CA1096527A - Smoke-retardant chlorinated polymer compositions - Google Patents
Smoke-retardant chlorinated polymer compositionsInfo
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- CA1096527A CA1096527A CA265,396A CA265396A CA1096527A CA 1096527 A CA1096527 A CA 1096527A CA 265396 A CA265396 A CA 265396A CA 1096527 A CA1096527 A CA 1096527A
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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)
Abstract
°
SMOKE-RETARDANT CHLORINATED POLYMER COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
The addition of cobalt, zinc, iron or manganese salts of hydroxycarboxylic or dicarboxylic acids containing 2 to 6 carbon atoms to vinyl chloride resin compositions greatly reduces the evolution of smoke when the compositions undergo combustion processes. These salts exhibit synergistic action when used along with aluminum hydroxide.
SMOKE-RETARDANT CHLORINATED POLYMER COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
The addition of cobalt, zinc, iron or manganese salts of hydroxycarboxylic or dicarboxylic acids containing 2 to 6 carbon atoms to vinyl chloride resin compositions greatly reduces the evolution of smoke when the compositions undergo combustion processes. These salts exhibit synergistic action when used along with aluminum hydroxide.
Description
~09~5'~'7 This invention relates to smoke-retardant chlorinated polymer compositions.
There is much art on flame-retardants, but little on smoke-retarders or suppressants. A paper entitled SMOKE
GENERATION FROM THE BURNING OF SOME POLYMERIC MATERIALS BY
Brauman et al, given at the 32nd Annual Technical Conference of the Society of Plastic Engineers held in San Francisco in May 1974 discusses the problem and the effect of several smoke deterrents, but does not suggest the invention. U.S. patent No. 3,821rl51 ~L.C. Mitchell; June 28, 1974) suggests the use of molybdenum oxide in conjunction with iron powder and copper oxide as a smoke retardant in polyvinyl chloride, but no data are given. Miscellaneous patents on smoke retardants for vinyl chloride resins include, for example, U.S. Patents No. 3,725,313 (K.C. Frisch; April 3, 1973), No. 3,746,664 (H.P. Doerge et al;
July 17, 1963), No. 3,758,638 (H.P. Doerge et al; September 11, 1973), No. 3,819,577 (A.W. McRowe; June 25, 1974), No. 3,822,234 (A.W. McRowe; July 2, 1974), and No. 3,g00,441 (T.Y. King;
August 19, 1975); but these include no suggestion of the invention.
The present invention provides a polymer composition ha~ing a reduced tendency to smoke under combustion conditions, which consists essentially of (a) 100 parts by weight of at least one polymer having a chlorine content of from about 5 to about 70%, based on the weight of the polymer, (b) from 1 to 10 parts of at least one cobalt, zinc, iron or manganese salt of a dicarboxylic aliphatic acid or a hydroxycarboxylic acid con-taining 2 to 6 carbon atoms, and (c) from about 10 to about 150 parts by weight of hydrated aluminum hydroxide.
Cobalt, zinc, iron and manganese salts of dicarboxylic and hydroxycarboxylic acids containing 2 to 6 carbon atoms are very effective smoke suppressants when added to halogen-contai-ning polymer~ or copolymers, including chlorinated polyethylene and propylene, chlorinated paraffins, oils and waxes, polyvinyl- -idene chloride and preferably vinyl chloride polymers and chlorinated vinyl chloride polymers and blends of the foregoing polymers. The chlorine content of p_ y~i~y~
~965~!7 chloride is about 57 percent. If copolymers of vinyl chloride are used, the chlorine content is less if the comonomer (such as vinyl acetate) does not contain chlorine, and is higher if the comonomer contains chloride, (such as vinylidene chloride).
