CA1045269A - Flame retardant and drip resistant thermoplastics - Google Patents
Flame retardant and drip resistant thermoplasticsInfo
- Publication number
- CA1045269A CA1045269A CA203,599A CA203599A CA1045269A CA 1045269 A CA1045269 A CA 1045269A CA 203599 A CA203599 A CA 203599A CA 1045269 A CA1045269 A CA 1045269A
- Authority
- CA
- Canada
- Prior art keywords
- thermoplastic
- resin
- weight
- melting point
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
Abstract
Abstract of the Disclosure A method of improving the drip resistance of burning thermoplastics by incorporating polytetrafluoro-ethylene and a nonflammable fibrous material into the thermoplastics in combination with flame retardant systems.
Description
~5'~69 mis lnvention relates to a method for reducing the amount of dripping that occurs when thermoplastic com-positlons are unrestrained and in molten condition, and to thermoplastic compositions prepared by this method and ;
having nondrip characteristics when said materials are sub-jected to temperatures above the melting point of the ori-ginal thermoplastic material~
It is an object of the present invention to pro-vide a method to reduce or prevent dripping which usually accompanies melting of thermoplastic materials when s~lch ~ materials are exposed to combustion conditions such as those - in ASTM D-635 flammability test. It is a further ob~ect of ~ the present invention to provide a method to prevent the . ~ ~
spread of fire which usually accompanies such dripping.
, 15 Other objects will become apparent as the description pro-ceeds.
When suspended thermoplastics burn, molten polymer ~`~ drips carrying flame with it and spreading the fire. Such ,,~
;~ thermoplastics can not meet the requirement set up as indus-( 20 try's standards such as those of ASTM D-635 and Underwrite~s Laboratory UL-9~ for a self-extinguishing rating (SE-O).
~ For example, the UL-9~ test requires that a 5"xl/2"xl/8" bar :,a; of the material tested b0 supported vertically at one end. ~ ~
~' The free end is exposed to a specified gas ~lame for two 10- ~ ~-;, 25 second ignitions. Thermoplastics which drip and ignite dry 1 absorbent surgical cotton placed 12 inches beneath the bar at any time longer than 10 seconds after the second removal ~ of the specified gas flame fail to earn the SE-O rating.
-1, It has been discovered according to this inven-~' 30 tion that a thermoplastic polymer containing flame :, .~ ~'~ ~
:, ~,.. . . . .. . . . . .
.,:~ : ,...................... .. . .
;,", 104S~6~
retardant agents, a nonflammable fibrous material and poly-tetrafluoroethylene is nondripping when subjected to com-~` bustion temperatures as described in ASTM D-63~ and UL-94.
The amounts of both polytetrafluoroethylene and the non-flammable fibrous material used can be varied~ usually between about .1 and 5.0 percent of each by weight of the ., total composition. Generally the amounts used will be varied with changes in the flame retardant agents used in ,.
; the base resin ...
. ,,.
Representative examples of nonflammable fibrous material useful in this invention are potassium titanate (DuPont's FybexTh), fiberglass, asbestos, graphite fiber and carbon fiber.
Materials such as octabromobiphenyl, decabromobi-phenyl oxide~ hexabromobenzene, triphenyl phosphate~ bis(2, 6-tribromophenyl)carbanate, ethoxylated tetrabromobiphenol-3 A, 2,5-dibromoterephthalic acid, tris(2,3-dibromopropyl) phosphate and antimony oxide can be used to impart flame ~ retarding properties to the resin. These materials can be .,,~
used alone or in mixtures with the resins.
The polytetrafluoroethylene and nonflammable , ~ .
`~ fibrous material can be added to the thermoplastic resin by methods well known to those skilled in this art.
Representative examples of thermoplastic resins useful in the practice of this invention are thermoplastic polyesters such as poly(ethylene terephthalate), poly (tetramethylene terephthalate), 80/20 poly(tetramethylene terephthalate/isophthalate), 70/10/20 poly(tetramethylene/
isophthalate~sebacate); polyamides such as Nylon 6/6, Nylo~
6, Nylon 6/10, Nylon 6/12 and polyolefins such as high ., ., ~ j -2-.~ , lV~5269 density polyethylene~ low density polyethylene, polypro-pylene. Other thermoplastic resins useful in the practice of this invention are polyphenylene oxide, acrylonitrile/
butadiene/styrene (~BS) resins, polyacetals (polyoxymethy-lene), polystyrene and polycarbonates such as poly(4,~'-dihydroxy-diphenyl-2,2-propane)-carbonate and poly(4,4'-dihydroxy-diphenyl-methyl-phenyl-methane)-carbonate.
