DE3020860A1 - POLYOL BLEND, Possibly. IN MIXABLE FORM, AND METHOD FOR PRODUCING A POLYISOCYANURATE FOAM USED THEREOF - Google Patents

Description

Henkel, Kern, Feiler & Hänzel

η w ä 11 e

Registered Representatives

before the

European Patent Office

THE UPJOHN COMPANY Kalamazoo, Mich., V.St.A. Möhlstrasse 37 D-8OOO Munich 80

Tel .: 089 / 982085-87 Telex: 0529802 hnkl d Telegrams: ellipsoid

TUC 3525-F - Dr.F / rm

Polyol mixture, optionally in a miscible form, and process for producing a polyisocyanurate foam using the same

030051/0738

description

The invention relates to cellular polymers and intermediates for their production, in particular new polyol mixtures and their use in a process for the production of polyisocyanurate foams or cellular polyisocyanurates ^

Cellular polyisocyanurates and their utilization in a wide variety of ways Areas of application for thermal insulation are known. It is also known that polyisocyanurate foams are heat and flame resistant (see U.S. Patents 3,745,133, 3,986,991 and 4,003,859). To modify the foam properties Sometimes minor amounts of polyols are incorporated into the components forming the foam. If fluorocarbon propellants are used, the possibly occurring problem of incompatibility between the polyol, especially one primary hydroxyl polyol, and the fluorocarbon in the premix usually by dissolving the main part or the total amount of the fluorocarbon premixed with the polyisocyanate (see. The stated US Pat.).

Polyisocyanurate foams are used particularly in the production of composite structures made of foam and board or plate-shaped structures using the most varied Visible materials are used. Difficulties encountered in making such composite structures can include 1) the lack of uniform foam core strength, 2) poor adhesion between the foam core and the face material, 3) retention

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good fire resistance of the foam and 4) the difficulty of protecting the foam as much as possible from cracking. These difficulties have been solved in that minor amounts of a low equivalent weight having polyols, especially diols, co-used in the formulation and the finished composite structure in a furnace to a temperature of 71 ° to 88 ⁰ C heated (see. US-PS 3 903 346).

The polyols having a low equivalent weight, especially those having only primary hydroxyl groups preferred diols (see. Column 4, lines 59 to 61 of US Pat. No. 3,903,346) cannot be used beforehand as component B. be (pre) mixed with the fluorocarbon propellant, because the diol / fluorocarbon pair has poor solubility having. This requires a (pre) mixing of the fluorocarbon with the polyisocyanate in component A. Wegen the lack of miscibility fluorocarbon / diol, US Pat. No. 3,903,346 states that a third component C, which contains the catalyst component in a low molecular weight containing glycol dissolved, must be used (see. Column 2, lines 32 and 33 and the examples U.S. Patent 3,903,346).

In addition, a composite structure made according to the teachings of US Pat. No. 3,903,346 must be heated in an oven. to ensure a uniform foam core strength in the product.

Surprisingly, it has been found that large amounts of fluorocarbon propellants with primary hydroxyl groups containing low molecular weight polyols completely mixed

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are bar if new mixtures with certain types of amine or amide diols or amine triols with the primary Hydroxyl polyols can be used. Other ingredients that may be present in the mixable mixtures, are surfactants, catalysts, and the like.

Furthermore, it has been shown that the same type of miscible mixtures containing primary hydroxyl groups can be used obtained by replacing the fluorocarbon component with water.

Finally, it has also been shown that the new polyol mixtures can be used as a component in minor amounts B in the production of polyisocyanurate foams with low friability, fine cell structure, good dimensional stability and low flame spread in the context of a two components, namely components A and B, using the method.

The fluorocarbon and water components act as propellants in the corresponding foam formulations.

According to the invention, the (described in more detail later) Types of amide or amine diols or amine triols as the sole polyol component in combination with the fluorocarbon or water, catalyst, surfactants and other ingredients used in manufacture used by polyisocyanurate foams.

Most unexpectedly, the presence of the amide or amine diol or amine triol in component B provides

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- γ-

for excellent (reactant) compatibility between the polyisocyanate and the other components. This leads to a faster reaction than with known ones Foam recipes and a very good release of heat of reaction, i.e. for a very good exothermic Reaction. The high reaction heat release is of particular advantage in the production of foam composites, because in this way an excellent adhesion between the foam and the visible material is achieved without having to heat the composite structure in an oven.

The invention relates to polyol mixtures from (1) about 20 to about 85% by weight (based on the total weight of the Mixture) of at least one compound of the formulas:

l-Nf

R ₁ CH ₂ CHOfJ-H 0 ^ CH ₂ CH0fj-, H

ο Ai

X Η jT

II

i i

R ₁ R ₁

(CH ₂ CHOf ^ ₁ H

NCH ₂ CHOf ^ 1

where mean: ^ΙΙτ

R is an aliphatic radical with 8 up to and including

18 carbon atoms!

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-W-

an aliphatic radical having 7 to 17 carbon atoms inclusive;

(which can be the same or different) in each case a hydrogen atom or a methyl radical;

χ and y each have an average value from about 4 to about 15, inclusive;

x ¹ and y ¹ each have an average value from about 1 to about 3, inclusive;

x ", y ⁿ and ζ each have an average value from about 1 to about 5 and inclusive

η = 2 or 3,

and (2) about 15 to about 80 weight percent of a primary hydroxyl polyol having a molecular weight of about 60 to about 1,000.

The invention also provides miscible mixtures of the aforementioned polyol mixtures and a fluorocarbon or water propellants.

The invention also relates to miscible mixtures of a polyol mixture of the type specified, a fluorocarbon or water blowing agent and an isocyanate trimerization catalyst.

The invention also relates to processes for the production of polyisocyanurate foams in which at least one compound of the formulas I, II or III with respective average values χ and y of about 1 to about 15, preferably from about 4 to about 15, and x ¹ , y ¹ , x ", y", z, n, R, R ₁ and R ₂ in the given meaning in combination with a fluorocarbon or

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Water blowing agent and a trimerization catalyst are used in the Ito setting with an organic polyisocyanate will. The mixture component preferably also contains the polyol IV, the diol I then with respect to χ and y in a narrower range, namely from about 4 to about 15, is defined.

The invention also relates to the cellular polymers produced by the process described.

Finally, the invention also relates to plate-shaped Composite structure with a polyisocyanurate foam core produced in the manner described.

An "aliphatic radical" (R) is an alkyl or alkenyl radical with 8 to 18 carbon atoms inclusive, e.g. an octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radical or an isomeric radical thereto or an octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl or octadecenyl radical or an isomeric radical thereto, to be understood.

An “aliphatic radical” (R ₂ ) is to be understood as meaning an alkyl or alkenyl radical with 7 to 17 carbon atoms inclusive, for example a heptyl or heptenyl radical up to a heptadecyl or heptadecenyl radical or an isomeric radical thereto.

The polyol mixtures according to the invention can also be used as polyol components in the production of polyurethane foams get used. Polyurethane foams are just like their use for heat and sound insulation

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- ψ-

N- 302086Q

known in industrial and residential buildings.

As already mentioned, the polyol mixtures are used in particular as minor components during manufacture of polyisocyanurate foams, in particular such polyisocyanurate foams, as they produce with the help of spray foam systems in foam composite structures Machines are created for use. Such foams are known for their heat and fire resistance. you will be in particular for the production of plate-shaped composite structures and foam blocks that are used on the building sector Heat and sound insulation are used, used.

The polyol mixtures according to the invention are obtained by simply mixing the amine diol (I), amide diol (II) and / or amine triol (III) and a primary hydroxyl polyol (IV) in the specified amounts by weight in a suitable mixing vessel, storage tank and the like. Components (I), (II) and / or (III) are preferably used in an amount of about 25 to about 60% by weight of the mixture. The primary hydroxyl polyol IV is employed in an amount of from about 40 to about 75 percent by weight .

Preferred constituents of the formulas I, II and / or III are those in which R ₁ always represents a hydrogen atom.

A preferred diol is one of the formula I in which both radicals R _{1 are} hydrogen atoms and χ and y each have an average value of about 5 to about 10 inclusive.

A preferred amidiol is one of the formula II, in which both radicals R. stand for hydrogen atoms and x ^!

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-W-

and y ^f each have an average value of about 2 to about 3, inclusive.

A preferred amine triol is one of the formula III in which all radicals R _{1 are} hydrogen atoms, x ", y" and ζ each have an average value of about 3 to about 5 inclusive and η = 3.

