CH653692A5 - POLYOL MIXTURE, POLYOL-BLOWING AGENT MIXTURE AND METHOD FOR PRODUCING A CELLED POLYMER. - Google Patents

Description

The present invention relates to a polyol mixture, a polyol blowing agent mixture and a process for producing a cellular polymer, namely a polyisocyanurate foam using the polyol mixture mentioned.

Cellular polyisocyanurates and their use in a wide variety of heat insulation applications are known. It is also known that polyisocyanurate foams are heat and flame resistant (cf. US Pat. Nos. 3,745,133,3,986,991 and 4,003,859). To modify the foam properties, minor amounts of polyols are sometimes incorporated into the constituents of the foam. If fluorocarbon blowing agents are used, the potential problem of an incompatibility between the polyol, especially a primary hydroxyl polyol, and the fluorocarbon in the premix can usually be solved by adding most or all of the fluorine5

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carbon premixed with the polyisocyanate (see the specified US-PS).

Polyisocyanurate foams are used in particular in the production of composite structures made of foam and sheet-like or plate-like structures using a wide variety of visible materials. Difficulties that can arise in the production of such composite structures are 1. the lack of a uniform foam core strength, 2. poor adhesion between the foam core and the visible material, 3. the retention of good fire resistance of the foam and 4. the difficulty of largely reshaping the foam to protect against becoming crumbly. These difficulties have so far been solved by using minor amounts of low equivalent weight polyols, in particular diols, in the formulation and heating the finished composite structure in an oven to a temperature of 710 to 88 ° C (cf. US Pat. No. 3,903 346).

The low equivalent weight polyols, especially the preferred primary diols containing only primary hydroxyl groups (see column 4, lines 59 to 61 of US Pat. No. 3,903,346) cannot be (component) previously mixed as component B with the fluorocarbon blowing agent because the diol / fluorocarbon pair has only a low solubility. This requires (pre-) mixing the fluorocarbon with the polyisocyanate in component A. Because of the lack of miscibility in 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 of US Pat. No. 3,903,346).

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

Surprisingly, it has been found that large amounts of fluorocarbon blowing agents with low molecular weight polyols containing primary hydroxyl groups are completely miscible when new mixtures with certain types of amine or amide diols or amine triols with the primary hydroxyl polyols are 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 mixable and primary hydroxyl group-containing mixtures can be obtained by replacing the fluorocarbon component with water.

Finally, it has been shown that the new polyol mixtures are used in minor amounts as component 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 component, namely components A and B. Procedure can be used.

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

In the most unexpected way, the presence of the amide or amine diol or amine triol in component B ensures excellent (reactant) compatibility between the polyisocyanate and the other constituents. This leads to a faster reaction than with known foam formulations and to a very good heat of reaction release, i.e. for a very good exothermic reaction. The high reaction heat release is of particular advantage in the production of composite foam structures, since excellent adhesion between the foam and the visible material is achieved in this way without the composite structure having to be heated in an oven.

The invention relates to a polyol mixture of 20 to 85% by weight, based on the total mixture of (a) and (b), of io (a) at least one polyol from the polyol class which consists of the amine diols of the formula I.

Ri

, (CH2CHO) x -H ■ (CHJCHOVH

I.

Ri

15

r-n:

(i)

20th

25th

O

R2-C-N;

the amide diols of the formula II Ri

I.

(CH2CHO) x-H ^ (CH2CHO) y-H

I.

Ri and the amine triols of formula III

Ri

(II)

35

R-N;

40

, (CHRi) n-N:

- (CH2CHO) z-H

I.

Ri

(CH2CHO) X »-H (CH2CHOV-H Ri

(III)

exists, in these formulas

R is an aliphatic radical with 8 to 18 carbon atoms, R2 is an aliphatic radical with 7 to 17 carbon atoms, 45 and the symbols

Ri independently of one another each represent a hydrogen atom or a methyl radical,

x and y each have an average value of 4 to 15,

x 'and y' each have an average value of 1 to 3 and 50 x "and y" and z each have an average value of 1 to 5, and n = 2 or 3, and 80 to 15% by weight of (b) is not Polyol IV belonging to the polyol class mentioned under (a) with primary hydroxyl in the molecule and with a molecular weight of 60 to 1000.

The invention further relates to a polyol blowing agent mixture which consists of at least 20% by weight of a fluorocarbon blowing agent or 1 to 6% by weight of water as blowing agent and the remainder of the polyol mixture according to the invention and one clear solution is.

The process for the production of a cellular polymer with repeating isocyanurate units by trimerization of organic polyisocyanate in the presence of polyol, a blowing agent and a trimerization catalyst is characterized in that it is allowed to react with one another:

A. organic polyisocyanate and

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B. 10 to 120 grams per gram equivalent of component A of a mixture of:

(Bi) 2 to 20% by weight of a polyisocyanate trimerization catalyst and

(B2) 98 to 80% by weight of a mixture of:

(B21) 20 to 80% by weight of a fluorocarbon blowing agent or 1 to 6% by weight of water as a blowing agent and

(B22) 80 to 20% by weight of the polyol mixture according to the invention if the blowing agent is a fluorocarbon blowing agent or 99 to 94% by weight of the polyol mixture according to the invention if the blowing agent is water, the total amount of mixture B contained Hydroxyl equivalents are in the range of 0.05 to 0.5 equivalents per isocyanate equivalent.

An "aliphatic radical" R is preferably an alkyl or alkenyl radical having 8 to 18 carbon atoms, e.g. an octyl, decyl, dodecyl, tetradecyl, hexydecyl or octadecyl radical or an isomeric radical therefor to be understood.

An "aliphatic radical" R2 is in particular an alkyl or alkenyl radical with 7 to 17 carbon atoms, e.g. a heptyl or heptenyl radical to a heptadecyl or heptadecenyl radical or an isomeric radical therefor.

Polyurethane foams are known, as is their use for heat and sound insulation in industrial and residential buildings.

As already mentioned, the polyol mixtures are used in particular as subordinate constituents in the production of polyisocyanurate foams, in particular those polyisocyanurate foams such as are produced with the aid of spray foam systems in machines producing foam composite structures. Such foams are known for their heat and fire resistance. They are used in particular for the production of plate-shaped composite structures and foam blocks, which are used in the construction sector for heat and sound insulation.

The polyol mixtures according to the invention can be obtained by simply mixing the amine diol (I), amide diol

(II) and / or amine triols (III) and a primary hydroxyl polyol (IV) in the stated amounts by weight in a suitable mixing vessel, storage tank and the like. The components (I), (II) and / or are preferably obtained

(III) in an amount of 25 to 60% by weight of the mixture. The primary hydroxyl polyol IV is usually used in an amount of 40 to 75% by weight.