The products of the invention are useful as flame re-sistant and drip resistant molding compositions.
, . . .
^ 10 ~he term "thermoplastic resin" as employed in this disclosure is understood to include base thermoplastic resin as well as those thermoplastic resins compounded l~th ..
- lubricating and nucleating agents or other additives. The thermoplastic resins are crystalline in form. The crystal-line thermoplastic resins employed in this invention have a melting point at or abore 100 C. me melting point is the maximum useful service temperature of a crystalline solid - i .
and is the temperature at which a highly ordered crystalline solid is transformed into a liquid.
, 20 ~he term "polyester" as employed in this disclo-;'!
sure is intended to include both homopolyester and copoly- ~;
`~ ester.
, These polyesters are conveniently prepared by -; reacting aromatic dicarboxylic acids or ester forming derivatives thereof with a glycol of the formula HO(C ~ )nOH
~ where n is an integer ranging from 2 to 10 to form the -~ corresponding glycol ester and then polycondensing the glycol ester with-elimination of glycol under conditions of elevated temperatures and reduced pressures to form high molecular weight linear polyester or copolyester resins.
Representative examples of such polycondensation . polyester resins include resins derived from dicarboxylic . _ 3 _ lV45Z69 acids such as terephthalic acid, aliphatic dicarboxylic ' acids such as adipic acid~ sebacic acid, azelaic acid and `Y- aromatic dicarboxylic acids such as orthophthalic acid,isophthalic acid, terephthalic acid~ bibenzoic acid~ naph-.
~^ 5 thalic acid and the like. The resins can be made from various glycols such as those of the formula HO(CH2)IlOH
where n is an integer ranging from 2 to 10 and including ethylene glycol, propylene glycol, tetramethylene glycol, ~ pentamethylene glycol~ hexamethylene glycol, decamethylene `~ 10 glycol and the like~ alkyl substituted polymethylens gly-~;, cols such as neopentyl glycol and 2-methyl-2-ethylene and cyclic glycols such as cyclohexanedimethanol and 2,274,4-tetramethyl-1,3-cyclobutene diol. Ethylene glycol is a preferred glycol because of its low cost and ready avail--~j 15 ability.
i The examples below illustrate the invention. me resin used is an .80 Intrinsic Viscosity (IV) poly(tetra-methylene terephthalate). In this application intrinsic ~i viscosity was measured in a Cannon-Ubbelhode viscometer using a 60 phenol/40 tetrachloroethane solvent at 30 C.
PHR in the examples is parts by weight per hundred parts of .
resin by weight. All parts and percentages are by weight unless otherwise specified. Examples 1 to 3 and a portion of 6 are comparative examples. Examples 4~ 5 and a portion , 25 of 6 illustrate the invention. ~ ;
Example 1 Poly(tetramethylene terephthalate) (PTMT) was produced in a stirred tank reactor by reacting one mole of dimethylterephthalate (DMT) with 1.2 moles of tetramethyl-ene glycol at 190 C. and at atmospheric pressure until ,, .
-: ~
85 percent of the theoretical amount of methanol had evolved then the oligomers were polymerized under reduced pressure ' at 2500 C. At the polymerization stage 8 PHR of octabromo- -~- biphenyl and ~ PHR of antimony trioxide were added. An o.80 . . , '~ 5 IV PTMT containing these flame retardants was obtained.
'~ ~nis was molded into a bar of 5" x 1/2" x 1/8" at 250~ C.
by injection molding prQcess. The bar was tested for flam-mability according to AS~M D-635 and UL-9~ flammability test ''~ methods. The polymer started dripping five seconds after ~ 10 the application of flame. me droplets carrying the flame ::;
" ` ignited cotton placed one foot b'elow the bar. me polymer ~ . ~
~-~ thus failed to meet the requirements to earn an SE-0 rating.
~ - - - Example_2 ,'`~ m e process, polymer composition, and testing are the same as those in Example 1 except that 10 PHR of octa~
bromobiphenyl were used in place of 8 PHR octabromobiphenyl '~'Y~ ' and one percent by weight polytetrafluoroethylene (DuPont's ;~ ' TeflonTM)was added. The polymer failed to pass the flamma-bility-test because of dripping.
. .. -~ .
~ 20 ~3~EL~
. ,~.~ . - .
lhe product of Example 1 was dry blended with one weight percent of potassium titanate fibers (DuPont's FybexTM) ~ ~ .
