US 3,976,685 AGrant
Carboxyalkyl and Carbamoylalkyl Substituted Poly(phosphine Oxide) Flame-Retardants
Issue Date:1976-08-24
•5 Claims
Abstract
Compounds having the formula ##EQU1## wherein X is OH or NH.sub.2 and n is a whole, positive integer of from 1-4, inclusive.
Metadata
Assignee
- American Cyanamid Company
Inventor
- Joseph Adrian Hoffman
Application Information
Application Number:US 6034632
Filing Date:1975-08-11
Priority Date:1975-08-11
Art Unit:126
Classifications
IPC:
C07C 6314
Field of Search:
260515 R;515 M
Patent Drawings
This patent does not have any drawings.
Description
EXAMPLE 1
PREPARATION OF 1,4-BIS[BIS(2-CARBOXYETHYL) PHOSPHONYLMETHYL]-2,3,5,6-TETRAMETHYLBENZENE
To 1 liter of concentrated hydrochloric acid are added 103 parts of 1,4-bis[bis(2-cyanoethyl)phosphonylmethyl]-2,3,5,6-tetramethylbenzene. The reaction mixture is refluxed for 24 hours and 800 ml. of hot water are then added. The resultant reaction mixture is cooled to 25.degree.C. and the product is filtered, washed with water and dried. The yield is 137 parts of 1,4-bis[bis(2-carboxyethyl)phosphonylmethyl]-2,3,5,6-tetramethylbenzene having a melting point of 265.degree.-267.degree.C.
EXAMPLE 2
PREPARATION OF 1,4-BIS[BIS(2-CARBOXYETHYL) PHOSPHONYLMETHYL]-2-METHYLBENZENE
The procedure of Example 1 is again followed except that the charge material is 1,4-bis[bis(2-cyanoethyl)phosphonylmethyl]-2-methylbenzene. Good yields of the subject compound are recovered.
EXAMPLE 3
PREPARATION OF 1,4-BIS[BIS(2-CARBOXYETHYL) PHOSPHONYL METHYL]-2,5-DIMETHYLBENZENE
Again following the procedure of Example 1, good yields of 1,4-bis[bis(2-carboxyethyl)phosphonylmethyl]-2,5-dimethylbenzene are recovered when the charge 2-cyanoethyl compound thereof is replaced by 1,4-bis[bis(2-cyanoethyl)phosphonylmethyl]-2,5-dimethylbenzene.
EXAMPLE 4
PREPARATION OF 2,4-BIS[BIS(2-CARBOXYETHYL) PHOSPHONYLMETHYL]-1,3,5-TRIMETHYLBENZENE
When the charged 2-cyanoethyl compound of Example 1 is replaced by 2,4-bis[bis(2-cyanoethyl)phosphonylmethyl]-1,3,5-trimethylbenzene, the subject compound is recovered in a good yield, the same procedure being followed.
EXAMPLE 5
PREPARATION OF 1,4-BIS[BIS(2-CARBAMOYLETHYL) PHOSPHONYLMETHYL]-2,3,5,6-TETRAMETHYLBENZENE
109 Parts of the 1,4-bis[bis(2-carboxyethyl)phosphonylmethyl]-2,3,5,6-tetramethylbenzene of Example 1, 600 ml. of methanol, 100 ml. of benzene and 1 ml. of concentrated sulfuric acid are heated at reflux until complete solution is achieved (4 hrs.) and heating is then continued for an additional 5 hours. The resultant solution is then cooled and 15 parts of sodium bicarbonate are added. The solution is stirred for 30 minutes and filtered. The filtrate is cooled in an ice/acetone bath, stirred for an additional 1-1/2 hr., filtered, washed with methanol and dried. 111 Parts of 1,4-bis[bis(2-carbomethoxyethyl)phosphonylmethyl]-2,3,5,6-tetramethylbenze ne are recovered of 149.degree.-150.degree.C. m.p.
40 Parts of the carbomethoxyethyl compound are then admixed with 300 ml. of concentrated, aqueous ammonia. The mixture is stirred for 2 hours at 10.degree.C. and then allowed to come to room temperature. Stirring at ambient temperature for 48 hours, filtering, washing with water and drying results in the recovery of 30 parts of 1,4-bis[bis(2-carbamoylethyl)phosphonylmethyl]-2,3,5,6-tetramethylbenzene having a melting point of 322.degree.C. dec.