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

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

A preferred amide diol is one of the formula II in which both R 1 are hydrogen atoms and x 'and y' each have an average value of 2 to 3.

A preferred amine triol is one of the formula III in which all the radicals R 1 are hydrogen atoms, x ", y" and z each have an average value of 3 to 5 and n = 3.

The amine diols of the formula I can be obtained in a conventional manner. Some are also commercially available. Typically, the amine diols of formula I are obtained e.g. by reacting a suitable dialkanolamine with a suitable aliphatic halide of the formula RX or a mixture of different compounds RX, the aliphatic radical (s) (R) falling under the definition given and X being a halogen atom, preferably a chlorine atom, or bromine atom.

If the desired number of alkyleneoxy groups is not present in the dialkanolamine before the reaction with the aliphatic halide, they can be introduced subsequently without difficulty by reacting the alkylated dialkanolamine with a suitable number of moles of ethylene and / or propylene oxide , whereby the amine diols of formula I are obtained.

The amine diols of the formula I 10 are preferably obtained by reacting a suitable primary fatty amine R-NH 2 or a mixture of fatty amines, all of the radicals R falling under the definition given, with 8 to 30, preferably 10 to 20, moles of ethylene or propylene oxide per mole fraction Fatty amine (see Bulletin 1294 "Ethoxy-ls lated Fatty Amines", Ashland Chemical Company, Division of Ashland Oil Inc., Box 2219, Columbus, Ohio 43216, for a detailed teaching on the preparation of the amine diols in question).

Examples of suitable starting fatty amines are octylamine, 20 decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and their isomers. Examples of suitable alkenylamines are octenylamine, decenylamine, dodecenylamine, tetradecenylamine, hexadecenylamine, octadecenylamine and their isomers. Examples of other suitable fatty 25 amines are mixtures of alkyl and alkenyl amines, e.g. Coconut amine consisting of a mixture of the following listed ingredients in approximate percentages: 2% decylamine, 53% dodecylamine, 24% tetradecylamine, 11% hexadecylamine, 5% octadecylamine and 5% octa-30 decenylamine; Soyamine, which consists of the following components in the approximate proportions: 11.5% hexadecylamine, 4% octadecylamine, 24.5% oleylamine, 53% linoleylamine and 7% linolenylamine; and tallow amine, which consists of the following components in the approximate proportions 35. 4% tetradecylamine, 29% hexadecylamine, 20% octadecylamine and 47% octadecenylamine. Further examples of suitable starting fatty amines are halogenated fatty amines, in particular the chlorinated and brominated fatty amines, which are obtained, for example, by chlorinating or brominating 40 coconut amine, soy amine, tallow amine and the like.

A particularly preferred group of fatty amines includes coconut amine blends, soy amine blends and taigamine blends, especially coconut amine.

The amide diols of the formula II can be obtained in a conventional manner known in the art. Typically they are obtained e.g. by reacting a suitable dialkanolamine with a suitable fatty acid, a suitable fatty acid ester or a suitable fatty acid chloride according to the equation:

50

Ri

^ (CH2CHO) x -H R2COR3 + HNC ^ - II + HR3

55 \ (CH2CHO) y-H

Ri wherein R2, Ri, x 'and y' have the meaning given 60 and R3 for -OH, -OR4 or X with R4 being a typical esterifying group, e.g. a short chain alkyl group, an aryl group, a cycloalkyl group and the like, and X is a halogen atom, preferably a chlorine or bromine atom. In the event that 65 diethanolamine and / or diisopropanolamine is (are) used as the starting dialkanolamine and amide diols with an average value for x 'and y' of over 1 are to be prepared, the dialkanolamide intermediate can easily be obtained in one molar form

5

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Quantity with 1 to 4 mol (s) of ethylene and / or propylene oxide are reacted (see Bulletin 1295 "Varamide Alkanol Amides", Ashland Chemical Company, Division of Ashland Oil, Inc., Box 2219, Columbus, Ohio 43216 for a detailed teaching on the production of fatty acid dialkanol amides).

The amide diols of the formula II are preferably obtained by converting the fatty acids to the corresponding fatty acid amides (R2CONH2) and reacting the respective amide with 2 to 6 moles (per mole of amide) of ethylene and / or propylene oxide.

Examples of starting fatty acids (from which the corresponding esters, acid halides and amides originate) are caprylic, capric, lauric, myristic, palmitic or stearic acid and their isomers. Examples of unsaturated fatty acids are decylene, dodecylene, pamitolic, oleic or linoleic acid and their 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, 3% linolenic acid) and fatty acid mixtures from 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, in particular chlorinated and brominated fatty acids, which can be obtained, for example, by chlorination or bromination of coconut, soybean and tallow fatty acid mixtures.

A particularly preferred group of starting fatty acids and fatty acid amide intermediates consists of the coconut, soybean and tallow oil mixtures described and the corresponding coconut amide, soy amide and tallow amide mixtures, in particular coconut oil mixtures and the corresponding coconut amide mixtures.

Preferred amide diols of the formula II are coconut amide, soy amide and tallow amide diol mixtures, in which all 15 radicals R 1 are hydrogen atoms and x 'and y' both have a value of 3. A particularly preferred amide diol is a coconut amide diol mixture which can be referred to as an N, N-bis (8-hydroxy-3,6-dioxaoctyl) coco amide mixture.

20 The amine triols of the formula III can be obtained in a conventional manner without difficulty. Some amine triols are also commercially available.

Generally speaking, the type of production of aminetriols with n = 2 differs somewhat from the production of aminetriols with n = 3. The former aminetriols can be obtained without difficulty using the following equation:

RNH2 + CHRi-CHRi O

(NHs)

RNHCHR ^ HRJOH - RNHCHR1CHR1NH2 (V) (VI)

^ (Ethylene oxide and / or propylene oxide

In the equation, R and Ri have the meaning given. The starting amine is e.g. reacted with an equimolar amount of ethylene or propylene oxide to give an amino alcohol (V). The latter is typically converted to diamine VI by reaction with ammonia.

Then a molar amount of VI can be reacted with about 3 to 15 molar parts of ethylene and / or propylene oxide, giving the amine triol of the formula III.

Amine triols with n = 3 can typically be obtained using the following equation:

RNH2 + RiCH = CRiCN (VII)

RNHCHR1CHR1-CN (VIII)

(IH) ^

(H)

RNHCHRiC HR1CH2NH2 (IX)

Ethylene oxide and / or propylene oxide

In the equation, R and Ri have the meaning given. The starting amine is e.g. cyanoethylated with a suitably substituted acrylonitrile of formula VII to a compound of formula VIII. The latter can be reduced to the diamine of formula IX. This is usually followed by alkoxylation with 3 to 15 molar proportions of ethylene and / or propylene oxide, a compound of the formula III being obtained.

