CA1059676A - Flame retardant polyester compositions - Google Patents
Flame retardant polyester compositionsInfo
- Publication number
- CA1059676A CA1059676A CA200,006A CA200006A CA1059676A CA 1059676 A CA1059676 A CA 1059676A CA 200006 A CA200006 A CA 200006A CA 1059676 A CA1059676 A CA 1059676A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- percent
- polyester compositions
- flame retardant
- linear polyester
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
- C08K5/1539—Cyclic anhydrides
-
- 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
- C08L27/04—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 chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
ABSTRACT OF THE DISCLOSURE
Polyester compositions having flame retardant characteristics comprising (A) a high molecular weight linear polyester selected from the group consisting of copolyesters and blends of copolyesters and homopolyesters and (B) a synergistic mixture of from 5 to 10 percent by weight, based on the total weight of said compositions of polyvlnyl chloride and from 5 to 10 percent by weight, based on the total weight of said composition, of at least one compound selected from the group consisting of antimony trioxide, boron trioxide, tetrabromophthalic anhydride, tetrachlorophthalic anhydride and chlorendic acid anhydride. The compositions of the invention are useful for the preparation of flame retardant fibers and fabrics.
Polyester compositions having flame retardant characteristics comprising (A) a high molecular weight linear polyester selected from the group consisting of copolyesters and blends of copolyesters and homopolyesters and (B) a synergistic mixture of from 5 to 10 percent by weight, based on the total weight of said compositions of polyvlnyl chloride and from 5 to 10 percent by weight, based on the total weight of said composition, of at least one compound selected from the group consisting of antimony trioxide, boron trioxide, tetrabromophthalic anhydride, tetrachlorophthalic anhydride and chlorendic acid anhydride. The compositions of the invention are useful for the preparation of flame retardant fibers and fabrics.
Description
1~967~
This invention relates to polyester resin compositions having improved flame retardant characteris~
tics. More specifically the invention relates to flame retardant polyester resin compositions consisting of high molecular weight linear copolyesters and blends of high molecular weight linear copolyesters and homopolyesters in admixture wlth synergistic combinations of polyvinyl chloride with metallic oxides and/or halogen containing acid anhydrides.
The use of certain add1tives for the purpose of reducing the flammability and/or improving the flame extinguishing properties of various thermoplastic polymers is well known in the art. Among the additives that ha~e been employed for such a use are various types of phosphorous containing compounds. The phosphorous compounds are generally used either alone or in combination with other materials such as antimony compounds. Certain ~-analogous materials such as chlorostyrene copolymers, chlorinated paraffin waxes~ alone or with antimony oxide, are also known to be effective flame retardants for resinous materials. One drawback of these known compounds and combinations~ however, has been the fact that generally large amounts, i.e. upwards of 35 percent of the additive, must be incorporated into the polymer in order to render it reasonably flame retardant. Such large quantities of additive often times deleteriously alter the properties of the polymer and, moreover~ some additives tend to crystallize or bleed out of the polymer after a ~ i relatively short time of incorporation therein.
:, ~1 `.
~ 5~ ~ 7 Furthermore, some of the known flame retardan-t additives, such as chloropara~fin and chlorina-ted polye-thylene 9 are not compatible with the polymer compositlons and are not useful for many applications.
It is an object o~ this invention to provide polyester compositions with flame retardant properties.
It is also an object to provide such polyester composi-tions that are useful for coating articles such as electrical conductors. Other objects will appear as the description proceeds.
Accordingly, this invention comprises esse~ :~
tially linear polyester compositions possessing flame retardant properties, said polyester compositions com- -prising blends of ~A~ a high molecular weight essentialIy -linear polyester selected ~rom the group consisting of copolyesters having intrinsic viscosities of at least 0.5 and blends o~ from 75 to 25 percent by weight o copolyester and from 25 to 75 percent by weight of homo-polyesters each of which have intrinsic ~iscosities of at least 0.5 and is derived ~rom aromatic dicarboxylic acids or a lower alkyl ester thereof with a glycol~
- the intrinsic viscosity of said copolyester and ~aid homopolyester being determined in a 60i40 phenol/
s-tetrachloroe-thane solvent mixture having a resin concentration of 0.4 gram per 100 cubic centimeters o~
solution at ~0.0 C. and (B) a synergistic mixture com-prised o~ from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of poly~inyl : .
D `-1CJ 59671~
chloride having an in-trinsic VLiscosity o~ from 0~6 to 1.2 as measured in cyclohexanone solvent ha~ing a resin .
concentration of 0.2 gram per :L00 cubic centimeters of solution at 30 C. and ~rom 5 to 10 percent by weight, based on the total.weight of said polyester compositions9 of at least one material selected ~rom the group consisting of antimony trioxide, boron trioxide, tetrabromophthalic anhydride, tetrachlorphthalic .
anhydride and chlorendic acid anhydride. m ese polyester compositions were found to have excellent flame retardant properties and to possess good thermal and electrical properties.
D ` :~
:
... . . .. . .. , ... "... ... . . ., . . . ... ,. . ~ . .. . ... .. .. ..
