KR19990007838A - Polymer material - Google Patents

Abstract

Processes for the preparation of foamed polyurethane materials include alkanolamine salts (monomers 0 to 80% by weight, dimers 10 to 100) of fatty acids polymerized with organic polyisocyanates essentially hydroxyl terminated polyesters and / or polyether polyols Weight percent and trimer 0-75 weight percent) and 10 weight percent to 100 weight percent and inert (preferably free of halogen). Also claimed are foamed polyurethane materials and the use of alkanolamine salts as multifunctional additives in the manufacture of foamed polyurethane materials.

Description

Polymer material

The present invention is directed to a process for the preparation of foamed polyurethane materials by reacting essentially hydroxy terminated polyols with organic polyisocyanates. The present invention also relates to a foamed polyurethane material, wherein the material obtained can be a soft, semi-rigid or rigid foam material.

Polyurethane foam materials are used in large quantities in various applications. They are low or high density ductile, flexible foams, semi-rigid and rigid foams. Flexible, soluble foams and most semi-rigid and rigid polyurethane foams are produced using blowing agents. These blowing agents were usually chlorofluorocarbons (CFCs). CFCs have good volatility, flame retardancy and very good thermal properties, but their main drawback is high ozone consumption (ODP). This is why CFCs are prohibited in refrigeration and cooling technology and as polyurethane blowing agents. As alternatives alkanes, water and HCFCs have been proposed as blowing agents. However, the main problem is that the solubility and compatibility of these new blowing agents are so great that new compositions of components forming polyurethanes have to be developed. Thus, for example, polyether polyols used in the production of polyurethane materials exhibit low compatibility with these alternative blowing agents, in particular pentane.

Polyurethane component changes also make the characteristics of the pore size of the foam material formed, i.e., the insulation and flame retardancy of the polyurethane material more undesirable. One feature improvement is rarely gained at the expense of another.

It has been found that the use of polyols incorporating certain multifunctional additives significantly improves the compatibility of alternative blowing agents, in particular pentane and polyurethane forming components.

The term multifunctional additive is used intentionally because it has been found that the use of such multifunctional additives in polyol-based polyurethane foam systems produces highly uniform and fine pore size foam materials. The micropores obtained produce better insulation of the polyurethane foam material and at the same time have a lower volume weight. In addition, the use of multifunctional additives allows the use of polyols with high functionality, but at the same time results in low viscosity in the mixture of polyurethane forming components.

Finally, it was also surprisingly found that the flame retardancy of the resulting polyurethane material was significantly improved by the use of such multifunctional additives.

Thus, the use of additives has led to several property improvements at the same time, so the term multifunctional additive was considered appropriate. The multifunctional additive is an alkanolamine salt of polymerized fatty acid, and it is important to know that this multifunctional additive is a salt and is not an esterification and amidation product of the polymerized fatty acid. In order to obtain salts of alkanolamines and polymerized fatty acids, the temperature of the salt formation reaction is kept as low as possible, preferably at 90 ° C. or lower.

The present invention therefore relates to a process for the preparation of polyurethane materials by reacting organic polyisocyanates essentially in the presence of hydroxyl terminated polyols with an effective amount of an alkanolamine salt of polymerized fatty acid and an inert stable evaporable blowing agent. . Effective amounts of alkanolamine salts of polymerized fatty acids which are multifunctional additives are usually from 10% to 100% by weight and in particular from 25% to 45% by weight, based on the total weight of the polyol component.

In addition, the present invention

(a) organic polyisocyanates;

(b) essentially hydroxyl terminated polyols;

(c) effective amounts of alkanolamine salts of polymerized fatty acids; And

(d) a foamed polyurethane material selected from the group consisting of semi-rigid and rigid foams comprising the reaction product of an inert stable evaporable blowing agent.

