CA1199742A - Polyester and polyesterimide resins - Google Patents
Polyester and polyesterimide resinsInfo
- Publication number
- CA1199742A CA1199742A CA000364541A CA364541A CA1199742A CA 1199742 A CA1199742 A CA 1199742A CA 000364541 A CA000364541 A CA 000364541A CA 364541 A CA364541 A CA 364541A CA 1199742 A CA1199742 A CA 1199742A
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- polyesterimide
- polyester
- composition
- acid
- mixture
- Prior art date
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Abstract
ABSTRACT OF THE DISCLOSURE Novel polyester or polyesterimide compositions synthesized from alcohols having no less than three hydroxyl groups and dispersed in water or a non-acidic organic solvent are disclosed. The compositions are especially useful in coatings for electrical wires, as varnishes, and as paints where high thermal stability and flexibility are required. This invention relates to a polyester or a polyesterimide having a great degree of flexibility and thermal stability. More particularly, it relates to the synthesis of a polyester or a polyesterimide which involves the exclusive use of alcohols having at least three hydroxyl groups and dispersed in a water or a non-acidic organic solvent.
Description
~ ~9~
sACKGROUND OF THE INVENTION
It has been known that polyester and polyesterimi~e resins synthesized from acids, di~unctional alcohols, and higher poly-functional alcohols are particularly use~ul as an insulating coating for electrical wires. An noted in U.S. Patent No. 2,936,296 - issued May 10, 1960 - Precopio et al, the insulating material to be employed for these purposes must be able to withstand extreme mechanical, chemical and electrical stresses. More particularly, as increased currents are passed through the ~ires extreme heating takes place which will cause the insulation to break downO As is noted in U.S. Patent No. 3,345,429 - issued October 3, 1967 - Sattler, the addition of higher poly-functional alcohols ~e.g., those alcohols having three or more hydro~yl groups) to the composition, results in the polyester having a higher degree of thermal stability.
~owever, the poly-functional alcohols lack the flexibility which is desired for insulated or enameled wires.
Therefore, in the past, synthetic resins were formed with a mixture of both di-functional and higher polyfunctional alcohols. Examples of the prior art include U.S. Patent No 3,374,114 - issued March 19, 1968 - Wiener and U.S.
Patent No~ 3r378,402 - issued April 16, 1968 - Wiener, U.S. Patent No. 3,449,467 - issued June 10, 1969 - Winstra, U.S. Patent No. 3,296,024 - issued January 3, 1967 -Jordan et al, U.S. Patent No. 3,426,098 ~ issued February 4, 1969 - Meyer et al, and U.SO Patent No. 3l310,512 -issued March 21r 1967 - Curtice. As can be determined from the above cited patents, many attempts have been made to synthesize a polyester or a polyesterimide resin coating ~ 2 60 IN 529 composition having the requislte characteristics for the wire coatings in electrical devices.
In order to determine whether the composition has the required thermal stability and flexibility, the resin is applied to copper wire and convenkional tests are performed. These tests are discussed in U.S. Patent No. 2,936,296 - issued May lO, 1960 - Precopio et al, cited above~ More particularly, thermal stability is measured by "cut through" temperature which is the temperature at which electrical contact can be estahlished between two coated wires. The coated wires are placed perpendicular to each other, and a load oE l,000 grams is placed at the intersection of the wires. ~ potential of llO volts is applied to the end of each wire and a suitable indicator such as a buzzer is connected to the circuit.
The temperature of the crossed wires is increased at the rate of 3C per minute until the insulator coating softens sufficiently so that electrical contact is made between the tw,o wires thereby causing the buzzer to actuate. The temperature at which this occurs is measured as the "cut through" temperature~ Typical "cut through" temperatures ~or polyester or polyesterimide resins made from a combination of di-functional and tri-functional alcohols are in the range of 200~300C.
As was noted above, an increase in the percentage of tri-functional alcohols verses di-functional alcohols will increase the thermal stability of the coatin~ but will substantially impair its flexibility. The flexibi,lity of a resi,n coa1ing is determined by stretching the wire conductor an additional 25% of it,s original lenyth and wrapping the wlre around à mandrel. The wire is then studied under a mic~roscope to determine if there are any imperfections in the ~ 60 IN 529 enamel. The degree of lexibility is measured by determining the smallest diameter mandrel which the wire may be wound around withou-t exhibitlny imperfections. Conventional mandrel diameters are measured in multiples of -the wire diameter such that a 3X mandrel has a diameter three times the diameter of -the wire being tested. It is necessary for wires used in applications such as those noted-above to have a flexibility of at least 25% elongation on a 3X mandrel.