`~ and injection molded into a test bar~ which ~ras tested using ~' ' `~ the AS~M and UL test methods. The compounded polymer again ' failed to pass the test because of dripping. ~ -.~ ExamPle L~ ' -, The product in Example 1 was dry blended with one '~
weight percent of potassium titanate fibers (DuPont's Fybex~M) and one weight percent of polytetrafluoroethylene (DuPont's ' 30 Teflon~)and injection molded into a 5" x 1/2" x 1/8" test ' . . .
;' -5-. , .. , , . . .. ~ ,. .
11~)45Z69 1 bar. The compounded poly~er bar was tested in the flamma-bility test and did not drip during thirty seconds of flame application time. The poly(tetramethylene terephthalate) thus compounded passed both ASTM and UL tests and was rated , ; .
as SE-0.
,! Exam~le 5 At the polymerization stage of the preparation of polyttetramethylene terepht,halate) 8 PHR o~ decabromobi-~A, phenyl oxide (DBBP0)~ 4 PHR of antimo~y oxide~ .5 weight ;, 10 perce~t of polytetrafluoroethylene (DuPont~s Teflon) and ~..
.5 weight percent of potassium titanate ~DuPont's Fybex) were added to the reactor and mixed with the polymer under ~, condensation conditions. The compounded resin t.80 IV) was injection molded into a 5" x 1/2" x l/8" test bar. The test bar was tested for flammability and started to drip slowly after 24 seconds of flame application. me droplets did not spread the fire. me bar passed both ASTM and UL test re-., ,. ~ .
, quirements and was rated SE-0. This result indicates ~hat .5 weight percent of Fybex and .~ weight percent o~ Teflon l . .
- 20 are the minimum levels for retarding flame spreading.
^ Example 6 ; Dechlorane plus 515, plus 25 and 603(chlorinated , organic flame retarding agent~ from Hooker Chemical Cor-l poration containing 65 percent by weight of chlorine was . ~
used to impart self-extinguishing properties to polyester polymer rendering the poly (tetramethylene terephthalate) polymer self-extinguishing. At least 16 PHR of the ' Dechlorane and 5 PHR of the antimony trioxide Sb20~ are required. Dechlorane inherently induced less dripping .~, . __ ~.~ 1. .
of the polymer during burning. Poly (tetramethylene tere-phthalate) polymer with the above composition dripped after 20 seconds of burning. In con-trast the same polymer with one-half PHR of Teflon and one-half PHR of Fybex did not drip.
. .
The amount of polytetrafluoroethylene used will generally be in the range of from about 0.1 percent by : .
~ weight to about 5.0 percent by weight of the total composi-. '!
tion, more preferred from about .5 percent by weight to about 1.0 percent by weight of the total composition. The ; nonflammable fibrous material used will be in a concentra-~ tion of from about 0.1 percent by weight to about 5.0 per-, 1 :
~`;`3~ cent by weight of the total composition, more preferred from about .5 percent to about 1.0 percent by weight of the total ~ ~
1 15 composition. me amount of flame retardant used will be in ~-i the concentration sufficient to render the polymer self-extinguishing. When the polymer contains these ingredients in these amounts it becomes nondripping during the 30 second '?~' test burning in accordance with ASTM D~635 flammability tests and UL-94 flammability test, and the polymer is rated self-extinguishing.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in ~
this art that various changes and modifications may be ~ ;
made herein without departing from the spirit or scope of ~ ;
this invention.
,Y
.~ ', '? 7-.,' ~ , ~ :-. .
'::.......... . . .. .
,:: . . . .. .
.:::. . , ,. .. . :
having nondrip characteristics when said materials are sub-jected to temperatures above the melting point of the ori-ginal thermoplastic material~
It is an object of the present invention to pro-vide a method to reduce or prevent dripping which usually accompanies melting of thermoplastic materials when s~lch ~ materials are exposed to combustion conditions such as those - in ASTM D-635 flammability test. It is a further ob~ect of ~ the present invention to provide a method to prevent the . ~ ~
spread of fire which usually accompanies such dripping.
, 15 Other objects will become apparent as the description pro-ceeds.
When suspended thermoplastics burn, molten polymer ~`~ drips carrying flame with it and spreading the fire. Such ,,~
;~ thermoplastics can not meet the requirement set up as indus-( 20 try's standards such as those of ASTM D-635 and Underwrite~s Laboratory UL-9~ for a self-extinguishing rating (SE-O).
~ For example, the UL-9~ test requires that a 5"xl/2"xl/8" bar :,a; of the material tested b0 supported vertically at one end. ~ ~
~' The free end is exposed to a specified gas ~lame for two 10- ~ ~-;, 25 second ignitions. Thermoplastics which drip and ignite dry 1 absorbent surgical cotton placed 12 inches beneath the bar at any time longer than 10 seconds after the second removal ~ of the specified gas flame fail to earn the SE-O rating.