EXAMPLE 6
PREPARATION OF 2,4-BIS[BIS(2-CARBAMOYLETHYL) PHOSPHONYLMETHYL]-2,3,5-TRIMETHYLBENZENE
The procedure of Example 5 is again followed except that the starting 2-carboxyethyl compound is 2,4-bis[bis(2-carboxyethyl)phosphonylmethyl]-1,3,5-trimethylbenzene. The carbomethoxymethyl intermediate is recovered and converted to the corresponding carbamoylethyl product.
EXAMPLE 7
PREPARATION OF 1,4-BIS[BIS(2-CARBAMOYLETHYL) PHOSPHONYLMETHYL]-2-METHYLBENZENE
Again following the procedure of Example 5, the subject compound is recovered in a good yield, the charge being the product of Example 2.
EXAMPLE 8
PREPARATION OF 1,4-BIS[BIS(2-CARBAMOYLETHYL) PHOSPHONYLMETHYL]-2,5DIMETHYLBENZENE
When the product recovered in Example 3 is used as the charge and the procedure of Example 5 is again followed, 1,4-bis[bis(2-carbamoylethyl)phosphonylmethyl]-2,3-dimethylbenzene is recovered.
EXAMPLE 9
To 80 parts of unstabilized polypropylene are added, by milling at 175.degree.C., 0.1 part of pentaerythrityl tetrakis(3,4-di-t-butyl-4-hydroxyphenyl)propionate, 0.25 part of distearylthiodipropionate (as primary and secondary stabilizers) 10.0 parts of the product produced in Example 1, above, 10.0 parts of ammonium polyphosphate and 1.0 part of titanium dioxide. The resultant compounded polypropylene composition is molded at 200.degree.C. into test bars 6.times.0.5.times.0.125 inches and the bars are tested for flammability according to Underwriter's Test (UL)-94 (vertical). The flammability is rated according to the following definitions:
V-0: flame extinguishes in 0-5 seconds; non-dripping or, if dripping, the drippings do not ignite surgical cotton.
V-1: flame extinguishes in 6-25 seconds; non-dripping or, if dripping, the drippings do not ignite surgical cotton.
V-2: flame extinguishes in 0-25 seconds; drips and ignites surgical cotton.
The results are set forth in Table I, below, along with other test results utilizing other compounds and combinations of materials according to the instant invention and flame-retardant additives of the prior art. Comparative results are indicated by the letter (c). The flame-retardant compounds are set forth by reference to the following structural formula: ##STR3##
EXAMPLES 22-29
When the procedure of Example 9 is again followed except that the ammonium polyphosphate and titanium dioxide are excluded and 15.0 parts of flame-retardant compound are added to 85.0 parts of polypropylene, the following results are achieved.
EXAMPLES 30-41C
The compounds of Table I, above, are incorporated into polyethylene terphthalate by dry blending at 10%, by weight, based on the weight of the polyester. The blends are melted and stirred for 5-6 minutes at 290.degree.-310.degree.C. The resultant mixtures are cooled, ground into a powder and laminated onto fiberglass sheets by compression molding at 600.degree.F. The laminated sheets are cut into strips 2.times.6.times.0.03" and tested according to ASTM D 2863-70, modified to accept the test strips. In this test, the higher the oxygen index (O.I.), the better the flame-retardance. No ammonium polyphosphate or titanium dioxide are used. The results are set forth in Table III, below.
EXAMPLE 42
The procedure of Example 30 is again followed except that the polyester is polybutylene terphthalate. Similar results are achieved.
EXAMPLE 43
The procedure of Example 34 is again followed except that the polyester is poly(1,4-cyclohexanedimethylene)terephthalate. Substantially identical results are recorded.
Claims
I claim:
1. A compound having the formula ##EQU2## wherein X is OH an n is a whole, positive integer of 1-4, inclusive.
2. A compound according to claim 1 wherein n is 4.
3. A compound according to claim 1 wherein n is 1.
4. A compound according to claim 1 wherein n is 2.
5. A compound according to claim 1 wherein n is 3.
Patent Citations (2)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US3284543 | 1966-11-01 | Gillham et al. | |
| US3895048 | 1975-07-01 | Hoffman |
Non-Patent Literature (2)
- Wagner et al., Synthetic Organic Chemistry, John Wiley & Sons, Inc., N.Y., N.Y., p. 412 (1965).
- Ismagilov et al., Chem. Abst., vol. 77, 126773n, (1972).