The aminediols of the formula I are obtained in a conventional manner. Some are also available in stores. In typical The aminediols of the formula I are obtained by reacting a suitable dialkanolamine with a suitable one aliphatic halide of the formula R-X or a mixture of different compounds R-X, where the (the) aliphatic Residual (e) (R) fall under the definition given and X represents a halogen atom, preferably a chlorine or chlorine atom Bromine atom, stands. If the desired number, of alkyleneoxy groups is not yet present in the dialkanolamine before the reaction with the aliphatic halide, it can be used retrofit without difficulty by adding the alkylated dialkanolamine with a suitable number of Reacts moles of ethylene oxide and / or propylene oxide, the amine diols of the formula I being obtained.

The aminediols of the formula I are preferably obtained by reacting a suitable primary fatty amine R-NH2 or a mixture of fatty amines, all radicals R falling under the given definition, with about 2 to about 30, expediently about 8 to about 30, preferably 10 to 20 moles of ethylene oxide or propylene oxide per mole fraction Fettamin (see Bulletin 1294 "Ethoxylated Fatty Amines", Ashland Chemical Company, Division of Ashland Oil Inc.,

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- ¹ Z-

Box 2219, Columbus, Ohio 43216 for a detailed Teaching for the production of the amindiols concerned).

Examples of suitable starting fatty amines are octylamine, Decylamine, dodecylamine, tetradecylamine, hexadecylamine, Octadecylamine and its isomers. Examples of suitable alkenylamines are octenylamine, decenylamine, dodecenylamine, Tetradecenylaminej, hexadecenylamine, octadecenylamine and their Isomers. Examples of other suitable fatty amines are mixtures of alkyl and alkenyl amines, e.g. coconut amine, the best from a mixture of the following specified ingredients in the approximate percentage amounts "2% Decylamine, 53% dodecylamine, 24% tetradecylamine, 11 $ H »va.-decylamine, 5% octadecylamine and 5% octadecenylaminej So ^ aamine, which consists of the following ingredients in approximate proportions: 11.5% hexadecylamine, 4% octadecylamine, 24,596 oleylamine, 53% linoleylamine, and 7% linolenylamine; as well as sebum, which consists of the following ingredients in the approximate The proportions are: 4% tetradecylamine, 29% hexadecylamine, 20% octadecylamine and 47% octadecenylamine. Further examples of suitable starting fatty amines are halogenated fatty amines, especially the chlorinated and brominated ones Fatty amines, which can be obtained, for example, by chlorinating or brominating coconut amine, soybean amine, tallow amine and the like receives.

A particularly preferred group of fatty amines includes coconut amine mixtures, Soy amine blends and tallow amine blends, especially coconut amine.

The amide diols of the formula II are obtained in a conventional manner. They are typically obtained by converting

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zen of a suitable dialkanolamine with a suitable fatty acid, a suitable fatty acid ester or a suitable Fatty acid chloride according to the equation:

JkCfP

R ₂ COR ₃ + HN ^ f ^x (^ - II + HR:

^ - (CH ₂ CHOf- "

ι y '

R ₁ .

wherein R ₂ , R-, x ¹ and y ^{1 have} the meaning given and R, for -OH, -OR ^ or X with R ^ being a typical esterifying group, for example a short-chain alkyl radical, an aryl radical, a cycloalkyl radical and the like, and X is a halogen atom, preferably a chlorine or bromine atom. In the event that diethanolamine and / or diisopropanolamine is (are) used as the starting dialkanolamine and one wants to produce amide diols with an average value for x ¹ and y ¹ of more than 1, the dialkanolamide intermediate is simply added in a one-molar amount with about 1 to about 4 mol ( en) Ethylene and / or propylene oxide reacted (see. Bulletin 1295 "Varamide Alkanolamides", Ashland Chemical Company, Division of Ashland Oil, Inc., Box 2219, Columbus, Ohio 43216 with regard to a detailed teaching for the production of fatty acid dialkanolamides).

The amide diols of the formula II are preferably obtained by converting the fatty acids to the corresponding fatty acid amides (R ₂ COKH ₂ ) and reacting the respective amide with about 2 to about 6 moles (per mole of amide) of ethylene oxide and / or propylene oxide.

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- Y-

Examples of starting fatty acids (of which the corresponding Esters, acid halides and amides) are caprylic, capric, lauric, myristic, palmitic or stearic acid and their isomers. Examples of unsaturated fatty acids are decylene, dodecylene, palmitoleic, oil or linoleic acid and its isomers. Further examples of usable fatty acids are mixtures, for example Fatty acid mixtures from coconut oil (approximate composition: 8.0% caprylic acid, 7.0% capric acid, 48.0% lauric acid, 17.5% myristic acid, 8.2% palmitic acid, 2.0% stearic acid, 6.0% oleic acid and 2.5% linoleic acid), fatty acid mixtures from soybean oil (approximate composition: 6.5% Palmitic acid, 4.2% stearic acid, 33.6% oleic acid, 52.6% linoleic acid and 2.396 linolenic acid) and fatty acid mixtures Tallow (approximate composition: 2% myristic acid, 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 ones Fatty acids obtained, for example, by chlorinating or brominating coconut, soybean and tallow fatty acid mixtures receives.

A particularly preferred group of starting fatty acids and Fatty acid amide intermediates consist of the coconut, soybean and tallow oil mixtures described and the corresponding ones Eocosamide, soya amide and tallow amide mixtures, in particular coconut oil mixtures and the corresponding eocosamide mixtures.

Preferred amide diols of the formula II are cocamide, soya amide and tallow amide diol mixtures in which all R ₁ radicals represent hydrogen atoms and x ¹ and y ¹ both have a value

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of about 3. A particularly preferred amide diol is a coconut amide diol mixture, which is a mixture of N, N-bis (8-hydroxy-3,6-dioxaoctyl) coconut amides can be designated.

The amine triols of the formula III are obtained without difficulty in the usual known manner. Some amine triols are also commercially available.

Generally speaking, the way of making amine triols with η = 2 is somewhat different from making them of the amine triols with η = 3. The former amine triols can be obtained without difficulty using the following equation:

[NH _3] + RNH ₂ CHR ₁ - ₁ ^ ChR RNHCHR CHr _{1 1} OH fr RNHCHr ₁ CHR ₁ NH ₂

in <r

Ethylene oxide and / or propylene oxide

In the equation, R and R _{1 have} the meaning given. The starting amine is reacted with an equimolar amount of ethylene or propylene oxide to form an amino alcohol (V). The latter typically goes through! Mixing with ammonia into diamine VI. This is followed by a reaction of a molar amount VI with about 3 to about 15 molar proportions of ethylene oxide and / or propylene oxide, the amine triol of the formula III being obtained.

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Aia triols with η = 3 are typically obtained from following equation:

[H] RNH ₂ + RiCH = CRiCN ^ RNHCHRiCHRi-CN ^ RNHCHR ₁ CHR ₁ CH ₂ Nh ₂

VII VIII ΐχ

III

Ethylene oxide and / or propylene oxide

In the equation, R and R ^ have the specified 2 :, sign. The starting amine becomes a compound of the formula with a suitably substituted acrylonitrile of the formula VII VIII cyanoethylated. The latter is reduced to the diamine of the formula IX. This is followed by an alkoxylation with about 3 to about 15 molar parts of ethylene and / or propylene oxide, a compound of the formula III being obtained.

The starting fatty amines correspond to the fatty amines mentioned for the preparation of the amine diols of the formula I.

Examples of those which can be used in accordance with the invention in the preparation Acrylonitrile compounds which can be used for amine triols are acrylonitrile, cc-methacrylonitrile, ß-methacrylonitrile, oc, ß-dimethacrylonitrile and the like, especially acrylonitrile.

A preferred group of amine triols of the formula III are amine triol mixtures derived from coconut amine, soya amine and taigamine mixtures, in which all radicals R ^ are hydrogen atoms, η = 3 and x ⁿ , y "and ζ each approximately

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3 "to about 5. A particularly preferred amine triol mixture is derived from coconut amine, where all R ₁ radicals stand for hydrogen atoms, η = 3 and x", y "and ζ each stand for about 4.6.

The primary hydroxyl polyol IV can be any primary hydroxyl polyol having a molecular weight of about 60 to about 1000, suitably from about 60 to about 800, preferably from about 60 to about 600 exist. Examples for the polyols of the formula IV are diols, triols and tetrols, in particular diols.

