CA1121941A - Polyester production - Google Patents
Polyester productionInfo
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- CA1121941A CA1121941A CA000327551A CA327551A CA1121941A CA 1121941 A CA1121941 A CA 1121941A CA 000327551 A CA000327551 A CA 000327551A CA 327551 A CA327551 A CA 327551A CA 1121941 A CA1121941 A CA 1121941A
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Abstract
ABSTRACT OF THE DISCLOSURE
Thermosetting unsaturated polyesters produced from a mixture of glycols and oligomers. The mixture is a waste stream from a process for the production of linear polyesters from glycols and terephthalic acid. Prior to this invention, the waste stream had to be burned or buried but by the invention herein it can make useful polyester resins.
Thermosetting unsaturated polyesters produced from a mixture of glycols and oligomers. The mixture is a waste stream from a process for the production of linear polyesters from glycols and terephthalic acid. Prior to this invention, the waste stream had to be burned or buried but by the invention herein it can make useful polyester resins.
Description
This invention relates to unsaturated polyesters.
The preparation of linear polyesters of glycols and terephthalic acid by ester exchange and condensation is well known. Polyethylene terephthalate and polybutylene terephthalate are typical of the polyesters industry produces. These polyesters have found wides~read use in the manufacture of films, fibers, and molding compounds.
The processes for the production of linear polyesters often produce a waste stream. Most manufacturers remove ethylene glycol from these streams and then bury or burn the remains. In some cases these remains are a mixture of glycols and oligomers.
~ligomer, as used in this invention, means a low molecular weight polyester of terephthalic acid and one or more glycols. It is this mixture which is used to produce the thermosetting unsatura-ted polyester resins of this invention.
According to the present invention a method for produc-ing an unsaturated polyester resin from a mixture of glycols and ylycol terephthalate oligomers recovered from a waste stream from the production of linear polyesters of glycols and terephthalic ~0 acid, said method comprising the steps of: (a) forming a blend of said mixture with an alcohol selected from the group consist-ing of: an aliphatic polyhydric alcohol and an ether alcohol;(b) transesterifying said blend; a~(c) polyesterifying said transes-terified blend with an ethylenically unsaturated dicarboxylic acid.
It is important that -the properties of polyesters be consistent ~rom batch to batch. The waste streams that are used in this invention, however, vary widely from batch to batch. In-corporating them unchanged into the hackbone of higher molecular weight polyester resins would result in undesired variations in properties.
Accordingly, the thermosetting, unsaturated polyester is produced by first transesterifying the mixture of glycols and oligomers. This is achieved by heating (first cook) the mixture of glycols and oligomers to break up the oligomers by transesterification (depolymerization). The addition of ethylenically unsaturated dicarboxylic acids or thei~ anhydrides and a second cook follow this first cook. By breaking up the oligomers in the first cook, the viscosity drift is minimized in the resulting unsaturated resin during storage.
The additional glycol employed is added to either the first or second cook or both if necessary. The same is true for any saturated acid that is employed.
In another embodiment, the waste stream is heated in the first cook to transesterify the oligomers, additional glycol is added during a second cook and then unsaturated acid i~ added in a third cook. Again, additional glycols or saturated acids can be added to any one of the three stages of cook.
If desired, a catalyst can be added to the first stage of either the two or three stage cook. The important step is to break up the oligomers in the transesterification step before adding the unsaturated acid.
The mixture of glycols and oligomers and any additional saturated dicarbGxylic acids and glycols are charged to a reactor; and the reaction generallv is carried out at a temperature ranging from 170 to 2~5C, at a pressure ranging from 0 to 60 psi, and for a time ranging from 2 to 24 hours. The reaction should be continued until the starting acid number is at least halved, but preferably reduced to a range of 5 to 10.
The ethylenically unsaturated dicarboxylic acids then are charged to the reactor with any additional saturated acid or A
glycols; and the reaction is carried out at a temperature ranging from 170 to 220C, at a pressure ranging from 0 to 60 psi for the additional time required to reduce the acid number below about 35.
The mixture of glycols and glycol-terephthalic acid polyester oligomers which can be used to produce the polyesters under consideration will have the following analys~s.