Another important consideration in the formation o~ a resin, is that the polyester of polyesterimide resin be dissolvable in readily available, inexpensive solvents.
The solvents most often employed in the prior art were acidic organic solvents such as cresol and cresylic acid.
However, when these types of solvents are employed, the us~al fire and health hazards as well as the corrosive, acidic effect on the environment, and the cost factor associated with such organic solvents were inevitable present. It was suggested in the U.S. Patent No. 3,310,512 - issued March 12, 1967 - Curtice, that a water solvent be employed to obviate this problem. German Patent Publication No. 1,036~426 ~8/14/1952) also suggests water solvent to obviate health and fire hazards. Others have suggested the use of glycol ethers or glycol esters.
However, as noted in the Curtice patent, unless some di-functional alcohols are employed in the synthesis, problems arise with regard to the flexibility and toughness of the resin.
In contrast, U.S. Patent ~o. 3,342,780 - issued September 19, 1967 - Meyer suggests the forma-tion of a polyester coating made from -tris-2-hydroxyl-ethyl-isocyanurate, a poly-functional alcohol. And U.S. Patent No. 3,426,098 -issued February 4, 1969 - Meyer et al. makes the identical ~97~ 60 IN 529 suggestion with respect to polyesterimides. In U.S. Patent No. 3,342,780 - issued September 19, 1967 - Meyer, and in U.S. Patent No. 3,426,098 - issued February 4, 1969 - Meyer, an acidic organic solvent, cresylic acid, is used to disperse the mixture. As noted above in U.S. Patent No.
3,310,512 - issued March 12, 1967 - Curtice, in general/
an organic solvent is required to be employed in the formation of a resin in order to maintain acceptable characteristics of the resulting resin. More particularly, water, the safer and less expensive solvent, may be used only when the synthesis includes some amounts of di-functional alcohols.
Therefore, it is an object of the subject invention to provide a new and improved polyes-ter or polyesterimide composition wherein the alcohols are all higher poly-functional alcohols. It is a further object of -the subject invention to provide a polyester or polyesterimide composition which is characterized by both flexibility and high thermal stability. It is another object of -the subject invention to provide a polyester of polyesterimide resin which can be aispersed in a water or normally liquid nonacidic organic solvent, and yet maintain high thermal stability and flexibility.
DESCRIPTION OF THE INVENTION
According to the present invention, there is provided a new and improved polyester or polyesterimide, dispersed in a water or non-acidic organic solvent. The polyesterimide resin is a combination of an acid having at least two carboxyl groups and a tri-functional or higher -functional alcohol. Alcohols which may be employed in the synthesis are represented by the formula:
/ :. -- ~ _ ~ 7~2 60 IN 529 OH
HO - R - O~
wherein R may represent any aromatic, alkyl, cyclo alkyl or any combination thereof. X may be a fourth hydroxyl y,oup or a hydrogen or any other radical. Typical examples of suitable alcohols are glycerine, tri-methylol propane, triethanol propane, tris-~2-hydroxylethyltisocyanurate or any combination thereof. The tri-functional or higher functional alcohol is combined with a carboxylic acid, which can be a dibasic acid such as terephthalic, isophthalic or adipic. The acid can also be a mi~ture containing a dibasic acid and a tri-functional acid or even a tetra-functional acid such as trimellitic acid, its anhydride.
In a preferred feature of the invention, the polyester or polyesterimide will be prepared in the presence of a monofunctional alcohol, especially preferably a monoether of a glycol or a polyglycol, e.g~, a Cl-C6 ether of a Cl-C6 aklylene glycol or Cl-C6 alkylene polyglycol, ethylene glycol mono methyl ether or diethylene glycol monomethyl ether or diethylene glycol mono n-butyl ether, ~o mixtures of any of the foregoing, and the like.
To improve the abrasion properties of the polyesterimide, small amounts of metal additives are employed.
A typical metal additive is tetra-isopropyl titanate. The poly-functional alcohol, the acid and a metal additive are combine.s and heated. The poly-functional alcohol will genexally have a small percentage of water which should be distilled off during heatlng. When the mixture reaches a suitable acid number, e.~., below about 100, pxeferably helow about 60, it is cooled, whereupon a co-solvent such as butanol may be added. Xt is desirable -to use a small amount of co-solvent to produce a more stable dispersion of the polyester, or polyes-terimide, especially when the primary solvent comprises water. Generally the co-solvent can be added prior to, during, or after neutralization. To this mixture an amine, preferahly a tertiary amine, such as dimethylethanolamine, is added to neutralize the mixture.
Thereafter, water or a non-acidic organic solvent such as glycol ether or a glycol ester, e.g., diethylene ~lycol monomethyl ether, is added to obtain sufficient dispersability.