Primary hydroxyl-containing polyols which can also be used are those known from US Pat. No. 3,745,133 Diols, triols and tetrols containing hydroxyl groups, provided they have molecular weights within the specified molecular weight limits exhibit. The polyester polyols obtained from dibasic carboxylic acids are preferred and polyhydric alcohols including those based on 1,4,5,6,7,7-hexachloro- (2,2,1 ^ -heptene-Z ^ -dicarboxylic anhydride based, alkylene diols, alkoxyalkylene diols, polyalkylene ester diols, polyoxyalkylene ester diols, hydroxyalkylated aliphatic monoamines or diamines, resol polyols (cf. "Prep. Methods of Polymer Chemistry", edited by W.R. Sorenson et al., 1961, p. 293, Interscience Publishers, New York, N.Y.) and Polybutadiene resins with primary hydroxyl groups (cf. "Poly Bd Liquid Resins", Product Bulletin BD-3, October 1974, Arco Chemical Company, Div. of. Atlantic Richfield, New York, N.Y.).

The alkylene diols, short-chain alkoxyalkylene diols, Polyalkylene ester diols and polyoxyalkylene ester diols.

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Polyols preferred according to the invention are ethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerol, trimethylolpropane, pentaerythritol, diethylene glycol, by adding Ethylene oxide in water, ethylene glycol or diethylene glycol and the like obtained polyoxyethylene glycols, the triethylene glycol, Tetraethylene glycol and higher glycols provide, or mixtures thereof with molecular weights within the specified range, ethoxylated glycerine, ethoxylated trimethylolpropane, ethoxylated pentaerythritol and the like, bis (ß-hydroxyethyl) terephthalate, bis (ß-hydroxyethyl) phthalate and the like, Polyethylene succinate, polyethylene glutarate, polyethylene adipate, polybutylene succinate, polybutylene glutarate, polybutylene adipate, Mixed poly (ethylene / butylene) succinate, mixed poly (ethylene / butylene) glutarate, Mixed poly (ethylene / butylene) adipate and the like. Polyester with terminal hydroxyl groups, Polyoxyethylene succinate, polyoxyethylene glutarate, polyoxyethylene adipate, polyoxyethylene adipate glutarate and the like, diethanolamine, triethanolamine, N, N'-bis (β-hydroxyethyl) aniline and the like.

The preferred diols are diethylene glycol and the polyoxyethylene adipate glutarate polyester diols a molecular weight of from about 400 to about 600.

Mixtures of about 30 to about 50% by weight of diethylene glycol with about 50 to about 70% by weight are particularly preferred Polyoxyethylene adipate glutarate polyester diol of molecular weight from about 400 to about 600.

In the polyol blends preferred according to the invention are fluorocarbon or water blowing agents, in particular Fluorocarbon propellants.

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When the propellant consists of a fluorocarbon, the unexpected and beneficial features of FIG Polyol mixtures I, II and / or III with IV come into their own. Mixable polyol mixtures can be used here with at least about 20 weight percent of a fluorocarbon propellant and a (propellant-free) polyol mixture as the remainder. The one to be dissolved in the mixture Percentage of fluorocarbon determines in each case the ratio of IV on the one hand and I, II and / or

III anderserse.t ^; n. These proportions (within the specified range) can be determined without difficulty by a simple preliminary search.

Mixable polyol blends with more than 50% by weight of fluorocarbon and even up to 90% by weight of fluorocarbon is obtained with a suitable choice of the mixture components without difficulty with the individual components polyol mixtures according to the invention containing in the amounts indicated. Generally speaking, it rises as it falls Molecular weight of the primary hydroxyl polyol IV is the amount of polyol I, II in the mixture for a given amount and / or III soluble fluorocarbon (compared to a blend with a higher molecular weight IV polyol at the same proportion). In this context it should be noted that the alkylene diols and short-chain Alkoxyalkylene diols with molecular weights below 400 (especially the latter) are the preferred polyols of the formula

IV represent.

The respective proportions of polyol I, II and / or III to polyol IV can be for each special case with regard to maximum miscibility with a fluorocarbon can be determined by simple preliminary tests.

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Generally speaking, using an amine diol will result of the formula I together with a polyol of the formula IV, miscible polyol mixtures with at least about 25 $ To at least about 65% by weight of a fluorocarbon propellant and correspondingly 75% by weight to about 96% by weight mixture of I and IV.

If an amide diol of the formula II is combined with the polyol of the formula IV, miscible polyol mixtures are obtained with at least about 20 % by weight to at least about 60% by weight of a fluorocarbon propellant and correspondingly 80 % by weight to about 40% by weight .- # Polyol mixture from II and IV.

% To about 50 wt - when a Amintriol of formula is combined III with a polyol of the formula IV is obtained mixture capable polyol mixtures having at least about 20 parts by weight 96 to at least about 50 wt .-% of a fluorocarbon blowing agent and corresponding to 80 wt. .-96 Polyol mixture from III and IV.

If water is used as a propellant, its Amount from about 1 to about 6, preferably from about 2 to about 5% by weight. The rest, namely 94 to 99, preferably 95 to 9896, consists of I, II and / or III and IV.

As a fluorocarbon propellant, any of those skilled in the art can be used fluorocarbon propellants suitable for driving mixtures to be polymerized into cellular polymers are used will. As a rule, these blowing agents are halogenated aliphatic hydrocarbons, which, apart from fluorine, also by chlorine and /

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or bromine can be substituted (cf. US Pat. No. 3,745,133, column 11, lines 25 to 38).

In a preferred polyol mixture according to the invention, which is used in particular in the production of polyisocyanurate foams is used is in the mixture of propellant and components I, II and / or III and IV additionally contain an isocyanate trimerization catalyst. The relevant isocyanate trimerization catalysts will be described in more detail later. The amount of isocyanate trimerization catalyst is expediently about 2 to about 20, preferably about 2 to about 15% by weight. The rest, namely about 80 to about 98, preferably about 85 to 98-6 from the named components.

Surprisingly, the blowing agent and the polyol mixture are polyols containing primary hydroxyl groups Completely miscible in each other without separation during storage. This miscibility is due to the presence of the Aminediols I, amiddiols II and / or amine triols III. Apart from the advantages of a stable mixable Make a mixture of a polyol containing primary hydroxyl groups and a carbon or water in the production of polyisocyanurate foams also those attributable to the presence of nitrogen-containing diols or triols in minor amounts beneficial effects.

Other additives can also be added to the polyol mixtures without impairing their mixability and stability be incorporated. Such additives are further expedient

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ψ '■

ge polyol components, e.g. polyols containing secondary hydroxyl groups, dispersants, cell stabilizers, surfactants, flame retardants and the like commonly used in polyisocyanurate foam manufacture get used.

In the production of polyisocyanurate foam according to the invention The amine diol, amide diol and / or amine triol can be used as the only polyol component mixed with a fluorocarbon or water blowing agent and a trimerization catalyst as component B for the reaction with a component A consisting of an organic polyisocyanate can be used. In this case the Values for χ and y at (I) in the broader range from about 1 to about 15.

The percentages by weight of the components of the mixture are the same as those given for the proportions of the catalyst to be mixed with the blowing agent and the polyol component. Component B therefore consists of about 2 to about 20, preferably about 2 to about 15% by weight of a trimerization catalyst and about 80 to about 98, preferably about 85 to about 98% by weight of I, II and / or III and blowing agent . When using a fluorocarbon blowing agent amount thereof is about 20 to about 80, preferably about 20 to about 50 wt -.% With respect to I, II and / or III. The latter (s) is (are) therefore present in an amount from about 20 to about 80, preferably from about 50 to about 80% by weight.

When using water as a blowing agent, its amount is about 1 to about 6, preferably about 2 to about 5

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Weight # in relation to I, II and / or III. The latter (s) is (are) therefore present in an amount of from about 94 to about 99, preferably from 95 to 98% by weight.

The component (mixture) B comes in an amount of generally about 10 to about 120, expediently about 10 up to about 80, preferably about 20 to about 60 parts by weight per equivalent of polyocyanate are used. It applies that the total number of hydroxyl equivalents contained in component (mixture) B per equivalent of polyisocyanate is expediently about 0.05 to about 0.5, preferably about 0.08 to about 0.4 equivalent.

Component (mixture) preferably also contains B a minor amount of the primary hydroxyl-containing pole oil IV. This combination in the component (Mixture) B not only leads to a stabilized, miscible mixture of the type described, it provides in addition, polyisocyanurate foams with optimal properties. Leave with such a mixture produce foam composite structures that are used to bring about maximum foam strength and adhesion to the composite face, no heating in the oven need. In this case, the values for χ and y fall in the narrower range of about 4 to about 15.

