CA1322260C - High strength copolyester - Google Patents
High strength copolyesterInfo
- Publication number
- CA1322260C CA1322260C CA000564880A CA564880A CA1322260C CA 1322260 C CA1322260 C CA 1322260C CA 000564880 A CA000564880 A CA 000564880A CA 564880 A CA564880 A CA 564880A CA 1322260 C CA1322260 C CA 1322260C
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- contain
- dicarboxylic acids
- specified
- tire cord
- 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 - Fee Related
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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
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Abstract of the Disclosure HIGH STRENGTH COPOLYESTER
It has been determined that the mechanical and thermal properties of polyesters can be improved by incorporating hydroxyalkyl trimellitic imides therein.
Such polyesters are comprised of repeat units which are derived from (a) at least one diacid component, (b) at least one diol component, and (c) at least one hydroxyalkyl trimellitic imide.
It has been determined that the mechanical and thermal properties of polyesters can be improved by incorporating hydroxyalkyl trimellitic imides therein.
Such polyesters are comprised of repeat units which are derived from (a) at least one diacid component, (b) at least one diol component, and (c) at least one hydroxyalkyl trimellitic imide.
Description
1322~'60 ~1-~IIGH ~TRENGTH COPI:; L~ESTER
~ .
Polye~ter3 ~re u~ ed in many appli~tiona S wher~in ik i~ lmpor~an~ for ~h~m ~o h~v~ hi~h ~trength and good tharm~l propertie~ . For in~anee ~ polye~ter~
ar~ cornrnonly u~lli2ed in making t~re ~ord~ and molded articles wh~re~n hlg~ ~en~lle ~trength i~ requlred.
Su~h tlre cordc are c:ommonly made out of polye~hyl~n~
ter~p~thalate which h~ re~pect~.ble ten~ile ~tren~h.
However, it i~ hlghly desir~ble ~o mod~y ~ha poly~hylene tçr~phthal~te ln a mann~r tha~ incre~
lt~ ~ensila strength. For ex~mple, United St~te~
P~tent 4, 605, 728 di~lo~ea t~a~ ~:he m~ch~n 1 cal a~d therm~l proper~ies o~ polye8~e~ ~an be improv~d by in~orpora~ln~ bi~-hydrsxyalkyl pyromelli~ic di~mlde~
th~re in, S~ ~ o~ ve~ r It h~8 been di~covered that hydr~xya~ ;yl trimellitic ~mit~s ~sn be utilized ~o modly polyea~er~
~n order to improv~ their ~rength and ~o inc~ e ~heir ~la~6 tr~n~ltlon t~mp~ra~ure (Tg). Thi~ ~
modi:Eic~tion i~ accompli~hed by copolymerlzing the ~5 hydroxy~lkyl ~rimQlli~ic imide into ~he polye~er ~8 a monome~lc repe~t un4 t . In other word~, the :hydroxyalkyl ~rim~llitic imlde i9 polymerlzed lnto ~e pol~e~ter ~ ~n ~ddit~orl~l component ~long wi~h th~
di~cl~ component and t:he diol component.
The pre~en~ lnvention more ~peci~ically re~ate0 to a 'cire co~d which comprîg~ a poly~ter compris~d o;E
r~peat unit~ which are derlve~ ~rom (a~ at le~t one di~oi~ ~omponent, ~b) ~t lca~t one dlol compvne~t 7 and (c) a~ le~ on~ hydroxy~lkyl trlmellltic imide.
Gener~lly ~rom ~bou~ 2 ~el~h~
~,~
IY~
~ 3 ~
percent to about 90 weight percent of the repeat units in such polyesters will be derived from hydroxyalkyl trimellitic imides.
The present invention also reveals a process for preparing a high strength copolyester which comprises copolymerizing (a) at least one diacid component, ~b) at least one diol component, and tc) at least one hydroxyalkyl trimellitic imide. In most cases the diol component will be comprised of one or more members selected from the group consisting of glycols containing rom 2 to 12 carbon atoms, glycol ethers containing from 4 to 12 carbon atoms, and polyether glycols having the structural formula:
HO~A-O~nH
wherein A is an alkylene group containing from 2 to 6 carbon atoms and wherein n is an integer from 2 to 400.
