoplastic and thermoset resin products and 7 ohm applications.

These resins include polyamides, polyethylene oxide-polystyrene mixtures, polybutylene terephthalate, polyethylene terephthalate, styrenes, styrene-containing resins, polyacrylates, unsaturated polyesters, polyurethanes, polyolefins, polysulfones, etc. . The phosphine oxides are most effective in polyamide, polyethylene oxide and polyester systems. For example, Tris-
Nylon-66 containing 21 parts of 3-hydroxypropylphosphine oxide/pentaerythritol polyether has a 94V-0 rating in the UL-94 vertical flame test.
I got a grade. The UL-94 vertical combustion test is described in Example 3. In all cases, good compatibility with the resin was shown.

The following implementation will fully illustrate the invention. Unless otherwise specified, the reaction amounts in the examples are expressed on a weight basis.

Example ■ 22.4 t (0.1 mol) of tris-3-hydroxypropyl phosphine oxide, 3.4 t (0.1 mol) of tris-3-hydroxypropyl phosphine oxide, 3°4? (0,025 mol) and sulfuric acid 0.2
A mixture of F (0,002 mol) and 10 (l) of xylene (isomer mixture) were charged.

The mixture was heated to reflux in an oil bath for 16 hours. At this point, the mixture separated into two liquid phases with the lower phase containing a mixed ether composition containing unreacted phosphine oxide, pentaerythritol, and oligomer. Total 2 in 16 hours.
Of water was removed. Thin layer chromatography (silica gel in chloroform:methanol 4:1) showed traces of tris-(3-hydroxypropyl)phosphine oxide, with a large spot at the bottom of the plate and a few other spots with very low Rf. there was. The xylene layer was decanted from the cooled reaction mixture and the residue was dissolved in methanol-water (1
1) The mixed solution was dissolved in 200 yd, neutralized to pH 8 with sodium hydroxide, filtered through a sintered glass slit, and the solvent was removed on a rotary evaporator.

The residual viscous oil was vacuum dried at 60°C for 16 hours. The pale yellow viscous oil obtained was 23.0 f (yield 96%), and the viscosity of the 7030% aqueous solution was 34.5 centistokes at 20°C (
34.5 μm2/S). The proton nuclear magnetic resonance spectrum of the product shows two broad multiplets at δ1.9 and δ3.6 with a relative area of 12/8, which is tris-(3-
This was the expected product from a 4 part 1 mixture of hydroxypropyl)phosphine oxide and pentaerythritol. The average molecular weight measured by vapor phase number permeability was 865. The elemental analysis result of the product is C,50,
21:H, 9, 31:P, 12.30.

The divalent group -R- in the phosphine oxide ethers of this example is a diol such as ethylene glycol, dibromoneopentyl glycol, neopentyl glycol, bisphenol A1, tetrabromobisphenol A, or a diol such as pentaerythritol, glycerin, trimethylolpropane. Can be derived from polyols.

These mixed ether compositions can be produced by the reaction of dihydric or polyhydric alcohols with tris-(2-:cfl) or d)IJs-3-propyl)phosphine oxide.

Example ■ 50.1 parts of tris-(3-hydroxypropyl)-phosphine oxide, 0 sulfuric acid in a vessel with a Dean-Stark trap for water removal, a stirrer, and a nitrogen inlet.
．． A mixture of 2 parts and 100 parts of O-xylene was heated to reflux temperature.

After 6 hours 2 parts of water were removed. Thin layer chromatography showed a small amount of tris-hydroxypropyl phosphine oxide remaining, showing two large spots at the bottom of the plate. 47% by weight of a clear viscous oil was separated from this reaction mixture by the method described in Example IK. It has a significantly lower viscosity than the product of Example I. Solution viscosity at 20°C (30% solids in water)6. Ocs (6μm”
/s).

The proton nuclear magnetic resonance spectrum of this material is Tris-(
It was the same as 3-hydroxypropyl)phosphine oxide.

Example m Tris-(3-hydroxypropyl)phosphine oxide 134.4 m(0,
6 mol), cyfuromoneopentyl glycol 249
% (0.95 mol), 0.5 part of sulfuric acid and 400 parts of mixed isomers of xylene was heated under reflux under nitrogen to remove water. Heating was continued for 7 hours, at which point 13 parts of water were removed by azeotropic distillation.

The xylene layer was decanted and removed to yield 20 parts of unreacted dibromoneopentyl glycol. The remaining reaction mixture was worked up as in Example I to give 335.9 parts (96-yield) of a slightly cloudy sticky yellow oil. Thin layer chromatography showed essentially no residual tris-(3-hydroxypropyl)phosphine oxide, and most of the product mixture had a very low Rf. Elemental analysis of the product is C,32,9
1:H, 5,40:P, 5.15:Br,
It was 38.32.