The amine diol I, amide diol II and / or amine triol III, the polyol IV containing primary hydroxyl groups, the blowing agent and a trimerization catalyst Mixture is used in the same amount of parts per isocyanate equivalent as that free from polyol IV Component (mixture) B. This applies to the total number

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of hydroxyl equivalents per isocyanate equivalent is the same as for the component (mixture) free of polyol IV B. The percentages by weight of the individual ingredients in the mixture correspond to the percentages by weight Proportions of the polyol blends. For the amine diol I, amide diol II, amine triol III and the primary hydroxyl groups Containing polyol IV and the blowing agent apply the remarks already made.

The trimerization catalysts are all those skilled in the art for the catalysis of a trimerization of organic Iar> -

cyanate to the isocyanurate unit known Kataly. Lurs in

Question. If appropriate, urethane-forming catalysts can also be used can be combined with trimerization catalysts.

Examples of typical isocyanate trimerization catalysts can be found in "The Journal of Cellular Plastics" November / December 1975, page 329 and in US-PS

3 745 133, 3 896 052, 3 899 443, 3 903 018, 3 954 684 and

4 101 465.

Preferred catalysts are described in U.S. Patents 3,896,052 and 4,110,465. US Pat. No. 3,896,052 discloses catalyst combinations of (a) an alkali metal salt of an N-substituted amide with (b) an alkali metal salt of N- (2-hydroxyphenyl) methylglycine and optionally (c) a tertiary amine trimerization catalyst are known. the end of US Pat. No. 4,101,465 are catalyst combinations of the aforementioned components (a) and (b) and a hydroxyalkyltrialkylammonium carboxylate salt component known.

In the production of polyisocyanurate foams according to the invention can be used as organic polyisocyanates

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organic polyisocyanates previously used for this purpose are used. Appropriately and for production of foams with excellent heat resistance and structural strength are preferred as polyisocyanates Polymethylene polyphenyl polyisocyanates, in particular the polymethylene polyphenyl polyisocyanates known from US Pat. No. 3,745,133, for use. Preference is also given to polymethylene polyphenyl polyisocyanates, which are used to reduce acidic impurities according to US Pat. No. 3,793,362 were reacted with a minor amount of an epoxy compound. Further preferred polymethylene polyphenyl polyisocyanates are those which contain high levels of the 2,4'-isomer (see U.S. Patent 3,362,979).

Another particularly preferred organic polyisocyanate consists of a mixture of about 30 to about 85 wt -.% Methylenebis (phenyl isocyanate) and the balance being polymethylene polyphenyl polyisocyanates having a functionality of about 2.0.

In the production of polyisocyanurate foams according to the invention, In particular, those for the production of foam composite structures, one can take conventional measures and operate systems (cf. the US-PS mentioned). For full details of manufacture and use of polyisocyanurate foam composites, see US Pat. No. 3,896,052.

The following examples are intended to illustrate the invention in more detail.

example 1

Following the procedure described below, the

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Five designated foams A through E in Table I Polyisocyanurate foams produced.

Foam receptors are prepared by mixing components A and B by hand. The polyisocyanate component as the sole constituent of component A and the constituents of the component listed in Table I. B are premixed and before their implementation with the polyisocyanate observed. The mixing process is carried out by thoroughly mixing components A and B in a beaker using a high speed auger motor equipped with an impeller. The mixture is then quickly poured into a cardboard box, allowed to rise freely and cured at room temperature (about 20 ° C).

The foams B and E are foams according to the invention, the foams A, C and D are outside of the invention, since the amine diol component values for χ and y below the specified lower limit having. Component B of all formulations is clear with no evidence of cloudiness. In the case of foams A and C, secondary hydroxyl-containing polyols which dissolve fluorocarbons are present. In the case of the foam C there is also a phosphate plasticizer. The foam D also contains the plasticizing one Component.

Foam E has maximum foam properties in terms of a combination of maximum reaction heat release with rapid solidification as well as low Core and surface friability detectable.

030051/0738

The leaching of the surface with a rising foam sample corresponds to the point in time at which the
shiny and damp, unreacted surface of the rising foam becomes dull or dull or tarnishes and shows that an effective hardening or reaction has occurred on the surface. All foam samples show good surface tarnishing.

Table I.

Foams A
comparison B.
• rfin-
manic
according to C.
Ver
same • D.
Ver
same E.
invent
dungs
according to Components (in parts by weight): 1.25
25th Component A: 3 Polyisocyanate I 100 100 100 about 4 100 100 Component B: Diethylene glycol 5.7 5.4 6th 6th 8th So yes amine adduct 5.7 - 6th 6th - Coconut amine adduct ⁵ 23.5 - - 8th propoxylated GIy-
cerinproduct4 5.7 _ _ _ propoxylated pen
taerythritol product ⁵ _ 6th _ Tris- (dichloropropyl-
phosphate) 7.2 18th 18th prepoxylated poly
ol ⁶ 6th Silicone wetting agent ⁷ 1.25
Fluorocarbon 25 1.25
25th 1.25
25th 1.25
25th Catalyst I ⁹ 3 3 3 3 NCO / OH index about 4 about 4 about 4 about L

030051/0738

020860

Continuation of Tafeelle ι

Appearance of component B

clear and clear and clear and clear and clear not not not not and cloudy

Heat of reaction released during foam formation 170.6 C

Solidification of the nucleus rapidly, crumbly, strong

The surface is lacking in fragility

Tarnishing the surface, la

cloudy cloudy cloudy not
cloudy 156.1 ⁰ C 145.6 ⁰ C 147.8 ⁰ C 173.9 ° C slow middle quickly quickly small amount strong strong small amount is missing is missing is missing is missing

if.

there

Footnotes:

Polymethylene polyphenyl polyisocyanate at about 45% by weight Methylenebis (phenyl isocyanate) and about 55 wt. 96 polymethylene polyphenyl polyisocyanates a functionality of over 2 (isocyanate equivalent: 133);

Soy amine adduct obtained by reacting 2 molar fractions Ethylene oxide with soy amine (amine equivalent weight: about 360; hydroxyl equivalent weight: about 180);

^ Coconut amine adduct, obtained by reacting about 15 molar proportions Ethylene oxide with coconut amine (amine equivalent weight: about 885; hydroxyl equivalent weight: about 442);

propoxylated glycerin product having a hydroxyl equivalent weight of 243;

hydroxyl equivalent weight propoxylated pentaerythritol product of 148;

030051/0738

propoxylated polyol obtained by propoxylating a mixture of sorbitol and toluenediamine to a hydroxyl number of 360 (viscosity, determined at a temperature of 25 ° C.: 2500 mPas; specific weight »1.072);

Silicone wetting agent for the production of rigid foams a hydroxyl number of about 119;

monofluorotrichloromethane propellant stabilized with alloocimene;

Catalyst combination from A) 1 part by weight of a solution of (a) 45% by weight potassium N-phenyl-2-ethylhexamide, (b) 27% ethylene glycol and (c) 28% dimethylformamide; B) 3 parts of a solution of 50% by weight sodium N- (2-hydroxy-5-nonylphenyl) methyl-N-methylglycinate in diethylene glycol and C) 1 part of a solution of 50% by weight of 2-hydroxypropyltrimethylammonium formate and 50% dipropylene glycol and D) 1 part by weight of a polyethylene glycol of molecular weight from 200.

Example 2

Foams F to I are produced according to Example 1. The foams F and H are Comparative foams, foams G and I around foams according to the invention.

The constituents of components A and B can be found in Table II below. In the production of the foams F and G a different polyisocyanate is used than in the production of the foams H and I. In the

030051/0738

- 32

Making the foams F and H contains the component A, as usual, the fluorocarbon propellant. When to Determination of the miscibility the same amount of fluorocarbon is mixed into component B, separates in both cases the fluorocarbon from the other components, namely diethylene glycol, the wetting agent and the catalyst.

In the production of foams G and I is in the component B contain the ethoxylated coconut amine. In this case it is the fluorocarbon and other ingredients Completely miscible with the diethylene glycol component.

A comparison of the foam rise times for foams F and G or H and I shows that these according to the invention (foams G and I) are far faster than for comparison foams F and H. The significant increase in speed shows the increased compatibility of components A and B which leads to a better implementation of the two components. The faster rise times compared to the known recipes are due to this better implementation. The ethoxylated amine used in the production of foams G and I consists of a tertiary amine. These types of high molecular weight tertiary amines are not strong bases and are used (in the manufacture of foams G and I) in very small amounts based on amine equivalent (namely in an amount of 0.009 equivalent in each case). This small amount of weak amine would not be sufficient to explain the significant (foam increase) increase in speed in the production of foams G and I compared to the production of foams F and H solely on the basis of amine catalysis.