As the organic polyisocyanate, aromatic, aliphatic, cycloaromatic, aromatic aliphatic or heterocyclic isocyanates having at least one but preferably at least two reactive isocyanate groups can be used. Suitable organic polyisocyanates include m-phenylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), toluene 2,4-diisocyanate, toluene 2,6-diisocyanate (also commercially available toluene diisocyanate ( TDI)); Polyphenylene polymethylene polyisocyanates (called crude MDI) obtained by isophorone diisocyanate (IPDI), aniline-formaldehyde condensation and subsequent reaction with phosgene; Cyclohexane 1,4-diisocyanate; 4,4'-diphenylene methane diisocyanate (MDI); Toluene 2,4,6-triisocyanate; 3,3'-dimethyl-4,4'-diphenyl diisocyanate; 3,3'-diphenyl-4,4'-diphenylene diisocyanate; 4,4 ', 4' '-triphenylmethane triisocyanate; 1,5-naphthalene diisocyanate (NDI). In addition to mixtures of organic polyisocyanates, mixtures of monoisocyanates and polyisocyanates can also be used. In particular, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and polymethylene, polyphenylene polyisocyanate are useful because of their availability.

The essentially hydroxyl terminated polyols used comprise two or more reactive hydroxyl groups and may be polyester and / or polyether polyols. By the term essentially hydroxyl terminated, it is understood that polyols have few reactive groups other than hydroxyl groups which can react with isocyanate groups. This implies that the polyester polyol has an acid value of 5 or less and preferably 2 or less.

Suitable polyester polyols have a functionality of 2-4, preferably 3-4, and are aliphatic, cycloaliphatic, aromatic and / or heterocyclic, at least dicarboxylic acids or derivatives thereof, for example dicarboxylic acids. It can be prepared by methods known per se from anhydrides, dicarboxylic acid esters of lower monohydric alcohols having 1 to 4 carbon atoms and dicarboxylic acid dichlorides. The acid can be a straight or branched chain, saturated or unsaturated acid and can be substituted, for example, with a halogen atom. Suitable aliphatic dicarboxylic acids are those having 2 to 12 carbon atoms, for example succinic acid, glutaric acid, adipic acid, azelaic acid, dodecanedioic acid; Aromatic acids such as phthalic acid, terephthalic acid and isophthalic acid; Cyclic aromatic acids such as 1,4-cyclohexane dicarboxylic acid; Tetrahydrophthalic anhydride, tetrachlorophthalic anhydride; Maleic acid and maleic anhydride, fumaric acid and mixtures of these acids. In addition, monocarboxylic acids such as fatty acids having 8 to 22 carbon atoms can be used in admixture with polycarboxylic acids.

As the polyhydric alcohol, glycols such as ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, neopentyl glycol, polyalkylene glycol, 1,4-bis (hydroxymethyl) cyclohexane and mixtures thereof This can be used. In addition, alcohols comprising three or more hydroxy groups can be used with dihydric alcohols such as glycerol, trimethylol ethane, trimethylol propane, pentaerythritol and mixtures thereof. Alkanolamines such as diethanolamine, triethanolamine and the like can also be used, resulting in polyesteramides.

The polyester polyols preferably comprise residues of polymerized fatty acids or polymerized fatty alcohols. Polymerized fatty acids are obtained in a manner known per se by the polymerization of unsaturated fatty acids and the product is known as dimerized and / or trimerized fatty acids. The polymerized fatty acid comprises 20 to 100% by weight dimer acid, 0 to 30% by weight monomeric acid, the remainder being trimer acid and higher polymer. The polymerized fatty acid may be at least partially hydrogenated to remove any residual unsaturation. Suitably polymerized fatty acids are, for example, free having from 75 to 82% by weight of dimer acid, from 18 to 22% by weight of trimeric acid and from 1 to 3% by weight of monomeric acid, acid values of 192 to 197 and saponification of 195 to 202 One containing at least 75% by weight of a diacid is used, such as Pripol 1017 (trade name of Unicheme Chemie B. V., Gouda, Netherlands).

The polyester polyols also comprise polymerized fatty alcohols, which are obtained in a manner known per se, by hydrogenation of polymerized fatty acids or polymerized fatty acid ester hydrogenolysis in the presence of a copper chromite catalyst. Suitable products include Prepol 2033 (trade name of Unichema Chemie B. V., Gouda, Netherlands) comprising 195 to 205 hydroxyl number and 97.5 weight percent dimer diol and 0.5 weight percent monomer and trimer alcohol. have. The polymerized fatty alcohol may be at least partially hydrogenated to remove any residual unsaturation.

In addition, polyesters derived from lactones such as caprolactone may be used.