Detailed Description of the Invention The pol.yester compositions of this invention are prepared b~ reacting a diacid component with a diol component. The diacid component can, of course~ be a diester, such as dimethyl terephthalate. The term "diacid component" as used herein is thereore intended to include diesters. The term "diol component" as used herein is also deemed to include glycol ethers (diethers) and polyether glycols. These polyester compositions can be made in any conventional manner well known in the art. Thus, conventional temperatures, catalysts, amounts of catalysts, stabilizers, and the like, are utilized in manners well known in the literature and art.
'.~
~3222~0 The diacid component in the polyesters to which this inventioll pertains are normally alkyl dicarboxylic acids which contain from 4 to 36 carbon atoms, diesters of alkyl dicarboxylic acids which contain from 6 to 38 S carbon atoms, aryl dicarboxylic acids which contain from 8 to 20 carbon atoms, diesters of aryl dicarboxylic acids which contain from 10 to 22 carbon atoms, alkyl substituted aryl dicarboxylic acids which contain from 9 to 22 carbon atoms, or diesters of alkyl substituted aryl dicarboxylic acids which contain from 11 to 22 carbon atoms. The preferred alkyl dicarboxylic acids will contain from 4 'co 12 carbon atoms. Some representative examples of such alkyl dicarboxylic acids include glutaric acid, adipic acid, pimelic acid, and the like. The preferred diesters of alkyl dicarboxylic acids will contain ~rom 6 to 12 carbon atoms. A representative example of such a diester of an alkyl dicarboxylic acid is azelaic acid.
The preferred aryl dicarboxylic acids contain from 8 to 16 carbon atoms. Some representative examples of arvl dicarboxylic acids are terephthalic acid? isophthalic acid, and orthophthalic acid. The preferred diesters of aryl dicarboxylic acids contain from 10 to 18 carbon atoms. Some representative examples of diesters of aryl dicarboxylic acids include dimethyl terephthalate, dimechyl isophthalate, diethyl orthophthalate, dimethyl naphthalate, diethyl naphthalate and the like. The pre~erred alkyl substituted aryl dicarboxylic acids contain from 9 to 16 carbon atoms and the preferred diesters of alkyl substituted aryl dicarboxylic acids contain from 11 to 15 carbon atoms.
The diol cornponent utilized in preparing the copolyesters of the present invention will normally be selected from the group consisting of glycols ~`:
;
'''` .
:~3~2~1 containing from 2 to 12 carbon atoms, glycol ethers containing from 4 to 12 carbon atoms, and polyether glycols having the structural formula:
HO~A-O~nH
wherein A is an alkylene group containing from 2 to 6 carbon atoms and wherein n is an integer from 2 to 400.
Generally, such polyether glycols will have a molecular weight of 400 to about 4000.
Preferred glycols normally contain from 2 to 8 carbon atoms with preferred glycol ethers containing from 4 to 8 carbon atoms. Some representative examples of glycols that can be utilized as the diol component include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 2,2-diethyl-l,3 propane diol, 2,2-dimethyl-1,3-propane diol, 2-ethyl-2-butyl-1,3-propane diol, 2-ethyl-2-isobutyl-1,3-propane diol, 1,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol~
2,2,4-trimethyl-1,6-hexane diol, 1,3-cyclohexane ~ dimethanol, 1,4-cyclohexane dimethanol, ; 2,2,4,4-tetramethyl-1,3-cyclobutane diol, and the like.
Some representative examples of polyether glycols that - 25 can be used include polytetramethylene glycol (PolymegTM) and polyethylene glycol (CarbowaxT~).