030051/0738

Table II

Foams

FGHI Verification equal to the same measured

Components (in parts by weight): Component Αϊ Polyisocyasat ι Polyisocyanates 11 * fluorocarbon according to table I.

Component Bs diethylene glycol

1CO 100

105

(see.

Silicone mesh (see Table I)

Catalyst I (see Table I) fluorocarbon (see Table I)

NCO / OH index

Foam rise time (in s) Cream time

Gel time

Time to loss of stickiness

Heat of reaction released during foam formation 171.7 C core density (g / cm ³ ) 0.0282

Dry aging when heated to a temperature of 48.9 ° C / 24 h

% £ ± volume +4.6

Core friability,% ³

There is no surface fragility

Tarnishing the surface there

49

106

105

£ 1.5 8.0 22.5 8.0 8.3 8.0 8.3 8.0 , _ 1.25 - 1.25 1.25 3.0 1.25 3.0 3.0 23 3.0 24 _ 4.2 _ 4.2 4.6 19th 4.6 21 75 42 59 41 04 96

47

168.9 ° C 158.9 ⁰ C 157.8 ° C 0.0279 0.0287 0.0280

+4.1
30th

is missing
there

+2.9

is missing

+2.4 19

is missing there

030051/0738 P * D ORIGINAL

-ν-

Footnotes:

¹ see footnote 1, table I;

Polymethylene polyphenyl polyisocyanate with about 35 wt .-% Methylenebis (phenyl isocyanate) and about 65 wt .-? 6 polymethylene polyphenyl polyisocyanate a functionality of over 2 (isocyanate equivalent: 14O);

^ The friability is the percentage weight loss of the Test specimen for 10 minutes, determined according to US standard ASTM C-421.

Example 5

According to Example 1, using the ingredients indicated in Table III in the amounts indicated above two inventive polyisocyanurate foams J and K produced. Components B are in both cases clear.

Both foams have a very fine-cell structure, the surface is not crumbly and shows good tarnishing. The release of the heat of reaction in the foam Education is good in both cases. The rapid rise profiles show the quick responsiveness of both Foam recipes.

It should be noted that the catalyst mixture used in making foams J and K is a minor amount of the coconut amine adduct (amine diol) used in Example 1 as a means to improve the Compatibility of the various other catalyst

030051/0738

contains components. In the absence of this amine diol are the other catalyst components are not completely miscible with one another.

Table III

Foam J K

Components (in parts by weight): Component A:

Polyisocyanate III ¹ 135 135 Component B:

Coconut amine adduct

Coconut amine adduct according to Table I.

commercial silicone wetting agent

Fluorocarbon (see table I)

Catalyst Ή? UCD / OH index

Appearance of component B Foam rise time (in s) Cream time

Gel time

Time to loss of tack 30 40

Rise time

Heat of reaction released during foam formation. Surface fragility Tarnishing of the surface friability of the core appearance

- 75 1.5 1.5 22nd 27 3 3 4.5 4.5 clear clear 5 6th 20th 20th

164.4 ⁰ C 151.7 ⁰ C is missing is missing there there little little very fine very fine cellular cellular

030051/0738 ORIGINAL INSPECTED

Footnotes: /

^J * 3Ό20860

Polymethylene polyphenyl polyisocyanate with about 45 % by weight methylenebis (phenyl isocyanate) and about 55% by weight polymethylene polyphenyl polyisocyanate having a functionality of over 2 (isocyanate equivalent: 135);

Coconut amine adduct, obtained by reacting 5 molar proportions of ethylene oxide with coconut amine (amine equivalent weight: approx 445; Hydroxyl equivalent weight: about 222);

Catalyst combination of the following components: A) 1 part by weight of a 50% strength by weight solution of sodium N- (2-hydroxy-5-nonylphenyl) methyl-N-methylglycinate in diethylene glycol; B) 0.50 part potassium acetate j C) 0.30 part Water and D) 0.50 part of the coconut amine adduct from Example 1. This catalyst mixture is completely clear and forms a uniform mixture. Preparations of the same catalyst mixture without the coconut amine adduct of the Example 1 are cloudy and cloudy.

Example 4

According to Example 1, using the ingredients given in Table IV below, in the loc indicated amounts by weight of two water-blown polyisocyanurate foams L and M according to the invention. In both cases, components B are clear, miscible mixtures.

The foam rise parameters are very fast, whereby in particular, despite the use of water as a blowing agent, the foams lose their tackiness very quickly. Furthermore, high heat release values can also be determined during foam formation, which indicates excellent conversions suggests. The physical properties of the foams formed are good.

Ό30051 / 0738

Table IV

Foams L M

Components (in parts by weight): Component A:

Polyisocyanate (see Table III) 135 135

Component B:

Polyol mixture I 23 30

Silicone wetting agents (see Table I)

H ₂ O

Catalyst (see table III)

NCO / OH index (including H _£ 0) Appearance of component B Foam rise time (in s) Cream time

Gel time

Rise time

Time to loss of stickiness

Heat of reaction released during foam formation Density (g / cm ^)

K-factor ² (BTU (ft. ² ) (h) ° F / in) in parallel

in the vertical direction compressive strength (kg / cm ² ) parallel to the ascending direction perpendicular to the ascending direction

% £ ± volume at 70 ° C, 100% relative humidity after 24 h dry aging at 148.9 ° C % volume after 24 h

2 2 1 1 3 3 3 2.5 clear clear 15th 13th 31 26th 48 48 35 30th 191.1 ° C 195.0 ° C 0.0425 0.045 0.190 0,201 0.189 0.193 2.78 2.95 2.11 1.41 -7.7 -4.7 -2.9 +3.0

030051/0738

3020850

Footnotes:

Mixture of A) 40.8 parts of a polyoxyethylene adipate glutarate polyester diol a molecular weight of 500, B) 28.6 parts of diethylene glycol and C) 30.6 parts the coconut amine adduct of Table I;

² the K factor is a measure of the thermal conductivity of materials. It is determined via the heat flow in accordance with US standard ASTM C-518.

Example 5

According to Example 1 using the ingredients given in Table V by mixing by hand an inventive polyisocyanurate foam N produced.

Component B contains a mixture of a triol containing primary hydroxyl groups and diethylene glycol 41 wt% fluorocarbon. Nevertheless, the mixture remains clear without becoming cloudy.

The foam shows good rise times. In foam production there is a high release of heat of reaction. The foam shows good friability properties.

030051/0738

Table V

Foam N (according to the invention)

Components (in parts by weight): Component A:

Polyisocyanate (see Table III) 135 Component B:

trifunctional polyethylene glycol containing primary hydroxyl groups ¹ 8.5

-Diethylene glycol 6.5

Coconut amine adduct (see Table I) 10 commercial silicone wetting agent

(see Table III) 1.25

Catalyst (see Table III) 3.0

Fluorocarbon (see Table I) 20

Component B appears clear, without cloudiness

% Fluorocarbon in component B 41 foam rise time (in s)

Cream time 13

Gel time 30

Time to Loss of Tack 35

Heat of reaction released during the

Foaming 176.1 C

The surface is lacking in friability

Tarnishing the surface, yes

Little fragility of the core

Footnotes:

trifunctional polyethylene glycol containing primary hydroxyl groups and having a hydroxyl equivalent weight of 333

030051/0735

Example 6

Using the invention from the ingredients of the following Table VI produced foam 0 high temperature and flame resistant polyisocyanurate foam Composite structure produced.

A commercially available laminating device is used to produce the composite structure. The temperatures of the components A and B are 22.8 ° and 21.1 ⁰ C. The throughput through a low pressure impingement mixing head is 6.8 kg / min. Instead of a holding roller, a casting technique is used. The conveyor belt speed is 3.0 m / min. The curing oven temperature is maintained at 21.1 ° to 32.2 ° C.

5.1 cm thick composite structures with visible surfaces made of 0.038 mm thick aluminum foil or asphalt are produced. The foam properties given in Table VI relate to the foam core material according to Removal of the visible materials. Consequently, the visible material as such influences the foam properties not. The adhesion between the visible material and the foam is excellent.

Component B, although the polyester having primary hydroxyl groups, is diethylene glycol and 43% by weight fluorocarbon (according to Table I) containing, clear and not cloudy.

The composite structures are produced without the need to harden them in the oven at high temperatures,

which is due to the rapid reactivity of the recipe. The quick responsiveness is reflected also in the rapid rise profile and in the fact that the friability of the foam is very low despite the lack of hardening at high temperature. Furthermore, as already stated, good adhesion of the visible material to the foam can be determined.