...... .. .... ..... ., . ... . ~........ . . . ..... ... .... ... . . ....
f~--~ 5~ ~7 6 The (A) component of the polyester compositions of this invention include both high molecular weight ,`
essentially linear copolyesters and blends of high molecular weight essentially linear copolyesters and high molecular 5 weight essentially linear homopolyesters. Copolyesters useful as the (A) component include those copolyesters prepared by reacting two or more dicarboxylic acids selected from the group consisting of aliphatic and aromatic dicarboxylic acids, or the lower alkyl (Cl - C4) ' esters thereof with one or more glycols such as those of the series HO(C~2)nOH where n is an integer ranging from
This invention relates to polyester resin compositions having improved flame retardant characteris~
tics. More specifically the invention relates to flame retardant polyester resin compositions consisting of high molecular weight linear copolyesters and blends of high molecular weight linear copolyesters and homopolyesters in admixture wlth synergistic combinations of polyvinyl chloride with metallic oxides and/or halogen containing acid anhydrides.
The use of certain add1tives for the purpose of reducing the flammability and/or improving the flame extinguishing properties of various thermoplastic polymers is well known in the art. Among the additives that ha~e been employed for such a use are various types of phosphorous containing compounds. The phosphorous compounds are generally used either alone or in combination with other materials such as antimony compounds. Certain ~-analogous materials such as chlorostyrene copolymers, chlorinated paraffin waxes~ alone or with antimony oxide, are also known to be effective flame retardants for resinous materials. One drawback of these known compounds and combinations~ however, has been the fact that generally large amounts, i.e. upwards of 35 percent of the additive, must be incorporated into the polymer in order to render it reasonably flame retardant. Such large quantities of additive often times deleteriously alter the properties of the polymer and, moreover~ some additives tend to crystallize or bleed out of the polymer after a ~ i relatively short time of incorporation therein.
:, ~1 `.
~ 5~ ~ 7 Furthermore, some of the known flame retardan-t additives, such as chloropara~fin and chlorina-ted polye-thylene 9 are not compatible with the polymer compositlons and are not useful for many applications.
It is an object o~ this invention to provide polyester compositions with flame retardant properties.
It is also an object to provide such polyester composi-tions that are useful for coating articles such as electrical conductors. Other objects will appear as the description proceeds.
Accordingly, this invention comprises esse~ :~
tially linear polyester compositions possessing flame retardant properties, said polyester compositions com- -prising blends of ~A~ a high molecular weight essentialIy -linear polyester selected ~rom the group consisting of copolyesters having intrinsic viscosities of at least 0.5 and blends o~ from 75 to 25 percent by weight o copolyester and from 25 to 75 percent by weight of homo-polyesters each of which have intrinsic ~iscosities of at least 0.5 and is derived ~rom aromatic dicarboxylic acids or a lower alkyl ester thereof with a glycol~
- the intrinsic viscosity of said copolyester and ~aid homopolyester being determined in a 60i40 phenol/
s-tetrachloroe-thane solvent mixture having a resin concentration of 0.4 gram per 100 cubic centimeters o~
solution at ~0.0 C. and (B) a synergistic mixture com-prised o~ from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of poly~inyl : .
D `-1CJ 59671~
chloride having an in-trinsic VLiscosity o~ from 0~6 to 1.2 as measured in cyclohexanone solvent ha~ing a resin .
concentration of 0.2 gram per :L00 cubic centimeters of solution at 30 C. and ~rom 5 to 10 percent by weight, based on the total.weight of said polyester compositions9 of at least one material selected ~rom the group consisting of antimony trioxide, boron trioxide, tetrabromophthalic anhydride, tetrachlorphthalic .
anhydride and chlorendic acid anhydride. m ese polyester compositions were found to have excellent flame retardant properties and to possess good thermal and electrical properties.
D ` :~
:
... . . .. . .. , ... "... ... . . ., . . . ... ,. . ~ . .. . ... .. .. ..
...... .. .... ..... ., . ... . ~........ . . . ..... ... .... ... . . ....
f~--~ 5~ ~7 6 The (A) component of the polyester compositions of this invention include both high molecular weight ,`
essentially linear copolyesters and blends of high molecular weight essentially linear copolyesters and high molecular 5 weight essentially linear homopolyesters. Copolyesters useful as the (A) component include those copolyesters prepared by reacting two or more dicarboxylic acids selected from the group consisting of aliphatic and aromatic dicarboxylic acids, or the lower alkyl (Cl - C4) ' esters thereof with one or more glycols such as those of the series HO(C~2)nOH where n is an integer ranging from
2 to 10 and glycols of the series HOCH2C(R)2CH20H where R is selected from the group consisting of hydrogen and alkyl and aryl radicals or copolyesters prepared by reacting two or more of the above deflned glycols with one `, or more of the above defined dicarboxylic acids or lower ~ ' ' alkyl esters thereof. The esterification reaction is carried out under the usual esteriflcation or transesteri-fication conditions. The resulting esterification or transesterification product ls then polycondensed at elevated temperatures and reduced pressures to form the desired high,molecular weight linear copolyesters.
