CA1121538A - Flame retarded poly(butylene terephthalate) compositions - Google Patents
Flame retarded poly(butylene terephthalate) compositionsInfo
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- CA1121538A CA1121538A CA000319454A CA319454A CA1121538A CA 1121538 A CA1121538 A CA 1121538A CA 000319454 A CA000319454 A CA 000319454A CA 319454 A CA319454 A CA 319454A CA 1121538 A CA1121538 A CA 1121538A
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Abstract
ABSTRACT
A flame-retarded poly(butylene terephthalate) composition comprised of poly(butylene terephthalate) and from about 5 to about 35 percent (by weight of total composition) of a condensa-tion product derived from brominated phenol is disclosed.
A flame-retarded poly(butylene terephthalate) composition comprised of poly(butylene terephthalate) and from about 5 to about 35 percent (by weight of total composition) of a condensa-tion product derived from brominated phenol is disclosed.
Description
1121531~
F I ELD OF THE INV~NT I ON
A flame-retarded poly(butylene terephthalate) composition comprised of poly(butylene terephthalate) and from about 5 to about 35 percent (by weight of total composition) of a condensation product derived from brominated phenol.
. DESCRIPTION_ OF THE PRIOR ART
Poly(butylene terephthalate) polymers have been known to those skilled in the art for many years. They were generally disclosed in, e.~., U.S. Patent number 2,465,319;
and they have been described in many publications since then.
These poly(butylene terephthalate) compositions can be made by methods well known to the art. Thus, e.g., they can be produced from the corresponding bis(hydroxyalkyl) terephthalic acid or a dialkyl ester of terephthalic acid with a glycol having 4 carbon atoms such as, e.g., tetramethylene glycol. A process for preparing this composition is disclosed, e.g., in British patent 1,324,057.
For many applications, the poly(butylene terephthalate) composition must be flame retarded. However, the flame retardant to be used must be compatible with the poly(butylene terephthalate), i.e., it must not migrate to the surface of the polymer. Such migration has several very adverse effects:
it is aesthetically objectionable, it causes contamination of products in contact with the surface of the polymer, and it decreases the concentration of the flame retardant in the polymerO
.
ll~lS315 Decabromobiphenyl oxide is widely used to flame retard such thermoplastic compositions as hi~h impact polystyrene, poly(but~lene terephthalate), nylon, and the like. However, it is substantially incompatible ~7ith poly(butylene terephthalate); after being intimately admixed with said polymer, a substantial amount of it deposits on the surface of the polymer during normal conditions of use and at elevated temperatures. Conse~uently, poly(butylene terephthalate) flame retarded with decabromobiphenyl oxide is unsuitable for use in many applications. Thus, for example, it i5 ~enerally unsuitable for use in electrical and electronic applications where the migration of the halogen-containing flame retardant may cause corrosion. Thus, for example, it is disadvantageous to use it for injection molding plastic parts; for the decabromobiphenyl oxide, bein~ volatil~, "piates out", deposits itself on the mold, and causes surface imperfections in the finished molded parts.
Poly(phenylene oxide) compositions possess excellent flammability properties. These poly(phenylene oxides) are extensively described in the literature. See, e.g., Journal of the American Chemical Society, 1921 (43), pp. 131-159 (reactions of certain brominated phenol salts), ~ippon Kagaku Kaishi, 1976 (10), pp. 1608-1614 (polymerization of sodium
F I ELD OF THE INV~NT I ON
A flame-retarded poly(butylene terephthalate) composition comprised of poly(butylene terephthalate) and from about 5 to about 35 percent (by weight of total composition) of a condensation product derived from brominated phenol.
. DESCRIPTION_ OF THE PRIOR ART
Poly(butylene terephthalate) polymers have been known to those skilled in the art for many years. They were generally disclosed in, e.~., U.S. Patent number 2,465,319;
and they have been described in many publications since then.
These poly(butylene terephthalate) compositions can be made by methods well known to the art. Thus, e.g., they can be produced from the corresponding bis(hydroxyalkyl) terephthalic acid or a dialkyl ester of terephthalic acid with a glycol having 4 carbon atoms such as, e.g., tetramethylene glycol. A process for preparing this composition is disclosed, e.g., in British patent 1,324,057.
For many applications, the poly(butylene terephthalate) composition must be flame retarded. However, the flame retardant to be used must be compatible with the poly(butylene terephthalate), i.e., it must not migrate to the surface of the polymer. Such migration has several very adverse effects:
it is aesthetically objectionable, it causes contamination of products in contact with the surface of the polymer, and it decreases the concentration of the flame retardant in the polymerO
.
ll~lS315 Decabromobiphenyl oxide is widely used to flame retard such thermoplastic compositions as hi~h impact polystyrene, poly(but~lene terephthalate), nylon, and the like. However, it is substantially incompatible ~7ith poly(butylene terephthalate); after being intimately admixed with said polymer, a substantial amount of it deposits on the surface of the polymer during normal conditions of use and at elevated temperatures. Conse~uently, poly(butylene terephthalate) flame retarded with decabromobiphenyl oxide is unsuitable for use in many applications. Thus, for example, it i5 ~enerally unsuitable for use in electrical and electronic applications where the migration of the halogen-containing flame retardant may cause corrosion. Thus, for example, it is disadvantageous to use it for injection molding plastic parts; for the decabromobiphenyl oxide, bein~ volatil~, "piates out", deposits itself on the mold, and causes surface imperfections in the finished molded parts.
Poly(phenylene oxide) compositions possess excellent flammability properties. These poly(phenylene oxides) are extensively described in the literature. See, e.g., Journal of the American Chemical Society, 1921 (43), pp. 131-159 (reactions of certain brominated phenol salts), ~ippon Kagaku Kaishi, 1976 (10), pp. 1608-1614 (polymerization of sodium
2,4,6-tribromophenolate), Journal of the American Chemical Society, 1960 (82), pp~ 3632~363~ (polymerization of the silver salt o~ 2,4,6-tribromophenol by iodine), Bulletin of the Chemical Society of Japan, 1962 (35) pp. 1958-1965 (reaction of benzoyl peroxide with various substituted phenols), British patent 999,134 issued July 21, 1965 (preparation of various mb/~ 2 -~LlZ~38 haloge3lated ph~nylene oxide polymers by heating metal 4-halogenophenoxides in a ketone solvent), U.S. patent 3,361,851 (blend of a polyolefin and a polyphenylene oxide), U.S. patent
3,379,792 (blend of poly(phenylene oxide) and from Ool to 25 percent of a polyamide), U.S. patent 3,383,435 (blend of a polv[phenylene ether] and a styrene resin), U.S. patent 3,639,499 (blend of a high melting hydrocarbon resin and polyphenylene ether), U.S. patent 3,639,5Q6 (which discloses that ". . . the admixture of a polyphenylene ether with a styrene resin destroys the flame retardancy of the polyphenylene ethers"), U.S. patent 3,660,531 (blends of poly phenylene oxide with butadiene homopolymers and copolvmers), etc. There are many other prior art references, both domestic and foreign, which describe polvphenylene oxide compositions.
Polyphenylene oxides are generally incompatible with other polymers; see, e.g., pp. 251-314 of "Journal of rlacro-molecular Science--~eviews of Macromolecular Chemistry", C7(2), 1972 wherein S. Krause indicates that these compositions are incompatible with homopolymers and copolymers such as poly-carbonates, polysulfones, a copolymer of butadiene and acryloni-trile, a copolymer of epichlorohydrin and ethylene oxide, a copolymer of methyl vinyl ether and maleic anhvdride, polyester-ure'hane, a copolymer of styrene and acrylonitrile, a copolymer of styrene and methyl methacrylate, a copolymer of vinyl chloride and vinyl acetate, etc.
Applicant has discovered that, notwithstanding the indications of the prior art that it should be incompatible with poly(butylene terephthalate) polymers, a certain brominated poly~phenylene oxide) polymer allows one to obtain a flame retarded poly(butylene terephthalate) composition which, under ' ~^
mb~ _ 3 _ 1~21S3~
all conditions of use, exhihits substantially less surface migration than does a comparable polymer containing decabro-mobiphenyl o~ide.
SUM3!1ARY OF THE INVENTION
In accordance with this invention, there is provided a flame retarded, poly(butylene terephthalate) composition.
This composition is comprised of poly(butylene terephthalate) and from 5 to about 35 percent (by weight of total composition) of a condensation product derived from brominated phenol by the displacement of bromine from said phenol, wherein (a) said phenol is selected from the group consisting of tribromo-phenol, tetrabromophenol, pentabromophenol, and mixtures thereof; (b~ said condensation product has a repeating struetural unit of the formula (Br)a ~ )b (~ c wherein a is an integer of from about 0 to about 4, b is an integer of from about 0 to about 2, e is an integer of from about 1 to about 5, a plus b plus c equal 5, ~ is a mono~alent bond from a carbon atom in the aromatic nucleus of said repeating struetural unit to an oxygen atom bonded to an aromatie nucleus, and the polymerie units containing said repeating structural unit comprise at least 80 pereent (by weight) of said product; (c) said condensation product eontains from about 17 to about 31 percent (by weight) of elemental carbon, from about 0 to about 1.0 percent (by weight) of mb/ ~ ~ 4 ~
lS3~
elemental hydrogen, from about 3 to about 8 percent (by weight) of elemental oxygen, and at least 60 percent (by weight) of elemental bromine; and (d) said condensation product has a molecular weight of at least 750, and one or more polymeric units containing at least four aromatic nuclei per unit comprise at least 80 percent (by weight) of said product.