All foam physical properties including very low friability, good fire resistance, acceptable K-factor and moisture aging results have been found to be good.

Table VI Foam O (according to the invention)

Ingredients (in parts by weight) ι Component A:

Polyisocyanate (see Table I) Component B:

Polyester diol ¹ Diethylene glycol Coconut amine adduct (see Table I)

commercial silicone wetting agent (see Table III)

Catalyst (see Table III) Fluorocarbon (see Table Appearance of component B % fluorocarbon in component B NCO / OH index

Foam rise time (in s) Cream time Gel time Time to loss of stickiness

133

6.3

6.7

1.25 3.0 I) 20.0

clear, no haze 43% 4.9

19th 40 47

030051/0738

- ■■% / -

Table VI continued

The surface is lacking in friability

Tarnishing the surface 3a

The core's solubility is low (6%). Overall density (in g / cm ⁵ ) 0.0320

Core density (in g / cm ³ ) 0.0288

Compressive strength (in kg / cm)

parallel to the direction of rise 2.18

perpendicular to the direction of ascent. 1.48 closed cells 94%

K-Factor (BTU (ft. ² ) (h) ° F / in.) 0.14

Aging in a humid environment at a temperature of 70 ° C and a relative Humidity of 95%

Volume after 1 day + 6%

after 7 days + 6.5%

after 28 days + 7.0%

ASTM-E-84 test with 5.1 cm thick. . , ■

Test items:

Assessment of flame spread 38

Smoke 187 "

Footnotes:

Polyester diol according to footnote 1 of Table IV under A;

The proportion of closed cells is determined using an air pycnometer according to the US standard ASTM D-2856 determined.

Example 7

Corresponding to example 1 using the in table

030051/0738

- W-

9b ' 3Q2Q86Q

YII specified constituents in the weight amounts specified above a polyisocyanurate foam P according to the invention is produced.

Component B is in spite of the combination of the fluorocarbon with the primary hydroxyl groups of the amide diol clear and shows no evidence of cloudiness.

The foam obtained is characterized by a very fine-cell structure and has no crumbly surface and shows a good tarnishing of the surface.

The release of heat of reaction during foam formation is good. The rapid rise profile shows the quick responsiveness the reaction mixture to be foamed.

Table VII

Foam P (according to the invention)

Components (in parts by weight):
Component A:

Polyisocyanate (see table

III) 135

Component Bi

Coconut amide adduct 49

commercial silicone wetting agent 1.5

Fluorocarbon (see table

I) 23

Catalyst (see Table III) 3 NCO / OH index 4.5

Component B appears clear, without cloudiness

030051/0738

Continuation of table VIt

Foam rise time (in s)

Cream time 8

Gel time 42

Time to Loss of Tack 52

rise - Heat of reaction released during the Foam formation 164.4 ° C Surface friability is missing Tarnishing the surface there Fragility of the core moderately crumbly Appearance very fine-celled

Footnote:

Coconut amide adduct obtained by reacting 6 molar proportions Ethylene oxide with 1 molar proportion of coconut amide (amine equivalent weight: 290; hydroxyl equivalent weight: 193), too referred to as N, N-bis- (8-hydroxy-3,6-dioxaoctyl) cocamide mixture,

Example 8

According to example 1 xinter using the in table
VIII, polyisocyanurate foams Q and R according to the invention and a comparative foam S are produced.

In the case of the production of foams Q and R, component B is in spite of the mixing of the hydrocarbon with the components containing primary hydroxyl groups

30051 / 073S

ORIGINAL INSPECTED

clear and shows no signs of cloudiness.

The one used in making Comparative Foam S. As usual, component A contains the fluorocarbon propellant. If you have the same amount of fluorocarbon incorporated to determine the miscibility of component B, the fluorocarbon separates from the other ingredients, namely the diethylene glycol, the surfactant and the catalyst.

A comparison of the foam rise times of foams Q and R on the one hand and the comparison foam S on the other hand shows that it is much faster in the former cases (Q and R) than in the latter case (S). The significant increase in speed clearly shows the improved compatibility of components A and B, which results in a better reaction between the two and consequently a faster rise time compared to the known formulation.

Table VIII

Foams QRS

according to the invention comparison

Components (in parts by weight): Component A:

Polyisocyanate (see Table III) - 135

Polyisocyanate (see Table I) 100-100

Fluorocarbon (cf.

Table I) - - 21.5

Component B:

Polyester diol ¹ - 9 -

Diethylene glycol 8 6.3 8.3

030051/0738

Table VIII continued

Coconut amide adduct (see Table VII) 8 6.7 -

Silicone wetting agent (cf.

Table I) T, 25-1.25

Commercial silicone wetting agent (see Table III) 2

Fluorocarbon (cf.

Table I) 25 22

Catalyst (see Table III) 4.5 5

Catalyst (see table

I) - - 3.0

NCO / OH index about 4 about 4 about 4.6

Appearance of component B clear, oh- clear, without

ne cloudiness cloudiness

Foam rise time (in s) Cream time
Gel time

Time to loss of stickiness

rise

Heat of reaction released during foam formation Duration of solidification Friability of the surface Tarnishing of the surface Core density (in g / cnr) Friability of the core (%)

Dry aging at 148.9 ° C * Volume 96/24 h +7.4 +5.0 +4.6

16 0.0248 16 75 40 38.5 35 104 45 40 116 54 48 - 173.3 ° C 177.2 ° C 171.7 ° C quickly quickly - is missing is missing - there there - 0.0330 0.0282 32.0 31

Footnote:

Polyoxydiethylenadipatglutaratpolyesterdiol with a molecular weight of 500 vnä. an OH number of 211.5.

030051/0738

302Q86Q

Example 9

Corresponding to Example 1 using the components

of Table IX in dsn, loc. cit., the amounts by weight given

© produced in polyisocyanurate foam T according to the invention β

Despite the combination of the fluorocarbon with the primary ones Hydroxyl groups of the amine triol, component B is clear and shows no signs of turbidity.

The foam obtained is very fine-celled Structure marked and shows no surface friability as well as good tarnishing of the surface.

The release of heat of reaction during foam formation is Well. The rapid rise profile shows the rapid reactivity of the foam formulation »

Table IX

Foam T (according to the invention)

Ingredients (in parts by weight): Component As

Polyisocyanate (see Table III) 135 Component Bi

Ethoxylic mixture * 56

commercial silicone wetting agent 1.5

Fluorocarbon (see Table I) 23

Catalyst (see Table III) 2.5

-lBdes 4.5

^ · - © B clear, without turbidity

y J y ü D i / u

Table IX continued

Foam rise time (in s) Cream time Gel time Time until loss of slebrlgkei rise

Reaction to be released "b © I d © r Foam forms friability of the surface Tarnishing of the surface friability of the core appearance

4 17 50

IG ι ρ I Ks is missing slightly t / icy very rocky

Footnote %

' Ethoxylated GemiseIi _P © rlialtsa a ^ reh transfer from. Ethylene oxide with Kokosdiaiaia ia malarea Hc-ngsn from et »a 14 s 1 where the Kokosdiaiaia diK ⁵ © !! Use of coconut oil with one equivalent of acrylonitrile was used to reduce ethylated coconut mixture to coconut oil (amine equivalents 290? OH equivalents 193).

example

According to example 1 - asterisk use of the in table X

specified constituent © are two inventions © PolyisocyanuratsohaiaEstoff © ü una? vm. & © in Yergi®i © ias ° i "¥ made ο

The case of the manufacturing cost of the *

K © ü © Iaat £ © 2, des

S ^r \ η fi S '^; / η - ^ -

carbon with the primary hydroxyl-containing groups Components clear and show no signs of cloudiness.

In the case of the production of the comparative foam, component A contains, as usual, the fluorocarbon blowing agent. If the same amount of fluorocarbon is incorporated to determine the miscibility of component B, the fluorocarbon separates from the other components, namely diethylene glycol, the surface-active one Agent and the catalyst.

A comparison of the foam rise times in the production of foams U and V on the one hand and ¥ on the other shows that it is far more rapid in the former than in the latter. The significant increase in speed clearly shows the increased compatibility of components A and B, resulting in a better reaction between the two and consequently leads to a faster rise time compared to the prior art.

Table X

Foam U V ¥

according to the invention comparison

Components (in parts by weight): Component A:

Polyisocyanate (see Table III) - 135

Polyisocyanate (see Table I) 100-100

Fluorocarbon (cf.

Table I) - - 21.5

03005 1 / 073S

Table X continued

Component B:

Polyester diol
Diethylene glycol ethoxylated mixture (cf.Table IX) silicone wetting agent (cf.

