CA2183662A1 - Flame-retardant recycled polyester compositions - Google Patents
Flame-retardant recycled polyester compositionsInfo
- Publication number
- CA2183662A1 CA2183662A1 CA002183662A CA2183662A CA2183662A1 CA 2183662 A1 CA2183662 A1 CA 2183662A1 CA 002183662 A CA002183662 A CA 002183662A CA 2183662 A CA2183662 A CA 2183662A CA 2183662 A1 CA2183662 A1 CA 2183662A1
- Authority
- CA
- Canada
- Prior art keywords
- phosphinic acid
- polyester
- carboxy
- carboxyethyl
- recycled
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A flame-retardant linear polyester comprising the product of recycled polyesters such as polyethylene terephthalate and a flame-retarding amount of a carboxy-phosphinic acid, a process for producing the polyester and products produced from the polyester are disclosed.
Description
wo 95/24445 2 l ~ 3 6 ~ ~ r~l~u~
FJ AM~ R~TARn~NT RT'CyCT.~T2 POLY~TER Cm\qposTTToN~q RAoKt~R~TNr2 OF T~TT~ VFNTInN
This invention relates to new f lame retardant polyester compositions and a method for 5 producing the polyester compositions. More particularly, this invention relates to new flame retardant copolyesters produced from recycled polyesters and to a method f or producing the polyester compo9ition5. More particularly this invention 10 relates to new flame retardant copolyesters produced from recycled polyethylene terPrhth~ 23te and carboxy-pho8phinic acids, a process for producing the copolyesters and shaped articles produced from the copolyesters .
D~('RTPTInN OF TTT~ PRTOR ART
One of the major uses of polyesters is the production of shaped polyester articles and of woven and non-woven textiles such as fabrics, fil2 n~A, staples or yarn and of sheets. In recent years 20 efforts to make textiles less flammable, to improve the safety characteristics of products such as apparel, bedding, home fllrn;~h;ngs, aircraft and automobile interior fabrics and industrial fabrics, have increased. It is alæo reror,n; ~r2 that the 25 textiles may be blends, particularly blends of natural fibers, 6uch as cotton, and synthetic fibers, such as polyesters .
There are various methods known for flame retarding textiles. U.S. Patent 4,034,141 teaches the 3 0 use of brominated rhn~rhr~ramidates to treat combustible materials to impart f ire retardant properties. The combustible materials are fabrics such as cotton, rayon and paper and synthetic fibers such as polyesters. The fire retardant composition is 35 applied by treating the fabric with a solution of the composition, drying the fabric and curing the composition .
WO 95124445 ~18 ~ PCTIUS95102651 o U.S. Patent 3,969,437 teaches the use of a specif ic class of cyclic phosphorus estera to prepare a durable, flame retardant textile finish for cotton-polyester blends. The phosphorus ester used must contain at least one carbon-bonded primary alcohol group, and preferably two or more, plus a pentavalent phosphorus ester group.
Surface treatment to impart flame retardant characteristics, and even the admixture of flame retardant compounds into hardenable shaped compositions, has disadvantages. Surface treatments may be removed by cleaning and admixed ~ , ~q may exude or migrate f rom the product . Theref ore, attempts have been made to ~v~I~ these disadvantages by chemically building flame retardant compounds into the polyester.
U. S . Patent 3, 922, 323 teaches a process for improving the f lame resistance of polyesters, especially unsaturated polyesters, by chemically binding and/or A~1m;~;n~ organic ~hnq~hnrus compounds and, if desired, halogen ~~, ul-ds into the polyesters. ~Ialogen rnnt~;n;n~ at least bicyclic ~hnqphnn; c esters which are free from hydroxy and carboxylic groups are used.
U.S. Patent 3,941,752 teaches a flame retarded, synthetic linear polyester modified with carboxy-phosphinic acids. The linear polyester' is the polyrrnrlPnqation product of a dicarboxlyic acid, a diol and a flame-retarding carboxy-phosphinic acid monomer which may contain hetero atoms.
As the environment has received greater attention, the need for a~high value use for recycled polyester materials has grown. A need remains for flame retardant recycled polyethylene ter~orhth~l ~te materials, with properties e~ual to, or better than, the properties of virgin polyethylene ter~rhth~l ~te, which will ~';nt~;n their flame retardant properties WO gs/244~S 2 ~ 8 3 6 S ~ 7~cl throughout their useful life and for a process to produce such a polyester.
STll~RY OF T~TF Tt~V~NTION
It is an obj ect o$ this invention to provide a flame retardant polyester material, a process to produce the polyester material and shaped articles produced from the polyester.
It is another object of this invention to provide a flame retardant copolyester composition, 10 produced from recycled polyester, in which the flame retardant material is (-~h~ml t-Al 1 y bound within the polymer structure.
These and other obj ects are met by this invention which is directed to copolyesters of 15 recycled polyethylene ter~rhthAl ~te and a carboxy-phosphinic acid monomer which have flame retardant properties. The copolyester is preferably a polyethylene dicarboxylate copolyester having from about 99 . 9~6 to about 90~ by weight of recycled 20 polyethylene ter~rhthAl ate and from about O .19~ to about 1096 by weight of the carboxy-rh~srhi nl C acid monomer. The copolyester is produced by placing the desired amounts of recycled polyethylene terl~rhthAl Ate and carboxy-phosphinic acid in a nitroge~ f illed 25 reactor in the presence of ethylene glycol and a catalyst which is preferably based upon antimony such as, for example, antimony oxide. The reactor is heated to a temperature within the range of f rom about 2630C. to about 293C. for a period of from about 1 3 0 hour to about 3 hours . A vacuum is applied slowly to reduce the pressure to a pressure within the range of f rom about O . 5 to about 1. 0 mm of mercury .