The hydroxyalkyl trimellitic imides utilized in - preparing the copolyesters of the present invention generally have the structural formula:
~ ~322~
O
HO-C ~ / -R-OH
O
-wherein R represents an alkylene group containing from 1 to 20 carbon atoms. The hvdroxyalkyl groups in the hydroxyalkyl trimellitic imides normally utilized in the practice of the present invention will normally contain from 2 to 8 carbon atoms. In other words, the alkylene group will normally contain from 2 to 8 carbon atoms. In most cases, the hydroxyalkyl trimellitic imides will contain hydroxyalkyl groups that contain from 2 to 4 carbon atoms. Hydroxyethyl trimellitic imide is a good example of a hydroxyalkyl trimellitic imide that can be utilized in ~odifying polyesters in accordance with the present invention. Typically the modified polyesters of this invention will contain from about 5 to about 80 weight percent hydroxyalkyl trimellitic imides, based upon total repeat units in the polymer. In most cases such modified polyesters will contain from 10 to 60 weight percent hydroxyalkyl trimellitic imides.
The modified polyesters prepared in accordance with the present invention can also be branched. Such branching is normally attained by utilizing a branching agent in the polyesterification reaction utilized in the synthesis of the polyester. Such branching agents normally contain three or more functional groups and preferably contain three or four functional groups.
The reactive groups may be carboxyl or aliphatic ` hydroxyl. The branching agent can contain both types of groups. Examples of acidic branching agents include `:~
~, .': `
: ' :.
: .
~3~22~
trimesic acid, trimellitic acid, pyromellitic acid, butane tetracarboxylic acid, naphthalene tricarboxylic acids, cyclohexane-1,3,5-tricarboxylic acids, and the like. Some representative examples of hydroxyl branching agents (polyols~ include glycerin, trimethylol propane, pentaerythritol, dipentaerythritol, 1,2,6-hexane triol, and 1,3,5-trime-thylol benzene. Generally, from 0 ~o 3 percent ot a polyol containing from 3 to 12 carbon atoms will be used as the branching agent (based upon the total diol component).
This invention is illustrated by the following examples which are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight.
, Example 1 Hydroxyethyl trimellitic imide was prepared by charging one mole of trimellitic anhydride, 105 ml of ethylene glycol, and 45 ml of water into a three-neck round bottom flask which was equipped with a stirrer and subsequently adding one mole of ethanol amine in 40 ml of water to the flask. The mixture was refluxed at 110C for three hours under a nitrogen atmosphere.
Upon cooling the mixture solidified and the solid was washed three times with water. The product was then dried in a forced air oven at 80C over night. A yield of about 65% was attained and the hydroxyethyl trimellitlc imide produced had a melting point of about 196C. The reaction that took place can be illustrated by the equation:
:L~222~
O O
HO-C ~ O ~ H2N-CH2-C~2-OH-~ HO-C ~ ~N~C~-CH2-OH
O O
Example 2 A polyethylene terephthalate oligomer was prepared by reacting terephthalic acid with ethylene glycol at a temperature of 280C and a pressure of 35 poun`ds per square inch (2.41 x 105 Pascals). The polyethylene terephthalate oligomer (PET heel) prepared had an average d gree of polymerization of about 5.
Forty grams of the PET heel, 10 grams of the hydroxyethyl trimellitic imide produced in Example 1, and 0.06 grams of antimony trioxide (Sb2O3) were charged into a glass polymerization reactor. The mixture in the reactor was heated to a temperature of 270C and stirred under a nitrogen atmosphere for 30 minutes. The pressure was then reduced to less than about 0.5 mm of mercury (66.6 Pascals) with the temperature being maintained at 270C and the -polymerization was continued for 2 additional hours.
The polymer produced was discharged from the reactor and was determined to have a glass transition ' temperature of 83C.