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

Examples of acrylonitrile compounds which can be used in the preparation of the amine triols which can be used are acrylonitrile, α-methacrylonitrile, β-methacrylonitrile and α, β-dimethacrylonitrile, in particular acrylonitrile.

A preferred group of aminetriols of the formula III are amine triol mixtures derived from coconut amine, soy amine and taigamine mixtures, in which all the radicals R 1 are hydrogen atoms, n = 3 and x ", y" and z each correspond to 3 to 5. A particularly preferred amine triol mixture

50 originates from coconut amine, with all the residues Ri representing hydrogen atoms, n = 3 and x ", y" and z each representing approximately 4.6.

The primary hydroxyl polyol IV can consist of any primary hydroxyl polyol with a molecular weight 55 of 60 to 1000, suitably from 60 to 800, preferably from 60 to 600. Examples of the polyols of the formula IV are diols, triols and tetrols, in particular diols.

Usable primary hydroxyl-containing 60 polyols are also the primary hydroxyl-containing diols, triols and tetrols known from US Pat. No. 3,745,133, provided that they have molecular weights within the stated molecular weight limits. Preferred are the polyester polyols which are obtained from dibasic car-65 acids and polyhydric alcohols, including those based on 1,4,5,6,7,7-hexachloro- (2,2,1) -5-hepten-2, 3-dicarboxylic acid anhydride, alkylene diols, alkoxy alkylene diols, polyalkylene ester diols, polyoxyalkylene ester

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diols, hydroxyalkylated aliphatic monoamines or diamines, resol polyols (see “Prep. Methods of Polymer Chemistry”, published by WR Sorenson and co-workers, 1961, page 293, Interscience Publishers, New York, NY) and polybutadiene resins with primary hydroxyl groups (see “ Poly Bd Liquid Resins », Product Bulletin BD-3, October 1974, Arco Chemical Company, Div. Of Atlantic Richfield, New York, NY).

The alkylene diols, short-chain alkoxy-alkylene diols, polyalkylene ester diols and polyoxyalkylene ester diols are preferred.

Preferred polyols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, polyoxyethylene glycols obtained by adding ethylene oxide to water, ethylene glycol or diethylene glycol and the like, which provide triethylene glycol, tetraethylene glycol, and higher glycol Mixtures thereof with molecular weights within the specified range, ethoxylated glycerol, 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. Hydroxyl-terminated polyesters, polyoxydiethyl succinate, polyoxydiethylene glutarate, polyoxydiethylene adipate, polyoxydiethylene adipate glutarate and the like, diethanolamine, triethanolamine, N, N'-bis (β-hydroxyethyl) aniline and the like.

The preferred diols are diethylene glycol and the polyoxydiethylene adipate glutarate polyester diols having a molecular weight of 400 to 600.

Mixtures of 30 to 50% by weight of diethylene glycol with 50 to 70% by weight of polyoxydiethylene adi-patglutarate polyester diol having a molecular weight of 400 to 600 are particularly preferred.

If the blowing agent e.g. consists of a fluorocarbon, the unexpected and advantageous features of the polyol mixtures I, II and / or III with IV come into their own. Mixable polyol mixtures with at least 20% by weight of a fluorocarbon blowing agent and a (blowing agent-free) polyol mixture can be produced as the remainder. The percentage of fluorocarbon to be dissolved in the mixture in each case determines the ratio of IV on the one hand and I, II and / or III on the other. These proportions (within the specified range) can be easily determined by simple preliminary tests.

Miscible polyol mixtures with more than 50% by weight of fluorocarbon and even up to 90% by weight of fluorocarbon can be obtained without difficulty with the polyol mixtures according to the invention containing the individual components in the stated amounts without difficulty if the mixture components are selected appropriately. Generally speaking, as the molecular weight of the primary hydroxyl polyol IV decreases, the amount of fluorocarbon soluble in the mixture for a given amount of polyol I, II and / or III increases (compared to a mixture with a higher molecular weight polyol IV at the same proportion). In this connection, it should be pointed out that the alkylene diols and short-chain alkoxyalkylene diols with molecular weights of less than 400 (in particular the latter) are the preferred polyols of the formula IV.

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

Generally speaking, when an amine diol of the formula I is used together with a polyol of the formula IV, miscible polyol mixtures with at least 25% by weight to at least 65% by weight of a fluorocarbon blowing agent and correspondingly from 75% by weight to 35% by weight are obtained. Mixture of I and IV.

If e.g. an amide diol of formula II is combined with the polyol of formula IV, miscible polyol mixtures with at least 20 wt.% to at least 60 wt.% of a fluorocarbon blowing agent and correspondingly 80 wt.% to 40 wt.% polyol mixture of II and IV receive.

If a e.g. If aminetriol of the formula III is combined with a polyol of the formula IV, miscible polyol mixtures with at least 20% by weight to at least 50% by weight of a fluorocarbon blowing agent and correspondingly 80% by weight to 50% by weight polyol mixture of III and IV can be obtained .

If water is used as the blowing agent, its amount is 1 to 6, preferably 2 to 5,% by weight. The rest, namely 94 to 99, preferably 95 to 98%, then consists of I, II and / or III and IV.

Any fluorocarbon propellant suitable for the person skilled in the art to propel mixtures to be polymerized into cellular polymers can be used as the fluorocarbon propellant. As a rule, these blowing agents are halogenated aliphatic hydrocarbons which, apart from fluorine, can also be substituted by chlorine and / or bromine (cf. US Pat. No. 3,745,133, column 11, lines 25 to 38).

In the polyol mixture which is used in the production of polyisocyanurate foams, the mixture of blowing agent and constituents I, II and / or III and IV additionally contains an isocyanate trimerization catalyst. The relevant isocyanate trimerization catalysts will be described in more detail later. The amount of isocyanate trimerization catalyst is 2 to 20, preferably 2 to 15,% by weight. The rest, namely 80 to 98, preferably 85 to 98%, consists of the above-mentioned components.

Surprisingly, the blowing agent and the polyol mixture with primary hydroxyl-containing polyols are completely miscible with one another without separation during storage. This miscibility is due to the presence of amine diol I, amide diol II and / or amine triols III. In addition to the advantages of a stable, miscible mixture of a primary hydroxyl group-containing polyol and a fluorocarbon or water, the production of polyisocyanurate foams also has the beneficial effects attributable to the presence of nitrogen-containing diols or triols in minor amounts.