The chlorine content of chlorinated polyethylene, chlorinated polypropylene, or other chlorinated paraffins can vary over a wide range depending upon the physical properties desired in the polymer composition. Generally, a range of from about 5 to about 70 percent chlorine is present. The chlorine content of a flexible polyvinyl chloride composition will ~enerally be less than 57 percent unless chlorinated plasticizer is present. Thus, the chlorine content of the polymer composition can range from ~ about 5 to about 70 percent. The incorporation of the above-- named salts retards and lessens the smoke generated by the burning polymer. One can use 1 to 10 parts by weight of the salts, or more, if desired, per 100 parts by weight o~ the poly-mer. Preferably there should be used 4 to 8 parts by weight of the salts per 100 parts by weight of the halogenated polymer.
It has been found that the cobalt, zinc, iron, and manganese salts of hydroxy- and dicarboxylic acids, besides being excellent smoke retardants when used alone, have a particularly excellent synergistic effect when used in combination with hydrated aluminum hydroxide. Not only does there result a degree of smoke suppression greater than is obtained with the use of the individual materia~s, but also there is a substantial reduction in flammability. This last is particularly surprising, since the use of the fire retardant salts alone sometimes results in a slight increase in flammability. To obtain this synergistic effect, the hydrated aluminum oxide should be used in amounts of from 3Q about 10 to as high as 150 parts by weight of aluminum hydroxide per 100 parts by weight ., .
_ ~ _ ~L~ 3 9 6 5 Z~
of chlorine-containing polymer; the upper limit selected for said aluminum hydroxide is one based on practicality.
The acid moieties of the salts of cobalt, zinc, iron or manganese can be those of any aliphatic organic hydroxy-carboxylic or dicarboxylic acid containing 2-6 carbon atoms;
mixtures can be utilized. Examples of such acids include oxalic, malonic, succinic, glutaric, adipic and similar di-carboxylic acids; hydroxyacetic, tartaric, ascorbic, citric, - hydroxypropionic and similar hydroxy acids.
Before referring to the results, it is advantageous to know the meaning of the terms utilized. Definitions follow.
NATIONAL BUREAU OF STANDARDS SMOKE DENSITY CHAMBER
- Evaluations for the density of visible smoke were made using a commercial smoke density chamber modeled after one developed at the National Bureau of Standards by the Fire Research Group (see D. Gross, J.J. Loftus and A.F. Robertson, ASTM Special Technical Plublication 422 pages 1~6-204 (1969~.
This chamber contains a radiant heater producing 2.5 W/cm2 of heat at the surface o~ a 3" x 3" sample, a propane-air pilot burner and a vertical beam of light with a photomultiplier tube detector and microphotometer to record the attenuation of light by smoke developing in the chamber. During smoke testing, the chamber is sealed to enclose the combustion products and smoke~ The smoke developed is measured as Specific Optical Density, Ds, where S AL logl0 o = 132 logl0 To V = volume of chamber ~ = area of test specimen L = Length of light path To = initial light transmittance through the chamber T = transmittance of light during test 9~;5~7 At the peak of smoke build-up DS = Dm~ and for purposes of the report, corrected maximum smoke is recorded as DmC = Dm ~ Dc where Dc is the clear beam specific optical density occurring after the smoke test, when the chamber has been exhausted of smoke. Lower values of DmC indicate less obscuration of light , . ~ .
due to smoke.
Several other quantities measured include the time in minutes to 90 percent of Dm (t.9D~) and the time (in minutes~
to DS = 16 (t D16), which are indicative of the rate of smoke development (higher numbers signify slower rates), as well as the smoke obscuration number for the first four minutes of test, SON4, where.
SON4 = DS (1 min.) + DS (2 min.) + DS (3 min.) + DS ~4 min,) which also represents the early rate of smoke development (lower numbers mean less smoke). The definitions of terms are summarized below.
DmC = Specific optical density at maximum smoke - intensity, corrected for fogging of lens seals.