Example ■ Tris-(3-hydroxypropyl)phosphine oxide 22.4 parts (0.1 mol), rhodecanol 49
．． A mixture of 0 parts (0.3 mol) and 0.2 parts of sulfuric acid was heated to 150 ml under nitrogen in the same vessel as described in Example
Heated at ℃ for 16 hours. The reaction mixture became homogeneous and thin layer chromatography showed no residual tris-(3-hydroxypropyl)phosphine oxide, but the presence of five new compounds.

The reaction mixture was raised to 200° C. for 2 hours, but neither the appearance nor the thin layer chromatography of the reaction mixture changed. Unreacted decanol (26.3 parts) was removed by vacuum distillation. The residue was soluble in toluene but insoluble or slightly soluble in water. The residue was dissolved in 800 parts of toluene, washed with 5% sodium carbonate, dried over magnesium sulfate, filtered and the solvent removed in vacuo to give 38.6 parts of a cloudy sticky yellow oil.

Proton nuclear magnetic resonance spectroscopy of this composition shows the presence of decyl groups, similar to phosphine oxide molecules! >1.2
This indicated that 5 decyl groups were added. C per synatom
The calculated elemental analysis value for 21,5H4604P (1,25 decyl group) is C, 64,66:I (, 11,53:P
, 7.77, and the measured value is C964,49:H
, 10,89:P, 7.00.

Example V A mixture of 24.8 parts (0.1 mol) of cyclohexyl bis-3-hydroxypropyl phosphine oxide, 10.4 parts (0.1 mol) of neopentyl glycol, 0.2 parts of sulfuric acid and 100 parts of xylene was mixed with the above mixture. The mixture was heated to reflux while removing water under a nitrogen atmosphere. 30
3.1 parts of water had been removed by the end of the heating period. The mixture was a single-phase mixture while hot, but became a translucent reflective yellow and blue color upon cooling.

The xylene was removed from the mixture and the residue was neutralized by dissolving it in methanol-water, filtering, purging and vacuum drying at 60°C overnight. The product, a sticky yellow oil, was 30.1 parts (yield: 95%). Thin layer chromatography showed two major spots with Rf close to the starting material. The proton nuclear magnetic resonance spectrum is Q
1.1-2.2 (broad multiplet), (10,9 (singlet)
, C3,35 (singlet), and C3,4-3,7 (broad multiplet) exhibiting 4 signals with a relative area of 5.5°1.5,1.
1 (theoretical ratio: 4.8, 1.5, 1, 1). The elemental analysis result of the product is C,58,96:H,10,
00:P.

It was 9.75.

Example ■ A mixture of 22.4 parts (0.1 mol) of tris-(3-hydroxypropyl)phosphine oxide, 40.8 parts (0.075 mol) of tetrabromobisphenol A, and 0.5 part of sulfuric acid was heated to 170 ml in a container. heated to ℃. A stream of nitrogen was bubbled through the reaction mixture for 2 hours to remove the water produced by the etherification reaction. The product obtained on cooling was a brittle glass, and thin layer chromatography showed no residual phosphine oxide starting material. This glass was ground, neutralized by dissolving it in an aqueous methanol solution, filtered, and evaporated to dryness to yield 60.8 parts of amber facets. Unreacted tetrabromobisphenol A was removed by extraction with refluxing chloroform. The amount remaining after chloroform extraction (37.7 parts) corresponded to a reaction of approximately 3:1 hydroxypropyl phosphine oxide to bisphenol. The differential scan side heat of this product is approximately 3
It was shown that it is stable up to 10°C and that rapid heat generation occurs at that temperature. On the contrary, the starting materials have a wide endothermic range starting at about 250°C.

Examples ■ Hydroxypropyl phosphine oxide ether derivatives are used as flame retardants for thermoplastic resins. A phosphine oxide derivative was added to the following thermoplastics (see Table 1 and ■) in the following amount per 100 parts of resin (PHR) and completely dispersed in the resin. Additives and resin are mixed using a Brabender type mixer (2 units, Jersey, USA).
7662 Saddle Plutsk, Saddle River Road
244 Herc Rheomics 600 type manufactured by Herc
This was done using Record EU10 (with accessories). Mixing was performed at the following hot water temperature. Underwriter Lab
oratories Bulletin-94, Standard Flammability Test for Plastic Materials for Machinery and Appliance Parts.

The flammability test was conducted using the method according to the second edition published on July 30, 1976 (as the revised edition of February 1974). A vertical combustion test was used to classify the materials described in Chapter 3 of this publication as 94V-0, 94V-1, or 94V-2. In this test, the V-Q grade shows the best flame resistance and the V-2 grade shows the poorest flame resistance. Oxygen index test is ASTM
D2863. The flame retardant effects are summarized in Tables I and ■.

Table 1 Tris-(3-H)'roxypropyl)-phosphine oxide of Example ■ in thermoplastics Ether-induced nylon 662 - Completely combusted nylon 66 21 V-04,13,
5 Modified PPO/PS 5 V-110
,2p B T 4s 'II *10
．． 3 V-110, 3 1 Sample thickness 178", 2 Mixing temperature 260-250°C, 3 Mixing temperature 225°C, 4 Mixing temperature 235-255°C, 5 Noryl (35ts polyphenylene oxide, 6
5% polystyrene) 6 Polybutylene terephthalate.