Essentially hydroxyl terminated polyester polyols are the addition reactions of alkylene oxides having 2 to 5 carbon atoms, for example ethylene oxide and / or propylene oxide, with polyhydric alcohols called starters or initiators. It is manufactured by.

Depending on the type of starting material, straight or branched polyether polyols are obtained. Substantially straight or linear polyether polyols are those derived from alkylene oxides, glycols, heterocyclic ethers and other materials. The primary hydroxyl content can be increased by the separation reaction of polyoxyalkylene polyols having ethylene oxide, resulting in block copolymers having oxyethylene end groups.

Examples of branched polyether polyols are glycerol, trimethylol propane pentaerythritol, 1,2,6-hexanetriol, styrene-vinyl alcohol copolymers, sucrose, sorbitol and other substances and reaction products of alkylene oxides . Typical triols are prepared by addition polymerization of 50 to 55 moles of propylene oxide and 10 to 15 moles of ethylene oxide to 1 mole of glycerol or trimethylolpropane.

In the present invention, it is also possible to use essentially hydroxyl terminated polyester polyols and polyether polyols.

Multifunctional additives are alkanolamine salts of polymerized fatty acids.

Alkanolamines are selected from alkanolamines wherein the alkyl moiety is usually lower alkyl, ie C1 to C5 alkyl. Other lower alkanolamines, such as dimethyl methanolamine, are also suitable because other substituents may be present in the amine group if more than one hydroxyl group remains.

Preferably the alkanolamine is triethanolamine or triisopropanolamine.

The polymerized fatty acids used in the preparation of the alkanolamine salts should be such compositions that, when blended into the formulation, the salts produce an acceptable viscosity of the mixture. Accordingly, the polymerized fatty acid preferably has 0 to 80% by weight of monomeric acid, 10 to 100% by weight of dimer acid and 0 to 75% by weight of trimeric acid. The polymerized fatty acid may be at least partially hydrogenated to remove any residual unsaturation. Preference is given to triethanolamine salts of polymerized fatty acids having 50% by weight dimer acid, 10% by weight trimer acid and 40% by weight monomeric acid.

In addition, other acid / amine equivalent ratios, such as 0.1 to 1.0 equivalent acid to 1 equivalent amine, may be used. Preferably, an equivalent ratio of 1.0 equivalent of acid per 1.0 equivalent of amine is used. Since it is essential that no ester and / or amide bonds are produced, the temperature in the salt formation reaction is maintained at 90 ° C. or lower, preferably 80 ° C. or lower.

The amount of multifunctional additive used may vary depending on the polyurethane material production technology and the particular application of the polyurethane material, but is usually from 10 to 100% by weight, preferably from 25 to 45% by weight, based on the total polyol component of the total composition. .

Inert, stable evaporative blowing agents are used in the process of making polyurethane materials. Such blowing agents are preferably selected from the group consisting of alkanes and cycloalkanes and mixtures thereof which have no hydrogen or have water, carbon dioxide, nitrogen, an inert gas (eg argon) and a molecular weight of up to 100. Preference is given to the use of pentane, isopentane and cyclopentane. Trichloromonofluoromethane, dichlorodifluoromethane and / or methylene chloride are also used.

In addition, an effective amount of various additives may be used, for example catalysts (alkali metal acetates, alkali metal octoates, tertiary amines such as N-methylmorpholine, 1,4-diazabicyclo ( 2.2.2) organometallic compounds such as octane, dimethylcyclohexylamine (DMCHA), tin salts of carboxylic acids, dibutyltin dilaurate and organic titanate); Pore stabilizers (eg, polydimethyl siloxane); Flame retardants (e.g., C1 to C5 alkyl esters of C1 to C5 alkane phosphonates, such as phosphoric acid, metaphosphoric acid, ammonium salts of polyphosphoric acid, methylphosphonic acid dimethyl ester (DMMP), ethylphosphonic acid diethyl ester, zinc borate, Barium metaborate, halogen compounds such as 2,3-dibromo-1,4-butanediol or tris (2-chloro-ethyl) phosphonate; tris (monochloro-isopropyl) phosphate; emulsifier or surface active agent (E.g. fatty acid alkanolamine ethoxylates, silicones, alkali metal salts of polymerized fatty acids; nonionics are preferred); pigments, dyes; fillers (e.g. silica gel, carbon black); stabilizers; flesh Fungicides and mixtures thereof Additives may be used in small amounts from 0.001% by weight of the total composition, and even up to 50% by weight of the total composition. It is used.