Table I) 1.25

commercial silicone wetting agent (see table

9
6.3

6.7

8.3

1.25

III)
Fluorocarbon (cf.
Table I) 25th 2
22nd 0.0364 3.0 Catalyst (see table
le III) 2.5 2.5 33.1 about 4.6 Catalyst (see table
le I) NCO / OH index about 4 about 4 Appearance of component B clear,
not
cloudy clear,
not
cloudy 75. Foam rise time (in s) 104 Cream time 16 15th 116 Gel time 39 42 - Time to loss of
Stickiness 46 50 171.7 ° C rise 56 60 - Released heat of reaction
the foam formation 166.1 ⁰ C 169.4 ° C - Duration until solidification quickly quickly - Surface friability is missing is missing 0.0282 Tarnishing the surface there Yes 31 Core density (in kg / cm) 0.0268 Friability of the core (in %) 18.8

Dry aging at a temperature of 148.9 ⁰ Q ^ volume # / 24 h

+10.8

+5.3

+4.6

030051/0738

Footnote:

Polyoxyethylene adipate glutarate polyester diol of molecular weight of 500 and an OH number of 211.5.

Example 11

There will be a number of hybrids from monofluorotrichlorometiian and two typical polyols which can be used according to the invention and which contain primary hydroxyl groups. The amounts by weight used including the amount of any amine diol of the formula I which may be present varies according to Table XI. The mixtures are checked for their ability to mix, their clarity or their turbidity and examining the deposition of the fluorocarbon from the solution.

T> he mixtures A to D contain diethylene glycol and fluorocarbon and no amine diol, i.e. 100% diethylene glycol, and the maximum solubility of the fluorocarbon is 15% by weight. The addition of 10% by weight of amine diol is not sufficient from, xim increases the fluorocarbon solubility to 25% by weight raise. With the addition of 20% amine diol (mixture D) a clear mixed solution containing 25% fluorocarbon.

The mixtures E to J contain a polyester diol of the specified Art, whereby the pure polyester diol is able to dissolve 20% by weight, but not 25% by weight of fluorocarbon. The break for 25% fluorocarbon solubility, starts at about 10 parts by weight of amine diol (Mixture G). At a 20% amine diol content dissolves the fluorocarbon up to 31% by weight.

0 3 0051/0738

Mixtures K to M show maximum fluorocarbon contents of over 90% and up to 67.5% for diethylene glycol or the polyester diol if a maximum of 85% by weight amine diol is present.

Mixtures H through Q show maximum fluorocarbon solubilities of 60% l) betw. 50% for diethylene glycol or the polyester diol in the case of 50% by weight mixtures of primary alcohol and amine diol.

030051/0 7 38

Table XI

Mixture ABCDEFGHI

Components (in parts by weight):

Diethylene glycol 100 100 90 80

Polyester diol ¹ - - - - 100 100 90 80 80

Coconut amine adduct (cf.

Table I) - - 10 20 - 10 20 20

Fluorocarbon (cf.
Table I)

_o wt -.% primary alcohol

w-96 amine diol

σ wt .-% fluorocarbon,

^ 2 Appearance of the mixture clear, cloudy, cloudy, clear, clear, cloudy, clear, -clear, clear, ^ mix- mix- mix- mix- mix- mix- mix-

o bar splittable splittable bar

* -3 manure manure

17, 6th 25th 33.3 33.3 25th 33, 3 33.3 40 45 100 100 90 80 100 100 90 80 80 0 0 10 20th 0 0 10 20th 20th 15th 20th 25th 25th 20th 25th 25th 28.5 31

Table XI continued

Mixture J K L M NO P Q

Components (in parts by weight):

Diethylene glycol - 15- - 50 50 -

Polyester diol ¹ 80 - 15 15 - - 50 50

Coconut amine adduct (cf.

Table I) 20 85 85 85 50 50 50 50

Fluorocarbon (cf.

Table I) 50 900 207.7 233.3 150

Weight-96 primary alcohol 80 15 15 15 50

96 amine diol 20 85 85 85 50

50 900 80 15th 20th 85 33.3 90 cloudy kla

175 6th 100 120 50 50 50 50 50 50 63, 50 55

ο 96% by weight of fluorocarbon 33.3 90 67.5 70 60

cn appearance of the mixture cloudy clear, clear, cloudy, clear, cloudy, clear, cloudy,

- »miso * - mix- mix- mix- mix-

"^ bar bar shiftable shiftable shiftable

°> manure manure manure

Footnote:

see Table IV, footnote 1, A.

O QO (J) CD

Example 12

It uses a number of mixtures of monofluorotrichloromethane prepared with three typical polyols containing primary hydroxyl groups which can be used according to the invention. The amounts by weight used including the amount of coconut amide diol of the formula which may be present II are varied according to Table XII. The mixtures are based on their miscibility, their clarity or their Turbidity and the deposition of the fluorocarbon from the solution were investigated.

Mixtures A to D contain diethylene glycol. In the absence of any amide diol one does not reach 20 weight percent fluorocarbon solubility. The addition of 10% Amide diol {mixture B) is insufficient to increase the fluorocarbon solubility to 20%. Not until at least 15% amide diol (mixture Ό) remains the mixture with one 20% fluorocarbon additive 4dar. Obvious is they are clear in a mixing ratio of 80/20 (mixture D).

Mixtures E through G contain ethylene glycol and at least 20% amide diol is required to maintain 20% fluorocarbon solubility.

Mixtures H through L are made using a polyester diol manufactured. In the pure diol, 20%, but not 25%, of fluorocarbon dissolve. With an amide diol content from 20% (Blends J through L) the highest possible fluorocarbon content is about 31%.

In the case of the mixtures M to 0, maximum fluorocarbon contents of over 90% or up to 60% by weight for di-

030051/0738

302086U

ethylene glycol or the polyester diol observed when a A maximum of 85 wt% amide diol is used.

Mixtures P through S show maximum fluorocarbon solubilities of 55 or 45% in the case of diethylene glycol or the polyester diol in the case of 50% by weight mixtures primary alcohol and amide diol.

030051/0738

Table XII

mixture

Beatand parts (in weight); Diethylene glycol 100 90 ethylene glycol

Polyesterdol (see Table IV)

85

80

100

85

100

100

Coconut amide (see Ta
belle VII) _ 10 15th 20th 25th 15th 20th 25th 33.3 20th Fluorocarbon
(see Table I) 25th 25th 25th 25th 100 25th 25th 100 100 AO approx
O Wt .- # primary Al
alcohol 100 · 90 85 80 0 85 80 0 0 80 O
cn Wt .- # Amiddiol 0 10 15th 20th 20th 15th 20th 20th 25th 20th —Λ
O 56 fluorocarbons by weight
material 20th 20th 20th 20th cloudy,
Away-
shit
manure 20th 20th clear cloudy,
away
shit
manure 28.5 738 Appearance of the mixture cloudy,
away
shit
manure cloudy,
away
shit
manure clear clear cloudy,
away
shit
manure clear clear

Continuation of Table XII

mixture

Ingredients (in parts by weight): diethylene glycol, ethylene glycol

Polyester diol (see Table IV)

Coconut amide (see Table VII)

Fluorocarbon (see table I)

96 wt% primary alcohol % amide diol wt % fluorocarbon Appearance of mixture

15th

50

50

85

15th

85

50

50

50

50

45 50 900 15 '? 166.7 125 150 81.8 100 80 80 15th 15th 15th 50 50 50 50 20th 20th ß5 85 85 50 50 50 50 31 33.3 90 60 62.5 55 60 45 50 just
clear cloudy,
away
shit
manure clear,
mix
bar clear,
mix
bar cloudy,
Away-
shit «
manure clear cloudy,
away
shit
manure clear cloudy,
Away-
SChjBl
manure

Example 13

A number of mixtures of monofluorotrichloromethane and three typical, usable according to the invention, primary hydroxyl-containing polyols prepared. The amounts of weight used, including the amount any amine triol of the formula III used are varied according to Table XIII. The mixes are checked for their miscibility, their clarity or turbidity and the separation of the fluorocarbon from the solution examined.

Mixtures A to D contain diethylene glycol. In the absence of amine triol, the fluorocarbon solubility is reached none 20 wt. 56. The addition of 10% amine triol (mixture B) is insufficient to ensure fluorocarbon solubility to increase to 20%. Only with at least 15% amine triol does the mixture remain clear with 20% fluorocarbon.

The ^ mixtures E to G contain ethylene glycol. There are at least 20% amine triol required to maintain 20% fluorocarbon solubility.