-1, It has been discovered according to this inven-~' 30 tion that a thermoplastic polymer containing flame :, .~ ~'~ ~
:, ~,.. . . . .. . . . . .
.,:~ : ,...................... .. . .
;,", 104S~6~
retardant agents, a nonflammable fibrous material and poly-tetrafluoroethylene is nondripping when subjected to com-~` bustion temperatures as described in ASTM D-63~ and UL-94.
The amounts of both polytetrafluoroethylene and the non-flammable fibrous material used can be varied~ usually between about .1 and 5.0 percent of each by weight of the ., total composition. Generally the amounts used will be varied with changes in the flame retardant agents used in ,.
; the base resin ...
. ,,.
Representative examples of nonflammable fibrous material useful in this invention are potassium titanate (DuPont's FybexTh), fiberglass, asbestos, graphite fiber and carbon fiber.
Materials such as octabromobiphenyl, decabromobi-phenyl oxide~ hexabromobenzene, triphenyl phosphate~ bis(2, 6-tribromophenyl)carbanate, ethoxylated tetrabromobiphenol-3 A, 2,5-dibromoterephthalic acid, tris(2,3-dibromopropyl) phosphate and antimony oxide can be used to impart flame ~ retarding properties to the resin. These materials can be .,,~
used alone or in mixtures with the resins.
The polytetrafluoroethylene and nonflammable , ~ .
`~ fibrous material can be added to the thermoplastic resin by methods well known to those skilled in this art.
Representative examples of thermoplastic resins useful in the practice of this invention are thermoplastic polyesters such as poly(ethylene terephthalate), poly (tetramethylene terephthalate), 80/20 poly(tetramethylene terephthalate/isophthalate), 70/10/20 poly(tetramethylene/
isophthalate~sebacate); polyamides such as Nylon 6/6, Nylo~
6, Nylon 6/10, Nylon 6/12 and polyolefins such as high ., ., ~ j -2-.~ , lV~5269 density polyethylene~ low density polyethylene, polypro-pylene. Other thermoplastic resins useful in the practice of this invention are polyphenylene oxide, acrylonitrile/
butadiene/styrene (~BS) resins, polyacetals (polyoxymethy-lene), polystyrene and polycarbonates such as poly(4,~'-dihydroxy-diphenyl-2,2-propane)-carbonate and poly(4,4'-dihydroxy-diphenyl-methyl-phenyl-methane)-carbonate.
The products of the invention are useful as flame re-sistant and drip resistant molding compositions.
, . . .
^ 10 ~he term "thermoplastic resin" as employed in this disclosure is understood to include base thermoplastic resin as well as those thermoplastic resins compounded l~th ..
- lubricating and nucleating agents or other additives. The thermoplastic resins are crystalline in form. The crystal-line thermoplastic resins employed in this invention have a melting point at or abore 100 C. me melting point is the maximum useful service temperature of a crystalline solid - i .
and is the temperature at which a highly ordered crystalline solid is transformed into a liquid.
, 20 ~he term "polyester" as employed in this disclo-;'!
sure is intended to include both homopolyester and copoly- ~;
`~ ester.
, These polyesters are conveniently prepared by -; reacting aromatic dicarboxylic acids or ester forming derivatives thereof with a glycol of the formula HO(C ~ )nOH
~ where n is an integer ranging from 2 to 10 to form the -~ corresponding glycol ester and then polycondensing the glycol ester with-elimination of glycol under conditions of elevated temperatures and reduced pressures to form high molecular weight linear polyester or copolyester resins.
Representative examples of such polycondensation . polyester resins include resins derived from dicarboxylic . _ 3 _ lV45Z69 acids such as terephthalic acid, aliphatic dicarboxylic ' acids such as adipic acid~ sebacic acid, azelaic acid and `Y- aromatic dicarboxylic acids such as orthophthalic acid,isophthalic acid, terephthalic acid~ bibenzoic acid~ naph-.
~^ 5 thalic acid and the like. The resins can be made from various glycols such as those of the formula HO(CH2)IlOH
where n is an integer ranging from 2 to 10 and including ethylene glycol, propylene glycol, tetramethylene glycol, ~ pentamethylene glycol~ hexamethylene glycol, decamethylene `~ 10 glycol and the like~ alkyl substituted polymethylens gly-~;, cols such as neopentyl glycol and 2-methyl-2-ethylene and cyclic glycols such as cyclohexanedimethanol and 2,274,4-tetramethyl-1,3-cyclobutene diol. Ethylene glycol is a preferred glycol because of its low cost and ready avail--~j 15 ability.
i The examples below illustrate the invention. me resin used is an .80 Intrinsic Viscosity (IV) poly(tetra-methylene terephthalate). In this application intrinsic ~i viscosity was measured in a Cannon-Ubbelhode viscometer using a 60 phenol/40 tetrachloroethane solvent at 30 C.