The viscosity and the percent solids of the mixture are adjusted based on the particular application of the resin.
Rolyesters or polyesterimides synthesized according to the subject invention will have increased thermal stability and high flexibility. The cut-through temperature of the polyesterimides of the subject i-nvention is in the order o~ over 300C. The polyester or polyes-~erimide enameled wire will pass a 2X flex test a~ter a 25% elongation.
In addition, since the resin is dispersed in a non-acidic medium, health hazards, as ~ell as costs, are minimized.
DESCRIPTIO~ OF THE PREFERRED EMBODIMENTS
Examples of polyester and polyesterimide resins synthesized in accordance with the subject invention is giYen below. They do not limit the inventionn -EX~U~LE 1 To make a water dispersed polyesterimide a flask is charged with thé following: - gms.
Trimellitic anhydride 22~
~ethylenedianiline 116 Tris-~2-hydroxylethyltisocyanurate 222 Isophthalic acid 150 M-pyrol* 180 7~
60 IN 52g Trimethylol propane 206 Tetraisopropyl titanate 18 * Also known a N-methyl pyrrolidone The above contents are stirred and heated to a maximum of 217C., while excess water is distilled in a Dean Stark trap. Heating is continued until an acid number o~ 35 is reached and then the contents are allowed to cool to 170C., whereupon 153 grams of the co-sol~ent butanol are slowly added. The mixture is then neutralized by the addition of 145 grams of dimethylethanolamine. The mixture is then dispersed with 1300 grams of water. The result is a clear solution with a percent solids of 35% and a viscosity o~ 25C. of 1643 centipoise.
The resulting enamel was applied in a 10 foot electric tower and run at speeds of 3Z and 35 feet per minute. Standard 18 AWG copper wire having an enamel thickness of between 2~9 - 3.1 mils is tested.
Each run passes the flexibility test of 25%
elongation wrapped around a 2~ mandrel. In addition, each run passes both the sudden snap test and the 70/30 alcohol/
toluene solvent resistance test. Cut-through ls measured ~t 353C. and 335C. for the 32 and 35 feet per minute runs, respectively. The wire is subjected to the standard repeat scrape tests using a knife edye and a 780 gram load. The test results indicate high abrasion resistance with the 32 and the 35 feet per minute runs withstanding 52 and 62 scrapes, respectively.
EX~PLE 2 To make a water dispersed polyester a flas]~ is charged with the ~ollowing:
9 7 ~ ~ 60 IN 529 ms Tris~2-hydroxyethyltisocyanurate 222 Isophthalic acid 150 Terephthalic acid 242 Trimethylolpropane 206 Tetraisopropyl titanate 18 M-pyrol 180 The contents are heated slowly with the evolution of water to a maximum temperature of 212C., whlle excess water is distilled into a Dean Stark trap~ Heating is continued until an acid number of 35 is reached. The contents are then cooled to 17QC. and 244.5 grams of a co-solvent, n-butanol, is slowly added. The mixture is then neutralized by the addition of 165 grams of dimethylethanolamine. The mixture is then dispersed with 1450 grams of water. The resultant clear solution has a percent solids of 28.13% and a viscosity at 25 C~ of 931 cs.
This enamel is applied at a maximum temperature of 915 F. in a 10-foot electric tower at 55 ft/min. using seven passes on 18 AWG copper wire. The following results are obtained.
Flexibility, 25% 2x Continuity (Breaks/200 ft.) 2 Sol~ent Resistance (70 alcohol/
30 toluene) Pass Dissipation Factor (170 C.) 7.0 Cut Through C., 2000 ym 384 Heat Age (100 hrs. at 175 C.) lx Heat Shock 0%-30 min. at 155 C. 2x Dielectric Strenyth (kv) 10.3 Burnout OF'M (O~erload Figure of ~erit) 7.52 Repeat Scrape 61.2 avg.
~ 7~ 60 IN 529 _X~MP~E 3 To make a glycol ether-dipersed polyester a flask is charged with the following: gmg Tris~2-hydroxyethyltisocyanurate 222 Isophthalic acid 150 Terephthalic acid 242 Trimethylolpropane 206 Tetraisopropyl titanate 18 M-pyrol 180 The contents are slowly heated with the evolution of water to a maximum temperature of 207C., while excess water is distilled into a Dean Stark trap. Heatin~ is continued unt~l an acid number of 3I.7 is reached. The contents are then cooled to 170C. and 153 grams of n-butanol, 571 grams of diethylene glycol mono methyl ether, and 190 grams of Solvesso 100 are added. The resultant clear solution has a percent solids of 39.75% and a viscosity at 25C. of 978 cs.