DmC ~ 25, light; 25~75, moderate; 100-400, dense, > 400 very dense.
t.9 Dm = time (minutes) to reach 90 percent of maximum optical density.
tD16 = time (minutes) to D = 16, corresponds to early visibility obscuration. tD16 < 1, very fast;
1-3 fast; 4-6 moderate; 7-10 510w; > 10, Yery slow smoker.
SON4 = Smoke obscuration number over first four minutes of test, indicates amount of smoke vs. rate of build-up early in the test.
SON4 < 3, very low; 4-10, low; 10-S0, moderate;
50-100, high; > 200, very high.
- ~39~ii5Z7 LOI is the abbreviation for Limiting Oxygen Index which is defined as the minimum volume percent oxygen content required in an oxygen/nitrogen mixture to maintain combustion of a vertical, top-lighted test specimen. The value is expressed in mathematical terms as follows :
LOI = ~ G2~7 x 100 ~ 2 7 ~ ~ N2 ~
where ~02_7 is the volume of oxygen and ~N2 J is the volume of nitrogen. The LOI is considered to be an accurate, reproduc-ible determination of the flammability of materials. From a practical standpoint, an LOI value of greater than 25 generally means that the test specimen will be self-extinguishing. For a more detailed discussiom of the LOI and method of determination, C.P. Fenimore and F. R. Martin's article in COMBUSTION AND
FLAME 10 No. 2, page 135 (1966), should be consulted.
Limiting Oxygen Indices were obtained using the Michigan Chemical LOI apparatus. An Aminco-NBS smoke density chamber was used to obtain data on the rate of smoke generation as well as intensity of visible smoke.
EXPERIMENTAL RESULTS
_ . _ Polyvinyl Chloride Resin 100 grams .. ,.. ", ~ .. .. ...
~"FPC-965" a product of The Firestone Tire &
Rubber Company) Calcium Stearate 2 grams Dilauryl Tin Mercaptide 3~75 grams Smoke Suppressant 5 grams (per-Table I) 3U A series of pla~ues was prepared in accordance with the foregoing recipe, using different smoke suppressants in the several runs as set forth in Table I. In each case, the :~965iZ7 ..
ingredients in the recipe were compounded, in the order in which they are listed, on a laboratory roll mill heated at 350F. (177C.). The compounded material was then pressed into sheets 0.030" ~0.762 mm.) thick in a laboratory press, ' ~ the platens of which were heated at 345F. (174C). Specimens from each sheet were submitted to NBS smoke density tests as de~cribed above. Also, specimens were pressed out at 345F. (174C.) with dimensions 0.25" x 5" x 1.0" (6.35 mm.
x 127 mm. x 25.4 mm) and subjected to oxygen index measurements as described above. Set ~orth herewith in Table I are the results of these experiments.
TABLE I
: .
~- Smoke tColor of TEST RESULTS
Used Specimen LOI DmC t-9Dm tD16 SON~ No.
None light 45.1 357 2.67 0.42 272 (Control)yellow Cobalt light 43.4 273 2.43 0.45 214 2 oxalate blue Zinc light 48.9 294 2.47 0.40 256 3 Tartrateyellow Ferric dark 40.9 283 2.93 0.38 223 4 Tartratebrown Manganese light tan- 43.0 317 2.16 0.39 265 5 Tartrate yellow Barium light 39.9 432 3.16 0.37 342 6 Tartrateyellow TABLE II
SmokeitC 1 of TEST RESULTS
Used o or LOI mc ~ NRuOn.
None cream 49.0 284 3.20 0.48 206 7 Cobalt light 57.4 216 3.34 0.56 145 8 Oxalate blue ~, - 7 .. . .
-TABLE I I ( su i te) Inhibitor Color of TEST RESULTS
Used Speclmen LOI Dmc t.9Dm tD16 14 No Zinc pale 59.4 206 2.81 0.56 142 9 Tartrate yellow Ferric brown 52.1 177 3.~8 0.74 110 10 Tartrate _ Runs Nos. 1-6 show the different eff~cts of the various compounds added. Thus cobalt oxalate, zinc tartrate, ferric tartrate, and manganese tartrate of the present invention (Runs Nos. 2-5) decreased the smoke in relation to the control tRun No. 1). Barium tartrate increased the smoke.