PHR in the examples is parts by weight per hundred parts of .
resin by weight. All parts and percentages are by weight unless otherwise specified. Examples 1 to 3 and a portion of 6 are comparative examples. Examples 4~ 5 and a portion , 25 of 6 illustrate the invention. ~ ;
Example 1 Poly(tetramethylene terephthalate) (PTMT) was produced in a stirred tank reactor by reacting one mole of dimethylterephthalate (DMT) with 1.2 moles of tetramethyl-ene glycol at 190 C. and at atmospheric pressure until ,, .
-: ~
85 percent of the theoretical amount of methanol had evolved then the oligomers were polymerized under reduced pressure ' at 2500 C. At the polymerization stage 8 PHR of octabromo- -~- biphenyl and ~ PHR of antimony trioxide were added. An o.80 . . , '~ 5 IV PTMT containing these flame retardants was obtained.
'~ ~nis was molded into a bar of 5" x 1/2" x 1/8" at 250~ C.
by injection molding prQcess. The bar was tested for flam-mability according to AS~M D-635 and UL-9~ flammability test ''~ methods. The polymer started dripping five seconds after ~ 10 the application of flame. me droplets carrying the flame ::;
" ` ignited cotton placed one foot b'elow the bar. me polymer ~ . ~
~-~ thus failed to meet the requirements to earn an SE-0 rating.
~ - - - Example_2 ,'`~ m e process, polymer composition, and testing are the same as those in Example 1 except that 10 PHR of octa~
bromobiphenyl were used in place of 8 PHR octabromobiphenyl '~'Y~ ' and one percent by weight polytetrafluoroethylene (DuPont's ;~ ' TeflonTM)was added. The polymer failed to pass the flamma-bility-test because of dripping.
. .. -~ .
~ 20 ~3~EL~
. ,~.~ . - .
lhe product of Example 1 was dry blended with one weight percent of potassium titanate fibers (DuPont's FybexTM) ~ ~ .
`~ and injection molded into a test bar~ which ~ras tested using ~' ' `~ the AS~M and UL test methods. The compounded polymer again ' failed to pass the test because of dripping. ~ -.~ ExamPle L~ ' -, The product in Example 1 was dry blended with one '~
weight percent of potassium titanate fibers (DuPont's Fybex~M) and one weight percent of polytetrafluoroethylene (DuPont's ' 30 Teflon~)and injection molded into a 5" x 1/2" x 1/8" test ' . . .
;' -5-. , .. , , . . .. ~ ,. .
11~)45Z69 1 bar. The compounded poly~er bar was tested in the flamma-bility test and did not drip during thirty seconds of flame application time. The poly(tetramethylene terephthalate) thus compounded passed both ASTM and UL tests and was rated , ; .
as SE-0.
,! Exam~le 5 At the polymerization stage of the preparation of polyttetramethylene terepht,halate) 8 PHR o~ decabromobi-~A, phenyl oxide (DBBP0)~ 4 PHR of antimo~y oxide~ .5 weight ;, 10 perce~t of polytetrafluoroethylene (DuPont~s Teflon) and ~..
.5 weight percent of potassium titanate ~DuPont's Fybex) were added to the reactor and mixed with the polymer under ~, condensation conditions. The compounded resin t.80 IV) was injection molded into a 5" x 1/2" x l/8" test bar. The test bar was tested for flammability and started to drip slowly after 24 seconds of flame application. me droplets did not spread the fire. me bar passed both ASTM and UL test re-., ,. ~ .
, quirements and was rated SE-0. This result indicates ~hat .5 weight percent of Fybex and .~ weight percent o~ Teflon l . .
- 20 are the minimum levels for retarding flame spreading.
^ Example 6 ; Dechlorane plus 515, plus 25 and 603(chlorinated , organic flame retarding agent~ from Hooker Chemical Cor-l poration containing 65 percent by weight of chlorine was . ~
used to impart self-extinguishing properties to polyester polymer rendering the poly (tetramethylene terephthalate) polymer self-extinguishing. At least 16 PHR of the ' Dechlorane and 5 PHR of the antimony trioxide Sb20~ are required. Dechlorane inherently induced less dripping .~, . __ ~.~ 1. .
of the polymer during burning. Poly (tetramethylene tere-phthalate) polymer with the above composition dripped after 20 seconds of burning. In con-trast the same polymer with one-half PHR of Teflon and one-half PHR of Fybex did not drip.
. .
The amount of polytetrafluoroethylene used will generally be in the range of from about 0.1 percent by : .
~ weight to about 5.0 percent by weight of the total composi-. '!
tion, more preferred from about .5 percent by weight to about 1.0 percent by weight of the total composition. The ; nonflammable fibrous material used will be in a concentra-~ tion of from about 0.1 percent by weight to about 5.0 per-, 1 :
~`;`3~ cent by weight of the total composition, more preferred from about .5 percent to about 1.0 percent by weight of the total ~ ~
1 15 composition. me amount of flame retardant used will be in ~-i the concentration sufficient to render the polymer self-extinguishing. When the polymer contains these ingredients in these amounts it becomes nondripping during the 30 second '?~' test burning in accordance with ASTM D~635 flammability tests and UL-94 flammability test, and the polymer is rated self-extinguishing.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in ~
this art that various changes and modifications may be ~ ;
made herein without departing from the spirit or scope of ~ ;
this invention.
,Y
.~ ', '? 7-.,' ~ , ~ :-. .
'::.......... . . .. .
,:: . . . .. .
.:::. . , ,. .. . :
Claims (16)
1. Thermoplastic compositions resistant to dripping when ignited by flame comprising a normally flammable high molecular weight crystalline thermoplastic polymer having a melting point above about 100° C., (a) a flame retardant additive in an amount sufficient to render the said crystalline thermoplastic polymer self-extinguishing, (b) a nonflammable fibrous material in an amount from about .1 percent by weight up to about 5 percent by weight of the total composition, and (c) a polytetrafluoroethylene resin in an amount from about .1 percent by weight up to about 5 percent by weight of the total composition.
2. The composition of claim 1 in which the thermoplastic polymer is selected from the group consisting of polyesters, polyamides, polyolefins, polyphenylene oxide, acrylonitrile/butadiene/styrenes (ABS), polyacetals, poly-styrenes and polycarbonates.
3. A composition according to claim 1 wherein the thermoplastic is a polyester resin selected from the group consisting of both homopolymer and copolymer having a melting point at or above about 100° C.
4. A composition according to claim 1 in which the thermoplastic is a polyamide resin having a melting point at or above about 100° C.
5. A composition according to claim 1 in which the thermoplastic is a polyolefin resin having a melting point at or above about 100° C.
6. A composition according to claim 1 in which the thermoplastic is a polyphenylene oxide resin having a melting point at or above about 100° C.
7. A composition according to claim 1 in which the thermoplastic is a acrylonitrile/butadiene/styrene resin having a melting point at or above about 100° C.
8. A composition according to claim 1 in which the thermoplastic is a polyacetal resin having a melting point at or above about 100° C.
9. A composition according to claim 1 in which the thermoplastic is a polystyrene resin having a melting point at or above about 100° C.
10. A composition according to claim 1 in which the thermoplastic is a polycarbonate resin having a melting point at or above about 100° C.
11. A composition according to claim 1 in which the nonflammable fibrous material is selected from the group consisting of potassium titanate, asbestos, fiber-glass, graphite fibers and carbon fibers.
12. A process of rendering a normally flammable high molecular weight thermoplastic resin nondripping by incorporating therein (a) a flame retardant additive in an amount sufficient to render the said thermoplastic resin self-extinguishing, (b) a nonflammable fibrous material in an amount from about .1 percent by weight to about 5 per-cent by weight of the total composition, and (c) a polytetrafluoroethylene resin in an amount from about .1 percent by weight to about 5 percent by weight of the total composition.
13. A process as described in claim 14 wherein the nonflammable material is selected from the group con-sisting of potassium titanate, asbestos, graphite fibers, fiberglass and carbon fibers.
14. A process as described in claim 14 wherein the thermoplastic polymer is selected from the group con-sisting of polyesters, polyamides, polyolefins, polyphenyl-ene oxides, acrylonitrile/butadiene/styrenes (ABS), poly-acetals, polystyrenes and polycarbonates.
15. A process as described in claim 14 wherein the nonflammable fibrous material and the polytetrafluoro-ethylene are added to the thermoplastic resin during the polymerization stage.
