CA1211886A - Crosslinkable compositions of poly(parabanic acid) with organic sulfonic acids or their derivatives - Google Patents
Crosslinkable compositions of poly(parabanic acid) with organic sulfonic acids or their derivativesInfo
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- CA1211886A CA1211886A CA000420159A CA420159A CA1211886A CA 1211886 A CA1211886 A CA 1211886A CA 000420159 A CA000420159 A CA 000420159A CA 420159 A CA420159 A CA 420159A CA 1211886 A CA1211886 A CA 1211886A
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Abstract
ABSTRACT
Crosslinked poly(parabanic acid) is obtained by heating poly(parabanic acid) at a temperature in the range of 200-300°C in the presence of a crosslinking amount of a sulfonic acid, ester or salt thereof. The presence of the sulfonic acid, ester or salt thereof provides for a shorter curing time as compared with thermal crosslinking in the absence of the sulfonic acid, ester or salt thereof, thereby avoiding oxidative degradation. The crosslinked poly(parabanic acids) are useful for the production of magnetic tapes, films for use in flexible printed circuits, cable wraps, fibers such as tire cord fibers and the like.
Crosslinked poly(parabanic acid) is obtained by heating poly(parabanic acid) at a temperature in the range of 200-300°C in the presence of a crosslinking amount of a sulfonic acid, ester or salt thereof. The presence of the sulfonic acid, ester or salt thereof provides for a shorter curing time as compared with thermal crosslinking in the absence of the sulfonic acid, ester or salt thereof, thereby avoiding oxidative degradation. The crosslinked poly(parabanic acids) are useful for the production of magnetic tapes, films for use in flexible printed circuits, cable wraps, fibers such as tire cord fibers and the like.
Description
lZ11886 The present invention r~lates to the discovery of a
2 specific class of crosslinking agents for polv~parabanic
3 acid) resins.
4 Poly(parabanic acids), their precursors the poly-
5 (iminoimidazolidinediones) and their methods of preparation
6 are known and described in detail in commonly assigned
7 U.S. Pat. 3,661,859. The poly(parabanic acias) may also be
8 prepared by other processes, such as shown in U.S. Pat. No.
9 3,609,113.
The poly(iminoimidazolidinediones)may be formed by 11 the reaction of hydrogen cyanide with a diisocyanate or mix-12 ture of diisoc~nates, the reaction of a dicyanoformamide with a di-13 isocyanate or mixtures of diisocyanates, or the polymerization of a 14 cyanoformamdiyl isocyanate, and contain a 1,3-imidazolidi-nedione-1,3-diyl ring-of the following structures in the 16 repeating units:
19 --N N and/o~ --N N
0=C -- C=NHHN=C C=0 21 wherein NH is in the 4 or 5 position.
22The poly(parabanic acids) also designated as 23 poly(l,3-imidazolidine-2,4,5-triorles) may be prepared, 24 for example, by the acid hydrolysis of poly(iminoimi-25 dazolidinediones) and contain the imidazolidinetrione 26 ring in the repeating unit.
28 ~C
30 - 0=C -- C=0 31 U.S. Pat. No. 3,609,113 and German Patent No. 1,770,146 32 describe other methods for preparing polymers which 33contain the poly(parabanic acid) rings.
34The present polymers may be broadly characterized 35as having the repeating unit:
. . ~
36LQ R - _ 37 n '~
~Z11l~86 1 wherein Q is 3 ",C
0=C - C=O
6 wherein R is an organic moiety which may be aliphatic, 7 alicyclic, aromatic or mixtures thexeof, and n is 8 su~ficiently large to produce a solid product.
The R is the organic moiety of the diisocyanate when the polymer is produced according to the procedure in 11 U.S. Pat. No. 3,661,859. Thus, the diisocyanates may be 12 selected from a broad group having a large variety of 13 organic moieties. The organic moieties of the diisocyanate 14 may be substituted with groups such as alkyl, aryl, halogen, sulfoxy, sulfonyl, alkoxy, aryloxy, oxo, ester, 16 alkylthio, arylthio, nitro and the like which do not react 17 with the isocyanate group. Functional groups which have 18 active hydrogen atoms, (e.g., carboxylic acids, phenols, 19 amines, etc.) should not be present. Specific diiso-cyanates which may be used are set out in the U.S. Pat.21 No. 3,661,859 and other patents, articles or organic 22 textbooks.
