USRE32473E - Flame-retardant polymer compositions containing metal salts - Google Patents
Flame-retardant polymer compositions containing metal salts Download PDFInfo
- Publication number
- USRE32473E USRE32473E US06/596,129 US59612984A USRE32473E US RE32473 E USRE32473 E US RE32473E US 59612984 A US59612984 A US 59612984A US RE32473 E USRE32473 E US RE32473E
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
Definitions
- This invention relates as indicated to certain flame-retardant polymer compositions and, more particularly, to such compositions which owe their flame-retardant properties to the presence of small proportions of amine or metal salts, more particularly defined hereinafter.
- Polymers vary widely in their resistance to burning. Some, such as the polyolefins, polystyrene, polyalkyl acrylates and methacrylates, and the like, burn readily. Polytetrafluoroethylene, polyvinylidene chloride and polyvinyl chloride, on the other hand, have a rather high resistance to burning. In any event, it obviously is highly desirable that, for certain applications, a polymer should have a high degree of flame retardance so that it will meet the requirements of various building codes or that it will meet safety standards imposed on toys, carpeting, drapery materials, automotive applications, etc.
- the formulator's goal, in preparing a flame-retardant polymer composition, is to add just enough of the flame retardant compound so as to provide the desired degree of flame retardance, but no more than this minimum amount, so as to preserve as much as possible the advantageous properties of the polymer. Frequently, it is not possible to select a flame-retardant which will meet these requirements satisfactorily.
- U.S. Pat. No. 4,041,012 shows the use of acrylate esters of dihaloneopentylglycol phosphates as flame-retardant additives in acrylic polymer compositions.
- the esters are incorporated in polyacrylate compositions by copolymerization with methyl methacrylate, for example, although at column 7, lines 15-59, it is stated that they may be used in combination with known synergists in other types of polymers "such as polystyrene" (see line 37).
- the present invention is a composition
- a composition comprising a normally flammable polymer and a minor proportion, sufficient to impart flame-retardant properties to said composition, of a salt of 5,5-bis(bromomethyl)-2-hydroxy-2-oxo-1,3,2-dioxaphosphorinane having the structure ##STR1## where A is a polyvalent metal or amine group and n is an interger corresponding to the valence of A.
- Polyvalent metals contemplated above include aluminum, calcium, magnesium, barium, chromium, strontium, silver, titanium, nickel, copper, zinc, iron, cobalt, manganese, molybdenum, zirconium, cadmium, bismuth, lead, tin, vanadium, antimony, etc.
- Aluminum and calcium are preferred.
- the amine preferably is an amino-s-triazine. Melamine is especially preferred.
- the polyvalent metal and amine salts herein may be prepared by reacting the corresponding acid or the acid chloride thereof with a polyvalent metal halide, a basic polyvalent metal base, or amine.
- a polyvalent metal halide a polyvalent metal halide
- a basic polyvalent metal base or amine.
- the process is described in more detail in an application for patent, Ser. No. 279,636, entitled “Salts of 5,5-Bis-(Bromomethyl)-2-Hydroxy-2-Oxo-1,3,2-Dioxaphosphorinane and Process for Preparing Same," filed concurrently herewith.
- Ser. No. 279,636 entitled “Salts of 5,5-Bis-(Bromomethyl)-2-Hydroxy-2-Oxo-1,3,2-Dioxaphosphorinane and Process for Preparing Same," filed concurrently herewith.
- the subject matter of that application is incorporated herewith by reference.
- Preparation of the flame-retardant compositions of this invention may be accomplished by mixing the ingredients in an electrically heated Brabender head for about 10 minutes at 200° C. and 60 rpm.
- the test specimens for which data is shown in the Table are prepared from compression molded slabs.
- the flame retardance of a plastic material can be determined by means of Underwriters Laboratories Test UL-94.
- the test specimen measures 5" ⁇ 0.5" ⁇ 0.125"; it is suspended vertically at a measured height above the flame from a Bunsen burner. After 10 seconds the flame again is removed and the duration of the flaming of the test specimen is noted. Immediately, the flame is placed again under the specimen and after 10 seconds the flame again is withdrawn and the duration of flaming and glowing is noted. Five test specimens are thus tested and the results of all five tests are considered in the determination of a rating for the plastic material.
