CA1134849A - Didodecylammonium beta-octamolybdate and composition containing same - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Didodecylammonium beta-octamolybdate is described as a novel amine molybdate and as a smoke retardant additive for vinyl chloride and vinylidene chloride polymer compositions.

Description

~13~9 BACK~;ROUND OF THE INVENTION
Amine molybdates may be produced by reacting an amine with a molybdenum compound such as molybdenum trioxide (MoO3), molybdic acid or a molybdenum salt in an acidic aqueous medium made acidic through the addition of a suitable acid such as an organic acid containing 1 to 12 carbon atoms (exemplified by acetic acid, propionic acid, benzoic acid, and the like) or an inorganic acid (exemplified by hydrochloric acid, nitric acid or sulfuric acid). The acidic mixture is refluxed, preferably while being stirred continuously, until the reaction is complete, usually for about 1/4 to 4 hours.
Amine molybdates also may be produced, as described in Canadian Patent No. 1,115,702, W.J. Kroenke, issued January 5, 1982, and entitled ~Proce~s For Making Amine Molybdates", by reacting essentially .
stoichiometric quantities of molybdenum trioxide with an amine in an aqueous medium essentially free of acid and in which a water-soluble ammonium or monovalent metal or divalent metal or trivalent rare earth metal salt of an inorganic or organic acid is dissolved.
The particular amine molybdate formed may depend upon which process is used to form the amine molybdate and the ~uantity of reactants present in the reaction mixture, as well as the reaction conditions.
SUMMARY OF THE INVENTION
The present invention pertains to a novel amine molybdate, namely, didodecylammonium beta-octamolybdate~ [H(cl2H25)2NHl4Mo8o26~
hibits major x-ray diffraction peaks at "d" spacings of 14 . 3A, 10. 4A, 9 . 41A and 7.10~. Like many other amine molybdates, didodecylammonium b~taoctamolybdate ~"`il.''-~ .
~k . . .

.. ' ' , -~3~8 ~9 functions as an effective smoke retardant additive for vinyl chloride and vinylidene chloride polymers.
DETAILED DESCRIPTION OF THE INVENTION
Didodècylammonium beta-octamolybdate may be 5 produced by reacting ammonium dimolybdate and didode-cylamine in essentially a 2/1 molybdenum/didodecylamine molar ratio in an acidic aqueous medium. Suitable acids include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and the like, or 10 mixtures thereof. The amount of acid used may be varied widely from about 1/2 to 10 or more molar equivalents of acid per molar equivalent of ammonium dimolybdate. However, about a 1/1 molar equivalent ratio is preferred. Sufficient water is included in 15 the reaction mixture to insure a reaction medium that has a consistency that enables it to be easily stirred. Desirably, the ammonium dimolybdate is dissolved in water and is added to an acidic solution of didodecylamine. If preferred, the ammonium dimolyb-20 date, didodecylamine, acid and water can be chargedessentially simultaneously to the reaction vessel.
The reaction materials desirably are refluxed while being stirred continuously for 0.25 to 16 hours.
Although the reaction can occur at room temperature (25C.), desirably the reaction mixture is heated to between 75 to 110C. in order to reduce the time for the reaction to be completed. After the reaction is completed, the crystalline didodecylammonium beta-octamolybdate formed can be separated from the liquid 30 phase by filtration, centrifugation or other suitable separation means, washed with water, alcohol or a mixture of water and alcohol, and then dried. The reaction mixture may be cooled to room temperature (about 25C.) before the separation of the solid 35 didodecylammonium beta-octamolybdate from the liquid 1~3~8 ~9 phase, although cooling the mixture before separation of the solid produce from the liquid phase is not necessary. The recovered didodecylammonium beta-octamolybdate may be air dried, preferably at about 5 100 to 200C., or may be vacuum dried, preferably at temperatures up to 150C. and higher. The didodecyl-ammonium beta-octamolybdate is readily identifiable by elemental, infrared or x-ray diffraction analysis.
The following example illustrates the 10 preparation of didodecylammonium beta-octamolybdate.
Example 1 5.00 grams of didodecylamine, 2.79 grams of a 37 percent hydrochloric acid solution, 50 milliliters of ethanol and 50 milliliters of water were added to a 15 500 milliliter round-bottom flask equipped with a water-cooled condenser and was brought to reflux.
4.80 grams of ammonium dimolybdate were added to 25 milliliters of water and the mixture was heated until the ammonium dimolybdate dissolved. The hot ammonium 20 molybdate solution was added to the flask and the reaction mixture was refluxed while being stirred continuously for 1/2 hour. The contents of the flask were cooled to room temperature (about 25C.) and were filtered. A crystalline solid was recovered. The 25 recovered solid was washed with a 50-50 water-ethanol wash and then with water. The washed solid was vacuum dried at 100C. for approximately 16 hours. 8.24 grams of the crystalline product were recovered.
Elemental, infrared analyses and x-ray diffraction 30 analyses identified the solid to be didodecylammonium beta-octamolybdate.
Didodecylammonium beta-octamolybdate has been found to be a smoke additive for vinyl chloride and vinylidene chloride polymer compositions. When 35 used as a smoke retardant additive, the didodecyl-ammonium beta-octamolybdate desirably has an average 113~8~9 particle size from about 0.1 to about 100 microns, and is present in an amount from about 0.1 to about 20 parts by weight per 100 parts by weight of the vinyl chloride or vinylidene chloride polymer.
Vinyl chloride and vinylidene chloride polymers with which the didodecylammoniumbeta-octamolyb-date can be used as a smoke retardant additive include homopolymers, copolymers and blends of homopolymers and/or copolymers. The vinyl chloride and vinylidene 10 chloride polymers may contain from 0 to 50 percent by weight of at least one other olefinically unsaturated monomer. Suitable monomers include l-olefins contain-ing from 2 to 12 carbon atoms such as ethylene, propylene, l-butene, isobutylene, l-hexene, 4-methyl-15 l-pentene, and the like; dienes containing from 4 to 10 carbon atoms, including conjugated dienes such as butadiene, isoprene, piperylene, and the like; ethyli-dene norbornene and dicyclopentadiene; vinyl esters and allyl esters such as vinyl acetate, vinyl chloro-20 acetate, vinyl propionate, vinyl laurate, alkyl ace-tate, and the like; vinyl aromatics such as styrene, a-methyl styrene, chlorostyrene, vinyl toluene, vinyl naphthalene, and the like; vinyl and allyl ethers and ketones such as vinyl methyl ether, allyl methyl 25 ether, vinyl isobutyl ether, vinyl n-butyl ether, vinyl chloroethyl ether, methylvinyl ketone, and the like; vinyl nitriles such as acrylonitrile, methacry-lonitrile, and the like; cyanoalkyl acrylates such as -cyanomethyl acrylate, the -,~- and ~-cyanopropyl 3~ acrylate, and the like, oleinically unsaturated carboxylic acids and esters thereo, including a,~-olefinically unsaturated acids and esters thereof such as methyl acrylate, ethyl acrylate, chloropropyl acrylate, butyl acrylate, hexyl acrylate, 2-ethyl-35 hexyl acrylate, dodecyl acrylate, octadecyl acrylate,cyclohexyl acrylate, phenyl acrylate, glycidyl 1~348~9 acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hexylthioethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, and the li~e; and including esters of maleic and 5 fumaric acid, and the like; amides of the a,~-olefini-cally unsaturated carboxylic acids such as acrylamide, and the like, divinyls, diacrylates and other polyfunc-tional monomers such as divinyl benzene, divinyl ether, diethylene glycol diacrylate, ethylene glycol 10 dimethacrylate, methylene-bis-acrylamide, allyl pen-taerythritol, and the like; and bis (B-chloroethyl) vinyl phosphonate, and the like.
The vinyl chloride and vinylidene chloride polymer, in addition to the didodecylammonium beta-15 octamolybdate additive, may contain the usual com-pounding ingredients known to the art such as fillers, stabilizers, opacifiers, lubricants, processing aids, impact modifiers, plasticizers, antioxidants, and the like.
Smoke retardancy may be mea~ured using an NBS Smoke Chamber according ~o procedures described in ASTM E662-79 "Test For Specific Optical Density Of Smoke Generated By Solid Materials". Maximum smoke density (DM) is a dimensionless number and has the 25 advantage of representing a smoke density independent of chamber volume, specimen size for photometer path length, provided a consistent dimensional system is used. Percent smoke reduction is calculated using the equation:
Dm/g of control - Dm/g of sample X 100 Dm/g of control The term "Dm/g" means maximum smoke density per gram of sample. Dm and other aspects of the physical optics of light transmission through smoke are dis-cussed fully in the ASTM publication.