Other additives can also be incorporated into the polyol mixtures without impairing their miscibility and stability. Such additives are other useful polyol components, e.g. polyols containing secondary hydroxyl groups, dispersants, cell stabilizers, surface-active agents, flame retardants and the like, as are customarily used in the production of polyisocyanurate foam.

Component (mixture) B is used in an amount of 10 to 120, advantageously 10 to 80, preferably 20 to 60 grams per gram equivalent of polyisocyanate. It applies that the total number of hydroxyl equivalents contained in component (mixture) B per equivalent of polyisocyanate is 0.05 to 0.5, preferably 0.08 to 0.4 equivalent.

6

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The presence in mixture B of a minor amount of the primary hydroxyl-containing polyol IV not only leads to a stabilized, miscible mixture of the type described, it also provides optimal properties of polyisocyanurate foams. Such a mixture can be used to produce composite foam structures which do not require any heating in the oven to bring about maximum foam strength and adhesion to the composite surface.

All catalysts known to the person skilled in the art for catalyzing a trimerization of organic isocyanates to form the isocyanurate unit are suitable as trimerization catalysts. Optionally, urethane-forming catalysts can also 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 Pat. Nos. 3,745 133,3 896 052.3 899 443.3 903 018.3 954 684 and 4101465.

Preferred catalysts are described in U.S. Patent Nos. 3,896,052 and 4101,465. From US Pat. No. 3,896,052, 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. From US Pat. No. 4,101,465, catalyst combinations of the constituents (a) and (b) mentioned and a hydroxyalkyltrialkylammonium carboxylate salt component are known.

In the production of polyisocyanurate foams, organic polyisocyanates customarily used hitherto for this purpose can be used as organic polyisocyanates. Expediently and for the production of foams having excellent heat resistance and structural strength, the polyisocyanates used are preferably polymethylene polyphenyl polyisocyanates, in particular the polymethylene polyphenyl polyisocyanates known from US Pat. No. 3,745,133. Poly-methylene polyphenyl polyisocyanates which have been reacted with a minor amount of an epoxy compound in accordance with US Pat. No. 3,793,362 to reduce acidic impurities are also preferred. Further preferred polymethylene polyphenyl polyisocyanates are those which have high levels of the 2,4'-isomer (cf. US Pat. No. 3,362,979).

Another particularly preferred organic polyisocyanate consists of a mixture of 30 to 85% by weight of methylenebis (phenyl isocyanate) and the remainder polymethylene polyphenyl polyisocyanates with a functionality of more than 2.0.

In the production of polyisocyanurate foams, in particular those for the production of composite foam structures, customary measures and systems can be used (cf. the aforementioned US Pat.). For detailed information on the production and use of polyisocyanurate foam composites, cf. U.S. Patent 3,896,052.

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

Example 1

The five polyisocyanurate foams designated with foams A to E in Table I are produced by the process described below.

Foam formulations are prepared by mixing components A and B by hand. The polyisocyanate constituent as the only constituent of component A and the constituents of component B listed in Table I are premixed and observed before they are reacted with the polyisocyanate. The mixing process is carried out by thoroughly mixing components A and B in a beaker using a high-speed drill 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).

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

With foam E, maximum foam properties can be determined with regard to a combination of maximum reaction heat release with rapid solidification 40 and low core and surface friability.

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

Table I

Foams A B C D E

Comparison according to the invention Comparison comparison according to the invention

Components (in parts by weight):

Component A:

Polyisocyanate I1 100 100 100 100 100

Component B:

Diethylene glycol 5.7 5.4 6 6 8

Soybean amine adduct2 5.7 - 6 6

Cocosamine adduct3 - 23.5 8

propoxylated glycerin product4 5.7 -

propoxylated pentaerythritol product5 6

Tris (dichloropropyl phosphate) - 7.2 18 18

propoxylated polyol6 6

Silicone wetting agent7 1.25 1.25 1.25 1.25 1.25

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Table I (continued)

Foams

A B C D E

Comparison according to the invention Comparison comparison according to the invention

Fluorocarbon8 catalyst I9

NCO / OH index

Appearance of component B

Heat of reaction released during foam formation

Become solid

Core fragility

Friability of the surface

Tarnishing the surface

25th

about 4

25 3

about 4

25 3

about 4

25 3

about 4

25 3

about 4

clear and not clear and not clear and not clear and not clear and not cloudy cloudy 170.6 ° C

quickly rapidly missing cloudy 156.1 ° C

slowly low missing yes cloudy 145.6 ° C

medium strong missing cloudy 147.8 ° C

quickly missing quickly

173.9 ° C

quickly missing is missing

Polymethylene polyphenyl polyisocyanate with about 45% by weight methylene bis (phenyl isocyanate) and about 55% by weight polymethylene polyphenyl polyisocyanates with a functionality of more than 2 (isocyanate equivalent: 133);

2 soy amine adduct obtained by reacting 2 molar parts of ethylene oxide with soy amine (amine equivalent weight: about 360: hydroxyl equivalent weight: about 180):

3 cocosamine adduct obtained by reacting about 15 molar parts of ethylene oxide with cocosamine (amine equivalent weight: about 885; hydroxyl equivalent weight: about 442);

4 propoxylated glycerol product with a hydroxyl equivalent weight of 243:

5 propoxylated pentaerythritol product with a hydroxyl equivalent weight of 148:

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

7 silicone wetting agents for the production of rigid foams with a hydroxyl number of about 119;

s Monofluorotrichloromethane blowing agent stabilized with Alloocimene;

"Catalyst combination of A) 1 part by weight of a solution of (a) 45% by weight of potassium N-phenyl-2-ethylhexamide, (b) 27% of ethylene glycol and (c) 28% of dimethylformamide; B) 3 parts of a solution 50% by weight of 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 one Polyethylene glycol with a molecular weight of 200.

Example 2

According to Example 1, foams F to I are produced. A comparison of the foam rise times is made in the. Foams F and H are foams F and G or H and I show that these comparative foams, foams G and I are (foams G and I) are much faster than foams according to the invention. 40 equal foams F and H. The clear speed-The components of components A and B are found in increased speed shows the increased compatibility of the compoders following Table II. In the production of foams A and B, which leads to a better implementation of the two substances F and G a different polyisocyanate is used than leads components. This better implementation results in the production of foams H and I. Compared to the known recipe for foams F and H, the component contains 45 doors. That in the production of the foam-A, as usual, the fluorocarbon blowing agent. If the ethoxylated amine used for the substances G and I consists of determining the miscibility, the same amount of fluorocarbon- a tertiary amine. These types of high molecular weight tertiary lenstoff is mixed into the component B, separates amines are not strong bases and are (in the manufacturer - in both cases the fluorocarbon from the other lung of the foams G and I) in a very small amount, components, namely the Diethylene glycol, the wetting agent so based on amine equivalent (namely in an amount of and the catalyst. 0.009 equivalent in each case) is used. This minor

In the production of foams G and I the amount of weak amine would not be sufficient

Component B contain the ethoxylated coconut amine. In a clear (increase in foam) speed in this case, the fluorocarbon and the others in the production of the foams G and I compared to the components with the diethylene glycol component are completely miscible only on the basis of the production of the foams F and H. explain the amine catalysis.