- duration of flaming after first flame application (2) duration of flaming after second flame application; (3) duration of flaming plus glowing after second flame application; (4) whether or not specimens burn up to their point of suspension; and (5) whether or not specimens drip flaming particles which ignite a cotton swatch placed 12 inches beneath the test specimen.
- the highest rating given to a material is "V-0".
- V-1 The next highest rating is "V-1". It indicates that (1) no specimen burns with flaming combustion for more than 30 seconds after each application of the test flame; (2) the material does not have a flaming combustion time exceeding 250 seconds for the 10 flame applications for each set of 5 specimens; (3) no specimen burns with flaming or glowing combustion up to the holding clamp; (4) no specimen drips flaming particles that ignite the dry surgical cotton beneath the specimen; and (5) no specimen glows for more than 60 seconds after the second removal of the flame.
- a "V-2" rating is given to a composition (1) when no specimen burns with flaming combustion for more than 30 seconds after each application of the test flame; (2) it does not have a total flaming combustion time exceeding 250 seconds for the 10 flame applications for each set of 5 specimens; (3) no specimen burns with flaming or glowing combustion up to the holding clamp; (4) some specimens drip flaming particles which burn only briefly, some of which ignite the dry cotton beneath the specimen; and (5) no specimen glows for more than 60 seconds after the second removal of the flame.
- NSE non-self-extinguishing
- Another test for the flammability of a plastic material measures the minimum concentration of oxygen that will just support combustion.
- the test is an ASTM test, D 2863-70. It is carried out in a glass column wherein the concentration of oxygen is varied until that concentration is found which will just support the burning of a test specimen, for 3 minutes or until 50 mm of the specimen has burned.
- the test specimen is 70-150 mm long by 6.5 mm wide by 3.0 mm thick. This concentration of oxygen is called the oxygen index.
- a high oxygen index (O.I.) indicates a highly flame-retardant specimen.
- the metal or amine salt additives herein should ordinarily be used in concentrations ranging from about 20 pph (parts per hundred parts of resin) to about 32 pph.
- antimony trioxide may be used as a synergist in concentrations ranging from about 2 pph to about 12pph.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
Description
__________________________________________________________________________ Additive pp.sup.1 HIPS.sup.2 PS.sup.3 ABS.sup.4 __________________________________________________________________________ Al salt.sup.5 20.6 20.6 24.7 Ca salt.sup.5 22.2 26.6 26.6 26.sup.4 Melamine 27 15.sup.6 12.sup.6 24 15.sup.6 salt.sup.5 Sb.sub.2 O.sub.3 4 4 4 4 4 4 4 UL-94 V-1 V-0 V-1 V-2 V-2 V-2 V-2 V-2 V-2 V-0 V-0 V-0 O.I. 26.2 33.0 31.1 25.9 20.7 22.7 23.5 23.8 26.0 24.5 24.2 25.1 __________________________________________________________________________ .sup.1 polypropylene .sup.2 high impact polystyrene (polystyrene grafted onto .sup.3 polystyrene .sup.4 a copolymer of styrene and acrylonitrile grafted onto .sup.5 of .sup.6 also contains 15 pph of ammonium polyphosphate rinane-
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/596,129 USRE32473E (en) | 1981-07-02 | 1984-04-02 | Flame-retardant polymer compositions containing metal salts |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/279,634 US4365033A (en) | 1981-07-02 | 1981-07-02 | Flame-retardant polymer compositions containing metal or amine salts |
US06/596,129 USRE32473E (en) | 1981-07-02 | 1984-04-02 | Flame-retardant polymer compositions containing metal salts |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/279,634 Reissue US4365033A (en) | 1981-07-02 | 1981-07-02 | Flame-retardant polymer compositions containing metal or amine salts |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE32473E true USRE32473E (en) | 1987-08-11 |