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11348~9 The smoke retardant property of didodecyl-ammonium beta-octamolybdate is illustrated by the ollowing examples:
Examples 2 - 3 The following recipe was used:
Material Parts by Weight Polyvinyl Chloride Resin* 100.00 Lubricant** 2.0 Tin Stabilizer**~ 2.0 Didodecylammonium Beta-Octamolybdate-varied *Homopolymer of vinyl chloride having an inherent viscosity of about 0.98 - 1.04;
ASTM Classification GP-5-15443.
**A commercial polyethylene powder lubricant (Microthenè 510).
***Tin thioglycolate.
The ingredients of the recipe were dry-mixed and bonded on a two-roll mill for about 5 minutes at 20 a roll temperature of about 165C. The milled compo-sitions were presse~ into 6 X 6 X 0.025 inch sheets.
Pressing was done at about 160C. for 5 minutes using 40,000 pounds (about 14,900 Kg) of force applied to a 4-inch ram. The sample received a 2 minute preheat 25 before being pressed.
The molded samples were cut into 2-7/8 X 2-7/8 X 0. 050 inch sections. Testing was performed using the flaming mode of the NBS Smoke Chamber Test (ASTM E662-79) described heretofore. Test results 30 are given in Table 1.
TABLE _ Didodecylammonium Smoke Beta-octamolybdate Reduction Example Parts by Welght Dm/g*

2 (control) 0 68,40

3 2.0 40.38 41 `'*" trade mark A`

, .

. . .
;: :
. .

113~8~9 *Dm/g maximum smoke density per gram of sample.
The improved smoke retardant vinyl chloride and vinylidene chloride polymer compositions obtained S by the addition of didodecylammonium beta-octamolyb-date to the compositions are useful wherever smoke resistance is desirable, such as in carpets, house siding, plastic components for airplane and passenger car interiors, and the like.

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Claims (4)

The embodiments of the invention in which an exclusive pro-perty or privilege is claimed are defined as follows:

1. Didodecylammonium beta-octamolybdate characterized by major X-ray diffraction peaks at "d"
spacings of 14.3.ANG., 10.4.ANG., 9.41.ANG. and 7.10.ANG..

2. A smoke retarded composition comprising a vinyl chloride or vinylidene chloride polymer together with a smoke retardant amount of didodecylammonium beta-octamolybdate characterized by major X-ray diffraction peaks at "d" spacings of 14.3.ANG., 10.4.ANG., 9.41.ANG. and 7.10.ANG..

3. The smoke retarded composition of claim 2, wherein said amine molybdate has an average particle size from about 0.1 to about 100 microns.

4. The composition of claim 2 or 3, wherein said amine molybdate is present in an amount from 0.01 to about 20 parts by weight per 100 parts by weight of said polymer.