A control experiment was also conducted wherein no hydroxyethyl trimellitic imide was utilized as a monomer in the polymerization. In other words, unmodified polyethylene terephthalate was made in the ; control experiment. The polyethylene terephthalate made in the control experiment was determined to have a glass transition temperature of 74C. This clearlv shows that hydroxyalkyl trimellitic imides can be ~322260 incorporated into polyesters in order to increase their glass ~ransition temperature. In fact, the modified polyester made in this experiment w~ich contained 20%
hydroxyethyl trimellitic imide had a glass transition temperature that was 9 C higher than the unmodified polyethylene terephthalate. .
Example 3 The procedure utilized in Example 2 was repeated in this experiment except that about 18 g of the hydroxyethyl trimellitic imide was added to the PET
heel along with the antimony trioxide catalyst. Thus, the modified polyethylene terephthalate produced contained about 31% hydroxyethyl trimellitic imide (based upon total repeat units) and was determined to have a glass transition temperature of 93C.
Example 4 - The procedure utilized in Example 2 was repeated in this experiment except that ahout 71 g of hydroxyethyl trimellitic imide was added to the polyethylene terephthalate oligomer in order to produce a polymer that contained 64 weight percent repeat units which were derived from the hydroxyethyl trimellitic imide.
The polyester produced in this experiment had a glass transition temperature of 126C.
:~
- Example 5 In this experiment a polyester containing 80%
hydroxyethyl trimellitic imide repeat units was made by utilizing the procedure specified in Example 2 with 160 g of the hydroxyethyl trimellitic imide being ~dded to ~;the PET heel. The modified polyethylene terephthalate produced had a glass transition temperature of 143C.
~322~6~
In order to be utilized in high performance applications, polyethylene terephthalate can be modified by incorporating hydroxyalkyl trimellitic imides therein in order to raise its glass transition temperature and modulus. By incorporating hydroxyalkyl trimellitic imides into the backbone of such polyesters, ~heir overall rigidity, bulkiness and melt vi.scosities are also greatly increased.
While certain representative embodiments have been shown for the purpose of illustrating the present invention, it will be apparent to those skilled in this art that various changes and modifications can be made : therein without departing from the scope of the present invention.
~ .
Polye~ter3 ~re u~ ed in many appli~tiona S wher~in ik i~ lmpor~an~ for ~h~m ~o h~v~ hi~h ~trength and good tharm~l propertie~ . For in~anee ~ polye~ter~
ar~ cornrnonly u~lli2ed in making t~re ~ord~ and molded articles wh~re~n hlg~ ~en~lle ~trength i~ requlred.
Su~h tlre cordc are c:ommonly made out of polye~hyl~n~
ter~p~thalate which h~ re~pect~.ble ten~ile ~tren~h.
However, it i~ hlghly desir~ble ~o mod~y ~ha poly~hylene tçr~phthal~te ln a mann~r tha~ incre~
lt~ ~ensila strength. For ex~mple, United St~te~
P~tent 4, 605, 728 di~lo~ea t~a~ ~:he m~ch~n 1 cal a~d therm~l proper~ies o~ polye8~e~ ~an be improv~d by in~orpora~ln~ bi~-hydrsxyalkyl pyromelli~ic di~mlde~
th~re in, S~ ~ o~ ve~ r It h~8 been di~covered that hydr~xya~ ;yl trimellitic ~mit~s ~sn be utilized ~o modly polyea~er~
~n order to improv~ their ~rength and ~o inc~ e ~heir ~la~6 tr~n~ltlon t~mp~ra~ure (Tg). Thi~ ~
modi:Eic~tion i~ accompli~hed by copolymerlzing the ~5 hydroxy~lkyl ~rimQlli~ic imide into ~he polye~er ~8 a monome~lc repe~t un4 t . In other word~, the :hydroxyalkyl ~rim~llitic imlde i9 polymerlzed lnto ~e pol~e~ter ~ ~n ~ddit~orl~l component ~long wi~h th~
di~cl~ component and t:he diol component.