23 Some of the parabanic acid polymers have been 23 found to have high glass transition temperatures, and 24 thus are especially suitable as magnetic tapes (where good dimensional stability at high temperatures is 26 required), films for use in flexible printed circuits, 27 cable wraps, etc., for fibers such as tire cord fibers 28 (where tensile strength and modulus are required), for 29 moldings for electrical connectors, bearings, magnetic wire insulation, coatings for cable, cookware, glass 31 fabrics, industrial belts (where high temperatures are 32 required) and the like.
33 Generally these polymers are very resistant 34 to thermal decomposition, which does not occur rapidly until at or above their glass transition temperatures.
1~11886 1 However, the poly(parabanic acid~ polymers are subject to 2 attack by some solvents so that in some applications they 3 can not be used as such but must be thermally crosslinked.
4 Thermal crosslinking is normally conducted at hightemper-atures, e.g., 225 to 280C for several hours. At these 7 temperatures in air oxidative degradation also occurs with 8 concomitant decrease in some desi~able properties. More-9 over, the long curing times make the crosslinking econom-ically unattractive.
11 It is an advantage of the present invention that 12 the present poly(parabanic acid) compositions crosslink in 13 much shorter curing times than previously required for the 14 polymers without the crosslinking agent.
Briefly, the present invention is a crosslinkable 16 composition comprising heterocyclic polymers characterized 17 in the repeating unit by the tri-substituted 1,3-imidazo-18 lidine-1,3-diyl ring:
~
21 _ N N
22 O=C C=O
23 specially polyme~s haYing the lepeating unit:
24 ~ Q R ~
n 26 whe~ein Q is 28 ~ C
30 O=C C=O
31 and R is an organic moiety which may be aliphatic, 32 alicyclic, aromatic or mixtures thereof and n is 33 sufficiently large to produce a solid product, and a 34 sufficient amount of a sulfonic acid or derivative thereof to cause crosslinking. The crosslinked polymer 36 is also an aspect of the present invention as is the 37 method of crosslinking the polymers.
1~i1886 1 More particularly, the polymers may be 2 poly(parabanic acids) characterized by tri-substituted 3 1,3-imidazolidine-3-diyl rings of the following structure:
~ C
7 O=C - C=O
8 or more specifically, polymers of the general structure:
9 ~
C
11_ -'' ~ N ~ ~ - respectively, 12 0=C C=0 13 n 14 wherein R and n have the significance given above.
The poly(parabanic acid) polymers are considered 16 to be crosslinked when they are insoluble in their normal 17 solvents. Hence, the term "a crosslinking amount" as that 18 term is used herein is understood to mean an amount of 19 the organic sulfonic acid or derivative which when .incoroor~t~d in and admi~ed with the polymer will produce 21 upon heating a polymeric material insoluble in solvents 22 for poly(parabanic acid) such as dimethyl formamide.
23 Crosslinking can also be detected in films by a decrease 24 in the tensile elongation; but small amounts of crosslink-ing are more readily detected by solubility tests.
26 The sulfonic acids are characterized by the 27 presence of the group:
O
31 on an organic moiety. The organic moiety may be an 32 aliphatic, cyclic, aromatic or polymeric radical. The 33 organic moiety may be a hydrocarbon which may be substi-34 tuted with groups which are not detrimental to the poly(parabanic acid) polymers, such as halogen, sulfoxy, 36 sulfonyl, alkoxy, aryloxy, oxo, ester,thio and nitro 37 groups. Functional groups which have active hydrogens . .
lZ13L886 1 (e.g., carboxylic acids, phenols, amines, etc.) should not 2 be present. The organic moiety may have more than one 3 -SO2OH group.
4 In addition to the free acid the derivatives of of the sulfonic acid may be used. Specifically esters 6 (-SO3R) and salts (-SO3M) of the sulfonic acids may be 7 employed to produce the crosslinkable poly(parabanic acids).
8 The R group in the esters may be aliphatic (1 to 4 carbons 9 in length), alicyclic, or aromatic and substituted as described above.
11 Suitable cations in the salts are alkali metal, 12 alkaline earth metals or metals, preferably from Groups lA, 13 2A, 3A, 4A, 2B, 3B, 6B, 7B and 8 of the Periodic Table, 14 particularly Na, K, Mg, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Ag or Pb. Reference is to the Periodic Table of Mendeleef as it 16 appears on the front cover leaf of the Handbook of 17 Chemistry and Physics 56th Edition 1975-1976, published by 18 CRC Press Cleveland, Ohio, USA.
19 Some specific crosslinking agents are methyl sulfonic acid~ ethylsulfonic acid, n-propylsulfonic acid, 21 isopropylsulfonic acid, cyclohexylsulfonic acid, p-toluene-22 sulfonic acid, 5-nitro-1,3-benzenedisulfonic acid,~ -naph-23 thalenesulfonic acid, ~ -naphthalenesulfonic acid, 24 anthracene sulfonic acid, 1,5 or 1,8 naphthalenedisulfonic acid, methyl-p-toluenesulfonate, the free acid form and the 26 sodium and copper salts of sulfonated polysytrene, 27 p-toluene sulfonic acid, 2-hydroxy-4, methoxy-5-sulfo-28 benzophenone, calcium benzenesulfonate, barium benzene-29 sulfonate, lead benzenesulfonaté, methyl methyl sulfonate, ethyl methyl sulfonate, methyl propyl sulfonate and the 31 like. Aromatic sulfonic acids and their derivatives are 32 preferred because of greater compatibility with the 33 polymers.
34 It has been found that very small amounts of the of the crosslinking agent may be used to obtain the cross-36 linked polymer and that excessively large amounts of cross-37 linking agents demonstrated no advantages. The amount of 38 crosslinking agent present to produce a crosslinkable lZ~1886 1 product is in the range of 0.25 to 16 weight percent based 2 on the poly(parabanic acid) with a preferred range being 3 about 0.5 wt.% to 8 wt.~. The gist of the present invent-4 ion, however, is the use of the least amount of crosslink-ing agent as described to obtain the desired crosslinked, 6 i.e., insoluble, poly(parabanic acid) composition. The use 7 of larger amounts than this are contemplated to be within 8 the scope of the invention, to the extent th~t the cross-9 linked product is not adversely affected thereby.
For purposes of illustration, the examples illus-11 trating the invention will be described in specific with 12 respect to a particular polymer. That is, a polyparabanic 13 acid prepared from diphenylmethane diisocyanate in accor-14 dance with proprietary techniques well described in patents assigned to Exxon Research and Engineering Company to 16 result in a high performance polymer having the repeating 17 unit shown below:
18 _ _ 29 ~ c ~ CH2 ~--21 O=C - C=O n 22 which Is also designated as poly(l,4-phenylenemethylene-1 23 4-phenylene-1,3-(imidazolidine-2,4,5-trione)) which is 24 also designated in chemical abstracts as poly (2,4,5-tri-oxo-l, 3 imidazolidinediyl)-1,4-phenylenemethylene-1,4-26 phenylene) designated PPA-M for convenience. It has a 27 high glass transition temperature of 290 C and can not be 28 extruded or molded.
29 In general, the preferred polymers of the polymer-plasticizer components are those which have suffi-31 cient repeating units at room temperature to be solids.
32 In addition to the polymer and crosslinking 33 agent, it is contemplated that other appropriate additives 34 such as those employed to stabilize the polymer against oxidation or ultraviolet light, flame retardants, pigments, 36 plasticizers, fillers and the like may be present.
37 The present crosslinking agents may be incor-121~886 1 porated into the polymers in solution and thereafter cast or 2 coated onto a substrate and cured or may be premixed with 3 polymer powder and thereafter dissolved. When plasticizers 4 are employed in the polymers they may be extruded and subse-5 quently cured.
6 The curing may be effected by heating the cast or ex-7 truded polymer containing the crosslinking agent at a temper-8 ature in the range of 200 to 300C, preferably of 240 to 280 9 C, for about one hour. The curing temperature and time may
The poly(iminoimidazolidinediones)may be formed by 11 the reaction of hydrogen cyanide with a diisocyanate or mix-12 ture of diisoc~nates, the reaction of a dicyanoformamide with a di-13 isocyanate or mixtures of diisocyanates, or the polymerization of a 14 cyanoformamdiyl isocyanate, and contain a 1,3-imidazolidi-nedione-1,3-diyl ring-of the following structures in the 16 repeating units:
19 --N N and/o~ --N N
0=C -- C=NHHN=C C=0 21 wherein NH is in the 4 or 5 position.
22The poly(parabanic acids) also designated as 23 poly(l,3-imidazolidine-2,4,5-triorles) may be prepared, 24 for example, by the acid hydrolysis of poly(iminoimi-25 dazolidinediones) and contain the imidazolidinetrione 26 ring in the repeating unit.
28 ~C
30 - 0=C -- C=0 31 U.S. Pat. No. 3,609,113 and German Patent No. 1,770,146 32 describe other methods for preparing polymers which 33contain the poly(parabanic acid) rings.
34The present polymers may be broadly characterized 35as having the repeating unit:
. . ~
36LQ R - _ 37 n '~
~Z11l~86 1 wherein Q is 3 ",C
0=C - C=O
6 wherein R is an organic moiety which may be aliphatic, 7 alicyclic, aromatic or mixtures thexeof, and n is 8 su~ficiently large to produce a solid product.
The R is the organic moiety of the diisocyanate when the polymer is produced according to the procedure in 11 U.S. Pat. No. 3,661,859. Thus, the diisocyanates may be 12 selected from a broad group having a large variety of 13 organic moieties. The organic moieties of the diisocyanate 14 may be substituted with groups such as alkyl, aryl, halogen, sulfoxy, sulfonyl, alkoxy, aryloxy, oxo, ester, 16 alkylthio, arylthio, nitro and the like which do not react 17 with the isocyanate group. Functional groups which have 18 active hydrogen atoms, (e.g., carboxylic acids, phenols, 19 amines, etc.) should not be present. Specific diiso-cyanates which may be used are set out in the U.S. Pat.21 No. 3,661,859 and other patents, articles or organic 22 textbooks.
23 Some of the parabanic acid polymers have been 23 found to have high glass transition temperatures, and 24 thus are especially suitable as magnetic tapes (where good dimensional stability at high temperatures is 26 required), films for use in flexible printed circuits, 27 cable wraps, etc., for fibers such as tire cord fibers 28 (where tensile strength and modulus are required), for 29 moldings for electrical connectors, bearings, magnetic wire insulation, coatings for cable, cookware, glass 31 fabrics, industrial belts (where high temperatures are 32 required) and the like.
33 Generally these polymers are very resistant 34 to thermal decomposition, which does not occur rapidly until at or above their glass transition temperatures.
1~11886 1 However, the poly(parabanic acid~ polymers are subject to 2 attack by some solvents so that in some applications they 3 can not be used as such but must be thermally crosslinked.
4 Thermal crosslinking is normally conducted at hightemper-atures, e.g., 225 to 280C for several hours. At these 7 temperatures in air oxidative degradation also occurs with 8 concomitant decrease in some desi~able properties. More-9 over, the long curing times make the crosslinking econom-ically unattractive.
11 It is an advantage of the present invention that 12 the present poly(parabanic acid) compositions crosslink in 13 much shorter curing times than previously required for the 14 polymers without the crosslinking agent.
Briefly, the present invention is a crosslinkable 16 composition comprising heterocyclic polymers characterized 17 in the repeating unit by the tri-substituted 1,3-imidazo-18 lidine-1,3-diyl ring:
~
21 _ N N
22 O=C C=O
23 specially polyme~s haYing the lepeating unit:
24 ~ Q R ~
n 26 whe~ein Q is 28 ~ C
30 O=C C=O
31 and R is an organic moiety which may be aliphatic, 32 alicyclic, aromatic or mixtures thereof and n is 33 sufficiently large to produce a solid product, and a 34 sufficient amount of a sulfonic acid or derivative thereof to cause crosslinking. The crosslinked polymer 36 is also an aspect of the present invention as is the 37 method of crosslinking the polymers.
1~i1886 1 More particularly, the polymers may be 2 poly(parabanic acids) characterized by tri-substituted 3 1,3-imidazolidine-3-diyl rings of the following structure:
~ C
7 O=C - C=O
8 or more specifically, polymers of the general structure:
9 ~
C
11_ -'' ~ N ~ ~ - respectively, 12 0=C C=0 13 n 14 wherein R and n have the significance given above.
The poly(parabanic acid) polymers are considered 16 to be crosslinked when they are insoluble in their normal 17 solvents. Hence, the term "a crosslinking amount" as that 18 term is used herein is understood to mean an amount of 19 the organic sulfonic acid or derivative which when .incoroor~t~d in and admi~ed with the polymer will produce 21 upon heating a polymeric material insoluble in solvents 22 for poly(parabanic acid) such as dimethyl formamide.
23 Crosslinking can also be detected in films by a decrease 24 in the tensile elongation; but small amounts of crosslink-ing are more readily detected by solubility tests.
26 The sulfonic acids are characterized by the 27 presence of the group:
O
31 on an organic moiety. The organic moiety may be an 32 aliphatic, cyclic, aromatic or polymeric radical. The 33 organic moiety may be a hydrocarbon which may be substi-34 tuted with groups which are not detrimental to the poly(parabanic acid) polymers, such as halogen, sulfoxy, 36 sulfonyl, alkoxy, aryloxy, oxo, ester,thio and nitro 37 groups. Functional groups which have active hydrogens . .
lZ13L886 1 (e.g., carboxylic acids, phenols, amines, etc.) should not 2 be present. The organic moiety may have more than one 3 -SO2OH group.
4 In addition to the free acid the derivatives of of the sulfonic acid may be used. Specifically esters 6 (-SO3R) and salts (-SO3M) of the sulfonic acids may be 7 employed to produce the crosslinkable poly(parabanic acids).
8 The R group in the esters may be aliphatic (1 to 4 carbons 9 in length), alicyclic, or aromatic and substituted as described above.
11 Suitable cations in the salts are alkali metal, 12 alkaline earth metals or metals, preferably from Groups lA, 13 2A, 3A, 4A, 2B, 3B, 6B, 7B and 8 of the Periodic Table, 14 particularly Na, K, Mg, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Ag or Pb. Reference is to the Periodic Table of Mendeleef as it 16 appears on the front cover leaf of the Handbook of 17 Chemistry and Physics 56th Edition 1975-1976, published by 18 CRC Press Cleveland, Ohio, USA.
19 Some specific crosslinking agents are methyl sulfonic acid~ ethylsulfonic acid, n-propylsulfonic acid, 21 isopropylsulfonic acid, cyclohexylsulfonic acid, p-toluene-22 sulfonic acid, 5-nitro-1,3-benzenedisulfonic acid,~ -naph-23 thalenesulfonic acid, ~ -naphthalenesulfonic acid, 24 anthracene sulfonic acid, 1,5 or 1,8 naphthalenedisulfonic acid, methyl-p-toluenesulfonate, the free acid form and the 26 sodium and copper salts of sulfonated polysytrene, 27 p-toluene sulfonic acid, 2-hydroxy-4, methoxy-5-sulfo-28 benzophenone, calcium benzenesulfonate, barium benzene-29 sulfonate, lead benzenesulfonaté, methyl methyl sulfonate, ethyl methyl sulfonate, methyl propyl sulfonate and the 31 like. Aromatic sulfonic acids and their derivatives are 32 preferred because of greater compatibility with the 33 polymers.
34 It has been found that very small amounts of the of the crosslinking agent may be used to obtain the cross-36 linked polymer and that excessively large amounts of cross-37 linking agents demonstrated no advantages. The amount of 38 crosslinking agent present to produce a crosslinkable lZ~1886 1 product is in the range of 0.25 to 16 weight percent based 2 on the poly(parabanic acid) with a preferred range being 3 about 0.5 wt.% to 8 wt.~. The gist of the present invent-4 ion, however, is the use of the least amount of crosslink-ing agent as described to obtain the desired crosslinked, 6 i.e., insoluble, poly(parabanic acid) composition. The use 7 of larger amounts than this are contemplated to be within 8 the scope of the invention, to the extent th~t the cross-9 linked product is not adversely affected thereby.
For purposes of illustration, the examples illus-11 trating the invention will be described in specific with 12 respect to a particular polymer. That is, a polyparabanic 13 acid prepared from diphenylmethane diisocyanate in accor-14 dance with proprietary techniques well described in patents assigned to Exxon Research and Engineering Company to 16 result in a high performance polymer having the repeating 17 unit shown below:
18 _ _ 29 ~ c ~ CH2 ~--21 O=C - C=O n 22 which Is also designated as poly(l,4-phenylenemethylene-1 23 4-phenylene-1,3-(imidazolidine-2,4,5-trione)) which is 24 also designated in chemical abstracts as poly (2,4,5-tri-oxo-l, 3 imidazolidinediyl)-1,4-phenylenemethylene-1,4-26 phenylene) designated PPA-M for convenience. It has a 27 high glass transition temperature of 290 C and can not be 28 extruded or molded.
29 In general, the preferred polymers of the polymer-plasticizer components are those which have suffi-31 cient repeating units at room temperature to be solids.
32 In addition to the polymer and crosslinking 33 agent, it is contemplated that other appropriate additives 34 such as those employed to stabilize the polymer against oxidation or ultraviolet light, flame retardants, pigments, 36 plasticizers, fillers and the like may be present.
37 The present crosslinking agents may be incor-121~886 1 porated into the polymers in solution and thereafter cast or 2 coated onto a substrate and cured or may be premixed with 3 polymer powder and thereafter dissolved. When plasticizers 4 are employed in the polymers they may be extruded and subse-5 quently cured.
6 The curing may be effected by heating the cast or ex-7 truded polymer containing the crosslinking agent at a temper-8 ature in the range of 200 to 300C, preferably of 240 to 280 9 C, for about one hour. The curing temperature and time may
10 vary according to the specific poly(parabanic acid) polymer
11 used (i.e., the R group). For example, PPA-M film cast from
12 solutions with various crpsslinking agents present therein at
13 various concentrations crosslinked within one hour at 260C.
14 Very generally, PPA and its precursor are soluble in moderate
15 hydrogen bonding dipolar, aprotic solvents. Suitable solvents include
16 dimethylformamide, dimethylacetamide, dime~hylsulfoxide, hexamethyl-
17 phosphoramide and N-methylpyrrolidone. These may be used in admixture
18 with each other or with other aprotic solvents such as benzene, toluene,
19 xylene, methylacetate, ethylaoetate, anisole, phenetole, butyl benzoate, chlorobenzene, etc.
21 Hence, the precipitation of the crosslinkable polymer 22 compositions from a suitable solvent either onto a casting 23 surface, from which the crosslinkable film may be removed 24 or onto a substrate to which the film is to be bonded 25 provides a very convenient method of producing the cross-26 linkable polymer films and coatings. The solution of cross-27 linkable polymer may be sprayed or brushed onto a surface 28 and the solvent removed to leave a polymer film, which is 29 subsequently cured and crosslinked by heating as described.
.30 This is a particularly useful way to produce electric motor 31 core coated wire.
32 The following examples il}ustrate the present 33 invention.
34 Example 1 This example shows that the presence of methyl 36 p-toluene sulfonate in a film of a poly(parabanic acid) 37 causes the film to become insoluble in dimethyl formamide 121~386 1 when it is exposed to heat for a short period of time.
2 Films (2 mils thick) were cast from each of the 3 following solutions; the poly(parabanic acid) used was 4 PPA-M.
Solution A was prepared by dissolving 600 g. PPA-M
6 and 0.24 g. zelec (a release agent) in 2400 g. dimethyl-7 formamide.
8 Solution B was prepared by dissolving 600 g. PPA-M, 9 0.24 g. zelec (release agent), and 3.0g. methyl p-toluene-sulfonate in 2400 g. dimethylformamide.
11 Solution B was prepared by dissolving 600 g. PPA-M, 0.24 g.
12 zelec (release agent), and 3.0 g. m2thyl p-toluenesulfonate in 2400 g.
13 dimethylformamide.
14Solubility in DMF
15 FilmBefore Aging A~ed 1 h~ at 260C
16 A soluble solubl~
17 B soluble insoluble 18Soluble polyme~s become insoluble when 19Soluble polymers become insoluble when they cross-link; therefore the sulfonate ester caused the polymer to 21 crosslink.
22 Example 2 23 This example shows that the sodium and copper 24 salts as well as the free acid form of sulfonated polysty-rene caused PPA-M to crosslink when heated.
26 Films which were 80% PPA-M and 20% of one of the 27 sulfonated polystyrene resins shown in the table below 28 were cast from dimethylformamide. For comparisons, a 29 film of PPA-M and film composed of 80~ PPA-M and 20~ poly-styrene were similarly cast.
31 The solubilities of the films in dimethyl-forma-32 mide before and after aging 1 hour at 260C are recorded 33 below (see Table). Only the films which contained a sul-34 fonated polystyrene crosslinked when heated 1 hour at 260C. Unsulfonatedpolystyrene did not cause crosslinking.
121~86 g 1 Solubility in DMF
2 Be~ore After Aging ~ Film No. Polystyrene Aging 1 hr at 260C
4 h None soluble soluble B 3~ sulfonated, sodium salt soluble insoluble C 5% sulfonated, sodium salt soluble insoluble D 2% sulfonated, free acid soluble insoluble 1 E 8% sulfonated, free acid soluble insoluble t F ~% sulfonated, coppe~ salt soluble insoluble G not sulfonated soluble soluble 14 Example 3 This example shows that the presence of 16 various sulfonated compounds in PPA-M films causes 17 the films to become insoluble in dimethylformamide 18 after they have been heated only 1 hour at 260C~
19 Solubility in DMF
Refore After Aging P lm Additive ~wt.~) Aging 1 hr at 26~C
A None soluble soluble B methvltoluene sulfonate ~1) soluble insoluble C p-toluene sulfonic acid (1) soluhle insoluble D 2-hydroxy-4 ~ethoxy-5-sulfo- soluble insoluble benzophenone ~1) E 5% sulfonated polystyrene, soluble insoluble F 8% sulfonated polystyrene, soluble ins free acid ~1)
21 Hence, the precipitation of the crosslinkable polymer 22 compositions from a suitable solvent either onto a casting 23 surface, from which the crosslinkable film may be removed 24 or onto a substrate to which the film is to be bonded 25 provides a very convenient method of producing the cross-26 linkable polymer films and coatings. The solution of cross-27 linkable polymer may be sprayed or brushed onto a surface 28 and the solvent removed to leave a polymer film, which is 29 subsequently cured and crosslinked by heating as described.
.30 This is a particularly useful way to produce electric motor 31 core coated wire.
32 The following examples il}ustrate the present 33 invention.
34 Example 1 This example shows that the presence of methyl 36 p-toluene sulfonate in a film of a poly(parabanic acid) 37 causes the film to become insoluble in dimethyl formamide 121~386 1 when it is exposed to heat for a short period of time.
2 Films (2 mils thick) were cast from each of the 3 following solutions; the poly(parabanic acid) used was 4 PPA-M.
Solution A was prepared by dissolving 600 g. PPA-M
6 and 0.24 g. zelec (a release agent) in 2400 g. dimethyl-7 formamide.
8 Solution B was prepared by dissolving 600 g. PPA-M, 9 0.24 g. zelec (release agent), and 3.0g. methyl p-toluene-sulfonate in 2400 g. dimethylformamide.
11 Solution B was prepared by dissolving 600 g. PPA-M, 0.24 g.
12 zelec (release agent), and 3.0 g. m2thyl p-toluenesulfonate in 2400 g.
13 dimethylformamide.
14Solubility in DMF
15 FilmBefore Aging A~ed 1 h~ at 260C
16 A soluble solubl~
17 B soluble insoluble 18Soluble polyme~s become insoluble when 19Soluble polymers become insoluble when they cross-link; therefore the sulfonate ester caused the polymer to 21 crosslink.
22 Example 2 23 This example shows that the sodium and copper 24 salts as well as the free acid form of sulfonated polysty-rene caused PPA-M to crosslink when heated.
26 Films which were 80% PPA-M and 20% of one of the 27 sulfonated polystyrene resins shown in the table below 28 were cast from dimethylformamide. For comparisons, a 29 film of PPA-M and film composed of 80~ PPA-M and 20~ poly-styrene were similarly cast.
31 The solubilities of the films in dimethyl-forma-32 mide before and after aging 1 hour at 260C are recorded 33 below (see Table). Only the films which contained a sul-34 fonated polystyrene crosslinked when heated 1 hour at 260C. Unsulfonatedpolystyrene did not cause crosslinking.
121~86 g 1 Solubility in DMF
2 Be~ore After Aging ~ Film No. Polystyrene Aging 1 hr at 260C
4 h None soluble soluble B 3~ sulfonated, sodium salt soluble insoluble C 5% sulfonated, sodium salt soluble insoluble D 2% sulfonated, free acid soluble insoluble 1 E 8% sulfonated, free acid soluble insoluble t F ~% sulfonated, coppe~ salt soluble insoluble G not sulfonated soluble soluble 14 Example 3 This example shows that the presence of 16 various sulfonated compounds in PPA-M films causes 17 the films to become insoluble in dimethylformamide 18 after they have been heated only 1 hour at 260C~
19 Solubility in DMF
Refore After Aging P lm Additive ~wt.~) Aging 1 hr at 26~C
A None soluble soluble B methvltoluene sulfonate ~1) soluble insoluble C p-toluene sulfonic acid (1) soluhle insoluble D 2-hydroxy-4 ~ethoxy-5-sulfo- soluble insoluble benzophenone ~1) E 5% sulfonated polystyrene, soluble insoluble F 8% sulfonated polystyrene, soluble ins free acid ~1)
Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A crosslinkable composition comprising heterocyclic polymers characterized in the repeating unit by the tri-substituted 1,3-imidazolidine-1,3-diyl ring:
and a crosslinking amount of a crosslinking agent of sulfonic acid, ester or salt thereof.
and a crosslinking amount of a crosslinking agent of sulfonic acid, ester or salt thereof.
2. A crosslinkable composition comprising a polymer having the repeating unit wherein Q is R is an organic moiety which may be aliphatic, alicyclic, aromatic or mixtures thereof and n is sufficiently large to produce a solid product, and a crosslinking amount of a crosslinking agent of a sulfonic acid, ester or salt thereof.
3. A crosslinked composition comprising a polymer having the repeating unit:
wherein Q is R is an organic moiety which may be aliphatic, alicyclic, aromatic or mixtures thereof and n is sufficiently large to produce a solid product and a crosslinking amount of a crosslinking agent of a sulfonic acid, ester or salt thereof.
wherein Q is R is an organic moiety which may be aliphatic, alicyclic, aromatic or mixtures thereof and n is sufficiently large to produce a solid product and a crosslinking amount of a crosslinking agent of a sulfonic acid, ester or salt thereof.
4. The composition according to claim 1, 2 or 3 wherein the organic moiety of the sulfonic acid crosslinking agent is an aliphatic, cyclic, aromatic or polymeric radical.
5. The composition according to claim 1, 2 or 3 wherein the organic moiety of the crosslinking agent is a hydrocarbon substituted with one or more functional groups not containing active hydrogens.
6. The composition according to claim 1, 2 or 3 wherein the crosslinking agent is p-toluene sulfonic acid.
7. The composition according to claim 1, 2 or 3 wherein the crosslinking agent is a p-toluenesulfonate.
8. The composition according to claim 1, 2 or 3 wherein the crosslinking agent is the free acid form of a sulfonated polystyrene.
9. The composition according to claim 1, 2 or 3 wherein the crosslinking agent is a salt of polystyrene sul-fonic acid.
10. The composition according to claim 1, 2 or 3 wherein the crosslinking agent is methyltoluene sulfonate.
11. The composition according to claim 1, 2 or 3 wherein the crosslinking agent is 2-hydroxy-4 methoxy-5-sulfobenzophenone.
12. The method of producing crosslinked poly(para-banic acid) polymers comprising:
(a) admixing poly(parabanic acid) polymer with (b) a crosslinking amount of a crosslinking agent of a sulfonic acid, ester or salt thereof, and (c) heating said mixture at a temperature in the range of 200 to 300°C, preferably 240 to 280°C for a sufficient period of time to crosslink said polymer.
(a) admixing poly(parabanic acid) polymer with (b) a crosslinking amount of a crosslinking agent of a sulfonic acid, ester or salt thereof, and (c) heating said mixture at a temperature in the range of 200 to 300°C, preferably 240 to 280°C for a sufficient period of time to crosslink said polymer.
13. The method according to claim 12 wherein said admixing is carried out in a solvent for said polymer.
14. The method according to claim 13 wherein the solvent is dimethylformamide.
15. The method according to claim 14 wherein the organic moiety of the sulfonic acid is aliphatic, cyclic, aromatic or polymeric radical.
16. The composition according to claim 1, 2 or 3 wherein the crosslinking agent is a salt of polystyrene sulfonic acid and said salt is the copper salt.
17. The composition according to claim 1, 2 or 3 wherein the crosslinking agent is a salt of polystyrene sulfonic acid and said salt is the sodium salt.
12.
12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34295182A | 1982-01-26 | 1982-01-26 | |
| US342,951 | 1994-11-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1211886A true CA1211886A (en) | 1986-09-23 |
Family
ID=23344007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000420159A Expired CA1211886A (en) | 1982-01-26 | 1983-01-25 | Crosslinkable compositions of poly(parabanic acid) with organic sulfonic acids or their derivatives |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS58129052A (en) |
| CA (1) | CA1211886A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221482A (en) * | 1989-10-16 | 1993-06-22 | Daicel Chemical Industries, Ltd. | Polyparabanic acid membrane for selective separation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4228066A (en) * | 1979-04-12 | 1980-10-14 | Exxon Research & Engineering Co. | Stabilized polymer compositions |
-
1983
- 1983-01-25 CA CA000420159A patent/CA1211886A/en not_active Expired
- 1983-01-26 JP JP999883A patent/JPS58129052A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0422942B2 (en) | 1992-04-20 |
| JPS58129052A (en) | 1983-08-01 |
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