CA1065834A - Catalyst and process for preparing rigid cellular polyurethane-modified polyisocyanurate foams - Google Patents
Catalyst and process for preparing rigid cellular polyurethane-modified polyisocyanurate foamsInfo
- Publication number
- CA1065834A CA1065834A CA237,239A CA237239A CA1065834A CA 1065834 A CA1065834 A CA 1065834A CA 237239 A CA237239 A CA 237239A CA 1065834 A CA1065834 A CA 1065834A
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- Canada
- Prior art keywords
- parts
- tris
- hexahydrotriazine
- catalyst
- alkylene oxide
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
-
- 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
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
-
- 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
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2036—Heterocyclic amines; Salts thereof containing one heterocyclic ring having at least three nitrogen atoms in the ring
-
- 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
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A S T R A C T
This invention relates to po?yurothane foams and compositions and processes for preparing rigid urethane foams comprising reacting a mix-ture of a polyalkylene polyol having at least two reactive hydrogen atoms, at least one organic polyisocyanate, and, as a trimerization and polymeriza-tion catalyst combi??tion, at least one member of the group consisting of 1,3,5-tris(N,N-dialkylaminoalkyl)-hexahydrotriazines and 2,4,6-tris-(N,N-dialkylaminoalkyl) phenols and their adducts with alkylene oxide and water and at least one member of the group consisting of the alkali metal salts of carboxylic acids exhibiting from 2 to 19 carbon atoms.
This invention relates to po?yurothane foams and compositions and processes for preparing rigid urethane foams comprising reacting a mix-ture of a polyalkylene polyol having at least two reactive hydrogen atoms, at least one organic polyisocyanate, and, as a trimerization and polymeriza-tion catalyst combi??tion, at least one member of the group consisting of 1,3,5-tris(N,N-dialkylaminoalkyl)-hexahydrotriazines and 2,4,6-tris-(N,N-dialkylaminoalkyl) phenols and their adducts with alkylene oxide and water and at least one member of the group consisting of the alkali metal salts of carboxylic acids exhibiting from 2 to 19 carbon atoms.
Description
~ ~583~ :
The present invention pertains to rigid cellular foam compositions and in particular to polyisocyanurate rigid cellular compositions whicll have been modiied by addition of polyurethane-producing species. More particularly, the present invention relates to the preparation of rigid cellular urethane-modified isocyanurate compositions catalyzed with a synergistic combina-tion of isocyanurate tri~erization catalyst.
The trimerization reaction of isocyanates to isocyan-urates using trie~thylphosphine was first reported by ~lofmann.
Since that time, many other catalysts for the trimerization of isocyanates have been described. The use of amines is described in United States Patents 2,993,870 and 2~979,485. Additional basic nitrogen compounds5 such as triazines and their derivatives are taught in United States Patent 3,80~,782. Salts of weak acids such as calcium acetate have been described by Frentzel, and potassium acetate and sodium carbonate by l-lofmann. The use of potassium octanoate (2-ethyl hexoate) is taught in Japanese Patent 71 ~2,386. The preparation of rigid cellular polyisocyanurate or poly~urethane-isocyanura*e) compositions generally entails the reaction of either a polyether or polyester polyol, an organic polyisocyanate, a surfactant, a blowing agent and a cata-lyst. In the preparation oE these oams, the function oE the catalyst is to accclera~e the formatlon o~ the cellular product, thereby making the process economical and eEficient. nhile amine catalysts such as 2,~,6-(N,N-dimethylaminomethyl)phenol and hexahydrotriazines are efEective, a combination of high use levels and toxicity limits the;r use. Thus, in preparing these foams, it is imperative to minimize the toxicity in handling the ingredients, as well as maximizing their efficiency, thereby maximizing the advantages accruing to these foams. It is the - 1- ~ :,,, i834 improvement of catalyst efficiency and diminishing catalyst toxicity to which the present învention is directed. `
The present invention generally concerns itself with rigid c~llular polyurethane-modified polyisocyanurate-based foam compositions which are prepared by the reaction of an or-gani.c compound having at least two active hydrogen atoms with an organic polyisocyanate employing a large excess of said polyiso-cyanate which is trimerized to isocyanurate concomitantly with polyurethane formation. This trimerization-polymerization of isocyanate with the active hydrogen species is catalyzed by a synergistic combination of caustic soap and tertiary amine. By use of this unique catalyst combination, concerted and balanced urethane formation and isocyanurate formation is obtained, with an unusually low catalyst requirement. The reaction of the active hydrogen species with a fraction of the polyisocyanate is balanced with the polyisocyanate trimerization reaction by this low level of caustic soap-tertiary amine combination. By employing this class of catalyst combination to promote the urethane and isocyanurate reaction, isocyanate indices of up to
The present invention pertains to rigid cellular foam compositions and in particular to polyisocyanurate rigid cellular compositions whicll have been modiied by addition of polyurethane-producing species. More particularly, the present invention relates to the preparation of rigid cellular urethane-modified isocyanurate compositions catalyzed with a synergistic combina-tion of isocyanurate tri~erization catalyst.
The trimerization reaction of isocyanates to isocyan-urates using trie~thylphosphine was first reported by ~lofmann.
Since that time, many other catalysts for the trimerization of isocyanates have been described. The use of amines is described in United States Patents 2,993,870 and 2~979,485. Additional basic nitrogen compounds5 such as triazines and their derivatives are taught in United States Patent 3,80~,782. Salts of weak acids such as calcium acetate have been described by Frentzel, and potassium acetate and sodium carbonate by l-lofmann. The use of potassium octanoate (2-ethyl hexoate) is taught in Japanese Patent 71 ~2,386. The preparation of rigid cellular polyisocyanurate or poly~urethane-isocyanura*e) compositions generally entails the reaction of either a polyether or polyester polyol, an organic polyisocyanate, a surfactant, a blowing agent and a cata-lyst. In the preparation oE these oams, the function oE the catalyst is to accclera~e the formatlon o~ the cellular product, thereby making the process economical and eEficient. nhile amine catalysts such as 2,~,6-(N,N-dimethylaminomethyl)phenol and hexahydrotriazines are efEective, a combination of high use levels and toxicity limits the;r use. Thus, in preparing these foams, it is imperative to minimize the toxicity in handling the ingredients, as well as maximizing their efficiency, thereby maximizing the advantages accruing to these foams. It is the - 1- ~ :,,, i834 improvement of catalyst efficiency and diminishing catalyst toxicity to which the present învention is directed. `
The present invention generally concerns itself with rigid c~llular polyurethane-modified polyisocyanurate-based foam compositions which are prepared by the reaction of an or-gani.c compound having at least two active hydrogen atoms with an organic polyisocyanate employing a large excess of said polyiso-cyanate which is trimerized to isocyanurate concomitantly with polyurethane formation. This trimerization-polymerization of isocyanate with the active hydrogen species is catalyzed by a synergistic combination of caustic soap and tertiary amine. By use of this unique catalyst combination, concerted and balanced urethane formation and isocyanurate formation is obtained, with an unusually low catalyst requirement. The reaction of the active hydrogen species with a fraction of the polyisocyanate is balanced with the polyisocyanate trimerization reaction by this low level of caustic soap-tertiary amine combination. By employing this class of catalyst combination to promote the urethane and isocyanurate reaction, isocyanate indices of up to
2~ about 1000 can be used in preparing these foams. By virtue of the high isocyanate index which can be employed, and the very effici~nt reduced combinat:ion catalyst levels required, economical polyurethane-modiEied polyisocyanurate fo~n can be produced.
Polyisocyanurate cellular foam products of this type are desirable owing to their reduced tendency to burn, thereby eliminating the need for addition of other agents to impart flame retardancy.
This and other advantages of polyurethane-modified polyisocyan-urate foams are discussed in the literature by Frisch et al.