This enamel is applied at a maximum temperature of 90Q F. in a ten-foot electric tower at 45 ft./min. using 2Q seVen passes on 18 AWG copper wire. The following results are obtained:
Flexibility/ 25% 2x Continuity (Breaks/200 ft.~ 2 Solvent Resistance (50 Alcohol/
50 Toluenel Pass Dissipation Factor (170 C.) 4.8 Cut Through C., 2000 g 415 Heat Shock 0~ - 30 min. at 155 C. 2X
Dielectric Strength (kv~ 8.9 Burnout OFM 7.64 Repeat Scrape 203.0 avg.
A~ ~
The enamel is applied again in five passes (2.4 mil. build) with an amide-imide top coat, two passes (0.Ç
mil build). Maximum temperature 900 F. in a ten--foot electric ~ower at 45 ft./min. on 18 AWG copper wire. The following results are obtained.
Flexibility, 25~ 2x Continuity (Breaks/200 ft.) 2 Solvent Resistance (50 Alcohol/50 Toluenel Pass lU Dissipation Factor (I70 C) 5.2 Cut Through C., 2000 g 411 Heat Shock 0% - 30 min. at 155 C. 2x Dielec-tric Strength (kv) 10.3 Burnout OFM 7.74 Repeat Scrape 153.4 av~.
To make a glycol ether dispersed polyesterimide in the presence of a mono-unctional ether glycol a flask is charged with the following: gms.
Trimellitic anhydride 224 Methylene dianiline 116 Tris~2-hydroxyethyl~isocyanurate 222 Isophthalic acid 150 Texephthalic acid 145 Trimethylolpropane 206 Tetraisopropyltitanate 18 Diethylene glycol mono n-butyl 180 ether The contents are heated slowly with the evolution of water to a maximum temperature of 215 C. The excess water being distilled into a Dean Stark trap. Heating is continued until an acid nur~er o~ 30 is reached. The contents are then cooled to 180C. and 220g. o* Solvesso 100 is added.
~ 2 60 IN 529 When -the batch has further cooled to 150 C. 660 g. of diethylene glycol monomethyl ether is added. To this solution is also added 57.2 g. blocked isocyanate (Mondur SH), 23.6g. tetraisopropyl titanate in 75 g. diethylene ylycol monomethyl ether and 25 g. Solvesso 100, 585 g.
diethylene glycol monomethyl ether, and 195 g. Solvesso 100.
The resultant solution has a percent solids of 37.71~ and a viscosity at 25C. of 1525 cs.
This enamel is applied to 18 AWG copper wire at a maximum temperature of 900F. in a ten-foot electric tower at 40 ft./min. in fi~e passes 2.4 mil. build) with an amide~imide top coat, two passes (0.6 mil. build). The following results are obtained.
Flexibility, 25% 3x Continuity (Breaks/200 ft.) 0 Solvent Resistance ~50 Alcohol/50 Toluene) Pass Dissipation Factor (220 C.) 11.9 Cut Through C.I 2000 g. 368 Heat Shock 0~ - 30 min. at 200 C. 2x Dielectric Strength ~kv~ 8.2 Repeat Scrape 195 avg.
The foregoing demons-trates that the present i~vention proyides a new and improved polyester or polyesterimide resin ha~ing increased thermal stability and a high degree o~ flexibility. The polyester or polyesterimide resins o~ the subject invention are synthesized with alcohols which are highly polyfunctional. In addition, the polyester or polyesterimide resins are dispersible in water and/or non-acidic organic solvents and this therefore reduces manufacturing costs, while minimizing safety hazards durin~ synthesis and transportation.
~1~9~ 60 IN 529 It is to be understood that changes may be made in the par-ticular embodiments of the i.nvention in liyhk oE
the above teachings and that these will be within the full scope oE the invention as de:Eined by the appended claims.
sACKGROUND OF THE INVENTION
It has been known that polyester and polyesterimi~e resins synthesized from acids, di~unctional alcohols, and higher poly-functional alcohols are particularly use~ul as an insulating coating for electrical wires. An noted in U.S. Patent No. 2,936,296 - issued May 10, 1960 - Precopio et al, the insulating material to be employed for these purposes must be able to withstand extreme mechanical, chemical and electrical stresses. More particularly, as increased currents are passed through the ~ires extreme heating takes place which will cause the insulation to break downO As is noted in U.S. Patent No. 3,345,429 - issued October 3, 1967 - Sattler, the addition of higher poly-functional alcohols ~e.g., those alcohols having three or more hydro~yl groups) to the composition, results in the polyester having a higher degree of thermal stability.