10.3 parts of tris-(3-hydroxypropyl)phosphine oxide ether derivative of Example I per 100 parts of resin 10.7 parts of decabromodiphenylene oxide.

Table ■ Test results of tris-(3-hydroxypropyl)phosphine oxide in thermoplastics Example I [1] Nylon 662 - 22.9 2 Nylon 66 17 27
．． 13 Nylon 66 21
26.04 Nylon 66 25
26.85 Modified P P O/P S3°'
24.96 Modified PPO/PS”°
'4 3α47 Denatured P P O/P S
3°56 29.38 PBT'°6
9” - Table ■ (Rizuki) Poly-Tris of Example ■ in Thermoplastics (
Test results of 3-hydroxypropyl) phosphine oxide 1 Complete combustion 249℃
2 V-18,8238℃ 3 V-03,4240'C 4V-02,5237℃ 5 Complete combustion - 6V-111,8- 7V-17,4- 8V-111- 1 Sample thickness 1/8#, 2 Mixing temperature 260-250C, 3 Mixing temperature 225C, 4 Mixing temperature 235-250C.

5 Noryl 731 (35% polyphenylene oxide, 65 tipolysterene), 6 Polybutylene terephthalate, Spicy 9 parts per 100 parts of poly-tris-(3-hydroxypropyl)phosphine oxide of Example 1, 12 per 100 parts of decabromodiphenylene oxide Department.

Table ■ Volatility data of hydroxypropyl phosphine oxide and polyether derivatives THPPo 235℃ 330℃ Poly-THPP0 without carbonization 300℃ 395℃
Foaming and carbon formation HPPO' 150℃ 3
00℃ Poly-BHPP0 without carbonization 225℃
360℃ Foaming and carbon formation I 5eC-Butyl bis-(3-hydroxypropyl)phosphine oxide, 2 1x-(3-hy)'roxypropyl)phosphine
oxide.

Claims (1)

[Claims] 1. Structural formula: ▲ Numerical formulas, chemical formulas, tables, etc. Represents the same or different groups selected from aliphatic groups, aromatic groups, halogenated aliphatic groups, halogenated cycloaliphatic groups, and halogenated aromatic groups, and R represents an aliphatic group, a cycloaliphatic group, and - (CH_2) Represents a group selected from the _nOX group; where X is hydrogen, Y, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The same or different species selected from the groups An oligomer-containing mixed ether composition useful as a flame retardant, characterized in that it is represented by the following group. 2. The composition according to claim 1, wherein Y is the same or different group selected from hydrogen and ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups, and n is 3. The composition according to claim 1, wherein 3 and Y are the same or different groups selected from hydrogen and decyl, and n is 3. The composition according to claim 1, wherein 4 and Y are the same or different groups selected from hydrogen and 2,3-dibromopropyl, and n is 3. 5. The composition according to claim 1, wherein Y are the same or different groups selected from hydrogen and butoxyethyl, and n is 3. 6. The composition according to claim 1, wherein Y is the same or different group selected from hydrogen and ▲a mathematical formula, chemical formula, table, etc.▼ group, and n is 3. 7. The composition according to claim 1, wherein R is a butyl group and n is 3. 8. The composition according to claim 1, wherein R is a cyclohexyl group and n is 3. 9. Structural formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. represents a group selected from a halogenated aliphatic group, a halogenated cycloaliphatic group, and a halogenated aromatic group, and R represents a group selected from an aliphatic group, a cycloaliphatic group, and a -(CH_2)_nOX group. represents the same or different groups selected from the following formulas; A flame-retardant resin composition comprising a resin containing the oligomer-containing mixed ether composition in an amount of 5 to 25 parts per 100 parts of the resin. 10.Resin is polyamide resin, propylene oxide-
polystyrene resin, polyethylene terephthalate resin,
and polybutylene terephthalate resin. 11. Structural formula characterized by heating polyhydroxyalkylphosphine oxide in the presence of a contact amount of strong acid and distilling off the water produced during the etherification reaction: ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, z is 1, 2, or 3, n is 2 or 3, and Y
each represents the same or different groups selected from hydrogen, an aliphatic group, a cycloaliphatic group, an aromatic group, a halogenated aliphatic group, a halogenated cycloaliphatic group, and a halogenated aromatic group; Represents a group selected from group groups, cycloaliphatic groups, and -(CH_2)_nOX groups; where X is hydrogen, Y, respectively. ▼ Represents the same or different groups selected from the group. 12. The method according to claim 11, wherein the acid catalyst is sulfuric acid. 13. The method according to claim 11, wherein polyhydroxyalkylphosphine oxide is heated in the presence of a polyfunctional alcohol. 14. The method according to claim 13, wherein the acid catalyst is sulfuric acid.