Accordingly, the i-nvention provides a catalyst com-position for the prepara~ion of rigid cellular polyurethane-~65834 modified polyisocyanurate :foam consisting essentially of a combination of 0.01 part to 5 parts of a 1,3,5-tris(N,N-dialkylaminoalkyl)-hexahydrotriazine or the alkylene oxide or water adduct of a 1,3,5-tris- .-(N,N-dialkylaminoalkyl)-hexahydrotriazine together with 0.01 part to 5 .
parts of a caustic soap being an alkali-metal neutralization product of a : .
carboxylic acid having from 6 to 19 oarbon atoms. . ~- -In ~nother embodiment, there is provided a process of making .
a rigid cellular polyurethane which comprises reacting a polyalkylene polyol having at least two active hydrogen atoms with an organic poly- ..
functional.isocyanate, said reaction being carried out in the presence of ~.
catalyst combination of 0.01 part to 5 parts of at least one member of the group consisting of 1,3,5-tris-(N,N-dialkylaminoalkyl)-hexahydrotriazine, and the adducts with alkylene oxide thereof, 0.01 part to 5 parts of an alkali metal neutralization product of a carboxylic acid exhibiting from 6 to : 19 carbon atoms.
For a more complete understanding of the present invention, ; .
reference is made to the following detailed description and examples thereof.
It has unexpectedly been found that when certain isocyanurate ; trimerization catalysts are employed in the preparation of polyurethane-modified isocyanurate foam in combination with each other, advantageous economical and synergistic use can be made of this combination. The use `~
of these reduced catalyst levels not only permits product:ion of the rosult-ing cellular products faster and mole economically, but reduces dramatically ..
tho levcls of toxic, i.r:r:itating and ...
- . , . . ~ " , . .
..
expensive tertiary amine required. All of these advantages are directly attributable to the use of the speci~ic catalyst combinations defined here.
According to another of its aspects this invention relates to polyurethane foams and compositions and processes for preparing rigid urethane foams comprising reacting a mixture of a polyalkylene polyol having at least two reactive hydrogen atoms, at least one organic polyisocyanate, and as a trimerization' and polymeriza~ion catalyst combina~ion 0.~1 part to 5 parts of at least one member of the group consisting of 1,3,5-tris(N,N -dialkylaminoalkyl) hexahydrotriazines and 2,4,6-tris(N,N -dialkylaminoalkyl) phenols and their adducts with alkylene oxide and water and 0.01 part to 5 parts of at least one member of ¦
the group consisting of the alkali metal salts of carboxylic acids exhibiting from 2 to 19 carbon atoms per 100 parts of organic polyisocyanate.
The preferred isocyanate-trimerization urethane-polymerization catalysts employed in the practice of the present invention ~re 1,3,5-tris(N,N-dialkylaminoalkyl)-hexahydro-triazines, or the a~kylene oxide and water additioll productsthereo~, in combination with an allcali-metal hy~roxide neukraliæat~on product o~ a carboxylic acid, for example potassium 2-ethylhexoate.
1,3,5-tris(N,N-dialkylaminoalkyl)-hexahydrotriazines are ~enerally prepared by reactin~ equimolar amounts of a dialkylaminoalkylamine and a 37 percent aqueous solution of Il l :
.
.
~: ~L~)65~334 formaldehyde (formalin) at a temperature ranging from about -20C. to 20C. and at atmospheric pressure. More particularly, the amine and formaldehyde are mixed together with gentle stirring at about 0C. Thereafter and with continuous gentle stirring the mixture is-allowed to heat up to room temperature.
The hexahydrotriazine compound is then recovered first by saltin~
out the hexahydrotriazine from the reaction mixture with a strong , base, such as potassium hydroxide, followed by purification by distillation. These hexahydrotriazine compounds and their methods of preparation are more particularly described by ¦ Nicholas et al. r Journal of Cellular Plastics, 1 (1), 85 (lg65), and Graymor~, Journal of the Chemical Society, 1493 (1931).
Representative of the 1,3,5-tri5(NtN-diallcylamino-alkyl)-hexahydrotriazines u6eul herein include, for example, 1,3,5-tris(N,N-dimethyl-2-aminoethyl)-s-hexahydrotriazine, 1,3,5-tris(N,N-dimethyl-2-aminopropyl)-s-hexahydrotriazine, and the li.ke; 1,3,5-tris(N,N-diethyl-2-aminoethyl)-s-hexa-hydrotriazine; 1,3,5-tris(N,N-diethyl~3-aminoethyl)-s-hexa-hydrotriazine and the like; 1,3,5-tris(N,N-dipropyl-2-am.ino-ethyl)-s-hexahydrotriazine and the l.ike, and so forth. The preerred compound is 1,3,5-tri.s(N,N-dimethyl-3-aminopropyl)-s-hexahydrotriazine which can also be designated as 1,3,5-tris(3-dimethylaminopropyl)-s-hexahydrotriazine. Related 2r preferred isocyanurate trimerization co-catalysts, as previously J noted, are the alkylene oxide and water adducts of the herein-be~ore described 1,3,5-tris(N,N-diethylaminoalkyl)-s-hexa-hydrotriazines. These compounds are, presumably, quaternary ~065~33fl~
.
ammonium hydroxides having the following postulated structure:
R'-N-R2"
~ ~ ~3 a R2 " -N-R ' -N~ N-R ' -N-R2 " OH
R-CH-CH-OH
R
: wherein each R, individually, is hydrogen or lower alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl and pentyl; R" is lower alkyl, such as those enumerated for R, and R' is alkylene, such as ethylene, propylene and butylene as derived from the useful hexahydrotriazines, with again the preferrecl hexahydrotriazine being the same as the one defined above.
In regard to the postulated structure, it is apparent that there are six available tertiary nitrogen sites capable of formati.on of the quaternary ammonium hydrox.ide and, thereEore, the above-depicted structure is only illustrative. It is further noted that the hydroxyl g.roup may be e.ither pr:;mary or secondary.
The alkylene oxides which may be used to prepare the adducts are, preferably, linear alkylene oxides, such as ethylene o*ide, propylene oxide, the butylene oxides, and the pentyl.ene oxides. Although not preferred, all cyclic oxides, such as cyclopentylene oxide, cyclohexylene oxide, and the like, can be use erein. ~l~o sub ~it ted alkylene oxides, su~h as ~ l : ~
. styrene oxid~s, can be used herein. The preferred alkylene oxide, though, is propylene oxide.
l When 1,3,5-tris(3-dimethylaminopropyl~-s-hexahydro-I triazine, propylene oxide and water are used to prepare the ~ 5 preferred adduct, the resultant is presumably:
I (CH2)3-N-(CH3)2 .~
~C~3)2-~~(CH2)3-N~V" N(CH2)3 1 3 2 OH
. CH2-CH-OH
These alkylene oxide and water adduct~s are generally prepared by reacting substantially e~uimolar amounts of hexahydrotriazine, alkylene oxide and water, at a temperature ranging from about 10C. to 80C. for a period of time ranging from about five minutes to two hours ana at a pressure ranging from about atmospheric pressure to fifty p.s..i.g. An~ conventional reaction mode can be employed such as:
(1) Reacting thc hexahydrotriaæine and alkylell~ oxlde at atmospheric or elevated pressure, for a period of from about fifteen to sixty minutes, preferably, fifteen to thirty minutes, and at a temperature of from about 10C. to 35C., preferably 20C. to 30C. and, then, adding and reacting therewith the water at a temperature of from about 25C. to 80C., preferably 40C. to 60C. for a period of from about ten to sixty minutes, preferably, from about fifteen to forty minutes;
~065834 (2) Adding water to the hexahydrotriazine followed thereafter by the alkylene oxide addition, this mode of reaction being carried out under the same reaction conditions defined above; or
Polyisocyanurate cellular foam products of this type are desirable owing to their reduced tendency to burn, thereby eliminating the need for addition of other agents to impart flame retardancy.
This and other advantages of polyurethane-modified polyisocyan-urate foams are discussed in the literature by Frisch et al.