Composition, Weight Percent Composition Range Preferred 10 Ethylene glycol 0-25 4-10 Diethylene glycol 0-10 3-7 Triethylene glycol 0-5 0-3 Ethylene glycol monomer 12-40 14-30 Diethylene glycol monomer 0-15 2-12 Mixed monomers 0-15 5-13 Higher oligomers of glycol15-70 40-65 terephthalate polyesters The mixture will usually have a hydroxyl number within - the range of from about 250 to about 1000 with a preferred range 20 being from about 250 to 650.
In the above mixture, the glycol terephthalate and higher oligomers can be considered as having the following formulas:
Ethylene glycol terephthalate monomer HOCH2CH200C ~ Cc~2cH2H
Diethylene ~lycol terephthalate monomer HOCH2CH20CH2CH200C ~ OOCH2CH2OCH2CH~Oll M_ d glycol_terephthalate monomers HocH2cH~oc~2cH2ooc~3 OOCH2CH20H
Higher glycol terephthalate oligomers ~I ~ocH2cH2ooc~3co~m~ocH2cH2ocH2cH2ooc~co~ncH2cH2oH
where~n m is, generally, greater than n and wherein the sum of m plus n is within the range of from about 2 to 4.
Mixtures of glycols and oligomers such as described above are commercially available as waste product from poly-alkylene terephthalate production.
Small amounts of compounds of inorganic metals such as titanium, zinc, lead, calcium, antimony, manganese, and the like also are present in the mixture. These metal com~ounds are residue from the catalysts employed in the various polyester processes.
The saturated dicarboxylic acids, polyhydric alcohols and unsaturated dicarboxylic acids that can react with this mixture of glycols and oligomers to produce the unsaturated resins of this invention are well known in the art.
The dicarboxylic acids which are either saturated or 0 only aromatically unsaturated include:
succinic acid adipic acid suberic acid azelaic acid sebacic acid phthalic acid isophthalic acid terephthalic acid tetrachlorophthaliG acid hexachloroendomethylenetetrahydrophthalic acid and the like. The anhydrides of these acids, where the anhydrides exist are, of course, embraced since the polyesters obtained therefrom are the same. Furthermore, for purposes of the present in~ention, the aromatic nuclei of such acids as phthalic acid are generally regarded as saturated since the double bonds do not react by addition, as do ethylenic groups, in the cross linking reactions of thermosetting polyesters. Therefore, wherever the term "saturated dicarboxylic acid" is utilized, it is to be understood that such term includes the aromatically unsaturated dicarboxylic acids.
The polyhydric alcohols include:
ethylene glycol diethylene glycol triethylene glycol polyethylene glycol propylene glycol dipropylene glycol polypropylene glycol glycerol neopentyl glycol pentaerythritol trimethylol propane trimethylol ethane 1,3 butylene glycol 1,4 butylene glycol and the like.
The ethylenically unsaturated dicarboxylic acids include such acids as:
;'~' maleic acid fumaric acid aconitic acid mesaconic acid citraconic acid itaconic acid and halo and alkyl derivatives of such acids and the like; the preferred acid being maleic acid. The anhydrides of these acids, where the anhydrides exist, are, of course, embraced since the polyesters obtained therefrom are essentially the same whether the acid or anhydride is employed.
The amount of each material charged to the reactor, if employed, based on the parts by weight is as follows:
Parts by Weight edients Range _ Oligomer-glycol mixture20-75 Saturated dicarboxylic acids 2-35 Glycols 5-15 Ethylenically unsaturated dicarboxylic acids15-40 If desired, ethylenically unsaturated monomers (e.g. vinyl monomers) can be incorporated after the polyester is formed.
Examples of these vinyl monomers are:
styrene halogenated styrenes vinyl toluene divinyl benzene octyl acrylate octyl methacrylate diallyl phthalate and the like.
A
The proportional amounts of the various materials charged is governed by the properties required for the intended use of the final resin. Such uses include, among others, hand lay-up, spray-up, bulk molding compound, sheet molding compound, and the like.
The foll~wing examples further illustrate the present invention.
EXAMPLE I
The following ingredients were charged to a reactor:
Ingredients Moles Oligomer-glycol mixture having a hydroxyl number of 284 0.864 Dipropylene glycol 0.282 Isophthalic acid 0.091 The charge was heated at a temperature of 204C for a period of 2 hours. One mole of maleic anhydride was then charged to the reactor and the reaction continued for 5 hours at a temperature of 213C. The acid number at the end of the cook was 19.6.
Styrene was added to the resulting material to give an initial viscosity of 395 cps. After 22 days the viscosity was 424 cps. The change in viscosity was 1.3 cps per day.
EXAMPLE II
The following ingredients were charged to a reactor:
In~redients Moles Oligomer-glycol mixture of Example I 0.864 Dipropylene glycol 0.282 Isophthalic acid 0.091 Maleic anhydride 1.0 ~;~
9 ~1 The oligomer-glycol mixture had the same composition as the mixture used in Example I.
The charge was heated at a temperature of 213C, for a period of 4.75 hours. The acid number at the end of the cook was 19.7.
Styrene was added to the resulting material to give an initial viscosity of 370 cps. After 22 days the viscosity was 832 cps. The change in viscosity was 17 cps per day.
The only difference between Examples I and II is the two stage cooking of Example I. Yet, the stabilization of the viscosity in Example I is noticeably significant. Stabilization of viscosity in the two stage cook is very advantageous for storage and shelf life EXAMPLE III
The following ingredients were charged to a reactor:
Ingredients Moles Oligo~er-glycol mixture of Example I 0.495 Propylen~ glycol 0.210 Dibutyl tin oxide catalyst 30.2 grams The charge was cooked in a closed reactor for 2 hours at 450F and then cooled to 200F.
Next, the following second charge was added to -the reactor:
Ingr dients Moles Propylene glycol 0.974 Phthalic anhydride 0.348 Maleic anhydride 0.652 The second cook then lasted 5~ hours at 415F until the reaction had an acid num~er of 26.9. The reaction product was cooled to 350F and 46.45 pounds o~ styrene containing 11.4 grams of toluhydroquinone were slowly added. The final resin had an acid number of 17.1 and a viscosity of 626 cpsO
This example demonstrates the preparation of an unsaturated polyester wherein the mixture of glycols and oligomers is transesterified in the presence of an additional glycol and then reacted with an unsaturated acid and a saturated acid.
EXAMPLE IV
A typical analysis of the mixture of glycols and oligomers employed in this invention is;
Com~osition Weight Percent Ethylene glycol 12.5 Diethylene glycol 501 Triethylene glycol 0.9 Ethylene glycol monomer 33.5 Diethylene glycol monomer 1.5 Mixed monomers 10.7 Oligomers 35.8 Hydroxyl number 481 The apparent molecular weight of this mixture or any other glycol-o~igomer mixture employed can be calculated by the following formula:
molecular weight = 1.222 x 105 hydroxyl number To produce a thermosetting, unsaturated polyester resin from this typical mixture, about 56 parts by weight of it would be reacted with about 5 parts by weight of dipropylene glycol, about 4 parts by weight of propylene glycol and about 15 parts by weight of isophthalic acid. Twenty parts by weight of maleic acid then would be added during the second cook.
.~
The amount of glycols and dicarboxylic acids added to the first cook depends upon the hydroxyl number of the waste stream (mixture of oligomers and glycols) employed, while holding the amount of unsaturated dicarboxylic acid constant.
This insures consistency of product properties in spite of variations in the composition of the waste stream glycol from lot to lot.
To illustrate, if the waste stream had a hydroxyl number of 600, about 49 parts by weight of it would be reacted with about 5.6 parts by weight of dipropylene glycol, about 4.4 parts by weight of propylene glycol, and about 20 parts by weight of isophthalic acid. 21 Parts by weight of maleic anhydride then would be added during the second cook.
EXAMPLE V
An unsaturated, thermosetting polyester resin was prepared according to the procedures of Example I from a mixture of oligomers and glycols wherein the mixture had a hydroxyl number of 529. Castings of this resin cut with 30 weight percent styrene were prepared.
The castings were tested for flexural modulus, flexural strength, tensile strength, tensile modulus, elongation at break, and heat distortion temperature.
The same procedure was carried out with a commercially available polyester molding composition. These castings also were tested for the above properties. In these examples the tests were carried out according to the indicated ASTM
Specification.
Commercially Polyester of Available Example IV Polyester Flexural Strength (psi x 10 ) 22.38 14.50 (ASTM 0790) Flexural Modulus (psi x 10 ) 0.589 0O666 (ASTM 0790) Tensile Strength (psi x 10 ) 8.56 8.70 (ASTM D638) Tensile Modulus (psi x 10 ) 0.537 0.614 (ASTM D638) Elongation at Break (~) 1.9 1.8 Heat Distortion Temperature (F) 176 160 Thus, the polyesters produced by the process of this invention have physical properties comparable, or in many cases superior to, those of commercially available polyesters. Yet they were produced from waste streams from a polyester process.
Producing a useful polyester from these waste streams renders this invention an ecological and economical advantage.
A preferred embodiment of the invention being thus described, it will be obvious that the same may be varied in many ways. Such modiflcations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims.
FA
The preparation of linear polyesters of glycols and terephthalic acid by ester exchange and condensation is well known. Polyethylene terephthalate and polybutylene terephthalate are typical of the polyesters industry produces. These polyesters have found wides~read use in the manufacture of films, fibers, and molding compounds.
The processes for the production of linear polyesters often produce a waste stream. Most manufacturers remove ethylene glycol from these streams and then bury or burn the remains. In some cases these remains are a mixture of glycols and oligomers.
~ligomer, as used in this invention, means a low molecular weight polyester of terephthalic acid and one or more glycols. It is this mixture which is used to produce the thermosetting unsatura-ted polyester resins of this invention.
According to the present invention a method for produc-ing an unsaturated polyester resin from a mixture of glycols and ylycol terephthalate oligomers recovered from a waste stream from the production of linear polyesters of glycols and terephthalic ~0 acid, said method comprising the steps of: (a) forming a blend of said mixture with an alcohol selected from the group consist-ing of: an aliphatic polyhydric alcohol and an ether alcohol;(b) transesterifying said blend; a~(c) polyesterifying said transes-terified blend with an ethylenically unsaturated dicarboxylic acid.
It is important that -the properties of polyesters be consistent ~rom batch to batch. The waste streams that are used in this invention, however, vary widely from batch to batch. In-corporating them unchanged into the hackbone of higher molecular weight polyester resins would result in undesired variations in properties.
Accordingly, the thermosetting, unsaturated polyester is produced by first transesterifying the mixture of glycols and oligomers. This is achieved by heating (first cook) the mixture of glycols and oligomers to break up the oligomers by transesterification (depolymerization). The addition of ethylenically unsaturated dicarboxylic acids or thei~ anhydrides and a second cook follow this first cook. By breaking up the oligomers in the first cook, the viscosity drift is minimized in the resulting unsaturated resin during storage.
The additional glycol employed is added to either the first or second cook or both if necessary. The same is true for any saturated acid that is employed.
In another embodiment, the waste stream is heated in the first cook to transesterify the oligomers, additional glycol is added during a second cook and then unsaturated acid i~ added in a third cook. Again, additional glycols or saturated acids can be added to any one of the three stages of cook.
If desired, a catalyst can be added to the first stage of either the two or three stage cook. The important step is to break up the oligomers in the transesterification step before adding the unsaturated acid.
The mixture of glycols and oligomers and any additional saturated dicarbGxylic acids and glycols are charged to a reactor; and the reaction generallv is carried out at a temperature ranging from 170 to 2~5C, at a pressure ranging from 0 to 60 psi, and for a time ranging from 2 to 24 hours. The reaction should be continued until the starting acid number is at least halved, but preferably reduced to a range of 5 to 10.
The ethylenically unsaturated dicarboxylic acids then are charged to the reactor with any additional saturated acid or A
glycols; and the reaction is carried out at a temperature ranging from 170 to 220C, at a pressure ranging from 0 to 60 psi for the additional time required to reduce the acid number below about 35.
The mixture of glycols and glycol-terephthalic acid polyester oligomers which can be used to produce the polyesters under consideration will have the following analys~s.
Composition, Weight Percent Composition Range Preferred 10 Ethylene glycol 0-25 4-10 Diethylene glycol 0-10 3-7 Triethylene glycol 0-5 0-3 Ethylene glycol monomer 12-40 14-30 Diethylene glycol monomer 0-15 2-12 Mixed monomers 0-15 5-13 Higher oligomers of glycol15-70 40-65 terephthalate polyesters The mixture will usually have a hydroxyl number within - the range of from about 250 to about 1000 with a preferred range 20 being from about 250 to 650.