Representative examples of the copolyesters useful as the (A) component include poly(ethylene terephthalate/ ,, isophthalate)~ poly(ethylene terephthalate/2~6-naphthalate)~
poly(ethylene terephthalate/2~7-naphthalate)~ poly ;, (ethylene terephthalate/2~6-naphthalate/2~7-naphthalate)~
poly(tetramethylene terephthalate/isophthalate/sebacate), poly(ethylene/neopentyl terephthalate)~ poly(l,3-trime~hylene
Representative examples of the copolyesters useful as the (A) component include poly(ethylene terephthalate/ ,, isophthalate)~ poly(ethylene terephthalate/2~6-naphthalate)~
poly(ethylene terephthalate/2~7-naphthalate)~ poly ;, (ethylene terephthalate/2~6-naphthalate/2~7-naphthalate)~
poly(tetramethylene terephthalate/isophthalate/sebacate), poly(ethylene/neopentyl terephthalate)~ poly(l,3-trime~hylene
-3- ' ~59~i76 terephthalate/isophthalate)~ poly(ethylene~ 1~3~tri-methylene terephthalate)~ poly(tetramethylene terephthalate/
isophthalate)~ poly(ethylene terephthalate/sebacate) and the like~ ~;
The high molecular weight linear homopolyesters which can be blended with the above described copolyesters to form the (A) component of the flame retardant polyester compositions constituting the invention lnclude those -;
prepared by reacting a free aromatic dicarboxylic acid or lower alkyl (Cl - C4) ester thereof with a glycol such as those corresponding to the above formulae. Again~ as in the preparation of the copolyesters, the esterification or transesterification reaction and the subsequent poly-condensation reaction are carried out employing well known techniques and conditions. Representative examples of the homopolyesters which can be blended with the copolyesters include poly(ethylene terephthalate~ poly(trimethylene terephthalate)~ poly(tetramethylene terephthalate), poly ~
(hexamethylene terephthalate)~ poly~ethylene-2,6- i naphthalate)~ poly(ethylene-2~7~naphthalate)~ poly (ethylene phenylindanate) and the like.
When the (A) component of the flame retardant polyester composition consists of a blend of a copolyester and a homopolyester the amount of said copolyester will range from 75 to 25 percent by weight of the total weight of the blend and the amount of homopolyester will range from 25 to 75 percent by weight of the total weight of the blend. Representative examples of preferred blends include ~the blends of poly(tetramethylene terephthalate) and poly ' i ' ' , ~
: . .
~OS9676 tetramethylene terephthalate/isophthalate/sebacate) and the blends of poly(ethylene terephthalate) and poly (tetramethylene terephthalate/isophthalate/
sebacate).
Various other materials can be present in the -above copolyesters and homopolyesters useful in this invention and such materials can be added either during or after the preparation of the copolyesters and homopoly-esters. Such vario~s other materials inolude stabilizers :such as any of the polyester art recognized oxida`tive~
thermal, hydrolytic and ultraviolet light stabilizers : -and transesterification catalysts such as zinc acetate~
manganese acetate, litharge and the like and polyconden-sation catalysts such as antimony trioxide and titanium compounds. In addition~ pigments5 delusterants~ chain branching agents and other similar additives can be present in the copolyesters and homopolyesters.
The (B) component of the polyester compositions ~: .
of this invention consists of a synergistic mixture of polyvinyl chloride and at least one compound selected from the group consisting of antimony trioxide, boron trioxide, tetrabromophthalic anhydride~ tetrachlorophthalic anhydride ;
and chlorendic acid anhydride~ the latter being represented by the formula H 0 ;-1 ~ C~
The polyvinyl chloride component useful in the synergistic .,~
. . ~
~ 5~676 mixture is an essentially rigid polyvinyl chloride having an intrinsic viscosity which can range from 0.6 to 1.2 as measured în cyclohexanone solvent have a resin concentration of 0.2 grams per 100 cubic cen-timeters of solvent at 30 C.
and which can contain stabilizers such as organotin mercap-tide or carboxylate 9 barium cadmium s-tearate and lead stearate. In addition, the essentially rigid polyvinyl chloride can contain up to 10 mol percent of a modifying monomer unit but preferably the modifying monomer unit is ;
kept below 5 percent. Suitable modifying monomers for the -polyvinyl compounds are vinyl acetate, vinyl ethers, vinyl acrylate, vinyl pyridine, vinyl benzene, vinyl chlorobenzenes, vinyl methacrylates, ethylene vinyl acetate copolymers, poly- `
vinyl pyridine 9 propylene vinyl acetate, polyvinyl acrylates and polyvinyl benzenes.
me following e~amples illustrate but do not limit the scope o~ our invention. All references are to weight percent where not otherwise specified.
To a mixture of 4 . 40 pounds of dimethyl terephthalate and 4. 50 pounds of tetramethylene glycol was added 3.0 grams of litharge catalyst (0.15 weight percent based on dimethyl tereph-thalate). The transesteri~ication was carried out in a 12 liter glass reactor with agitation over a four hour period at a temperature ranging from 140 C. to 235 C. The transesterification product was then transferred into a stainless steel polymeriza-tion reactor and polycondensed under 0.5 -to 1.5 millimeters of mercury pressure at a temperature ranging from 235 C. at ~ .
~ C~S96~S~
the star-t of the reaction to 259 C. at the end of the reaction. The polycondensation product, poly(-tetramethylene terephthalate), had an intrinsic viscosity of 0.795 measured at 30 C. in a 60/40 phenol/s-tetrachloroethane mixture.
EX~MPLE 2 Preparation of Polytetramethylene Terephthalate~
Isophthalate~Sebaca-te (70110 LO Mol ~ CoEolyester To a glass esterification reactor was added 1.82 pounds sebacic acid, 0.73 pound isophthalic acid and 5.114 pounds tereph-thalic acid, to which was added 9.82 pounds (tetramethylene glycol and 10.27 grams lead ace-tate trihydrate catalyst. The esterification reaction was carried out at a temperature ranging from 198 C. at the start o~ the reaction to 240 C. at the end over a six hour period.
The glycol esters were -then transferred to a polycondensa-tion stainless steel reactor and polycondensed at a pressure of 0.1 millimeter of mercury over a three hour period at a temperature in the range of 240 to 255 C.
to yield a 70/10/20 molar ratio poly(tetramethylene -terephthalate/isophthalate/sebacate copolyester having an intrinsic viscosity of 0.875.
~ '~ ', ' Three and one half pounds of the poly(te-tra-methylene terephthalate) prepared in Example 1 and 3.5 pounds of the poly(tetramethylene terephthalate/isoph-thalate/
sebacate) copolyes-ter prepared in Example 2 were added to a small double cone blender-dryer. Then 95.3 grams of the hindered phenolic phosphite described in Example 1 of U. S.
pa-tent 3,386,952 were added and the mixture tumbled in a f~
~". ' . . .
105967~
blender-dryer at 170 C. for two hours under a reduced pressure of 0.1 millime-ter of mercury.
me copolyester-homopolyester blend prepared in Example 3 was dry blended with 10 percent by weight of a rigid polyvinyl chloridè having an intrinsic viscosity of 0.68 as measured in cyclohexanone solvent having a resin concentration of 0.2 grams per 100 cubic centimeters o~
solvent at 30 C. and 5 percent by weight of tetrabromo-phthalic anhydride. This dry blended composition was then extrusion coated onto a 0.021 inch diameter electrical conducting wire. The coating thickness average 0.01 inch and was smooth and free of cracks. The coated wire was then subjected to the Underwriter's Horizontal Flame Test. The burning rate for this sample was found to be 2 inches/
minute.
An experiment was carried out similar to Example
isophthalate)~ poly(ethylene terephthalate/sebacate) and the like~ ~;
The high molecular weight linear homopolyesters which can be blended with the above described copolyesters to form the (A) component of the flame retardant polyester compositions constituting the invention lnclude those -;
prepared by reacting a free aromatic dicarboxylic acid or lower alkyl (Cl - C4) ester thereof with a glycol such as those corresponding to the above formulae. Again~ as in the preparation of the copolyesters, the esterification or transesterification reaction and the subsequent poly-condensation reaction are carried out employing well known techniques and conditions. Representative examples of the homopolyesters which can be blended with the copolyesters include poly(ethylene terephthalate~ poly(trimethylene terephthalate)~ poly(tetramethylene terephthalate), poly ~
(hexamethylene terephthalate)~ poly~ethylene-2,6- i naphthalate)~ poly(ethylene-2~7~naphthalate)~ poly (ethylene phenylindanate) and the like.
When the (A) component of the flame retardant polyester composition consists of a blend of a copolyester and a homopolyester the amount of said copolyester will range from 75 to 25 percent by weight of the total weight of the blend and the amount of homopolyester will range from 25 to 75 percent by weight of the total weight of the blend. Representative examples of preferred blends include ~the blends of poly(tetramethylene terephthalate) and poly ' i ' ' , ~
: . .
~OS9676 tetramethylene terephthalate/isophthalate/sebacate) and the blends of poly(ethylene terephthalate) and poly (tetramethylene terephthalate/isophthalate/
sebacate).
Various other materials can be present in the -above copolyesters and homopolyesters useful in this invention and such materials can be added either during or after the preparation of the copolyesters and homopoly-esters. Such vario~s other materials inolude stabilizers :such as any of the polyester art recognized oxida`tive~
thermal, hydrolytic and ultraviolet light stabilizers : -and transesterification catalysts such as zinc acetate~
manganese acetate, litharge and the like and polyconden-sation catalysts such as antimony trioxide and titanium compounds. In addition~ pigments5 delusterants~ chain branching agents and other similar additives can be present in the copolyesters and homopolyesters.
The (B) component of the polyester compositions ~: .
of this invention consists of a synergistic mixture of polyvinyl chloride and at least one compound selected from the group consisting of antimony trioxide, boron trioxide, tetrabromophthalic anhydride~ tetrachlorophthalic anhydride ;
and chlorendic acid anhydride~ the latter being represented by the formula H 0 ;-1 ~ C~
The polyvinyl chloride component useful in the synergistic .,~
. . ~
~ 5~676 mixture is an essentially rigid polyvinyl chloride having an intrinsic viscosity which can range from 0.6 to 1.2 as measured în cyclohexanone solvent have a resin concentration of 0.2 grams per 100 cubic cen-timeters of solvent at 30 C.
and which can contain stabilizers such as organotin mercap-tide or carboxylate 9 barium cadmium s-tearate and lead stearate. In addition, the essentially rigid polyvinyl chloride can contain up to 10 mol percent of a modifying monomer unit but preferably the modifying monomer unit is ;
kept below 5 percent. Suitable modifying monomers for the -polyvinyl compounds are vinyl acetate, vinyl ethers, vinyl acrylate, vinyl pyridine, vinyl benzene, vinyl chlorobenzenes, vinyl methacrylates, ethylene vinyl acetate copolymers, poly- `
vinyl pyridine 9 propylene vinyl acetate, polyvinyl acrylates and polyvinyl benzenes.
me following e~amples illustrate but do not limit the scope o~ our invention. All references are to weight percent where not otherwise specified.
To a mixture of 4 . 40 pounds of dimethyl terephthalate and 4. 50 pounds of tetramethylene glycol was added 3.0 grams of litharge catalyst (0.15 weight percent based on dimethyl tereph-thalate). The transesteri~ication was carried out in a 12 liter glass reactor with agitation over a four hour period at a temperature ranging from 140 C. to 235 C. The transesterification product was then transferred into a stainless steel polymeriza-tion reactor and polycondensed under 0.5 -to 1.5 millimeters of mercury pressure at a temperature ranging from 235 C. at ~ .
~ C~S96~S~
the star-t of the reaction to 259 C. at the end of the reaction. The polycondensation product, poly(-tetramethylene terephthalate), had an intrinsic viscosity of 0.795 measured at 30 C. in a 60/40 phenol/s-tetrachloroethane mixture.
EX~MPLE 2 Preparation of Polytetramethylene Terephthalate~
Isophthalate~Sebaca-te (70110 LO Mol ~ CoEolyester To a glass esterification reactor was added 1.82 pounds sebacic acid, 0.73 pound isophthalic acid and 5.114 pounds tereph-thalic acid, to which was added 9.82 pounds (tetramethylene glycol and 10.27 grams lead ace-tate trihydrate catalyst. The esterification reaction was carried out at a temperature ranging from 198 C. at the start o~ the reaction to 240 C. at the end over a six hour period.
The glycol esters were -then transferred to a polycondensa-tion stainless steel reactor and polycondensed at a pressure of 0.1 millimeter of mercury over a three hour period at a temperature in the range of 240 to 255 C.
to yield a 70/10/20 molar ratio poly(tetramethylene -terephthalate/isophthalate/sebacate copolyester having an intrinsic viscosity of 0.875.
~ '~ ', ' Three and one half pounds of the poly(te-tra-methylene terephthalate) prepared in Example 1 and 3.5 pounds of the poly(tetramethylene terephthalate/isoph-thalate/
sebacate) copolyes-ter prepared in Example 2 were added to a small double cone blender-dryer. Then 95.3 grams of the hindered phenolic phosphite described in Example 1 of U. S.
pa-tent 3,386,952 were added and the mixture tumbled in a f~
~". ' . . .
105967~
blender-dryer at 170 C. for two hours under a reduced pressure of 0.1 millime-ter of mercury.
me copolyester-homopolyester blend prepared in Example 3 was dry blended with 10 percent by weight of a rigid polyvinyl chloridè having an intrinsic viscosity of 0.68 as measured in cyclohexanone solvent having a resin concentration of 0.2 grams per 100 cubic centimeters o~
solvent at 30 C. and 5 percent by weight of tetrabromo-phthalic anhydride. This dry blended composition was then extrusion coated onto a 0.021 inch diameter electrical conducting wire. The coating thickness average 0.01 inch and was smooth and free of cracks. The coated wire was then subjected to the Underwriter's Horizontal Flame Test. The burning rate for this sample was found to be 2 inches/
minute.
An experiment was carried out similar to Example
4 above except 5 percent by weight of antimony trioxide was employed in place of the tetrabromophthalic anhydride. The burning rate for this sample was found to be 3.Q inches/
minute.
A control experiment was carried out on an extrusion coated wire mploying as the coating material the blend prepared in Example 3. This blend as employed did not contain any mixture of polyvinyl chloride and tetrabromophthalic anhydride or antimony trioxide. This coating, in the absence of the additive mixture, exhibited a burning rate of 7.5 inches/minu-te.
~' '.
,~,"j `' EXAM ?,LE ,Z
Preparation of Pol~5Ethylene Terephthalate~
~ive pounds dimethyl terephthalate and 3.57 pounds ethylene glycol and an amount of manganese octoate catalyst containing 0.0756 gram manganese (calculated as manganese metal) were charged into a reaction vessel.
The mixture was stirred and reacted in a nltrogen atmosphere at a tamperature ranging from about 155 C. to about 2400 C. until ester interchange reaction was complete. The mixture was then transferred to a stainless steel reaction vessel and an amount of antimony trioxide polymerization catalyst equivalent to 0.021 gram antimony metal was added. The polycondensation reaction was per~ormed by slowly heating to 2800 C. with stirring as the pressure was reduced to about one millimeter mercury pressure.
After about 10 minutes of polycondensation, 8.o grams of diphenylbenzene phosphonate stabilizer were added. The polycondensation was continued until the polymer had a molecular weight equivalent to an intrinsic viscosity of 0.80.
~ .' .
A blend of 50 percent by weight of the poly (ethylene terephthalate) from E~ample 7 and 50 percent by weight of the poly(tetramethylene terephthalate/lsophtha-late/sebacate) copolyester from Example 2 were added in ground form to a small double cone blender-dryer. Then 2 percent by weight~ based on the weight of the blend~ of the hindered phenolic phosphite stabilizer described in Example 1 of U. S~ patent 3,386,952 was added and the ;` ~
_9_ ' ~5~9676 mixture tumbled in the blender-dryer at loO C. for 2.5 hours at about 1 millimeter of mercury pressure. An electrical conducting wire~ 0.021 inch in diameter~ was e~trusion coated with this control mixture to give a coating of 15 mils wall thickness. The burning rate of this control sample in the Underwriters' Horizontal Flame Tester was over 7 inches/minute.
The copolyester-homopolyester blend prepared in Example 8 was then dry blended with 5 percent by weight of antimony trioxide, 5 percent by weight o~ polyvinyl chloride having an intrinsic viscosity of 0.68 and 5 J` -percent by weight of chlorendic acid anhydrlde (Chlora~ `
542~. This dry blended composition was extrusion coated onto a 0.021 inch diameter electrical conducting wire as a 0.01 inch wall thickness coating. The burning rate of this sample was 4 inches/minute.
The Underwriters' Horizontal Flame Test was used to evaluate the ~lame retardancy of the compositions o~ this invention. In this test a sample of coated wirff 20 inches long is laid and held tautly in a horizontal position on supports approximately 8 inches apart.
Distances of 2, 7 a~d 13 inches are marked from one end of the sample. A Bunsen burner, with a vertical flame height of 2 inches with the inner blue cone of the flame one third the vertical flame height~ is employed as the source of ignition. The burner is placed in a vertical position under the sample so that the inner blu~ cone of the flame just touches the und~r side of the sample at the ' ~
. ~ , .
lC~S967~
2 inch mark. The flame is directed against the sample for a period of 30 seconds and removed. During this test observation was made to determine the rate of burning of the sample within the marked 6 inch length and whether or not any burning particles fell from the samples. Control samples were also run to determine the degree of improved flame retardancy.
As employed throughout this disclosure the intrinsic viscosit~ is defined as limit ln (~r) as C
approaches zero in which ~ r is the viscos~ty of a dilute solution of the resin in a 60/40 phenol/s-tetrachloroethane solvent mixture in the same units at the same temperature.
For the intrinsic viscosities reported in this specifica-tion a sufficient sample of each resin was dissolved in a 60/40 phenol/s-tetrachloroethane solvent mixture to form a solution having a resin concentration of appxoximately 0.~ gram per 100 cubic centimeters of solution. The time ~ ~ -of flow of each solution and of the solvent was measured in a No. 1 Ubbelohde Viscometer at 30.00 C. and these times were used in the respective viscosities i~ the equation above.
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 therein without departing from the spirit or scope of the invention.
..~ .
-11 - .' ,,;
minute.
A control experiment was carried out on an extrusion coated wire mploying as the coating material the blend prepared in Example 3. This blend as employed did not contain any mixture of polyvinyl chloride and tetrabromophthalic anhydride or antimony trioxide. This coating, in the absence of the additive mixture, exhibited a burning rate of 7.5 inches/minu-te.
~' '.
,~,"j `' EXAM ?,LE ,Z
Preparation of Pol~5Ethylene Terephthalate~
~ive pounds dimethyl terephthalate and 3.57 pounds ethylene glycol and an amount of manganese octoate catalyst containing 0.0756 gram manganese (calculated as manganese metal) were charged into a reaction vessel.
The mixture was stirred and reacted in a nltrogen atmosphere at a tamperature ranging from about 155 C. to about 2400 C. until ester interchange reaction was complete. The mixture was then transferred to a stainless steel reaction vessel and an amount of antimony trioxide polymerization catalyst equivalent to 0.021 gram antimony metal was added. The polycondensation reaction was per~ormed by slowly heating to 2800 C. with stirring as the pressure was reduced to about one millimeter mercury pressure.
After about 10 minutes of polycondensation, 8.o grams of diphenylbenzene phosphonate stabilizer were added. The polycondensation was continued until the polymer had a molecular weight equivalent to an intrinsic viscosity of 0.80.
~ .' .
A blend of 50 percent by weight of the poly (ethylene terephthalate) from E~ample 7 and 50 percent by weight of the poly(tetramethylene terephthalate/lsophtha-late/sebacate) copolyester from Example 2 were added in ground form to a small double cone blender-dryer. Then 2 percent by weight~ based on the weight of the blend~ of the hindered phenolic phosphite stabilizer described in Example 1 of U. S~ patent 3,386,952 was added and the ;` ~
_9_ ' ~5~9676 mixture tumbled in the blender-dryer at loO C. for 2.5 hours at about 1 millimeter of mercury pressure. An electrical conducting wire~ 0.021 inch in diameter~ was e~trusion coated with this control mixture to give a coating of 15 mils wall thickness. The burning rate of this control sample in the Underwriters' Horizontal Flame Tester was over 7 inches/minute.
The copolyester-homopolyester blend prepared in Example 8 was then dry blended with 5 percent by weight of antimony trioxide, 5 percent by weight o~ polyvinyl chloride having an intrinsic viscosity of 0.68 and 5 J` -percent by weight of chlorendic acid anhydrlde (Chlora~ `
542~. This dry blended composition was extrusion coated onto a 0.021 inch diameter electrical conducting wire as a 0.01 inch wall thickness coating. The burning rate of this sample was 4 inches/minute.
The Underwriters' Horizontal Flame Test was used to evaluate the ~lame retardancy of the compositions o~ this invention. In this test a sample of coated wirff 20 inches long is laid and held tautly in a horizontal position on supports approximately 8 inches apart.
Distances of 2, 7 a~d 13 inches are marked from one end of the sample. A Bunsen burner, with a vertical flame height of 2 inches with the inner blue cone of the flame one third the vertical flame height~ is employed as the source of ignition. The burner is placed in a vertical position under the sample so that the inner blu~ cone of the flame just touches the und~r side of the sample at the ' ~
. ~ , .
lC~S967~
2 inch mark. The flame is directed against the sample for a period of 30 seconds and removed. During this test observation was made to determine the rate of burning of the sample within the marked 6 inch length and whether or not any burning particles fell from the samples. Control samples were also run to determine the degree of improved flame retardancy.
As employed throughout this disclosure the intrinsic viscosit~ is defined as limit ln (~r) as C
approaches zero in which ~ r is the viscos~ty of a dilute solution of the resin in a 60/40 phenol/s-tetrachloroethane solvent mixture in the same units at the same temperature.
For the intrinsic viscosities reported in this specifica-tion a sufficient sample of each resin was dissolved in a 60/40 phenol/s-tetrachloroethane solvent mixture to form a solution having a resin concentration of appxoximately 0.~ gram per 100 cubic centimeters of solution. The time ~ ~ -of flow of each solution and of the solvent was measured in a No. 1 Ubbelohde Viscometer at 30.00 C. and these times were used in the respective viscosities i~ the equation above.
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 therein without departing from the spirit or scope of the invention.
..~ .
-11 - .' ,,;
Claims (10)
1. Flame retardant linear polyester composi-tions comprising blends of (A) a high molecular weight essentially linear polyester selected from the group consisting of copolyesters having intrinsic viscosities of at least 0.5 and blends of from 75 to 25 percent by weight of copolyester and from 25 to 75 percent by weight of homopolyesters each of which have intrinsic viscosities of at least 0.5 and is derived from aromatic dicarboxylic acids or a lower alkyl ester thereof with a glycol, the intrinsic viscosity of said copolyester and said homo-polyester being determined in a 60/40 phenol/s-tetrachloro-ethane solvent mixture having a resin concentration of 0.4 gram per 100 cubic centimeters of solution at 30.0°C.-and (B) a synergistic mixture comprised of from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of polyvinyl chloride having an intrinsic viscosity of from 0.6 to 1.2 as measured in cyclohexanone solvent having a resin concentration of 0.2 gram per 100 cubic centimeters of solution at 30°C. and from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of at least one material selected from the group consisting of antimony trioxide, boron trioxide, tetrabromophthalic anhydride, tetrachlor-phthalic anhydride and chlorendic acid anhydride.
2. The flame retardant essentially linear polyester compositions of claim l wherein (A) is a blend comprised of from 25 to 75 percent by weight, based on the total weight of the blend, of a copolyester having an intrinsic viscosity of at least 0.7 and from 75 to 25 percent by weight, based on the total weight of the blend, of a homopolyester having an intrinsic viscosity of at least 0.7, the intrinsic viscosity of the copolyester and of the homopolyester being determined in a 60/40 phenol/
s-tetrachloroethane solvent mixture at 30.0° C.
s-tetrachloroethane solvent mixture at 30.0° C.
3. The flame retardant linear polyester compositions of Claim 2 wherein (A) is a blend of poly (tetramethylene terephthalate/isophthalate/sebacate) and poly(tetramethylene terephthalate).
4. The flame retardant linear polyester compositions of Claim 2 wherein (A) is a blend of poly (tetramethylene terephthalate/isophthalate/sebacate and poly(ethylene terephthalate).
5. The flame retardant essentially linear polyester compositions of Claim 1 wherein (B) is a synergistic mixture comprised of from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of polyvinyl chloride and from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of a material selected from the group consisting of antimony trioxide and tetrabromophthalic anhydride.
6. The flame retardant linear polyester compositions of Claim 1 wherein the polyvinyl chloride compound of the synergistic mixture (B) is an essentially rigid polyvinyl chloride having an intrinsic viscosity ranging from 0.6 to 1.2 as measured in cyclohexanone solvent having a resin concentration of 0.2 grams per 100 cubic centimeters of solution at 30.0° C.
7. The flame retardant linear polyester compositions of Claim 1 in the form of a fiber.
8. The flame retardant linear polyester compositions of Claim 1 in the form of a film.
9. The flame retardant linear polyester compositions of Claim 1 in the form of a molded article.
10. A coating of flame retardant linear polyester compositions comprising (A) a high molecular weight essentially linear polyester selected from the group consisting of copolyesters having intrinsic viscosities of at least 0.5 and blends of from 75 to 25 percent by weight of copolyester and from 25 to 75 percent by weight of homopolyesters each of which have intrinsic viscosities of at least 0.5 the intrinsic viscosity of said copolyester and said homopolyester being determined in a 60/40 phenol/
s-tetrachloroethane solvent mixture having a resin concentration of 0.4 gram per 100 cubic centimeters of solution at 30.0° C. and (B) a synergistic mixture comprised of from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of polyvinyl chloride having an intrinsic viscosity of from 0.6 to 1.2 as measured in cyclohexanone solvent having a resin concentration of 0.2 gram per 100 cubic centimeters of solution at 30° C. and from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of at least one material selected from the group consisting of antimony trioxide, boron trioxide, tetrabromophthalic anhydride, tetrachlorphthalic anhydride and chlorendic acid anhydride on a substrate.
s-tetrachloroethane solvent mixture having a resin concentration of 0.4 gram per 100 cubic centimeters of solution at 30.0° C. and (B) a synergistic mixture comprised of from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of polyvinyl chloride having an intrinsic viscosity of from 0.6 to 1.2 as measured in cyclohexanone solvent having a resin concentration of 0.2 gram per 100 cubic centimeters of solution at 30° C. and from 5 to 10 percent by weight, based on the total weight of said polyester compositions, of at least one material selected from the group consisting of antimony trioxide, boron trioxide, tetrabromophthalic anhydride, tetrachlorphthalic anhydride and chlorendic acid anhydride on a substrate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US37012573A | 1973-06-14 | 1973-06-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1059676A true CA1059676A (en) | 1979-07-31 |
Family
ID=23458330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA200,006A Expired CA1059676A (en) | 1973-06-14 | 1974-05-15 | Flame retardant polyester compositions |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5043153A (en) |
| CA (1) | CA1059676A (en) |
| DE (1) | DE2428533A1 (en) |
| FR (1) | FR2233368B1 (en) |
| GB (1) | GB1417535A (en) |
| IT (1) | IT1013417B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2515473B2 (en) * | 1975-04-09 | 1978-11-23 | Basf Ag, 6700 Ludwigshafen | Flameproof, linear polyesters |
| CH594715A5 (en) | 1976-02-26 | 1978-01-31 | Ciba Geigy Ag | |
| DE2908949C2 (en) * | 1979-03-07 | 1982-07-15 | Amazonen-Werke H. Dreyer Gmbh & Co Kg, 4507 Hasbergen | Centrifugal fertilizer spreader |
| US4259458A (en) * | 1979-08-09 | 1981-03-31 | Union Carbide Corporation | Polyarylate containing blends |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3718715A (en) * | 1971-05-19 | 1973-02-27 | Du Pont | Blends of thermoplastic copolyester elastomers with vinyl chloride polymers |
| US4013613A (en) * | 1971-10-01 | 1977-03-22 | General Electric Company | Reinforced intercrystalline thermoplastic polyester compositions |
-
1974
- 1974-05-15 CA CA200,006A patent/CA1059676A/en not_active Expired
- 1974-05-22 GB GB2278574A patent/GB1417535A/en not_active Expired
- 1974-05-28 FR FR7418373A patent/FR2233368B1/fr not_active Expired
- 1974-06-07 IT IT51450/74A patent/IT1013417B/en active
- 1974-06-13 DE DE19742428533 patent/DE2428533A1/en not_active Withdrawn
- 1974-06-13 JP JP49067612A patent/JPS5043153A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2428533A1 (en) | 1975-02-13 |
| JPS5043153A (en) | 1975-04-18 |
| IT1013417B (en) | 1977-03-30 |
| FR2233368B1 (en) | 1978-10-13 |
| FR2233368A1 (en) | 1975-01-10 |
| GB1417535A (en) | 1975-12-10 |
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