Accordingly, the i-nvention provides a catalyst com-position for the prepara~ion of rigid cellular polyurethane-~65834 modified polyisocyanurate :foam consisting essentially of a combination of 0.01 part to 5 parts of a 1,3,5-tris(N,N-dialkylaminoalkyl)-hexahydrotriazine or the alkylene oxide or water adduct of a 1,3,5-tris- .-(N,N-dialkylaminoalkyl)-hexahydrotriazine together with 0.01 part to 5 .
parts of a caustic soap being an alkali-metal neutralization product of a : .
carboxylic acid having from 6 to 19 oarbon atoms. . ~- -In ~nother embodiment, there is provided a process of making .
a rigid cellular polyurethane which comprises reacting a polyalkylene polyol having at least two active hydrogen atoms with an organic poly- ..
functional.isocyanate, said reaction being carried out in the presence of ~.
catalyst combination of 0.01 part to 5 parts of at least one member of the group consisting of 1,3,5-tris-(N,N-dialkylaminoalkyl)-hexahydrotriazine, and the adducts with alkylene oxide thereof, 0.01 part to 5 parts of an alkali metal neutralization product of a carboxylic acid exhibiting from 6 to : 19 carbon atoms.
For a more complete understanding of the present invention, ; .
reference is made to the following detailed description and examples thereof.
It has unexpectedly been found that when certain isocyanurate ; trimerization catalysts are employed in the preparation of polyurethane-modified isocyanurate foam in combination with each other, advantageous economical and synergistic use can be made of this combination. The use `~
of these reduced catalyst levels not only permits product:ion of the rosult-ing cellular products faster and mole economically, but reduces dramatically ..
tho levcls of toxic, i.r:r:itating and ...
- . , . . ~ " , . .
..
expensive tertiary amine required. All of these advantages are directly attributable to the use of the speci~ic catalyst combinations defined here.
According to another of its aspects this invention relates to polyurethane foams and compositions and processes for preparing rigid urethane foams comprising reacting a mixture of a polyalkylene polyol having at least two reactive hydrogen atoms, at least one organic polyisocyanate, and as a trimerization' and polymeriza~ion catalyst combina~ion 0.~1 part to 5 parts of at least one member of the group consisting of 1,3,5-tris(N,N -dialkylaminoalkyl) hexahydrotriazines and 2,4,6-tris(N,N -dialkylaminoalkyl) phenols and their adducts with alkylene oxide and water and 0.01 part to 5 parts of at least one member of ¦
the group consisting of the alkali metal salts of carboxylic acids exhibiting from 2 to 19 carbon atoms per 100 parts of organic polyisocyanate.
The preferred isocyanate-trimerization urethane-polymerization catalysts employed in the practice of the present invention ~re 1,3,5-tris(N,N-dialkylaminoalkyl)-hexahydro-triazines, or the a~kylene oxide and water additioll productsthereo~, in combination with an allcali-metal hy~roxide neukraliæat~on product o~ a carboxylic acid, for example potassium 2-ethylhexoate.
1,3,5-tris(N,N-dialkylaminoalkyl)-hexahydrotriazines are ~enerally prepared by reactin~ equimolar amounts of a dialkylaminoalkylamine and a 37 percent aqueous solution of Il l :
.
.
~: ~L~)65~334 formaldehyde (formalin) at a temperature ranging from about -20C. to 20C. and at atmospheric pressure. More particularly, the amine and formaldehyde are mixed together with gentle stirring at about 0C. Thereafter and with continuous gentle stirring the mixture is-allowed to heat up to room temperature.
The hexahydrotriazine compound is then recovered first by saltin~
out the hexahydrotriazine from the reaction mixture with a strong , base, such as potassium hydroxide, followed by purification by distillation. These hexahydrotriazine compounds and their methods of preparation are more particularly described by ¦ Nicholas et al. r Journal of Cellular Plastics, 1 (1), 85 (lg65), and Graymor~, Journal of the Chemical Society, 1493 (1931).
Representative of the 1,3,5-tri5(NtN-diallcylamino-alkyl)-hexahydrotriazines u6eul herein include, for example, 1,3,5-tris(N,N-dimethyl-2-aminoethyl)-s-hexahydrotriazine, 1,3,5-tris(N,N-dimethyl-2-aminopropyl)-s-hexahydrotriazine, and the li.ke; 1,3,5-tris(N,N-diethyl-2-aminoethyl)-s-hexa-hydrotriazine; 1,3,5-tris(N,N-diethyl~3-aminoethyl)-s-hexa-hydrotriazine and the like; 1,3,5-tris(N,N-dipropyl-2-am.ino-ethyl)-s-hexahydrotriazine and the l.ike, and so forth. The preerred compound is 1,3,5-tri.s(N,N-dimethyl-3-aminopropyl)-s-hexahydrotriazine which can also be designated as 1,3,5-tris(3-dimethylaminopropyl)-s-hexahydrotriazine. Related 2r preferred isocyanurate trimerization co-catalysts, as previously J noted, are the alkylene oxide and water adducts of the herein-be~ore described 1,3,5-tris(N,N-diethylaminoalkyl)-s-hexa-hydrotriazines. These compounds are, presumably, quaternary ~065~33fl~
.
ammonium hydroxides having the following postulated structure:
R'-N-R2"
~ ~ ~3 a R2 " -N-R ' -N~ N-R ' -N-R2 " OH
R-CH-CH-OH
R
: wherein each R, individually, is hydrogen or lower alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl and pentyl; R" is lower alkyl, such as those enumerated for R, and R' is alkylene, such as ethylene, propylene and butylene as derived from the useful hexahydrotriazines, with again the preferrecl hexahydrotriazine being the same as the one defined above.
In regard to the postulated structure, it is apparent that there are six available tertiary nitrogen sites capable of formati.on of the quaternary ammonium hydrox.ide and, thereEore, the above-depicted structure is only illustrative. It is further noted that the hydroxyl g.roup may be e.ither pr:;mary or secondary.
The alkylene oxides which may be used to prepare the adducts are, preferably, linear alkylene oxides, such as ethylene o*ide, propylene oxide, the butylene oxides, and the pentyl.ene oxides. Although not preferred, all cyclic oxides, such as cyclopentylene oxide, cyclohexylene oxide, and the like, can be use erein. ~l~o sub ~it ted alkylene oxides, su~h as ~ l : ~
. styrene oxid~s, can be used herein. The preferred alkylene oxide, though, is propylene oxide.
l When 1,3,5-tris(3-dimethylaminopropyl~-s-hexahydro-I triazine, propylene oxide and water are used to prepare the ~ 5 preferred adduct, the resultant is presumably:
I (CH2)3-N-(CH3)2 .~
~C~3)2-~~(CH2)3-N~V" N(CH2)3 1 3 2 OH
. CH2-CH-OH
These alkylene oxide and water adduct~s are generally prepared by reacting substantially e~uimolar amounts of hexahydrotriazine, alkylene oxide and water, at a temperature ranging from about 10C. to 80C. for a period of time ranging from about five minutes to two hours ana at a pressure ranging from about atmospheric pressure to fifty p.s..i.g. An~ conventional reaction mode can be employed such as:
(1) Reacting thc hexahydrotriaæine and alkylell~ oxlde at atmospheric or elevated pressure, for a period of from about fifteen to sixty minutes, preferably, fifteen to thirty minutes, and at a temperature of from about 10C. to 35C., preferably 20C. to 30C. and, then, adding and reacting therewith the water at a temperature of from about 25C. to 80C., preferably 40C. to 60C. for a period of from about ten to sixty minutes, preferably, from about fifteen to forty minutes;
~065834 (2) Adding water to the hexahydrotriazine followed thereafter by the alkylene oxide addition, this mode of reaction being carried out under the same reaction conditions defined above; or
(3) Concurrently, but separately, adding to and reacting the alkylene oxide and water with the hexahydrotriazine at a temperature of from about 10C. to 80C., preferably, 20C. ~o 60C., for a period of from about five to sixty minutes, preferably, fifteen to forty minutes.
The resulting products are highly viscous products which can be employed as solutions thereof to $acilitate handling.
The preferred 2,4,6-tristN,N~dialkylaminoalkyl)phenol is 2,4,6-tris(dimethylaminomethyl)phenol.
: 15 The caustic soap or alkali metal hydroxide neutra-. lization products of carboxylic acids include the lithium, sodium and potassium hydroxide reaction products of acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acids up to and including C18 carboxylic acids, but not necessarl.ly limited to those. Unsatura~ed carboxylic acids ~erived rom tall oils or animal fats such as oleic acid or ~ linoleic acids may also be employed or mixtures thereof.
: Aromatic carboxylic acids such as benzoic acid and its derivatives, salicylic acids, and naphthenoic acids may be used.
Any suitable polycarboxylic acid may be used, such as oxalic : acid, malonic acid, succ nic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, a-hydroxymuconic acid, ~-hydroxymuconic acid, a-butyl-a-ethyl-glutaric acid, a,~-diethylsuccinic acid, isophthalic acid, terephthalic acid, hemimellitic acid and 1,4-cyclohexane dicarboxylic acid.
The caustic soap is prepared by neutralization of the carboxylic acid by an aqueous solution of the alkali-metal hydroxide with stirring. Careful control of the exotherm related to the heat of neutralization is required to maintain an ~- undiscolored product. The water of solution and neutralization is then removed under vacuum with stirring.
An optional procedure employs the use of a diluent as a viscosity suppressant and/or solvent for the reactants and products. In this procedure, the carboxylic acid is first dissolved in the diluent, followed by the neutralization by aqueous caustic solution. The water is similarly removed.
Suitable diluents include alcohols such as methanol, ethanol, propanol, butanol and the like; glycols such as ethylene glycol, diethylene glycol and poly(ethylene glycols), propylene glycol, dipropylene glycol and poly(propylene glycols) and ~he like.
In preparing a ~oam pxoduct in the presence o~ these combined catalysts, substantially reduced levels of total combined catalyst may be used, especially in regard to the hexahydrotriazine, which is less effective on a weight basis than the caustic soaps, for example, potassium-2-ethyl hexoate.
I .
106b834 While up to 12 parts of hexahydrotriazine per hundred parts of polyisocyanate or 3-4 parts of a 65% solution of potassium-2-ethyl hexoate in poly(propylene glycol) per hundred parts of polyisocyanate need to be used as sole catalysts, as little as one part per hundred of each comprises a more effective catalyst combina~ion than either alone at that combined level (two parts per hundred parts of polyisocyanate~.
The cellular polyurethane-modified polyisocyanurate foam products which are prepared ln accordance herewith generally comprise the reaction product of an isocyanate with itself to form a poly~isocyanurate), modified by the simultaneous reaction . of a fraction of the polyisocyanate with an organic compound containing at least two active hydrogen atoms, such as a hydroxy-terminated polyester, polyesteramine, amide or polyether.
In general, any organic compound containing at least two active hydrogen atoms may be employed. herein for reaction with the polyisocyanate to produce the necessary urethane modification of the cellular foam. Examples of suitable types of organic compounds containing at least two active hydrogen groups are castor oil, hydroxy-containing polyesters, polyalkylene polyether polyols, hydroxy-terminated polyurethane polymers, polyhydria polythioethers, alkylene oxide adduc~s of acids of phosphorus, polyacetals, aliphatic polyols, simple, oligomeric and polymeric glycols such as ethylene glycol, propylene glycol, ~S butylene glycol, poly(ethylene glycol), poly(propylene glycol) and poly(butylene glycol).
1~65834 Any suitable polyisocyanate may be used, for example polymethylene polyphenylene polyisocyanate lcrude MDI) in conjunction with an aforementioned organic compound containing at least two active hydrogen atoms. These polyols generally have an average equivalent weight of from about 31 for ethylene glycol to 2000 for a polyoxypropylene adduct of glycerine. Also, ¦
polyol blends such as a mixture of hi~h molecular weight polyether' polyols with lower molecular weight polyether polyols or mono-meric polyols can be used.
The organic polyisocyanates which are advantageously employed in the present invention can be represented by the formula:
R~NCO)z wherein R is a polyvalent organic radical selected from the group of aliphatic, aromatic, aralalkyl and alkaryl organic radicals as well as mixtures thereof; and z is an integer corresponding to the valence number of R and is at least 2.
Representative of the organic polyisocyanates contemplated herein includes, for example, the aromatic diisocyanates, such ¦ as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures ¦ of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate, ¦ methylene diphenyl diisocyanate t crude methylene diphenyl I diisocyanate and the like; the aromatic triisocyanates such as ¦ tris-(4-isocyanatophenyl)-methane. 2,4,6-toluene trisisocyanates;
¦ the aromatia tetraisocyanates, such as 4,4l-dimethyldiphenyl-¦ methane-2,2', 5',5'-tetraisocyanate, and the likej alkylaryl '' '; , ' ~ . ...
~065834 poly isocyanates, such as xylene diisocyanate; aliphatic poly-isocyanates, such as hexamethylene-1,6-diifiocyanate, lysine diisocyanate methylester and the like, and mixtures thereof.
Other organic polyisocyanates include polymethylene polyphenyl-isocyanate, hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate~ naphthylene-,15-diisocyanate, 1-methoxyphenyl-2,
The resulting products are highly viscous products which can be employed as solutions thereof to $acilitate handling.
The preferred 2,4,6-tristN,N~dialkylaminoalkyl)phenol is 2,4,6-tris(dimethylaminomethyl)phenol.
: 15 The caustic soap or alkali metal hydroxide neutra-. lization products of carboxylic acids include the lithium, sodium and potassium hydroxide reaction products of acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acids up to and including C18 carboxylic acids, but not necessarl.ly limited to those. Unsatura~ed carboxylic acids ~erived rom tall oils or animal fats such as oleic acid or ~ linoleic acids may also be employed or mixtures thereof.
: Aromatic carboxylic acids such as benzoic acid and its derivatives, salicylic acids, and naphthenoic acids may be used.
Any suitable polycarboxylic acid may be used, such as oxalic : acid, malonic acid, succ nic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, a-hydroxymuconic acid, ~-hydroxymuconic acid, a-butyl-a-ethyl-glutaric acid, a,~-diethylsuccinic acid, isophthalic acid, terephthalic acid, hemimellitic acid and 1,4-cyclohexane dicarboxylic acid.
The caustic soap is prepared by neutralization of the carboxylic acid by an aqueous solution of the alkali-metal hydroxide with stirring. Careful control of the exotherm related to the heat of neutralization is required to maintain an ~- undiscolored product. The water of solution and neutralization is then removed under vacuum with stirring.
An optional procedure employs the use of a diluent as a viscosity suppressant and/or solvent for the reactants and products. In this procedure, the carboxylic acid is first dissolved in the diluent, followed by the neutralization by aqueous caustic solution. The water is similarly removed.
Suitable diluents include alcohols such as methanol, ethanol, propanol, butanol and the like; glycols such as ethylene glycol, diethylene glycol and poly(ethylene glycols), propylene glycol, dipropylene glycol and poly(propylene glycols) and ~he like.
In preparing a ~oam pxoduct in the presence o~ these combined catalysts, substantially reduced levels of total combined catalyst may be used, especially in regard to the hexahydrotriazine, which is less effective on a weight basis than the caustic soaps, for example, potassium-2-ethyl hexoate.
I .
106b834 While up to 12 parts of hexahydrotriazine per hundred parts of polyisocyanate or 3-4 parts of a 65% solution of potassium-2-ethyl hexoate in poly(propylene glycol) per hundred parts of polyisocyanate need to be used as sole catalysts, as little as one part per hundred of each comprises a more effective catalyst combina~ion than either alone at that combined level (two parts per hundred parts of polyisocyanate~.
The cellular polyurethane-modified polyisocyanurate foam products which are prepared ln accordance herewith generally comprise the reaction product of an isocyanate with itself to form a poly~isocyanurate), modified by the simultaneous reaction . of a fraction of the polyisocyanate with an organic compound containing at least two active hydrogen atoms, such as a hydroxy-terminated polyester, polyesteramine, amide or polyether.
In general, any organic compound containing at least two active hydrogen atoms may be employed. herein for reaction with the polyisocyanate to produce the necessary urethane modification of the cellular foam. Examples of suitable types of organic compounds containing at least two active hydrogen groups are castor oil, hydroxy-containing polyesters, polyalkylene polyether polyols, hydroxy-terminated polyurethane polymers, polyhydria polythioethers, alkylene oxide adduc~s of acids of phosphorus, polyacetals, aliphatic polyols, simple, oligomeric and polymeric glycols such as ethylene glycol, propylene glycol, ~S butylene glycol, poly(ethylene glycol), poly(propylene glycol) and poly(butylene glycol).
1~65834 Any suitable polyisocyanate may be used, for example polymethylene polyphenylene polyisocyanate lcrude MDI) in conjunction with an aforementioned organic compound containing at least two active hydrogen atoms. These polyols generally have an average equivalent weight of from about 31 for ethylene glycol to 2000 for a polyoxypropylene adduct of glycerine. Also, ¦
polyol blends such as a mixture of hi~h molecular weight polyether' polyols with lower molecular weight polyether polyols or mono-meric polyols can be used.
The organic polyisocyanates which are advantageously employed in the present invention can be represented by the formula:
R~NCO)z wherein R is a polyvalent organic radical selected from the group of aliphatic, aromatic, aralalkyl and alkaryl organic radicals as well as mixtures thereof; and z is an integer corresponding to the valence number of R and is at least 2.
Representative of the organic polyisocyanates contemplated herein includes, for example, the aromatic diisocyanates, such ¦ as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures ¦ of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate, ¦ methylene diphenyl diisocyanate t crude methylene diphenyl I diisocyanate and the like; the aromatic triisocyanates such as ¦ tris-(4-isocyanatophenyl)-methane. 2,4,6-toluene trisisocyanates;
¦ the aromatia tetraisocyanates, such as 4,4l-dimethyldiphenyl-¦ methane-2,2', 5',5'-tetraisocyanate, and the likej alkylaryl '' '; , ' ~ . ...
~065834 poly isocyanates, such as xylene diisocyanate; aliphatic poly-isocyanates, such as hexamethylene-1,6-diifiocyanate, lysine diisocyanate methylester and the like, and mixtures thereof.
Other organic polyisocyanates include polymethylene polyphenyl-isocyanate, hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate~ naphthylene-,15-diisocyanate, 1-methoxyphenyl-2,
4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-biphenyl-ene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'biphenyl diisocyanate, and 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate. -These polyisocyanates are prepared by conventionalmethods known in the art such as the phosgenation of the corresponding organic amine.
¦ Still another class of organic polyisocyanates ¦ contemplated by the present invention are the so-called ¦ "quasi-prepolymers". These quasi-prepolymers are prepared by ¦ reacting an excess of organic polyisocyanate or mixtures thereof ¦ with a minor amount of an active hydrogen containing compound ¦ as determined by the well-known Zerewitinoff test, as described ¦ by Kohler in Journal of Amexican Chemical Society, 49, 3181 ¦ (1927). These compounds and their method of preparation are ¦ well known in the art. The use o any one speci~ic active ¦ hydrogen compound is not critical hereto, rather, any such ¦ compound that can be used to prepare a ~uasi-prepolymer can be ¦ employed herein. Generally speaking, the ~uasi-prepolymers are l prepared by reactin~ an organic polyisocyanate with less than : ~. ' . '' . ':
.. .
a stoichiometric amount, based on the weight of the polyiso-cyanate o the active hydrogen-containing compound. Suitable active hydrogen-containing groups are those hereinbefore described.
In the practice of the present invention, the preferred isocyanate is polymethylene polyphenylene polyisocyanate This polyisocyanate is employed at an isocyanate index of from - about 200 to 1000, preferably from about 3~0 to 500. As used herein, the term isocyanate index means the actual amount of isocyanate used divided by the theoretically reguired stoichio-metric amount of isocyanate multiplied by one hundred. See Berder, Handbook of ~oam Plastics, Lake Publishing Corporation, Libertyville, Illinois (1965).
In addition to the previously defined ingredients use~ul in the preparation of the foam, other ingredients such as surfactants, fillers, pigments and blowing agents can also be included. Surfactants which can be used are the conventional surfactants used in urethane preparation such as the poly-siloxanes or the alkylene oxide adducts of organic compounds containing reactive hydrogen atoms. The surfac~ant is generally used in an amount ranging from about 0.01 part to 5 parts by weight ther~of per hundred parts o polyisocyanake.
The expansion to a reduced-density cellular product is accomplished by use of a blowing agent. Volatile organic solvents which vaporize during the reaction exotherm are suitable, such as methylene chloride, ethylene chloride, ,~
.
' trichlorofluoromethane, dichlorodifluor~methane, chlorotri-fluoromethane, tetrachloromethane, difluorotetrachloroethane, and the like. The blowing agent used in the preferred embodiment is trichlorofluoromethane. Water may be used as a supplemental blowing agent to the halocarbons. The use of water as a blowing agent in urethane chemistry is described in Saunders and Frisch, Advances in Polyurethane Chemistry, Volume 1, Page 76.
In addition to the previously defined ingredients useful in the pre~aration of the foam, other ingredients such as ~illers, pigments and the like may also be included~ Conventional fillers for use herein include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium ; sulfate, calcium sulfate, carbon black and silicon. The iller is nominally present in the amount ranging from about 5 parts to 50 parts by weight thereof per hundred parts of total foam compos.ition.
The pigmient which can be used herein is selected from any conventional pigment heretofore disclosed in the art, such as, titanium dioxide, zinc oxide, iron oxides, antimony oxide, chrome green, chrome yellow, iron blue siennas, molybdate oranges, organic pigments such as para reds, benæidine yellow, toluidine red, toners and phthalocyanines.
In preparing the rigid foams of the present invention any general procedure convehtionally used for the preparation of a urethane foam can be practical. Generally speaking, such a procedure entails the admixture o~ the participating ingredients with agitation. The reacting mass is dispersed into a suitable .
,...~ 11. . . . . ~
. : . , , :
106583~
container immediately prior to the onset of the cellular expansion.
For a more complete understanding of the present invention reference is made to the following non-limiting examples. In the examples all parts are by weight unless other-wise noted. The rise profiles of the foams described was determined in accordance with the industry standards.
In a one-liter glass jar a mixture of 275 parts Pluracol*P-410 ~425 hydroxyl number poly(oxypropylene) supplied by BASF Wyandotte], 276 parts of trichlorofluoromethane and 30 parts of Niax silicone L~5340*(polyoxyalkylene polysiloxane supplied by Union Carbide Corporation) was stirred for five minutes at 1000 rpm. The mixture was allowed to stand overnight and formed a clear solution.
EXA~PLE 2 .
A 50 part portion of the masterbatch whose preparation is described in Example 1 is weighed into an eight-ounce plas~ic-lined paper cup. Polycat 41*(1,3,5-tris-(dimethylaminopropyl)-hexahydrotriazine from Abbott Laboratories), 4.0 parts, wasthen added. The mixture was stirred for two minutes at 500 rpm and weighed~ The loss oE blowing agent aue to its vola~ility was then compensated for by subsequent addition of fluorocarbon from a wash bottle. PAPI (polymethylene polyphenylene polyiso-cyanate, Upjohn Company) 100 parts was then added all at onceand mixed for ten seconds a~ 2000 rpm using a malted mixer.
. :
* Trade Mark _ 15 ~
;, :L065834 The material was then poured into an 8 x 8 x 6 inch cardboard box and allowed to expand freely. The cream, rise, gel and tack-free times were 20~ 76, 127 and 400 seconds respectively.
The foam was dark colored.
The procedure of Example 2 was followed using 8.0 parts of 1,3,5-tris-(dimethylaminopropyl)-hexahydrotriazine per hundred parts of polyisocyanate. The cream, rise, gel and tack-free times were 20, 53, 97, and 215 seconds respectively.
The foam was dark colored.
The procedure of Example 2 was followed using 12.0 parts of 1,3,5-tris-(dimethylaminopropyl)-hexahydrotriazine per hundred parts of polyisocyanate. The cream, rise, gel and tack-free times were 16, 47, 102 and 200 seconds respectively.
It can be seen that an activity plateau has been reached with this system by comparison of Examples 3 and 4, since little ¦ activity increase accompanies the catalyst increase.
~he procedure of Example 2 was ollowed using 1.0 ¦ parts of a 65 percent solution of potassium 2-ethylhexoate in Poly(oxypropylene) exhibiting a hydroxyl number of 425 as the ¦ sole catalyst. No reaction was observed.
I
¦ The procedure of Example 2 was followed using 2.0 l parts of a 65 percent solution of potassium 2-ethylhexoate in ¦ poly(oxypropylene) exhibiting a hydroxyl number of 425.
" ' ' . ~ . :
~96~;i834 The cream, rise, gel and tack-free times were 17, 35, 55, and 70 seconds respectively. The foam was light colored.
~X~MPLE 7 . _ The procedure of Example 2 was followed using 4.0 S parts of 1,3,5-tris-~dimethylaminopropyl~-hexahydrotriazine and l.0 parts of a 65 percent solution of potassium 2-ethylhexoate in poly(oxypropylene) exhibiting a hydroxyl number of 425 as a synergistic combination catalyst. The cream, rise, gel and tack-free times were 13, 26, 40 and 60 seconds respectively.
Foam color was light.
., The procedure for Example 2 was followed using 1.0 part of 1,3,5-tris-(dimethylaminopropyl)-hexah~drotriazine and l.0 part of a 65~ solution of potassium 2-ethylhexoate in poly(oxypropylene) exhibiting a hydroxyl number of 425 as the synergistic catalyst combination. The cream, rise, gel and tack-free tirnes were 14t 28, 45 and 125 seconds respectively.
It can be seen from the above examples that addition of as little as 1.0 part of a 65% solution of potassium 2-ethyl-hexoate in poly(oxy~ropylene) exhibiting a hydroxyl number of 425per hundred parts of polyisocyanate to a 1,3,5-txis-~dimethyl-aminopropyl)-~hexahydrotria2ine~catalyzed system causes a synergistic increase in activity, since 1.0 parts of a 65%
solution of potassium 2-ethylhexoate in poly(oxypropylene) exhibiting a hydroxyl number of 4~5 alone is not an effective catalyst. Higher levels of a 65% solution of potassium 2-ethyl-hexoate in poly(oxypropylene) exhibiting a hydroxyl number of _ 17 1~)6~i83~ ~ ~
425 do successfully catalyze foam formation but use of such a system is limited by the lack of strength of the resulting cellular product.
..
The masterbatch of Example 1 was reformulated replacing poly(propylene glycol) with poly(ethylene glycol) on an equal weight basis.
A 50 part portion of the masterbatch described in Example 9 was weighed into an eight-ounce plastic-lined paper cup. 1.0 parts of 1~3~5-tristdimethylaminopropyl)-hexahydro-triazine and 1.0 parts of a 65% solution of potassium 2-ethyl-hexoate in poly(oxypropylene) exhibiting a hydroxyl number of 425 are weighed into the cup. Agitation for two mlnutes at 500 rpm using a malted mixer is followed by replacement of the volatilized fluorocarbon. Polymethylene polyphenylene poly-isocyanate, 100 parts, was added all at once. The reacting mixture was mixed for 10 seconds at 2000 rpm with a malted mixer.
The resulting mass was then poured into an 8 x 8 x 6 cardboard ¦ box and all~wed to rise freely. The aream, rise, gel and tack-free times were 14, 27, 46 and 120 seconds respectively.
~X~MPIIE 11 . .., .. -..-- .
The procedure of Example 10 was repeated where the l 1.0 parts of a 65% solution of potassium 2-ethyl hexoate in ¦ poly~oxypropylene) exhibiting a hydroxyl number of 425 was l replaced by 0.90 grams of a 65~ by weight solution of sodium ¦ 2-ethyl hexoate in poly(oxypropylene) exhibiting a hydroxyl . , : , '' . : :, .: : ' : ` `
---~65~33 .
. number of 425. The cream, rise, gel and tack-free times were 14, 21, 47 and 125 seconds respectively.
; The procedure of Example 10 was followed replacing 1.0 parts of a 65% solution of potassium 2-ethylhexoate in poly(oxypropylene) exhibiting a hydroxyl number of 425 with 1.8 parts of a 65% solution of potassium oleate in poly(oxypropylene) . exhibiting a hydroxyl number of 425. The cream, rise, gel and : tack-free times were 15, 30, 49 and 130 seconds respectively.
The purpose of the foregoing Examples was to demonstrate~
replacement of potassium 2-ethyl hexoate by similar caustic soaps at eq molar levels results in similar periormarce.
,,, .- ' , ' , l -19- ' Il .
.
..
¦ Still another class of organic polyisocyanates ¦ contemplated by the present invention are the so-called ¦ "quasi-prepolymers". These quasi-prepolymers are prepared by ¦ reacting an excess of organic polyisocyanate or mixtures thereof ¦ with a minor amount of an active hydrogen containing compound ¦ as determined by the well-known Zerewitinoff test, as described ¦ by Kohler in Journal of Amexican Chemical Society, 49, 3181 ¦ (1927). These compounds and their method of preparation are ¦ well known in the art. The use o any one speci~ic active ¦ hydrogen compound is not critical hereto, rather, any such ¦ compound that can be used to prepare a ~uasi-prepolymer can be ¦ employed herein. Generally speaking, the ~uasi-prepolymers are l prepared by reactin~ an organic polyisocyanate with less than : ~. ' . '' . ':
.. .
a stoichiometric amount, based on the weight of the polyiso-cyanate o the active hydrogen-containing compound. Suitable active hydrogen-containing groups are those hereinbefore described.
In the practice of the present invention, the preferred isocyanate is polymethylene polyphenylene polyisocyanate This polyisocyanate is employed at an isocyanate index of from - about 200 to 1000, preferably from about 3~0 to 500. As used herein, the term isocyanate index means the actual amount of isocyanate used divided by the theoretically reguired stoichio-metric amount of isocyanate multiplied by one hundred. See Berder, Handbook of ~oam Plastics, Lake Publishing Corporation, Libertyville, Illinois (1965).
In addition to the previously defined ingredients use~ul in the preparation of the foam, other ingredients such as surfactants, fillers, pigments and blowing agents can also be included. Surfactants which can be used are the conventional surfactants used in urethane preparation such as the poly-siloxanes or the alkylene oxide adducts of organic compounds containing reactive hydrogen atoms. The surfac~ant is generally used in an amount ranging from about 0.01 part to 5 parts by weight ther~of per hundred parts o polyisocyanake.
The expansion to a reduced-density cellular product is accomplished by use of a blowing agent. Volatile organic solvents which vaporize during the reaction exotherm are suitable, such as methylene chloride, ethylene chloride, ,~
.
' trichlorofluoromethane, dichlorodifluor~methane, chlorotri-fluoromethane, tetrachloromethane, difluorotetrachloroethane, and the like. The blowing agent used in the preferred embodiment is trichlorofluoromethane. Water may be used as a supplemental blowing agent to the halocarbons. The use of water as a blowing agent in urethane chemistry is described in Saunders and Frisch, Advances in Polyurethane Chemistry, Volume 1, Page 76.
In addition to the previously defined ingredients useful in the pre~aration of the foam, other ingredients such as ~illers, pigments and the like may also be included~ Conventional fillers for use herein include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium ; sulfate, calcium sulfate, carbon black and silicon. The iller is nominally present in the amount ranging from about 5 parts to 50 parts by weight thereof per hundred parts of total foam compos.ition.
The pigmient which can be used herein is selected from any conventional pigment heretofore disclosed in the art, such as, titanium dioxide, zinc oxide, iron oxides, antimony oxide, chrome green, chrome yellow, iron blue siennas, molybdate oranges, organic pigments such as para reds, benæidine yellow, toluidine red, toners and phthalocyanines.
In preparing the rigid foams of the present invention any general procedure convehtionally used for the preparation of a urethane foam can be practical. Generally speaking, such a procedure entails the admixture o~ the participating ingredients with agitation. The reacting mass is dispersed into a suitable .
,...~ 11. . . . . ~
. : . , , :
106583~
container immediately prior to the onset of the cellular expansion.
For a more complete understanding of the present invention reference is made to the following non-limiting examples. In the examples all parts are by weight unless other-wise noted. The rise profiles of the foams described was determined in accordance with the industry standards.
In a one-liter glass jar a mixture of 275 parts Pluracol*P-410 ~425 hydroxyl number poly(oxypropylene) supplied by BASF Wyandotte], 276 parts of trichlorofluoromethane and 30 parts of Niax silicone L~5340*(polyoxyalkylene polysiloxane supplied by Union Carbide Corporation) was stirred for five minutes at 1000 rpm. The mixture was allowed to stand overnight and formed a clear solution.
EXA~PLE 2 .
A 50 part portion of the masterbatch whose preparation is described in Example 1 is weighed into an eight-ounce plas~ic-lined paper cup. Polycat 41*(1,3,5-tris-(dimethylaminopropyl)-hexahydrotriazine from Abbott Laboratories), 4.0 parts, wasthen added. The mixture was stirred for two minutes at 500 rpm and weighed~ The loss oE blowing agent aue to its vola~ility was then compensated for by subsequent addition of fluorocarbon from a wash bottle. PAPI (polymethylene polyphenylene polyiso-cyanate, Upjohn Company) 100 parts was then added all at onceand mixed for ten seconds a~ 2000 rpm using a malted mixer.
. :
* Trade Mark _ 15 ~
;, :L065834 The material was then poured into an 8 x 8 x 6 inch cardboard box and allowed to expand freely. The cream, rise, gel and tack-free times were 20~ 76, 127 and 400 seconds respectively.
The foam was dark colored.
The procedure of Example 2 was followed using 8.0 parts of 1,3,5-tris-(dimethylaminopropyl)-hexahydrotriazine per hundred parts of polyisocyanate. The cream, rise, gel and tack-free times were 20, 53, 97, and 215 seconds respectively.
The foam was dark colored.
The procedure of Example 2 was followed using 12.0 parts of 1,3,5-tris-(dimethylaminopropyl)-hexahydrotriazine per hundred parts of polyisocyanate. The cream, rise, gel and tack-free times were 16, 47, 102 and 200 seconds respectively.
It can be seen that an activity plateau has been reached with this system by comparison of Examples 3 and 4, since little ¦ activity increase accompanies the catalyst increase.
~he procedure of Example 2 was ollowed using 1.0 ¦ parts of a 65 percent solution of potassium 2-ethylhexoate in Poly(oxypropylene) exhibiting a hydroxyl number of 425 as the ¦ sole catalyst. No reaction was observed.
I
¦ The procedure of Example 2 was followed using 2.0 l parts of a 65 percent solution of potassium 2-ethylhexoate in ¦ poly(oxypropylene) exhibiting a hydroxyl number of 425.
" ' ' . ~ . :
~96~;i834 The cream, rise, gel and tack-free times were 17, 35, 55, and 70 seconds respectively. The foam was light colored.
~X~MPLE 7 . _ The procedure of Example 2 was followed using 4.0 S parts of 1,3,5-tris-~dimethylaminopropyl~-hexahydrotriazine and l.0 parts of a 65 percent solution of potassium 2-ethylhexoate in poly(oxypropylene) exhibiting a hydroxyl number of 425 as a synergistic combination catalyst. The cream, rise, gel and tack-free times were 13, 26, 40 and 60 seconds respectively.
Foam color was light.
., The procedure for Example 2 was followed using 1.0 part of 1,3,5-tris-(dimethylaminopropyl)-hexah~drotriazine and l.0 part of a 65~ solution of potassium 2-ethylhexoate in poly(oxypropylene) exhibiting a hydroxyl number of 425 as the synergistic catalyst combination. The cream, rise, gel and tack-free tirnes were 14t 28, 45 and 125 seconds respectively.
It can be seen from the above examples that addition of as little as 1.0 part of a 65% solution of potassium 2-ethyl-hexoate in poly(oxy~ropylene) exhibiting a hydroxyl number of 425per hundred parts of polyisocyanate to a 1,3,5-txis-~dimethyl-aminopropyl)-~hexahydrotria2ine~catalyzed system causes a synergistic increase in activity, since 1.0 parts of a 65%
solution of potassium 2-ethylhexoate in poly(oxypropylene) exhibiting a hydroxyl number of 4~5 alone is not an effective catalyst. Higher levels of a 65% solution of potassium 2-ethyl-hexoate in poly(oxypropylene) exhibiting a hydroxyl number of _ 17 1~)6~i83~ ~ ~
425 do successfully catalyze foam formation but use of such a system is limited by the lack of strength of the resulting cellular product.
..
The masterbatch of Example 1 was reformulated replacing poly(propylene glycol) with poly(ethylene glycol) on an equal weight basis.
A 50 part portion of the masterbatch described in Example 9 was weighed into an eight-ounce plastic-lined paper cup. 1.0 parts of 1~3~5-tristdimethylaminopropyl)-hexahydro-triazine and 1.0 parts of a 65% solution of potassium 2-ethyl-hexoate in poly(oxypropylene) exhibiting a hydroxyl number of 425 are weighed into the cup. Agitation for two mlnutes at 500 rpm using a malted mixer is followed by replacement of the volatilized fluorocarbon. Polymethylene polyphenylene poly-isocyanate, 100 parts, was added all at once. The reacting mixture was mixed for 10 seconds at 2000 rpm with a malted mixer.
The resulting mass was then poured into an 8 x 8 x 6 cardboard ¦ box and all~wed to rise freely. The aream, rise, gel and tack-free times were 14, 27, 46 and 120 seconds respectively.
~X~MPIIE 11 . .., .. -..-- .
The procedure of Example 10 was repeated where the l 1.0 parts of a 65% solution of potassium 2-ethyl hexoate in ¦ poly~oxypropylene) exhibiting a hydroxyl number of 425 was l replaced by 0.90 grams of a 65~ by weight solution of sodium ¦ 2-ethyl hexoate in poly(oxypropylene) exhibiting a hydroxyl . , : , '' . : :, .: : ' : ` `
---~65~33 .
. number of 425. The cream, rise, gel and tack-free times were 14, 21, 47 and 125 seconds respectively.
; The procedure of Example 10 was followed replacing 1.0 parts of a 65% solution of potassium 2-ethylhexoate in poly(oxypropylene) exhibiting a hydroxyl number of 425 with 1.8 parts of a 65% solution of potassium oleate in poly(oxypropylene) . exhibiting a hydroxyl number of 425. The cream, rise, gel and : tack-free times were 15, 30, 49 and 130 seconds respectively.
The purpose of the foregoing Examples was to demonstrate~
replacement of potassium 2-ethyl hexoate by similar caustic soaps at eq molar levels results in similar periormarce.
,,, .- ' , ' , l -19- ' Il .
.
..
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A catalyst composition for the preparation of rigid cellular polyurethane-modified polyisocyanurate foam consisting essentially of a combination of 0.01 part to 5 parts of a 1,3,5-tris(N,N-dialkylaminoalkyl)-hexahydrotriazine or the alkylene oxide or water adduct of a 1,3,5-tris-(N,N-dialkylaminoalkyl)-hexahydrotriazine together with 0.01 part to 5 parts of a caustic soap being an alkali-metal neutralization product of a carboxylic acid having from 6 to 19 carbon atoms.
2. A catalyst combination as described in claim 1 wherein said caustic soap is the lithium, sodium, or potassium hydroxide neutralization product of a carboxylic acid.
3. A catalyst combination as described in claim 1 wherein said caustic soap is potassium 2-ethyl hexoate, or its solution in an active-hydrogen containing diluent.
5. A catalyst combination as described in claim 1 wherein said combination is the alkylene oxide or water adduct of a 1,3,5-tris(N,N-dialkylaminoalky)-hexahydrotriazine combined with a 65 percent solution of potassium 2-ethyl hexoate.
5. The process of making a rigid cellular polyurethane which comprises reacting a polyalkylene polyol having at least two active hydrogen atoms with an organic poly-functional isocyanate, said reaction being carried out in the presence of catalyst combination of 0.01 part to 5 parts of at least one member of the group consisting of 1,3,5-tris-(N,N-dialkyl-aminoalkyl)-hexahydrotriazine, and the adducts with alkylene oxide thereof 0.01 part to 5 parts of an alkali metal neutralization product of a carboxylic acid exhibiting from 6 to 19 carbon atoms.
6. A process of simultaneously trimerizing polyisocyanate and forming a rigid polyurethane foam comprising reacting a mixture of a polyalkylene polyol having at least two reactive hydrogen atoms, at least one organic polyisocyanate, and as a trimerization and polymerization catalyst combination 0.01 part to 5 parts of at least one member of the group consisting of 1,3,5-tris-(N,N-dialkylaminoalkyl)-hexahydrotria-zines and the adducts with alkylene oxide and water thereof and 0.01 part to 5 parts of an alkali metal neutralization product of a carboxylic acid exhibiting from 6 to 19 carbon atoms, per 100 parts of organic polyisocyanate.
7. A novel composition suitable for use in the production of rigid polyurethane foams by reaction of a polyol exhibiting at least two active hydrogen atoms, an organic polyfunctional isocyanate and a blowing agent consisting of 0.01 part to 5 parts of 1,3,5-tris-(N,N-dialkylaminoalkyl)-hexahydrotriazine, and the adducts with alkylene oxide, thereof and 0.01 part to5 parts of an alkali-metal neutralization product of a carboxylic acid exhibiting from 6 to 19 carbon atoms.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56628975A | 1975-04-09 | 1975-04-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1065834A true CA1065834A (en) | 1979-11-06 |
Family
ID=24262274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA237,239A Expired CA1065834A (en) | 1975-04-09 | 1975-10-08 | Catalyst and process for preparing rigid cellular polyurethane-modified polyisocyanurate foams |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS51127200A (en) |
| AR (1) | AR218607A1 (en) |
| AT (1) | AT350279B (en) |
| BE (1) | BE834239A (en) |
| BR (1) | BR7506526A (en) |
| CA (1) | CA1065834A (en) |
| DE (1) | DE2545118A1 (en) |
| ES (2) | ES441593A1 (en) |
| FR (1) | FR2307003A1 (en) |
| GB (1) | GB1529821A (en) |
| IT (1) | IT1049114B (en) |
| NL (1) | NL7511764A (en) |
| SE (1) | SE7511261L (en) |
| SU (1) | SU673151A3 (en) |
| ZA (1) | ZA755593B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176218A (en) * | 1977-10-17 | 1979-11-27 | Basf Wyandotte Corporation | High resilience flexible foamed polyurethanes, foamable mixtures and process therefor |
| DE2825569A1 (en) * | 1978-06-10 | 1979-12-20 | Basf Ag | PROCESS FOR THE MANUFACTURING OF LIGHT-STABLE POLYURETHANE INTEGRAL FOAM |
| DE2829670A1 (en) * | 1978-07-06 | 1980-01-17 | Bayer Ag | HEXAHYDROTRIAZINE CARBOXYLATES AND THEIR USE AS CATALYSTS FOR THE PRODUCTION OF POLYISOCYANURATE PLASTICS |
| JPS5565214A (en) * | 1978-11-10 | 1980-05-16 | Bridgestone Corp | Preparation of flame-resistant polyisocyanurate foam |
| JPS55155015A (en) * | 1979-05-23 | 1980-12-03 | Achilles Corp | Preparation of flame-retardant, low-smoke generating rigid foam |
| DE3271787D1 (en) * | 1982-11-08 | 1986-07-24 | Amoco Corp | Foam |
| US4520042A (en) * | 1983-06-20 | 1985-05-28 | Thermocell Development, Ltd. | High-modulus, flexible urethane coating and method of preparation |
| JPS61159414A (en) * | 1984-12-18 | 1986-07-19 | Nippon Polyurethan Kogyo Kk | Production of rapid-curing, heat-resistant resin |
| EP0615526A4 (en) * | 1991-03-25 | 1994-11-17 | Material Tech & Science | Water blown foam. |
| US10889681B2 (en) | 2014-12-31 | 2021-01-12 | Jiangsu Osic Performance Materials Co. Ltd. | Polyurethane catalyst and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1318925A (en) * | 1970-11-27 | 1973-05-31 | Baxenden Chem | Catalysts for the formation of polyurethane-type polymers |
| US3804782A (en) * | 1972-06-19 | 1974-04-16 | Basf Wyandotte Corp | Flexible cellular polyurethane foam compositions having increased flame retardance |
| LU68552A1 (en) * | 1973-10-03 | 1975-06-16 |
-
1975
- 1975-09-02 ZA ZA00755593A patent/ZA755593B/en unknown
- 1975-09-17 GB GB38258/75A patent/GB1529821A/en not_active Expired
- 1975-10-06 BE BE160731A patent/BE834239A/en unknown
- 1975-10-06 FR FR7530539A patent/FR2307003A1/en active Granted
- 1975-10-07 NL NL7511764A patent/NL7511764A/en not_active Application Discontinuation
- 1975-10-07 BR BR7506526*A patent/BR7506526A/en unknown
- 1975-10-08 SE SE7511261A patent/SE7511261L/en unknown
- 1975-10-08 IT IT9577/75A patent/IT1049114B/en active
- 1975-10-08 SU SU752177551A patent/SU673151A3/en active
- 1975-10-08 CA CA237,239A patent/CA1065834A/en not_active Expired
- 1975-10-08 ES ES441593A patent/ES441593A1/en not_active Expired
- 1975-10-08 DE DE19752545118 patent/DE2545118A1/en not_active Withdrawn
- 1975-10-09 AT AT773875A patent/AT350279B/en active
- 1975-10-16 AR AR260829A patent/AR218607A1/en active
-
1976
- 1976-03-31 JP JP51034559A patent/JPS51127200A/en active Pending
- 1976-11-12 ES ES453247A patent/ES453247A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2307003A1 (en) | 1976-11-05 |
| BE834239A (en) | 1976-02-02 |
| DE2545118A1 (en) | 1976-10-21 |
| SE7511261L (en) | 1976-10-10 |
| IT1049114B (en) | 1981-01-20 |
| SU673151A3 (en) | 1979-07-05 |
| ES453247A1 (en) | 1977-11-01 |
| GB1529821A (en) | 1978-10-25 |
| ZA755593B (en) | 1976-08-25 |
| ATA773875A (en) | 1978-10-15 |
| AT350279B (en) | 1979-05-25 |
| AR218607A1 (en) | 1980-06-30 |
| BR7506526A (en) | 1976-10-05 |
| NL7511764A (en) | 1976-10-12 |
| JPS51127200A (en) | 1976-11-05 |
| AU8550975A (en) | 1977-04-21 |
| FR2307003B1 (en) | 1979-10-12 |
| ES441593A1 (en) | 1977-07-01 |
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