In the above mixture, the glycol terephthalate and higher oligomers can be considered as having the following formulas:
Ethylene glycol terephthalate monomer HOCH2CH200C ~ Cc~2cH2H
Diethylene ~lycol terephthalate monomer HOCH2CH20CH2CH200C ~ OOCH2CH2OCH2CH~Oll M_ d glycol_terephthalate monomers HocH2cH~oc~2cH2ooc~3 OOCH2CH20H
Higher glycol terephthalate oligomers ~I ~ocH2cH2ooc~3co~m~ocH2cH2ocH2cH2ooc~co~ncH2cH2oH
where~n m is, generally, greater than n and wherein the sum of m plus n is within the range of from about 2 to 4.
Mixtures of glycols and oligomers such as described above are commercially available as waste product from poly-alkylene terephthalate production.
Small amounts of compounds of inorganic metals such as titanium, zinc, lead, calcium, antimony, manganese, and the like also are present in the mixture. These metal com~ounds are residue from the catalysts employed in the various polyester processes.
The saturated dicarboxylic acids, polyhydric alcohols and unsaturated dicarboxylic acids that can react with this mixture of glycols and oligomers to produce the unsaturated resins of this invention are well known in the art.
The dicarboxylic acids which are either saturated or 0 only aromatically unsaturated include:
succinic acid adipic acid suberic acid azelaic acid sebacic acid phthalic acid isophthalic acid terephthalic acid tetrachlorophthaliG acid hexachloroendomethylenetetrahydrophthalic acid and the like. The anhydrides of these acids, where the anhydrides exist are, of course, embraced since the polyesters obtained therefrom are the same. Furthermore, for purposes of the present in~ention, the aromatic nuclei of such acids as phthalic acid are generally regarded as saturated since the double bonds do not react by addition, as do ethylenic groups, in the cross linking reactions of thermosetting polyesters. Therefore, wherever the term "saturated dicarboxylic acid" is utilized, it is to be understood that such term includes the aromatically unsaturated dicarboxylic acids.
The polyhydric alcohols include:
ethylene glycol diethylene glycol triethylene glycol polyethylene glycol propylene glycol dipropylene glycol polypropylene glycol glycerol neopentyl glycol pentaerythritol trimethylol propane trimethylol ethane 1,3 butylene glycol 1,4 butylene glycol and the like.
The ethylenically unsaturated dicarboxylic acids include such acids as:
;'~' maleic acid fumaric acid aconitic acid mesaconic acid citraconic acid itaconic acid and halo and alkyl derivatives of such acids and the like; the preferred acid being maleic acid. The anhydrides of these acids, where the anhydrides exist, are, of course, embraced since the polyesters obtained therefrom are essentially the same whether the acid or anhydride is employed.
The amount of each material charged to the reactor, if employed, based on the parts by weight is as follows:
Parts by Weight edients Range _ Oligomer-glycol mixture20-75 Saturated dicarboxylic acids 2-35 Glycols 5-15 Ethylenically unsaturated dicarboxylic acids15-40 If desired, ethylenically unsaturated monomers (e.g. vinyl monomers) can be incorporated after the polyester is formed.
Examples of these vinyl monomers are:
styrene halogenated styrenes vinyl toluene divinyl benzene octyl acrylate octyl methacrylate diallyl phthalate and the like.
A
The proportional amounts of the various materials charged is governed by the properties required for the intended use of the final resin. Such uses include, among others, hand lay-up, spray-up, bulk molding compound, sheet molding compound, and the like.
The foll~wing examples further illustrate the present invention.
EXAMPLE I
The following ingredients were charged to a reactor:
Ingredients Moles Oligomer-glycol mixture having a hydroxyl number of 284 0.864 Dipropylene glycol 0.282 Isophthalic acid 0.091 The charge was heated at a temperature of 204C for a period of 2 hours. One mole of maleic anhydride was then charged to the reactor and the reaction continued for 5 hours at a temperature of 213C. The acid number at the end of the cook was 19.6.
Styrene was added to the resulting material to give an initial viscosity of 395 cps. After 22 days the viscosity was 424 cps. The change in viscosity was 1.3 cps per day.
EXAMPLE II
The following ingredients were charged to a reactor:
In~redients Moles Oligomer-glycol mixture of Example I 0.864 Dipropylene glycol 0.282 Isophthalic acid 0.091 Maleic anhydride 1.0 ~;~
9 ~1 The oligomer-glycol mixture had the same composition as the mixture used in Example I.
The charge was heated at a temperature of 213C, for a period of 4.75 hours. The acid number at the end of the cook was 19.7.
Styrene was added to the resulting material to give an initial viscosity of 370 cps. After 22 days the viscosity was 832 cps. The change in viscosity was 17 cps per day.
The only difference between Examples I and II is the two stage cooking of Example I. Yet, the stabilization of the viscosity in Example I is noticeably significant. Stabilization of viscosity in the two stage cook is very advantageous for storage and shelf life EXAMPLE III
The following ingredients were charged to a reactor:
Ingredients Moles Oligo~er-glycol mixture of Example I 0.495 Propylen~ glycol 0.210 Dibutyl tin oxide catalyst 30.2 grams The charge was cooked in a closed reactor for 2 hours at 450F and then cooled to 200F.
Next, the following second charge was added to -the reactor:
Ingr dients Moles Propylene glycol 0.974 Phthalic anhydride 0.348 Maleic anhydride 0.652 The second cook then lasted 5~ hours at 415F until the reaction had an acid num~er of 26.9. The reaction product was cooled to 350F and 46.45 pounds o~ styrene containing 11.4 grams of toluhydroquinone were slowly added. The final resin had an acid number of 17.1 and a viscosity of 626 cpsO
This example demonstrates the preparation of an unsaturated polyester wherein the mixture of glycols and oligomers is transesterified in the presence of an additional glycol and then reacted with an unsaturated acid and a saturated acid.
EXAMPLE IV
A typical analysis of the mixture of glycols and oligomers employed in this invention is;
Com~osition Weight Percent Ethylene glycol 12.5 Diethylene glycol 501 Triethylene glycol 0.9 Ethylene glycol monomer 33.5 Diethylene glycol monomer 1.5 Mixed monomers 10.7 Oligomers 35.8 Hydroxyl number 481 The apparent molecular weight of this mixture or any other glycol-o~igomer mixture employed can be calculated by the following formula:
molecular weight = 1.222 x 105 hydroxyl number To produce a thermosetting, unsaturated polyester resin from this typical mixture, about 56 parts by weight of it would be reacted with about 5 parts by weight of dipropylene glycol, about 4 parts by weight of propylene glycol and about 15 parts by weight of isophthalic acid. Twenty parts by weight of maleic acid then would be added during the second cook.
.~
The amount of glycols and dicarboxylic acids added to the first cook depends upon the hydroxyl number of the waste stream (mixture of oligomers and glycols) employed, while holding the amount of unsaturated dicarboxylic acid constant.
This insures consistency of product properties in spite of variations in the composition of the waste stream glycol from lot to lot.
To illustrate, if the waste stream had a hydroxyl number of 600, about 49 parts by weight of it would be reacted with about 5.6 parts by weight of dipropylene glycol, about 4.4 parts by weight of propylene glycol, and about 20 parts by weight of isophthalic acid. 21 Parts by weight of maleic anhydride then would be added during the second cook.
EXAMPLE V
An unsaturated, thermosetting polyester resin was prepared according to the procedures of Example I from a mixture of oligomers and glycols wherein the mixture had a hydroxyl number of 529. Castings of this resin cut with 30 weight percent styrene were prepared.
The castings were tested for flexural modulus, flexural strength, tensile strength, tensile modulus, elongation at break, and heat distortion temperature.
The same procedure was carried out with a commercially available polyester molding composition. These castings also were tested for the above properties. In these examples the tests were carried out according to the indicated ASTM
Specification.
Commercially Polyester of Available Example IV Polyester Flexural Strength (psi x 10 ) 22.38 14.50 (ASTM 0790) Flexural Modulus (psi x 10 ) 0.589 0O666 (ASTM 0790) Tensile Strength (psi x 10 ) 8.56 8.70 (ASTM D638) Tensile Modulus (psi x 10 ) 0.537 0.614 (ASTM D638) Elongation at Break (~) 1.9 1.8 Heat Distortion Temperature (F) 176 160 Thus, the polyesters produced by the process of this invention have physical properties comparable, or in many cases superior to, those of commercially available polyesters. Yet they were produced from waste streams from a polyester process.
Producing a useful polyester from these waste streams renders this invention an ecological and economical advantage.
A preferred embodiment of the invention being thus described, it will be obvious that the same may be varied in many ways. Such modiflcations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims.
FA
Claims (25)
1. A method for producing an unsaturated polyester resin from a mixture of glycols and glycol terephthalate oligomers recovered from a waste stream from the production of linear poly-esters of glycols and terephthalic acid, said method comprising the steps of:
(a) forming a blend of said mixture with an alcohol selected from the group consisting of: an aliphatic polyhydric alcohol and an ether alcohol;
(b) transesterifying said blend; and (c) polyesterifying said transesterified blend with an ethylenically unsaturated dicarboxylic acid.
(a) forming a blend of said mixture with an alcohol selected from the group consisting of: an aliphatic polyhydric alcohol and an ether alcohol;
(b) transesterifying said blend; and (c) polyesterifying said transesterified blend with an ethylenically unsaturated dicarboxylic acid.
2. A method for producing an unsaturated polyester resin from a mixture of glycols and oligomers, said mixture hav-ing a hydroxyl number of about 250 to about 1000 and comprising a waste stream from the production of linear polyesters of gly-cols and terephthalic acid, where said glycols in said mixture are selected from the group consisting of ethylene glycol, die-thylene qlycol, triethylene glycol and monoesters, diesters and mixed esters of ethylene glycol, dietbylene glycol and triethy-lene glycol with terephthalic acid, and where said oligomers in said mixture are low molecular weight polyesters of terephthalic acid with ethylene glycol, diethylene glycol, triethylene glycol and mixtures thereof which contain about two to four terephthalic acid residues per molecule, said method comprising the steps of:
(a) forming a blend of said mixture with a polyhydric alcohol selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, pro-pylene glycol, dipropylene glycol, polypropylene glycol, glycerol, neopentyl glycol, pentaerythritol, trimethylol propane, trimethylol ethane, 1,3-butylene glycol and 1,4-butylene glycol;
(b) transesterifying said blend at a temperature of 170°C to 235°C and a pressure of up to 60 psi for 2 to 24 hours;
(c) adding an ethylenically unsaturated dicarboxylic acid to said transesterified blend; and (d) further reacting said transesterified blend containing said added ethylenically unsaturated dicarboxylic acid to reduce the acid number below about 35.
(a) forming a blend of said mixture with a polyhydric alcohol selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, pro-pylene glycol, dipropylene glycol, polypropylene glycol, glycerol, neopentyl glycol, pentaerythritol, trimethylol propane, trimethylol ethane, 1,3-butylene glycol and 1,4-butylene glycol;
(b) transesterifying said blend at a temperature of 170°C to 235°C and a pressure of up to 60 psi for 2 to 24 hours;
(c) adding an ethylenically unsaturated dicarboxylic acid to said transesterified blend; and (d) further reacting said transesterified blend containing said added ethylenically unsaturated dicarboxylic acid to reduce the acid number below about 35.
3. The method of claim 1 or 2, wherein said waste stream is from the production of linear polyesters selected from the group consisting of: polyethylene and polybutylene tereph-thalates.
4. The method of claim 1 or 2, wherein the anhydride of said ethylenically unsaturated dicarboxylic acid is used in step (c).
5. The process of claim 2, wherein said waste stream comprises: 0.0 to 25 weight percent ethylene glycol, 0.0 to 10 weight percent diethylene glycol, 0.0 to 5 weight percent triethylene glycol, 12 to 40 weight percent ethylene glycol/
terephthalic acid monoester, 0.0 to 15 weight percent diethylene glycol/terephthalic acid monoester, 0.0 to 15 weight percent mixed ethylene glycol/diethylene glycol/terephthalic acid diester and 15 to 70 weight percent of said oligomers.
terephthalic acid monoester, 0.0 to 15 weight percent diethylene glycol/terephthalic acid monoester, 0.0 to 15 weight percent mixed ethylene glycol/diethylene glycol/terephthalic acid diester and 15 to 70 weight percent of said oligomers.
6. The process of claim 2, wherein said waste stream comprises: 4 to 10 weight percent ethylene glycol, 3 to 7 percent diethylene glycol, 0.0 to 3 weight percent triethylene glycol, 14 to 30 weight percent ethylene glycol/terephthalic acid monoester, 2 to 12 weight percent diethylene glycol/
terephthalic acid monoester, 5 to 13 weight percent mixed ethylene glycol/diethylene glycol/terephthalic acid diester and 40 to 65 weight percent of said oligomers.
terephthalic acid monoester, 5 to 13 weight percent mixed ethylene glycol/diethylene glycol/terephthalic acid diester and 40 to 65 weight percent of said oligomers.
7. The method of claim 1 or 2, wherein said blend formed in step (a) contains a catalyst.
8. The method of claim 2, wherein said mixture of glycols and oligomers has a hydroxyl number of about 250 to about 650.
9. The method of claim 2, wherein compounds selected from the group consisting of: polyhydric alcohols, saturated dicarboxylic acids and mixtures thereof are added to said transesterified blend in step (c).
10. The method of claim 2, wherein compounds selected from the group consisting of: polyhydric alcohols, saturated dicarboxylic acids and mixtures thereof are added to said blend in step (b).
11. The method of claim 2, wherein compounds selected from the group consisting of: polyhydric alcohols, saturated dicarboxylic acids and mixtures thereof are added to said blend in steps (b) and (c).
12. The method of claim 9, 10 or 11, wherein said poly-hydric alcohol is selected from the group consisting of diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerol, neopentyl glycol, pentaerythritol, trimethylol propane, trimethylol ethane, 1,3-butylene-glycol and 1,4-butylene glycol.
13. The method of claim 9, 10 or 11, wherein said saturated dicarboxylic acid is selected from the group consisting of: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, tetrachloroph-thalic acid, hexachloroendomethylenetetrahydrophthalic acid and anhydrides thereof.
14. The method of claim 2, wherein a saturated dicarboxylic acid is added to said blend in step (a).
15. The method of claim 14, wherein said saturated dicarboxylic acid is selected from the group consisting of:
succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, hexachloroendomethylenetetrahydrophthalic acid and anhydrides thereof.
succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, hexachloroendomethylenetetrahydrophthalic acid and anhydrides thereof.
16. The method of claim 2, 14 or 15, wherein in step (b) the acid number of said transesterified blend is reduced to less than half that of said blend.
17. The method of claim 2, 14 or 15, wherein step (b) the acid number of said transesterified blend is reduced to a range of 5 to 10.
18. The method of claim 1 or 2, wherein said ethyleni-cally unsaturated carboxylic acid is selected from the group consisting of: maleic acid, fumaric acid, aconitic acid, mesaconic acid, citraconic acid, itaconic acid and halo, alkyl and anhydride derivatives thereof.
19. The method of claim 9, 10 or 11, wherein said blend comprises from 20 to 75 parts by weight of said oligomer-glycol mixture, 2 to 35 parts by weight of said saturated dicarboxylic acids, 5 to 15 parts by weight of said polyhydric alcohols, and 15 to 40 parts by weight of said ethylenically unsaturated dicarboxylic acids.
20. The method of claim 2, wherein subsequent to the formation of said unsaturated polyester an ethylenically unsatur-ated monomer is incorporated therein.
21. The method of claim 20, wherein said unsaturated monomer is a vinyl monomer selected from the group consisting of: styrene, halogenated styrenes, vinyl toluene, divinyl benzenene, octyl acrylate, octyl methacrylate and diallyl phthalate.
22. An unsaturated polyester resin when produced by the method of claim 1, 2 or 5.
23. An unsaturated polyester resin when produced by the method of claim 6, 8 or 9.
24. An unsaturated polyester resin when produced by the method of claim 10, 11 or 14.
25. An unsaturated polyester resin when produced by the method of claim 15, 20 or 21.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000327551A CA1121941A (en) | 1979-05-14 | 1979-05-14 | Polyester production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000327551A CA1121941A (en) | 1979-05-14 | 1979-05-14 | Polyester production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121941A true CA1121941A (en) | 1982-04-13 |
Family
ID=4114202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000327551A Expired CA1121941A (en) | 1979-05-14 | 1979-05-14 | Polyester production |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1121941A (en) |
-
1979
- 1979-05-14 CA CA000327551A patent/CA1121941A/en not_active Expired
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