Table II

Foams F G H I

Comparison according to the invention Comparison according to the invention

Components (in parts by weight): Component A:

Polyisocyanate I1 polyisocyanate II2 fluorocarbon according to Table I

100

21.5

100

105 22.5

105

9 653 692

Table II (continued)

Foams

F

G

H

1

Comparison according to the invention

Comparison according to the invention

Component B:

Diethylene glycol

8.3

8.0

8.3

8.0

Coconut amine adduct (see Table I)

-

8.0

-

8.0

Silicone wetting agents (see Table I)

1.25

1.25

1.25

1.25

Catalyst I (see Table I)

3.0

3.0

3.0

3.0

Fluorocarbon (see Table I)

-

23

-

24th

NCO / OH index

4.6

4.2

4.6

4.2

Foam rise time (in s)

Cream time

75

19th

59

21st

Gel time

104

42

96

41

Time to lose stickiness

116

49

106

47

Heat of reaction released during foam formation

171.7 ° C

168.9 ° C

158.9 ° C

157.8 ° C

Core density (g / cm3)

0.0282

0.0279

0.0287

0.0280

Dry aging when heated to a temperature of

148.9 ° C / 24h

% À volume

+4.6

+ 4.1

+ 2.9

+2.4

Core fragility,% 3

31

30th

22

19th

Fragility of the surface missing missing missing missing

Tarnishing the surface yes yes yes yes

1 cf. Footnote 1, Table I;

2 polymethylene polyphenyl polyisocyanate with about 35% by weight methylene bis (phenyl isocyanate) and about 65% by weight polymethylene polyphenyl polyisocyanate with a functionality of more than 2 (isocyanate equivalent: 140);

J The friability is the percentage weight loss of the test specimen over 10 minutes, determined according to the US standard ASTM C-421.

Example 3 The foam increase parameters are very fast, whereby

According to Example 1, using in particular in spite of the use of water as a propellant

the following table III ingredients in the medium the foams very quickly lose their stickiness,

specified amounts of weight two according to the invention. Furthermore, high heat-driven polyisocyanurate foams L and 40 release values can also be found during foam formation, indicating excellent results

M manufactured. In both cases, component B indicates conversions. The physical properties are clear, miscible mixtures. The foams formed are good.

Table III

Foams L M

Components (in parts by weight):

Component A:

Polyisocyanate (see Table IV) 135 135 Component B:

Polyol mixture I1 23 30

Silicone wetting agents (see Table I) 2 2

H2O 1 1

Catalyst (see Table IV) 3 3

NCO / OH index (including h2o) 3 2.5

Appearance of component B clearly clear

Foam rise time (in s)

Cream time 15 13

Gel time 31 26

Rise time 48 48

Time to lose stickiness 35 30

Heat of reaction released during foam formation 191.1 ° C 195.0 ° C

Density (g / cm3) 0.0425 0.0450

653692

II)

Table III (continued)

Foams

M

K-factor2 in kilowatts (h)

in the parallel direction in the vertical direction

Compressive strength in Pa-103 parallel to the ascending direction perpendicular to the ascending direction

% A volume at 70 ° C, 100% relative humidity after 24 h

Dry aging at 148.9 ° C,% À volume after 24 h

0.00005567 0.000055377

272.63 206.93

-7.7

-2.9

0.000058893 0.000056549

289.31 138.28

-4.7

+ 3.0

Mixture of A) 40.8 parts of a polyoxydiethylene adipate glutarate polyester diol having a molecular weight of 500, B) 28.6 parts of diethylene glycol and C) 30.6 parts of the cocoamine adduct from Table I;

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

Example 4

According to Example 1, a polyisocyanurate foam N according to the invention is produced by mixing by hand using the constituents given in Table V.

20 triol containing hydroxyl groups and diethylene glycol with 41% by weight fluorocarbon. Nevertheless, the mixture remains clear without becoming cloudy.

The foam shows good rise times. A high level of reaction heat is released during foam production.

Component B contains a mixture of a primary zs. The foam shows good solubility properties.

Table IV

Foam N (according to the invention)

Components (in parts by weight):

Component A:

Polyisocyanate 2

Component B:

trifunctional polyethylene glycol containing primary hydroxyl groups1 diethylene glycol

Coconut amine adduct (see Table I)

commercially available silicone wetting agent catalyst 3

Fluorocarbon (see Table I)

Appearance of component B

% Fluorocarbon in component B

Foam rise time (in s)

Cream time gel time

Time to lose stickiness

Heat of reaction released during foam formation. Surface friability. Toughening of the surface. Core friability

135

8.5 6.5 10 1.25 3.0 20

clear, without cloudiness 41

13 30 35

176, FC

little is missing

'trifunctional polyethylene glycol containing primary hydroxyl groups and having a hydroxyl equivalent weight of 333; 2 polymethylene polyphenyl polisocyanate with about 45% by weight methylene bis (phenyl isocyanate) and about 55% by weight polymethylene polyphenyl

polyisocyanate with a functionality of more than 2 (isocyanate equivalent: 135);

1 catalyst combination of the following components:

A) 1 part by weight of a 50% by weight solution of sodium N- (2-hydroxy-5-nonylphenyl) methyl-N-methylglycinate in diethylene glycol;

B) 0.50 part of potassium acetate;

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 cocosamine adduct of Example 1 are cloudy and cloudy.

Example 5

Using the foam O produced from the components in Table V below, high-temperature and flame-resistant polyisocyanurate foam composite structures are produced.

To produce the composite structures, 65 a commercially available laminating device is used. The temperatures of components A and B are 22.8 ° and 21.1 ° C, respectively. The throughput through a low-pressure impact mixing head is 6.8 kg / min. Operated instead of a holding roller

you look at a casting tray technique. 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 are made from a 0.038 mm thick aluminum foil or from asphalt. The foam properties given in Table V refer to the foam core material after removal of the visible materials. As a result, the face material as such does not affect the foam properties. The adhesion between the visible material and the foam is excellent.

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

11 653 692

The composites are made without the need to oven cure at high temperature due to the quick reactivity of the formulation. The rapid reactivity is also reflected in the rapid rise profile and the fact that the friability of the foam is very low despite the lack of curing at high temperatures. Furthermore, as already stated, good adhesion of the visible material to the foam can be determined.