Runs Nos. 7-10 of Table II illustrate the synergistic effect of the smoke suppressants of the present invention when used in connection with aluminum hydroxide, which itself is used as a flame retardant and smoke suppressant for a variety of resins.
The compositions of Table II contained, in addition - to the ingredients of the foregoing recipe and the indicated smske inhibitors, 30 grams of hydrated aluminum oxide (aluminum .,,,"~.. " ,.,,~,. , hydroxide, Al(OH3) ). Comparing the control Run No. 1 of Table I with the other runs, in Run No. 7 of Table II, the aluminum hydroxide alone cuts down thevisible smoke (DmC) by 20%, and at the same time, increases LOI by 9% (decreased flammability).
In contrast, ferric tartrate alone (Run No. 4) cuts down visible smoke (D~c) by 20%, but decreases LOI by 10% (increased flammability). However, when both are used together (Run No.
10), the visible smoke (DmC) is reduced by 50% and the LOI
(inverse to flammability) is increased by 15%.
It is understood that the preceding examples are representative and that they can be varied within the context of my total specification, as it would be understood by one skilled in the art, to achieve substantially the same results.
,.~
There is much art on flame-retardants, but little on smoke-retarders or suppressants. A paper entitled SMOKE
GENERATION FROM THE BURNING OF SOME POLYMERIC MATERIALS BY
Brauman et al, given at the 32nd Annual Technical Conference of the Society of Plastic Engineers held in San Francisco in May 1974 discusses the problem and the effect of several smoke deterrents, but does not suggest the invention. U.S. patent No. 3,821rl51 ~L.C. Mitchell; June 28, 1974) suggests the use of molybdenum oxide in conjunction with iron powder and copper oxide as a smoke retardant in polyvinyl chloride, but no data are given. Miscellaneous patents on smoke retardants for vinyl chloride resins include, for example, U.S. Patents No. 3,725,313 (K.C. Frisch; April 3, 1973), No. 3,746,664 (H.P. Doerge et al;
July 17, 1963), No. 3,758,638 (H.P. Doerge et al; September 11, 1973), No. 3,819,577 (A.W. McRowe; June 25, 1974), No. 3,822,234 (A.W. McRowe; July 2, 1974), and No. 3,g00,441 (T.Y. King;
August 19, 1975); but these include no suggestion of the invention.
The present invention provides a polymer composition ha~ing a reduced tendency to smoke under combustion conditions, which consists essentially of (a) 100 parts by weight of at least one polymer having a chlorine content of from about 5 to about 70%, based on the weight of the polymer, (b) from 1 to 10 parts of at least one cobalt, zinc, iron or manganese salt of a dicarboxylic aliphatic acid or a hydroxycarboxylic acid con-taining 2 to 6 carbon atoms, and (c) from about 10 to about 150 parts by weight of hydrated aluminum hydroxide.
Cobalt, zinc, iron and manganese salts of dicarboxylic and hydroxycarboxylic acids containing 2 to 6 carbon atoms are very effective smoke suppressants when added to halogen-contai-ning polymer~ or copolymers, including chlorinated polyethylene and propylene, chlorinated paraffins, oils and waxes, polyvinyl- -idene chloride and preferably vinyl chloride polymers and chlorinated vinyl chloride polymers and blends of the foregoing polymers. The chlorine content of p_ y~i~y~
~965~!7 chloride is about 57 percent. If copolymers of vinyl chloride are used, the chlorine content is less if the comonomer (such as vinyl acetate) does not contain chlorine, and is higher if the comonomer contains chloride, (such as vinylidene chloride).