In addition to copolyesters of polyethylene terephthalate, the invention also includes 35 copolyesters of other polyalkylene dicarboxylates such as polybutylene ter~rhthAl ate and polyethylene nArhth;lnAte .
WO 9S124445 2 1 g 3 6 ~ ~ p~
DE.~RTPTION OF l~TR ~ ) EMR-)T)IMRNTS
The present invention relates to copolyesters of recycle~d,polyesters having flamè
retardant properties. The copolyesters of this 5 invention have an intrinsic viscosity greater than about 0.7, and preferably within the range of from about O . 7 to about 1. 2 and a glass transition temperature greater than about 65C. The copolyesters of the preferred recycled polyethylene ter~rhthAl ~t~
10 are preferably a polyethylene dicarboxylate copolyester having from about 99 . 9~ to about 909~ by weight recycled polyethylene ter~rhth~l ~te and from about O .196 to about 1096 by weight of a f lame retarding carboxy-phosphinic acid monomer having the general 15 formula:
O O
Il HO - ~ - R - C - OH
;~1 wherein R is a saturated open-chain or cyclic alkylene radical having f rom one to about 15 carbon atoms, preferably from 2 to about 10 carbon atoms, or an 25 arylene or aralkylene radical such as, for example, methyl, ethyl, propyl, isopropyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, iso-octyl, decyl, isodecyl, dodecyl, tetradecyl, -C6H,-, -C6H~-CH2-, and -C6H4-CH2-CH2-, and Rl is an alkyl radical 3 0 having up to about 6 carbon atoms, an aryl radical or an alkaryl radical wherein the alkyl substituent has f rom 1 to about 6 carbon atoms such as, f or example, methyl, ethyl and n- and i-propyl . The carboxy-phosphinic acid is preferably 2-carboxyethyl 35 (phenyl) phosphinic acid, 2-carboxyethyl (methyl) phosphinic acid, the cyclic anhydride of 2-uclrbu~Ly~:thyl (phenyl)phosphinic acid or the cyclic anhydride of 2 - carboxyethyl (methyl ) rh~rh i n i c acid .
WO 9S/2444S ~ ~ 8 3 ~ PCTlUSgSI02651 Polymerization of 90g6 by weight recycled polyethylene ter.orhth~l ~te and 109~ by weight 2-carboxyethyl (phenyl)pho8phinic acid produced a flame retardant polyester having an intrinsic viscosity of 5 about 0 . 70 . The polyester, however, had a slight drop in the glass transition temperature, the melting point and the crystallinity when compared to virgin polyethylene terPrhth~l ~te, but the color of the polyester was improved.
Recycling polyethylene ter~rhth~l ~te produces a polyester which has a lower molecular weight than virgin polyethylene ter~rhth~l ~te. The inclusion of the rhnsph;n;c acid moiety in the process of this invention promotes chain bonding to produce 15 longer carbon chains and, thus, higher molecular weights . The; nrl~Rl nn of the phosphinic acid moiety is a complex process in which the intrinsic visc06ity of the process fluid drops originally from the viscosity of the polyethylene ter,orhth~l ~t~ to as low 20 as about 0.25 before it begins to rise and the intrinsic viscosity of the copolyester may reach as hiyh as about 1. 2 if the process is allowed to go to completion .
The preferred acid, 2-carboxyethyl (phenyl) 25 phosphinic acid, may be prepared in accordance with the t~2nh;n~ in U.S. Patent 4, 081,463 . The 2 -carboxyethyl (phenyl ) rhnsrh; n; C acid is prepared in two stages by first reacting dichloro(phenyl)rhnsph;n~
with acrylic acid employed at a molar excess of 25 30 to 459~ to form a mixture of three int~L, ';~t"c, 3-( chlorophenylphosphinyl ) propionyl chloride, the cyclic anhydride of 2-~:cLLLu~y~thyl (phenyl) phosphinic acid and the mixed anhydride of acrylic acid with 3-chlorocarbonylethyl (phenyl)phosphinic acid. The 35 second stage of the process is the hydrolysis of the of the mixture of the three ; nt~ t~R to obtain the desired product, 2-~ b-~yc:thyl(phenyl)rhnsrh;n;c acid .
WO 95/24441i ~ 1 ~ 3 ~ fi 2 PCT/lJS9!;/026~i1 The f lame retardant copolyesters of recycled polyethylene ter~rhth~l ~te are preferably polyethylene dicarboxylate copcl'yesters having from about 99 . 996 to 90% by weight recycled polyethylene terPrhth~l ~te and from about 0.196 to about 10% of the flame retarding 2-carboxyethyl (phenyl)phosphinic acid, or the cyclic anhydride thereof. ~ i The desired polyester of this invention may be produced by the polymerization of from about~ 99.996 to about 90~6 by weight recycled polyethylene ter~rhth~l ~te and from about O .19~ to about 1096 by weight of 2-uc~Lbu~Ly~thyl(phenyl)rhn~rh;n;c acid. The expected decrease in reactivity during the polymerization reaction, resulting from the ~ l;t;nn of the phosphinic acid rather than another carbonyl acid group, was not observed. The high molecular weight of the product polyester indicated that the phosphinic acid group was highly reactive and the end-group analysis did not show terminal rhnsph;n;c~ acid groups in a high proportion. Further, the addition of E~hn8rhnrug ,~ ~C usually creates additional observable color in the product. Surprisingly, the addition of the carboxy-phnsph;n;c acid in this invention allowed the use of higher amounts of catalyst and still had less color in the product than polyesters produced without the included acid.