Preparation of urethane-based foam materials in the presence of diethanolamine salts of stearic acid, usually secondary aliphatic amine salts of C10 to C20 fatty acids, is described in German patent specification DE-A-960,855 (Farbenfabricken Bayer A, G. Is known. However, such additives are used as shrinkage regulators.

The invention will be explained with the following examples.

Example 1

Triethanolamine salts of polymerized fatty acids were prepared as follows;

325 grams of polymerized fatty acid (41.3 wt% monomeric acid, 50.6 wt% dimer acid and 8.1 wt% trimer acid) were heated to 60 ° C. to 90 ° C. with stirring under nitro, followed by triethanolamine (85 wt% triethanolamine, the rest) 165 grams were added, after which the mixture was kept at the same temperature under nitro for 1 hour with stirring. A clear liquid was obtained. Triethanolamine salts of polymerized fatty acids were mixed with hydroxyl terminated polyester polyols having a hydroxyl number of 400, an acid value of 1.5 and a functional value of 3.0. This polyester polyol is 1.78 mol of phthalic anhydrides. It was obtained by reacting 1.31 mol of oleic acid, 1.01 mol of diethylene glycol and 3.12 mol of glycerol.

The essentially hydroxyl terminated polyester polyol with the addition of the functional additive was tested for its response to pentane and cyclopentane solubility. This evaluation was carried out with a mixture of the following compositions.

Polyester polyol 100 parts in weight Teegostab B-8450 ¹ ) 1.0 Dimethyl cyclohexylamine 0.9 water 1.5 Tris (monochloroisopropyl) phosphate 10 Dimethyl Methylphosphonate 10 ¹ ) TH. Goldschmidt A.G., Essen, Germany. Polyester siloxane

Compatibility with pentane and cyclopentane was measured by adding a blowing agent to the polyurethane foam system by titration. At the moment the mixture began to become cloudy, the components were no longer compatible. Thereafter, the amounts of added pentane and cyclopentane were weighed out and calculated.

Titrated samples were stored for an additional 48 hours at room temperature in tightly sealed glass flasks to observe possible separation of pentane or cyclopentane. If separation occurred, the compatibility results were recalculated.

The following results were obtained:

Compatibility: Pentane: Cyclopentane: Polyether polyols 4.3 6.3 Polyester polyol 9.3 10.4 Polyester Polyols with Multifunctional Additives 27.4 61.5

Compatibility is expressed in weight percent alkanes based on total mixture. The effect of the triethanolamine salt of the polymerized fatty acid on the compatibility with the blowing agent was pronounced. The polyether polyol was an aliphatic polyether polyol of hydroxyl number 590 (polyether based on sucrose, trade name Cardol LP 585-01 from Shell Chemicals, UK).

The use of new blowing agents for polyurethane foams has made it difficult to produce polyurethane foams of the same low lambda value as using CFCs. Pentane-bulged foam was at or about 20% or more (initial) above the CFC-bulged material. Apart from the amount of cell closed and blowing agent type, cell size and cell size distribution are important factors for obtaining low initial lambda values. The cell size can be influenced in particular by the selection of a suitable surface active agent, but also by the compatibility of the blowing agent with the polyurethane-based components.

Experiments were performed using the same system used in the pentane compatibility test, using pentane as blowing agent. After 24 hours of foam hardening, the insulation value was measured according to the German industry standard DIN 52,612 part 1 (hot protection plate, intermediate temperature 23 ° C.).

The hydroxyl terminated polyester polyols were hydroxyl-valent 410 aliphatic polyester polyols (polyether polyol trade name from Dow Chemical, USA; Boranol RN-411) and 70 weight percent polyether polyol and 30 weight percent polyester polyol. It mixed in the weight ratio of.

The composition used is as follows:

Composition (parts by weight) A B Boranol RN-411 65 20 Polyester polyol - 22.5 Functional Polyol Blends 3.7 3.7 water 2.0 2.0 Tego Staff B-8450 1.0 1.0 Dimethyl cyclohexylamine 1.6 1.6 Tris (Monochloro-isopropyl) phosphate 7 7 Dimethyl Methylphosphonate 10 10 n-pentane 13 13 Triethanolamine salts of polymerized fatty acids - 22.5 Triethanolamine 2 2 Glycerol 7 7 Diphenylmethane-4,4 'diisocyanate 144 148 (NCO is 30.7; British I.C.I.P.C., product name of functional group 2,7 Suprasec DNR)

The composition (containing no polyisocyanate) was mixed in one liter of polyethylene coated cardboard cups and, if necessary, after mixing, the amount of blowing agent was adjusted. A measurand of polyisocyanate was then added to the mixture and the blend was mixed for 10 seconds at 3500 rpm using a Pendraulik high speed experimental mixer equipped with a 64 mm diameter mixing blade. Thereafter, the mixture was poured into 10 liters of polyethylene sacks to allow foam to freely develop.

Before testing the physical properties of the material, the foams were post-cured at 70 ° C. for 24 hours in a hot air oven where the foam was recycled, and then the condition was adjusted for 24 hours at 23 ° C. and 50% relative humidity.

Insulation was determined according to the following German industry standard DIN 52,612: The insulation value for the polyurethane foam material obtained with composition B was 20.8 mW / m. K and the insulation for the polyurethane foam material obtained with composition A It was thin 23.8 mW / m.K, thus clearly showing that the polyurethane material obtained according to the invention had the lowest initial lambda value. Close examination showed that the foam material obtained with Composition B was the best system. Both foams had a significant density (about 30 kg / m ³ ).

Finally, the flame retardancy of the polyurethane foam material prepared for the insulation test was investigated. In order to classify the flame retardancy according to the German industry standard DIN 4102, part 1, (Kantbeflammung, B-2 test, flame retardant additives must be formulated. Tris (monochloro-isopropyl) phosphate and dimethyl Mixtures of methylphosphonates were used because they are known to be very effective in improving flame retardancy due to synergistic effects.

The following composition was used (parts by weight):

Composition (parts by weight) A B Polyester polyol - 22.5 Triethanolamine salts of polymerized fatty acids - 22.5 Boranol RN-411 (polyether polyol tradename having hydroxyl number 410 from Dow Chemical, USA) 65 20 Triethanolamine 2 2 Glycerol 7 7 Tris (Monochloro-isopropyl) phosphate 7 7 Dimethyl methyl phosphonate 10 10 Tego Staff B-8450 1.0 1.0 Dibutyltin dilaurate 0.05 0.05 Dimethyl cyclohexylamine 1.6 1.6 water 2.0 2.0 n-pentane 13 13 Sugrasec DNR 144 148

The amount of polyisocyanate exceeded 10% based on the hydroxyl value of the polyol and the amount of water used. Composition A exhibited a flame height of 18 cm and Composition B exhibited a flame height of 13.5 cm. The limit according to German industry standards is a maximum flame height of 15 cm. This means that if composition A has to reach this limit, the amount of flame retardant must be increased by 50 to 100%, which leads to a significant increase in cost.

Claims (32)

A process for producing a foamed polyurethane material by reacting an organic polyisocyanate essentially in the presence of a hydroxyl terminated polyol with an effective amount of an alkanolamine salt of polymerized fatty acid and an inert stable evaporable blowing agent. The process of claim 1 wherein the alkanolamine salt of the polymerized fatty acid is used at 10% to 100% by weight based on the total weight of the polyol components. The process of claim 1 wherein the alkanolamine salt of the polymerized fatty acid is used at 25% to 45% by weight based on the total weight of the polyol components. The method of claim 1 wherein the hydroxyl terminated polyol comprises at least two reactive hydroxyl groups and is selected from the group consisting of polyester polyols, polyether polyols, and mixtures thereof. The method of claim 1 wherein the hydroxyl terminated polyol is a polyester polyol comprising polymerized fatty acid residues. The method of claim 1 wherein the hydroxyl terminated polyol is a polyester polyol comprising polymerized fatty alcohol residues. The method of claim 5, wherein the polymerized fatty acid is at least partially hydrogenated. The method of claim 6, wherein the polymerized fatty alcohol is at least partially hydrogenated. The method of claim 1 wherein the hydroxyl terminated polyol is a polyester polyol having an acid value of 5 or less. The method of claim 1, wherein the alkanolamine is selected from the group of alkanolamines having 1 to 5 carbon atoms. The method of claim 1, wherein the alkanolamine is triethanolamine or triisopropanolamine. The alkanolamine salt of the polymerized fatty acid according to claim 1, wherein the alkanolamine salt of the polymerized fatty acid is derived from polymerized fatty acids having from 0 to 80% by weight of monomeric acid, from 10 to 100% by weight of dimer acid and from 0 to 75% by weight of trimeric acid. How to be. The process according to claim 1, wherein a triethanolamine salt of polymerized fatty acid having 40% by weight monomeric acid, 50% by weight dimer acid and 10% by weight trimer acid is used. The process of claim 1 wherein the inert stable evaporative blowing agent is selected from the group consisting of water, carbon dioxide, nitrogen, inert gas, alkanes and cycloalkanes having a molecular weight of 100 or less, and mixtures thereof. The method of claim 1 wherein the inert stable evaporable blowing agent is an alkane or cycloalkane having a molecular weight of 100 or less. The method of claim 1 wherein the inert stable evaporable blowing agent is selected from the group consisting of pentane, isopentane, cyclopentane and mixtures thereof. The additive of claim 1 wherein the additive selected from the group consisting of catalysts, pore stabilizers, flame retardants, emulsifiers, pigments, dyes, fillers, stabilizers, fungicides and mixtures thereof is 0.001% to 50% by weight, based on the total composition. Used as. (a) organic polyisocyanates; (b) essentially hydroxyl terminated polyols; (c) from 10% to 100% by weight of alkanolamine salts of polymerized fatty acids, based on the total weight of polyol; And (d) inert, stable evaporative blowing agents; Foamed polyurethane material consisting of the reaction product of. 19. The foamed polyurethane material according to claim 18, wherein the alkanolamine salt of the polymerized fatty acid is used at 25% to 45% by weight based on the polyol. 19. The polyurethane material of claim 18, wherein the hydroxyl terminated polyol is a polyester polyol comprising polymerized fatty acid residues. 19. The polyurethane material of claim 18, wherein the hydroxyl terminated polyol is a polyester polyol comprising polymerized fatty alcohol residues. The polyurethane material of claim 20, wherein the polymerized fatty acid is at least partially hydrogenated. The polyurethane material of claim 21, wherein the polymerized fatty alcohol is at least partially hydrogenated. 19. The polyurethane material of claim 18, wherein the alkanolamine is selected from the group of alkanolamines having 1 to 5 carbon atoms. 19. The polyurethane material of claim 18, wherein the alkanolamine is triethanolamine or triisopropanolamine. The polyurethane material according to claim 18, wherein the alkanolamine salt is derived from polymerized fatty acids having 0 to 80% by weight of monomeric acid, 10 to 100% by weight of dimer acid and 0 to 75% by weight of trimeric acid. . 19. The polyurethane material of claim 18, wherein a triethanolamine salt of polymerized fatty acid is used having 40% by weight monomeric acid, 50% by weight dimer acid and 10% by weight trimer acid. 19. The polyurethane material of claim 18, wherein the inert, stable evaporative blowing agent is selected from the group consisting of water, carbon dioxide, nitrogen, inert gas, alkanes and cycloalkanes having a molecular weight of 100 or less, and mixtures thereof. 19. The polyurethane material of claim 18, wherein the inert stable evaporable blowing agent is an alkan or cycloalkane having a molecular weight of 100 or less. 19. The polyurethane material according to claim 18, wherein the inert stable evaporable blowing agent is selected from the group consisting of pentane, isopentane, cyclopentane and mixtures thereof. Alkanolamine salts of polymerized fatty acids having from 0 to 80% by weight of monomeric acid, from 10 to 100% by weight of dimer acid and from 0 to 75% by weight of trimeric acid, wherein the alkanolamines contain from 1 to 5 carbon atoms Branches are selected from the group of alkanolamines) as multifunctional additives in the preparation of foamed polyurethane materials. Use of a triethanolamine salt of polymerized fatty acids having 40% by weight monomeric acid, 50% by weight dimer acid and 10% by weight trimer acid as a multifunctional additive in the preparation of foamed polyurethane materials.