The chlorine content of chlorinated polyethylene, chlorinated polypropylene, or other chlorinated paraffins can vary over a wide range depending upon the physical properties desired in the polymer composition. Generally, a range of from about 5 to about 70 percent chlorine is present. The chlorine content of a flexible polyvinyl chloride composition will ~enerally be less than 57 percent unless chlorinated plasticizer is present. Thus, the chlorine content of the polymer composition can range from ~ about 5 to about 70 percent. The incorporation of the above-- named salts retards and lessens the smoke generated by the burning polymer. One can use 1 to 10 parts by weight of the salts, or more, if desired, per 100 parts by weight o~ the poly-mer. Preferably there should be used 4 to 8 parts by weight of the salts per 100 parts by weight of the halogenated polymer.
It has been found that the cobalt, zinc, iron, and manganese salts of hydroxy- and dicarboxylic acids, besides being excellent smoke retardants when used alone, have a particularly excellent synergistic effect when used in combination with hydrated aluminum hydroxide. Not only does there result a degree of smoke suppression greater than is obtained with the use of the individual materia~s, but also there is a substantial reduction in flammability. This last is particularly surprising, since the use of the fire retardant salts alone sometimes results in a slight increase in flammability. To obtain this synergistic effect, the hydrated aluminum oxide should be used in amounts of from 3Q about 10 to as high as 150 parts by weight of aluminum hydroxide per 100 parts by weight ., .
_ ~ _ ~L~ 3 9 6 5 Z~
of chlorine-containing polymer; the upper limit selected for said aluminum hydroxide is one based on practicality.
The acid moieties of the salts of cobalt, zinc, iron or manganese can be those of any aliphatic organic hydroxy-carboxylic or dicarboxylic acid containing 2-6 carbon atoms;
mixtures can be utilized. Examples of such acids include oxalic, malonic, succinic, glutaric, adipic and similar di-carboxylic acids; hydroxyacetic, tartaric, ascorbic, citric, - hydroxypropionic and similar hydroxy acids.
Before referring to the results, it is advantageous to know the meaning of the terms utilized. Definitions follow.
NATIONAL BUREAU OF STANDARDS SMOKE DENSITY CHAMBER
- Evaluations for the density of visible smoke were made using a commercial smoke density chamber modeled after one developed at the National Bureau of Standards by the Fire Research Group (see D. Gross, J.J. Loftus and A.F. Robertson, ASTM Special Technical Plublication 422 pages 1~6-204 (1969~.
This chamber contains a radiant heater producing 2.5 W/cm2 of heat at the surface o~ a 3" x 3" sample, a propane-air pilot burner and a vertical beam of light with a photomultiplier tube detector and microphotometer to record the attenuation of light by smoke developing in the chamber. During smoke testing, the chamber is sealed to enclose the combustion products and smoke~ The smoke developed is measured as Specific Optical Density, Ds, where S AL logl0 o = 132 logl0 To V = volume of chamber ~ = area of test specimen L = Length of light path To = initial light transmittance through the chamber T = transmittance of light during test 9~;5~7 At the peak of smoke build-up DS = Dm~ and for purposes of the report, corrected maximum smoke is recorded as DmC = Dm ~ Dc where Dc is the clear beam specific optical density occurring after the smoke test, when the chamber has been exhausted of smoke. Lower values of DmC indicate less obscuration of light , . ~ .
due to smoke.
Several other quantities measured include the time in minutes to 90 percent of Dm (t.9D~) and the time (in minutes~
to DS = 16 (t D16), which are indicative of the rate of smoke development (higher numbers signify slower rates), as well as the smoke obscuration number for the first four minutes of test, SON4, where.
SON4 = DS (1 min.) + DS (2 min.) + DS (3 min.) + DS ~4 min,) which also represents the early rate of smoke development (lower numbers mean less smoke). The definitions of terms are summarized below.
DmC = Specific optical density at maximum smoke - intensity, corrected for fogging of lens seals.