PREFERRED EMBODIi`lENTS
The condensation product described hereinabove which flame retards the poly(butylene terephthalate) composition of this invention has a repeating structural unit of the formula (Br)a (H)b (Q)c wherein a is an integer of from about 0 to about 4, b is an integer of from about 0 to about 2, c is an integer of from about 1 to about 5, a plus b plus c equal 5, Q is a monovalent ~0 bond from a carbon atom in the aromatic nucleus of said repeating structural unit to an oxygen atom bonded to an aromatic nucleus. This monovalent bond may exist any place on the aromatic nuclei in the composition wherein there was a carbon-bromine bond; it is formed by the displacement of bromine. Thus, for example, it may exist in the position para to the oxygen-carbon bond. One repeating structural unit which has this para bond may be represented by the formula : ~ .
mb/l~,~ - ~ 5 ~
~2153~
(Br)x to~
wherein x is 1, 2, 3, or 4 (and preferrably is 2 or 3); th~s repeating unit forms linear chains. Thus, in other instances - where c is 1, the monovalent bond may exist at the ortho position (hereinafter referred to as "II"). The hond may exist at both the ortho and para positions when c is 2 (hereinafter referred to as "III"); and it may exist ortho, ortho, and para to the carbon-oxygen bond when c is 3 (herein-after referred to as "IV"). The flame retarding condensation product contains at least one of the repeating structural units denoted I, II, III, and IV. At least 80 percent (by weight3 of this product is comprised of polymer chains containing one or more of these units.
The flame retarding condensation product is dexived from a brominated phenol selected from the group consisting of tribromophenol, tetrabromophenol, pentabromophenol, and mix-ture~-thereof. It i5- preferred that the brominated phenol be `~
selected from the group consisting of tribromophenol and tetra-bromophenol; and it is most preferred th~t the brominated phenol be ~ribromophenolO
This condensation nroduct has a molecular weight of at least about 750, and one or more polvmeric units containing at least four aromatic nuclei per unit comprise at least ~0 percent (b~ ~ei~ht) of the nroduct~ The molecular weight of the product .
mb/ ~ - 6 -1121S31~
is determined in accor~ance with the vapor phase osmometry method specified by test A.s.T.r1~ D2503-67.
The flame retarding condensation product contains from about 17 to about 31 percent (by weight) of carbon, from about 0 to about 1.0 percent (by weight) of elemental hydrogen, from about 3 to about 8 percent (by weight) of elemental oxygen, and at least about 60 percent (~y weight) of elemental bromine. It is preferred that said condensation product contain from about 62 to about 66 percent (by weight) of elemental bromine.
It is preferred that the flame retarding condensation product used in the composition of this invention, when fused to form test specimens 0.125" thick, have a notched Izod impact strength of less than about 0.5 foot-pounds per inch (A.S.T.~I. D256), and an elongation of less than about 2.0 percent and a tensile strength of less than about 200 pounds per square inch (A . S . T . M . D6 383.
In one of the preferred embodiments, the flame retarding condensation product contains less than about 200 aromatic nuclei and has an intrinsic viscositv (in tetrah~dro-furan at 25 degrees centigrade) of less than about 1.8.
The flame retarding condensation product may be prepared by any of several methods well known to those skilled in the art~ Generally, the brominated phenol is contacted ; with an effective amount of activating agent and allowed to condense for a period of up to about 300 degxees centigrade.
Suitable activating agents include, without limitation, heat, light, organic and inorganic peroxides such as benzoyl peroxide, hydrogen peroxide, dimethane sulfonyl peroxide r lauroyl mb/~lr ~121538 peroxide, caprylyl peroxide, succinic peroxide, acetyl peroxide, p-tertiarybutyl benzoyl peroxide, tertiary-hutyl-peroxy isopropyl carbonate peroxide, hydroxyheptyl peroxide, cyclophexane peroxide, 2,5-dimethylhexane-2,5-di(peroxybenzoate~
peroxide, tertiary-butyl peracetate peroxide, di-tertiarybutyl diperphthalate peroxide, tertiary butyl perbenzoate peroxide, and the like; azo compounds, such as azobisisobutyronitrile, for example; persulfates, such as ammonium persulfate, potassium persulfate, and sodium persulfate; hypochlorites;
ferricyanides; ferric chloride; metal oxides, such as lead oxide, mercury oxide, silver oxide, and the like; halogen, such as iodine, bromine, and chlorine; lead tetracetate; sodium bismuthate; etcO Generally, any of the activators known to promote free radical chain initiation may he used.
Alternatively, one may use a metal sait of the brominated phenol with the activating agentsO Suitable salts which may be utilized include, without limitation, the lithium, sodium, potassium, bariumr zinc, and tin salts of the brominated phenol.
Other phenolates well known to those s]cilled in the art may also be used.
The brominated phenol (or the metallic salt derived from it) may be contacted with the activating agent in the solid state. Alternatively, one may conduct the polymerization of the brominated phenol (or its salt) in a suitable inert solvent.
In general, any of the inert aqueous or organic solvents in which phenol or its salt are known to be solukle may be used to prepare th~ flame retarding condensation product. Suitable solvents include, without limitation, water, dimethylsulfoxide, acetone, hexane, methanol, ethanol, propanol, butanol, benzene, mb/iJ- - 8 -~21538 toluene, tetrahydrof~ran, etc. A~ueous salt solutions wherein the salt is selected from the group consisting of barium chloride, calcium chloride, magnesium chloride, strontium chloride, potassium chloride, lithium chloride, sodium chloride, and the like may also be utilized. ~lixtures of organic solvents and water may be used; thus aqueous acetone solutions, benzene and water, aqueous alkaline solution and organic compounds insoluble in water (such as octyl alcohol, toluene, and heptane), carbon tetrachloride and water, amyl alcohol and water, and the like are suitable.
One of many methods ~7hich may be used to prepare the condensation product involves dissolving a metal hydroxide in water and, to the solution thus formed, adding activating agent and the brominated phenol; thereafter, the reacfion mixture is maintained at a specified temperature.
In this method, an emulsifying agent may be used to suspend the condensation product in aqueous media; when so used, from about 0.1 to about 5.0 percent of it (by weight of water in the hydroxide solution) should be present in the reaction mixture. The emulsifying agent may be added prior to or simultaneously with the addition of the brominated phenol to the reaction mixture.
In this method, an alkali or alkaline earth metal hydroxide may be used. It is preferred to use a metal hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide; sodium hydroxide is the most preferred. ~ron about 0.5 to about 5.0 moles of the hydroxide per liter of water is utilized. It is preferred to use from about 1 to about 3 moles of hydroxide mb/~- ~ 9 ~
. .
~lZ:~S38 per liter of water; it is most preferred to use about 2 moles of the hydroxide per liter of water.
The brominated phenol descrihed hereinabove is added to the reaction mixture at a concentration of from about 0.5 to about 5 moles per liter of water to make up the hydroxide solution in this method. It is preferred to use from about 1 to about 3 moles of phenol per liter of water. It is most preferred that the concentration be about 2 moles of phenol per liter of water.
In this method, although it is not essential, organic solvent may be added to the reaction mixture; any of the organic solvents listed hereinabove may be utilizedO When organic solvent is used, it is preferred that from 1 to about 20 percent of it ~by volume of water used to make up the hydroxide solution) be utilized. It is more preferred to use from about 3 to about 10 percent of organic solvent in this process; and it is most preferred to use from about 4 to about 8 percent of organic solvent. Some of the preferred organic solvents include toluene, benzene, chloroform, chlorinated benzenes, and the like.
Activating agent is contacted with the reaction mixture after all of the other components are present in this process.
When the activating agent is solid, liquid, or gaseous, at least about 1 x 10 5 moles of it (based upon liters of water used to make up the hydroxide solution) is used; it is preferred to use from about 0.01 to about 0.1 moles of these activating agents.
After the activating agent has been contacted with the reaction mixture, the reaction mixture is maintained at a mb/ - 10 -.
L53~
temperature of from about 20 to about 180 degrees centigrade for from about 5 to about 300 minutes in this process. It is preferred to maintain the reaction mixture at a temperature of from about 20 to about 100 degrees centigrade for from ahout 15 to about 120 minutes. It is most preferred to maintain the reaction mixture at a temperature of from ahout 45 to about 65 degrees centigrade for from about 20 to about 40 minutes.
In this process, it is preferred that the reaction be run at a pressure of from ahout 1.0 to about 20 atmospheres.
It is more preferred to use a pressure of about 1.0 atmosphere during the reaction.
The flame retarded composition of this invention contains from about 5 to about 35 percent (by weight of total composition) of the flame retarding condensation product referred to hereinabove. It is preferred that it contain from about 9 to about 22 percent (by weight of total composition) of said flame retarding condensation product.
The method of adding the flame retardant additive to the polv(butylene terephthalate) is not critical; any means well known to those skilled in the art may be utilized.
Similarly, other additives may be incoxporated into the poly-(hutylene terephthalate) composition of this invention bymeans well known to those skilled in the art. It is preferred that each ingredient be added as part of a blend premix and the premix be mixed, e.g., by passage through an extruder or by fluxing on a mill at a temperature dependent on the needs of the particular compositions. The mixed composition can be cooled and cut up into molding granules and molded or extruded , ~ mb/, i~ - 11 -~LZlS38 or formed into any desired shape.
The flame retarded composition of this invention may also contain enhancing agents which, when used with said condensation product, promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant composition as compared to the flame retardancy of compositions containing either component alone. Those skilled in the art are familiar with these enhancing agents.
Some of the enhancing agents well known to those skilled in the art include the oxides and halides of the metals of groups IVA and VA of the Periodic Table such as the oxides and halides of antimony, bismuth, arsenic, tin, lead, and germanium; antimony oxychloride, antimony chloride, antimony oxide, stannic oxide, stannic chloride, arsenous oxide, arsenous chloride, and the like are enhancing agents well known to the art. Other enhancing agents well known to those skilled in the art are the organic and inorganic compounds of phosphorous, nitrogen, boron, and sulfur; thus, e.g., triphenyl phosphate, ammonium phosphate, zinc borate, thiourea, urea, stannic sulfide, and the like are suitable enhancing agents. The oxides and halides of titanium, vanadium, chromium, magnesium are also used as enhancing agents as are the hydrates of these compounds; thus, e.g., titanium dioxide, titanium chloride, vanadium pentoxide, chromic bromide, manganous oxide, molybdenum trioxide, ammonium molybdate, stannous oxide hydrate, lead hydrate, and combinations thereof may be used. Many antimony compounds, both organic and inorganic, are useful as enhancing agents; antimony sulfide, sodium antimonite, potassium antimonite, antimony butyrate, antimony valerate, antimony mb/~,r - 12 -caproate, anti~ony heptylate, antimony caprylate, antimony perlargonate, antimony caprate, antimony cinnamate, antimony anisate, tris(n-octyl) antimonite, tris(2-ethvlhexyl) antimoni-te, tribenzyl antimonite, trimethylolpropane antir,lonite, pentaervthritol antimonite, glycerol antimonite, and compounds which on decomposition (as by ignition) vield antimony oxide are well known to the art as enhancing agents.
The preferred enhancing agents are the oxides of antimony, arsenic, and bismuth. The more preferred enhancing agents are the oxides of antimony~ The most preferred enhancing agent is antimony trioxide.
When enhancing agent is incorporated into the flame retarded composition of this invention, from 1 to about 20 percent of it (by weight of the combined polybutylene terephthalate, flame retardant, and enhancing agen-t) may be used. It is preferred to utilize from about 3 to about 10 percent (by weight) of enhancing agent.
It is also within the scope of the present invention to employ other materials in the compositions of the invention where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promotors;
antioxidants; antistatic agents; antimicrobial agents;
colorants; other flame retardants (in addition to the flame retarding condensation product described herein); heat stabilizers; light stabilizers; fillers; reinforcing agents;
and other materials well known to those skilled in the art which have been or could be used in poly(butylene kerephthalate) compositions. These materials may be employed in any amounts which will not substantially adversely affect the properties ~; J
mb~ 13 ~
1~2~S3~
of the poly(butylene terephthalate) of this invention. Thus, the amount used can be zero (0) percent, based on the 'cotal weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about 0~ to about 80~.
Glass reinforced poly(butylene terephthalate) comprised of from ahout 6 to about 60 percent (by weight) of fiberglass and the poly(butylene terephthalate) composition of this invention is within the scope of this invention. The glass fibers used to make this composition may be treated with couplin~ agents well known to those skilled in the art so that the polymer will bond strongly to the surface of the glass.
Additionally, or alternatively, other agents (such as, e.g., asbestos) may be utilized in the composition of this invention.
The terephthalate component of the composition of this invention consists of linear polymer containing at least about ~5 percent ~by weight~ of poly(butylene terephthalate).
It may be prepared by reacting terephthalic acid or its dialkyl ester and polymethylene glycol of the formula HO(CH2)nOH
wherein n is from 2 to 8. At least 85 percent of said polymer is prepared from a glycol wherein n is 4(1,4-butanediol), and some of all of the remaining 15 percent may be prepared from ethylene glycol, trimethylene glycol, 1,4-butanediol, and the like. The polymethylene glycol used to prepare some or all of said remaining 15 percent may be replaced entirely or in part with other glycols such as 1,4-cyclohexanedimethanol;
1,4-bis(2-hydroxyethyloxy~ benzene, and the like. It is preferred that no more than about 10 percent of the polymer will be prepared from a glycol which is not a polymethylene ~r mb/~ - 14 -l~Zl~;3S
glycol.
Other dicarboxylic acids and their esters may be used to prepare the terephthalate used in this invention.
Thus, e.g., from about 1 to about 10 weight percent (based on the weight of terephthalic acid or the dialkyl ester thereof used to make the polymer) of a dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid, and HOOC-R-COOR ~wherein R is alkylene of from about 2 to about 15 carbon atoms) may be used. ~Jhen said dicarboxylic acid is used in the preparation of the terephthalate, it is preferred to use from about 3 to about 8 weight percent thereof. Some of the dicarboxylic acids which may be used to prepare the terephthalate of this invention include, e.g., succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like.
Subject to the limitation described above (viz., at least 85 weight percent of the terephthalate component is poly(butylene terephthalate), the composition of this invention may contain other materials than the ones hereinbefore described such as, e.g., dye site additives, delustrants, antistatic agents, optical brighteners, mold release agents, nucleating agents, etc.
Under all conditions of use, the flame retarded poly-(butylene terephthalate) composition of this invention exhibits substantially less surface migration than does a comparable poly(butylene terephthalate) composition containing decabromo-biphenyl oxide.
~ 15 -~1531!~
The following examples are provided for the purpose of further illustration only and are not intended to be limitations on the invention disclosed. Unless othe~ise specified, all parts are by weight, all wei~hts are in grams, all temperatures are in degrees centigrade, and all volumes are in milliliters.
PREP~RATIVN OF THE FL~IE RETARDIN~. CON~ENSATION PRODUCTS
. . . .
EX~IPLE I
T~JO hundred milliliters of chloroform were added to a 10- one liter, three-necked, round-bottomed flask fitted with mechanical stirring, addition funnel, reflux condenser, and nitroyen flush. Sixteen and one-half grams of 2,4,6-tribromo-phenol were added to the chloroform. Thereafter, 2.8 grams of potassium hydroxide were dissolved in 100 milliliters of water, and this solution was then added to the reaction mixture.
An a~ueous solution of potassium ferricyanide was prepared;
1.6 grams of the potassium ~erricyanide were dissolved in 100 milliliters of water. This solution was added over a period of one hour to the reaction mixture. Thereafter, the reaction mixture was maintained at ambient temperature and stirred for
Polyphenylene oxides are generally incompatible with other polymers; see, e.g., pp. 251-314 of "Journal of rlacro-molecular Science--~eviews of Macromolecular Chemistry", C7(2), 1972 wherein S. Krause indicates that these compositions are incompatible with homopolymers and copolymers such as poly-carbonates, polysulfones, a copolymer of butadiene and acryloni-trile, a copolymer of epichlorohydrin and ethylene oxide, a copolymer of methyl vinyl ether and maleic anhvdride, polyester-ure'hane, a copolymer of styrene and acrylonitrile, a copolymer of styrene and methyl methacrylate, a copolymer of vinyl chloride and vinyl acetate, etc.
Applicant has discovered that, notwithstanding the indications of the prior art that it should be incompatible with poly(butylene terephthalate) polymers, a certain brominated poly~phenylene oxide) polymer allows one to obtain a flame retarded poly(butylene terephthalate) composition which, under ' ~^
mb~ _ 3 _ 1~21S3~
all conditions of use, exhihits substantially less surface migration than does a comparable polymer containing decabro-mobiphenyl o~ide.
SUM3!1ARY OF THE INVENTION
In accordance with this invention, there is provided a flame retarded, poly(butylene terephthalate) composition.
This composition is comprised of poly(butylene terephthalate) and from 5 to about 35 percent (by weight of total composition) of a condensation product derived from brominated phenol by the displacement of bromine from said phenol, wherein (a) said phenol is selected from the group consisting of tribromo-phenol, tetrabromophenol, pentabromophenol, and mixtures thereof; (b~ said condensation product has a repeating struetural unit of the formula (Br)a ~ )b (~ c wherein a is an integer of from about 0 to about 4, b is an integer of from about 0 to about 2, e is an integer of from about 1 to about 5, a plus b plus c equal 5, ~ is a mono~alent bond from a carbon atom in the aromatic nucleus of said repeating struetural unit to an oxygen atom bonded to an aromatie nucleus, and the polymerie units containing said repeating structural unit comprise at least 80 pereent (by weight) of said product; (c) said condensation product eontains from about 17 to about 31 percent (by weight) of elemental carbon, from about 0 to about 1.0 percent (by weight) of mb/ ~ ~ 4 ~
lS3~
elemental hydrogen, from about 3 to about 8 percent (by weight) of elemental oxygen, and at least 60 percent (by weight) of elemental bromine; and (d) said condensation product has a molecular weight of at least 750, and one or more polymeric units containing at least four aromatic nuclei per unit comprise at least 80 percent (by weight) of said product.
PREFERRED EMBODIi`lENTS
The condensation product described hereinabove which flame retards the poly(butylene terephthalate) composition of this invention has a repeating structural unit of the formula (Br)a (H)b (Q)c wherein a is an integer of from about 0 to about 4, b is an integer of from about 0 to about 2, c is an integer of from about 1 to about 5, a plus b plus c equal 5, Q is a monovalent ~0 bond from a carbon atom in the aromatic nucleus of said repeating structural unit to an oxygen atom bonded to an aromatic nucleus. This monovalent bond may exist any place on the aromatic nuclei in the composition wherein there was a carbon-bromine bond; it is formed by the displacement of bromine. Thus, for example, it may exist in the position para to the oxygen-carbon bond. One repeating structural unit which has this para bond may be represented by the formula : ~ .
mb/l~,~ - ~ 5 ~
~2153~
(Br)x to~
wherein x is 1, 2, 3, or 4 (and preferrably is 2 or 3); th~s repeating unit forms linear chains. Thus, in other instances - where c is 1, the monovalent bond may exist at the ortho position (hereinafter referred to as "II"). The hond may exist at both the ortho and para positions when c is 2 (hereinafter referred to as "III"); and it may exist ortho, ortho, and para to the carbon-oxygen bond when c is 3 (herein-after referred to as "IV"). The flame retarding condensation product contains at least one of the repeating structural units denoted I, II, III, and IV. At least 80 percent (by weight3 of this product is comprised of polymer chains containing one or more of these units.
The flame retarding condensation product is dexived from a brominated phenol selected from the group consisting of tribromophenol, tetrabromophenol, pentabromophenol, and mix-ture~-thereof. It i5- preferred that the brominated phenol be `~
selected from the group consisting of tribromophenol and tetra-bromophenol; and it is most preferred th~t the brominated phenol be ~ribromophenolO
This condensation nroduct has a molecular weight of at least about 750, and one or more polvmeric units containing at least four aromatic nuclei per unit comprise at least ~0 percent (b~ ~ei~ht) of the nroduct~ The molecular weight of the product .
mb/ ~ - 6 -1121S31~
is determined in accor~ance with the vapor phase osmometry method specified by test A.s.T.r1~ D2503-67.
The flame retarding condensation product contains from about 17 to about 31 percent (by weight) of carbon, from about 0 to about 1.0 percent (by weight) of elemental hydrogen, from about 3 to about 8 percent (by weight) of elemental oxygen, and at least about 60 percent (~y weight) of elemental bromine. It is preferred that said condensation product contain from about 62 to about 66 percent (by weight) of elemental bromine.
It is preferred that the flame retarding condensation product used in the composition of this invention, when fused to form test specimens 0.125" thick, have a notched Izod impact strength of less than about 0.5 foot-pounds per inch (A.S.T.~I. D256), and an elongation of less than about 2.0 percent and a tensile strength of less than about 200 pounds per square inch (A . S . T . M . D6 383.
In one of the preferred embodiments, the flame retarding condensation product contains less than about 200 aromatic nuclei and has an intrinsic viscositv (in tetrah~dro-furan at 25 degrees centigrade) of less than about 1.8.
The flame retarding condensation product may be prepared by any of several methods well known to those skilled in the art~ Generally, the brominated phenol is contacted ; with an effective amount of activating agent and allowed to condense for a period of up to about 300 degxees centigrade.
Suitable activating agents include, without limitation, heat, light, organic and inorganic peroxides such as benzoyl peroxide, hydrogen peroxide, dimethane sulfonyl peroxide r lauroyl mb/~lr ~121538 peroxide, caprylyl peroxide, succinic peroxide, acetyl peroxide, p-tertiarybutyl benzoyl peroxide, tertiary-hutyl-peroxy isopropyl carbonate peroxide, hydroxyheptyl peroxide, cyclophexane peroxide, 2,5-dimethylhexane-2,5-di(peroxybenzoate~
peroxide, tertiary-butyl peracetate peroxide, di-tertiarybutyl diperphthalate peroxide, tertiary butyl perbenzoate peroxide, and the like; azo compounds, such as azobisisobutyronitrile, for example; persulfates, such as ammonium persulfate, potassium persulfate, and sodium persulfate; hypochlorites;
ferricyanides; ferric chloride; metal oxides, such as lead oxide, mercury oxide, silver oxide, and the like; halogen, such as iodine, bromine, and chlorine; lead tetracetate; sodium bismuthate; etcO Generally, any of the activators known to promote free radical chain initiation may he used.
Alternatively, one may use a metal sait of the brominated phenol with the activating agentsO Suitable salts which may be utilized include, without limitation, the lithium, sodium, potassium, bariumr zinc, and tin salts of the brominated phenol.
Other phenolates well known to those s]cilled in the art may also be used.
The brominated phenol (or the metallic salt derived from it) may be contacted with the activating agent in the solid state. Alternatively, one may conduct the polymerization of the brominated phenol (or its salt) in a suitable inert solvent.
In general, any of the inert aqueous or organic solvents in which phenol or its salt are known to be solukle may be used to prepare th~ flame retarding condensation product. Suitable solvents include, without limitation, water, dimethylsulfoxide, acetone, hexane, methanol, ethanol, propanol, butanol, benzene, mb/iJ- - 8 -~21538 toluene, tetrahydrof~ran, etc. A~ueous salt solutions wherein the salt is selected from the group consisting of barium chloride, calcium chloride, magnesium chloride, strontium chloride, potassium chloride, lithium chloride, sodium chloride, and the like may also be utilized. ~lixtures of organic solvents and water may be used; thus aqueous acetone solutions, benzene and water, aqueous alkaline solution and organic compounds insoluble in water (such as octyl alcohol, toluene, and heptane), carbon tetrachloride and water, amyl alcohol and water, and the like are suitable.
One of many methods ~7hich may be used to prepare the condensation product involves dissolving a metal hydroxide in water and, to the solution thus formed, adding activating agent and the brominated phenol; thereafter, the reacfion mixture is maintained at a specified temperature.
In this method, an emulsifying agent may be used to suspend the condensation product in aqueous media; when so used, from about 0.1 to about 5.0 percent of it (by weight of water in the hydroxide solution) should be present in the reaction mixture. The emulsifying agent may be added prior to or simultaneously with the addition of the brominated phenol to the reaction mixture.
In this method, an alkali or alkaline earth metal hydroxide may be used. It is preferred to use a metal hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide; sodium hydroxide is the most preferred. ~ron about 0.5 to about 5.0 moles of the hydroxide per liter of water is utilized. It is preferred to use from about 1 to about 3 moles of hydroxide mb/~- ~ 9 ~
. .
~lZ:~S38 per liter of water; it is most preferred to use about 2 moles of the hydroxide per liter of water.
The brominated phenol descrihed hereinabove is added to the reaction mixture at a concentration of from about 0.5 to about 5 moles per liter of water to make up the hydroxide solution in this method. It is preferred to use from about 1 to about 3 moles of phenol per liter of water. It is most preferred that the concentration be about 2 moles of phenol per liter of water.
In this method, although it is not essential, organic solvent may be added to the reaction mixture; any of the organic solvents listed hereinabove may be utilizedO When organic solvent is used, it is preferred that from 1 to about 20 percent of it ~by volume of water used to make up the hydroxide solution) be utilized. It is more preferred to use from about 3 to about 10 percent of organic solvent in this process; and it is most preferred to use from about 4 to about 8 percent of organic solvent. Some of the preferred organic solvents include toluene, benzene, chloroform, chlorinated benzenes, and the like.
Activating agent is contacted with the reaction mixture after all of the other components are present in this process.
When the activating agent is solid, liquid, or gaseous, at least about 1 x 10 5 moles of it (based upon liters of water used to make up the hydroxide solution) is used; it is preferred to use from about 0.01 to about 0.1 moles of these activating agents.
After the activating agent has been contacted with the reaction mixture, the reaction mixture is maintained at a mb/ - 10 -.
L53~
temperature of from about 20 to about 180 degrees centigrade for from about 5 to about 300 minutes in this process. It is preferred to maintain the reaction mixture at a temperature of from about 20 to about 100 degrees centigrade for from ahout 15 to about 120 minutes. It is most preferred to maintain the reaction mixture at a temperature of from ahout 45 to about 65 degrees centigrade for from about 20 to about 40 minutes.
In this process, it is preferred that the reaction be run at a pressure of from ahout 1.0 to about 20 atmospheres.
It is more preferred to use a pressure of about 1.0 atmosphere during the reaction.
The flame retarded composition of this invention contains from about 5 to about 35 percent (by weight of total composition) of the flame retarding condensation product referred to hereinabove. It is preferred that it contain from about 9 to about 22 percent (by weight of total composition) of said flame retarding condensation product.
The method of adding the flame retardant additive to the polv(butylene terephthalate) is not critical; any means well known to those skilled in the art may be utilized.
Similarly, other additives may be incoxporated into the poly-(hutylene terephthalate) composition of this invention bymeans well known to those skilled in the art. It is preferred that each ingredient be added as part of a blend premix and the premix be mixed, e.g., by passage through an extruder or by fluxing on a mill at a temperature dependent on the needs of the particular compositions. The mixed composition can be cooled and cut up into molding granules and molded or extruded , ~ mb/, i~ - 11 -~LZlS38 or formed into any desired shape.
The flame retarded composition of this invention may also contain enhancing agents which, when used with said condensation product, promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant composition as compared to the flame retardancy of compositions containing either component alone. Those skilled in the art are familiar with these enhancing agents.
Some of the enhancing agents well known to those skilled in the art include the oxides and halides of the metals of groups IVA and VA of the Periodic Table such as the oxides and halides of antimony, bismuth, arsenic, tin, lead, and germanium; antimony oxychloride, antimony chloride, antimony oxide, stannic oxide, stannic chloride, arsenous oxide, arsenous chloride, and the like are enhancing agents well known to the art. Other enhancing agents well known to those skilled in the art are the organic and inorganic compounds of phosphorous, nitrogen, boron, and sulfur; thus, e.g., triphenyl phosphate, ammonium phosphate, zinc borate, thiourea, urea, stannic sulfide, and the like are suitable enhancing agents. The oxides and halides of titanium, vanadium, chromium, magnesium are also used as enhancing agents as are the hydrates of these compounds; thus, e.g., titanium dioxide, titanium chloride, vanadium pentoxide, chromic bromide, manganous oxide, molybdenum trioxide, ammonium molybdate, stannous oxide hydrate, lead hydrate, and combinations thereof may be used. Many antimony compounds, both organic and inorganic, are useful as enhancing agents; antimony sulfide, sodium antimonite, potassium antimonite, antimony butyrate, antimony valerate, antimony mb/~,r - 12 -caproate, anti~ony heptylate, antimony caprylate, antimony perlargonate, antimony caprate, antimony cinnamate, antimony anisate, tris(n-octyl) antimonite, tris(2-ethvlhexyl) antimoni-te, tribenzyl antimonite, trimethylolpropane antir,lonite, pentaervthritol antimonite, glycerol antimonite, and compounds which on decomposition (as by ignition) vield antimony oxide are well known to the art as enhancing agents.
The preferred enhancing agents are the oxides of antimony, arsenic, and bismuth. The more preferred enhancing agents are the oxides of antimony~ The most preferred enhancing agent is antimony trioxide.
When enhancing agent is incorporated into the flame retarded composition of this invention, from 1 to about 20 percent of it (by weight of the combined polybutylene terephthalate, flame retardant, and enhancing agen-t) may be used. It is preferred to utilize from about 3 to about 10 percent (by weight) of enhancing agent.
It is also within the scope of the present invention to employ other materials in the compositions of the invention where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promotors;
antioxidants; antistatic agents; antimicrobial agents;
colorants; other flame retardants (in addition to the flame retarding condensation product described herein); heat stabilizers; light stabilizers; fillers; reinforcing agents;
and other materials well known to those skilled in the art which have been or could be used in poly(butylene kerephthalate) compositions. These materials may be employed in any amounts which will not substantially adversely affect the properties ~; J
mb~ 13 ~
1~2~S3~
of the poly(butylene terephthalate) of this invention. Thus, the amount used can be zero (0) percent, based on the 'cotal weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about 0~ to about 80~.
Glass reinforced poly(butylene terephthalate) comprised of from ahout 6 to about 60 percent (by weight) of fiberglass and the poly(butylene terephthalate) composition of this invention is within the scope of this invention. The glass fibers used to make this composition may be treated with couplin~ agents well known to those skilled in the art so that the polymer will bond strongly to the surface of the glass.
Additionally, or alternatively, other agents (such as, e.g., asbestos) may be utilized in the composition of this invention.
The terephthalate component of the composition of this invention consists of linear polymer containing at least about ~5 percent ~by weight~ of poly(butylene terephthalate).
It may be prepared by reacting terephthalic acid or its dialkyl ester and polymethylene glycol of the formula HO(CH2)nOH
wherein n is from 2 to 8. At least 85 percent of said polymer is prepared from a glycol wherein n is 4(1,4-butanediol), and some of all of the remaining 15 percent may be prepared from ethylene glycol, trimethylene glycol, 1,4-butanediol, and the like. The polymethylene glycol used to prepare some or all of said remaining 15 percent may be replaced entirely or in part with other glycols such as 1,4-cyclohexanedimethanol;
1,4-bis(2-hydroxyethyloxy~ benzene, and the like. It is preferred that no more than about 10 percent of the polymer will be prepared from a glycol which is not a polymethylene ~r mb/~ - 14 -l~Zl~;3S
glycol.
Other dicarboxylic acids and their esters may be used to prepare the terephthalate used in this invention.
Thus, e.g., from about 1 to about 10 weight percent (based on the weight of terephthalic acid or the dialkyl ester thereof used to make the polymer) of a dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid, and HOOC-R-COOR ~wherein R is alkylene of from about 2 to about 15 carbon atoms) may be used. ~Jhen said dicarboxylic acid is used in the preparation of the terephthalate, it is preferred to use from about 3 to about 8 weight percent thereof. Some of the dicarboxylic acids which may be used to prepare the terephthalate of this invention include, e.g., succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like.
Subject to the limitation described above (viz., at least 85 weight percent of the terephthalate component is poly(butylene terephthalate), the composition of this invention may contain other materials than the ones hereinbefore described such as, e.g., dye site additives, delustrants, antistatic agents, optical brighteners, mold release agents, nucleating agents, etc.
Under all conditions of use, the flame retarded poly-(butylene terephthalate) composition of this invention exhibits substantially less surface migration than does a comparable poly(butylene terephthalate) composition containing decabromo-biphenyl oxide.
~ 15 -~1531!~
The following examples are provided for the purpose of further illustration only and are not intended to be limitations on the invention disclosed. Unless othe~ise specified, all parts are by weight, all wei~hts are in grams, all temperatures are in degrees centigrade, and all volumes are in milliliters.
PREP~RATIVN OF THE FL~IE RETARDIN~. CON~ENSATION PRODUCTS
. . . .
EX~IPLE I
T~JO hundred milliliters of chloroform were added to a 10- one liter, three-necked, round-bottomed flask fitted with mechanical stirring, addition funnel, reflux condenser, and nitroyen flush. Sixteen and one-half grams of 2,4,6-tribromo-phenol were added to the chloroform. Thereafter, 2.8 grams of potassium hydroxide were dissolved in 100 milliliters of water, and this solution was then added to the reaction mixture.
An a~ueous solution of potassium ferricyanide was prepared;
1.6 grams of the potassium ~erricyanide were dissolved in 100 milliliters of water. This solution was added over a period of one hour to the reaction mixture. Thereafter, the reaction mixture was maintained at ambient temperature and stirred for
4.5 hours. Then the reaction mixture was poured into a separatory funnel~ The bottom chloroform phase was dropped directly into vi~orously stirred methanol. The white precipi tate which formed was filtered and dried. This product softened at a temperature of from ahout 220 to about 240 degrees centigrade. It had an intrinsic viscosity (in chloroform~ at 25 degrees centigrade) of 0.050 deciliters per ~ram.
mb~ --16 ~LZ~538 EX~1PLE II
.
To a one liter, three-necked, round-bottomea flask fitted with mechanical stirring, reflux condenser, and nitrogen flush were added 100 milliliters of 1,2,4-trichloro-benzene. Thereafter, 58.7 grams of pentabromophenol were added with stirring; and then 2.9 grams of benzovl peroxide were added to the reaction mixture. A solution of potassium hydroxide (6.8 grams of KOH in 100 milliliters of water) was prepared; and this solution was quic~l~ added to the reaction mixture. T~o milliliters of dimethyl sulfoxide and four milliliters of dimethyl formamide were then added to the reaction mixture, causing a mild exotherm. Stirring was -continued at ambient temperature for five hours. The reaction mixture was then poured into a separatorv funnel. The 1,2,4-trichlorobenzene layer (bottom) was then dropped directly into vigorously stirred acetone. The precipitated product was aissolved in 100 milliliters of tetrahydrofuran and reprecipi-tated in 450 milliliters of acetone. The product had a softening point of about 290 degrees centigrade.
EX~1PLES III-VI
.
These experiments were conducted in substantial accordance with the procedure described in Example I, but different catalysts and/or different brominated phenols (or mixtures thereof) were used. The results of these experiments are su~arized in Table I, below. In Examples III and IV, 2,4,6-tribromophenol was utilized as the reactant. Examples V and VI utilized pentabromophenol.
@~ .
mb/~ --17--~Z~L538 T~BLE I
INTRINSIC VISCOSITY
EXAM~LE C~TALYST POLY~IER SOFTENIN~ (25 C chloroform NU~fBER (10 MOLE %? YIELD (%) POINT (C.) deciiiters/gram) III K3Fe(CN)6 80 240-260 0.050 IV BENZOYL 100 225-250 0.050 PEROXIDE
V K3Fe(cN)6 ln 290 0.0 VI BENZOYL 86 290 0.0 PEROXIDE
EX~IPLES VII_and VIII
l'he procedure described in Example I was substantially followed with the exception that equimolar amounts of 2,4,6-tribromophenol and pentabromophenol were utilized as the reactant.
In Example VII, potassium ferricyanide was utilized as the -catalyst (10 mole ~); a 12 percent yield of a product with a softening point of from about 210 to about 220 degrees centigrade was obtained. In Examples VIII, benzoyl peroxide was utilized as a catalyst (10 mole %); a 98 percent yield of a product with a softening point of 250 degrees centigrade and an intrinsic viscosity (at 25 degrees centigrade in chloroform) of 0.032 deciliters per gram was obtained.
EX~IPLE IX ;~
Two thousand milliliters of water, 164 grams of sodium hydroxide, 10.7 grams of "Emulsifier 334" (an aryl polyether emulsifier sold bv the Milliken Chemical Corporation), 0.7 grams of ~ocecyl sodium sulfate, and 1324 grams of 2,4,6-tribromophenol were charged to a five-liter f]ask fitted with mechanical stirring, a thermometer, and a reflux condenser. The reaction mixture was first heated to 100 degrees centigrade and maintained ~ mb~ 18 -~1 Z~lS3~
at that temperature for one minute; then it was cooled to a temperature of 33 degrees centigrade~ To this mixture was charged 133 milliliters of toluene and 20 grams of benzoyl peroxide. An exothermic reaction occurred, and the reaction temperature was then maintained at 55 degrees centigrade for 0.5 hours. Thereafter, 25 grams of sodium hydroxide were added to the reaction mixture. The reaction mixture was then filtered, the filter cake was washed with 15 liters of water, and the filter cake was dried to give 932 grams of product.
FL~IE RETARDED POLYIIERIC COMPOSITIONS
EX~lPLE X
Four hundred and twenty grams of glass-filled poly-(butylene terephthalate) comprised of 30 percent (bv weight) of glass fiber, 60 grams of the flame retardant product of Example IX, and 20 grams of antimonv trioxide were dry blended and compounded by adding these ingredients to a Brabender mixer ("Prep Center" Model R6, C.W~ ~rabender Instruments Inc., Hackensack, N.J.); the compounding was conducted for about 2 minutes at a temperature of 240 degrees centigrade. The mixture was then cooled, granulated, and fed into a Newhury injection molding machine (Model HI-30RS manufactured by Newbury Instruments Inc., Newbury, Ohio~. Test specimens were molded using a stock `;
temperature of 470 degrees Fahrenheit, and injection pressure of 2000 pounds per square inch, and a cycle time of 55 seconds.
The specimens contained 12 percent (by weight) of the product of Example IX and 4 percent (hy weight) of antimony trioxide.
mb/.?~ - l9 -L.S3~
The test specimens were tested for flamma~ility in accordance Wit]l Underwri-ter's Laboratory Subject No. 94 test (U.L. Tests for Flam~ability of Plastic ~laterials, U.L. 94, February 1, 1974). In this test, the test specimen was supported from the upper end, with the longest dimension vertical, by a clamp on a ring stand so that the lower end of the specimen was 3/8" above the top of the burner tube.
The burner was then placed remote from the sample, ignited, and adjusted to produce a blue flame 3/4" in height. The test flame was placed centrally under the lower end of the test specimen and allowed to remain for 10 seconds. The test flame was then withdrawn, and the duration of flaming or glowing combustion of the specimen was noted. If flaming or glowing combustion of the specimen ceased within 30 seconds after removal of the test flame, the test flame was again placed under the specimen for 10 seconds immediately after flaming or glowing combustion of the specimen stopped. The test flame was again withdrawn, and the duration of flaming - or glowing combustion of the specimen was noted. If the specimen dripped flaming particles or droplets while burning in this test~ these drippings were allowed to fall onto a horizontal layer of cotton fibers (untreated surgical cotton) placed one foot below the test specimen. Significantly flaming particles were considered to be those capable of igniting the cotton fibers. The duration of flaming or glowing combustion of vertical specimens after application of the test flame (average of 5 specimens with 10 flame applications) should not exceed 25 seconds (maximum not more than 30 seconds) and the portion of the specimen outside the clamp should not ''. " ' 3~
be completely burned in the test.
~Iaterials ~hich complied with the above requirements and did not drip any flaming particles or droplets during the burning test were classified as "V-l". Materials which complied with the above requirement but dripped flaming particles or droplets which burned briefly during the test were classified as "V-2". A "V-0" rating was given to materials wherein the duration of flaming or glowing combustion averaged less than 5 seconds under the conditions specified above.
The test specimens were also tested for migration by being subjected to a temperature of lO0 degrees centigrade for 100 hours and then being visually observed to determine whether any flame retardant had migrated to the surface.
The poly(butylene terephthalate) composition of this Example had a U.L. 94 1/8" rating of V-0, and U.L. 94 l/16"
rating of V-0, and did not exhibit exudation of the flame retardant to the surface after being subjected to a temperature of 100 degrees centigrade for 100 hours.
A comparable poly(butylene terephthalate) composition comprised of 12 weight percent of decabromobiphenyl oxide `
and 4 weight percent of antimony trioxide exhibited heavy exudation after being subjected to a temperature of 100 degrees for lO0 hours.
EXAMPLE_XI
The procedure of Examp:Le X was substantially followed with the exception that an unfilled poly(butylene terephthalate) was utilized and compounded with 3.~ percent (by total weight~
of anti~ony trioxide and lO percent (by total weight) of either ~ - 21 -11;Z ~538 flame retardant pro~uct made in substantial accordance with the procedure o~ Example IX or decabromobiphenyl oxide. Test specimens were prepared in accordance with the procedure of Example X and were subjected to accelerated aging at a temperature of 100 degrees centigrade.
The specimens containing decabromobiphenyl oxide exhibited moderate surface exudation after 18 hours exposure at 100 degrees centigrade and heavy surface exudation after 100 hours exposure at 100 degrees centigrade. The specimens containing the flame retardant prepared in accordance with the procedure of Example IX exhibited no surface exudation after being exposed to a temperature of 100 degrees centigrade for either 18 hours or 100 hours.
EX~1PLE XII
The procedure of Example X was substantiallv followed with the exception that an unfilled poly(butylene terephthalate) was utilized and compounded with antimony trioxide and either the flame retardant product of Example IX or decabromobiphenyl oxide; test specimens comprised of 12 percent (hy weight) of flame retardant and 4 percent (by weight) of antimony trioxide were prepared.
After being subjected to accelerated aging for 100 hours at 100 degrees centigrade, test specimens containing the flame retardant of Example IX were visually examined; they did not exhibit any migration to the surface of the flame retardant.
However, tlle specimens containing the decabromobiphenyl oxide flame retardant exhibited heavy surface migration.
mb/~^ - 22 -. .
l~LZ~3~
The test specimens were also subjected to accelerated aging for 72 hours at 150 degrees centigrade. The test specimens containing the flame retardant of Example IX
exhibited very slight surface migration after heing subjected to these accelerated aging conditions. The test specimens containin~ the decabromobiphenyl oxide flame retardant again exhibited heavy surface migration under these conditions.
mb/ - 23 ~
~ 7~
SUPPl.EMEl`l'rARY DJ.SC_OSURE
As previously indicated in the principal disclosure, it is prefexred that the flame retard~nt condensation product of this invention be derived from tri~romophenol. It has been found that the condensation product of tribromopheno'L in accordance with the present invention has a novel molecular structure exhibiting desirable properties over closely related compositions.
More specifically, the preferred flame retarding condensation product of this invention is a branched polymer having a hydroxyl number of from 2.8 to about 30 and the structural formula t I ~ ~ ~ o ~ r (E)q m wherein each repeating unit set out within the brackets of the structural formula is attached in an ortho or para configuration to its adjacent phenyl and phenoxy moiety; and wherein E is an Br end group of the formula _o~ Br Br Y is a side chain of the same structure and configuration as said repeating unit; the substituents Br, E and Y on each phenyl ring are attached only to the ortho or para positions relative the hydroxyl group in the structural formula and the oxygen ,~ . _ ~ .
~ r ~Z~53~
atom in the repeatillg unit; each t, p and q are independently the integer 0 or 1, provided that the sum of t plus p plus q equals 2, and provided that from about 10 to about 80 percent of the repeat-ing units have the side chain and end unit -Y-E attached thereto;
and m is an integer such that the total molecular weight of the polymer ranges from about 2,000 to about 20~000O
The novelty and unexpec~ed desired properties of the polymer described above are attributed to both the chemical as well as its structural configuration. First the polymer, because it is a condensation product of a phenol, necessarily has a residual hydroxyl group. This group can be titrated and accordingly the polymer has a hydroxyl number dependent on its molecular weight.
As stated, this hydroxyl number typically ranges from 2.8 to about 30 mg per gram of sample.
It has also been found that the condensation of tribromophenol, as described herein, results in a 1-2 and 1-4 sub-stitution of bromine relative the phenolic moiety. Therefore, each repeating phenoxy group in the polymer is attached to an ortho or para position relative the phenolic group on the adjacent ring.
Thus, any two repeating units have the following structural con-figuration (Br)t (Br)t I- _ 0 ~ ~ = or (Y) (Y) ( ~
(E)~ (E)q o?~
;38 (Br)t 0 ~
~ E)q ~/~
( ~t ~ E
~X
~Y-E)q wherein Y, E, t, p and q are heretofore described. Similarly, the side chains represented by Y and the end groups represented by E
are attached to the ortho or para position of the respective phenoxy ring.
An important aspect of the preferred fire retard-ant condensation product is its branching, i.e., the existence of side groups on otherwise linear polymer backbone. These side groups can be one or more repeating units as in the backbone of the polymer terminated by an end group or simply an end group by itself. The degree of branching in the preferred product can vary such that at least one in ten of the phenoxy units are substituted by a side chain or end group and as many as eight in 10 are so substituted. It is believed that this degree of branching significantly contributes to the non-blooming properties of poly-ester compositions containing the preferred product.
The preferred condensation product of the present invention has a number average molecular weight that ranges from about 2000 to about 20,000, and most preferably from about 2000 to about 12,000 as determined by vapor phase osmometry (VPO).
The preferred condensation product of tribromophenol ~lZi53~-of the presel-t invention can be prepared by the general procedure heretofore described. A further more specific exemplary preparation is set forth in the following example.
EX~MPLE XIII
Sodium tri~romophenate (387 grams) dissolved in water to obtain a 37 percent by weight solution is charged into a reaction vessel equipped with stirring and heating means. Hydro-chloric acid (1.9 grams; 31.5% concentration) is added and the resulting mixture is warmed ~o 40C with stirring. Potassium persulfate (~.3 grams) is added to the reaction vessel and stirring is continued for a period of about 30 minutes. A reaction tem-perature of 55 to 60C is maintained during this period. After this time the pH of the reaction mixture is adjusted to about 13 by the addition of 50% aqueous caustic soda and thereafter hydrazine (1 gram; 64% conc.) is added with stirring. Stirring is continued for a period of 15 minutes and the reaction mixture is thereafter heated to a temperature of 95 to 100 C with further stirring for a period of 4 hours. After this time the mixture is cooled to room temperature and the desired product is recovered by filtration and dried.
mb~ --16 ~LZ~538 EX~1PLE II
.
To a one liter, three-necked, round-bottomea flask fitted with mechanical stirring, reflux condenser, and nitrogen flush were added 100 milliliters of 1,2,4-trichloro-benzene. Thereafter, 58.7 grams of pentabromophenol were added with stirring; and then 2.9 grams of benzovl peroxide were added to the reaction mixture. A solution of potassium hydroxide (6.8 grams of KOH in 100 milliliters of water) was prepared; and this solution was quic~l~ added to the reaction mixture. T~o milliliters of dimethyl sulfoxide and four milliliters of dimethyl formamide were then added to the reaction mixture, causing a mild exotherm. Stirring was -continued at ambient temperature for five hours. The reaction mixture was then poured into a separatorv funnel. The 1,2,4-trichlorobenzene layer (bottom) was then dropped directly into vigorously stirred acetone. The precipitated product was aissolved in 100 milliliters of tetrahydrofuran and reprecipi-tated in 450 milliliters of acetone. The product had a softening point of about 290 degrees centigrade.
EX~1PLES III-VI
.
These experiments were conducted in substantial accordance with the procedure described in Example I, but different catalysts and/or different brominated phenols (or mixtures thereof) were used. The results of these experiments are su~arized in Table I, below. In Examples III and IV, 2,4,6-tribromophenol was utilized as the reactant. Examples V and VI utilized pentabromophenol.
@~ .
mb/~ --17--~Z~L538 T~BLE I
INTRINSIC VISCOSITY
EXAM~LE C~TALYST POLY~IER SOFTENIN~ (25 C chloroform NU~fBER (10 MOLE %? YIELD (%) POINT (C.) deciiiters/gram) III K3Fe(CN)6 80 240-260 0.050 IV BENZOYL 100 225-250 0.050 PEROXIDE
V K3Fe(cN)6 ln 290 0.0 VI BENZOYL 86 290 0.0 PEROXIDE
EX~IPLES VII_and VIII
l'he procedure described in Example I was substantially followed with the exception that equimolar amounts of 2,4,6-tribromophenol and pentabromophenol were utilized as the reactant.
In Example VII, potassium ferricyanide was utilized as the -catalyst (10 mole ~); a 12 percent yield of a product with a softening point of from about 210 to about 220 degrees centigrade was obtained. In Examples VIII, benzoyl peroxide was utilized as a catalyst (10 mole %); a 98 percent yield of a product with a softening point of 250 degrees centigrade and an intrinsic viscosity (at 25 degrees centigrade in chloroform) of 0.032 deciliters per gram was obtained.
EX~IPLE IX ;~
Two thousand milliliters of water, 164 grams of sodium hydroxide, 10.7 grams of "Emulsifier 334" (an aryl polyether emulsifier sold bv the Milliken Chemical Corporation), 0.7 grams of ~ocecyl sodium sulfate, and 1324 grams of 2,4,6-tribromophenol were charged to a five-liter f]ask fitted with mechanical stirring, a thermometer, and a reflux condenser. The reaction mixture was first heated to 100 degrees centigrade and maintained ~ mb~ 18 -~1 Z~lS3~
at that temperature for one minute; then it was cooled to a temperature of 33 degrees centigrade~ To this mixture was charged 133 milliliters of toluene and 20 grams of benzoyl peroxide. An exothermic reaction occurred, and the reaction temperature was then maintained at 55 degrees centigrade for 0.5 hours. Thereafter, 25 grams of sodium hydroxide were added to the reaction mixture. The reaction mixture was then filtered, the filter cake was washed with 15 liters of water, and the filter cake was dried to give 932 grams of product.
FL~IE RETARDED POLYIIERIC COMPOSITIONS
EX~lPLE X
Four hundred and twenty grams of glass-filled poly-(butylene terephthalate) comprised of 30 percent (bv weight) of glass fiber, 60 grams of the flame retardant product of Example IX, and 20 grams of antimonv trioxide were dry blended and compounded by adding these ingredients to a Brabender mixer ("Prep Center" Model R6, C.W~ ~rabender Instruments Inc., Hackensack, N.J.); the compounding was conducted for about 2 minutes at a temperature of 240 degrees centigrade. The mixture was then cooled, granulated, and fed into a Newhury injection molding machine (Model HI-30RS manufactured by Newbury Instruments Inc., Newbury, Ohio~. Test specimens were molded using a stock `;
temperature of 470 degrees Fahrenheit, and injection pressure of 2000 pounds per square inch, and a cycle time of 55 seconds.
The specimens contained 12 percent (by weight) of the product of Example IX and 4 percent (hy weight) of antimony trioxide.
mb/.?~ - l9 -L.S3~
The test specimens were tested for flamma~ility in accordance Wit]l Underwri-ter's Laboratory Subject No. 94 test (U.L. Tests for Flam~ability of Plastic ~laterials, U.L. 94, February 1, 1974). In this test, the test specimen was supported from the upper end, with the longest dimension vertical, by a clamp on a ring stand so that the lower end of the specimen was 3/8" above the top of the burner tube.
The burner was then placed remote from the sample, ignited, and adjusted to produce a blue flame 3/4" in height. The test flame was placed centrally under the lower end of the test specimen and allowed to remain for 10 seconds. The test flame was then withdrawn, and the duration of flaming or glowing combustion of the specimen was noted. If flaming or glowing combustion of the specimen ceased within 30 seconds after removal of the test flame, the test flame was again placed under the specimen for 10 seconds immediately after flaming or glowing combustion of the specimen stopped. The test flame was again withdrawn, and the duration of flaming - or glowing combustion of the specimen was noted. If the specimen dripped flaming particles or droplets while burning in this test~ these drippings were allowed to fall onto a horizontal layer of cotton fibers (untreated surgical cotton) placed one foot below the test specimen. Significantly flaming particles were considered to be those capable of igniting the cotton fibers. The duration of flaming or glowing combustion of vertical specimens after application of the test flame (average of 5 specimens with 10 flame applications) should not exceed 25 seconds (maximum not more than 30 seconds) and the portion of the specimen outside the clamp should not ''. " ' 3~
be completely burned in the test.
~Iaterials ~hich complied with the above requirements and did not drip any flaming particles or droplets during the burning test were classified as "V-l". Materials which complied with the above requirement but dripped flaming particles or droplets which burned briefly during the test were classified as "V-2". A "V-0" rating was given to materials wherein the duration of flaming or glowing combustion averaged less than 5 seconds under the conditions specified above.
The test specimens were also tested for migration by being subjected to a temperature of lO0 degrees centigrade for 100 hours and then being visually observed to determine whether any flame retardant had migrated to the surface.
The poly(butylene terephthalate) composition of this Example had a U.L. 94 1/8" rating of V-0, and U.L. 94 l/16"
rating of V-0, and did not exhibit exudation of the flame retardant to the surface after being subjected to a temperature of 100 degrees centigrade for 100 hours.
A comparable poly(butylene terephthalate) composition comprised of 12 weight percent of decabromobiphenyl oxide `
and 4 weight percent of antimony trioxide exhibited heavy exudation after being subjected to a temperature of 100 degrees for lO0 hours.
EXAMPLE_XI
The procedure of Examp:Le X was substantially followed with the exception that an unfilled poly(butylene terephthalate) was utilized and compounded with 3.~ percent (by total weight~
of anti~ony trioxide and lO percent (by total weight) of either ~ - 21 -11;Z ~538 flame retardant pro~uct made in substantial accordance with the procedure o~ Example IX or decabromobiphenyl oxide. Test specimens were prepared in accordance with the procedure of Example X and were subjected to accelerated aging at a temperature of 100 degrees centigrade.
The specimens containing decabromobiphenyl oxide exhibited moderate surface exudation after 18 hours exposure at 100 degrees centigrade and heavy surface exudation after 100 hours exposure at 100 degrees centigrade. The specimens containing the flame retardant prepared in accordance with the procedure of Example IX exhibited no surface exudation after being exposed to a temperature of 100 degrees centigrade for either 18 hours or 100 hours.
EX~1PLE XII
The procedure of Example X was substantiallv followed with the exception that an unfilled poly(butylene terephthalate) was utilized and compounded with antimony trioxide and either the flame retardant product of Example IX or decabromobiphenyl oxide; test specimens comprised of 12 percent (hy weight) of flame retardant and 4 percent (by weight) of antimony trioxide were prepared.
After being subjected to accelerated aging for 100 hours at 100 degrees centigrade, test specimens containing the flame retardant of Example IX were visually examined; they did not exhibit any migration to the surface of the flame retardant.
However, tlle specimens containing the decabromobiphenyl oxide flame retardant exhibited heavy surface migration.
mb/~^ - 22 -. .
l~LZ~3~
The test specimens were also subjected to accelerated aging for 72 hours at 150 degrees centigrade. The test specimens containing the flame retardant of Example IX
exhibited very slight surface migration after heing subjected to these accelerated aging conditions. The test specimens containin~ the decabromobiphenyl oxide flame retardant again exhibited heavy surface migration under these conditions.
mb/ - 23 ~
~ 7~
SUPPl.EMEl`l'rARY DJ.SC_OSURE
As previously indicated in the principal disclosure, it is prefexred that the flame retard~nt condensation product of this invention be derived from tri~romophenol. It has been found that the condensation product of tribromopheno'L in accordance with the present invention has a novel molecular structure exhibiting desirable properties over closely related compositions.
More specifically, the preferred flame retarding condensation product of this invention is a branched polymer having a hydroxyl number of from 2.8 to about 30 and the structural formula t I ~ ~ ~ o ~ r (E)q m wherein each repeating unit set out within the brackets of the structural formula is attached in an ortho or para configuration to its adjacent phenyl and phenoxy moiety; and wherein E is an Br end group of the formula _o~ Br Br Y is a side chain of the same structure and configuration as said repeating unit; the substituents Br, E and Y on each phenyl ring are attached only to the ortho or para positions relative the hydroxyl group in the structural formula and the oxygen ,~ . _ ~ .
~ r ~Z~53~
atom in the repeatillg unit; each t, p and q are independently the integer 0 or 1, provided that the sum of t plus p plus q equals 2, and provided that from about 10 to about 80 percent of the repeat-ing units have the side chain and end unit -Y-E attached thereto;
and m is an integer such that the total molecular weight of the polymer ranges from about 2,000 to about 20~000O
The novelty and unexpec~ed desired properties of the polymer described above are attributed to both the chemical as well as its structural configuration. First the polymer, because it is a condensation product of a phenol, necessarily has a residual hydroxyl group. This group can be titrated and accordingly the polymer has a hydroxyl number dependent on its molecular weight.
As stated, this hydroxyl number typically ranges from 2.8 to about 30 mg per gram of sample.
It has also been found that the condensation of tribromophenol, as described herein, results in a 1-2 and 1-4 sub-stitution of bromine relative the phenolic moiety. Therefore, each repeating phenoxy group in the polymer is attached to an ortho or para position relative the phenolic group on the adjacent ring.
Thus, any two repeating units have the following structural con-figuration (Br)t (Br)t I- _ 0 ~ ~ = or (Y) (Y) ( ~
(E)~ (E)q o?~
;38 (Br)t 0 ~
~ E)q ~/~
( ~t ~ E
~X
~Y-E)q wherein Y, E, t, p and q are heretofore described. Similarly, the side chains represented by Y and the end groups represented by E
are attached to the ortho or para position of the respective phenoxy ring.
An important aspect of the preferred fire retard-ant condensation product is its branching, i.e., the existence of side groups on otherwise linear polymer backbone. These side groups can be one or more repeating units as in the backbone of the polymer terminated by an end group or simply an end group by itself. The degree of branching in the preferred product can vary such that at least one in ten of the phenoxy units are substituted by a side chain or end group and as many as eight in 10 are so substituted. It is believed that this degree of branching significantly contributes to the non-blooming properties of poly-ester compositions containing the preferred product.
The preferred condensation product of the present invention has a number average molecular weight that ranges from about 2000 to about 20,000, and most preferably from about 2000 to about 12,000 as determined by vapor phase osmometry (VPO).
The preferred condensation product of tribromophenol ~lZi53~-of the presel-t invention can be prepared by the general procedure heretofore described. A further more specific exemplary preparation is set forth in the following example.
EX~MPLE XIII
Sodium tri~romophenate (387 grams) dissolved in water to obtain a 37 percent by weight solution is charged into a reaction vessel equipped with stirring and heating means. Hydro-chloric acid (1.9 grams; 31.5% concentration) is added and the resulting mixture is warmed ~o 40C with stirring. Potassium persulfate (~.3 grams) is added to the reaction vessel and stirring is continued for a period of about 30 minutes. A reaction tem-perature of 55 to 60C is maintained during this period. After this time the pH of the reaction mixture is adjusted to about 13 by the addition of 50% aqueous caustic soda and thereafter hydrazine (1 gram; 64% conc.) is added with stirring. Stirring is continued for a period of 15 minutes and the reaction mixture is thereafter heated to a temperature of 95 to 100 C with further stirring for a period of 4 hours. After this time the mixture is cooled to room temperature and the desired product is recovered by filtration and dried.
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A flame retarded, poly(butylene terephthalate) composition comprised of poly(butylene terephthalate) and from about 5 to about 35 percent (by weight) of a condensation product derived from brominated phenol by displacement of bromine from said phenol, wherein: (a) said phenol is selected from the group consisting of tribromophenol, tetrabromophenol, pentabromophenol, and mixtures thereof; (b) said condensation product has a repeating structural unit of the formula wherein a is an integer of from about 0 to about 4, b is an integer of from about 0 to about 2, c is an integer of from about 1 to about 5, a plus b plus c equal 5, Q is a monovalent bond from a carbon atom in the aromatic nucleus of said repeating structural unit to an oxygen atom bonded to an aromatic nucleus, and the polymeric unit(s) containing said repeating structural unit comprise at least about 80 percent (by weight) of said product; (c) said condensation product contains from about 17 to about 31 percent (by weight) of elemental carbon, from about 0 to about 1.0 percent (by weight) of elemental hydrogen, from about 3 to about 8 percent (by weight) of elemental oxygen, and at least 60 percent (by weight) of elemental bromine; and (d) said condensation product has a molecular weight of at least 750, and one or more polymeric units containing at least four aromatic nuclei per unit comprise at least 80 percent (by weight) of said product
2. The poly(butylene terephthalate) composition of claim 1, wherein said condensation product has a notched Izod impact strength of less than about 0.5 foot-pounds per inch, an elonaation of less than about 2.0 percent, and a tensile strength of less than about 200 pounds per square inch.
3. The poly(butylene terephthalate) composition of claim 2, wherein said brominated phenol is selected from the group consisting of tribromophenol, tetrabromophenol, and mixtures thereof; a is at least 1; and c is selected from the group consisting of 1, 2, 3, and mixtures thereof.
4. The poly(butylene terephthalate) composition of claim 3, wherein said brominated phenol is tribromophenol and said condensation product contains from about 62 to about 66 percent (by weight) of elemental bromine.
5. The poly(butylene terephthalate) composition of clalm 4, wherein said brominated phenol is 2,4,6-tribromophenol and said composition contains from about 9 to about 22 percent (by weight) of said condensation product.
6. The poly(butylene terephthalate) composition of claim 1, wherein said composltion contains from about 1 to about 20 percent (by weight) of enhancing agent.
7. The poly(butylene terephthalate) composition of claim 6, wherein sald enhancing agent is selected from the group consisting of the oxides of antimony, arsenic, and bismuth.
8. The poly(butylene terephthalate) composition of claim 5, wherein sald composition contains from about 3 to about 10 percent (by weight) of antimony trioxide.
9. The composition of claim 1 to which has been added from about 6 to about 60 percent (by weight of total composition) of glass fiber.
10. The composition of claim 9, wherein:
a) said brominated phenol is selected from the group consisting of tribromophenol, tetrabromophenol, and mixtures thereof;
b) a is at least l; and c) c is selected from the group consisting of 1,2,3, and mixtures thereof.
a) said brominated phenol is selected from the group consisting of tribromophenol, tetrabromophenol, and mixtures thereof;
b) a is at least l; and c) c is selected from the group consisting of 1,2,3, and mixtures thereof.
11. The composition of claim 10, wherein said brominated phenol is tribromophenol and said condensation product contains from about 62 to about 66 percent (by weight of condensation product) of elemental bromine.
12. The composition of claim 11, wherein said brominated phenol is 2,4,6-tribromophenol and said poly-(butylene terephthalate) is comprised of from about 9 to about 22 percent (by weight) of enhancing agent.
13. The composition of claim 12, wherein said enhancing agent is selected from the group consisting of the oxides of antimony, arsenic, and bismuth.
14. The composition of claim 13, wherein said poly(butylene terephthalate) is comprised of from about 3 to about 10 percent (by weight) of antimony trioxide.
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
15. A flame retarded poly(butylene terphthalate) com-position comprised of poly(butylene terphthalate) and from about 5 to about 35% by weight of a branched polymer having a hydroxyl number of from 2.8 to about 30 of the structural formula wherein each repeating unit set out within the brackets of the structural formula is attached in an ortho or para configuration to its adjacent phenyl and phenoxy moiety; and wherein E is an end group of the formula Y is a side chain of the same structure and configuration as said repeating unit; the substituents Br, E and Y on each phenyl ring are attached only to the ortho or para positions relative the hydroxyl group in the structural formula and the oxygen atom in the repeating unit; each t, p and q are independently the integer 0 or 1, provided that the sum of t plus p plus q equals 2, and provided that from about 10 to about 80 percent of the repeating units have the side chain and end unit -Y-E attached thereto; and m is an integer such that the total molecular weight of the polymer ranges from 2000 to 20,000.
16. The flame retarded composition of claim 15, wherein said composition contains from about 9 to about 22% by weight of the branched polymer.
17. The flame retarded composition of claim 15, wherein said composition contains from about 1 to about 20% by weight of enhancing agent selected from the group consisting of the oxides of antimony, arsenic and bismuth.
18. The flame retarded composition of claim 17, wherein the enhancing agent is antimony trioxide.
19. The flame retarded composition of claim 15 to which has been added from about 6 to about 60% by weight of the total composition glass fiber.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87715778A | 1978-02-13 | 1978-02-13 | |
| US877,157 | 1978-02-13 | ||
| US74,363 | 1979-09-10 | ||
| US06/074,363 US4242473A (en) | 1979-09-10 | 1979-09-10 | Flame retarded poly(butylene terephthalate) composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121538A true CA1121538A (en) | 1982-04-06 |
Family
ID=26755568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000319454A Expired CA1121538A (en) | 1978-02-13 | 1979-01-11 | Flame retarded poly(butylene terephthalate) compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1121538A (en) |
-
1979
- 1979-01-11 CA CA000319454A patent/CA1121538A/en not_active Expired
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