CA1213394A - Method of making mixed aliphatic/aromatic polycarbodiimides - Google Patents
Method of making mixed aliphatic/aromatic polycarbodiimidesInfo
- Publication number
- CA1213394A CA1213394A CA000446741A CA446741A CA1213394A CA 1213394 A CA1213394 A CA 1213394A CA 000446741 A CA000446741 A CA 000446741A CA 446741 A CA446741 A CA 446741A CA 1213394 A CA1213394 A CA 1213394A
- Authority
- CA
- Canada
- Prior art keywords
- aromatic
- aliphatic
- mono
- diisocyanate
- diisocyanates
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
Abstract
METHOD OF MAKING MIXED ALIPHATIC/AROMATIC
POLYCARBODIIMIDES
ABSTRACT OF THE INVENTION
Mixed aliphatic/aromatic polycarbodiimides can be prepared by first heating aliphatic mono- and diisocyanates with a phospholene oxide catalyst and then feeding the aromatic mono and/or diisocyanates in an inert solvent to the reaction mixture.
POLYCARBODIIMIDES
ABSTRACT OF THE INVENTION
Mixed aliphatic/aromatic polycarbodiimides can be prepared by first heating aliphatic mono- and diisocyanates with a phospholene oxide catalyst and then feeding the aromatic mono and/or diisocyanates in an inert solvent to the reaction mixture.
Description
33~
DESCRIPTION
Method of ~aking ~ixed Aliphatic/Aromatic Polycarbodiimides BACKGROUND OF THE INVENTION
This invention pertains to mixed aliphatic/aromatic polycarbodiimides and more particularly to a method for their preparation.
~ he use of polycarbodiimides as the crosslinker for well-known carboxylated latexes has been demonstrated to provide a requisite combination of control as well as rapid reaction. In the search for polycarbodiimides useful as crosslinking aqents, it was found that aliphatic polycarbodiimides were very useful. Unfortunately, the raw materials used to prepare the aliphatic materials are quite expensive. In an attempt to prepare lower cost Polycarbodiimides~ it was found that the aromatic isocyanates used to prepare aromatic polycarbodiimides were considerably less expensive.
However, aromatic polycarbodiimides failed to yield acceptable rates and degree of crosslinkinq. Thus, it was felt that a co-polycarbodiimide containing the combination of both aliphatic and aromatic constituents formed by a proper mixture of aliphatic and aromatic isocyanates would yield the re~uisite crosslinking rate and acceptable cost parameters.
In the attempts to prepare the aliphatic/aromatic co-polycarbodiimiae, it was found that these materials were much more difficult to prepare than either the fully aromatic or the fully aliphatic system. Usinq a procedure which satisfactorily yielded either of the all aliphatic or all aromatic polycarbodiimides, the mixed syste~
often yielded gelled or e~tremely viscous materials having severe discoloration.
It is therefore an object of this invention to provide a method for preparing mixed aliphatic/aromatic polycarbodiimides in satisfactory yields.
Other objects will become apparent to those skilled in the art upon a further reading of the specification.
SUMMARY OF THE INVENTION
A facile and economic method of preparin~
mixed aliphatic and aromatic polycarbodiimides has been found which comprises the followinq steps seriatim:
(A~ charging a mixture of cyclo-aliphatic or saturated aliphatic mono- and diisocyanates to a reactor with agitation under an inert atmosphere;
(~) heating the resultant mixture to about 120 to about 160C;
(C) adding a catalytic amount of a phospholene o~ide catalyst to the reactor:
(D) feeaing a mixture of a non-reactive solvent and aromatic mono- and/or diisocyanate to the reactor; ana (E) maintaininq agitation at about 120 to about 160C until all of the isocyanate functionality is converted to carbodiimide functionality; with the provisos that (a~ said cycloaliphatic moieties coDtain 6 to about 10 carbons, (b) said saturated aliphatic moieties contain from about 4 to about 12 carbons, (c) said aromatic moieties contain from 6 to about 12 carbons, 1~ 4 (d) the molar ratio of all of the mono- to diisocyanates ran~es from about
DESCRIPTION
Method of ~aking ~ixed Aliphatic/Aromatic Polycarbodiimides BACKGROUND OF THE INVENTION
This invention pertains to mixed aliphatic/aromatic polycarbodiimides and more particularly to a method for their preparation.
~ he use of polycarbodiimides as the crosslinker for well-known carboxylated latexes has been demonstrated to provide a requisite combination of control as well as rapid reaction. In the search for polycarbodiimides useful as crosslinking aqents, it was found that aliphatic polycarbodiimides were very useful. Unfortunately, the raw materials used to prepare the aliphatic materials are quite expensive. In an attempt to prepare lower cost Polycarbodiimides~ it was found that the aromatic isocyanates used to prepare aromatic polycarbodiimides were considerably less expensive.
However, aromatic polycarbodiimides failed to yield acceptable rates and degree of crosslinkinq. Thus, it was felt that a co-polycarbodiimide containing the combination of both aliphatic and aromatic constituents formed by a proper mixture of aliphatic and aromatic isocyanates would yield the re~uisite crosslinking rate and acceptable cost parameters.
In the attempts to prepare the aliphatic/aromatic co-polycarbodiimiae, it was found that these materials were much more difficult to prepare than either the fully aromatic or the fully aliphatic system. Usinq a procedure which satisfactorily yielded either of the all aliphatic or all aromatic polycarbodiimides, the mixed syste~
often yielded gelled or e~tremely viscous materials having severe discoloration.
It is therefore an object of this invention to provide a method for preparing mixed aliphatic/aromatic polycarbodiimides in satisfactory yields.
Other objects will become apparent to those skilled in the art upon a further reading of the specification.
SUMMARY OF THE INVENTION
A facile and economic method of preparin~
mixed aliphatic and aromatic polycarbodiimides has been found which comprises the followinq steps seriatim:
(A~ charging a mixture of cyclo-aliphatic or saturated aliphatic mono- and diisocyanates to a reactor with agitation under an inert atmosphere;
(~) heating the resultant mixture to about 120 to about 160C;
(C) adding a catalytic amount of a phospholene o~ide catalyst to the reactor:
(D) feeaing a mixture of a non-reactive solvent and aromatic mono- and/or diisocyanate to the reactor; ana (E) maintaininq agitation at about 120 to about 160C until all of the isocyanate functionality is converted to carbodiimide functionality; with the provisos that (a~ said cycloaliphatic moieties coDtain 6 to about 10 carbons, (b) said saturated aliphatic moieties contain from about 4 to about 12 carbons, (c) said aromatic moieties contain from 6 to about 12 carbons, 1~ 4 (d) the molar ratio of all of the mono- to diisocyanates ran~es from about
2:1 to about 2:10; and (e) the molar ratio of cycloaliphatic and/or saturated aliphatic isocyanate groups to aromatic isocyanate qroups ranges from about 0.5:1 to about 2:1.
Pressure and time are not critical.
Although superatmospheric or sub-atmospheric pressures can be used, it is preferred to use atmospheric pressures for economic reasons.
While temperatures of about 120C to about 160C can be used, it is preferred to use a range of about 120C to about 140C.
The term "catalytic amount" is used herein to mean about 0.1 to about 0.8% by weight based on the total weight of isocyanates charged.
~any variations of the catalyst can be used. Examples include the monoxidized phospholene as well as phospholene sulfide. Alternatives include derivatives derived by substituting on and for the phenyl groups attached to the phosphorus atom such as by an ethyl moiety. Additional substitutions on the cyclic phosphorus ring can be made by subsituting hydrogen, alkenyl, aryl, aralkyl, alkoxy, chlorine or bromine qroups.
Exemplary cycloaliphatic and saturated aliphatic mono and diisocyanates include:
butylisocyanate isophorone diisocyanate 1,6-hexane diisocya~ate dicyclohexylmethane diisocyanate 1,4-tetramethylene diisocyanate 1,12-dodecane diisocyanate cyclohexane diisocyanate 39~
E~emplary aromatic mono and diisocyanates include:
phenyl isocyanate 4,4l-diisocyanotodiphenylmethane toluene diisocyanate naphthalenediisocyanate Although the molar eatios of all of tbe mono- to diis~cyanate groups can range from about 2:1 to about 2:10 it is preferred to use ratios of about 2:1 to about 4:1.