10th

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

Table V

Foam O (according to the invention)

Components (in parts by weight):

Component A:

Polyisocyanate (see Table I)

133

Component B:

Polyester diol 1

9

Diethylene glycol

6.3

Coconut amine adduct (see Table I)

6.7

commercially available silicone wetting agent

1.25

Catalyst (see Table IV)

3.0

Fluorocarbon (see Table I)

20.0

Appearance of component B

% Fluorocarbon in component B

NCO / OH index

Foam rise time (in s)

Cream time gel time

Time to lose stickiness

Friability of the surface

Tarnishing the surface

Core fragility

Total density (in g / cm3)

Core density (in g / cm3)

Compressive strength (in Pa-103)

Cells closed parallel to the ascending direction perpendicular to the ascending direction2

K factor (in kilowatts • h)

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

A volume after 1 day after 7 days after 28 days

ASTM-E-84 test with 5.1 cm thick test specimens:

Assessment of flame spread smoke clear, without turbidity 43 4.9

19 40 47

little is missing (6%)

0.0320 0.0288

213.79 145.16

94%

0.00004102

+ 6% + 6.5% + 7.0%

38 187

'Polyesterdiol according to footnote 1 of Table III under A);

3 The proportion of closed cells is determined using an air pycnometer in accordance with the US standard ASTM D-2856.

653692

12

Example 6

Polyisocyanurate foams Q and R and a comparative foam S are produced in accordance with Example 1 using the constituents given in Table VI.

In the case of the production of foams Q and R, component B is clear despite the mixing of the hydrocarbon with the components containing primary hydroxyl groups and shows no signs of cloudiness.

Component A used in the production of the comparative foam S contains, as usual, the fluorocarbon blowing agent. If the same amount of fluorocarbon is incorporated to determine component B's miscibility, the fluorocarbon separates from the other ingredients, namely diethylene glycol, surfactant and catalyst. 5 A comparison of the foam rise times of the foams Q and R on the one hand and the comparison foam S on the other hand shows that in the former cases (Q and R) it is far faster than in the latter case (S). The significant increase in speed clearly shows the improved compatibility of io 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 VI

Foams

Q R

according to the invention

S

comparison

Components (in parts by weight): Component A:

Polyisocyanate

-

135

-

Polyisocyanate (see Table I)

100

-

100

Fluorocarbon (see Table I)

-

-

21.5

Component B:

Polyester diol 1

-

9

-

Diethylene glycol

8th

6.3

8.3

Coconut amide adduct (see Table V)

8th

6.7

-

Silicone wetting agents (see Table I)

1.25

-

1.25

commercially available silicone wetting agent

-

2nd

-

Fluorocarbon (see Table I)

25th

22

-

Catalyst (see Table IV)

4.5

5

-

Catalyst (see Table I)

-

-

3.0

NCO / OH index about 4

about 4

about 4.6

Appearance of component B

clear, without clear, without

-

Cloudiness

Cloudiness

Foam rise time (in s)

Cream time

16

16

75

Gel time

40

35

104

Time to lose stickiness

45

40

116

rise

54

48

-

Heat of reaction released during foam formation

173.3 ° C

177.2 ° C

171.7 ° C

Duration of solidification quickly quickly

-

The surface lacks brittleness

-

Tarnishing the surface yes yes

-

Core density (in g / cm3)

0.0248

0.0330

0.0282

Core fragility (%)

38.5

32.0

31

Dry aging at 148.9 ° C, A volume% / 24 h

+ 7.4

+ 5.0

+ 4.6

Polyoxydiethylene adipate glutarate polyester diol with a molecular weight of 500 and an OH number of 211.5.

Example 7

According to Example 1, using the constituents given in Table VII, two polyisocyanurate foams U and V and a comparative foam W are produced in accordance with the invention.

The components B used in the production of the foams U and V are clear despite the combination of the fluorocarbon with the components containing primary hydroxyl groups and show no signs of cloudiness.

In the case of the production of the comparative foam W, component A contains, as usual, the fluorocarbon

Propellant. If the same amount of fluorocarbon is incorporated to determine component B's miscibility, the fluorocarbon will separate from the other ingredients, namely diethylene glycol, surfactant, and catalyst.

A comparison of the foam rise times in the production of foams U and V on the one hand and W on the other hand shows that it is far faster in the former case than in the latter case. The significant increase in speed clearly shows the increased compatibility of components A and B for 6 seconds, which leads to a better reaction between the two and consequently to a faster rise time compared to the prior art.

13

Table VII

653692

Foams

U V

according to the invention

W

comparison

1.25

25 2.5

9

6.3 6.7

2nd

22 2.5

Components (in parts by weight):

Component A:

Polyisocyanate - 135

Polyisocyanate (see table!) 100

Fluorocarbon (see Table I)

Component B:

Polyesterdiol1 diethylene glycol ethoxylated mixture2 silicone wetting agent (see Table I)

commercially available fluorocarbon silicone wetting agent (see Table I)

Catalyst (see Table IV)

Catalyst (see Table I)

NCO / OH index

Appearance of component B

Foam rise time (in s)

Cream time 16 15

Gel time 39 42

Time to lose stickiness 46 50

Ascent 56 60

Heat of reaction released during foam formation 166.1 ° C 169.4 ° C

Time to solidify quickly quickly

The surface lacks brittleness

Tarnishing the surface yes yes

Core density (in g / cm3) 0.0268 0.0364

Fragility of the core (in%) 18.8 33.1

Dry aging at a temperature of 148.9 ° C, А volume% / 24 h + 10.8 + 5.3

about 4 about 4

clear, not cloudy clear, not cloudy

100 21.5

8.3 1.25

3.0 about 4.6

75 104 116

171.7 ° C

0.0282 31 + 4.6

1 polyoxydiethylene adipate glutarate polyester diol having a molecular weight of 500 and an OH number of 211.5;

2 ethoxylated mixture obtained by reacting ethylene oxide with coconut diamine in molar amounts of about 14: 1, the coconut diamine being obtained by reacting coconut amine with an equivalent of acrylonitrile and reducing the cyanoethylated coconut amine mixture to coconut diamine (amine equivalent weight: 290; OH equivalent weight: 193).

Example 8

A series of mixtures of monofluorotrichloromethane and two typical polyols containing primary hydroxyl groups are prepared. The amounts by weight used, including the amount of amine diol of the formula I, if any, are varied in accordance with Table VIII. The mixtures are examined for their mixing ability, their clarity or their turbidity and the deposition of the fluorocarbon from the solution. ss

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 amindiol is not sufficient to increase the fluorocarbon solubility to 25% by weight. When 20% amine diol (mixture D) is added, a clear solution mixture with 25% fluorocarbon is obtained.