The mixtures H to M are made using a poly -esterdiols produced. The pure polyester diol dissolves 20%, but not 25% fluorocarbon. There are at least 15 wt% amine triol is required to make a 25% fluorocarbon ensure solubility (mixture K). At 20% by weight amine triol content, the maximum is fluorocarbon solubility about 28.6% by weight.

030051/0738

The mixtures N to P show a maximum fluorocarbon solubility of over 9096 or up to 50 wt .- # for Diethylene glycol or the polyester diol with a maximum amine triol presence of 85% by weight.

Mixtures Q through T show maximum fluorocarbon solubility of 5096 or 40% for diethylene glycol or « the polyester diol for 50% by weight mixtures of primary alcohol and amine triol. .

030051/0738

Table XIII

Mixture A B C D E F G H I J

Components (in parts by weight):

Diethylene glycol 100 90 85 80

Ethylene glycol - - - 100 85 80 polyester diol (cf.

Table IV) - - 100 100 90

Coconut diamine (cf.

Table IX) - 10 15 20 - 15 20 - 10

- * wt .- # amine triol 0 10 15 20 0 15 20 0 0 10

ο wt .-% fluorocarbon no

- ^ fabric 20 20 20 20 20 20 20 20 25 25 \

f »Appearance of the mixture cloudy, cloudy, clear, clear, trtib, cloudy, clear, clear, cloudy, cloudy,? N

Mixing Mixing Mixing Mixing Mixing * Ab- Abr- ^{V / i} *

divisible divisible divorce dung dung 'dung dung

Fluorocarbon
(see Table I) 100 25th 25th 25th 25th 25th 25th 25th 33.3 33 Wt. -96 primary Al
alcohol 0 90 85 80 100 85 80 100 100 90 % By weight amine triol 10 15th 20th 0 15th 20th 0 • 0 10

K) Q OO

Continuation of Table XIII

mixture K L. - ■ » M. N 0 P. Q R. S. T Components (in parts by weight): 85 80 Diethylene glycol
Ethylene glycol 15th 20th - 15th - - 50 50 mm M. Polyester diol (cf.
Table IV) 33.3 40 80 15th 15th _. _ 50 50 Coconut diamine (cf.
Table IX) 85 80 20th 85 85 85 50 50 50 50 Fluorocarbon
(see Table I) 15th 20th 45 900 100 110.5 100 122.2 66.7 81.8 Wt -.% Primary Al
alcohol 80 15th 15th 15th 50 50 50 50 96 wt amine triol 20th 85 85 85 50 50 50 50

O
OJl
O

o wt. -96 fluorocarbons- ^

-J fabric 25 28.6 31 90 50 52.5 50 55 40 45 \

«Ο Appearance of the mixture clear, clear, cloudy, clear, clear, cloudy, clear, cloudy, clear, cloudy, '

mix- mix- mix- mix- mix- mix- mix- dismountable switchable separable separable separation manure manure

to O K) O OO

Claims (16)

Claims . 1. polyol mixture of (1) about 20 to about 85 wt -% (based on the total weight of the mixture) at least one compound of the formulas: fi hE .9 JCH ₂ CHOW-H ^x ; R ₂ -cN < ^x ίγ'γ τν »« 2 ^w " ^v '..ι R ₁ R ₁ II f ¹ ^ NCH ₂ CHOf-H CHOfH · y " III where mean: R is an aliphatic radical having 8 to 18 carbon atoms inclusive; an aliphatic radical having 7 "up to and including 17 carbon atoms; (which can be the same or different) in each case a hydrogen atom or a methyl radical; χ and y each have an average value from about 4 to about 15, inclusive; x ¹ and y ¹ each have an average value from about 1 to about 3, inclusive; 030051/0738 ORIGINAL IiNSfECTED χ ", y" and ζ each have an average value of about 1 up to and including about 5 and η = 2 or 3, and (2) about 15 "to about 80 weight percent of a primary hydroxyl polyol having a molecular weight of about 60 to about 1,000. 2. Mixable polyol mixture of at least about 20% by weight a fluorocarbon blowing agent and the remainder of a polyol blend according to claim 1. 3. Polyol mixture of about 1 to about 6 wt .-% water and from about 94 to about 99 percent by weight of a polyol blend according to claim 1. 4. polyol mixture according to claim 1, characterized in that R ₁ always stands for a hydrogen atom and the component (2) is formed from a primary hydroxyl diol. 5. Polyol mixture according to claim 4, characterized in that component (1) corresponds to formula I and consists of an ethoxylated coconut amine diol mixture obtained by reacting about 15 moles of ethylene oxide with coconut amine consists. 6. polyol mixture according to claim 4, characterized in that the component (1) corresponds to the formula II and from an N, N-bis (8-hydroxy-3,6-dioxaoctyl) cocamide mixture consists. 030051/0738 7. polyol mixture according to claim 4, characterized in that component (1) corresponds to formula III and consists of an amine triol mixture derived from coconut amine, that each component of the amine triol mixture has average values x ", y ^w and ζ of 4.6 and η = 3. 8. polyol mixture according to one of claims 5, 6 or 7, characterized in that the primary hydroxyl diol (2) consists of diethylene glycol. 9. polyol mixture according to one of claims 5, 6 or 7, characterized in that the primary hydroxyl diol (2) consists of a polyoxydiethylene adipate glutarate polyester diol having a molecular weight of about 400 to about. 10. polyol mixture according to one of claims 5, 6 or 7, characterized in that the primary hydroxyl diol (2) consists of a mixture of about 30 to about 50% by weight Diethylene glycol and about 50 to about 70 percent by weight of one Polyoxyethylene adipate glutarate polyester diol having a molecular weight of from about 400 to about 600. 11. Miscible polyol mixture of at least about 20% by weight a fluorocarbon blowing agent and the remainder of a polyol blend according to any one of claims 8, 9 or 10. 12. A polyol blend of about 2 to about 20% by weight of an isocyanate trimerization catalyst and about 80 to about 98% by weight a polyol mixture according to the claims 2 or 3. 030061/0738 13. Process for the production of a cellular polymer with mainly repeating isocyanurate units by trimerization of an organic polyisocyanate in the presence of a minor amount of a polyol, a blowing agent and a trimerization catalyst, characterized in that the following are allowed to react with one another: A. an organic polyisocyanate with B. about 10 to about 120 parts by weight (per equivalent of polyisocyanate) of a mixture of: a) about 2 to about 20 % by weight of a polyisocyanate trimerization catalyst and b) about 80 to about 98 wt. 5K> a mixture of: 1. about 20 to about 80 weight percent of a fluorocarbon propellant and 2. about 20 to about 80% by weight of at least one compound of the formulas: Rl Ri ^ CH ₂ CHOi-H J? ^ CH ₂ CHOi-TH Cf; R ₂ -CN ^ ^x or CHOi-TR ₁ R ₁ II III 03 0051/0738 where mean: R is an aliphatic radical having 8 to 18 carbon atoms inclusive; R _{2 is} an aliphatic radical having 7 to 17 carbon atoms inclusive; R ₁ (which can be the same or different) each represent a hydrogen atom or a methyl radical; χ and y each have an average value from about 1 to about 15 inclusive » x ¹ and y ¹ each have an average value from about 1 to about 3, inclusive; x ", y" and ζ each have an average value from about 1 up to and including about 5 and η = 2 or 3, ^£ with the proviso that the total amount of hydroxy equivalents contained in mixture B is about 0.05 to about 0.5 Equivalent per isocyanate equivalent. 14. Process for the production of a cellular polymer with mainly repeating isocyanurate units by trimerization of an organic polyisocyanate in the presence of a minor amount of a polyol, a blowing agent and a trimerization catalyst, characterized in that the following are allowed to react with one another: A. an organic polyisocyanate with 030051/0738 B. about 10 to about 120 parts by weight (per equivalent Polyisocyanate) a miscible mixture of: a) about 2 to about 20% by weight of a polyisocyanate trimerization catalyst and b) about 80 to about 98 Ge \ r, -% of a mixture of: 1. at least about 20 weight percent of a fluorocarbon propellant and 2. to the rest of a polyol mixture according to claim 4, with the proviso that the total amount of in mixture B contained hydroxyl equivalents is about 0.05 to about 0.5 equivalent per polyiso cyanate equivalent. 15. The method according to claim 14, characterized in that the polyisocyanate is a polymethylene polyphenyl polyisocyanate used. 16. The method according to claim 15, characterized in that there is a mixture of as component B b) 1. at least about 20 weight percent of a fluorocarbon propellant and 2. to the remainder a polyol mixture according to one of claims 8, 9 or 10 used. 030051/0738