DmC ~ 25, light; 25~75, moderate; 100-400, dense, > 400 very dense.
t.9 Dm = time (minutes) to reach 90 percent of maximum optical density.
tD16 = time (minutes) to D = 16, corresponds to early visibility obscuration. tD16 < 1, very fast;
1-3 fast; 4-6 moderate; 7-10 510w; > 10, Yery slow smoker.
SON4 = Smoke obscuration number over first four minutes of test, indicates amount of smoke vs. rate of build-up early in the test.
SON4 < 3, very low; 4-10, low; 10-S0, moderate;
50-100, high; > 200, very high.
- ~39~ii5Z7 LOI is the abbreviation for Limiting Oxygen Index which is defined as the minimum volume percent oxygen content required in an oxygen/nitrogen mixture to maintain combustion of a vertical, top-lighted test specimen. The value is expressed in mathematical terms as follows :
LOI = ~ G2~7 x 100 ~ 2 7 ~ ~ N2 ~
where ~02_7 is the volume of oxygen and ~N2 J is the volume of nitrogen. The LOI is considered to be an accurate, reproduc-ible determination of the flammability of materials. From a practical standpoint, an LOI value of greater than 25 generally means that the test specimen will be self-extinguishing. For a more detailed discussiom of the LOI and method of determination, C.P. Fenimore and F. R. Martin's article in COMBUSTION AND
FLAME 10 No. 2, page 135 (1966), should be consulted.
Limiting Oxygen Indices were obtained using the Michigan Chemical LOI apparatus. An Aminco-NBS smoke density chamber was used to obtain data on the rate of smoke generation as well as intensity of visible smoke.
EXPERIMENTAL RESULTS
_ . _ Polyvinyl Chloride Resin 100 grams .. ,.. ", ~ .. .. ...
~"FPC-965" a product of The Firestone Tire &
Rubber Company) Calcium Stearate 2 grams Dilauryl Tin Mercaptide 3~75 grams Smoke Suppressant 5 grams (per-Table I) 3U A series of pla~ues was prepared in accordance with the foregoing recipe, using different smoke suppressants in the several runs as set forth in Table I. In each case, the :~965iZ7 ..
ingredients in the recipe were compounded, in the order in which they are listed, on a laboratory roll mill heated at 350F. (177C.). The compounded material was then pressed into sheets 0.030" ~0.762 mm.) thick in a laboratory press, ' ~ the platens of which were heated at 345F. (174C). Specimens from each sheet were submitted to NBS smoke density tests as de~cribed above. Also, specimens were pressed out at 345F. (174C.) with dimensions 0.25" x 5" x 1.0" (6.35 mm.
x 127 mm. x 25.4 mm) and subjected to oxygen index measurements as described above. Set ~orth herewith in Table I are the results of these experiments.
TABLE I
: .
~- Smoke tColor of TEST RESULTS
Used Specimen LOI DmC t-9Dm tD16 SON~ No.
None light 45.1 357 2.67 0.42 272 (Control)yellow Cobalt light 43.4 273 2.43 0.45 214 2 oxalate blue Zinc light 48.9 294 2.47 0.40 256 3 Tartrateyellow Ferric dark 40.9 283 2.93 0.38 223 4 Tartratebrown Manganese light tan- 43.0 317 2.16 0.39 265 5 Tartrate yellow Barium light 39.9 432 3.16 0.37 342 6 Tartrateyellow TABLE II
SmokeitC 1 of TEST RESULTS
Used o or LOI mc ~ NRuOn.
None cream 49.0 284 3.20 0.48 206 7 Cobalt light 57.4 216 3.34 0.56 145 8 Oxalate blue ~, - 7 .. . .
-TABLE I I ( su i te) Inhibitor Color of TEST RESULTS
Used Speclmen LOI Dmc t.9Dm tD16 14 No Zinc pale 59.4 206 2.81 0.56 142 9 Tartrate yellow Ferric brown 52.1 177 3.~8 0.74 110 10 Tartrate _ Runs Nos. 1-6 show the different eff~cts of the various compounds added. Thus cobalt oxalate, zinc tartrate, ferric tartrate, and manganese tartrate of the present invention (Runs Nos. 2-5) decreased the smoke in relation to the control tRun No. 1). Barium tartrate increased the smoke.