Mixtures E to J contain a polyester diol of the type indicated, the pure polyester diol being able to dissolve 20% by weight but not 25% by weight of fluorocarbon. The break for 25% fluorocarbon solubility begins at about 10 parts by weight of amine diol (Mixture G). With a 20% amine diol content, the fluorocarbon dissolves up to 31% by weight.

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

The mixtures N to Q show maximum fluorocarbon solubilities of 60% or 50% for diethylene glycol or the polyester diol with 50% by weight mixtures of primary alcohol and amine diol.

Table VIII

Mixture ABCDEFGHI

Components (in parts by weight): diethylene glycol

100 100 90 80

653692 14

Table VIII (continued)

mixture

A

B

c

D

E

F

G

H

1

Polyester diol 1

-

-

-

-

100

100

90

80

80

Coconut amine adduct (see Table I)

-

-

10th

20th

-

-

10th

20th

20th

Fluorocarbon (see Table I)

17.6

25th

33.3

33.3

25th

33.3

33.3

40

45

% By weight primary alcohol

100

100

90

80

100

100

90

80

80

% Amindiol

0

0

10th

20th

0

0

10th

20th

20th

% By weight fluorocarbon

15

20th

25th

25th

20th

25th

25th

28.5

31

Appearance of the mixture clear

cloudy,

cloudy,

clear,

clear,

cloudy,

clear,

clear,

clear,

mix

Disgust

• Abgei

■ mixed mixed

Disgust

• mixed mixed mixed

bar dung dung bar bar dung bar bar bar

Table VIII (continued)

mixture

j

K

L

M

N

0

p

Q

Components (in parts by weight):

Diethylene glycol

-

15

-

-

50

50

-

-

Polyester diol 1

80

-

15

15

-

-

50

50

Coconut amine adduct (see Table I)

20th

85

85

85

50

50

50

50

Fluorocarbon (see Table I)

50

900

207.7

233.3

150

175

100

120

% By weight primary alcohol

80

15

15

15

50

50

50

50

% Amindiol

20th

85

85

85

50

50

50

50

% By weight fluorocarbon

33.3

90

67.5

70

60

63.6

50

55

Appearance of the mixture cloudy clear,

clear,

cloudy,

clear,

cloudy,

clear,

cloudy,

mix mix

Shitty

Shitty

Absei

bar bar dung bar dung bar dung

1 cf. Table III, footnote 1, A).

Example 9

A series of mixtures of monofluorotrichloromethane with three typical polyols containing primary hydroxyl groups 35 are prepared. The amounts of weight used, including the amount of coconut amide di of formula II which may be present, are varied in accordance with Table IX. The mixtures are examined for their miscibility, their clarity or their turbidity and the deposition of the fluorocarbon from the solution.

The Abis D mixtures contain diethylene glycol. In the absence of any amide diol, 20% by weight fluorocarbon solubility is not achieved. The addition of 10% 45 amide diol (mixture B) is not sufficient to increase the fluorocarbon solubility to 20%. Only with at least 15% amide diol (mixture C) does the mixture remain clear with a 20% fluorocarbon additive. Obviously she is in the

Mixing ratio 80/20 clear (mixture D).

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

Mixtures H to L are made using a polyester diol. 20%, but not 25% fluorocarbon dissolves in the pure diol. With an amide diol content of 20% (mixtures J to L), the highest possible fluorocarbon content is about 31%.

In the case of the mixtures M to O, maximum fluorocarbon contents of over 90% or up to 60% by weight are observed for diethylene glycol or the polyester diol if a maximum of 85% by weight amide diol is used.

Mixtures P to 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 of primary alcohol and amide diol.

Table IX

mixture

D

Components (in parts by weight):

Diethylene glycol

100

90

85

80

-

-

-

-

-

-

Ethylene glycol

-

-

-

-

100

85

80

-

-

-

Polyester diol (see table

-

-

-

-

-

-

-

100

100

80

III)

Coconut amide (see Table V)

-

10th

15

20th

-

15

20th

-

-

20th

Fluorocarbon (cf.

25th

25th

25th

25th

25th

25th

25th

25th

33.3

40

Table I)

% By weight primary alcohol

100

90

85

80

100

85

80

100

100

80

% Amide diol

0

10th

15

20th

0

15

20th

0

0

20th

% By weight fluorocarbon

20th

20th

20th

20th

20th

20th

20th

20th

25th

28.5

Appearance of the mixture cloudy,

cloudy,

clearly clearly cloudy,

cloudy,

clearly clearly cloudy,

clear

Disgust

■ Abgei

Disgust

Disgust

Disgust

dung dung

dung dung

dung

653 692

Table IX (continued)

mixture

K

L

M

N

O

P

Q

R

S

Components (in parts by weight):

Diethylene glycol

-

-

15

-

-

50

50

-

-

Ethylene glycol

-

-

-

-

-

-

-

-

-

Polyester diol (see Table III)

80

80

-

15

15

-

-

50

50

Coconut amide (see Table V)

20th

20th

85

85

85

50

50

50

50

Fluorocarbon (see Table I)

45

50

900

150

166.7

125

150

81.8

100

% By weight primary alcohol

80

80

15

15

15

50

50

50

50

% Amide diol

20th

20th

85

85

85

50

50

50

50

% By weight fluorocarbon

31

33.3

90

60

62.5

55

60

45

50

Appearance of the mixture,

cloudy,

clear,

clear,

cloudy,

clearly cloudy,

clearly cloudy,

clear

Abschei mixed mixed

Disgust

Disgust

Disgust

dung bar bar dung

dung

dung

Example 10

A series of mixtures of monofluorotrichloromethane and three typical polyols containing primary hydroxyl groups are prepared. The amounts by weight used, including the amount of amine triol of the formula III which may be used, are varied in accordance with Table X. The mixtures are examined for their miscibility, their clarity or turbidity and the deposition of the fluorocarbon from the solution.

Mixtures A to D contain diethylene glycol. In the absence of aminetriol, the fluorocarbon solubility does not reach 20% by weight. The addition of 10% aminetriol (mixture B) is not sufficient to increase the fluorocarbon solubility to 20%. Only with at least 15% aminetriol does the mixture remain clear with 20% fluorocarbon.

Mixtures E to G contain ethylene glycol. At least 20% amine triol is required to maintain 20% fluorocarbon solubility.

Mixtures H to M are made using a polyester diol. The pure polyester diol dissolves 25 20, but not 25% fluorocarbon. At least 15% by weight of aminetriol is required to ensure 25% fluorocarbon solubility (mixture K). With a 20% by weight amine triol content, the maximum fluorocarbon solubility is approximately 28.6% by weight.

30 The mixtures N to P show a maximum fluorocarbon solubility of over 90% or up to 50% by weight for diethylene glycol or the polyester diol with a maximum amine triol presence of 85% by weight.

The mixtures Q to T show a maximum fluorocarbon solubility of 50% or 40% for diethylene glycol or the polyester diol with 50% by weight mixtures of primary alcohol and amine triol.

Table X

Mixture ABCDEFGHI J

Components (in parts by weight):

Diethylene glycol

100

90

85

80

-

-

-

-

-

-

Ethylene glycol

-

-

-

-

100

85

80

-

-

-

Polyester diol (see table

-

-

-

-

-

-

-

100

100

90

III)

Coconut diamine 1

-

10th

15

20th

-

15

20th

-

-

10th

Fluorocarbon (cf.

25th

25th

25th

25th

25th

25th

25th

25th

33.3

33.3.

Table I)

% By weight primary alcohol

100

90

85

80

100

85

80

100

100

90

% By weight aminetriol

0

10th

15

20th

0

15

20th

0

0

10th

% By weight fluorocarbon

20th

20th

20th

20th

20th

20th

20th

20th

25th

25th

Appearance of the mixture cloudy,

cloudy,

clear,

clear,

cloudy,

cloudy,

clear,

clear,

cloudy,

cloudy,

Disgust

■ Separate mix

Disgust

Abschei mixed mixed

Disgust

Disgust

dung bar bar dung bar bar dung

Table X (continued)

Mixture KLMNOPQRST

15

653 692

To you

Table X (continued)

mixture

K

L

M

N

O

p

Q

R

s

T

Polyester diol (see table

85

80

80

_

15

15

_

_

50

50

III)

Coconut diamine 1

15

20th

20th

85

85

85

50

50

50

50

Fluorocarbon (cf.

33.3

40

45

900

100

110.5

100

122.2

66.7

81.8

Table I)

% By weight primary alcohol

85

80

80

15

15

15

50

50

50

50

% By weight aminetriol

15

20th

20th

85

85

85

50

50

50

50

% By weight fluorocarbon

25th

28.6

31

90

50

52.5

50

55

40

45

Appearance of the mixture clear

clear,

cloudy,

clear,

clear,

cloudy,

clear,

cloudy,

clear,

cloudy,

mix mix

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1 ethoxylated mixture obtained by reacting ethylene oxide with coconut diamine in molar amounts of about 14: 1, the coconut diamine being obtained by reacting coconut amine with one equivalent of acrylonitrile and reducing the cyanoethylated coconut amine mixture to coconut diamine (amine equivalent weight: 290; OH equivalent weight: 193 ).

Claims (7)

653 692 1. Polyol mixture of 20 to 85% by weight, based on the total mixture, of (a) and (b), of (a) at least one polyol from the polyol class consisting of the amine diols of the formula I Ri I. , (CHzCHO) x-H R-N ^ (I) \ (CH2CHO) y-H I. Ri the amide diols of the formula II Ri O | II. (CH2CHO) x-H R2-C-NC ^ (n) ^ • (CmCHOV-H Ri and the amine triols of formula III Ri I. (CH2CHO) X »-H ^ (CHRi> -N <^ R-N <"\ (CH2CHO) y» -H (III) \ (CH2CHO) z-H i | Ri Ri exists, being in these formulas R is an aliphatic radical with 8 to 18 carbon atoms, R2 is an aliphatic radical with 7 to 17 carbon atoms, and the symbols Ri independently of one another each represent a hydrogen atom or a methyl radical, x and y each have an average value of 4 to 15, x 'and y' each have an average value of 1 to 3 and x "and y" and z each have an average value of 1 to 5, and n = 2 or 3, and 80 to 15% by weight of (b) does not increase the polyol IV belonging to (a) mentioned and having primary hydroxyl in the molecule and having a molecular weight of 60 to 1000. 2. Polyol mixture according to claim 1, characterized in that component (a) corresponds to formula I and represents an amine diol mixture, as can be obtained by reacting cocosamine with 15 moles of ethylene oxide per mole of coconut amine. 2nd PATENT CLAIMS 3. Polyol mixture according to claim 1, characterized in that the component (a) corresponds to the formula II and an N, N-bis (8-hydroxy-3,6-dioxaoctyl) coconut amide mixture. 4. Polyol mixture according to claim 1, characterized in that component (a) corresponds to formula III and is an amine triol mixture derived from coconut amine, each component of the amine triol mixture having an average value of x ", y" and z of 4.6 each and n = 3. 5. Polyol mixture according to claim 2, 3 or 4, characterized in that the polyol (b) is diethylene glycol. 6% by weight of water as a blowing agent and the rest of a polyol mixture according to claim 1 and is a clear solution. 9. A process for the preparation of a cellular polymer with recurring isocyanurate units by trimerization of organic polyisocyanate in the presence of polyol, a blowing agent and a trimerization catalyst, characterized in that the following are allowed to react with one another: A. organic polyisocyanate and B. 10 to 120 grams per gram equivalent of component A of a mixture of: (Bi) 2 to 20% by weight of a polyisocyanate trimerization catalyst and (B2) 98 to 80% by weight of a mixture of: (B21) 20 to 80% by weight of a fluorocarbon blowing agent or 1 to 6% by weight of water as a blowing agent and (B22) 80 to 20% by weight of a polyol mixture according to Claim 1 if the blowing agent is a fluorocarbon blowing agent or 99 to 94% by weight of a polyol mixture according to Claim 1 if the blowing agent is water, the total amount of in the hydroxyl equivalents contained in mixture B are in the range from 0.05 to 0.5 equivalents per isocyanate equivalent. 10. The method according to claim 9, characterized in that (B22) is a polyol mixture according to claim 1, in the component (a) Ri only means hydrogen. 11. The method according to claim 10, characterized in that A is a polymethylene polyphenyl polyisocyanate and (B22) is a polyol mixture according to claim 5,6 or 6. Polyol mixture according to claim 2, 3 or 4, characterized in that the polyol (b) is polyoxydiethylene adipate-glutarate polyester diol with a molecular weight of 400 to 600. 7. Polyol mixture according to claim 2, 3 or 4, characterized in that the polyol (b) is a mixture of 30 to 50% by weight of diethylene glycol and 70 to 50% by weight of a polyoxy-diethylene adipate glutarate polyester diol with a molecular weight of 400 to 600. 8. Polyol blowing agent mixture which consists of at least 20% by weight of a fluorocarbon blowing agent or 1 to 7.