Although the molar rati~ of cycloali~hatic and/or saturated alipbatic isocyanate ~roups to aromatic isocyanate groups can range from about 0.5:1 to about 2~ is preferred to use a range of about 0.75:1 to about 1.25:1.
The ~ethod of the instant invention is preferably carried out in a non-reactive or~anic solvent such as, ~lycol diesters or aliphatic esters each bavin~ about 8 to about 20 carbons, aromatic hydrocarbons having 6 to about 12 carbons, and tbe like. Exemplary solvents include diethylene~
glycolether diacetate, dipropylene glycol dibutyrate, he~ylene glycol diacetate, amyl ace~ate, butyl acetate, propryl propionate, ethyl butyrate toluene, o-, m- a~d p- ~ylene, benzene, diethyl benzene, and tbe like.
In the prior art pKeparation of polycarbodiimides, a catalyst is employed Preferably with an inert organic solvent and combinations of mono- and dii~ocyanates as desired to control the product ~olycarbodiimide molecular weight and functionality. The combination of two isocyanate mDieties yield.~ ~arbodiimide ~roup with evolution of carbon dioxide:
.
~-13570 ~Z13394 CATALYST
'R-NCO ~ OCN-R ~ R-NCN-R + CO2 It was, found that during the preparation of mixed aliphatic ana aromatic polycar~odiimides where the correspondin~ aliphatic and aromatic isocyanates are chargea to the reactor toqether with solvent and catalyst that the rate of carbon dio~ide evolution ana carbodiimiae functionality formation decreased significantly during the process. The time of the decrease corresponded to the amount of aromatic isocyanate present due to the preferential reaction of aromatic isocyanate at the e~pense of the alipbatic isocyanate. When the aliphatic isocyanate and solvent are charged first to the reactor followed by the catalyst, the reac~or raised ~o the reaction temperature and the aromatic isocyanate fed to the reactor last, a superior alipbatic/aromatic polycarbodiimide product was obtained. The product was superior to that obtained by charging all of the isocyanates to the reactor at the same time in having less discoloration and a much lower viscosity. It was une~pectedly found that the reactivity of the product obtained by the practice of this invention e~hibitea a reactivity in crosslinking carboxylated latexes which appro~imated that of aliphatic carbodiimides which are known to be more reactive crosslinkers than aromatic polycarbodiimides. The low reactivity of the latter makes them unsuitable for crosslinking carboxylated latexes.
~ any variations may be used in the practice of the instant invention. In addition to the temperature ranqe mentioned above almost any solvent can be used so long as the boilinq point is sufficiently high to allow _arbodiimide formation to - lZ~3394 ,;
i take place and there ase no active hydrogen groups on tbe solvent which could react witb either the isocyanates or the product carbodiimides. The ~olven~ ran ~e placed in either the reactor charge or in tbe feed tank as preferred or split between them.
GLOSSARY OF MATERIALS USED
-LPCA 5011 - 20~ Cellosolve acetate solution of a carboxylated resin described in U.S.
4,096,125. Cellosolve is a trademark of Union Carbide Corporation.
NIAX Polyol PCP - 0300 - Tra~emark of Union Carbide Corporation for polycaprolactone triol.
NIAX Polyol PCP - 0301 - Trademark of Union Carbide Corporation for polycaprolactone triol.
Butyl Carbitol acetate - Trademark of Union Carbide Corporation for the butyl monoether of diethylene glycol monoacetate.
Ucar Latex 153 - Trademark of Union Carbide Corporation for carboxylated emulsion polymer.
Ucar Late~ 4584 - Trademark of Union Carbide Corporation for carboxylated emu~sion polymer.
Ucar Latex 175 - Trademark of Union Carbide - Corporation for carboxylated emul&ion polymer.
CoIloid 677 - Trademark of Colloid Inc. for defoamer.
Mineralite 3X - Trademark of Mineral Co. for mica.
!
~ D-13570 .
;:
TiPure R901 - Trademark of Dupont Co. for titanium dioxide. iPure R960 - Tra~emark of Dupont Co. for titanium dioxide. SP - 400 ^ Trademark of Minerals and Chemicals for clay. hlorowa~ 40 - Trademark of Diamond Shamrock for chlorinated wax. ~A - 30 - Trademark of Troy Chemical Co. for mildewcide. elite 281 - Trademark of Johns-Manville for diatomaceous silica. erosol A - 196 - Trademark of American Cyanamid Co. for the sodium salt of dial~yl sulfosuccinate. aniels Disperse-Ayd W-22 - Trademark of Daniel Products Co, for dispersant. qepal Ca - 630 surfactant Trademark of GAF Corp.
for ethoxylated alkyl phenol. oamaster ~.F. - Trademark of NOPCO Chemical for defoamer. opocide N-96 - Trademark of Diamond Shamrock for tetrachloroisopbthalonitrile. nowflake - Trademark of Allied Chemical Co. for calcium carbonate. urfynol 104 surfactant - Trademark of Air Products and Chemicals Inc. for an acetylenic glycol. hrome Chem 895 - Trademark of Tenneco for pre-dispersed carbon black.
~2~3394 Cellosolve solvent - Trademark of Union Carbide Corpora~ion for a monalkyl ether of ethylene glycol.
Hexyl Cellosoive - Trademark of Union Carbide Corporation for a monohe~yl ether of ethylene glycol.
Polyol WSRN ~4% active) - Trademark of Union Carbide Corporation for mixed alkylene oxide water soluble polyethers.
CYMEL 303 - Trademark of American Cyanamid Co. for hexamethoxymethylmelamine.
Tergital NP - 10 Surfactant - Trademark of Union Carbide Corporation for alkylated ethoxylated phenols.
Tamol 731 - Trademark of Rohn and Haas for dispersant.
Butyl Carbitol - Trademark of Union Carbide Corporation for the butyl monoether of diethylene glycol.
XAMA-7 is a polyfunctional aziridene crosslinker available from Cordova Co.
TESTS AND TERMS
The followinq tests and terms were used in demonstrating the efficacy of this invention.
Double ~ub Test - A piece of cheesecloth is saturated with methyl ethyl ketone, then rubbed on the substrate until penetration occurs. One back and forth rub is a double rub.
Reactivity Test - Time for gelation at 50C
as described in Example 10.
Theoretical functionality - An ideali~ed value based on the theoretical structure assumin~
pure materials with no side reactions.
g Tensile Stren~th - ASTM D 638-60T
% Elongation - ASTM D 638-60T
~ Length Increase - Sample measured with a ruler.
~ Weight Gain - Sample mesaured on a balance.
Formulation Stability - visual inspection.
Peel Strength (Cf Example 12) Sheer Failure (Cf Example 12) EXAMPLES
The invention is further described in the E~amples which follow. All parts and percenta~es are by weiqht unless otherwise specified.
The following examples demonstrate the value ~nd versatility of the invention. The following guide may be useful in analyzinq the examples:
13 Examples 1 and 2 demonstrate the difficulties of preparing the desired compounds by the batch process.
23 Examples 3 and 4 demonstrate the ability to make the desired composition by the process of this invention.
Pressure and time are not critical.
Although superatmospheric or sub-atmospheric pressures can be used, it is preferred to use atmospheric pressures for economic reasons.
While temperatures of about 120C to about 160C can be used, it is preferred to use a range of about 120C to about 140C.
The term "catalytic amount" is used herein to mean about 0.1 to about 0.8% by weight based on the total weight of isocyanates charged.
~any variations of the catalyst can be used. Examples include the monoxidized phospholene as well as phospholene sulfide. Alternatives include derivatives derived by substituting on and for the phenyl groups attached to the phosphorus atom such as by an ethyl moiety. Additional substitutions on the cyclic phosphorus ring can be made by subsituting hydrogen, alkenyl, aryl, aralkyl, alkoxy, chlorine or bromine qroups.
Exemplary cycloaliphatic and saturated aliphatic mono and diisocyanates include:
butylisocyanate isophorone diisocyanate 1,6-hexane diisocya~ate dicyclohexylmethane diisocyanate 1,4-tetramethylene diisocyanate 1,12-dodecane diisocyanate cyclohexane diisocyanate 39~
E~emplary aromatic mono and diisocyanates include:
phenyl isocyanate 4,4l-diisocyanotodiphenylmethane toluene diisocyanate naphthalenediisocyanate Although the molar eatios of all of tbe mono- to diis~cyanate groups can range from about 2:1 to about 2:10 it is preferred to use ratios of about 2:1 to about 4:1.