16. A process as described in claim 14 wherein-the nonflammable fibrous material and the polytetrafluoro-ethylene are added to the thermoplastic resin by mechanical mixing.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38386973A | 1973-07-30 | 1973-07-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1045269A true CA1045269A (en) | 1978-12-26 |
Family
ID=23515070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA203,599A Expired CA1045269A (en) | 1973-07-30 | 1974-06-27 | Flame retardant and drip resistant thermoplastics |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5044241A (en) |
| CA (1) | CA1045269A (en) |
| CH (1) | CH592712A5 (en) |
| DE (1) | DE2433966A1 (en) |
| FR (1) | FR2239512B1 (en) |
| GB (1) | GB1459648A (en) |
| IT (1) | IT1018747B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9006333B2 (en) | 2010-09-30 | 2015-04-14 | Daikin Industries, Ltd. | Method for manufacturing fine polytetrafluoroethylene powder |
| US9309335B2 (en) | 2010-09-30 | 2016-04-12 | Daikin Industries, Ltd. | Process for producing polytetrafluoroethylene fine powder |
| US9458316B2 (en) | 2010-09-30 | 2016-10-04 | Daikin Industries, Ltd. | Dripping inhibitor and resin compound |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8671075A (en) * | 1974-12-06 | 1977-05-26 | Gen Electric | Flame retardant, non-dripping composition of polyphenylene ether and acrylonitrile - butadiene-styrene |
| DE2650924C2 (en) * | 1976-11-06 | 1986-01-09 | Basf Ag, 6700 Ludwigshafen | Fire-protected polyamide molding compounds |
| US4332714A (en) | 1976-12-21 | 1982-06-01 | General Electric Company | Drip-retardant plasticized polyphenylene ether compositions containing microfibrillar poly(tetrafluoroethylene) |
| NL7907435A (en) | 1979-10-08 | 1981-04-10 | Akzo Nv | Polyethylene terephthalate molding material with reduced flammability, and molded parts therefrom. |
| JPS56127643A (en) * | 1980-03-10 | 1981-10-06 | Showa Electric Wire & Cable Co Ltd | Flame-retardant polyolefin composition |
| DE3322260A1 (en) * | 1983-06-21 | 1985-01-03 | Bayer Ag, 5090 Leverkusen | SHAPING DIMENSIONS WITH FLAME-RESISTANT PROPERTIES |
| DE3403975A1 (en) * | 1984-02-04 | 1985-08-14 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING ABS MOLDS WITH IMPROVED FIRE BEHAVIOR |
| US4716196A (en) * | 1984-10-01 | 1987-12-29 | Monsanto Company | Flame retarded thermoplastic styrenic compositions |
| DE3444867A1 (en) * | 1984-11-22 | 1986-05-22 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS WITH FLAME-RESISTANT PROPERTIES |
| US4579902A (en) * | 1984-12-05 | 1986-04-01 | Celanese Corporation | Permanently antistatic thermoplastic molding composition |
| DE3444868A1 (en) * | 1984-12-08 | 1986-06-12 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS WITH FLAME-RESISTANT PROPERTIES |
| DE3516807A1 (en) * | 1985-05-10 | 1986-11-13 | Bayer Ag, 5090 Leverkusen | FLAME-RESISTANT, IMPACT TOE POLYCARBONATE MOLDS |
| DE3521388A1 (en) * | 1985-06-14 | 1986-12-18 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS WITH FLAME-RESISTANT PROPERTIES |
| US5234979A (en) * | 1985-06-29 | 1993-08-10 | Toedtemann Gert | Thermoplastic mounding compositions with flame-repellant properties |
| DE3523316A1 (en) * | 1985-06-29 | 1987-01-02 | Bayer Ag | THERMOPLASTIC MOLDS WITH FLAME-RESISTANT PROPERTIES |
| DE3523314A1 (en) * | 1985-06-29 | 1987-01-02 | Bayer Ag | THERMOPLASTIC POLYCARBONATE MOLDINGS |
| DE3742768A1 (en) * | 1987-12-17 | 1989-06-29 | Basf Ag | HALOGEN-FREE FLAME-RESISTANT MOLDING, METHOD FOR THE PRODUCTION AND THEIR USE |
| US4927870A (en) * | 1988-08-25 | 1990-05-22 | The Dow Chemical Company | Ignition resistant modified thermoplastic composition |
| DE4032315A1 (en) * | 1990-10-11 | 1992-04-16 | Alveo Ag | FLAME-PROTECTION FORMULATION FOR ORGANIC POLYMERS AND THEIR USE IN THE MANUFACTURE OF FIRE-RESISTANT POLYOLEFIN COMPOSITIONS |
| DE4301730A1 (en) * | 1992-01-24 | 1993-07-29 | Denki Kagaku Kogyo Kk | Flame-retardant resin - comprising polycarbonate resin, carboxylic acid zinc salt, filler, fluorine-contg. resin and silicone |