Runs Nos. 7-10 of Table II illustrate the synergistic effect of the smoke suppressants of the present invention when used in connection with aluminum hydroxide, which itself is used as a flame retardant and smoke suppressant for a variety of resins.
The compositions of Table II contained, in addition - to the ingredients of the foregoing recipe and the indicated smske inhibitors, 30 grams of hydrated aluminum oxide (aluminum .,,,"~.. " ,.,,~,. , hydroxide, Al(OH3) ). Comparing the control Run No. 1 of Table I with the other runs, in Run No. 7 of Table II, the aluminum hydroxide alone cuts down thevisible smoke (DmC) by 20%, and at the same time, increases LOI by 9% (decreased flammability).
In contrast, ferric tartrate alone (Run No. 4) cuts down visible smoke (D~c) by 20%, but decreases LOI by 10% (increased flammability). However, when both are used together (Run No.
10), the visible smoke (DmC) is reduced by 50% and the LOI
(inverse to flammability) is increased by 15%.
It is understood that the preceding examples are representative and that they can be varied within the context of my total specification, as it would be understood by one skilled in the art, to achieve substantially the same results.
,.~
Claims (20)
1. A polymer composition having reduced flammability and reduced tendency to smoke under combustion conditions, said composition consisting essentially of (a) 100 parts by weight of at least one polymer having a chlorine content of from about 5 to about 70%, based on the weight of said polymer, (b) from 1 to 10 parts of at least one cobalt, zinc, iron or manganese salt of a dicarboxylic aliphatic acid or a hydroxycarboxylic acid containing 2 to 6 carbon atoms, and (c) from about 10 to about 150 parts by weight of hydrated aluminum hydroxide.
2. Composition according to claim 1, wherein the hydrated aluminum hydroxide is present in an amount of from about 20 to about 75 parts by weight.
3. Composition according to claims 1 or 2, wherein said salt is present in an amount of from 4 to 8 parts by weight.
4. Composition according to claim 1, wherein the polymer is selected from the group consisting of chlorinated polyethylene, chlorinated polypropylene, polyvinylidene chloride, polyvinyl chloride and chlorinated polyvinyl chloride.
5. Composition according to claim 1, wherein the polymer is polyvinyl chloride.
6. Composition according to claim 1, wherein the polymer is chlorinated polyethylene.
7. Composition according to claim 1, wherein the salt is a salt of oxalic acid.
8. Composition according to claim 1, wherein the salt is a salt of tartaric acid.
9. Composition according to claim 1, wherein the salt is a salt of cobalt.
10. Composition according to claim 1, wherein the salt is a salt of zinc.
11. Composition according to claim 1, wherein the salt is a salt of iron.
12. Composition according to claim 1, wherein the salt is a salt of manganese.
13. Composition according to claim 1, wherein the salt is cobalt oxalate.
14. Composition according to claim 1, wherein the salt is zinc tartrate.
15. Composition according to claim 1, wherein the salt is ferric tartrate.
16. Composition according to claim 1, wherein the salt is manganese tartrate.
17. A polymer composition having reduced flammability and reduced tendency to smoke under combustion conditions, said composition consisting essentially of (a) 100 parts by weight of at least one polymer having a chlorine content of from about 5 to about 70%, based on the weight of said polymer, said polymer being chlorinated polyethylene, chlorinated polypropylene, polyvinylidene chloride, polyvinyl chloride or chlorinated poly-vinyl chloride, (b) from 1 to 10 parts cobalt oxalate, and (c) from about 10 to about 150 parts by weight hydrated aluminum hydroxide.
18. A polymer composition having reduced flammability and reduced tendency to smoke under combustion conditions, said composition consisting essentially of (a) 100 parts by weight of at least one polymer having a chlorine content of from about 5 to about 70%, based on the weight of said polymer, said polymer being chlorinated polyethylene, chlorinated poly-propylene, polyvinylidene chloride, polyvinyl chloride or chlorinated polyvinyl chloride, (b) from 1 to 10 parts manganese tartrate, and (c) from about 10 to about 150 parts by weight hydrated aluminum hydroxide.
19. A polymer composition having reduced flammability and reduced tendency to smoke under combustion conditions, said composition consisting essentially of (a) 100 parts by weight of polyvinyl chloride having a chlorine content of from about 5 to about 70%, based on the weight of said polymer, (b) from 1 to 10 parts cobalt oxalate, and (c) from about 10 to about 150 parts by weight hydrated aluminum hydroxide.
20. A polymer composition having reduced flammability and reduced tendency to smoke under combustion conditions, said composition consisting essentially of (a) 100 parts by weight of polyvinyl chloride having a chlorine content of from about 5 to about 70%, based on the weight of said polymer, (b) from 1 to 10 parts manganese tartrate, and (c) from about 10 to about 150 parts by weight hydrated aluminum hydroxide.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63233475A | 1975-11-17 | 1975-11-17 | |
| US632.334 | 1975-11-17 | ||
| US05/728,815 US4096116A (en) | 1975-11-17 | 1976-10-01 | Smoke-retardant chlorinated polymer compositions |
| US728.815 | 1976-10-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1096527A true CA1096527A (en) | 1981-02-24 |
Family
ID=27091602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA265,396A Expired CA1096527A (en) | 1975-11-17 | 1976-11-10 | Smoke-retardant chlorinated polymer compositions |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5263251A (en) |
| CA (1) | CA1096527A (en) |
| DE (1) | DE2651840A1 (en) |
| FR (1) | FR2332295A1 (en) |
| GB (1) | GB1570198A (en) |
| IT (1) | IT1123080B (en) |
| LU (1) | LU76201A1 (en) |
| NL (1) | NL7612569A (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1544425A (en) * | 1966-11-15 | 1968-10-31 | Basf Ag | Polypropylene molding materials |
| US3639319A (en) * | 1969-07-14 | 1972-02-01 | Synthetic Products Co | Pellucid halogen-containing resin compositions |
| ZA743281B (en) * | 1973-07-12 | 1975-05-28 | Ferro Corp | Smoke supressants for resinous organic materials |
| US3956139A (en) * | 1973-09-12 | 1976-05-11 | Uniroyal Inc. | Synergistic additive combinations for flame-retarding polymers |
| US3945974A (en) * | 1973-12-20 | 1976-03-23 | N L Industries, Inc. | Smoke suppressants for halogen-containing plastic compositions |
-
1976
- 1976-11-10 CA CA265,396A patent/CA1096527A/en not_active Expired
- 1976-11-11 NL NL7612569A patent/NL7612569A/en not_active Application Discontinuation
- 1976-11-13 DE DE19762651840 patent/DE2651840A1/en not_active Withdrawn
- 1976-11-15 LU LU76201A patent/LU76201A1/xx unknown
- 1976-11-15 JP JP51137193A patent/JPS5263251A/en active Pending
- 1976-11-16 FR FR7634475A patent/FR2332295A1/en active Granted
- 1976-11-16 GB GB47770/76A patent/GB1570198A/en not_active Expired
- 1976-11-17 IT IT29381/76A patent/IT1123080B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| GB1570198A (en) | 1980-06-25 |
| IT1123080B (en) | 1986-04-30 |
| FR2332295B1 (en) | 1983-02-04 |
| DE2651840A1 (en) | 1977-06-16 |
| NL7612569A (en) | 1977-05-20 |
| LU76201A1 (en) | 1977-06-06 |
| FR2332295A1 (en) | 1977-06-17 |
| JPS5263251A (en) | 1977-05-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |