JPS63455B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to foamed polymers and their intermediates, and more particularly to novel polyol mixtures and their use in processes for making foamed polyisocyanurates. Foamed polyisocyanurate polymers are well known in the art for use in various types of thermal insulation applications. They are also well known for their ability to withstand heat and flame, and are disclosed in US Pat. No. 3,745,133.
No. 3,986,991, and No. 4003,859.
Small amounts of polyols are sometimes added to the foam-forming components to modify the properties of the foam. When fluorocarbon blowing agents are used, problems of incompatibility between polyols, especially primary hydroxyl polyols, and fluorocarbons in the resin premix can be avoided by premixing most, if not all, of the fluorocarbons with the polyisocyanate. This is generally solved by Please refer to the above patents. Although polyisocyanurate foams have found particular utility in the production of laminated foam board materials, these materials are made with a variety of facing materials. Problems that can occur in manufacturing such laminated materials are
(1) Lack of uniform strength of the foam core; (2) Poor adhesion between the foam core and face; (3) Maintaining good fire resistance within the foam; and ( 4) Keeping foam brittleness to a low level; These problems can be overcome by employing small amounts of low equivalent weight polyols, especially diols, in the formulation.
Combinations of heating the foamed laminate product in baths of up to 190°C have been overcome in the art. However, the low equivalent weight polyols used, especially the preferred diols having only primary hydroxyl groups (U.S. Pat. No. 3,903,346, column 4, 59-61
) cannot be premixed with the fluorocarbon blowing agent in the "B" side component. This is because the diol-fluorocarbon pair has a low solubility. This requires mixing the fluorocarbon with the polyisocyanate in the "A" side component. Additionally, due to the incompatibility of fluorocarbons and diols, the above patents teach that a third component "C" containing the catalyst component dissolved in a low molecular weight glycol is required. Example of patent No. 3903346 and column 2, no. 32
-Please refer to line 33. Additionally, the laminates made according to the above patent must be heated in a bath to provide a product with a homogeneous foam core strength. Surprisingly, when using certain amine diols or amide diols, or novel mixtures containing amine triols together with primary hydroxyl polyols, high levels of fluorocarbon blowing agents contain low molecular weight compounds containing primary hydroxyl groups. It was discovered that it mixes perfectly with polyols. Additional components present in this compatible mixture include surfactants, catalysts, and the like. Furthermore, it has been discovered that compatible primary hydroxyl mixtures of the same type described above can also be obtained when replacing water with fluorocarbon. Moreover, the novel polyol mixture described above can be prepared by a two-component (i.e., A-side and B-side) process, producing a polyisocyanate characterized by low friability, microfoamed structure, good dimensional stability, and low flame propagation. It has been discovered that small amounts can be used to create nurate foams. The fluorocarbon and water components act as blowing agents in each foam-forming formulation. Additionally, certain amine diols or amide diols or amine triols described above may be used as sole polyols in combination with fluorocarbons or water, catalysts, surfactants, and other adjuvants to form polyisocyanurate foams according to the present invention. can be provided. Quite unexpectedly, the presence of the amide diol or amine diol or amine triol in the B-side component provides compatibility between the polyisocyanate and the other components. This results in faster reactivity and very good exothermicity compared to prior art foams. High heat generation is particularly advantageous when a foam laminate is being made, as it provides excellent adhesion between the foam and the facing, thereby making the foam laminate more stable. This is because it eliminates the need for heating in a bath. The present invention is based on the formula (i) as well as (wherein R is an aliphatic group containing from 8 to 18 carbon atoms, R ₂ is an aliphatic group containing from 7 to 17 carbon atoms, and each R ₁ consists of hydrogen or methyl. independently selected from the group, x and y each independently have an average value of about 4 to about 15, x' and y' each independently have an average value of about 1 to about 3;
x″, y″ and z each independently have an average value of about 1 to about 5, and n is 2 or 3), or a mixture of each member;
20 to 85% by weight of the polyol mixture; (ii) approx.
For primary hydroxyl polyols () characterized by molecular weights from 60 to about 1000, from about 15 to about
Consisting of a polyol mixture containing up to 80% by weight. The present invention also comprises a compatible mixture formed by combining the polyol mixture described above with a fluorocarbon blowing agent or a water blowing agent. The present invention also comprises a compatible mixture resulting from the above polyol mixture in combination with a fluorocarbon or water blowing agent and an isocyanate trimerization catalyst. The present invention also provides for the use of a member or a mixture of members selected from the compounds of formula (), () or () above, in which the values of x and y are from about 1 to 1, in reaction with an organic polyisocyanate. x′, with an independent average value of up to about 15, preferably from about 4 to about 15;
y′, x″, y″, z, n, R, R ₁ and R ₂ have the above definitions), a fluorocarbon or water blowing agent and a trimerization catalyst and preferably a polyol () (where diol () is defined as above with x and y in the narrow range of about 4 to about 15); Includes a method for producing foamed polymers. The present invention also includes foamed polymers made by the above method. The present invention also includes laminate panels having a polyisocyanurate foam core made by the improved method of the present invention. The term "aliphatic group" when referring to R:
means an alkyl or alkenyl group containing from 8 to 18 carbon atoms. Representative alkyls are octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and isomers thereof. Representative alkenyls are octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, and isomers thereof. The term "aliphatic group" with respect to R ₂ is alkyl and alkenyl having from 7 to 17 carbon atoms. Representative alkyls and alkenyls in this case are the same as above except for a lower range of carbon atoms starting from heptyl and heptenyl and ending with heptadecyl or heptadecenyl and the isomers. The polyol mixture according to the invention can be used as polyol component in the production of polyurethane foams. Polyurethane foams are well known in the art for use in a wide variety of applications including thermal and acoustic insulation for both industrial and residential architecture. This polyol mixture has particular utility in the production of polyisocyanurate foams, particularly those made in foam laminate machinery and by spray foam equipment, as described herein. are finding. Such foams are well known for their heat and fire resistance and are used in the production of laminates and foam materials, which are used for thermal and acoustic insulation in building construction. The polyol mixture according to the invention comprises amine diols (), amide diols (), as defined above,
Alternatively, the amine triol () and the primary hydroxyl polyol () can be mixed in the above-mentioned weight proportions in any suitable mixing container, holding tank, storage container,
produced by simply mixing them together. Preferably, (), (), or () is used in the range of about 25 to about 60% by weight of the mixture, while the primary hydroxyl polyol is in the range of about 40 to about 75% by weight of the mixture. used in The preferred ones of (), () and () are:
having the above formula where R ₁ is hydrogen in all cases. The most preferred diols are those having a formula corresponding to () in which both R ₁ groups are hydrogen and x and y each independently have an average value of from about 5 to about 10. The most preferred amide diols have a formula corresponding to () in which both R ₁ groups are hydrogen and x' and y' each independently have an average value of from about 2 to about 3. The most preferred amine triols are all
It has the formula corresponding to () where R ₁ is hydrogen, x″, y″ and z each have an average value of from about 3 to about 5, and n is 3. Amine diols () are made using standard reactions known to those skilled in the art and, in some cases, are commercially available. Typically, the amine diol () refers to a suitable dialkal amine, a suitable aliphatic halogen in which all aliphatic groups (R) are within the above definitions and x is halogen, preferably chlorine or bromine. compound (R-x) or a mixture of different R-x compounds. If the desired number of alkyleneoxy groups is not already present in the dialkanolamine prior to reaction with the aliphatic halide, the alkylated dialkanolamine can be combined with an appropriate number of moles of ethylene oxide or propylene oxide. Alternatively, it can be easily added later by reacting with a mixture thereof to provide the amine diol of formula (). Preferably, the amine diol () contains a suitable primary aliphatic amine R- _NH2 or aliphatic amine mixture in which the R group is defined above from about 2 to about 30 moles per mole fraction of aliphatic amine, preferably It is made by reacting with about 8 to about 30 moles, most preferably 10 to 20 moles of ethylene oxide or propylene oxide.
For a detailed description of the preparation of this subject amine diol, see Document 1294 (titled: Ethoxylated Aliphatic Amines) of Asyuland Chemical Co., a division of Asyuland Oil Co., Box 2219, Columbus, Ohio 43216. Illustrative starting aliphatic amines are octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and their isomers. Exemplary alkenylamines are octenylamine, decenylamine, dodecenylamine, tetradecenylamine, hexadecenylamine, octadecenylamine, and isomers thereof. Further illustrative of the aliphatic amines mentioned above are mixtures of alkyl amines and alkenyl amines, e.g. cocoa amine consisting of approximately the following weight percent proportions:
2% decylamine, 53% dodecylamine, 24% tetradecylamine, 11% hexadecylamine, 5% octadecylamine, and 5% octadecenylamine; soybean amines in approximate proportions of: hexadecylamine 11.5 %, 4% octadecylamine, 24.5% oleylamine, 53% linoleylamine, and 7% linolenylamine; and tallowamine in approximate proportions of:
Tetradecylamine 4%, Hexadecylamine 29
%, octadecylamine 20%, and octadecenylamine 47%; Further exemplary starting aliphatic amines are halogenated aliphatic amines, particularly chlorinated and brominated aliphatic amines, which can be made by chlorination or bromination of, for example, cocoa amine, soy amine, tallow amine, etc. can. A particularly preferred group of aliphatic amines consists of cocoa amine mixtures, soy amine mixtures, and tallow amine mixtures. A preferred member of this group is cocoamine. Amine diols () are made using standard reactions known to those skilled in the art. Typically, according to the following formula: prepared by reacting a suitable dialkanolamine with a suitable fatty acid, fatty acid ester, or fatty acid chloride, where R ₂ ,
R ₁ , x′ and y′ have the same definitions as above, and R ₃ is −
OH, -OR ₄ and x, where R ₄ represents any typical esterifying group such as lower alkyl, aryl, cycloalkyl, etc., and x is halogen, preferably chlorine or bromine. If diethanolamine or diisopropanolamine or a mixture thereof is the starting dialkanolamine and it is desired to obtain an amide diol with values of x' and y' greater than 1, the intermediate dialkanolamide is used in a 1 molar proportion. from about 1 to about 4 moles of ethylene oxide or propylene oxide, or mixtures thereof. See Document 1295 (titled: Varamide Alkanolamides) of Asyuland Chemical Co., a division of Asyuland Oil Co., Box 2219, Columbus, Ohio 43216, for detailed instructions on the production of fatty acid dialkanolamides. Preferably, the amide diol () converts the fatty acid to the corresponding fatty acid amide (R ₂ CONH ₂ ) and reacts the amide with from about 2 to about 6 moles of ethylene oxide or propylene oxide or mixtures thereof per mole of amide. created by Examples of starting fatty acids (from which the corresponding esters, acid halides and amides are also derived) are capric acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid and their isomers. Examples of unsaturated fatty acids are decylenic acid, dodecylenic acid, palmitoleic acid, oleic acid, linoleic acid and their isomers. Further exemplary of the above fatty acids are mixtures,
For example, the approximate weight percent proportion is: caprylic acid
8.0%, capric acid 7.0%, lauric acid 48.0%, myristic acid 17.5%, palmitic acid 8.2%, stearic acid 2.0%, oleic acid 6.0% and linoleic acid
A fatty acid mixture derived from coconut oil consisting of a mixture that is 2.5%; a fatty acid mixture from soybean oil, namely 6.5% palmitic acid, 4.2% stearic acid, 33.6% oleic acid, 52.6% linoleic acid.
and linolenic acid 2.5%; and fatty acid mixture from tallow oil; i.e. myristic acid 2%,
It is a mixture of 32.5% palmitic acid, 14.5% stearic acid, 48.3% oleic acid, and 2.7% linoleic acid. Further examples of starting fatty acids are halogenated fatty acids, especially chlorinated and brominated fatty acids, which can be made, for example, by chlorination or bromination of the coconut, soybean and tallow fatty acid mixtures mentioned above. A particularly preferred group of starting fatty acids and fatty acid amide intermediates consists of the coconut, soybean and tallow oil mixtures mentioned above and the corresponding cocoamide, soybean amide and tallow amide mixtures. Preferred in this group are coconut oil mixtures and their cocoamide mixture derivatives. A preferred group of amide diols () are cocoa amide diols, soy amide diols, and tallow amide derived from diol mixtures in which R ₁ is H and both x' and y' have values of about 3. A preferred class within this group of amide diols is the cocoa amide diol mixture described above, identified by the chemical name N.N-bis(8-hydroxy-3.6-dioxaoctyl) cocoa amide mixture. Amine triols () are readily made by standard reactions known to those skilled in the art, and in some cases are commercially available. Generally speaking, the process for preparing amine triols with n equal to 2 is somewhat different from that of amine triols with n equal to 3. The former amine triol can be easily produced by the following method. In the formula, R and R ₁ are as defined above. The amine starting material is reacted with an equimolar amount of ethylene oxide or propylene oxide to form an amino alcohol (), which can be readily converted to a diamine (), for example, typically by reaction with ammonia, and then 1 The amine triol () is prepared by reacting a molar proportion of () with about 3 to 15 molar proportions of ethylene oxide or propylene oxide or mixtures thereof.
to form. Amine triols where n is 3 are typically made by the following method. Here, in the formula, R and R ₁ are as defined above. The amine starting material is cyanoethylated with a suitably substituted acrylonitrile () to form (), which is reduced to the diamine and then treated with about 3 to 15 molar proportions of ethylene oxide or propylene oxide or mixtures thereof. and alkoxylation to form (). The starting aliphatic amines are the same as those described and exemplified above in the preparation of the amine diol (). Examples of acrylonitrile compounds that can be used in the preparation of amine triols according to the invention are acrylonitrile, α-methacrylonitrile, β-methacrylonitrile, α·β-dimethyl-acrylonitrile, and the like. Preferred is acrylonitrile. A preferred group of amine triols ( ) is such that all R ₁ groups are hydrogen and the value of n is equal to 3 and
An amine triol mixture derived from a respective mixture of cocoa amine, soy amine and tallow amine, where x'', y'' and z are each equal to from about 3 to about 5. The most preferred type is an amine triol mixture derived from cocoa amine in which R ₁ is all hydrogen, the value of n is equal to 3, and x'', y'' and z are each equal to about 4.6. The primary hydroxyl polyol () can be any primary hydroxyl polyol having a molecular weight from about 60 to about 1000, preferably from about 60 to about 800, and most preferably from about 60 to about 600. Included within this polyol are diols, triols, and tetrols. Preferred polyols are diols. Included within the class of primary hydroxyl-containing polyols are the various primary hydroxyl-containing diols, triols, and tetrols disclosed in U.S. Pat. No. 3,745,133, which meet the aforementioned molecular weight limitations. and the disclosures of the above patents regarding these polyols are incorporated herein by reference. Preferred types are dibasic carboxylic acids, chlorendic anhydride, alkylene diols, alkoxyalkylene diols, polyalkylene ester diols, polyoxyalkylene ester diols, hydroxyalkylated aliphatic mono- or diamines, resol polyols (interpub. (See page 293 of WR Sorenson et al., Methods of Manufacturing Polymer Chemistry (1961), published by Tsushyas).
and polybutadiene resins with primary hydroxyl groups (Alko
It is a polyester polyol made from a polyhydric alcohol; The most preferred types are alkylene diols, lower alkoxyalkylene diols, polyalkylene ester diols, and polyoxyalkylene ester diols. Illustrative examples of preferred types of polyols according to the invention include, without intending to be limiting, ethylene glycol, 1,3-propanediol,
1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol; made by adding water to diethylene glycol, ethylene oxide, and containing polyoxyethylene glycol, ethylene glycol, diethylene glycol, etc., with a molecular weight within the above range. triethylene glycol, tetraethylene glycol and higher glycols; ethoxylated glycerin, ethoxylated trimethylolpropane, ethoxylated pentaerythritol, etc.; bis(β-hydroxyethyl)
Tetraphthalate, bis(β-hydroxyethyl) phthalate, etc.; polyethylene succinate, polyethylene glutarate, polyethylene adipate, polybutylene succinate, polybutylene glutarate, polybutylene adipate, copolyethylene butylene succinate, copolyethylene Butylene glutarate, copolyethylene butylene adipate, and similar hydroxy-terminated polyesters; polyoxydiethylene succinate, polyoxydiethylene glutarate, polyoxydiethylene adipate, polyoxydiethylene adipate glutarate, etc.; diethanolamine, triethanolamine, N.N'-bis(β-hydroxyethyl)aniline, etc. The most preferred diols are diethylene glycol and polyoxydiethylene adipate glutarate polyester diols having molecular weights from about 400 to about 600. Particularly preferred is a mixture of about 30 to about 50 weight percent diethylene glycol and about 50 to about 70 weight percent polyoxydiethylene adipate glutarate polyester diol having a molecular weight of about 400 to 600. In the preferred polyol mixtures according to the invention, a fluorocarbon or water blowing agent is also present in the mixture, with fluorocarbon being the preferred blowing agent. When the blowing agent is fluorocarbon,
The unexpected and advantageous properties of polyol mixtures of (), () or () and () can be fully realized. Compatible polyol mixtures can thus be obtained consisting of at least 20% by weight of fluorocarbon blowing agent and the remainder of the mixture in the aforementioned proportion ranges. The particular percentage of fluorocarbon to be dissolved in this mixture, which governs the proportion of () and the proportion of (), (), or () to be used in a particular case, is within the ranges set forth above. These proportions can be readily determined by those skilled in the art by trial and error methods. Compatible polyol mixtures containing more than 50% by weight and even up to 90% by weight of fluorocarbons can easily be obtained according to the invention with mixtures in the proportion ranges mentioned above and depending on the selection of the mixture components. Can be done. Generally speaking, the lower the molecular weight of the primary hydroxyl polyol (), the greater the amount of fluorocarbon that must be dissolved in a given proportion mixture of polyol (), () or () than in the same proportion. Contrary to mixtures containing high molecular weight polyols (), there are many. In this connection, alkylene diols and lower alkoxyalkylene diols having a molecular weight of less than 400 are preferred polyols of formula (), with the latter lower alkoxyalkylene diols being the most preferred. The particular proportion of polyol (), (), or () to polyol () to be used in a particular polyol mixture to obtain maximum compatibility with the fluorocarbon can be determined by trial and error. Generally speaking, when amine diol () is used with (), at least about
A compatible polyol mixture is obtained comprising from 25% to at least about 65% by weight of a fluorocarbon blowing agent and a corresponding mixture of () and () from 75 to 35% by weight. At least about 20 to at least about 60% by weight when amide diol () and () are used
A compatible polyol mixture is obtained containing up to 80% to about 40% by weight of the polyol mixture of () and (). When amine triols () and () are used, they contain at least about 20 to at least about 50% by weight of the fluorocarbon blowing agent, with a corresponding 80 to about 50% by weight of () and ().
A compatible polyol mixture is obtained which is a polyol mixture of . When water is the blowing agent, it is present in a proportion by weight of from about 1 to about 6%, preferably from about 2 to about 5%, with the remaining 94 to 99% preferably
95 to 98% of cases are (), (), or () with (). The fluorocarbon blowing agent can be any of the fluorocarbons known to those skilled in the art and can be used to foam the polymer mixture into a foamed polymer. Generally speaking, such blowing agents are halogenated aliphatic hydrocarbons which, in addition to their fluorine content, are substituted by chlorine and/or bromine and which are well known to those skilled in the art. and U.S. Pat. No. 3,745,133, column 11, 25-38.
Please refer to the following lines. The disclosure regarding fluorocarbon blowing agents is cited herein. In one preferred embodiment of the polyol mixture according to the invention, which finds particular utility in the production of polyisocyanurate foams, the blowing agent and the components (), () or () and () Additionally, an isocyanate trimerization catalyst is present. This isocyanate trimerization catalyst component is discussed in detail below. The isocyanate trimerization catalyst has a molecular weight of from about 2 to about 20, preferably from about 2 to about 15
Advantageously, it is present in proportions up to % by weight, with the remaining approximately 80 to 98%, preferably approximately 85 to 98%, consisting of the aforementioned components. Surprisingly, the blowing agent and the primary hydroxyl-containing polyol mixture are completely miscible with each other and do not separate during storage, and this compatibility is limited to amine diols (), amide diols (), or amine This is due to the presence of triol (). In addition to the advantages that result from having a stable and compatible primary hydroxyl polyol mixture and fluorocarbon or water, there are also advantages of the presence of nitrogen-containing diols or triols as minor components during the production of polyisocyanurate foams. Its effectiveness has been recognized. Other optional additives may also be added without compromising the compatibility and stability of the polyol mixture. Such additives include those commonly used in the process of the present invention, such as secondary hydroxyl-containing polyols, dispersants, foam stabilizers, surfactants, flame retardants, and the like. In preparing polyisocyanurate foams according to the present invention, the amine diol, amide diol, or amine triol described above is used as the sole polyol component in admixture with a fluorocarbon or water blowing agent and trimerization catalyst to A B-side component can be formed for reaction with an A-side component consisting of an isocyanate. in this case,
The values of x and y in parentheses can have the wide range described above from about 1 to about 15. The weight percent proportions of the mixture components are the same as described above for the proportions of catalyst to be mixed with the blowing agent and polyol components. That is, the B mixture is from about 2 to about 20, preferably from about 2 to about 15% by weight.
and from about 80 to about 98, preferably from about 85 to 98% by weight of (), () or (), and a blowing agent. If a fluorocarbon blowing agent is used, it is approximately 20
from about 80 to about 80, preferably from about 20 to about 50% by weight, such that (), (), or () is from about 20 to 80, preferably from about 50 to about
Present in amounts up to 80% by weight. When water is used as a blowing agent, it is present from about 1 to about 6, preferably from about 2 to 5% by weight, so that (), () or () is from about 94 to about 6%, preferably from about 2 to 5% by weight.
It is present in an amount of up to 99%, preferably from 95 to 98% by weight. The B-side mixture contains from about 10 to 120, preferably from about 10 to about 80, per equivalent of polyisocyanate;
Most preferably, amounts are advantageously used in the range of from about 20 to about 60 parts by weight, provided that the total equivalents of hydroxyl present in mixture (B) are from about 0.05 to about
up to 0.5, preferably in the range from about 0.08 to about 0.4 equivalents. Preferably also a small amount of the above-mentioned primary hydroxyl polyol () is present in the B-side mixture. This combination in the mixture not only results in the stabilized compatible mixture described above, but also provides the polyisocyanurate with the optimal advantageous properties described above, and provides maximum foam strength and laminate facing properties. Foam laminates are also produced that do not require any bath heating to achieve adhesion. In this case, the values of x and y in parentheses are in the narrow range described above from about 4 to about 15. Primary hydroxyl polyol (), blowing agent,
and a trimerization catalyst containing an amine diol (), an amide diol (), or an amine triol () in an amount of parts by weight per isocyanate equivalent described above for the B mixture without (). However, the range of total equivalents of hydroxyl per equivalent of isocyanate is the same as above. The percentage proportions by weight of the mixture of each component in the mixture are the same as stated in the description regarding the polyol mixture. Amine diol (), amide diol (), amine triol (),
Primary hydroxyl polyol () and blowing agent all have the same definition and scope as above. The trimerization catalyst used can be any catalyst known to those skilled in the art that catalyzes the trimerization of organic isocyanate compounds to form isocyanurate moieties. Additionally, combinations of urethane-forming catalysts and trimerization catalysts can also be used if desired. For typical isocyanate trimerization catalysts, see Journal of Cellular Plastics, November/December 1975, p. 329; US Pat.
No. 3954684, and No. 4101465.
The contents of these cited documents are incorporated herein. A preferred catalyst is U.S. Pat. No. 3,896,052.
No. 4101465.
In the former patent, (a) an alkali metal salt of an N-substituted amide and (b) an alkali metal salt of N-(2-hydroxyphenyl)methylglycine, and optionally
(c) a tertiary amine trimerization catalyst. The latter patent discloses the same (a) and (b) above in combination with a hydroxyalkyltolualkylammonium carboxylate salt component. The organic polyisocyanates that can be used to prepare the polyisocyanurate foams according to the invention can be any of the organic polyisocyanates conventionally used in the art for this purpose. Advantageously, and in order to obtain foams with exceptionally high heat resistance and structural strength, preferred polyisocyanates are polymethylene polyphenyl polyisocyanates, especially U.S. Pat. No. 3,745,133.
This is what is stated in the issue. The disclosure of this patent regarding this isocyanate is incorporated herein by reference. Also, polymethylene polyphenyl polyisocyanates treated with small amounts of epoxy compounds to reduce acidic impurities according to U.S. Pat. No. 3,793,362; and U.S. Pat.
Also preferred are polymethylene polyphenyl polyisocyanates containing high levels of the 2,4'-isomer, as typically disclosed in No. 3,362,979. The most preferred organic polyisocyanate is about 30
methylene bis(phenyl isocyanate) up to about 85% by weight with the remainder consisting of polymethylene polyphenyl polyisocyanate having a functionality greater than 2.0. When carrying out the production of polyisocyanurate foams according to the method of the invention, in particular when producing polyisocyanurates for the production of foam laminates, methods and equipment customary in the art are used. (see above-cited patents), but see US Pat. No. 3,896,052 for a detailed description of the manufacturing methods and uses of polyisocyanurate foam laminates. The relevant description is cited herein. The following examples describe methods and processes for using the invention and set forth the best mode contemplated by the inventors for carrying out the invention. However, this should not be seen as a restriction. Example 1 The following five polyisocyanurate foams (Foams A through E) were made according to the following procedure. These foams were prepared as hand mix samples by mixing together the A side ingredients and the B side ingredients listed in Table 1 below in a 1 quart cup. The polyisocyanate component was the sole component of the A side, while the B side components listed in Table 1 were premixed and observed before reacting with the polyisocyanate. The mixing operation was carried out by thoroughly mixing the A and B sides in the cup with a high speed drill press motor equipped with stirring blades. This mixture is quickly poured into a cardboard box, allowed to rise freely, and left at room temperature (approximately 20
Cure). Foams B and E are according to the invention, but
A, C and D are not. This is because the amine diol component had x and y values below the required values. B in all prescriptions
The sides are clear with no signs of turbidity. However, in cases A and C a secondary hydroxyl polyol was present, which is a known fluorocarbon solubilizer, whereas in C there was additionally a phosphate plasticizer. . Foam D also contained plasticizing components. The greatest foam properties were observed for Foam E in terms of the combination of maximum exotherm of reaction and rapid solidification rate and low friability of the core and surface. Surface blushing on samples of rising foam is the point at which the shiny, wet, unreacted surface of the rising foam becomes cloudy or reddish, indicating that no effective curing or reaction has occurred at the surface. This is a point that shows that you have mastered it. All foam samples showed good surface brushing.

【table】

Table: Example 2 The following foams were prepared according to the procedure and equipment described in Example 1, except as indicated below. The foams in this example show a comparison between the conventional method (foams F and H) and the method according to the invention (foams G and I). The components of Side A and Side B are shown in the table below. The F and G pair contained a different polyisocyanate than the H and I pair. A of foams F and H
The side contained a conventional fluorocarbon blowing agent. When the same amount of fluorocarbon was mixed into the B side to test compatibility, in both cases the fluorocarbon separated from the other components: diethylene glycol, surfactant, and catalyst. In the case of foams G and I containing ethoxylated cocoamine in the B side, the fluorocarbon and other ingredients can be thoroughly mixed with the diethylene glycol component. A comparison of the foam rise times between F and G and H and I clearly shows a much faster rate for the foams according to the invention (G and I) than for the conventional pair (F and H). There is. The dramatic speed increase clearly indicates the increased compatibility between the A and B sides, which leads to better reaction between them and thus faster rise times than conventional methods. Although the ethoxylated amine used in Foams G and I is a tertiary amine, this type of high molecular weight tertiary amine is not a strong base and has a very small amount on an amine equivalent basis, i.e. 0.009 Equivalent amounts were used in each case. This low level of weak amine is not sufficient to explain the dramatic rate increase for G and I over F and H on the basis of amine catalysis alone.

【table】

EXAMPLE 3 The following two polyisocyanurate foams J and K according to the invention were prepared by the procedure and equipment described in Example 1 and using the components in the weight proportions shown in the following table. did. Component B was clear in both cases. Both foams had extremely fine cell-like structures, had no surface friability, and good surface brushing was observed. The foaming heat generation was good, and the appearance of rapid rise indicated quick reactivity for both foams. It is noteworthy that the catalyst mixture used for both J and K contains a very small amount of Baronik K-215 amine diol, which acts as a compatibilizer for various other catalyst components. . In the absence of Baronik K-215, the other catalyst components are not completely mixed.

[Table] R○
Baronik K−205 ² 37 −

【table】

EXAMPLE 4 The following two water-blown polyisocyanurate foams L and M were prepared using the procedure and equipment described in Example 1 and using the weight percentages of ingredients shown in the following table: Prepared according to the invention. The B side in both cases formed a clear and compatible mixture. It has been found that the foam rise characteristics are extremely rapid and have a fast tack-free time despite the fact that these foams are water-foamed. A high foaming exotherm was also observed demonstrating excellent conversion. The physical properties of the resulting foam were good.

【table】

EXAMPLE 5 This example describes a hand-mixed polyisocyanurate foam N made in accordance with the present invention using the procedure and equipment described in Example 1 and using the ingredients shown in the following table. are doing. The B side of sample N contained a mixture of primary hydroxyl triol and diethylene glycol together with a proportion of 4% by weight of fluorocarbon, and the mixture remained clear without turbidity. The foam had a fast rise time with good heat generation properties and good brittleness properties. Table foam N component (parts by weight) A side: Polyisocyanate 135 B side: TPEG-990 ¹ 8.5 Diethylene glycol 6.5 Baronik K-215 10 DC-193 1.25 Catalyst 3.0 Fluorocarbon R-11B 20 Appearance of B mixture Clear, no turbidity . % of R-11B in B mixture 41% Foaming rise time (seconds) Cream time 13 Gelation time 30 Stick-free time 35 Heat generation (〓) 349 Surface friability NoneSurface brushing With core friability Legs against small table Note 1 TPEG-990 is a primary hydroxyl-containing trifunctional polyethylene glycol with OH equivalent weight = 333; supplied by Union Carbide (New York, NY). Example 6 The following high temperature and flame resistant polyisocyanurate foam laminates were prepared in accordance with the present invention using Foam O made from the components shown in the following table. "A" component temperature and "B" component temperature respectively.
A Viking lamination machine was used using 73〓 and 70〓. The throughput rate was 15 lb/min through a low pressure impingement mixing head. Pour lay down method was used instead of nituprol. The conveyor speed was 10 feet/min and the curing bath temperature was ambient (70 to 90°). A 2 inch thick laminate was constructed with a 0.0015 inch aluminum foil facing and an asphalt facing. The foam properties reported in the following table are for the foam core after removal of the face material. Therefore, the facing material itself had no effect on this data. The adhesion between the facing and the foam was excellent. Component B, although containing primary hydroxyl polyester and diethylene glycol and 43% by weight Freon (R-11B), is clear and free of turbidity. Laminates were made without the need for high temperature bath curing due to the rapid reactivity of the formulation. This rapid reactivity is also reflected in rapid rise characteristics, and the brittleness of the foam was found to be very low despite the absence of a high temperature curing step. As mentioned above, good face material adhesion was also observed. The overall physical properties of the foam were found to be good including minimal friability, good fire resistance, K-factor, and humidity aging data. Table foam O component (parts by weight) A side: Polyisocyanate 133 B side: Polyester diol ¹⁹ Diethylene glycol 6.3 Baronik K-215 6.7 DC-193 1.25 Catalyst 3.0 Fluorocarbon R-11B 20.0 B mixture appearance Clear, no turbidity B R-11B% in the mixture 43% NCO/OH index 4.9 Foaming rise time (seconds) Cream time 19 Gelation time 40 Stick-free time 47 Surface friability None Surface brushing With core friability Small (6%) Overall Density (pcf) 2.0 Core Density 1.8 Compressive Strength (psi) Parallel to Rise 31 Perpendicular to Rise 21 Closed Cell ² 94% K-Factor in BTU. (ft ² ) (hr) / inch 0.14 Wet aging (158〓, 98%RH) Volume change After 1 day +6% After 7 days +6.5% After 28 days +7.0% ASTM E-84 test 2 inch thick About the sample Flame propagation degree 38 Smoke 187 Footnote 1 to the table Polyester diol is A in footnote 1 of the table.
This is the same diol mentioned in . 2 Closed cells are measured by air pycnometer test according to ASTM test method D-2856. Example 7 The following polyisocyanurate foams P were made in accordance with the invention using the procedure and equipment described in Example 1 using the weight percentages of ingredients shown in the table below. Side B was clear with no signs of turbidity despite the combination of fluorocarbon with the primary hydroxyl of the amide diol. The produced foam was characterized by an extremely fine cell structure, had no surface brittleness, and had good surface brushing. The foaming exotherm was good and its rapid rise characteristics indicated the rapid reactivity of the foam. Table foam P component (parts by weight) A side: Polyisocyanate ¹ 135 B side: Baramide 6-CM ² 49 DC-193 1.5 Fluorocarbon R-11B 23 Catalyst ³ 3 NCO/OH index 4.5 B side appearance Clear, turbidity None Foaming rise time (seconds) Cream time 8 Gelling time 42 Stick-free time 52 Rise − Heat generation (〓) 328 Surface friability None Surface brushing Core friability Moderate appearance Very fine cells Footnote 1 to Table The polyisocyanate is the same as defined in Example 3, footnote 1 of the table, polymethylene polyphenyl polyisocyanate. 2 Baramide 6-CM is a cocoaamide adduct obtained by the reaction of 6 moles of ethylene oxide with 1 mole of cocoamide; Amine equivalent weight = 290; OH equivalent weight = 193; Chemical Products Division of Asiland Chemical. (Columbus, Ohio) ;N・N-
Identified by the chemical name of the bis(8-hydroxy-3,6-dioxaoctyl)cocoamide mixture. 3 Catalysts are the same catalyst combinations as defined in Example 3, Table 1, Footnote 4. Example 8 The following polyisocyanurate foams Q, R and S
was made according to the procedure and equipment described in Example 1 and using the ingredients shown below in the Table. Foams Q and R are according to the invention, whereas S is not. The B-side component in the case of Foams Q and R was clear with no signs of turbidity, even though in each case it was a mixture of fluorocarbon and primary hydroxyl-containing components. The A side of the foam S contained a fluorocarbon blowing agent in accordance with conventional methods. When an equal amount of this fluorocarbon was mixed into the B side to test compatibility, the fluorocarbon separated from the other components, namely diethylene glycol, surfactant, and catalyst. A comparison of the foam rise times between foams Q and R on the one hand and foam S on the other hand shows that the foams according to the invention (Q and R) exhibit much higher speeds than those of the conventional method (S). clearly shows. This dramatic speed increase indicates increased compatibility between the A and B sides, leading to better reaction between the two, and thus faster rise times than conventional formulations.

TABLE EXAMPLE 9 The following polyisocyanurate foam T was prepared according to the invention according to the procedure and equipment described in Example 1, using the components in the weight proportions shown in the following table. This B side was clear with no signs of turbidity despite the combination of fluorocarbon and primary hydroxyl of the amine triol component. The resulting foam was characterized by a very fine cellular structure, had no surface friability, and had good surface brushing. The foaming exotherm was good and the rapid rise characteristics indicated the fast reactivity of this foam. Table Foam T component (parts by weight) A side: Polyisocyanate 135 B side: KD-214 ¹ 56 DC-193 1.5 Fluorocarbon R-11B 23 Catalyst 2.5 NCO/OH index 4.5 Appearance of B side Clear, foamed without turbidity Rise time (seconds) Cream time 4 Gel time 17 Stick-free time 50 Rise − Heat generation (〓) 323 Surface friability NoneSurface brushing Slight core friability Small appearance Legs against extremely fine cell surface Note 1 KD-124 is an ethoxylated mixture obtained by reacting ethylene oxide and cocodiamine in a molar ratio of about 14 to 1, respectively; in this case, cocodiamine is obtained by reacting cocoa amine with one equivalent of acrylonitrile and cyanoethylated. Obtained by reducing a cocoa amine mixture to cocodiamine: Amine equivalent weight = 290; OH equivalent weight = 193; supplied by Asiland Chemical, Chemical Products Division, Columbus, Ohio. Example 10 The following polyisocyanurate foams U, V and W
was prepared according to the procedure and equipment described in Example 1 using the ingredients shown in Table 1. Foams U and V are according to the invention, while foam W is not. The B-side component in the case of Foams U and V was clear and had no signs of turbidity, despite being a mixture of fluorocarbon and primary hydroxyl-containing components. The A side of the foam W contained fluorocarbon in accordance with conventional methods. When a compatibility test was performed by mixing the same amount of fluorocarbon into the B side, the fluorocarbon separated from the other components, namely diethylene glycol, surfactant, and catalyst. U and V of one foam and W of the other foam
Comparing the foaming start-up times between
It clearly shows a much faster speed. This dramatic increase in speed indicates increased compatibility between the A and B sides, which leads to better reactivity between them and thus faster rise times than conventional formulations. .

[Table] None None

EXAMPLE 11 A series of mixtures of fluorocarbon R-11B (monofluorotrichloromethane) and two representative primary hydroxyl polyols of the invention were prepared. The weight proportions used, including the amount of amine diol () when present, were varied according to the values shown in Table XI below. These mixtures were observed for their compatibility and clarity or turbidity and separation of the fluorocarbon from the solution. Mixtures A through D contained diethylene glycol along with fluorocarbon and the maximum solubility of fluorocarbon was 15% by weight when no amine diol was present, ie, 100% diethylene glycol. Addition of 10% by weight of amine diol was not sufficient to give fluorocarbon solubility at the level of 25% by weight, and an amine diol content of 20% (mixture D) actually resulted in a clear compatible solution of 25% fluorocarbon. Ta. Mixtures E through J contained a polyester diol as defined above, which pure polyester diol was capable of dissolving 20%, but not 25%, by weight of the fluorocarbon. The branch point for a 25% fluorocarbon solubility begins at about 10 parts by weight of amine diol (mixture G), whereas at the 20% level of amine diol, the fluorocarbon is at 31 parts by weight.
was able to reach. Mixtures K to M are 90% for each of diethylene glycol and polyester diol when using up to 85% by weight of amine diol.
It was observed that the fluorocarbons had a maximum level of 67.5% and a maximum level of 67.5%. It was observed that the N-Q mixture had a maximum fluorocarbon solubility of 60% and 50% for diethylene glycol and polyester diol, respectively, when the primary alcohol-amine diol mixture was 50/50% by weight.

【table】 %
Mixture appearance Clear, cloudy, cloudy,
Clear, clear, cloudy, clear, clear,
Sumiaki,
Compatibility Separation Separation Compatibility Compatibility Separation Compatibility Compatibility Compatibility

[Table] Compatibility Compatibility Separation Compatibility Separation Compatibility Separation
Footnotes to Table XI
1. Polyester diol as described in A of footnote 1 of the table.
2. K-215 is an amine diol () as specified in footnote 3 of the table.
Example 12 A series of mixtures of fluorocarbon R-11B (monofluorotrichloromethane) and three representative primary hydroxyl polyols of the invention were prepared.
The parts by weight used, including the amount of cocoamide diol () when present, were varied according to the values shown in Table XII below. These mixtures were observed for their compatibility and clarity or turbidity and separation of fluorocarbon from solution. Mixtures A through D contained diethylene glycol and the maximum fluorocarbon solubility did not reach 20% by weight when no amide diol was present. Addition of 10% amide diol (mixture B) was not sufficient to impart fluorocarbon solubility at the 20% level. It was not until at least 15% amide diol (mixture C) that the mixture actually remained clear at 20% fluorocarbon, and apparently not at the 80/20 mix level (mixture D). It was clear and bright. Mixtures E through G contained ethylene glycol and at least 20% amide diol was required to maintain 20% fluorocarbon solubility. It was observed that the H to L mixture separated from the polyester diol and that 20% fluorocarbon solubility was possible with respect to the pure diol, but 25% was not. Aamide diol level is 20%
(Mixtures J to L), the highest fluorocarbon level that could be reached was about 31%. The mixture of M to O shall have a maximum level of fluorocarbon of 90% by weight and up to 60% by weight for diethylene glycol and polyester diol, respectively, when using up to 85% by weight of amide diol. was observed. The mixture from P to S is a primary alcohol-
It was observed that when the mixture of amide diols was 50/50% by weight, the fluorocarbon maximum solubility was 55% and 45% for diethylene glycol and polyester diol, respectively.

[Table] Separation Separation
separation separation separation

[Table] Footnotes to Table XII
1. The same polyester diols listed in the footnotes to the table.
2. 6-CM is the same cocoaamide identified in footnote 2 of the table.
Example 13 A series of mixtures of fluorocarbon R-11B (monofluorotrichloromethane) and three representative primary hydroxyl polyols of the invention were prepared. The weight proportions used, including the amount of amine triol () when present, were varied according to the values shown in the following table. These mixtures were observed for their compatibility and clarity or turbidity as well as separation of the fluorocarbon from solution. Mixtures A through D contain diethylene glycol and when no amine triol is present, the fluorocarbon solubility is 20% by weight.
was not reached. Addition of 10% amine triol (mixture B) was not sufficient to provide fluorocarbon solubility at the 20% level. fluorocarbon
It was not until at least 15% of the amine triol that the mixture remained clear at 20%. Mixtures E through G contained ethylene glycol and required at least 20% amine triol to maintain 20% fluorocarbon solubility. Blends from H to M are prepared from polyester diols, and while 20% fluorocarbon solubility is possible, 25% fluorocarbon solubility is not possible for pure diols, and to maintain 25% fluorocarbon solubility requires at least 15% fluorocarbon solubility. % by weight of amine triol was required (mixture K). When the content of amine triol was 20% by weight, the maximum fluorocarbon solubility was about 28.6% by weight. The mixture of N to P is 90% for each of diethylene glycol and polyester diol when using up to 85% by weight of amine triol.
% and up to 50% by weight. The mixture from Q to T is a primary alcohol-
It was observed that when the mixture of amine triols was 50/50% by weight, the maximum fluorocarbon solubility was 50% and 40% for diethylene glycol and polyester diol, respectively.

[Table] Separation Separation Compatibility Compatibility Separation Separation Compatibility Compatibility Separation Separation
sex sex
sex

【table】

Claims (1)

[Claims] 1 (i) Formula as well as (wherein R is an aliphatic group with 8 to 18 carbon atoms, R ₂ is an aliphatic group with 7 to 17 carbon atoms, and each R ₁ is from the group consisting of hydrogen and methyl. independently selected, and x and y are each independently from about 4 to about
It has an average value of 15, and x' and y' each independently range from about 1 to
x'', y'' and z each independently have an average value of about 1 to about 5, and n is 2 or 3, or a mixture thereof. of, approximately 20% by weight of the total mixture.
and (ii) about 15 to about 80% by weight of a primary hydroxy polyol characterized by a molecular weight of about 60 to about 1000.
Compatible polyol mixture for producing foamed polyisocyanurates containing 20% by weight of a fluorocarbon blowing agent. 2 (a) 2 to about 20% by weight of an isocyanate trimerization catalyst; and (b) about 80 to 98% by weight of (1) at least about 20%.
fluorocarbon blowing agent and (2) a polyol mixture, the polyol mixture comprising (i) from about 20% to about 85% by weight, based on the total weight of the mixture; about 15
An ethoxylated cocoa amine diol mixture obtained by the reaction of mol of ethylene oxide with cocoa amine, an N·N-bis(8-hydroxy-3·6-dioxyoctyl) cocoa amide mixture, and a general formula (R in the formula represents an aliphatic mixed residue representing a residue from cocoa amine, and x″, y″ and z are each
(ii) a member selected from ethoxylated diamines (representing an average value of 4.6) or a mixture thereof;
15% to about 80% by weight diethylene glycol,
A polyol mixture for producing a foamed polyisocyanurate which is a mixture with a primary hydroxy diol selected from polyoxydiethylene adipate glutarate having a molecular weight of about 400 to about 600 and mixtures thereof.