The copolyesters were produced by placing the desired amounts of recycled polyethylene ter~rhth~l~te and 2-carboxyethyl(phenyl)rhnsph; jn;c 3 0 acid in a nitrogen f illed reactor in the presence of ethylene glycol and a catalyst which is pref erably antimony oxide. The reactor was heated to a temperature within a range of from about 250C. to about 293C., preferably within a range of from about 263C. to about 293C., for a period of from about 1 hour to about 3 hours. A vacuum was applied slowly to reduce the pressure to a pressure of from about 0 . 5 to about 1.0 mm of mercury. The reaction rnnt;nllPd at wo gs/24445 ~ 1 8 3 6 6 ~ F~ IlU . ;A Sl those conditions for an additional 45 minutes before the heat and vacuum were removed.
Ethylene glycol was used in the description of the process and it is the preferred diol. However, 5 other aliphatic diols such as, for example, iql irhi~ti c diols having from 3 to about 7 carbon atoms, may also be used.
The carboxy-~hnsrh;n;c acid and its cyclic anhydride are not volatile under the process conditions for production of the polyesters so they can be incorporated in the polyester by inclusion in the ~nn~i~nRatiOn reaction. When incorporated into the molecule during the cnnfi~nci~t;nn reaction the ~hngrhr~ru6 rnnti~;n;n~ structural unit is randomly distributed in the linear polyester product.
The polyesters of this invention may be made into shaped articles . They may be spun into f; 1 i t c and f ibers using well known processes and the standard additional tr~ c. The polyesters may also be extruded into sheets or formed into shaped articles which may be solid or hollow by press molding, injection molding and extrusion. All of these shaped articles (fibers, sheets and other shapes) are also an object of this invention.
The fibers and f;l; c have very good and permanent flame retardant and self-extinguishing properties. Since they have a good degree of whiteness, they have very good dyeing properties for disperse dyestuf f s and their receptivity includes acid 3 o dyestuf f s in color shades of average to deep intensity. The tensile gtrength of the f;li tc and f ibers, second order transition temperature and melting point apprn~r; r -t~l y correspond to the values for polyesters which do not contain the flame retardant carboxy-~hncrh;nic acid. The fibers and f;l: tc are generally usefu- for appl;ci~t;nnc where readily ignitable textiles cannot be tolerated and it is possible to use these fibers in c ' ;ni~t;on with Wo 95l2444s 2 ~ S ~ PCTiUS95/0265 natural fibers, such as cotton, and other synthetic f ibers .
Sheets and shaped articles produced f rom the flame retardant polyester are generally used in 5 locations where it is desired to reduce the possible serious risks if ignition and a fire occur. If; the transparency of the shaped articles is not of concern, their solidity and flame retarding properties can be ~nhAnr-~r1 by the inclusion of inorganic fiber materials 10 such as, for example, glass and quartz fibers and carbon in the usual quantities, in the polyester before molding.
This invention will be ~rlA; n~d in detail in accordance with the examples below, which are for 15 illustrative purposes only and shall not limit the present invention.
El~7~MPl.~ 1 After the label was removed, a polyethylene ter~rhthAl Ate bottle, such as those which contain soft 20 drinks, was washed with detergent and water, cut into pieces and dried at a temperature of about 60C. for 7 hours in a vacuum oven. A mixture of 18 grams of recycled bottle polyethylene ter~rhthAl Ate, 2 grams of 2-carboxyethyl(phenyl)rhn~h;n;c acid, 3.2 grams of 25 ethylene glycol and 0.02 grams of Ant; y oxide was placed within a 50 milliliter flask with a stainless steel stirrer . The f lask had a nitrogen inlet and outlet and a provision for pulling a vacuum. The flask was evacuated and filled with nitrogen 3 times 30 at room temperature and then a continuous, slow flow of nitrogen was m~;ntA;n~tl through the flask. The flask was placed in a salt bath which had been preheated to about 250C. The temperature of the salt bath was raised from 250C. to about 285C over a 35 period of about 1. 5 hours and ethylene glycol was distilled off. The pressure was then reduced to 150 millitorr over a period of about 1 hour. The pressure in the flask was further reduced to about 50 millitorr 21~6~2 Wo 95/~4445 ! _ . r~ u",~
over a period of about 3 0 minutes and the reaction was continued at these conditions for an additional 45 minutes at which time the heat and vacuum were removed. The resulting copolymer had an intrinsic 5 viscosity of 0.85 at a cr~n~Pnt~ation of 0.5 grams/deciliter in a solution of 60~ phenol/40~
tetrachloroethane at 25C. The glass transition temperature was determined to be 69C. by differential scanning calorimeter.
T~MPLT~ 2 The reaction of Example 1 was modified. In this reaction, 19 grams of recycled bottle polyethylene ter~rhthAl Ate, 1 gram of 2-carboxyethyl (phenyl ) ~h- 8rh; n; c acid and 1. 6 grams of 15 ethylene glycol were reacted in the presence of o . 004 grams of antimony oxide. The conditions of the reaction were as set f orth in ~xamplé 1 above . The reEulting copolymer had an intrinsic viscosity of O . 83 at a c~ln~ntration of 0.5 grams/deciliter in a solution of 609~ phenol/40~ tetrachloroethane at 25C.
The glass transition temperature was determined to be 6 9 . 8 C . by dif f erential scanning calorimeter .
E~PT.~ 3 In this reaction, 19.4 grams of recycled bottle polyethylene ter~rhthAl Ate, O . 6 grams of 2-carboxyethyl (phenyl)phosphinic acid and O .41 grams of ethylene glycol were reacted in the presence of o . 004 grams of antimony oxide. The conditions of the reaction were as set forth in Example 1 above. The 3 0 resulting copolymer had an intrinsic viscosity of O . 93 at a cr~n~ontration of O . 5 grams/deciliter in a solution of 60~ phenol/40~ tetrachloroethane at 25C.
The glass transition temperature was ~l~t~rrn; n/~d to be 6 9 . 5 0 C . by di f f erent i al s canning cal orimet er .
3 5 The polyesters produced in Examples 1 and 2 were tested f or their f lame retarding properties . The limiting oxygen index (LOI) was measured to be:
WO 95/24445 ~ '~ 8 3 6 6 ~ PCTIUS95/02651 23.4 for recycled polyethylene ter-~rhth~l~te without additives;
26 . 9 for the flame retardant polyethylene ter~phth~l ~te copolymer produced in Example 1; and 25.4 for the flame retardant polyethylene ter~rhth~l ~te copolymer produced in Example 2 .
These numbers are relative numbers which ~how the ; _ uv. t in the flame retardant properties provided by the inclusion of the carboxy-rhnsrh; n; C acid moiety in the polyethylene ter~rhth~l ~te copolymer. The numbers are not absolute numbers as the test was not performed in accordance with ASTM standard procedures.
A strand of each material was tested instead of the molded tensile bars required by the ASTM procedures.
Conforming to the ASTM re~auirements might change the numbers shown above; however, it is believed that the results of such a test would still indicate a similar ; ,_uvl ~ in the flame retardant properties.
While certain preferred ~ R of the invention have been illustrated and described herein, it is to be understood that the invention is not limited thereby and that the invention may be ~
variously practiced within the scope of the following claims .
FJ AM~ R~TARn~NT RT'CyCT.~T2 POLY~TER Cm\qposTTToN~q RAoKt~R~TNr2 OF T~TT~ VFNTInN
This invention relates to new f lame retardant polyester compositions and a method for 5 producing the polyester compositions. More particularly, this invention relates to new flame retardant copolyesters produced from recycled polyesters and to a method f or producing the polyester compo9ition5. More particularly this invention 10 relates to new flame retardant copolyesters produced from recycled polyethylene terPrhth~ 23te and carboxy-pho8phinic acids, a process for producing the copolyesters and shaped articles produced from the copolyesters .
D~('RTPTInN OF TTT~ PRTOR ART
One of the major uses of polyesters is the production of shaped polyester articles and of woven and non-woven textiles such as fabrics, fil2 n~A, staples or yarn and of sheets. In recent years 20 efforts to make textiles less flammable, to improve the safety characteristics of products such as apparel, bedding, home fllrn;~h;ngs, aircraft and automobile interior fabrics and industrial fabrics, have increased. It is alæo reror,n; ~r2 that the 25 textiles may be blends, particularly blends of natural fibers, 6uch as cotton, and synthetic fibers, such as polyesters .
There are various methods known for flame retarding textiles. U.S. Patent 4,034,141 teaches the 3 0 use of brominated rhn~rhr~ramidates to treat combustible materials to impart f ire retardant properties. The combustible materials are fabrics such as cotton, rayon and paper and synthetic fibers such as polyesters. The fire retardant composition is 35 applied by treating the fabric with a solution of the composition, drying the fabric and curing the composition .
WO 95124445 ~18 ~ PCTIUS95102651 o U.S. Patent 3,969,437 teaches the use of a specif ic class of cyclic phosphorus estera to prepare a durable, flame retardant textile finish for cotton-polyester blends. The phosphorus ester used must contain at least one carbon-bonded primary alcohol group, and preferably two or more, plus a pentavalent phosphorus ester group.
Surface treatment to impart flame retardant characteristics, and even the admixture of flame retardant compounds into hardenable shaped compositions, has disadvantages. Surface treatments may be removed by cleaning and admixed ~ , ~q may exude or migrate f rom the product . Theref ore, attempts have been made to ~v~I~ these disadvantages by chemically building flame retardant compounds into the polyester.
U. S . Patent 3, 922, 323 teaches a process for improving the f lame resistance of polyesters, especially unsaturated polyesters, by chemically binding and/or A~1m;~;n~ organic ~hnq~hnrus compounds and, if desired, halogen ~~, ul-ds into the polyesters. ~Ialogen rnnt~;n;n~ at least bicyclic ~hnqphnn; c esters which are free from hydroxy and carboxylic groups are used.
U.S. Patent 3,941,752 teaches a flame retarded, synthetic linear polyester modified with carboxy-phosphinic acids. The linear polyester' is the polyrrnrlPnqation product of a dicarboxlyic acid, a diol and a flame-retarding carboxy-phosphinic acid monomer which may contain hetero atoms.
As the environment has received greater attention, the need for a~high value use for recycled polyester materials has grown. A need remains for flame retardant recycled polyethylene ter~orhth~l ~te materials, with properties e~ual to, or better than, the properties of virgin polyethylene ter~rhth~l ~te, which will ~';nt~;n their flame retardant properties WO gs/244~S 2 ~ 8 3 6 S ~ 7~cl throughout their useful life and for a process to produce such a polyester.
STll~RY OF T~TF Tt~V~NTION
It is an obj ect o$ this invention to provide a flame retardant polyester material, a process to produce the polyester material and shaped articles produced from the polyester.
It is another object of this invention to provide a flame retardant copolyester composition, 10 produced from recycled polyester, in which the flame retardant material is (-~h~ml t-Al 1 y bound within the polymer structure.
These and other obj ects are met by this invention which is directed to copolyesters of 15 recycled polyethylene ter~rhthAl ~te and a carboxy-phosphinic acid monomer which have flame retardant properties. The copolyester is preferably a polyethylene dicarboxylate copolyester having from about 99 . 9~6 to about 90~ by weight of recycled 20 polyethylene ter~rhthAl ate and from about O .19~ to about 1096 by weight of the carboxy-rh~srhi nl C acid monomer. The copolyester is produced by placing the desired amounts of recycled polyethylene terl~rhthAl Ate and carboxy-phosphinic acid in a nitroge~ f illed 25 reactor in the presence of ethylene glycol and a catalyst which is preferably based upon antimony such as, for example, antimony oxide. The reactor is heated to a temperature within the range of f rom about 2630C. to about 293C. for a period of from about 1 3 0 hour to about 3 hours . A vacuum is applied slowly to reduce the pressure to a pressure within the range of f rom about O . 5 to about 1. 0 mm of mercury .
In addition to copolyesters of polyethylene terephthalate, the invention also includes 35 copolyesters of other polyalkylene dicarboxylates such as polybutylene ter~rhthAl ate and polyethylene nArhth;lnAte .
WO 9S124445 2 1 g 3 6 ~ ~ p~
DE.~RTPTION OF l~TR ~ ) EMR-)T)IMRNTS
The present invention relates to copolyesters of recycle~d,polyesters having flamè
retardant properties. The copolyesters of this 5 invention have an intrinsic viscosity greater than about 0.7, and preferably within the range of from about O . 7 to about 1. 2 and a glass transition temperature greater than about 65C. The copolyesters of the preferred recycled polyethylene ter~rhthAl ~t~
10 are preferably a polyethylene dicarboxylate copolyester having from about 99 . 9~ to about 909~ by weight recycled polyethylene ter~rhth~l ~te and from about O .196 to about 1096 by weight of a f lame retarding carboxy-phosphinic acid monomer having the general 15 formula:
O O
Il HO - ~ - R - C - OH
;~1 wherein R is a saturated open-chain or cyclic alkylene radical having f rom one to about 15 carbon atoms, preferably from 2 to about 10 carbon atoms, or an 25 arylene or aralkylene radical such as, for example, methyl, ethyl, propyl, isopropyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, iso-octyl, decyl, isodecyl, dodecyl, tetradecyl, -C6H,-, -C6H~-CH2-, and -C6H4-CH2-CH2-, and Rl is an alkyl radical 3 0 having up to about 6 carbon atoms, an aryl radical or an alkaryl radical wherein the alkyl substituent has f rom 1 to about 6 carbon atoms such as, f or example, methyl, ethyl and n- and i-propyl . The carboxy-phosphinic acid is preferably 2-carboxyethyl 35 (phenyl) phosphinic acid, 2-carboxyethyl (methyl) phosphinic acid, the cyclic anhydride of 2-uclrbu~Ly~:thyl (phenyl)phosphinic acid or the cyclic anhydride of 2 - carboxyethyl (methyl ) rh~rh i n i c acid .
WO 9S/2444S ~ ~ 8 3 ~ PCTlUSgSI02651 Polymerization of 90g6 by weight recycled polyethylene ter.orhth~l ~te and 109~ by weight 2-carboxyethyl (phenyl)pho8phinic acid produced a flame retardant polyester having an intrinsic viscosity of 5 about 0 . 70 . The polyester, however, had a slight drop in the glass transition temperature, the melting point and the crystallinity when compared to virgin polyethylene terPrhth~l ~te, but the color of the polyester was improved.
Recycling polyethylene ter~rhth~l ~te produces a polyester which has a lower molecular weight than virgin polyethylene ter~rhth~l ~te. The inclusion of the rhnsph;n;c acid moiety in the process of this invention promotes chain bonding to produce 15 longer carbon chains and, thus, higher molecular weights . The; nrl~Rl nn of the phosphinic acid moiety is a complex process in which the intrinsic visc06ity of the process fluid drops originally from the viscosity of the polyethylene ter,orhth~l ~t~ to as low 20 as about 0.25 before it begins to rise and the intrinsic viscosity of the copolyester may reach as hiyh as about 1. 2 if the process is allowed to go to completion .
The preferred acid, 2-carboxyethyl (phenyl) 25 phosphinic acid, may be prepared in accordance with the t~2nh;n~ in U.S. Patent 4, 081,463 . The 2 -carboxyethyl (phenyl ) rhnsrh; n; C acid is prepared in two stages by first reacting dichloro(phenyl)rhnsph;n~
with acrylic acid employed at a molar excess of 25 30 to 459~ to form a mixture of three int~L, ';~t"c, 3-( chlorophenylphosphinyl ) propionyl chloride, the cyclic anhydride of 2-~:cLLLu~y~thyl (phenyl) phosphinic acid and the mixed anhydride of acrylic acid with 3-chlorocarbonylethyl (phenyl)phosphinic acid. The 35 second stage of the process is the hydrolysis of the of the mixture of the three ; nt~ t~R to obtain the desired product, 2-~ b-~yc:thyl(phenyl)rhnsrh;n;c acid .
WO 95/24441i ~ 1 ~ 3 ~ fi 2 PCT/lJS9!;/026~i1 The f lame retardant copolyesters of recycled polyethylene ter~rhth~l ~te are preferably polyethylene dicarboxylate copcl'yesters having from about 99 . 996 to 90% by weight recycled polyethylene terPrhth~l ~te and from about 0.196 to about 10% of the flame retarding 2-carboxyethyl (phenyl)phosphinic acid, or the cyclic anhydride thereof. ~ i The desired polyester of this invention may be produced by the polymerization of from about~ 99.996 to about 90~6 by weight recycled polyethylene ter~rhth~l ~te and from about O .19~ to about 1096 by weight of 2-uc~Lbu~Ly~thyl(phenyl)rhn~rh;n;c acid. The expected decrease in reactivity during the polymerization reaction, resulting from the ~ l;t;nn of the phosphinic acid rather than another carbonyl acid group, was not observed. The high molecular weight of the product polyester indicated that the phosphinic acid group was highly reactive and the end-group analysis did not show terminal rhnsph;n;c~ acid groups in a high proportion. Further, the addition of E~hn8rhnrug ,~ ~C usually creates additional observable color in the product. Surprisingly, the addition of the carboxy-phnsph;n;c acid in this invention allowed the use of higher amounts of catalyst and still had less color in the product than polyesters produced without the included acid.
The copolyesters were produced by placing the desired amounts of recycled polyethylene ter~rhth~l~te and 2-carboxyethyl(phenyl)rhnsph; jn;c 3 0 acid in a nitrogen f illed reactor in the presence of ethylene glycol and a catalyst which is pref erably antimony oxide. The reactor was heated to a temperature within a range of from about 250C. to about 293C., preferably within a range of from about 263C. to about 293C., for a period of from about 1 hour to about 3 hours. A vacuum was applied slowly to reduce the pressure to a pressure of from about 0 . 5 to about 1.0 mm of mercury. The reaction rnnt;nllPd at wo gs/24445 ~ 1 8 3 6 6 ~ F~ IlU . ;A Sl those conditions for an additional 45 minutes before the heat and vacuum were removed.
Ethylene glycol was used in the description of the process and it is the preferred diol. However, 5 other aliphatic diols such as, for example, iql irhi~ti c diols having from 3 to about 7 carbon atoms, may also be used.
The carboxy-~hnsrh;n;c acid and its cyclic anhydride are not volatile under the process conditions for production of the polyesters so they can be incorporated in the polyester by inclusion in the ~nn~i~nRatiOn reaction. When incorporated into the molecule during the cnnfi~nci~t;nn reaction the ~hngrhr~ru6 rnnti~;n;n~ structural unit is randomly distributed in the linear polyester product.
The polyesters of this invention may be made into shaped articles . They may be spun into f; 1 i t c and f ibers using well known processes and the standard additional tr~ c. The polyesters may also be extruded into sheets or formed into shaped articles which may be solid or hollow by press molding, injection molding and extrusion. All of these shaped articles (fibers, sheets and other shapes) are also an object of this invention.
The fibers and f;l; c have very good and permanent flame retardant and self-extinguishing properties. Since they have a good degree of whiteness, they have very good dyeing properties for disperse dyestuf f s and their receptivity includes acid 3 o dyestuf f s in color shades of average to deep intensity. The tensile gtrength of the f;li tc and f ibers, second order transition temperature and melting point apprn~r; r -t~l y correspond to the values for polyesters which do not contain the flame retardant carboxy-~hncrh;nic acid. The fibers and f;l: tc are generally usefu- for appl;ci~t;nnc where readily ignitable textiles cannot be tolerated and it is possible to use these fibers in c ' ;ni~t;on with Wo 95l2444s 2 ~ S ~ PCTiUS95/0265 natural fibers, such as cotton, and other synthetic f ibers .
Sheets and shaped articles produced f rom the flame retardant polyester are generally used in 5 locations where it is desired to reduce the possible serious risks if ignition and a fire occur. If; the transparency of the shaped articles is not of concern, their solidity and flame retarding properties can be ~nhAnr-~r1 by the inclusion of inorganic fiber materials 10 such as, for example, glass and quartz fibers and carbon in the usual quantities, in the polyester before molding.
This invention will be ~rlA; n~d in detail in accordance with the examples below, which are for 15 illustrative purposes only and shall not limit the present invention.
El~7~MPl.~ 1 After the label was removed, a polyethylene ter~rhthAl Ate bottle, such as those which contain soft 20 drinks, was washed with detergent and water, cut into pieces and dried at a temperature of about 60C. for 7 hours in a vacuum oven. A mixture of 18 grams of recycled bottle polyethylene ter~rhthAl Ate, 2 grams of 2-carboxyethyl(phenyl)rhn~h;n;c acid, 3.2 grams of 25 ethylene glycol and 0.02 grams of Ant; y oxide was placed within a 50 milliliter flask with a stainless steel stirrer . The f lask had a nitrogen inlet and outlet and a provision for pulling a vacuum. The flask was evacuated and filled with nitrogen 3 times 30 at room temperature and then a continuous, slow flow of nitrogen was m~;ntA;n~tl through the flask. The flask was placed in a salt bath which had been preheated to about 250C. The temperature of the salt bath was raised from 250C. to about 285C over a 35 period of about 1. 5 hours and ethylene glycol was distilled off. The pressure was then reduced to 150 millitorr over a period of about 1 hour. The pressure in the flask was further reduced to about 50 millitorr 21~6~2 Wo 95/~4445 ! _ . r~ u",~
over a period of about 3 0 minutes and the reaction was continued at these conditions for an additional 45 minutes at which time the heat and vacuum were removed. The resulting copolymer had an intrinsic 5 viscosity of 0.85 at a cr~n~Pnt~ation of 0.5 grams/deciliter in a solution of 60~ phenol/40~
tetrachloroethane at 25C. The glass transition temperature was determined to be 69C. by differential scanning calorimeter.
T~MPLT~ 2 The reaction of Example 1 was modified. In this reaction, 19 grams of recycled bottle polyethylene ter~rhthAl Ate, 1 gram of 2-carboxyethyl (phenyl ) ~h- 8rh; n; c acid and 1. 6 grams of 15 ethylene glycol were reacted in the presence of o . 004 grams of antimony oxide. The conditions of the reaction were as set f orth in ~xamplé 1 above . The reEulting copolymer had an intrinsic viscosity of O . 83 at a c~ln~ntration of 0.5 grams/deciliter in a solution of 609~ phenol/40~ tetrachloroethane at 25C.
The glass transition temperature was determined to be 6 9 . 8 C . by dif f erential scanning calorimeter .
E~PT.~ 3 In this reaction, 19.4 grams of recycled bottle polyethylene ter~rhthAl Ate, O . 6 grams of 2-carboxyethyl (phenyl)phosphinic acid and O .41 grams of ethylene glycol were reacted in the presence of o . 004 grams of antimony oxide. The conditions of the reaction were as set forth in Example 1 above. The 3 0 resulting copolymer had an intrinsic viscosity of O . 93 at a cr~n~ontration of O . 5 grams/deciliter in a solution of 60~ phenol/40~ tetrachloroethane at 25C.
The glass transition temperature was ~l~t~rrn; n/~d to be 6 9 . 5 0 C . by di f f erent i al s canning cal orimet er .
3 5 The polyesters produced in Examples 1 and 2 were tested f or their f lame retarding properties . The limiting oxygen index (LOI) was measured to be:
WO 95/24445 ~ '~ 8 3 6 6 ~ PCTIUS95/02651 23.4 for recycled polyethylene ter-~rhth~l~te without additives;
26 . 9 for the flame retardant polyethylene ter~phth~l ~te copolymer produced in Example 1; and 25.4 for the flame retardant polyethylene ter~rhth~l ~te copolymer produced in Example 2 .
These numbers are relative numbers which ~how the ; _ uv. t in the flame retardant properties provided by the inclusion of the carboxy-rhnsrh; n; C acid moiety in the polyethylene ter~rhth~l ~te copolymer. The numbers are not absolute numbers as the test was not performed in accordance with ASTM standard procedures.
A strand of each material was tested instead of the molded tensile bars required by the ASTM procedures.
Conforming to the ASTM re~auirements might change the numbers shown above; however, it is believed that the results of such a test would still indicate a similar ; ,_uvl ~ in the flame retardant properties.
While certain preferred ~ R of the invention have been illustrated and described herein, it is to be understood that the invention is not limited thereby and that the invention may be ~
variously practiced within the scope of the following claims .
Claims (22)
1. A flame retardant linear polyester comprising the product of recycled polyester and a flame-retarding amount of a carboxy-phosphinic acid.
2. The flame retardant linear polyester of claim 1 wherein the recycled polyester is recycled polyethylene terephthalate or recycled polybutylene terephthalate.
3. The flame retardant linear polyester of claim 2 wherein the carboxy-phosphinic acid monomer is present in an amount of from about 0.1% to about 10%
by weight based upon the total weight of the polyester.
by weight based upon the total weight of the polyester.
4. The flame retardant linear polyester of claim 3 wherein the carboxy-phosphinic acid monomer is selected from the group consisting of 2-carboxy-ethyl(phenyl)phosphinic acid, 2-carboxyethyl (methyl)phosphinic acid, the cyclic anhydride of 2-carboxyethyl(phenyl)phosphinic acid and the cyclic anhydride of 2-carboxyethyl(methyl) phosphinic acid.
5. The flame retardant linear polyester of claim 4 wherein the carboxy-phosphinic acid monomer is 2-carboxyethyl(phenyl)phosphinic acid.
6. The flame retardant linear polyester of claim 4 wherein the carboxy-phosphinic acid monomer is 2-carboxyethyl(methyl)phosphinic acid.
7. A process for the production of a flame retardant linear polyester comprising condensing a mixture of recycled polyester and a flame-retarding carboxy-phosphinic acid monomer, the carboxy-phosphinic acid monomer being present in an amount of from about 0.1% to about 10% by weight based upon the total weight of said polyester, in the presence of a catalyst at a temperature between about 250°C. and about 293°C.
8. The process of claim 7 wherein the recycled polyester is recycled polyethylene terephthalate or recycled polybutylene terephthalate.
9. The process of claim 7 wherein the carboxy-phosphinic acid monomer is selected from the group consisting of 2-carboxyethyl(phenyl)phosphinic acid, 2-carboxyethyl(methyl)phosphinic acid, the cyclic anhydride of 2-carboxyethyl(phenyl)phosphinic acid and the cyclic anhydride of 2-carboxyethyl (methyl)phosphinic acid.
10. The process of claim 9 wherein the carboxy-phosphinic acid monomer is 2-carboxyethyl (phenyl)phosphinic acid.
11. Shaped articles made from a flame retardant linear polyester comprising the product of recycled polyester and a flame-retarding amount of a carboxy-phosphinic acid.
12. The shaped articles of claim 11 wherein the recycled polyester is recycled polyethylene terephthalate or recycled polybutylene terephthalate.
13. The shaped articles of claim 12 wherein the recycled polyester is recycled polyethylene terephthalate.
14. The shaped articles of claim 11 wherein the carboxy-phosphinic acid is present in an amount of from about 0.1% to about 10% by weight based upon the total amount of the polyester.
15. The shaped articles of claim 14 wherein the carboxy-phosphinic acid monomer is selected from the group consisting of 2-carboxyethyl(phenyl) phosphinic acid, 2-carboxyethyl(methyl)phosphinic acid, the cyclic anhydride of 2-carboxyethyl (phenyl)phosphinic acid and the cyclic anhydride of 2-carboxyethyl(methyl)phosphinic acid.
16. The shaped articles of claim 15 wherein the carboxy-phosphinic acid monomer is 2-carboxyethyl(phenyl)phosphinic acid.
17. Fiber produced from a flame retardant linear polyester comprising the product of recycled polyester and a flame-retarding amount of carboxy-phosphinic acid.
18. The fiber of claim 17 wherein the recycled polyester is recycled polyethylene terephthalate or recycled polybutylene terephthalate.
19. The fiber of claim 18 wherein the recycled polyester is recycled polyethylene terephthalate.
20. The fiber of claim 17 wherein the carboxy-phosphinic acid is present in an amount of from about 0.1% to about 10% by weight based upon the total amount of the polyester.
21. The fiber of claim 20 wherein the carboxy-phosphinic acid monomer is selected from the group consisting of 2-carboxyethyl (phenyl) phosphinic acid, 2-carboxyethyl(methyl)phosphinic acid, the cyclic anhydride of 2-carboxyethyl (phenyl) phosphinic acid and the cyclic anhydride of 2-carboxyethyl (methyl )phosphinic acid.
22. The fiber of claim 21 wherein the carboxy-phosphinic acid monomer is 2-carboxy-ethyl(phenyl)phosphinic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20993194A | 1994-03-11 | 1994-03-11 | |
| US209,931 | 1994-03-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2183662A1 true CA2183662A1 (en) | 1995-09-14 |
Family
ID=22780922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002183662A Abandoned CA2183662A1 (en) | 1994-03-11 | 1995-03-03 | Flame-retardant recycled polyester compositions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0754202A1 (en) |
| JP (1) | JPH09510245A (en) |
| KR (1) | KR970701757A (en) |
| CA (1) | CA2183662A1 (en) |
| MX (1) | MX9604038A (en) |
| TW (1) | TW333542B (en) |
| WO (1) | WO1995024445A2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997035903A1 (en) * | 1996-03-26 | 1997-10-02 | Ems-Inventa Ag | Process for direct chemical modification of (co)polyesters |
| DE102006012881A1 (en) | 2006-03-21 | 2007-09-27 | Clariant International Limited | Phosphorus-containing mixtures, a process for their preparation and their use |
| DE102006012879A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Limited | Phosphorus-containing mixtures, a process for their preparation and their use |
| DE102006012878A1 (en) * | 2006-03-21 | 2007-09-27 | Clariant International Limited | Phosphorus-containing mixtures, a process for their preparation and their use |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2454189C3 (en) * | 1974-11-15 | 1980-08-14 | Hoechst Ag, 6000 Frankfurt | Process for the production of flame-retardant linear polyesters |
| JPS60248646A (en) * | 1984-05-25 | 1985-12-09 | Toray Ind Inc | Depolymerization of waste polyester |
| IT1252236B (en) * | 1991-12-18 | 1995-06-05 | Enichem Sintesi | LINEAR COPOLYESTER CONTAINING PHOSPHORUS, PREPARATION PROCEDURE AND USE AS AN ANTI-FLAME ADDITIVE |
-
1995
- 1995-03-03 MX MX9604038A patent/MX9604038A/en unknown
- 1995-03-03 KR KR1019960705013A patent/KR970701757A/en not_active Application Discontinuation
- 1995-03-03 EP EP95912042A patent/EP0754202A1/en not_active Withdrawn
- 1995-03-03 WO PCT/US1995/002651 patent/WO1995024445A2/en not_active Application Discontinuation
- 1995-03-03 JP JP7523534A patent/JPH09510245A/en active Pending
- 1995-03-03 CA CA002183662A patent/CA2183662A1/en not_active Abandoned
- 1995-03-07 TW TW084102145A patent/TW333542B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09510245A (en) | 1997-10-14 |
| KR970701757A (en) | 1997-04-12 |
| EP0754202A1 (en) | 1997-01-22 |
| MX9604038A (en) | 1997-09-30 |
| TW333542B (en) | 1998-06-11 |
| WO1995024445A2 (en) | 1995-09-14 |
| WO1995024445A3 (en) | 1995-11-16 |
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