| DE19621732A1 (en) | 1996-05-30 | 1997-12-04 | Basf Ag | Flame-retardant thermoplastic molding compounds with improved drip resistance |
| KR100901949B1 (en) * | 2003-01-15 | 2009-06-10 | 삼성토탈 주식회사 | Flame retardant polypropylene resin composition with excellent weatherability |
| WO2019004127A1 (en) | 2017-06-28 | 2019-01-03 | 帝人株式会社 | Reinforced polycarbonate resin composition |
| CN113363009B (en) * | 2021-06-09 | 2022-05-31 | 安徽天康(集团)股份有限公司 | Fireproof fire-resistant high-frequency special litz wire cable |
-
1974
- 1974-06-27 CA CA203,599A patent/CA1045269A/en not_active Expired
- 1974-07-08 GB GB3009974A patent/GB1459648A/en not_active Expired
- 1974-07-15 DE DE2433966A patent/DE2433966A1/en active Pending
- 1974-07-26 FR FR7426119A patent/FR2239512B1/fr not_active Expired
- 1974-07-29 IT IT52325/74A patent/IT1018747B/en active
- 1974-07-30 JP JP49087449A patent/JPS5044241A/ja active Pending
- 1974-07-30 CH CH1049174A patent/CH592712A5/xx not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9006333B2 (en) | 2010-09-30 | 2015-04-14 | Daikin Industries, Ltd. | Method for manufacturing fine polytetrafluoroethylene powder |
| US9309335B2 (en) | 2010-09-30 | 2016-04-12 | Daikin Industries, Ltd. | Process for producing polytetrafluoroethylene fine powder |
| US9458316B2 (en) | 2010-09-30 | 2016-10-04 | Daikin Industries, Ltd. | Dripping inhibitor and resin compound |
| US9475935B2 (en) | 2010-09-30 | 2016-10-25 | Daikin Industries, Ltd. | Dripping inhibitor and resin compound |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2239512A1 (en) | 1975-02-28 |
| CH592712A5 (en) | 1977-11-15 |
| JPS5044241A (en) | 1975-04-21 |
| GB1459648A (en) | 1976-12-22 |
| IT1018747B (en) | 1977-10-20 |
| FR2239512B1 (en) | 1979-02-16 |
| DE2433966A1 (en) | 1975-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1045269A (en) | Flame retardant and drip resistant thermoplastics | |
| US3624024A (en) | Flame retardant poly(tetramethylene terephthalate) molding compositions | |
| US4222926A (en) | Flame-retardant thermoplastic polyester resin compositions | |
| CA1052489A (en) | Glass fibre-reinforced flame-resistant thermoplastic polyester moulding compositions | |
| EP0239986A2 (en) | Low smoke generating, high char forming, flame retardant thermoplastic multi-block copolyesters | |
| JPS5930184B2 (en) | Flame retardant polyester composition | |
| US4344878A (en) | Flame retardant, non-dripping linear polyester compositions | |
| WO2007040075A1 (en) | Flame-retardant polyester resin composition | |
| US3867336A (en) | Flame retardant thermoplastic compositions | |
| US3909489A (en) | Polyesters and copolyesters having improved flame retardancy | |
| KR970701756A (en) | Flame-retardant Recycled Polyester Copolymer (FLAME-RETARDANT RECYCLED POLYESTER COPOLYMERS) | |
| US3883611A (en) | Copolyester(ethylene terephthalate/tetramethylene dibromoterephthalate) a new block polymer | |
| US4070332A (en) | Flame retardant, non-dripping, shape-retaining polyester molding composition | |
| US4288561A (en) | Foamable polyester composition | |
| JP2000265072A (en) | Flame-retarded resin composition and molded article thereof | |
| US3904707A (en) | Flame retardant polyester compositions | |
| US20230235116A1 (en) | High-temperature self-crosslinking-based flame-retardant anti-dripping copolyester, and preparation method therefor and application thereof | |
| CA1058348A (en) | Flame-retardant resin composition | |
| US3923728A (en) | Flame-retardant and self-extinguishing molding compositions | |
| JP2011144237A (en) | Non-halogen flame retardant antistatic polyester resin composition and molded product thereof | |
| JP2000212411A (en) | Flame-retarded polyester resin composition | |
| EP0383978A1 (en) | Flame retardant polyester resins | |
| EP0469354A2 (en) | Flame-resistant polyolefinic fibres and films | |
| US5919848A (en) | Magnetic polyester compositions | |
| CA1059676A (en) | Flame retardant polyester compositions |