Although the molar rati~ of cycloali~hatic and/or saturated alipbatic isocyanate ~roups to aromatic isocyanate groups can range from about 0.5:1 to about 2~ is preferred to use a range of about 0.75:1 to about 1.25:1.
The ~ethod of the instant invention is preferably carried out in a non-reactive or~anic solvent such as, ~lycol diesters or aliphatic esters each bavin~ about 8 to about 20 carbons, aromatic hydrocarbons having 6 to about 12 carbons, and tbe like. Exemplary solvents include diethylene~
glycolether diacetate, dipropylene glycol dibutyrate, he~ylene glycol diacetate, amyl ace~ate, butyl acetate, propryl propionate, ethyl butyrate toluene, o-, m- a~d p- ~ylene, benzene, diethyl benzene, and tbe like.
In the prior art pKeparation of polycarbodiimides, a catalyst is employed Preferably with an inert organic solvent and combinations of mono- and dii~ocyanates as desired to control the product ~olycarbodiimide molecular weight and functionality. The combination of two isocyanate mDieties yield.~ ~arbodiimide ~roup with evolution of carbon dioxide:
.
~-13570 ~Z13394 CATALYST
'R-NCO ~ OCN-R ~ R-NCN-R + CO2 It was, found that during the preparation of mixed aliphatic ana aromatic polycar~odiimides where the correspondin~ aliphatic and aromatic isocyanates are chargea to the reactor toqether with solvent and catalyst that the rate of carbon dio~ide evolution ana carbodiimiae functionality formation decreased significantly during the process. The time of the decrease corresponded to the amount of aromatic isocyanate present due to the preferential reaction of aromatic isocyanate at the e~pense of the alipbatic isocyanate. When the aliphatic isocyanate and solvent are charged first to the reactor followed by the catalyst, the reac~or raised ~o the reaction temperature and the aromatic isocyanate fed to the reactor last, a superior alipbatic/aromatic polycarbodiimide product was obtained. The product was superior to that obtained by charging all of the isocyanates to the reactor at the same time in having less discoloration and a much lower viscosity. It was une~pectedly found that the reactivity of the product obtained by the practice of this invention e~hibitea a reactivity in crosslinking carboxylated latexes which appro~imated that of aliphatic carbodiimides which are known to be more reactive crosslinkers than aromatic polycarbodiimides. The low reactivity of the latter makes them unsuitable for crosslinking carboxylated latexes.
~ any variations may be used in the practice of the instant invention. In addition to the temperature ranqe mentioned above almost any solvent can be used so long as the boilinq point is sufficiently high to allow _arbodiimide formation to - lZ~3394 ,;
i take place and there ase no active hydrogen groups on tbe solvent which could react witb either the isocyanates or the product carbodiimides. The ~olven~ ran ~e placed in either the reactor charge or in tbe feed tank as preferred or split between them.
GLOSSARY OF MATERIALS USED
-LPCA 5011 - 20~ Cellosolve acetate solution of a carboxylated resin described in U.S.
4,096,125. Cellosolve is a trademark of Union Carbide Corporation.
NIAX Polyol PCP - 0300 - Tra~emark of Union Carbide Corporation for polycaprolactone triol.
NIAX Polyol PCP - 0301 - Trademark of Union Carbide Corporation for polycaprolactone triol.
Butyl Carbitol acetate - Trademark of Union Carbide Corporation for the butyl monoether of diethylene glycol monoacetate.
Ucar Latex 153 - Trademark of Union Carbide Corporation for carboxylated emulsion polymer.
Ucar Late~ 4584 - Trademark of Union Carbide Corporation for carboxylated emu~sion polymer.
Ucar Latex 175 - Trademark of Union Carbide - Corporation for carboxylated emul&ion polymer.
CoIloid 677 - Trademark of Colloid Inc. for defoamer.
Mineralite 3X - Trademark of Mineral Co. for mica.
!
~ D-13570 .
;:
TiPure R901 - Trademark of Dupont Co. for titanium dioxide. iPure R960 - Tra~emark of Dupont Co. for titanium dioxide. SP - 400 ^ Trademark of Minerals and Chemicals for clay. hlorowa~ 40 - Trademark of Diamond Shamrock for chlorinated wax. ~A - 30 - Trademark of Troy Chemical Co. for mildewcide. elite 281 - Trademark of Johns-Manville for diatomaceous silica. erosol A - 196 - Trademark of American Cyanamid Co. for the sodium salt of dial~yl sulfosuccinate. aniels Disperse-Ayd W-22 - Trademark of Daniel Products Co, for dispersant. qepal Ca - 630 surfactant Trademark of GAF Corp.
for ethoxylated alkyl phenol. oamaster ~.F. - Trademark of NOPCO Chemical for defoamer. opocide N-96 - Trademark of Diamond Shamrock for tetrachloroisopbthalonitrile. nowflake - Trademark of Allied Chemical Co. for calcium carbonate. urfynol 104 surfactant - Trademark of Air Products and Chemicals Inc. for an acetylenic glycol. hrome Chem 895 - Trademark of Tenneco for pre-dispersed carbon black.
~2~3394 Cellosolve solvent - Trademark of Union Carbide Corpora~ion for a monalkyl ether of ethylene glycol.
Hexyl Cellosoive - Trademark of Union Carbide Corporation for a monohe~yl ether of ethylene glycol.
Polyol WSRN ~4% active) - Trademark of Union Carbide Corporation for mixed alkylene oxide water soluble polyethers.
CYMEL 303 - Trademark of American Cyanamid Co. for hexamethoxymethylmelamine.
Tergital NP - 10 Surfactant - Trademark of Union Carbide Corporation for alkylated ethoxylated phenols.
Tamol 731 - Trademark of Rohn and Haas for dispersant.
Butyl Carbitol - Trademark of Union Carbide Corporation for the butyl monoether of diethylene glycol.
XAMA-7 is a polyfunctional aziridene crosslinker available from Cordova Co.
TESTS AND TERMS
The followinq tests and terms were used in demonstrating the efficacy of this invention.
Double ~ub Test - A piece of cheesecloth is saturated with methyl ethyl ketone, then rubbed on the substrate until penetration occurs. One back and forth rub is a double rub.
Reactivity Test - Time for gelation at 50C
as described in Example 10.
Theoretical functionality - An ideali~ed value based on the theoretical structure assumin~
pure materials with no side reactions.
g Tensile Stren~th - ASTM D 638-60T
% Elongation - ASTM D 638-60T
~ Length Increase - Sample measured with a ruler.
~ Weight Gain - Sample mesaured on a balance.
Formulation Stability - visual inspection.
Peel Strength (Cf Example 12) Sheer Failure (Cf Example 12) EXAMPLES
The invention is further described in the E~amples which follow. All parts and percenta~es are by weiqht unless otherwise specified.
The following examples demonstrate the value ~nd versatility of the invention. The following guide may be useful in analyzinq the examples:
13 Examples 1 and 2 demonstrate the difficulties of preparing the desired compounds by the batch process.
23 Examples 3 and 4 demonstrate the ability to make the desired composition by the process of this invention.
3) Examples 5, 6, and 7 show that the process can be used to prepare other aliphatic/aromatic Polycarbodiimides~
4) Examples 8, 9 and 10 show the unexpected high reactivity of the aliphatic/aromatic polycarbodiimide preparable by the process of this invention.
5) Examples ~1-14 ~emonstrate the utility of tbe Prepared aliphatic/aromatic polycarbodiimides.
lZ13394 Example 1 Preparation of Aliphatic/Aromatic Polycarbodiimide by Batch Process Into a 1 liter 3 neck round bottom flask equipped with a heating mantle, thermometer, mecha~ical stirrer, and nitrogen sparge were placed 77.3 9 butyl isocyanate, 135.9 9 toluene diisocyanate (2,4 and 2,6 mixed isomers), 86.7 9 isophorone diisocyanate, 282 9 of he~ylene glycol diacetate, and 18 9 of a 10% solution of 3-methyl-1-phenyl-2-phospholene -l-oxide in xylene.
The mixture was heated with stirring and nitrogen sparge at 1~5C. After four hours reaction and before complete conversion of the isocyanate groups to carbodiimide groups as observed with infrared spectrophotometry, the reaction mixture gelled to a solid mass.
E~amp]e 2 Preparation of Aliphatic/Aromatic Polycarbodiimide by Batch Process To the apparatus of Example 1 were charged 83.4 9 phenyl isocyanate, 155.6 9 isophorone diisocyanate, 61.0 9 toluene diisocyanate, 288 9 hexylene glycol diacetate, and 12 9 of 10%
3-methyl-1-phenyl-2-phospholene-1-oxide in ~ylene.
The materials were heated with stirring and nitrogen sparge to 145C. After 10 hours reaction the material appeared close to completion of reaction but was extremely viscous and dark colored. Shortly thereafter the material solidified to a solid ~el.
Example 3 Preparation of Aliphatic/Aromatic Polycarbodiimide by a Feed Process The apparatus of Example 1 was employed with the addition of a feed tank and pump. To the 1;~13394 feed tank were charged 61.0 9 toluene diisocyanate, 83.4 9 phenyl isocyanate, and 285 9 amyl acetate.
To the reactor were charged 155.6 q isophorone diisocyanate and 15 g of a 10% solution of 3-methyl-1-phenyl-2-phospholene-1-oxide in xylene.
The reactor was heated to 140C with stirring and nitrogen sparge, and the material in the feed tank was added over a 5.5 hour period. After two additional hours of reaction the material was completed and cooled. The product had a viscosity of 0.5 Sto~e (Gardner Bubble Viscometer) and a color of 5+ using a Gardner Hellige Comparator. Titration of the carbodiimide functionality ~ave a value of 9.75~ by the procedure of Zaremko and Watts (~icrochem. J. Symp. Ser., 2, 591(1962)).
Example 4 Preparation of Aliphatic/Aromatic Polycarbodiimide by a Feed Process (~odified Conditions) The previous Example 3 was repeated with the exceptions being that a 5.25 hour feed time and a reaction temperature of 120C was employed. The material required 21 hours to react to completion.
Using the tests of Example 3, the product had a viscosity of 0.5 Stoke, a color rating of 5+, and a percent carbodiimide of 8~80.
Example 5 Preparation of Alternate Composition by the Feed Process Using the apparatus of Example 3, to the feed tan~ were charged 76.3 9 phenyl isocyanate, 55.8 9. toluene diisocyanate, and 280 ~. of hexylene qlycol di~cetate. The the reactor were charged 167.9 9 bis-(4-isocyanatocyclohexyl)-methane and 20 q of a 10% solution of 3-methyl-1-phenyl-2-phospholene-l-oxide in xylene. A feed time of 3 lZ133~4 hours was employed with a reaction temperature of 140C. The reaction was completed after 26 hours.
Analysis of the product as described in Example 3 gave a viscosity of 3.20 Stoke, a color rating of 12, and a percent carbodiimide of 8.78.
Example 6 Preparation of Alternate Composition by the Feed Process Using the apparatus of Example 3, to the feed tank were charged 140.3 q toluene diisocyanate and 280 9 amyl acetate. To the reactor were charged 159.7 9 butyl isocyanate and 20 9 of 10~ 3-methyl-1-phenyl-2-phospholene-1-oxide in xylene. A feed time of 3 hours was employed along with a reaction temperature of 140C. The reaction required a total time of 5 hours for completion. Evaluation by the procedures in Example 3 gave a viscosity of less than 0.5 Stoke and a color ratinq of 7.
Example 7 Preparation_of Alternate Composition by the Feed Process Using the apparatus of Example 3, to the feed tank were charged 155.2 9 phenyl isocyanate and 280 9 amyl acetate and to the reactor were charged 144.8 9 isophorone diisocyanate and 20 9 of 10%
3-methyl-1-phenyl-2-phospholene-1-oxide in xylene.
A reaction temperature of 140C and a feed time of 3 hours were employed. The reaction required 22 hours for completion. Evaluation by the procedures in Example 3 qave a viscosity of less than 0.5 Stoke and a color ratin~ of 5.
Example 8 -Preparation of Aliphatic Polycarbodiimide for Reactivity Test In the apparatus of E~ample 1 were charqed 1~3394 68.7 9 butyl isocyanate, 231.2 9 isophorone diisocyanate, 270 9 amyl acetate, and 30 q of 10%
3-methyl-1-phenyl-2-phospholene-1-oxide in xylene.
The mixture was heated with stirring at 140C under a nitrogen sparge for 10 hours. Evaluation by the procedures in Example 3 qave a viscosity of less than 0.5 Stoke, a color rating of 3, and a percent carbodiimide of 9.79.
Example 9 Preparation of Aliphatic Polycarbodiimide - for-Reactivity Test Into the apparatus of Example 1 were charged 93.9 9 phenyl isocyanate, 206.1 9 toluene diisocyanate, 270 9 amyl acetate, and 30 9 of a 10%
3-methyl-1-phenyl-2-phospholene-1-oxide. The mixture was heated with stirring under a nitrogen sparge to 140C. After 1 hour reaction time, the reaction was complete. Evaluation by the procedures of Example 3 gave a viscosity of less than 0.5 Stoke, a color rating of 7, and a percent carbodiimide of 11.36.
~xample 10 Comparison of Polycarbodiimide Structures in Reactivity for Crosslinking A mate~ial termed LPCA 5011 described in U.S. 4,096,125 (20% CELLOSOLVE Acetate, 50%
phthallic anhydride, 15% NIAX polyol PCP-0300, 15%
NIAX Polyol PCP-0301 to an approximate acid equivalent weight of 363) was used to prepare the following master batch:
LPCA 5011 363 9 (one acid equivalent) Tr~ethyl~mine 101 9 (one acid equivalent) CE1LOSOLV~ Ace~ate 536 9 This master batch was blended with the polycarbodiimide solution of E~ample 8:
~aster ~atch 36.0 9 (0.036 acid equivalents) Polycarbodiimide 14.0 9 (0.036 carbodiimide equivalents) This well-stirred mix was placed in an oven at 50C
and found to gel in 2.3 hr.
The master batch was additionally blended with the aromatic polycarbodiimide solution of ExamPle 9.
~aster Batch 37.4 9 (0.0347 acid equivalents) Polycarbodiimide 12.6 9 (0.0374 carbodiimide equivalents After three days in a 50~C oven the mix was unchanged (no gelation).
Finally the master batch was blended with the aliphatic/aromatic polycarbodiimide solution of Example 4:
Master Batch 36.1 9 0.0361 acid equivalents) Polycarbodiimide 13.9 9 (0.0361 carbodiimide equivalents) This mi~ture was placed in a 50C oven and found to gel in 2 hours showing the surprising reactivity of the lower cost aliphatic/aromatic polycar~odiimide.
E~ample 11 Evaluation of the Aliphatic/Aromatic PolYcarbodiimide in a Coil Coating Formulation The polycarbodiimide solution of E~ample 3 was emulsified in wa~er using the following materials and ratios:
Polycarbodiimide Solution45 parts AEROSOL A-196 tAmerican Cyanamid) 1 part Triethylamine 0.68 part Water 55.33 part ~213394 A base coating formulation was prepared as listed below:
Pigment Grind Water 185~6 Ammonia (28%) 0.4 Ethylene glycol 13.2 TERGITOL NP-10 8.8 TAMOL 731 28.8 FOAMASTER VF2.4 TI-PURE R-960847.6 1086.g Let Down Pigment Grind 1086.8 FOAMASTER VF9.2 Water 141.6 Ammonia 28~22.4 UCAR 45112173.6 Butyl CARBITOL 159.2 3592.8 Ammonia to pH9 From this base coating the following formula~ions were prepared:
Base Polycar-Formula- bodiimide CYMEL
System Crosslinkertion, 9 Emulsion, 9 303, q A None 106 B Polycarbodiimide 106 13.2 Emulsion C CYMEL 303 106 - 2.5 CYMEL 303 Hexamethoxymethylmelamine The formulations were coated on Bonderite # 37 panels and cured at two different peak metal temperatures and evaluated by rubbing with cheesecloth soa~ed with methyl ethyl ketone (MEK).
The results are shown below:
MEK DOUBLE RUBS
Systems 250F 4~0F
B 24 50+
C 10 50+
~Z13394 These results showed that the polycarbodiimide cure~ at a lower temperature than the melamine system and gave strong performance at the standard high cure temperature.
E~ample 12 ~valuation of the Ali~hatic/Aromatic Polycarbodiimide in a Roof Coatin9 Application A master batch of roof coating formulation was prepared as detailed below:
CHLOROhAX 40 22 Antimony Oxide 2 Tricresyl Phosphate 63 Triethylamine 10.5 Water 200 1273.5 This material was used along with the Polycarbodiimide emulsion of Example 11 to prepare the following formulations:
Master Polycarbodiimide System Batch, q Water, 9 Emulsion, q XAMA-7, 9 A 200 9.6 B 200 - 9.6 C 200 7.9 - 1.~
XA~A-7- Multifunctional aziridine crosslinker from Cordova Chemical.
The final formulations were air-dried for two weeks at ambient te~perature. The resultant films were evaluatea for water swellinq by ambient temperature soakinq for two days and for tensile properties.
lZ~3394 Water Swelling System % Weight Gain Dry Film Tensile Strength ~ Elonqation These results showed that the polycar~odiimide cured --at ambient temperature and gave improved properties to the roof coating.
Example 13 Evaluation of the Aliphatic/Aromatic Polycarbodiimide in a Hardboard Coating -A base hardboard primer formulation was prepared as shown below:
Pigment Grind Water 256.2 Daniels DISPERSE-AID W-22 20.4 IGEPAL CA-630 6.9 FOAMASTER VF 5.7 NOPOCIDE N-96 17.1 SNO~FLAKE 1109.7 SURFYNOL 104 8.4 TI-PURE R-960 369.6 CHROME CHEM 895 0.9 Water 28.5 182~.4 Let Down Pigment Grid 1800.0 UCAR 4580 1248.0 FOAMASTER VF 3.0 CELLOSOLVE 127.0 Hexyl CELLOSOLVE 84.0 Dibutyl phthallate 60.0 Water 180.0 POLYOL WSRN 40.6 Ammonia ~14~ 59.0 Water 100.4 3702.
Ammonia to pH 9 lZ~3394 This material, along with the polycarbodiimide emulsion of Exa~ple 11 was employed to prepare the followinq formulations:
Base Polycarbodi-Formula- imide System tion, q Emulsion, ~ CY~EL 303, 9 ~ater, 9 A 159 - - 18.9 B 159 18.9 C 159 ~ 3~ 6 l5o 3 These formulations were coated on hardboard and air-dried at ambient temperature. The cure state of the coatings was evaluate~ by rubbing with cheeseclotb soaked in metbyl ethyl ketone (MEK) MEK DOUBLE RUBS
Systems 1 day 3 days Continued evaluation at further time periods failed to show any substantive change. These results showed the rapid low temperature crosslinking of the polycarbodiimide.
Example 14 Evaluation of the Aliphatic/Aromatic Polycarbodiimide in Pressure Sensitive Adhesives The polycarbodiimide emulsion of Example 11 was employed to crosslink a water-borne pressure sensitive adhesive, VCAR 175. Initially, the followin~ formulations were prepared with the UCAR
175 being adjusted to pH 9 with triethylamine:
UCAR Polycarhodiimide System 175,9 Emulsion, q XAMA-7, Q ~ater, 9 A 117 - - 10.6 B 117 10.6 C 117 - 1.9 8.7 The materials were applied to MYLAR tape and cured at 100C for 30 min. The resultant adhesive tapes were placed on steel substrates and evaluated for 1'~13394 their adhesive strength by measuring the force required to peel the tape (pli = pounds per linear inch) and the time which the tape would hold a 500 q weight in a vertical position. The results are shown below:
System Shear, hours Peel, pli A 0.1 4.80 B 48 0.15 C 2.9 0.26 These results showed that the polycarbodiimide crosslinked the adhesive latex reducing its tac~iness (peel) while greatly increasing the adhesive strength (shear).
Although tbe invention has been described in its preferred forms with a certain degree of particularity, it is understood that the present disclosure of the preferred form has been made only by way of example and ~hat numerous changes may be made without departinq from the spirit and the scope of ~he invention.
lZ13394 Example 1 Preparation of Aliphatic/Aromatic Polycarbodiimide by Batch Process Into a 1 liter 3 neck round bottom flask equipped with a heating mantle, thermometer, mecha~ical stirrer, and nitrogen sparge were placed 77.3 9 butyl isocyanate, 135.9 9 toluene diisocyanate (2,4 and 2,6 mixed isomers), 86.7 9 isophorone diisocyanate, 282 9 of he~ylene glycol diacetate, and 18 9 of a 10% solution of 3-methyl-1-phenyl-2-phospholene -l-oxide in xylene.
The mixture was heated with stirring and nitrogen sparge at 1~5C. After four hours reaction and before complete conversion of the isocyanate groups to carbodiimide groups as observed with infrared spectrophotometry, the reaction mixture gelled to a solid mass.
E~amp]e 2 Preparation of Aliphatic/Aromatic Polycarbodiimide by Batch Process To the apparatus of Example 1 were charged 83.4 9 phenyl isocyanate, 155.6 9 isophorone diisocyanate, 61.0 9 toluene diisocyanate, 288 9 hexylene glycol diacetate, and 12 9 of 10%
3-methyl-1-phenyl-2-phospholene-1-oxide in ~ylene.
The materials were heated with stirring and nitrogen sparge to 145C. After 10 hours reaction the material appeared close to completion of reaction but was extremely viscous and dark colored. Shortly thereafter the material solidified to a solid ~el.
Example 3 Preparation of Aliphatic/Aromatic Polycarbodiimide by a Feed Process The apparatus of Example 1 was employed with the addition of a feed tank and pump. To the 1;~13394 feed tank were charged 61.0 9 toluene diisocyanate, 83.4 9 phenyl isocyanate, and 285 9 amyl acetate.
To the reactor were charged 155.6 q isophorone diisocyanate and 15 g of a 10% solution of 3-methyl-1-phenyl-2-phospholene-1-oxide in xylene.
The reactor was heated to 140C with stirring and nitrogen sparge, and the material in the feed tank was added over a 5.5 hour period. After two additional hours of reaction the material was completed and cooled. The product had a viscosity of 0.5 Sto~e (Gardner Bubble Viscometer) and a color of 5+ using a Gardner Hellige Comparator. Titration of the carbodiimide functionality ~ave a value of 9.75~ by the procedure of Zaremko and Watts (~icrochem. J. Symp. Ser., 2, 591(1962)).
Example 4 Preparation of Aliphatic/Aromatic Polycarbodiimide by a Feed Process (~odified Conditions) The previous Example 3 was repeated with the exceptions being that a 5.25 hour feed time and a reaction temperature of 120C was employed. The material required 21 hours to react to completion.
Using the tests of Example 3, the product had a viscosity of 0.5 Stoke, a color rating of 5+, and a percent carbodiimide of 8~80.
Example 5 Preparation of Alternate Composition by the Feed Process Using the apparatus of Example 3, to the feed tan~ were charged 76.3 9 phenyl isocyanate, 55.8 9. toluene diisocyanate, and 280 ~. of hexylene qlycol di~cetate. The the reactor were charged 167.9 9 bis-(4-isocyanatocyclohexyl)-methane and 20 q of a 10% solution of 3-methyl-1-phenyl-2-phospholene-l-oxide in xylene. A feed time of 3 lZ133~4 hours was employed with a reaction temperature of 140C. The reaction was completed after 26 hours.
Analysis of the product as described in Example 3 gave a viscosity of 3.20 Stoke, a color rating of 12, and a percent carbodiimide of 8.78.
Example 6 Preparation of Alternate Composition by the Feed Process Using the apparatus of Example 3, to the feed tank were charged 140.3 q toluene diisocyanate and 280 9 amyl acetate. To the reactor were charged 159.7 9 butyl isocyanate and 20 9 of 10~ 3-methyl-1-phenyl-2-phospholene-1-oxide in xylene. A feed time of 3 hours was employed along with a reaction temperature of 140C. The reaction required a total time of 5 hours for completion. Evaluation by the procedures in Example 3 gave a viscosity of less than 0.5 Stoke and a color ratinq of 7.
Example 7 Preparation_of Alternate Composition by the Feed Process Using the apparatus of Example 3, to the feed tank were charged 155.2 9 phenyl isocyanate and 280 9 amyl acetate and to the reactor were charged 144.8 9 isophorone diisocyanate and 20 9 of 10%
3-methyl-1-phenyl-2-phospholene-1-oxide in xylene.
A reaction temperature of 140C and a feed time of 3 hours were employed. The reaction required 22 hours for completion. Evaluation by the procedures in Example 3 qave a viscosity of less than 0.5 Stoke and a color ratin~ of 5.
Example 8 -Preparation of Aliphatic Polycarbodiimide for Reactivity Test In the apparatus of E~ample 1 were charqed 1~3394 68.7 9 butyl isocyanate, 231.2 9 isophorone diisocyanate, 270 9 amyl acetate, and 30 q of 10%
3-methyl-1-phenyl-2-phospholene-1-oxide in xylene.
The mixture was heated with stirring at 140C under a nitrogen sparge for 10 hours. Evaluation by the procedures in Example 3 qave a viscosity of less than 0.5 Stoke, a color rating of 3, and a percent carbodiimide of 9.79.
Example 9 Preparation of Aliphatic Polycarbodiimide - for-Reactivity Test Into the apparatus of Example 1 were charged 93.9 9 phenyl isocyanate, 206.1 9 toluene diisocyanate, 270 9 amyl acetate, and 30 9 of a 10%
3-methyl-1-phenyl-2-phospholene-1-oxide. The mixture was heated with stirring under a nitrogen sparge to 140C. After 1 hour reaction time, the reaction was complete. Evaluation by the procedures of Example 3 gave a viscosity of less than 0.5 Stoke, a color rating of 7, and a percent carbodiimide of 11.36.
~xample 10 Comparison of Polycarbodiimide Structures in Reactivity for Crosslinking A mate~ial termed LPCA 5011 described in U.S. 4,096,125 (20% CELLOSOLVE Acetate, 50%
phthallic anhydride, 15% NIAX polyol PCP-0300, 15%
NIAX Polyol PCP-0301 to an approximate acid equivalent weight of 363) was used to prepare the following master batch:
LPCA 5011 363 9 (one acid equivalent) Tr~ethyl~mine 101 9 (one acid equivalent) CE1LOSOLV~ Ace~ate 536 9 This master batch was blended with the polycarbodiimide solution of E~ample 8:
~aster ~atch 36.0 9 (0.036 acid equivalents) Polycarbodiimide 14.0 9 (0.036 carbodiimide equivalents) This well-stirred mix was placed in an oven at 50C
and found to gel in 2.3 hr.
The master batch was additionally blended with the aromatic polycarbodiimide solution of ExamPle 9.
~aster Batch 37.4 9 (0.0347 acid equivalents) Polycarbodiimide 12.6 9 (0.0374 carbodiimide equivalents After three days in a 50~C oven the mix was unchanged (no gelation).
Finally the master batch was blended with the aliphatic/aromatic polycarbodiimide solution of Example 4:
Master Batch 36.1 9 0.0361 acid equivalents) Polycarbodiimide 13.9 9 (0.0361 carbodiimide equivalents) This mi~ture was placed in a 50C oven and found to gel in 2 hours showing the surprising reactivity of the lower cost aliphatic/aromatic polycar~odiimide.
E~ample 11 Evaluation of the Aliphatic/Aromatic PolYcarbodiimide in a Coil Coating Formulation The polycarbodiimide solution of E~ample 3 was emulsified in wa~er using the following materials and ratios:
Polycarbodiimide Solution45 parts AEROSOL A-196 tAmerican Cyanamid) 1 part Triethylamine 0.68 part Water 55.33 part ~213394 A base coating formulation was prepared as listed below:
Pigment Grind Water 185~6 Ammonia (28%) 0.4 Ethylene glycol 13.2 TERGITOL NP-10 8.8 TAMOL 731 28.8 FOAMASTER VF2.4 TI-PURE R-960847.6 1086.g Let Down Pigment Grind 1086.8 FOAMASTER VF9.2 Water 141.6 Ammonia 28~22.4 UCAR 45112173.6 Butyl CARBITOL 159.2 3592.8 Ammonia to pH9 From this base coating the following formula~ions were prepared:
Base Polycar-Formula- bodiimide CYMEL
System Crosslinkertion, 9 Emulsion, 9 303, q A None 106 B Polycarbodiimide 106 13.2 Emulsion C CYMEL 303 106 - 2.5 CYMEL 303 Hexamethoxymethylmelamine The formulations were coated on Bonderite # 37 panels and cured at two different peak metal temperatures and evaluated by rubbing with cheesecloth soa~ed with methyl ethyl ketone (MEK).
The results are shown below:
MEK DOUBLE RUBS
Systems 250F 4~0F
B 24 50+
C 10 50+
~Z13394 These results showed that the polycarbodiimide cure~ at a lower temperature than the melamine system and gave strong performance at the standard high cure temperature.
E~ample 12 ~valuation of the Ali~hatic/Aromatic Polycarbodiimide in a Roof Coatin9 Application A master batch of roof coating formulation was prepared as detailed below:
CHLOROhAX 40 22 Antimony Oxide 2 Tricresyl Phosphate 63 Triethylamine 10.5 Water 200 1273.5 This material was used along with the Polycarbodiimide emulsion of Example 11 to prepare the following formulations:
Master Polycarbodiimide System Batch, q Water, 9 Emulsion, q XAMA-7, 9 A 200 9.6 B 200 - 9.6 C 200 7.9 - 1.~
XA~A-7- Multifunctional aziridine crosslinker from Cordova Chemical.
The final formulations were air-dried for two weeks at ambient te~perature. The resultant films were evaluatea for water swellinq by ambient temperature soakinq for two days and for tensile properties.
lZ~3394 Water Swelling System % Weight Gain Dry Film Tensile Strength ~ Elonqation These results showed that the polycar~odiimide cured --at ambient temperature and gave improved properties to the roof coating.
Example 13 Evaluation of the Aliphatic/Aromatic Polycarbodiimide in a Hardboard Coating -A base hardboard primer formulation was prepared as shown below:
Pigment Grind Water 256.2 Daniels DISPERSE-AID W-22 20.4 IGEPAL CA-630 6.9 FOAMASTER VF 5.7 NOPOCIDE N-96 17.1 SNO~FLAKE 1109.7 SURFYNOL 104 8.4 TI-PURE R-960 369.6 CHROME CHEM 895 0.9 Water 28.5 182~.4 Let Down Pigment Grid 1800.0 UCAR 4580 1248.0 FOAMASTER VF 3.0 CELLOSOLVE 127.0 Hexyl CELLOSOLVE 84.0 Dibutyl phthallate 60.0 Water 180.0 POLYOL WSRN 40.6 Ammonia ~14~ 59.0 Water 100.4 3702.
Ammonia to pH 9 lZ~3394 This material, along with the polycarbodiimide emulsion of Exa~ple 11 was employed to prepare the followinq formulations:
Base Polycarbodi-Formula- imide System tion, q Emulsion, ~ CY~EL 303, 9 ~ater, 9 A 159 - - 18.9 B 159 18.9 C 159 ~ 3~ 6 l5o 3 These formulations were coated on hardboard and air-dried at ambient temperature. The cure state of the coatings was evaluate~ by rubbing with cheeseclotb soaked in metbyl ethyl ketone (MEK) MEK DOUBLE RUBS
Systems 1 day 3 days Continued evaluation at further time periods failed to show any substantive change. These results showed the rapid low temperature crosslinking of the polycarbodiimide.
Example 14 Evaluation of the Aliphatic/Aromatic Polycarbodiimide in Pressure Sensitive Adhesives The polycarbodiimide emulsion of Example 11 was employed to crosslink a water-borne pressure sensitive adhesive, VCAR 175. Initially, the followin~ formulations were prepared with the UCAR
175 being adjusted to pH 9 with triethylamine:
UCAR Polycarhodiimide System 175,9 Emulsion, q XAMA-7, Q ~ater, 9 A 117 - - 10.6 B 117 10.6 C 117 - 1.9 8.7 The materials were applied to MYLAR tape and cured at 100C for 30 min. The resultant adhesive tapes were placed on steel substrates and evaluated for 1'~13394 their adhesive strength by measuring the force required to peel the tape (pli = pounds per linear inch) and the time which the tape would hold a 500 q weight in a vertical position. The results are shown below:
System Shear, hours Peel, pli A 0.1 4.80 B 48 0.15 C 2.9 0.26 These results showed that the polycarbodiimide crosslinked the adhesive latex reducing its tac~iness (peel) while greatly increasing the adhesive strength (shear).
Although tbe invention has been described in its preferred forms with a certain degree of particularity, it is understood that the present disclosure of the preferred form has been made only by way of example and ~hat numerous changes may be made without departinq from the spirit and the scope of ~he invention.
Claims (11)
1. Method of preparing mixed aliphatic and aromatic polycarbodiimides which comprises the following steps seriatim:
(A) charging a mixture of cycloaliphatic or saturated aliphatic mono-and diisocyanates to a reactor with agitation under an inert atmosphere;
(B) heating the resultant mixture to about 120 to about 160°C;
(C) adding a catalytic amount of a phospholene oxide catalyst to the reactor;
(D) feeding a mixture of a non-reactive solvent and aromatic mono- and/or diisocyanate to the reactor; and (E) maintaining agitation at about 120 to about 160°C until all of the isocyanate functionality is converted to carbodiimide functionality, with the provisos that:
(a) said cycloaliphatic moieties contain 6 to about 10 carbons;
(b) said saturated aliphatic moieties contain from about 4 to about 12 carbons;
(c) said aromatic moieties contain from 6 to about 16 carbons;
(d) The molar ratio of all of the mono-to-diisocyanates range from about 2:1 to about 2:10; and (e) The molar ratio of cycloaliphatic and/or saturated aliphatic isocyanate groups to aromatic isocyanate groups ranges from about 0.5:1 to about 2:1.
(A) charging a mixture of cycloaliphatic or saturated aliphatic mono-and diisocyanates to a reactor with agitation under an inert atmosphere;
(B) heating the resultant mixture to about 120 to about 160°C;
(C) adding a catalytic amount of a phospholene oxide catalyst to the reactor;
(D) feeding a mixture of a non-reactive solvent and aromatic mono- and/or diisocyanate to the reactor; and (E) maintaining agitation at about 120 to about 160°C until all of the isocyanate functionality is converted to carbodiimide functionality, with the provisos that:
(a) said cycloaliphatic moieties contain 6 to about 10 carbons;
(b) said saturated aliphatic moieties contain from about 4 to about 12 carbons;
(c) said aromatic moieties contain from 6 to about 16 carbons;
(d) The molar ratio of all of the mono-to-diisocyanates range from about 2:1 to about 2:10; and (e) The molar ratio of cycloaliphatic and/or saturated aliphatic isocyanate groups to aromatic isocyanate groups ranges from about 0.5:1 to about 2:1.
2. Method claimed in claim 1 wherein the molar range of all of the mono- to diisocyanates range from about 2:1 to about 4:1.
3. Method claimed in claim 1 wherein the molar ratio of cycloaliphatic and/or saturated aliphatic mono- and diisocyanates to aromatic mono-and diisocyanates ranges from about 0.75:1 to about 1.25:1.
4. Method claimed in claim 2 wherein the aliphatic monoisocyanate is butyl isocyanate and the cycloaliphatic diisocyanate is isophorone diisocyanate.
5. Method claimed in claim 3 wherein the aromatic diisocyanate is toluene diisocyanate.
6. Method claimed in claim 1 using phenyl isocyanate, isophorone diisocyanate and toluene diisocyanate.
7. Method claimed in claim 1 carried out in a non-reactive organic solvent.
8. Method claimed in claim 7 wherein the solvent is a glycol diester.
9. Method claimed in claim 7 wherein the solvent is an aliphatic ester.
10. Method claimed in claim 1 wherein the phospholene oxide catalyst is 3-methyl-1-phenyl-2-phospholene-1-oxide.
11. Method claimed in claim 1 wherein the temperature in steps (B) and (E) is about 120° to about 160°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US469,434 | 1983-02-24 | ||
| US06/469,434 US4487964A (en) | 1983-02-24 | 1983-02-24 | Method of making mixed aliphatic/aromatic polycarbodiimides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1213394A true CA1213394A (en) | 1986-10-28 |
Family
ID=23863788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000446741A Expired CA1213394A (en) | 1983-02-24 | 1984-02-03 | Method of making mixed aliphatic/aromatic polycarbodiimides |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4487964A (en) |
| EP (1) | EP0120305B1 (en) |
| JP (1) | JPS59193916A (en) |
| KR (1) | KR900008527B1 (en) |
| AT (1) | ATE21386T1 (en) |
| AU (1) | AU559037B2 (en) |
| CA (1) | CA1213394A (en) |
| DE (1) | DE3460449D1 (en) |
Families Citing this family (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4820863A (en) * | 1986-03-31 | 1989-04-11 | Union Carbide Corporation | Surface active polycarbodiimides |
| US5108653A (en) * | 1986-03-31 | 1992-04-28 | Union Carbide Chemicals & Plastics Technology Corporation | Surface active polycarbodiimides and their dispersions |
| BR8707104A (en) * | 1986-12-30 | 1988-08-02 | Union Carbide Corp | PROCESS TO PREPARE A TENSIVE-ACTIVE POLYCARBODIIMIDE, PROCESS TO MOVE RESINS CONTAINING CARBOXYL AND CONSTUICATION WATER OR ORGANIC RESINS SOLUBLE IN NEUTRALIZED AND CARBOXYLATED WATER, AND RETICULABLE COMPOSITION |
| US5352831A (en) * | 1987-09-02 | 1994-10-04 | Ciba-Geigy Corporation | Oligomeric cyanoguanidines |
| IT1230088B (en) * | 1989-05-26 | 1991-10-05 | Italiane Vernici Ind | QUICK-SETTING COATING COMPOSITION. |
| JP2796385B2 (en) * | 1989-12-22 | 1998-09-10 | ミネソタ マイニング アンド マニユフアクチユアリング カンパニー | Water and oil repellent treatment agent |
| US5008363A (en) * | 1990-03-23 | 1991-04-16 | Union Carbide Chemicals And Plastics Technology Corporation | Low temperature active aliphatic aromatic polycarbodiimides |
| US5240811A (en) * | 1991-04-15 | 1993-08-31 | Ocg Microelectronic Materials, Inc. | Photogenerated polycarbodiimides from poly(tetrazole-5-thiones) and use in the preparation of coatings and deep-UV photoresists |
| US5276096A (en) * | 1991-08-28 | 1994-01-04 | Basf Corporation | Two package coating composition comprising a polycarbodimide with improved rheology control |
| JP3165971B2 (en) * | 1991-12-26 | 2001-05-14 | 日清紡績株式会社 | Polytetramethylxylylenecarbodiimide |
| US5352400A (en) * | 1992-04-29 | 1994-10-04 | E. I. Du Pont De Nemours And Company | Carbodiimides and processes therefor |
| JP3188959B2 (en) * | 1992-08-10 | 2001-07-16 | 日清紡績株式会社 | Method for producing polycarbodiimide resin |
| JP3438957B2 (en) * | 1994-08-11 | 2003-08-18 | 日清紡績株式会社 | Aqueous surface treatment agent for reinforcement, reinforcement treated with the aqueous surface treatment, and composite reinforced with reinforcement |
| US5936043A (en) | 1995-12-22 | 1999-08-10 | Rohm And Haas Company | Polymers crosslinkable with aliphatic polycarbodiimides |
| KR100304475B1 (en) * | 1996-01-18 | 2001-11-22 | 야마모토 히데키 | Aromatic polycarbodiimide and films made therefrom |
| JP3518149B2 (en) † | 1996-02-29 | 2004-04-12 | 日清紡績株式会社 | Aqueous pre-coated metal paint |
| JP3393752B2 (en) * | 1996-04-26 | 2003-04-07 | 日清紡績株式会社 | Hydrolysis-resistant stabilizer for resin having ester group and method for stabilizing hydrolysis-resistant resin having ester group by said stabilizer |
| US5885662A (en) † | 1997-01-31 | 1999-03-23 | Atoma International, Inc. | Decorative automotive interior trim articles with integral light stable polyurethane elastomer covering and process for making the same |
| US6362247B1 (en) | 2000-05-08 | 2002-03-26 | Rohm And Haas Company | Method of improving stability of aromatic polycarbodiimides |
| US6566437B2 (en) | 2000-06-05 | 2003-05-20 | Rohm And Haas Company | Wear-resistant coating composition and method of producing a coating |
| US7045571B2 (en) * | 2001-05-21 | 2006-05-16 | 3M Innovative Properties Company | Emulsion polymerization of fluorinated monomers |
| US6737489B2 (en) | 2001-05-21 | 2004-05-18 | 3M Innovative Properties Company | Polymers containing perfluorovinyl ethers and applications for such polymers |
| AU2002311389B2 (en) * | 2001-12-13 | 2008-01-31 | Rohm And Haas Company | Crosslinkable composition |
| US6890360B2 (en) | 2001-12-17 | 2005-05-10 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
| CA2487067A1 (en) * | 2002-05-24 | 2003-12-04 | 3M Innovative Properties Company | Fluorochemical composition for treatment of a fibrous substrate |
| US7094829B2 (en) * | 2002-05-24 | 2006-08-22 | 3M Innovative Properties Company | Fluorochemical composition comprising a fluorinated polymer and treatment of a fibrous substrate therewith |
| US7425279B2 (en) * | 2002-05-24 | 2008-09-16 | 3M Innovative Properties Company | Fluorochemical composition for treatment of a fibrous substrate |
| WO2003100159A1 (en) * | 2002-05-24 | 2003-12-04 | 3M Innovative Properties Company | Fluorochemical composition comprising perfluoropolyether and an extender for the treatment of fibrous substrates |
| EP1685200B1 (en) * | 2003-11-12 | 2007-08-15 | E.I. Dupont De Nemours And Company | Inkjet ink, ink set and method of printing |
| US7504523B2 (en) * | 2006-03-10 | 2009-03-17 | Basf Corporation | Uretonimine-modified isocyanate composition and method of forming the same |
| US7541397B2 (en) * | 2006-03-10 | 2009-06-02 | Basf Corporation | Uretonimine-modified isocyanate composition and method of forming the same |
| US20080116414A1 (en) * | 2006-11-22 | 2008-05-22 | 3M Innovative Properties Company | Fluorochemical composition for treatment of a fibrous substrate |
| US8993116B2 (en) * | 2007-06-08 | 2015-03-31 | 3M Innovative Properties Company | Blends of fluoroalkyl-containing ester oligomers with polydicarbodiimide(S) |
| MX2012010068A (en) * | 2010-03-02 | 2012-12-17 | Ppg Ind Ohio Inc | One-component, ambient curable waterborne coating compositions, related methods and coated substrates. |
| US9701846B2 (en) | 2012-11-28 | 2017-07-11 | Evonik Roehm Gmbh | Type of road markings for supporting the environment detection of vehicles |
| DE102013206116A1 (en) | 2013-04-08 | 2014-10-09 | Evonik Industries Ag | New road markings to support the perception of the surroundings of vehicles |
| CN108003313B (en) * | 2017-12-21 | 2020-08-04 | 上海朗亿功能材料有限公司 | Block type polycarbodiimide water-based cross-linking agent and preparation method thereof |
| CN113490724B (en) | 2019-03-05 | 2022-11-04 | 日清纺化学株式会社 | Aqueous resin crosslinking agent, aqueous resin crosslinking agent-containing solution, and aqueous resin composition |
| KR102219875B1 (en) * | 2019-10-07 | 2021-02-24 | 공주대학교 산학협력단 | Liquid fuel-injection injector for incineration |
| JP7413771B2 (en) | 2019-12-25 | 2024-01-16 | 日清紡ケミカル株式会社 | Crosslinking agent composition for aqueous resin and aqueous resin composition |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1005726B (en) * | 1955-10-26 | 1957-04-04 | Bayer Ag | Stabilizing agent against the effects of heat and moisture in polyester compounds modified by polysocyanates |
| US2853473A (en) * | 1956-08-27 | 1958-09-23 | Du Pont | Production of carbodiimides |
| FR1310138A (en) * | 1960-12-02 | 1963-03-06 | ||
| NL273087A (en) * | 1960-12-31 | |||
| DE1190176B (en) * | 1961-04-25 | 1965-04-01 | Bayer Ag | Use of carbodiimides together with organosilicon compounds as stabilizing agents in polyurethanes containing ester groups |
| FR1469946A (en) * | 1965-02-25 | 1967-02-17 | Bayer Ag | Process for preparing carbodiimides |
| US3639353A (en) * | 1970-03-20 | 1972-02-01 | Goodrich Co B F | Polymers crosslinked with polycarbodiimides |
| US3929733A (en) * | 1974-10-02 | 1975-12-30 | Upjohn Co | Polycarbodiimides from 4,4{40 -methylenebis(phenyl isocyanate) and certain carbocyclic monoisocyanates |
| DE2536493A1 (en) * | 1975-08-16 | 1977-02-24 | Bayer Ag | POLYMERIZATION PRODUCTS |
| DE2624198C2 (en) * | 1976-05-29 | 1984-10-04 | Bayer Ag, 5090 Leverkusen | Polymerization products |
-
1983
- 1983-02-24 US US06/469,434 patent/US4487964A/en not_active Expired - Fee Related
-
1984
- 1984-02-03 CA CA000446741A patent/CA1213394A/en not_active Expired
- 1984-02-23 JP JP59031572A patent/JPS59193916A/en active Granted
- 1984-02-23 AT AT84101922T patent/ATE21386T1/en active
- 1984-02-23 KR KR1019840000874A patent/KR900008527B1/en not_active IP Right Cessation
- 1984-02-23 AU AU24864/84A patent/AU559037B2/en not_active Ceased
- 1984-02-23 DE DE8484101922T patent/DE3460449D1/en not_active Expired
- 1984-02-23 EP EP84101922A patent/EP0120305B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ATE21386T1 (en) | 1986-08-15 |
| DE3460449D1 (en) | 1986-09-18 |
| JPS59193916A (en) | 1984-11-02 |
| KR850000484A (en) | 1985-02-27 |
| EP0120305A1 (en) | 1984-10-03 |
| EP0120305B1 (en) | 1986-08-13 |
| US4487964A (en) | 1984-12-11 |
| AU2486484A (en) | 1984-08-30 |
| JPS6411051B2 (en) | 1989-02-23 |
| KR900008527B1 (en) | 1990-11-24 |
| AU559037B2 (en) | 1987-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1213394A (en) | Method of making mixed aliphatic/aromatic polycarbodiimides | |
| US4587301A (en) | Method of using mixed aliphatic/aromatic polycarbodiimides | |
| US4977219A (en) | Low temperature crosslinking of water-borne resins | |
| CA1244589A (en) | Low-temperature crosslinking of water-borne resins | |
| KR940008986B1 (en) | Polyisocyanato-isocyanurate and preparation process and use of the same | |
| US4435559A (en) | β-Hydroxy urethane low temperature curing agents | |
| EP0053766B2 (en) | Process for the preparation of coatings | |
| US4939213A (en) | Triazine crosslinking agents and curable compositions containing the same | |
| EP1522547A1 (en) | Highly reactive liquid uretdione groups-containing polyurethane systems which are curable at low temperature | |
| GB1568029A (en) | Pulveruletn two-component polyurethane coating composition | |
| KR101515273B1 (en) | Method of making cyclic guanidine from dicyandiamide and coating compositions containing same | |
| US2855421A (en) | Polyisocyanates and method of preparing polyisocyanates | |
| EP2580287B1 (en) | Anticrater agent for electrocoating composition | |
| JPS61207421A (en) | Manufacture of mercapto group-containing oligourethane, oligourethane thereby and use for various polymers | |
| US4068086A (en) | Blocked polyisocyanates obtained from 2,2,4-trimethylhexamethylene-diisocyanate and acetoacetic acid alkyl esters | |
| US2797232A (en) | Hidden polyisocyanates | |
| KR102042239B1 (en) | Cationic urethane curing agent and electro-deposition paint composition comprising the same | |
| GB2080305A (en) | Carbocyclic Triisocyanates and Powder Coating Compositions Containing Polyisocyanates Derived therefrom | |
| US5098949A (en) | Electrodepositable aqueous coating composition with a component having cyclic urea groups | |
| JPH0749462B2 (en) | Blocked isocyanate compound, and low temperature curable composition, coating composition and adhesive composition containing the same | |
| EP1349888B1 (en) | Polymeric crosslinkable compositions containing spiroorthocarbonates | |
| US4305977A (en) | Use of hydroxyl alkyl amines optionally containing ether groups or their salts as additives reducing resistance to the diffusion of water vapor in polyurethane-based coating compositions | |
| EP0042701B2 (en) | Isocyanate composition | |
| EP0160642B1 (en) | Polymeric light stabilizers containing polyalkylpiperidine groups | |
| JPH10130353A (en) | Self-emulsification type polyisocyanate composition and aqueous coating material composition and aqueous adhesive composition using the same composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |