Non-volatile catalysts, containing imine bonds and tertiary amines and polyurethane material obtained using said catalysts

FIELD: chemistry.

SUBSTANCE: catalyst is a product of reacting compounds (a) and (b). Compound (a) is a mixture of (i) a compound which contains at least one opxy group with (ii) a compound which contains an alcohol, amino-, thio- or carboxyl group and an aldehyde or ketone group. Compound (b) contains at least one primary amino group and at least one tertiary amino group.

EFFECT: use of the proposed non-volatile catalyst to produce polyurethane foam reduces the need for traditional volatile amine catalysts, speeds up bonding of organic polyisocyanates to polyhydroxyl or polyamino compounds and the reaction between isocyanate and foaming substance, and reduces the time for holding polyurethane foam material in the die mould and improves characteristics of the foam.

14 cl, 24 ex

The present invention relates to non-volatile catalysts containing kinoway communication and tertiary amine, and a polyurethane polymer materials obtained by using such catalysts.

Simple polyester polyols derived from polymerization of alkalisation, and/or a complex of the polyester polyols are the basic components of a polyurethane system along with isocyanates. These systems usually contain additional components, such as cross-linking agents, chain extenders, surfactants, regulators then, stabilizers, antioxidants, flame retardants and, finally, fillers, and the usual catalysts, such as tertiary amines and/or ORGANOMETALLIC salt.

ORGANOMETALLIC catalysts, such as salts of lead or mercury, can cause problems in relation to the environment due to leaching during aging of polyurethane products. Others, such as salts of tin, adversely affect the aging of polyurethanes.

Commonly used catalysts based on tertiary amine present a number of challenges, particularly when applying to get a soft, semi-rigid and rigid foams. Their foams with the use of such catalysts often have a characteristic odor of amines and are characterized by increased turbidity (from which the group of volatile products). The presence or vapour formation of the catalyst based on the tertiary amine in polyurethane products, which represents a vinyl film or sheet elastomers based on polycarbonate or a complex of the polyester/polyether, such as a thermoplastic complex polyester elastomer Hytrel* (trademark of DuPont), and exposed to external influence, are likely to be adverse. Such products are usually used in cars, as well as for many economic purposes. In particular, present in the polyurethane foam catalysts based on tertiary amine leads to the formation spotted vinyl film and destruction of the sheet of polycarbonate or Hytrel. Is the appearance of the spots on the PVC and the problems of degradation of polycarbonate or Hytrel especially prevalent in environments where for a long period of time there are elevated temperatures, such as inside a car when the coatings remain in the sun.

Have been proposed various solutions to the above problems. One solution is the use of amine catalysts containing reactive isocyanate group, i.e. the hydroxyl and/or primary and/or secondary amine. This connection is described in the publication EP 747407. Other types of reactive catalysts based on monola described in U.S. patent 4122038, 4368278 and 410269. Because monali are monofunctional, these reactive amines act as breaking a chain agents and have a negative impact on the growth of the polymer chain and affect the physical characteristics of the polyurethane material.

The use of specific, amine-initiated polyols proposed in EP 539819, in U.S. patent 5672636 and in WO 01/58976.

In several other publications described polyols with autocatalytic activity and is able to replace fully or partially conventional amine catalysts. See, for example, U.S. patent 5672636; European patent publication 0047371, 1268598 and 1319034 and publications WO 03/016372, 03/029320 and 03/055930.

Blocking simple polyester polyols conventional type using N,N-diacylglyceride claimed in U.S. 3428708. Although this method gives polyols with autocatalytic activity, this method is limited by dialkylaminomethyl, which mainly consists of catalysis interaction water - isocyanate and, to a much lesser extent, the interaction between the polyol - isocyanate.

Despite progress in this area advances, a need remains in the superior catalysts for polyurethane materials and/or catalysts, are able to reduce in quantity or exclude volatile amine catalysts and/or metalloorganic the definition of salt, used in the preparation of polyurethanes.

It is also desirable to develop an industrial method to produce polyols having an autocatalytic properties, where an autocatalytic polyols would not be a hindrance to the implementation of the conventional methods for producing polyols or obtain polyurethanes and would not infringe on the characteristics of these products.

The purpose of the present invention consists in obtaining polyurethane materials with low levels of conventional catalysts based on tertiary amine, a reduced level of reactive amine catalysts or polyurethane materials, the production of which does not require such amine catalysts. Another objective of the present invention is to obtain polyurethane materials with low ORGANOMETALLIC catalyst or the receipt of these materials in the absence of ORGANOMETALLIC catalysts.

Another object of the invention is a method of regulating the process conditions, or reactivity, of polyurethane materials by applying non-volatile catalysts of the present invention.

Another objective of the present invention is to increase productivity by combining non-volatile catalysts with conventional catalysts for the development of more b is strych methods for industrial preparation of polyurethane materials.

Another objective of the invention is to obtain non-volatile catalysts containing kinoway communication and tertiary amine, so that these catalysts do not have an adverse effect on industrial production method of polyurethane material with the use of these compounds and the physical characteristics obtained on the basis of the above catalysts of polyurethane materials and even improved the method by reducing the number of conventional catalysts or reactive amine catalysts, or exclusion of amine catalyst, and/or by reducing the number or exclusion of ORGANOMETALLIC catalysts.

The present invention relates to catalytic compositions, where the catalyst has at least one kinoway connection and at least one tertiary amino group.

In another variant implementation, the present invention relates to paleologou compositions containing from about 99.9 to 50 weight percent Paleologo connection with the functionality of 2-8 and a hydroxyl number of from 20 to 800 and from 0.1 to 50 percent of the catalytic composition, where the catalyst has at least one kinoway connection and at least one tertiary amino group. Preferably the amount present catalyst is from 0.5 to 10 mass parts of polyol.

For one the option of implementing the present invention relates to a method of producing polyurethane by reacting a mixture of

(a) at least one organic MDI

(b) paleologou composition with a polyol having a design nominal functionality of from 2 to 8 and a hydroxyl number of from 20 to 800 mg KOH/g, and

(c) at least one non-volatile catalyst containing at least one kinoway connection and at least one tertiary amino group,

(d) optionally, in the presence of other catalysts and/or foaming agents and

(e) optionally, additives or auxiliaries, which are known to have direct implications for obtaining the production of polyurethane foams, elastomers or coatings.

In another variant implementation, the present invention is the above method, where the catalyst (c) contains at least one reactive isocyanate hydrogen atom.

According to another variant implementation, the catalyst (c) is a gelling catalyst, i.e. catalyzes the interaction between the polyol and the isocyanate.

In another variant implementation, the catalyst (c) is a liquid polymer with a molecular weight of more than 500.

In another variant implementation, the catalyst (c) contains more than one component in the form of catalytically active tertiary amine.

In another variant implementation, the catalyst (c) contains n is how many of the aldehyde and/or ketone components.

According to another variant implementation, the catalyst (c) is stable to hydrolysis at room temperature.

In another variant implementation, upon receipt of the polyurethane material, the catalyst (c) is combined with the polyol having an autocatalytic properties.

In another variant implementation, the present invention is the above method, where the catalyst (c) contains at least one reactive isocyanate hydrogen atom.

In another variant implementation, the present invention is the above method, where the catalyst (c) contains at least one reactive isocyanate hydrogen atom and the polyisocyanate (a) contains at least one polyisocyanate, which is a product of the interaction of an excess of MDI with catalyst (c).

In another variant implementation, the present invention is the above method, where the catalyst (c) contains at least one reactive isocyanate hydrogen atom and the polyol (b) contains a prepolymer obtained by the interaction of an excess of catalyst (c) with polyisocyanate.

In addition, the invention relates to polyurethane materials, obtained by any of the above methods.

The non-volatile catalyst (c) accelerate the reaction of the accession of organic polyisocyanates which polyhydroxyethyl or polyamidoamine and the interaction between the isocyanate and a blowing agent, such as water or carboxylic acid, or a salt of carboxylic acid. The addition of these catalysts (c) to the polyurethane reaction mixture reduces or eliminates the need for the inclusion in the mixture of conventional catalyst based on tertiary amine or ORGANOMETALLIC catalyst. In combination with conventional aminovymi catalysts and/or autocatalytic polyols considered the catalyst (c) can also reduce the dwell time in the mold upon receipt of cast polyurethanes or improve some characteristics of the polyurethane material.

The use of such catalysts (c) reduces the need for conventional volatile amine catalysts and reduces related defects in the appearance of spots on a vinyl film or destruction of a sheet of polycarbonate or elastomer Hytrel. The advantages of the examined catalysts (c) are provided, or the inclusion in the reaction mixture for polyurethane materials of non-volatile catalyst (c), containing minovia communication and tertiary amines, or by inclusion of a catalyst (c)containing reactive hydrogen atoms, as a source of raw material for obtaining the copolymer polyols with SAN, PIPA or PHD, or the addition of these catalysts for the polyurethane reaction mixture, or by the use of such catalysts (c) in the prepolymer with only p is diisocyanates or isocyanate and a second polyol.

As used here, the term “polyol” means those compounds which have at least one group containing an active hydrogen atom capable to react with isocyanate. Preferred among such compounds are those compounds which have at least two hydroxyl groups, primary or secondary, or at least two amino groups, primary or secondary, carboxyl or thiol group in the molecule.

Compounds containing at least two hydroxyl groups or at least two amino groups per molecule, especially preferred by reason of a suitable reactivity against polyisocyanates.

Suitable polyols that can be used to produce polyurethane materials with non-volatile catalyst (c) according to the present invention, are well known in the art and include these polyols and any other industrially produced polyols and/or copolymer polyols with SAN, PIPA or PHD. Such polyols are described in "Polyurethane Handbook", by G. Oertel, Hanser publishers. Mixtures of one or more polyols and/or one or more of copolymer polyols can also be used to produce polyurethane materials of the present invention.

Typical examples of polyols include simple polyester polyols, complex p is lifornia polyols, polyacetale resin with terminal hydroxyl groups, amines with terminal hydroxyl groups and polyamine. Examples of these and other suitable reactive with isocyanate compounds described more fully in U.S. patent 4394491. Alternative polyols that may be used include polyols based polyalkylacrylate and polyols on the basis of polyphosphate. Preferred are polyols obtained by adding accelerated, such as ethylene oxide, propylene oxide, butylenes or combinations of these oxides to the initiator containing from 2 to 8, preferably from 2 to 6 active hydrogen atoms. Catalysis for such polymerization may be either anionic or cationic, with the help of catalysts, such as KOH, CsOH, boron TRIFLUORIDE, or double complex catalyst based on metal cyanide (DMC), such as cyncexcineund or Quaternary phosphazenes connection. The unsaturation of these polyols is from 0.001 to 0.1 mEq/g After receipt of the catalyst, if it is alkaline, are removed. The polyol may be neutralized by adding inorganic or organic acids, such as carboxylic acid or hydroxycarbonate acid.

Used polyol or mixture of polyols is selected depending on the final destination of the obtained polyurethane material. Molecule the Naya weight or hydroxyl number of primary polyol can be selected that will result in soft, semi-soft, the entire structure of the shell or rigid foams, elastomers or coatings, or adhesives, with the transformation of the polymer/polyol derived from a primary polyol in the polyurethane material by reaction with the isocyanate, and, depending on the final product, in the presence of a blowing agent. Hydroxyl number and molecular weight of the polyol or polyols can vary within wide limits. In most cases, the hydroxyl number of the polyols used may vary from 20 to 800. The choice of polyol with a suitable hydroxyl number, the level of ethylene oxide, propylene oxide and butilenica, functionality and equivalent weight exercise using standard techniques, well known to the person skilled in the art. For example, the polyols with a high level of ethylene oxide are hydrophilic, whereas the polyols with a large number of propylene oxide or butilenica will be more hydrophobic.

To obtain soft polyurethane foam, the polyol preferably is a simple polyester polyol and/or a complex of the polyester polyol. The polyol is generally characterized by an average range of functionality from 2 to 5, preferably from 2 to 4 and an average range of hydroxyl numbers of from 20 to 100 mg KOH/g, p is edocfile from 20 to 70 mg KOH/g In order for further clarification, the specific application of the foam also affects the selection of the preferred polyol. For example, molded foam, the hydroxyl number of the main polyol may be in the order of 20-60 when blocking the ethylene oxide (EO)and for block foams hydroxyl number may be on the order of 25-75 and is either mixed raw EO/PO (propylene oxide), or only slightly blocked using EO or 100 percent based on PO. For use as elastomers generally require basic polyols of high molecular weight of from 2000 to 8000, which is characterized by relatively low hydroxyl numbers, for example, 20-50.

To obtain viscoelastic foams, i.e. soft foams with very low elasticity, use a combination of polyols with different hydroxyl numbers, up to 300, and a functionality in the range from 1 to 4.

Usually polyols suitable for the production of rigid polyurethane include polyols with an average molecular weight from 100 to 10,000 and preferably from 200 to 7000. It is also advisable that such polyols had a functionality of 2, preferably 3, and up to 8, preferably up to 6 active hydrogen atoms per molecule. The polyol used for rigid foams typically have a hydroxyl number of from 200 to 1200 and more predpochtitel is but from 300 to 800.

To obtain semi-rigid foams, it is preferable to use trifunctional polyols with a hydroxyl number of from 30 to 80.

Initiators for obtaining polyols typically have 2 to 8 functional groups capable of interacting with alkalization. Examples of suitable molecules initiators are water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, and polyhydric, in particular diatomic-vospitanie alcohols, or dialkylamino, for example, ethanediol, 1,2 - and 1,3-propandiol, diethylene glycol, dipropyleneglycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and sucrose, or mixtures of these compounds. Other initiators include linear and cyclic amine compounds such as ethanolamine, triethanolamine, and the various isomers of tolualdehyde.

Polyols having autocatalytic activity, can also be used as polyol or in combination with the above-mentioned polyols. Typically, such an autocatalytic polyols contain easily accessible group of tertiary amine. The description of such autocatalytic polyols can be found in U.S. patent 5672636; European patent publications 0047 371, 1268598 and 1319034; and publications WO 03/016372, 03/029320 and 03/055930, the content of which is s included here as a reference.

The dependence of the structural characteristics of the autocatalytic polyols from the destination polyurethane material is essentially the same as for the above-described polyols. Usually the tertiary amine such autocatalytic polyols may be part of the initiator, the chain polyol and/or the composition of the protection of end groups of the polyol. These tertiary amino give such polyols autocatalytic properties.

It is understood that the restrictions pertaining to the characteristics described above polyols are not restrictive but only illustrative in relation to the large number of possible combinations used polyol or polyols.

Obtaining non-volatile catalyst (c)containing at least one kinoway connection and one group of tertiary amine, based on the interaction between the aldehyde or ketone and a molecule containing as a primary amino group and tertiary amino group. It is believed that deletecell catalyst (c) may be due to either a large molecular weight that is at least 150 g/mol, and reacting with isocyanate components or both features. Alternatively, aminogroup can interact with the isocyanate in the interactions of polyurethane products described in EP 363008, although no catalytic effect, according to this is the last document. A further advantage of the non-volatile catalyst (c) is that educated Eminova connection resistant to hydrolysis at room temperature.

A number of chemical compositions can be used to obtain a non-volatile catalyst (c), as explained below under point (c1), (c2), (C3), (C4), (C5), (C6), (c7), (c8) and (c9).

The catalyst (c1) is produced by interaction of molecules containing either at least one aldehyde, or ketone group, primary amino group of a molecule containing a primary amino group and at least one tertiary amino group. The target compound has a molecular weight of more than 150. Ketones and aldehydes for use in the present invention can be labeled, as it is well known from the prior art, through R-C(O)-R¹and R-C(O)-H, respectively, where R and R¹mean components that do not interact with the primary amine in the conditions necessary for the formation of imine. Typically, R and R¹independently denote C1-C20-, preferably C1-C15-, substituted or unsubstituted, linear or branched alkyl, cyclic, heterocyclic or aromatic compounds containing 4 to 20 atoms, preferably 5 to 15 atoms in the cycle, or R and R¹can be connected to each other to form a cyclic structure containing 5-20 atoms in the cycle. Cyclic patterns more the tion can be substituted. A variety of substituted cyclic structures is illustrated by the listed compounds. Not limiting the substituents include the groups: hydroxyl, amine, carboxylic acid, alkyl or alkyloxy. The term “cyclic structure”, as used here, includes compounds that contain more than one cycle, such as naphthalene aromatic structure.

Examples of aldehydes are salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, benzaldehyde, furfural, anisic aldehyde, Truelove aldehyde, isophthalic aldehyde, phthalic dicarboxaldehyde, terephthalic dicarboxaldehyde, 4-(dimethylamino)benzaldehyde, 4-(diethylamino)benzaldehyde, 4-(dibutylamino)benzaldehyde,

4-[3-(dimethylamino)propoxy]benzaldehyde, nitrobenzaldehyde, chlorobenzaldehyde, 2-carboxybenzene,

phenyl-1,3-dicarboxaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, piperonal, beta-hydroxybutiric aldehyde (Haldol), omega-hydroxymethylfurfural,

hydroxyacetaldehyde, 5-hydroxypentanal, acetaldol,

2,5-dimethyl-2-hydroxy dialdehyde,

3-(beta-hydroxyethoxy)propanal, beta-hydroxyacetaldehyde.

The preferred compounds are aldehydes with aromatic basis, such as salicylaldehyde,

4-dimethylamine is benzaldehyde, 4-hydroxybenzaldehyde or vanilla.

Examples of the ketone is cyclohexanone, methylcyclohexanone, Cyclopentanone, methyl isobutyl ketone, tropolone, tropan, 2'-hydroxyacetophenone, 4'-hydroxyacetophenone,

3'-hydroxyacetophenone, 3-acetyl-l-propanol,

4-hydroxy-3-methyl-2-butanone, 4-hydroxy-4-methyl-2-pentanon,

4'-hydroxyacetophenone, dihydroxyacetophenone,

benzyl-4-hydroxyphenylacetic, acetovanillone, aminobenzophenone,

aminobenzophenone.

Examples of amines containing both primary and tertiary amino group are 3-(dimethylamino)Propylamine,

l-(3-aminopropyl)imidazole, 1-(3-aminopropyl)-2-Mei, N,N-dimethylpiperidinium, N,N-dimethylethylenediamine,

N,N-diethylethylenediamine, N,N-dibutylethanolamine,

3-(diethylamino)Propylamine, 3-(dibutylamino)Propylamine,

N,N,2,2-tetramethyl-l,3-propandiamine,

2-amino-5-diethylaminopentane, N-methyl-N'-amino-ethyl)piperazine,

1,4-bis-(3-aminopropyl)piperazine, 3-aminoquinuclidine,

4-(2-amino-ethyl)morpholine, 4-(3-aminopropyl)morpholine,

N,N-dimethyl-1,4-phenylenediamine, 5-amino-1-aripirazole,

2-aminopyridine, 2-(aminomethyl)pyridine, 2-(aminoethyl)pyridine,

4-aminopyridine, 3-aminopyridine, 3-(aminomethyl)pyridine,

N-aminopropylmorpholine-2-aminophylline, diaminopyridine,

2-aminopyrimidine, 4-aminopyrimidine, aminopyrazine, 3

-amino-1,2,4-triazine, Aminah Nalini,

N,N-dimethylpiperidinium and 3,3'-diamino-N-methyldiphenylamine, N-methyl-1,3-propertiesin.

The catalyst (c2) is produced by interaction of molecules containing at least one aldehyde or a ketone group and at least one tertiary amino group with a molecule containing a primary amino group and, optionally, other amino and/or alcohol groups.

Ketones and aldehydes containing a tertiary amino group, can be generally represented via (R²)₂N-R³-C(O)-R and (R²)₂N-R³-C(O)H, where R takes values above, R²means C1-C6 linear or branched alkyl, and R³means C1-C12 linear or branched alkyl, aromatic or alkylaromatic group with 6-20 atoms, preferably 6 to 15 carbon atoms, substituted by at least one tertiary amino group, or R³and R can be connected to each other to form a cyclic structure containing 5-20 atoms, preferably 5 to 15 atoms in the cycle. R³can also mean a cyclic or bicyclic group with 5-20 atoms, where at least one nitrogen included in a cyclic structure. Alkyl and cyclic groups may be substituted by various groups, as described above.

Examples of aldehydes and ketones containing tertiary nitrogen, are binucleation, tropine, l-m is Tyl-4-piperidinol,

4-(dimethylamino)benzaldehyde, 4-(diethylamino)benzaldehyde,

4-(dibutylamino)benzaldehyde,

4-[3-(dimethylamino)propoxy]benzaldehyde.

Compounds containing primary amines well known in the prior art. Typical examples of the preferred compounds containing primary amines are Ethylenediamine, 1,6-hexanediamine, aniline, N,N-dimethylpiperidinium, 3,3'-diamino-N-methyldiphenylamine, 3-aminopropyl-N-methylethanolamine and 3-(dimethylamino)Propylamine, monoethanolamine, 2-amino-1-butanol.

Catalysts (c3) are the catalysts obtained by modification amoxilonline molecules with compounds containing aldehyde or ketone group, and reacting with the epoxy group, such as alcohol, amine, thiol or carboxylic acid, and subsequent implementation of the interaction with the molecule a primary amine containing a tertiary amino group, leading to the formation of kinoway communication. Catalysts (c3) preferably contain more than one kinoway connection and more than one tertiary amino group in the molecule.

With regard to the present invention compounds having aldehyde functionality and reacting with the epoxide functionality (alcohol, amine, thiol or carboxylic acid), are C3-C30-, preferably C5-C18-, aliphatic, aromatic or polyaromatics is their connection and cyclic structures, containing a heteroatom, where the aldehyde group is connected directly with the cycle and reacting with the epoxide group is associated directly with the cycle or through a C1-C6 linear or branched alkyl group. Such compounds may contain more than one reactive epoxide group or more than one aldehyde group. Cyclical components may be optionally substituted by groups that do not interact with epoxides, such as alkyl or alkoxygroup.

Examples of alcohols having aldehyde functionality are salicylaldehyde, vanilla, 5-(hydroxymethyl)furfural,

3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, dihydroxybenzaldehyde and trihydroxybenzaldehyde.

Examples of carboxylic acids containing aldehyde functionality, are 2-carboxybenzene and 3-carboxybenzene.

For the purposes of this invention, compounds having a ketone functionality and reacting with the epoxide functionality (alcohol, amine, thiol or carboxylic acid), are C3-C30-, preferably C5-C18-, aliphatic, aromatic or polyaromatic compounds and cyclic structure containing a heteroatom, where the reactive epoxide group are connected directly with the cycle or through a C1-C6 linear or branched alkyl group. Ket is h may also be part of a cyclic structure. Such compounds may contain more than one reactive epoxide group or more than one ketone group. Cyclical components may be optionally substituted by groups that do not interact with epoxides, such as alkyl or alkoxygroup.

Examples of the alcohols having a ketone functionality, are 2'-hydroxyacetophenone, 4'-hydroxyacetophenone,

3'-hydroxyacetophenone, 3-acetyl-1-propanol,

4-hydroxy-3-methyl-2-butanone, 4-hydroxy-4-methyl-2-pentanon,

4'-hydroxyacetophenone, dihydroxyacetophenone,

benzyl-4-hydroxyphenylacetic and acetovanillone.

Examples of amine-containing ketone functionality, are 3'-aminoacetophenone, 4'-aminoacetophenone and aminobenzophenone. Examples of carboxylic acids containing a ketone functionality, are 4-acetylbenzoic acid and 2-benzoylbenzene acid.

Examples of epoxides or epoxy resins suitable for the preparation of catalysts (c3), known from the prior art. See, for example, U.S. patent 4609685, the content of which is incorporated herein by reference. Epoxy compounds may be Monomeric or polymeric, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted, if desired, other substituents, in addition to apachegroup, is for example, the hydroxyl groups, ether radicals and halogen atoms. A preferred group of epoxides can be represented by the formula

where R⁴means substituted or unsubstituted aromatic, aliphatic, cycloaliphatic or heterocyclic group and n has an average value from 1 to 8.

Examples of preferred epoxides are simple phenylglycidyl ether, aromatic apoximately from bisphenol A, bisphenol F and resorcinol and the corresponding hydrogenated derivatives; and epoxy resin on the basis of simple aliphatic polyesters, such as D.E.R. 736, D.E.R. 732 and ERL-4221 (cyclic aliphatic epoxide), all supplied by The Dow Chemical Company. Other preferred epoxy resins include epoxydecane oils, such as epoxydecane soybean oil and epoxydecane linseed oil. A mixture of any two or more epoxides can be used to implement the present invention. Preferably the epoxy resin has srednekamennogo weight of from 90 to 1000. More preferably, Apeksimova srednekamennogo weight of from 150 to 500.

The preferred epoxides are aliphatic or cycloaliphatic polyepoxide, more preferred diepoxide, such as D.E.R. 732 or D.E.R. 736, or apoximately low is by cutting down chlorine and similar structures.

Examples of amines containing both primary and tertiary amino groups, described above in section (c1).

Catalysts (c4) are obtained analogously to catalyst (c3), except that the part of the aldehyde or ketone containing reactive epoxide functionality that interacts with polyepoxides, replace reagent containing functionality, only reacting with the epoxide. This replacement can improve srednemolekularna weight of the final catalyst (c4) by chain elongation of polyepoxide through the use of polyfunctional compounds, or reduced by stopping the growth of chain polyepoxide through the use of monofunctional compounds, to obtain a product with desired properties designed for specific applications. Examples of molecules that are suitable to replace a fraction of aldehyde or ketone containing reactive epoxide functionality, include such as phenol, cresol, bisphenol A, bisphenol F, noworoczne polyols, resorcinol, Ethylenediamine, 3,3'-diamino-N-methyldiphenylamine, monoethanolamine, acetic acid, adipic acid, succinic acid, isophthalic acid, phthalic acid and terephthalic acid.

The catalyst (c5) are obtained analogously to catalyst (c3), except that the part of the primary amine, substituted tertiary amines, substituted poly is unctionally primary amine. This replacement allows you to increase or decrease the weight the weight of the final catalyst (c5) to obtain a product with desired properties designed for specific applications. Examples of molecules that are suitable for such replacement, include monoethanolamine, 2-amino-1-butanol, 2-amino-2-ethyl-l,3-propandiol, Ethylenediamine, butanediamine, hexanediamine, polyoxyalkylene JEFFAMINE® (trademark of Huntsman Chemical Corporation), methylenedianiline and diaminobenzoic.

Another possible way to obtain non-volatile catalyst with plenty of active centers (C6) is based on the interaction of polyols, blocked primary amines, such as polyoxyalkylene JEFFAMINE®molecule containing aldehyde or ketone group and a tertiary amine, such as molecules that are specified for (c2). General patterns of polyoxyalkylene JEFFINE known from Huntsman's technical bulletin 1008-1002.

Catalysts (c7) is identical to (c3) and/or (c4), but part of apoximately undergoes interaction with a compound containing reactive epoxide group, such as amine, before the introduction of aldehyde or ketone containing reactive epoxide functionality. For example, the epoxide is subjected to interaction with a secondary amine containing tertiary amine functionality (such as imidazole), or a primary amine, such as monoethanolamine, or aniline that p is allowed to adjust the functionality and molecular weight of the final product. Compounds contributing to the lengthening of the chain, are the compounds listed for case (c3). Preferably the connection, previously subjected to interaction with polyepoxides, also contains a tertiary amine group. Usually at this stage is subjected to interaction 1-50 percent of apachegroup.

In General, secondary amines can be identified and OTHERS₂⁵and primary amines as H₂NR⁵where each R⁵independently means a component with 1-20 carbon atoms or may be connected to the nitrogen atom and, optionally, other heteroatoms and alkyl substituted by heteroatoms to form a saturated heterocyclic ring.

Examples of the reactive epoxide amine, commercially available and suitable for use in order for industrial preparation of catalyst (c7)are methylamine, dimethylamine, diethylamine, N,N-dimethylethanolamine, N,N'-dimethylethylenediamine, N,N-dimethyl-N'-Ethylenediamine, 3-dimethylamino-1-propanol,

1-dimethylamino-2-propanol, 3-(dimethylamino)Propylamine,

dicyclohexylamine, 4,6-dihydroxypyrimidine,

1-(3-aminopropyl)imidazole, 3-hydroxypyrrolidine,

2-Mei, 1-(2-amino-ethyl)piperazine, 1-methylpiperazine,

3-hinokitiol, 2,4-diamino-6-hydroxypyrimidine,

2,4-diamino-6-methyl-1,3,5-triazine, 3-aminopyridine,

2,4-diaminopirimidina,

2 phenylimino-3-(2-guide the oxyethyl)oxazolidin,

N-(2-hydroxyethyl)-2-methyltetrahydrofuran,

N-(2-hydroxyethyl)imidazoline,

2,4-bis-(N-methyl-2-hydroxyethylamino)-6-phenyl-1,3,5-triazine, bis(dimethylaminopropyl)amino-2-propanol, Tetraethylenepentamine, 2-(2-aminoethoxy)ethanol

N,N-dimethylaminoethyl-N'-methylethanolamine, 2-(methylamino)ethanol, 2-(2-methylaminomethyl)pyridine, 2-(methylamino)pyridine,

2-methylaminomethyl-1,3-dioxane, dimethylaminopropylamine.

Compounds containing at least one tertiary nitrogen and at least one reactive epoxide hydrogen molecule can be represented as ((H)_x-A-R⁶z-M-(R⁷)y, where A stands for nitrogen or oxygen, x is 2, when A stands for nitrogen, and 1, when A denotes oxygen, R⁶and R⁷mean linear or branched alkyl group with 1-20 carbon atoms; M indicates the amine or polyamine, linear or cyclic, with at least one tertiary amino group; y represents an integer from 0 to 6, and z denotes an integer from 1 to 6.

Compounds containing tertiary nitrogen and the primary amine may be represented by the formula: H₂N-R⁸-N(R⁹)₂where R⁸means aliphatic or cyclic chain with 1-20 carbon atoms and R⁹means C1-C3 alkyl group.

The catalyst (c8) is produced by interaction of the isocyanate with alcohol containing aldagen the Yu or ketone functionality, with the subsequent implementation of the interaction with the primary amine containing tertiary amine to form kinoway connection with the polyol.

Examples of isocyanates are colorvision, isophorondiisocyanate, phenylisocyanate, methyldiphenylamine, or an appropriate mixture of the prepolymers. The preferred isocyanates are polyisocyanates, more preferably diisocyanates.

Examples of alcohols containing aldehyde or ketone functionality and amines containing both primary and tertiary amino groups, described above.

The catalyst (c9) based on a combination of chemical compositions described for (c3) and (c8), i.e. receive a mixture of catalysts for epoxy and isocyanate-based.

The raw materials for the preparation of the catalyst (c) are for sale or can be obtained by methods known to experts in this field, as well as known and reaction conditions for the preparation of the catalyst (c). In General, the ratio of the compounds on the particular reaction stage is close to the stoichiometric molar equivalent of reactive components, i.e. from 0.9:1, preferably from 0.95:1 to 1:1. For example, upon receipt of the catalyst (c3), in the case of interaction between functionalized with epoxide, for example, aldehyde group and a primary amine, the molar ratio of equival now aldehyde and the primary amine is approximately 1:1. However, this ratio may be increased to 1.2:1, if it is desirable to minimize the amount of free amine in the catalyst (c). In the case of catalysts (c4) and (c5) you can adjust this ratio to obtain a molar excess of one of the reactive groups in order of increasing molecular weight.

The mass ratio of non-volatile catalyst (c) and polyol varies depending on the amount of additional catalyst, which is supposed to add to the reaction mixture, and the reaction profile required for the specific application. Usually, if the reaction mixture with a standard level of catalyst has a certain curing time, the non-volatile catalyst (c) is added in an amount such that the curing time was equivalent, with the reaction mixture contains at least 10 weight percent of the catalyst is less. Preferably (c) is made to obtain the reaction mixture containing the catalyst is 20 percent below the standard level. More preferably (c) reduces the amount of catalyst required 30 percent relative to the standard level. For a number of applications, the most preferred level of administration (c) is level when there is no need for volatile tertiary amine or a reactive amine catalysts, Il is in ORGANOMETALLIC salt. For a number of other goals, such as reducing the time of discharge form, it is desirable to maintain the standard number of conventional amine or ORGANOMETALLIC catalyst and to consider adding the catalyst (c) in an amount that enhances the time of demoulding. For the last specified event, typically 0.1-10 mass parts or more catalyst (c) is added to 100 mass parts of polyol.

Regulation of the level of catalyst (c), allowing separate use or in combination with conventional polyurethane catalysts or polyols having autocatalytic activity, depending on the particular purpose, are familiar to a person skilled in this field.

A combination of two or more non-volatile catalyst (c) type can also be used with satisfactory results in the individual obtaining the polyurethane, when required, for example, regulation of steam formation and gelation, through modification of the structure of the catalysts (c) through the use of various tertiary amines, functionalities, equivalent mass, the ratio of EO/PO, etc., and the relative amounts of the compounds.

The non-volatile catalyst (c), relating to the same type (c1), (c2), (c3), (c4), (c5), (c6), (c7), (c8) and (c9), can also be performed with a combination of tretin the x amines, for example, by interaction of the aldehyde or ketone with more than one primary amine containing a tertiary amine group as defined for (c1).

Conversely, the catalyst (c) can be obtained from several types of aldehyde and/or ketone groups capable of interacting with one or more primary amines containing a tertiary amino group.

Acid neutralization of the catalyst (c) may also be considered when you need to slow the action. However, this may adversely affect the catalytic composition as the above-mentioned composition must be stable when mixed with uterine solutions for polyols; i.e. water, surface-active agent, a binder, etc., preferably, at least one week at room temperature. Preferably the catalyst (c) must be stable in the premix based polyol, at least for 6 months. Preferred acids are carboxylic acids, more preferably, with the OH group and/or halogen group.

The catalysts (c), previously subjected to an interaction with polyisocyanates and polyol (b1), not containing free isocyanate functions, can also be used to produce polyurethane. The isocyanate prepolymers based catalyst (c), can be obtained on standard equipment using conventional methods, such as heating of the catalyst (c) in the reactor and the slow addition of isocyanate with stirring, and then the final addition of the polyol, or pre-engagement first polyol with a diisocyanate and then adding catalyst (c).

Isocyanates that can be used with autocatalytic polyols of the present invention include aliphatic, cycloaliphatic, arylaliphatic and aromatic isocyanates. Preferred aromatic isocyanates, in particular aromatic polyisocyanates.

Examples of suitable aromatic isocyanates include 4,4'-, 2,4'- and 2,2'- isomers of diphenylmethanediisocyanate (MDI), mixtures of these isomers and a mixture of polymeric and Monomeric MDI blends, toluene-2,4 - and 2,6-diisocyanates (TDI), m - and

n-delete the entry, chlorphenesin-2,4-diisocyanate,

diphenylene-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyldiphenyl, 3-methyldiphenylamine-4,4'-diisocyanate and the diisocyanate diphenyl ether, 2,4,4'-triisocyanate and

2,4,4'-triisocyanate ether.

Can be used a mixture of isocyanates, such as existing in the sale of a mixture of 2,4 - and 2,6-isomers of colordistance. Technical polyisocyanate may also be used to great the political implementation of the present invention, such as technical colorvision received by postironium mixture of tolualdehyde, or technical diphenylmethanediisocyanate received by postironium technical methylenedianiline. Can also be used a mixture of TDI/MDI. Can also be used prepolymers based on MDI or TDI, received or polyol (b1), the polyol (b2), or any other above-mentioned polyol. The prepolymers with terminal isocyanate groups obtained when the interaction of an excess of MDI with a polyol, including aminirovanie polyols or appropriate imine/enamines, or polyamine.

Examples of aliphatic polyisocyanates include atlantaatlanta, 1,6-hexamethylenediisocyanate, isophoronediisocyanate, cyclohexane-1,4-diisocyanate,

4,4'-dicyclohexylmethane, saturated analogues of the above-mentioned aromatic isocyanates and mixtures of these compounds.

Preferred polyisocyanates for the production of rigid or semi-rigid foams are polymethylenepolyphenylisocyanate, 2,2'-, 2,4'- and 4,4'- isomers diphenylmethanediisocyanate and mixtures of these compounds. To obtain soft foams, the preferred polyisocyanates are toluene-2,4 - and 2,6-diisocyanate, or MDI, or a combination of TDI/MDI, or derived from these compounds the prepolymers.

A prepolymer with terminal isocyanate the groups on the basis of non-volatile catalyst (c) can also be used to produce polyurethane. It is believed that the use of such autocatalytic isocyanate in the reaction mixture polyisocyanate should reduce/eliminate the presence of unreacted isocyanate monomers. This is particularly interesting in the case of volatile isocyanates, such as TDI and/or aliphatic isocyanates in the case of use as coatings and adhesives, as improved technological conditions and safety of workers.

In the case of rigid foams organic polyisocyanates and compounds that react with isocyanates, put together in such amounts that the isocyanate index, defined as the ratio between the number of equivalents of NCO groups and the total number of equivalents of hydrogen atoms reactive with isocyanate, multiplied by 100, varies from 80 to less than 500, preferably from 90 to 100, in the case of polyurethane foams, and from 100 to 300 in the case of a combination of polyurethane foams-polyisocyanurate. For soft foams this isocyanate index typically varies from 50 to 120 and preferably from 75 to 110.

For elastomers, coatings and adhesives isocyanate index typically varies from 80 to 125, preferably from 100 to 110.

To obtain a foam based on polyurethane is usually required foaming substance. Upon receipt soft propoline the ANOVA as a foaming substance preferred water. The amount of water mainly varies from 0.5 to 10 mass parts, more preferably from 2 to 7 mass parts per 100 mass parts of polyol. Carboxylic acid or salt is also used as reactive foaming agents.

Upon receipt of the hard polyurethane foaming substances include water and mixtures of water with the hydrocarbon either partially or completely halogenosilanes aliphatic hydrocarbon. The amount of water mainly varies from 2 to 15 mass parts, more preferably from 2 to 10 mass parts per 100 mass parts of polyol. Excessive amounts of water curing rate becomes lower, the range of the churning process narrows the density of the foam is lower or formability becomes poor. The number of hydrocarbon, chlorofluorocarbon or ftoruglevodorodnye combined with water, it is advisable to choose depending on the desired foam density, and this value is preferably not more than 40 mass parts, more preferably not more than 30 mass parts per 100 mass parts of polyol. When water is present as an additional foaming substances, the amount of water is usually from 0.5 to 10, preferably from 0.8 to 6 and, more preferably, from 1 to 4 and is, most preferably, from 1 to 3 parts by weight of the total aggregate paleologou composition.

Hydrocarbon blowing agents are volatile C₁-C₅-hydrocarbons. The use of hydrocarbons is known in the art and are described in EP 421269 and EP 695322. Preferred hydrocarbon foaming agents are butane and related isomers, pentane and related isomers (including cyclopentane), and combinations of these compounds.

Examples of fluorocarbons include methylphenid, performer, Tilford, 1,1-differetn, 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluoropropane (HPC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), Heptafluoropropane (HFC-227ea), pentaborate, deformity, perforated, 2,2-ditropan, 1,1,1-tryptophan, perftoran, dichlorprop, ditropan, perftoran, perftorsilanami or mixtures of these compounds. Preferred combinations are combinations that include a combination of two or more 245, 265 and 227 foaming agents.

Partially halogenated chloropeta and chlorofluorocarbons for use in this invention include methyl chloride, methylene chloride, ethylchloride, 1,1,1-trichloroethane,

1,1-dichloro-l-foraten (FCFC-141b), 1-chloro-l,1-deflorated

(HCFC-142b), 1,l-dichloro-2,2,2-trifluoroethane (HCHC-123) and

1-chloro-l,2,2,2-Tetrafluoroethane (HCFC-124).

Fully halogenated chlorine is oroperty include trichloromonofluoromethane (CFC-11), DICHLORODIFLUOROMETHANE (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane, pentaborate, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane and dichlorohexafluoropropane. Halogenosilanes foaming agents may be used in combination with low-boiling hydrocarbons such as butane, pentane (including the respective isomers), hexane or cyclohexane, or with water.

The use of carbon dioxide as a gas and in liquid form, as a subsidiary or wholly self-foaming substances in particular is of interest from the point of view of the technologies under consideration. Using an artificially low or high atmospheric pressure can also be used in this technology.

In addition to the foregoing critical components upon receipt of polyurethane polymers often require the use of some other ingredients. Among these additional ingredients include surfactants, preservatives, flame retardants, colorants, antioxidants, reinforcing fillers, stabilizers and fillers.

Upon receipt of the polyurethane foam is usually advisable to use some amount of surfactant to stabilize the foaming reaction mixture before curing. Such surface-AK is active substances usually consist of a liquid or solid silicone surface active substances. Other surface active substances include polietilenglikolya esters of long-chain alcohols, salts of tertiary amine or alkanolamine and long-chain alilovic acid sulfate esters, alkylsulfonic esters and alkylarylsulfonate acids. Such surfactants are used in amounts sufficient to stabilize the foaming reaction mixture, preventing the decay of the foam and the formation of large, irregular pores. Usually for this purpose it is enough of 0.2-3 mass parts of surface active substances on 100 mass parts in total of the polyol (b).

You can use one or more catalysts interaction polyol (and water, if present) with the polyisocyanate. Can be used any suitable urethane catalysts, including tertiary amine compounds, amines with reactive isocyanate groups, and ORGANOMETALLIC compounds. Preferably, the interaction is carried out in the absence of a volatile amine or ORGANOMETALLIC catalyst or with a reduced amount, as described above. Typical examples of the tertiary amine compounds include triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, simple bis(dimethylaminoethyl)new ester, l-methyl-4-dimethylaminomethylphenol,

3-IU is hydroxy-N-dimethylpropylene, N-ethylmorpholine,

dimethylethanolamine, N-cocomotion,

N,N-dimethyl-N',N'-dimethylsulphoniopropionate,

N,N-diethyl-3-diethylaminopropylamine and dimethylbenzylamine.

Typical examples of ORGANOMETALLIC catalysts include catalysts based on organo-mercury compounds, organic lead compounds, organic iron compounds and ORGANOTIN compounds, from which the catalysts based on ORGANOTIN compounds are preferred. Suitable catalysts based on tin include tin chloride, tin salt with carboxylic acids, such as dibutyltindilaurate and other metaloorganicheskih compounds such as described in U.S. patent 2846408. Here also, optionally, may be used a catalyst for the trimerization of polyisocyanates, leading to polyisocyanurate, such as an alkali metal alkoxide.

The amount of amine catalysts in the composition may vary from 0.02 to 5 percent or composition can be used metaloorganicheskih catalysts in the range from 0.001 to 1 percent. In the preferred embodiment, none of these catalysts is not required in case of application of the non-volatile catalyst (c).

If necessary, may be added a crosslinking agent or chain extension. A crosslinking agent or AF extension cable-the circuit includes a low molecular weight polyhydric alcohols, such as ethylene glycol, diethylene glycol, 1,4-butanediol, and glycerin; low AMINOPHENYL, such as diethanolamine and triethanolamine; polyamine, such as Ethylenediamine, Cialdini and Methylenebis(o-Chloroaniline). The use of such crosslinking agents or chain extenders known in the prior art, as described in U.S. patent 4863979 and 4963399 and EP 549120.

Upon receipt of rigid foams for use in structures as supplements usually include the moderator burning. Any known liquid or solid moderator combustion can be used with autocatalytic polyols of the present invention. Typically, these flame retardants are halogen-substituted phosphates and inorganic flame-retardant means. Conventional halogen-substituted phosphates are tricresylphosphate, Tris-(1,3-dichloropropylene, Tris-(2,3-dibromopropyl)phosphate and tetrakis-(2-chloroethyl)ethylendiamin. Inorganic flame retardants include red phosphorus, hydrate, aluminum oxide, antimony trioxide, ammonium sulfate, expanding graphite, urea or melincourt, or a mixture of at least two flame retardants. In General, if present, flame-retardants are added at a level from 5 to 50 mass parts, preferably from 5 to 25 mass parts of the retardation of combustion per 100 mass parts in total PR is ststuga polyol.

The fillers include, for example, barium sulfate, calcium carbonate, recyclery foaming powder, such as described in EP 711221 or GB 922306.

The application of the foams obtained according to the present invention, well-known specialists in the field of technology. For example, rigid foams used in construction and insulation in appliances and refrigerators. Soft foams and elastomers are used in the furniture industry, for the manufacture of protective coverings, Shoe soles, car seats, sun visors, steering wheels, armrests for seats, door panels, sound insulation parts and dashboards.

Technology for producing polyurethane materials are well known in the prior art. In most cases, components polyurethanebased mixture can be mixed together in any conventional manner, for example, using any mixing equipment known in the art and used for a specified purpose, such as described in "Polyurethane Handbook", by G. Oertel, Hanser publisher.

Polyurethane materials are given either continuous or periodic manner by injection molding, casting, spraying, pouring, calendering, etc., - by getting a free lift or in the conditions of forming, in the presence or absence of R is deletelines lubrication, cover the mold cavity or any inclusions or protective film is made in the form. In the case of soft foams foams can be reinforced with one or both of the parties.

For the production of rigid foams, the known one-step methods of obtaining the prepolymer or the formation of the prepolymer at an intermediate stage can be used in conjunction with conventional methods of mixing, including percussion mix. Rigid foam can also be obtained in the form of a block, molded products, aggregates of voids, foam, obtained by spray foam obtained by foaming, or laminates with other materials such as paper, metal, plastics or wood stove. Soft foams are produced either in a free ascent, or in conditions of molding, while microcellular elastomers are usually cast.

The following examples are given to illustrate the invention and in no way can be considered as limiting. Unless otherwise noted, all parts and percentages are mass. The designation of mol is used to mole or moles.

Designation of source materials below.

All foams receive in the laboratory by pre-mixing polyols, surfactants, cross-linking agents, catalysts and water. This Royal blend is machine tank apparatus for working under high pressure (produced by Krauss-Maffei or Cannon), with isocyanate side filled Voranate T-80. The reagents are poured into aluminum shape, heated to 60°C, which was subsequently closed. Before using the spray form of the separation means. Curing at specied times demoulded appreciate, manually removing the part from the mold and finding defects. Reach the minimum time demoulded, in which there are no surface defects.

Test free upgrade is done using a plastic bucket 22.7 liters (5 UK gallons) and the pouring out of the apparatus for working under high pressure, a small portion, sufficient to fill the bucket to about 30 cm cap of foam over the top edge of the bucket. Then visually determine the stability of the foam.

BVT-test reactivity (test viscosity Brookfield) carried out as follows : the m: 100 grams polyol incubated at 25°C and then mixed with of 0.26 grams of Dabco 33 LV. Then add Voranate T-80 at a concentration corresponding to the index 110. The viscosity increasing with time, register to complete gelation. In the case of a non-volatile catalyst (c) catalysts are mixed in different ratios with the reference sample polyol and Dabco 33 LV do not use. Record time to reach the final target viscosity of 20,000 mPa.s (corresponding to 100% of the twisting moment).

Example 1

Adduct of salicylaldehyde and 1-(3-aminopropyl)imidazole

In a two-neck round bottom flask of 100 ml, equipped with a magnetic rod stirrer, addition funnel and a fridge load of 15.0 g (0,123 mol) of salicylaldehyde. 1-3-(Aminopropyl)imidazole (15,4 g, 0,123 mol) is placed into the addition funnel. The amine is added dropwise while stirring the reaction mixture under nitrogen atmosphere. When you are finished adding brown-yellow transparent oil was poured from the flask into the flask. The output of the selected substance = 28,5, When standing product is solidified and has the following characteristics.¹H NMR (DMSO): 8,55 (s, 1H), 7,65 (s, 1H), 7,45 (d, 1H), and 7.3 (t, 1H), 7,2 (s, 1H), 6,9 (m, 3H), 4,1 (t, 2H), 3,5 (t, 2H), 3,3 (users, ~3H), 2,1 (m, 2H);¹³C NMR (DMSO-d₆) 166,4, 160,5, 137,3, 132,3, 131,7, 128,5, 119,3, 118,7, 118,6, 116,4, 55,5, 43,9, 31,6. theoretical amount of water in the product to 7.3 wt.%.

Example 2

Adduct of salicylaldehyde and 3-dimethylaminopropylamine

In the TLD the astronomical clock round bottom flask 100 ml, equipped with a magnetic rod stirrer, addition funnel and a fridge load of 15.0 g (0,123 mol) of salicylaldehyde. 3-Dimethylaminopropylamine (12,55 g, 0,123 mol) is placed into the addition funnel. The amine is added dropwise while stirring the reaction mixture under nitrogen atmosphere. When you are finished adding brown-yellow transparent oil was poured from the flask into the flask. The output of the selected substance = 26,9 g characteristics the following.¹H NMR (DMSO): 8,55 (s, 1H), 7,45 (d, 1H), and 7.3 (t, 1H), 6,9 (m, 2H), 3,6 (t, 2H), 3,4 (users, ~3H),of 2.25 (t, 2H); of 2.15 (s, 6H), of 1.75 (m, 2H),¹³C NMR (DMSO-d₆) 165,5, 160,6, 131,8, 131,2, 118,2, 118,0, 116,2, 56,2, 55,9, 44,8, 28,0. theoretical amount of water in the product to 8.0 wt.%.

Example 3

Adduct of epoxy resin A, salicylaldehyde and 3-dimethylaminopropylamine

In a two-neck round bottom flask of 1 l, equipped with a mechanical stirrer, a nozzle Clausen and nozzle for gas inlet connected to a source of vacuum/nitrogen load 444,0 g (1.5 mol apachegroup) of epoxy resin A, 183,2 g (1.5 mol) of salicylaldehyde and 5.8 g (3.42 g active, 9.0 mmol) tetrabutylphosphonium (59 wt.% in methanol). The vacuum apparatus to 20 mm Hg and then connect with nitrogen. Alternating cycle vacuum/nitrogen repeat in the amount of 5 times, ending with nitrogen. The device is left in a dynamic nitrogen atmosphere and immersed in an oil bath, maintaining at 120°C. After 1 hour the temperature is in the bath was raised to 150°C and the reaction mixture was stirred over night. After 20 hours selected sample of the reaction mixture and analyzed by NMR to ensure that all of the epoxide used. The flask is removed from the oil bath and supply dropping funnel containing shall be 152.3 g (1,49 mol) of 3-(dimethylamino)Propylamine. The amine is added dropwise to a stirred warm the reaction mixture for 1 hour. When you are finished adding brown-red transparent oil was poured from the flask into the flask. The output of the selected substance = 775,2 g characteristics the following.¹H NMR (DMSO): 8,7 (s, 1H), a 7.85 (d, 1H), and 7.4 (m, 1H), 7,0 (m, 2H), 5,2 (users, OH), 4,0 (m, H s easy polyester), 3,4 (osirm formed by a simple polyester + Amin H s in), 2.25 (t, 2H), 2,1 (s, 6H), 1,7 (m, 2H), 1.0 (users, CH3 from polyether). theoretical amount of water in the product of 3.4 wt/%. theoretical number of dimethylaminopropyl in a sample of 1.9 mEq/g

Example 4

Adduct of epoxy resin A, salicylaldehyde and 1-(3-aminopropyl)imidazole

In a two-neck round bottom flask of 1 l, equipped with a mechanical stirrer, a nozzle Clausen and nozzle for gas inlet connected to a source of vacuum/nitrogen load 450,3 g (1.54 mol apachegroup) of epoxy resin A, 187,7 g (1.54 mol), salicylaldehyde and 5.8 g (3.42 g active, 9.0 mmol) tetrabutylphosphonium (59 wt.% in methanol). The vacuum apparatus to 20 mm Hg and then connect with nitrogen. Alternating cycle vacuum/nitrogen repeat Aut in the amount of 5 times, to nitrogen. The device is left in a dynamic nitrogen atmosphere and immersed in an oil bath, maintaining at 140°C. After 2 hours, the bath temperature was raised to 150°C, and the reaction mixture was stirred over night. After 20 hours selected sample of the reaction mixture and analyzed by NMR to ensure that all of the epoxide used. The flask is removed from the oil bath and supply dropping funnel containing 188,5 g (1,51 mol) of 1-(3-aminopropyl)imidazole. The amine is added dropwise to a stirred, warm the reaction mixture for 30 minutes. When you are finished adding orange transparent oil was poured from the flask into the flask. The output of the selected substance = 816,7 g characteristics the following.¹H NMR (DMSO): 8,7 (s, 1H), a 7.85 (d, 1H), and 7.6 (s, 1H), and 7.4 (m, 1H), 7,2 (s, 1H), 7,0 (m, 3H), 5,2 (users, OH), 4,0 (m, polyester + H s formed by amine), 3,4 (osirm formed by a simple polyester + Amin H s), is 2.05 (m, 2H), 1,7, 1,0 (users, CH3 from polyether). theoretical amount of water in the product of 3.3 wt.%. theoretical number of imidazole groups in the sample is 1.81 mEq/g

Example 5

Adduct DER 732, salicylaldehyde and 3-dimethylaminopropylamine

Using the method of example 3, which was charged to the reactor to 450.0 g (1.4 mol apachegroup) DER 732 (aliphatic liquid epoxy resin with an epoxy equivalent weight of 322), 170,7 g (1.4 mol) of salicylaldehyde and 5.4 g (3,17 aktivnih, 8.4 mmol) tetrabutylphosphonium. After a reaction period of 20 hours is added dropwise 141,8 (1,39 mol) of 3-(dimethylamino)Propylamine in 1 hour. When you are finished adding orange transparent oil was poured from the flask into the flask. The output of the selected substance=760,1 g characteristics the following.¹H NMR (DMSO): 8,7 (s, 1H), a 7.85 (d, 1H), and 7.4 (m, 1H), 7,0 (m, 2H), 5,2 (osirm, HE), 4,0 (m, N s polyether), 3,4 (osirm formed by a simple polyester+Amin H s in), 2.25 (t, 2H), 2,1 (s, 6N), and 1.7 (m, 2H), 1.0 (users, CH3 from polyether). theoretical amount of water in the product of 3.3 wt.%. theoretical number of dimethylaminopropyl in the sample 1.82 mEq/g

Example 6

Adduct PER 383, salicylaldehyde and 3-dimethylaminopropylamine

In the apparatus according to example 3 loads of 30.6 g (169,6 mmol of apachegroup) DER 383, 20.7 g (169, 5mm mmol) salicylaldehyde and 660,2 mg (to 389.5 mg active 1,03 mmol) tetrabutylphosphonium. After cycle vacuum/nitrogen as in example 3, the apparatus is left in a dynamic nitrogen atmosphere and immersed in an oil bath, maintaining at 85°C. After 2 hours, the bath temperature was raised to 100°C. and the reaction mixture was stirred over night. After 20 hours selected sample of the reaction mixture and analyzed by NMR to ensure that all of the epoxide used. The oil bath containing the reaction mixture was cooled to 70°C. and the flask supply dropping funnel, containing the th 17.0 g (166,4 mmol) of 3-(dimethylamino)Propylamine. The amine is added dropwise to a stirred warm the reaction mixture for 10 minutes. When you are finished adding viscous, yellow, transparent oil was poured from the flask into the flask still warm. The output of the selected substance = 64 g characteristics the following.¹H NMR (DMSO): 8,7 (s, 1H), a 7.85 (d, 1H), and 7.4 (m, 1H), and 7.1 (d 2H), 7,0 (m, 2H), 6,85 (d, 2H), 5,5 (users, OH), 4,1 (m, H s easy polyester), 3,5 (t, H s, formed by amine), 3,4 (ushers in), 2.25 (t, 2H), 2,1 (s, 6H), 1,7 (m, 2H), 1.55V (users, CH3, formed by bisphenola). theoretical amount of water in the product 4,36 wt.%. theoretical number of dimethylaminopropyl in the sample 2,42 mEq/g

Example 7

Adduct DEN 438, salicylaldehyde and 3-dimethylaminopropylamine

In the apparatus according to example 3 loads of 33.6 g (187,5 mmol of apachegroup) DEN 438 (epoxy equivalent weight 179,2), 22.9 grams (187,5 mmol) salicylaldehyde and 647,6 mg (382,1 mg, 1.0 mmol) tetrabutylphosphonium. The vacuum apparatus to 20 mm Hg and then connect with nitrogen. Alternating cycle vacuum/nitrogen repeat in the amount of 3 times, ending with nitrogen. The device is left in a dynamic nitrogen atmosphere and immersed in an oil bath, maintaining at 90°C. After 30 minutes, the bath temperature was raised to 100°C and the reaction mixture was stirred over night. After 20 hours selected sample of the reaction mixture and analyzed by NMR to ensure that all of the epoxide used. Oil b is Nude, containing the reaction mixture was cooled to 90°C and the flask supply dropping funnel containing 19,0 g (185,9 mmol) of 3-(dimethylamino)Propylamine. The amine is added dropwise to a stirred, warm the reaction mixture for 30 minutes. When you are finished adding viscous, red, transparent syrup poured from the flask into the flask still warm. The output of the selected substance = 68, After cooling to ambient temperature the product becomes transparent, red, glassy mass, which has the following characteristics.¹H NMR (DMSO): 8,7 (s, 1H), a 7.85 (d, 1H), and 7.4 (m, 1H), 6,9 (osirm 5H), 5,6 (users, OH), 3-4,3 (osirm in), 2.25 (m, 2H), 2,1 (users, 6H), 1,7 (m, 2H). theoretical amount of water in the product to 4.41 wt.%. theoretical number of dimethylaminopropyl in a sample of 2.45 mEq/g

Example 8

Adduct of epoxy resin A, vanillin and 3-dimethylaminopropylamine

Using the method of example 3, which was charged to the reactor 30.0 g (101,4 mmol of apachegroup) of epoxy resin A, of 15.4 g (101,2 mmol) of vanillin and 487 mg (287,3 mg active 0,76 mmol) tetrabutylphosphonium. After the interaction in the night added dropwise over 10 minutes 10.3 g (101,2 mmol) 3-dimethylaminopropylamine. When you are finished adding receive light orange/brown, clear oil. The output of the selected substance = 50,8 g characteristics the following.¹H NMR (DMSO): 8,2 (s, 1H), 7,35 (s, 1H), 7,15 (d, 1H), ,95 (d, 1H), 5,1 (users, OH), 4,0 (m, H s easy polyester), and 3.8 (s, 3H, OCH3 formed vanilla), 3,4 (osirm formed by a simple polyester + Amin H s in), 2.25 (t, 2H), 2,1 (s, 6H), 1,7 (m, 2H), 1.0 (users, CH3 from polyether). theoretical amount of water in the product to 3.25 wt.%. theoretical number of dimethylaminopropyl in a sample of 1.8 mEq/g

Example 9

Adduct epoxidizing soybean oil, vanillin and 3-dimethylaminopropylamine

In the apparatus according to example 3 download 30.0 g (127,7 mmol of apachegroup) epoxidizing soybean oil (Paraplex G-62 from CP Hall Co. with an epoxy equivalent weight of 235), and 19.4 g (of 127.5 mmol) of vanillin and 491,2 mg (289,8 mg active 0,76 mmol) tetrabutylphosphonium. The vacuum apparatus to 20 mm Hg and then connect with nitrogen. This cycle is repeated 4 times, and the apparatus is left in a dynamic nitrogen atmosphere and immersed in an oil bath, maintaining at 150°C. After 30 minutes, the bath temperature was raised to 165°C, and the reaction mixture was stirred over night. After 14 hours selected sample of the reaction mixture and analyzed by NMR to ensure that all of the epoxide used. The oil bath containing the reaction mixture was cooled to 60°C, and the flask supply dropping funnel containing 13,0 g (127,2 mmol) of 3-(dimethylamino)Propylamine. The amine is added dropwise over 10 minutes. When you are finished adding get warm, viscous syrup. The output is dedicated substances = 57.4 g, in the following the results of the analysis.¹H NMR (DMSO): 8,2 (s, 1H), 7,35 (m, 1H), 7,0 (osirm, 2H), 5,2 (users, OH), a 3.2-4,6 (osirm in), 2.25 (m, 2H), 2,1 (s, 6H), 1,7, (m, 2H), 1,0-1,6 (m)0,8 (users). theoretical amount of water in the product of 3.65 wt.%. theoretical number of dimethylaminopropyl in the sample 2.03 mEq/g

Examples 10, 11 and 12

Data on the reactivity on BVT-tests

Example 10: use of the adduct according to example 2;

2200 SDR reaches for 10 minutes

Example 11: use of the adduct according to example 3;

20000 SDR reaches for 5 min and 20 sec.

Example 12: use of the adduct according to example 4;

20000 SDR reaches for 5 min 45 sec.

Data confirm that the catalyst (c) catalyzes the interaction polyisocyanat is, therefore, a gelling catalyst. This is confirmed by the example of the comparison 12C.

Example comparison 12C

Complete gelation (20.000 SDR) is achieved within 5 minutes and 40 seconds

Examples 13 and 14

Duplicate experiments foaming perform using the machine to work under high pressure, equipped with a mixing head Krauss-Maffei'a and the adduct according to example 3.

Molded foam: time demoulded 4', the density of the cast in the form of 38.4 kg/m³.

Examples 13 and 14 show that a good, stable foams get when the catalyst (c) is combined with the polyol with catalytic activity (polyol A) and conventional polyols. In examples 13 and 14 other catalysts are not used. When pulling from the form of amine odor not found.

Examples 15, 16

For example 15 use of the adduct according to example 4 instead of the adduct according to example 3 formulation examples 13/14; index 100: measured reactivity: the period between the mixture components and the transition into a creamy substance 5; the gelation time of 70 s; the rising time of 157 C. Get a good foam with a density in the free rise of 28.5 kg/m³.

For example 16 use of the adduct at approx the ru 5 instead of the adduct according to example 3, with formulation examples 13/14. Index 100: measured reactivity: the period between the mixture components and the transition into a creamy substance 4; time of gelation 58; time lifting 126 S. Get a good foam with a density in the free rise of 28 kg/m³.

Examples 17 and 18

Tests foaming perform using machine Cannon'a.

For example 17 use of the adduct according to example 3 in the following structure.

Yield: 600 grams of a 5 gallon bucket. The measured reactivity: the period between the mixture components and the transition into a creamy substance 5 s; the rising time of 8 C. Get a good foam with a density in the free rise of 28 kg/m³.

For example 18 use of the adduct from example 5 formulation according to example 17.

Yield: 600 grams of a 5 gallon bucket. The measured reactivity: the period between the mixture components and the transition into a creamy substance 5 s; the rising time of 83 C. Get a good foam with a density in the free rise of 28.4 kg/m³.

Example 19

The adduct according to example 3 is mixed with polyol and at different levels, and the study of aging carry out, carrying out the measurement of the reactivity by BVT-tests and visual inspection to check for any sign of separation of the phases. After 13 weeks at 60°C no loss of reactivity, and there is no sign of separation of the phases for the following mixtures:

Example 20

The mixture of polyols get the following mass composition:

This mixture is foamed using Voranate T-80, using the mixing head Krauss-Maffei'and on different days

These data extract show that the mixture of polyols containing water and catalyst (C) on the basis of the imine, stable for a few days.

Example 21

Adduct PER 732, salicylaldehyde, 1- (3-aminopropyl)imidazole and 3-dimethylaminopropylamine

Follow the method of example 3, which was charged to the reactor 475,0 g (1,498 mol apachegroup) DER 732, 173,8 g (1,424 mol) of salicylaldehyde and 5.8 g (3.42 g active, 9.0 mmol) tetrabutylphosphonium. The interaction allowed to proceed for 16 hours, after the specified time 72,7 g (0,712 mol) of 3-(dimethylamino)Propylamine and 89.1 g (0,712 mol) of 1-(3-aminopropyl)imidazole is added dropwise from a dropping funnel. The amine is added dropwise to a stirred, warm the reaction mixture for 1 hour. When you are finished adding get orange, transparent oil. The output of the selected substance =805,9, theoretical amount of water in the product of 3.15 wt.%. theoretical amount of total amidofunctional in a sample of 1.75 mEq/g, divided equally between dimethylaminopropane and imidazole groups.

Example 22

Foaming is performed with 1.5 mass parts of the adduct according to example 21, using the composition and conditions for examples 14 and 15.

This composition is used, molding parts made of foam with a density in the molded form 38 kg/m³and good curing, when the time demoulded 4 minutes.

Example 23

Adduct of epoxy resin a, salicylaldehyde, bisphenol A and 3-dimethylaminopropylamine

In a two-neck round bottom flask of 1 l, equipped with a mechanical stirrer, a nozzle Clausen and nozzle for gas inlet connected to a source of vacuum/nitrogen load 500.0 g (1,69 mol apachegroup) of epoxy resin A, 103, g (0,845 mol) of salicylaldehyde, 96,45 g (0,4435 mol) of bisphenol A and 6.5 g of tetrabutylphosphonium (59% in methanol). The vacuum apparatus to 20 mm Hg and then connect with nitrogen. Alternating cycle vacuum/nitrogen repeat in the amount of 5 times, ending with nitrogen. The device is left in a dynamic nitrogen atmosphere and immersed in an oil bath, maintaining at 120°C. After 1 hour, the bath temperature was raised to 150°C, and the reaction mixture was stirred over night. After 20 hours selected sample of the reaction mixture and analyzed by NMR to ensure that all of the epoxide used. The flask is removed from the oil bath and supply dropping funnel containing 86,4 g (0,845 mol) of 3-(dimethylamino)Propylamine. The amine is added dropwise to a stirred, warm the reaction mixture for 1 hour. After added the orange transparent oil was poured from the flask into the flask. The output of the selected substance = 780,4,

Example 24

Adduct of epoxy resin A, 3,3'-diamino-N-methyldiphenylamine and 3-dimethylaminopropylamine

Follow the method of example 23, using 444 g (1.5 mol apachegroup) of epoxy resin A, 183,2 g (1.5 mol) of salicylaldehyde and 5.8 g of tetrabutylphosphonium (59 wt.% in methanol). After interaction overnight at 150°C for reagents add the mixture to 76.6 g (0.75 mol) of 3-dimethylaminopropylamine and of 54.5 g (0,375 mol) of 3,3'-diamino-N-methyldiphenylamine. The output of the selected substance = 752,9,

Other embodiments of the invention will be obvious to the person skilled in the art given this description and the examples of practical implementation of the invention. Understood that the description and examples be considered only as illustrative, and the true scope of the volume and nature of the invention are defined by the enclosed claims.

1. Catalyst to obtain a polyurethane foam, which is a product of the reaction between the compounds (a) and (b), where
(a) a mixture of (i) compounds containing at least one apachegroup with (ii) a compound containing an alcohol, amino, thio or carboxyl group and aldehyde or ketone group, and
(b) a compound containing at least one primary amino group and at least one Tr is part of the amino group.

2. The catalyst according to claim 1, where the ketone is designated as R-C(O)-R¹where R and R¹mean, independently, C1-C20 substituted or unsubstituted, linear or branched alkyl, cyclic, heterocyclic or aromatic compounds containing 4 to 20 atoms, or R and R¹can be connected to each other to form a cyclic structure containing 5-20 atoms in the loop.

3. The catalyst according to claim 1 where the aldehyde is designated as R-C(O)-H, where R is C1-C20 substituted or unsubstituted, linear or branched alkyl, cyclic, heterocyclic or aromatic compounds containing 4-20 atoms.

4. The catalyst according to claim 1, where the compound having both primary and tertiary amino groups, may be represented by the formula:
H₂N-R⁸-N(R⁹)₂where R⁸means aliphatic or cyclic chain with 1-20 carbon atoms and R⁹means C1-C3 alkyl group.

5. The catalyst according to claim 1, where the compound having both primary and tertiary amino group represents 3-(dimethylamino)Propylamine, 1-(3-aminopropyl)imidazole, 1-(3-aminopropyl)-2-Mei, N,N-dimethylpiperidinium, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethanolamine, 3-(diethylamino)Propylamine, 3-(dibutylamino)Propylamine, N,N,2,2-tetramethyl-1,3-propandiamine, 2-amino-5-diethylaminopentane, N-methyl-N'-amino-ethyl)Pieper is Zin, 1,4-bis-(3-aminopropyl)piperazine, 3-aminoquinuclidine, 4-(2-amino-ethyl)morpholine, 4-(3-aminopropyl)morpholine, N,N-dimethyl-1,4-phenylenediamine, 5-amino-1-aripirazole, 2-aminopyridine, 2-(aminomethyl)pyridine, 2-(aminoethyl)pyridine, 4-aminopyridine, 3-aminopyridine, 3-(aminomethyl)pyridine, N-aminopropylmorpholine-2-aminophylline, diaminopyridine, 2-aminopyrimidine, 4-aminopyrimidine, aminopyrazine, 3-amino-1,2,4-triazine, aminoquinoline, N,N-dimethylpiperidinium and 3,3'-diamino-N-methyldiphenylamine, N-methyl-1,3-propertiesin.

6. The catalyst according to claim 1, which is the reaction product of stages, including:
(a) a mixture of (i) compounds containing at least one apachegroup, with (ii) a compound containing reactive epoxide group and an aldehyde or ketone group, and
(b) mixing the product of stage (a) with a compound containing at least one primary amino group and at least one tertiary amino group.

7. The catalyst according to claim 6 where the compound having aldehyde group and reacting with the epoxide group is a C3-C30 - aliphatic, aromatic or polyaromatic compound or a cyclic structure containing a heteroatom, with the proviso that when the compound having aldehyde and epoxy group includes a cyclic structure, aldehyde group is connected directly to the loop and responsive to apex the house group is associated directly with the cycle or associated with loop through C3-C6 linear or branched alkyl.

8. The catalyst according to claim 7 where the compound having a reactive epoxide group and aldehyde group means salicylaldehyde, vanilla, 5-(hydroxymethyl)furfural, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, 2-carboxybenzoyl, 3-carboxybenzoyl or a mixture of these compounds.

9. The catalyst according to claim 6 where the compound having a ketone and an epoxy functional group means a C3-C30 - aliphatic, aromatic or polyaromatic compound or a cyclic structure containing a heteroatom, with the proviso that when the compound having a ketone and an epoxy group includes a cyclic structure, reacting with the epoxide group is associated directly with the cycle or associated with loop through C1-C6 linear or branched alkyl.

10. The catalyst according to claim 1, where the compound having a ketone and epoxide functionality means 2'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3'-hydroxyacetophenone, 3-acetyl-1-propanol, 4-hydroxy-3-methyl-2-butanone, 4-hydroxy-4-methyl-2-pentanone, 4'-hydroxyacetophenone, dihydroxyacetophenone, benzyl-4-hydroxyphenylacetic, acetovanillone, 3'-aminoacetophenone, 4'-aminoacetophenone, aminobenzophenone, 4-acetylbenzoic acid and 2-benzoylbenzene acid or mixture of such compounds.

11. The catalyst according to claim 6, where the unity, containing at least one epoxy group represented by the formula:

where R⁴means substituted or unsubstituted aromatic, aliphatic, cycloaliphatic or heterocyclic group and n has an average value from 1 to 8.

12. The catalyst according to claim 6, where at the stage of (a) the mixture additionally contains phenol, cresol, bisphenol a, bisphenol F, polyol novolak, Ethylenediamine, 3,3'-diamino-N-methyldiphenylamine, resorcinol, adipic acid, succinic acid, isophthalic acid, phthalic acid, terephthalic acid, acetic acid, or combinations of these compounds.

13. The catalyst according to claim 6, where at stage (b) a compound containing a primary amino group and tertiary amino group contains two or more primary amine.

14. The catalyst according to claim 6, where 1-50 percent of apachegroup present at stage (a), interacts with a compound containing reactive epoxide group and a tertiary amino group.