Family
ID=26959801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/596,129 Expired - Lifetime USRE32473E (en) | 1981-07-02 | 1984-04-02 | Flame-retardant polymer compositions containing metal salts |
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US (1) | USRE32473E (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999036468A1 (en) * | 1998-01-14 | 1999-07-22 | Bayer Aktiengesellschaft | Polycarbonate abs moulding compounds |
US6617379B2 (en) | 2001-12-04 | 2003-09-09 | Albemarle Corporation | Flame retardant polymer compositions |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3780142A (en) * | 1971-07-20 | 1973-12-18 | Marubishi Oil Chemical | Flame-retardant polyolefin compositions |
US3810850A (en) * | 1973-01-08 | 1974-05-14 | Jefferson Chem Co Inc | Piperazine phosphates as fire retardants for organic polymers |
US3959220A (en) * | 1970-10-27 | 1976-05-25 | Cincinnati Milacron Chemicals, Inc. | Polymer additives comprising transition metal complexes with trivalent phosphorous compounds |
US4003861A (en) * | 1973-08-31 | 1977-01-18 | American Cyanamid Company | Melamine pyrophosphate as flame-retardant in polyurethane foam compositions |
US4061605A (en) * | 1976-03-03 | 1977-12-06 | Eli Simon | Reaction products of benzenephosphonic acid and melamine as flame-retardant additives |
US4080501A (en) * | 1973-06-21 | 1978-03-21 | American Cyanamid Company | Melamine phosphate |
US4098759A (en) * | 1973-08-07 | 1978-07-04 | Hoechst Aktiengesellschaft | Bromine-containing cyclic phosphonic acid esters |
US4143101A (en) * | 1970-09-25 | 1979-03-06 | Sandoz Ltd. | 5,5-bis(halomethyl)1,3,2-dioxaphosphorinane compounds |
US4201705A (en) * | 1978-08-28 | 1980-05-06 | Borg-Warner Corporation | Intumescent flame retardant polyolefin compositions |
GB2101602A (en) * | 1981-07-02 | 1983-01-19 | Borg Warner Chemicals Inc | Salts of 5,5-bis-(bromomethyl)-2-hydroxy-2-oxo-1,3,2-dioxaphosphorinane and process for preparing same |
-
1984
- 1984-04-02 US US06/596,129 patent/USRE32473E/en not_active Expired - Lifetime
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4143101A (en) * | 1970-09-25 | 1979-03-06 | Sandoz Ltd. | 5,5-bis(halomethyl)1,3,2-dioxaphosphorinane compounds |
US3959220A (en) * | 1970-10-27 | 1976-05-25 | Cincinnati Milacron Chemicals, Inc. | Polymer additives comprising transition metal complexes with trivalent phosphorous compounds |
US3780142A (en) * | 1971-07-20 | 1973-12-18 | Marubishi Oil Chemical | Flame-retardant polyolefin compositions |
US3810850A (en) * | 1973-01-08 | 1974-05-14 | Jefferson Chem Co Inc | Piperazine phosphates as fire retardants for organic polymers |
US4080501A (en) * | 1973-06-21 | 1978-03-21 | American Cyanamid Company | Melamine phosphate |
US4098759A (en) * | 1973-08-07 | 1978-07-04 | Hoechst Aktiengesellschaft | Bromine-containing cyclic phosphonic acid esters |
US4003861A (en) * | 1973-08-31 | 1977-01-18 | American Cyanamid Company | Melamine pyrophosphate as flame-retardant in polyurethane foam compositions |
US4061605A (en) * | 1976-03-03 | 1977-12-06 | Eli Simon | Reaction products of benzenephosphonic acid and melamine as flame-retardant additives |
US4201705A (en) * | 1978-08-28 | 1980-05-06 | Borg-Warner Corporation | Intumescent flame retardant polyolefin compositions |
GB2101602A (en) * | 1981-07-02 | 1983-01-19 | Borg Warner Chemicals Inc | Salts of 5,5-bis-(bromomethyl)-2-hydroxy-2-oxo-1,3,2-dioxaphosphorinane and process for preparing same |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999036468A1 (en) * | 1998-01-14 | 1999-07-22 | Bayer Aktiengesellschaft | Polycarbonate abs moulding compounds |
US6326423B1 (en) * | 1998-01-14 | 2001-12-04 | Bayer Aktiengesellschaft | Polycarbonate-ABS moulding compounds |
US6617379B2 (en) | 2001-12-04 | 2003-09-09 | Albemarle Corporation | Flame retardant polymer compositions |
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