~owever, the poly-functional alcohols lack the flexibility which is desired for insulated or enameled wires.
Therefore, in the past, synthetic resins were formed with a mixture of both di-functional and higher polyfunctional alcohols. Examples of the prior art include U.S. Patent No 3,374,114 - issued March 19, 1968 - Wiener and U.S.
Patent No~ 3r378,402 - issued April 16, 1968 - Wiener, U.S. Patent No. 3,449,467 - issued June 10, 1969 - Winstra, U.S. Patent No. 3,296,024 - issued January 3, 1967 -Jordan et al, U.S. Patent No. 3,426,098 ~ issued February 4, 1969 - Meyer et al, and U.SO Patent No. 3l310,512 -issued March 21r 1967 - Curtice. As can be determined from the above cited patents, many attempts have been made to synthesize a polyester or a polyesterimide resin coating ~ 2 60 IN 529 composition having the requislte characteristics for the wire coatings in electrical devices.
In order to determine whether the composition has the required thermal stability and flexibility, the resin is applied to copper wire and convenkional tests are performed. These tests are discussed in U.S. Patent No. 2,936,296 - issued May lO, 1960 - Precopio et al, cited above~ More particularly, thermal stability is measured by "cut through" temperature which is the temperature at which electrical contact can be estahlished between two coated wires. The coated wires are placed perpendicular to each other, and a load oE l,000 grams is placed at the intersection of the wires. ~ potential of llO volts is applied to the end of each wire and a suitable indicator such as a buzzer is connected to the circuit.
The temperature of the crossed wires is increased at the rate of 3C per minute until the insulator coating softens sufficiently so that electrical contact is made between the tw,o wires thereby causing the buzzer to actuate. The temperature at which this occurs is measured as the "cut through" temperature~ Typical "cut through" temperatures ~or polyester or polyesterimide resins made from a combination of di-functional and tri-functional alcohols are in the range of 200~300C.
As was noted above, an increase in the percentage of tri-functional alcohols verses di-functional alcohols will increase the thermal stability of the coatin~ but will substantially impair its flexibility. The flexibi,lity of a resi,n coa1ing is determined by stretching the wire conductor an additional 25% of it,s original lenyth and wrapping the wlre around à mandrel. The wire is then studied under a mic~roscope to determine if there are any imperfections in the ~ 60 IN 529 enamel. The degree of lexibility is measured by determining the smallest diameter mandrel which the wire may be wound around withou-t exhibitlny imperfections. Conventional mandrel diameters are measured in multiples of -the wire diameter such that a 3X mandrel has a diameter three times the diameter of -the wire being tested. It is necessary for wires used in applications such as those noted-above to have a flexibility of at least 25% elongation on a 3X mandrel.
Another important consideration in the formation o~ a resin, is that the polyester of polyesterimide resin be dissolvable in readily available, inexpensive solvents.
The solvents most often employed in the prior art were acidic organic solvents such as cresol and cresylic acid.
However, when these types of solvents are employed, the us~al fire and health hazards as well as the corrosive, acidic effect on the environment, and the cost factor associated with such organic solvents were inevitable present. It was suggested in the U.S. Patent No. 3,310,512 - issued March 12, 1967 - Curtice, that a water solvent be employed to obviate this problem. German Patent Publication No. 1,036~426 ~8/14/1952) also suggests water solvent to obviate health and fire hazards. Others have suggested the use of glycol ethers or glycol esters.
However, as noted in the Curtice patent, unless some di-functional alcohols are employed in the synthesis, problems arise with regard to the flexibility and toughness of the resin.
In contrast, U.S. Patent ~o. 3,342,780 - issued September 19, 1967 - Meyer suggests the forma-tion of a polyester coating made from -tris-2-hydroxyl-ethyl-isocyanurate, a poly-functional alcohol. And U.S. Patent No. 3,426,098 -issued February 4, 1969 - Meyer et al. makes the identical ~97~ 60 IN 529 suggestion with respect to polyesterimides. In U.S. Patent No. 3,342,780 - issued September 19, 1967 - Meyer, and in U.S. Patent No. 3,426,098 - issued February 4, 1969 - Meyer, an acidic organic solvent, cresylic acid, is used to disperse the mixture. As noted above in U.S. Patent No.
3,310,512 - issued March 12, 1967 - Curtice, in general/
an organic solvent is required to be employed in the formation of a resin in order to maintain acceptable characteristics of the resulting resin. More particularly, water, the safer and less expensive solvent, may be used only when the synthesis includes some amounts of di-functional alcohols.
Therefore, it is an object of the subject invention to provide a new and improved polyes-ter or polyesterimide composition wherein the alcohols are all higher poly-functional alcohols. It is a further object of -the subject invention to provide a polyester or polyesterimide composition which is characterized by both flexibility and high thermal stability. It is another object of -the subject invention to provide a polyester of polyesterimide resin which can be aispersed in a water or normally liquid nonacidic organic solvent, and yet maintain high thermal stability and flexibility.
DESCRIPTION OF THE INVENTION
According to the present invention, there is provided a new and improved polyester or polyesterimide, dispersed in a water or non-acidic organic solvent. The polyesterimide resin is a combination of an acid having at least two carboxyl groups and a tri-functional or higher -functional alcohol. Alcohols which may be employed in the synthesis are represented by the formula:
/ :. -- ~ _ ~ 7~2 60 IN 529 OH
HO - R - O~
wherein R may represent any aromatic, alkyl, cyclo alkyl or any combination thereof. X may be a fourth hydroxyl y,oup or a hydrogen or any other radical. Typical examples of suitable alcohols are glycerine, tri-methylol propane, triethanol propane, tris-~2-hydroxylethyltisocyanurate or any combination thereof. The tri-functional or higher functional alcohol is combined with a carboxylic acid, which can be a dibasic acid such as terephthalic, isophthalic or adipic. The acid can also be a mi~ture containing a dibasic acid and a tri-functional acid or even a tetra-functional acid such as trimellitic acid, its anhydride.
In a preferred feature of the invention, the polyester or polyesterimide will be prepared in the presence of a monofunctional alcohol, especially preferably a monoether of a glycol or a polyglycol, e.g~, a Cl-C6 ether of a Cl-C6 aklylene glycol or Cl-C6 alkylene polyglycol, ethylene glycol mono methyl ether or diethylene glycol monomethyl ether or diethylene glycol mono n-butyl ether, ~o mixtures of any of the foregoing, and the like.
To improve the abrasion properties of the polyesterimide, small amounts of metal additives are employed.
A typical metal additive is tetra-isopropyl titanate. The poly-functional alcohol, the acid and a metal additive are combine.s and heated. The poly-functional alcohol will genexally have a small percentage of water which should be distilled off during heatlng. When the mixture reaches a suitable acid number, e.~., below about 100, pxeferably helow about 60, it is cooled, whereupon a co-solvent such as butanol may be added. Xt is desirable -to use a small amount of co-solvent to produce a more stable dispersion of the polyester, or polyes-terimide, especially when the primary solvent comprises water. Generally the co-solvent can be added prior to, during, or after neutralization. To this mixture an amine, preferahly a tertiary amine, such as dimethylethanolamine, is added to neutralize the mixture.
Thereafter, water or a non-acidic organic solvent such as glycol ether or a glycol ester, e.g., diethylene ~lycol monomethyl ether, is added to obtain sufficient dispersability.
The viscosity and the percent solids of the mixture are adjusted based on the particular application of the resin.
Rolyesters or polyesterimides synthesized according to the subject invention will have increased thermal stability and high flexibility. The cut-through temperature of the polyesterimides of the subject i-nvention is in the order o~ over 300C. The polyester or polyes-~erimide enameled wire will pass a 2X flex test a~ter a 25% elongation.
In addition, since the resin is dispersed in a non-acidic medium, health hazards, as ~ell as costs, are minimized.
DESCRIPTIO~ OF THE PREFERRED EMBODIMENTS
Examples of polyester and polyesterimide resins synthesized in accordance with the subject invention is giYen below. They do not limit the inventionn -EX~U~LE 1 To make a water dispersed polyesterimide a flask is charged with thé following: - gms.
Trimellitic anhydride 22~
~ethylenedianiline 116 Tris-~2-hydroxylethyltisocyanurate 222 Isophthalic acid 150 M-pyrol* 180 7~
60 IN 52g Trimethylol propane 206 Tetraisopropyl titanate 18 * Also known a N-methyl pyrrolidone The above contents are stirred and heated to a maximum of 217C., while excess water is distilled in a Dean Stark trap. Heating is continued until an acid number o~ 35 is reached and then the contents are allowed to cool to 170C., whereupon 153 grams of the co-sol~ent butanol are slowly added. The mixture is then neutralized by the addition of 145 grams of dimethylethanolamine. The mixture is then dispersed with 1300 grams of water. The result is a clear solution with a percent solids of 35% and a viscosity o~ 25C. of 1643 centipoise.
The resulting enamel was applied in a 10 foot electric tower and run at speeds of 3Z and 35 feet per minute. Standard 18 AWG copper wire having an enamel thickness of between 2~9 - 3.1 mils is tested.
Each run passes the flexibility test of 25%
elongation wrapped around a 2~ mandrel. In addition, each run passes both the sudden snap test and the 70/30 alcohol/
toluene solvent resistance test. Cut-through ls measured ~t 353C. and 335C. for the 32 and 35 feet per minute runs, respectively. The wire is subjected to the standard repeat scrape tests using a knife edye and a 780 gram load. The test results indicate high abrasion resistance with the 32 and the 35 feet per minute runs withstanding 52 and 62 scrapes, respectively.
EX~PLE 2 To make a water dispersed polyester a flas]~ is charged with the ~ollowing:
9 7 ~ ~ 60 IN 529 ms Tris~2-hydroxyethyltisocyanurate 222 Isophthalic acid 150 Terephthalic acid 242 Trimethylolpropane 206 Tetraisopropyl titanate 18 M-pyrol 180 The contents are heated slowly with the evolution of water to a maximum temperature of 212C., whlle excess water is distilled into a Dean Stark trap~ Heating is continued until an acid number of 35 is reached. The contents are then cooled to 17QC. and 244.5 grams of a co-solvent, n-butanol, is slowly added. The mixture is then neutralized by the addition of 165 grams of dimethylethanolamine. The mixture is then dispersed with 1450 grams of water. The resultant clear solution has a percent solids of 28.13% and a viscosity at 25 C~ of 931 cs.
This enamel is applied at a maximum temperature of 915 F. in a 10-foot electric tower at 55 ft/min. using seven passes on 18 AWG copper wire. The following results are obtained.
Flexibility, 25% 2x Continuity (Breaks/200 ft.) 2 Sol~ent Resistance (70 alcohol/
30 toluene) Pass Dissipation Factor (170 C.) 7.0 Cut Through C., 2000 ym 384 Heat Age (100 hrs. at 175 C.) lx Heat Shock 0%-30 min. at 155 C. 2x Dielectric Strenyth (kv) 10.3 Burnout OF'M (O~erload Figure of ~erit) 7.52 Repeat Scrape 61.2 avg.
~ 7~ 60 IN 529 _X~MP~E 3 To make a glycol ether-dipersed polyester a flask is charged with the following: gmg Tris~2-hydroxyethyltisocyanurate 222 Isophthalic acid 150 Terephthalic acid 242 Trimethylolpropane 206 Tetraisopropyl titanate 18 M-pyrol 180 The contents are slowly heated with the evolution of water to a maximum temperature of 207C., while excess water is distilled into a Dean Stark trap. Heatin~ is continued unt~l an acid number of 3I.7 is reached. The contents are then cooled to 170C. and 153 grams of n-butanol, 571 grams of diethylene glycol mono methyl ether, and 190 grams of Solvesso 100 are added. The resultant clear solution has a percent solids of 39.75% and a viscosity at 25C. of 978 cs.
This enamel is applied at a maximum temperature of 90Q F. in a ten-foot electric tower at 45 ft./min. using 2Q seVen passes on 18 AWG copper wire. The following results are obtained:
Flexibility/ 25% 2x Continuity (Breaks/200 ft.~ 2 Solvent Resistance (50 Alcohol/
50 Toluenel Pass Dissipation Factor (170 C.) 4.8 Cut Through C., 2000 g 415 Heat Shock 0~ - 30 min. at 155 C. 2X
Dielectric Strength (kv~ 8.9 Burnout OFM 7.64 Repeat Scrape 203.0 avg.
A~ ~
The enamel is applied again in five passes (2.4 mil. build) with an amide-imide top coat, two passes (0.Ç
mil build). Maximum temperature 900 F. in a ten--foot electric ~ower at 45 ft./min. on 18 AWG copper wire. The following results are obtained.
Flexibility, 25~ 2x Continuity (Breaks/200 ft.) 2 Solvent Resistance (50 Alcohol/50 Toluenel Pass lU Dissipation Factor (I70 C) 5.2 Cut Through C., 2000 g 411 Heat Shock 0% - 30 min. at 155 C. 2x Dielec-tric Strength (kv) 10.3 Burnout OFM 7.74 Repeat Scrape 153.4 av~.
To make a glycol ether dispersed polyesterimide in the presence of a mono-unctional ether glycol a flask is charged with the following: gms.
Trimellitic anhydride 224 Methylene dianiline 116 Tris~2-hydroxyethyl~isocyanurate 222 Isophthalic acid 150 Texephthalic acid 145 Trimethylolpropane 206 Tetraisopropyltitanate 18 Diethylene glycol mono n-butyl 180 ether The contents are heated slowly with the evolution of water to a maximum temperature of 215 C. The excess water being distilled into a Dean Stark trap. Heating is continued until an acid nur~er o~ 30 is reached. The contents are then cooled to 180C. and 220g. o* Solvesso 100 is added.
~ 2 60 IN 529 When -the batch has further cooled to 150 C. 660 g. of diethylene glycol monomethyl ether is added. To this solution is also added 57.2 g. blocked isocyanate (Mondur SH), 23.6g. tetraisopropyl titanate in 75 g. diethylene ylycol monomethyl ether and 25 g. Solvesso 100, 585 g.
diethylene glycol monomethyl ether, and 195 g. Solvesso 100.
The resultant solution has a percent solids of 37.71~ and a viscosity at 25C. of 1525 cs.
This enamel is applied to 18 AWG copper wire at a maximum temperature of 900F. in a ten-foot electric tower at 40 ft./min. in fi~e passes 2.4 mil. build) with an amide~imide top coat, two passes (0.6 mil. build). The following results are obtained.
Flexibility, 25% 3x Continuity (Breaks/200 ft.) 0 Solvent Resistance ~50 Alcohol/50 Toluene) Pass Dissipation Factor (220 C.) 11.9 Cut Through C.I 2000 g. 368 Heat Shock 0~ - 30 min. at 200 C. 2x Dielectric Strength ~kv~ 8.2 Repeat Scrape 195 avg.
The foregoing demons-trates that the present i~vention proyides a new and improved polyester or polyesterimide resin ha~ing increased thermal stability and a high degree o~ flexibility. The polyester or polyesterimide resins o~ the subject invention are synthesized with alcohols which are highly polyfunctional. In addition, the polyester or polyesterimide resins are dispersible in water and/or non-acidic organic solvents and this therefore reduces manufacturing costs, while minimizing safety hazards durin~ synthesis and transportation.
~1~9~ 60 IN 529 It is to be understood that changes may be made in the par-ticular embodiments of the i.nvention in liyhk oE
the above teachings and that these will be within the full scope oE the invention as de:Eined by the appended claims.
Claims (11)
1. A polyester or polyesterimide composition having high thermal stability and flexibility for use in coating electrical wires obtained by heating at a temperature slightly above the boiling point of water, a mixture consisting essentially of an acid having at least two carboxyl groups, or a mixture of said acid and an aromatic diamine, and an alcohol represented by the formula wherein R may be any aromatic, alkyl, cycloalkyl or any combination thereof and X may be a hydroxyl group, hydrogen or any other radical and said alcohol may be a mixture of alcohols, until the mixture has an acid number of below about 60 is reached, cooling said mixture to about 180°C, neutralizing said composition with a neutralizing agent and dispersing said composition with water, a non-acidic normally liquid organic compound, or a mixture thereof, as a solvent.
2. A polyester or polyesterimide composition as defined in claim 1 wherein said tri-functional alcohol is selected from the group consisting of glycerin, trimethyol propane, triethanol propane and tris-2-hydroxyl-ethyl-isocy-anurate.
3. A polyester or polyesterimide composition as defined in claim 1 wherein said neutralizing agent is an amine.
4. A polyester or polyesterimide composition as defined in claim 3 wherein said amine is dimethylethanolamine.
5. A polyester or polyesterimide composition as defined in claim 1 wherein said solvent comprises water.
6. A polyester or polyesterimide composition as defined in claim 1 wherein said non-acidic normally liquid organic compound comprises a glycol ether or a glycol ester.
7. A polyester or polyesterimide composition as defined in claim 1 wherein a co-solvent is added after heating to provide a more stable dispersion.
8. A polyesterimide composition as defined in claim 7 wherein said co-solvent is butanol.
9. A polyester or polyesterimide composition as defined in claim 1 wherein said acid is selected from a group consisting of a dibasic acid, a tribasic acid, and a tetra-basic acid or a mixture of any of the foregoing.
10. A polyester or polyesterimide composition as defined in claim 1 further including a metal drier for improving abrasion resistance.
11. A polyesterimide composition as defined in claim 10 wherein said metal drier is tetra-isopropyl titanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000364541A CA1199742A (en) | 1980-11-13 | 1980-11-13 | Polyester and polyesterimide resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000364541A CA1199742A (en) | 1980-11-13 | 1980-11-13 | Polyester and polyesterimide resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1199742A true CA1199742A (en) | 1986-01-21 |
Family
ID=4118429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000364541A Expired CA1199742A (en) | 1980-11-13 | 1980-11-13 | Polyester and polyesterimide resins |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1199742A (en) |
-
1980
- 1980-11-13 CA CA000364541A patent/CA1199742A/en not_active Expired
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