The pre~en~ lnvention more ~peci~ically re~ate0 to a 'cire co~d which comprîg~ a poly~ter compris~d o;E
r~peat unit~ which are derlve~ ~rom (a~ at le~t one di~oi~ ~omponent, ~b) ~t lca~t one dlol compvne~t 7 and (c) a~ le~ on~ hydroxy~lkyl trlmellltic imide.
Gener~lly ~rom ~bou~ 2 ~el~h~
~,~
IY~
~ 3 ~
percent to about 90 weight percent of the repeat units in such polyesters will be derived from hydroxyalkyl trimellitic imides.
The present invention also reveals a process for preparing a high strength copolyester which comprises copolymerizing (a) at least one diacid component, ~b) at least one diol component, and tc) at least one hydroxyalkyl trimellitic imide. In most cases the diol component will be comprised of one or more members selected from the group consisting of glycols containing rom 2 to 12 carbon atoms, glycol ethers containing from 4 to 12 carbon atoms, and polyether glycols having the structural formula:
HO~A-O~nH
wherein A is an alkylene group containing from 2 to 6 carbon atoms and wherein n is an integer from 2 to 400.
Detailed Description of the Invention The pol.yester compositions of this invention are prepared b~ reacting a diacid component with a diol component. The diacid component can, of course~ be a diester, such as dimethyl terephthalate. The term "diacid component" as used herein is thereore intended to include diesters. The term "diol component" as used herein is also deemed to include glycol ethers (diethers) and polyether glycols. These polyester compositions can be made in any conventional manner well known in the art. Thus, conventional temperatures, catalysts, amounts of catalysts, stabilizers, and the like, are utilized in manners well known in the literature and art.
'.~
~3222~0 The diacid component in the polyesters to which this inventioll pertains are normally alkyl dicarboxylic acids which contain from 4 to 36 carbon atoms, diesters of alkyl dicarboxylic acids which contain from 6 to 38 S carbon atoms, aryl dicarboxylic acids which contain from 8 to 20 carbon atoms, diesters of aryl dicarboxylic acids which contain from 10 to 22 carbon atoms, alkyl substituted aryl dicarboxylic acids which contain from 9 to 22 carbon atoms, or diesters of alkyl substituted aryl dicarboxylic acids which contain from 11 to 22 carbon atoms. The preferred alkyl dicarboxylic acids will contain from 4 'co 12 carbon atoms. Some representative examples of such alkyl dicarboxylic acids include glutaric acid, adipic acid, pimelic acid, and the like. The preferred diesters of alkyl dicarboxylic acids will contain ~rom 6 to 12 carbon atoms. A representative example of such a diester of an alkyl dicarboxylic acid is azelaic acid.
The preferred aryl dicarboxylic acids contain from 8 to 16 carbon atoms. Some representative examples of arvl dicarboxylic acids are terephthalic acid? isophthalic acid, and orthophthalic acid. The preferred diesters of aryl dicarboxylic acids contain from 10 to 18 carbon atoms. Some representative examples of diesters of aryl dicarboxylic acids include dimethyl terephthalate, dimechyl isophthalate, diethyl orthophthalate, dimethyl naphthalate, diethyl naphthalate and the like. The pre~erred alkyl substituted aryl dicarboxylic acids contain from 9 to 16 carbon atoms and the preferred diesters of alkyl substituted aryl dicarboxylic acids contain from 11 to 15 carbon atoms.
The diol cornponent utilized in preparing the copolyesters of the present invention will normally be selected from the group consisting of glycols ~`:
;
'''` .
:~3~2~1 containing from 2 to 12 carbon atoms, glycol ethers containing from 4 to 12 carbon atoms, and polyether glycols having the structural formula:
HO~A-O~nH
wherein A is an alkylene group containing from 2 to 6 carbon atoms and wherein n is an integer from 2 to 400.
Generally, such polyether glycols will have a molecular weight of 400 to about 4000.
Preferred glycols normally contain from 2 to 8 carbon atoms with preferred glycol ethers containing from 4 to 8 carbon atoms. Some representative examples of glycols that can be utilized as the diol component include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 2,2-diethyl-l,3 propane diol, 2,2-dimethyl-1,3-propane diol, 2-ethyl-2-butyl-1,3-propane diol, 2-ethyl-2-isobutyl-1,3-propane diol, 1,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol~
2,2,4-trimethyl-1,6-hexane diol, 1,3-cyclohexane ~ dimethanol, 1,4-cyclohexane dimethanol, ; 2,2,4,4-tetramethyl-1,3-cyclobutane diol, and the like.
Some representative examples of polyether glycols that - 25 can be used include polytetramethylene glycol (PolymegTM) and polyethylene glycol (CarbowaxT~).
The hydroxyalkyl trimellitic imides utilized in - preparing the copolyesters of the present invention generally have the structural formula:
~ ~322~
O
HO-C ~ / -R-OH
O
-wherein R represents an alkylene group containing from 1 to 20 carbon atoms. The hvdroxyalkyl groups in the hydroxyalkyl trimellitic imides normally utilized in the practice of the present invention will normally contain from 2 to 8 carbon atoms. In other words, the alkylene group will normally contain from 2 to 8 carbon atoms. In most cases, the hydroxyalkyl trimellitic imides will contain hydroxyalkyl groups that contain from 2 to 4 carbon atoms. Hydroxyethyl trimellitic imide is a good example of a hydroxyalkyl trimellitic imide that can be utilized in ~odifying polyesters in accordance with the present invention. Typically the modified polyesters of this invention will contain from about 5 to about 80 weight percent hydroxyalkyl trimellitic imides, based upon total repeat units in the polymer. In most cases such modified polyesters will contain from 10 to 60 weight percent hydroxyalkyl trimellitic imides.
The modified polyesters prepared in accordance with the present invention can also be branched. Such branching is normally attained by utilizing a branching agent in the polyesterification reaction utilized in the synthesis of the polyester. Such branching agents normally contain three or more functional groups and preferably contain three or four functional groups.
The reactive groups may be carboxyl or aliphatic ` hydroxyl. The branching agent can contain both types of groups. Examples of acidic branching agents include `:~
~, .': `
: ' :.
: .
~3~22~
trimesic acid, trimellitic acid, pyromellitic acid, butane tetracarboxylic acid, naphthalene tricarboxylic acids, cyclohexane-1,3,5-tricarboxylic acids, and the like. Some representative examples of hydroxyl branching agents (polyols~ include glycerin, trimethylol propane, pentaerythritol, dipentaerythritol, 1,2,6-hexane triol, and 1,3,5-trime-thylol benzene. Generally, from 0 ~o 3 percent ot a polyol containing from 3 to 12 carbon atoms will be used as the branching agent (based upon the total diol component).
This invention is illustrated by the following examples which are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight.
, Example 1 Hydroxyethyl trimellitic imide was prepared by charging one mole of trimellitic anhydride, 105 ml of ethylene glycol, and 45 ml of water into a three-neck round bottom flask which was equipped with a stirrer and subsequently adding one mole of ethanol amine in 40 ml of water to the flask. The mixture was refluxed at 110C for three hours under a nitrogen atmosphere.
Upon cooling the mixture solidified and the solid was washed three times with water. The product was then dried in a forced air oven at 80C over night. A yield of about 65% was attained and the hydroxyethyl trimellitlc imide produced had a melting point of about 196C. The reaction that took place can be illustrated by the equation:
:L~222~
O O
HO-C ~ O ~ H2N-CH2-C~2-OH-~ HO-C ~ ~N~C~-CH2-OH
O O
Example 2 A polyethylene terephthalate oligomer was prepared by reacting terephthalic acid with ethylene glycol at a temperature of 280C and a pressure of 35 poun`ds per square inch (2.41 x 105 Pascals). The polyethylene terephthalate oligomer (PET heel) prepared had an average d gree of polymerization of about 5.
Forty grams of the PET heel, 10 grams of the hydroxyethyl trimellitic imide produced in Example 1, and 0.06 grams of antimony trioxide (Sb2O3) were charged into a glass polymerization reactor. The mixture in the reactor was heated to a temperature of 270C and stirred under a nitrogen atmosphere for 30 minutes. The pressure was then reduced to less than about 0.5 mm of mercury (66.6 Pascals) with the temperature being maintained at 270C and the -polymerization was continued for 2 additional hours.
The polymer produced was discharged from the reactor and was determined to have a glass transition ' temperature of 83C.
A control experiment was also conducted wherein no hydroxyethyl trimellitic imide was utilized as a monomer in the polymerization. In other words, unmodified polyethylene terephthalate was made in the ; control experiment. The polyethylene terephthalate made in the control experiment was determined to have a glass transition temperature of 74C. This clearlv shows that hydroxyalkyl trimellitic imides can be ~322260 incorporated into polyesters in order to increase their glass ~ransition temperature. In fact, the modified polyester made in this experiment w~ich contained 20%
hydroxyethyl trimellitic imide had a glass transition temperature that was 9 C higher than the unmodified polyethylene terephthalate. .
Example 3 The procedure utilized in Example 2 was repeated in this experiment except that about 18 g of the hydroxyethyl trimellitic imide was added to the PET
heel along with the antimony trioxide catalyst. Thus, the modified polyethylene terephthalate produced contained about 31% hydroxyethyl trimellitic imide (based upon total repeat units) and was determined to have a glass transition temperature of 93C.
Example 4 - The procedure utilized in Example 2 was repeated in this experiment except that ahout 71 g of hydroxyethyl trimellitic imide was added to the polyethylene terephthalate oligomer in order to produce a polymer that contained 64 weight percent repeat units which were derived from the hydroxyethyl trimellitic imide.
The polyester produced in this experiment had a glass transition temperature of 126C.
:~
- Example 5 In this experiment a polyester containing 80%
hydroxyethyl trimellitic imide repeat units was made by utilizing the procedure specified in Example 2 with 160 g of the hydroxyethyl trimellitic imide being ~dded to ~;the PET heel. The modified polyethylene terephthalate produced had a glass transition temperature of 143C.
~322~6~
In order to be utilized in high performance applications, polyethylene terephthalate can be modified by incorporating hydroxyalkyl trimellitic imides therein in order to raise its glass transition temperature and modulus. By incorporating hydroxyalkyl trimellitic imides into the backbone of such polyesters, ~heir overall rigidity, bulkiness and melt vi.scosities are also greatly increased.
While certain representative embodiments have been shown for the purpose of illustrating the present invention, it will be apparent to those skilled in this art that various changes and modifications can be made : therein without departing from the scope of the present invention.
Claims (12)
1. A tire cord which comprises a polyester comprised of repeat units which are derived from (a) at least one diacid component, (b) at least one diol component, and (c) at least one hydroxyalkyl trimellitic imide.
2, A tire cord as specified in claim 1 wherein said diacid component is selected from the group consisting of alkyl dicarboxylic acids which contain from 4 to 36 carbon atoms, diesters of alkyl dicarboxylic acids which contain from 6 to 38 carbon atoms, aryl dicarboxylic acids which contain from a 8 to 20 carbon atoms, diesters of aryl dicarboxylic acids which contain from 10 to 22 carbon atoms, alkyl substituted aryl dicarboxylic acids which contain from 9 to 22 carbon atoms, and diesters of alkyl substitutes aryl dicarboxylic acids which contain from 11 to 2 carbon atoms; and wherein the diol component is selected from the group consisting of glycols containing from 2 to 12 carbon atoms, glycol ethers containing from 4 to 12 carbon atoms, and polyether glycols having the structural formula:
HO?A-O?nH
wherein A is an alkylene group containing from 2 to 6 carbon atoms and wherein n is an integer from 2 to 400.
HO?A-O?nH
wherein A is an alkylene group containing from 2 to 6 carbon atoms and wherein n is an integer from 2 to 400.
3. A tire cord as specified in claim 2 wherein said hydroxyalkyl trimellitic imides have the structural formula:
wherein R represents an alkylene group containing from 2 to 8 carbon atoms.
wherein R represents an alkylene group containing from 2 to 8 carbon atoms.
4. A tire cord as specified in claim 3 wherein said diacid components are selected from the group consisting of alkyl dicarboxylic acids which contain from 4 to 12 carbon atoms, diesters of alkyl dicarboxylic acids which contain from 6 to 12 carbon atoms, aryl dicarboxylic acids which contain from 8 to 16 carbon atoms, and diesters of aryl dicarboxyl acids which contain from 10 to 15 carbon atoms,
5. A tire cord as specified in claim 4 wherein said glycols contain from 2 to 8 carbon atoms; wherein said glycol ethers contain from 4 to 8 carbon atoms;
and wherein said polyester is comprised of from about 5 to about 80 weight percent hydroxyalkyl trimellitic imides.
and wherein said polyester is comprised of from about 5 to about 80 weight percent hydroxyalkyl trimellitic imides.
6. A tire cord as specified in claim 5 wherein the hydroxyalkyl group in said hydroxyalkyl trimellitic imide contains from 2 to 4 carbon atoms.
7. A tire cord as specified in claim 6 wherein said diacid component is selected from the group consisting of aryl dicarboxylic acids containing from
8 to 16 carbon atoms and diesters of aryl dicarboxylic acids containing from 10 to 18 carbon atoms.
8. A tire cord as specified in claim 7 wherein the hydroxyalkyl group in said hydroxyalkyl trimellitic imide contains from 2 to 4 carbon atoms.
8. A tire cord as specified in claim 7 wherein the hydroxyalkyl group in said hydroxyalkyl trimellitic imide contains from 2 to 4 carbon atoms.
9. A tire cord as specified in claim 8 wherein said polyester contains from about 2 to 80 weight percent of hydroxyalkyl trimellitic imide.
10. A tire cord as specified in claim 9 wherein said diacid component is terephthalic acid or a diester thereof.
11. A tire cord as specified in claim 10 wherein said hydroxyalkyl trimellitic imide is hydroxyethyl trimellitic imide.
12. A tire cord as specified in claim 11 wherein said member selected from the group consisting of glycols, glycol ethers, and polyether glycols is ethylene glycol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4152087A | 1987-04-23 | 1987-04-23 | |
| US41,520 | 1987-04-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1322260C true CA1322260C (en) | 1993-09-14 |
Family
ID=21916951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000564880A Expired - Fee Related CA1322260C (en) | 1987-04-23 | 1988-04-22 | High strength copolyester |
Country Status (3)
| Country | Link |
|---|---|
| CA (1) | CA1322260C (en) |
| DE (1) | DE3812302A1 (en) |
| GB (1) | GB2203748B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201310837D0 (en) | 2013-06-18 | 2013-07-31 | Dupont Teijin Films Us Ltd | Polyester film -IV |
| GB201317705D0 (en) | 2013-10-07 | 2013-11-20 | Dupont Teijin Films Us Ltd | Copolyesters |
| GB201411044D0 (en) | 2014-06-20 | 2014-08-06 | Dupont Teijin Films Us Ltd | Copolyestermides and films made therefrom |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5826749B2 (en) * | 1975-12-27 | 1983-06-04 | 東洋紡績株式会社 | Method for producing N-hydroxyalkyl trimellitic acid imide |
-
1988
- 1988-04-13 DE DE19883812302 patent/DE3812302A1/en not_active Ceased
- 1988-04-22 GB GB8809559A patent/GB2203748B/en not_active Expired - Fee Related
- 1988-04-22 CA CA000564880A patent/CA1322260C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3812302A1 (en) | 1988-11-10 |
| GB8809559D0 (en) | 1988-05-25 |
| GB2203748B (en) | 1991-02-06 |
| GB2203748A (en) | 1988-10-26 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |