WO2001098388A1

WO2001098388A1 - Polymeric aldehyde/polyetheramine networks

Info

Publication number: WO2001098388A1
Application number: PCT/EP2001/007134
Authority: WO
Inventors: Serguei Evsioukov; Gunnar Schornick; Jan Nouwen; Arthur Höhn
Original assignee: Basf Aktiengesellschaft
Priority date: 2000-06-23
Filing date: 2001-06-22
Publication date: 2001-12-27
Also published as: AU2001283881A1; DE10030684A1

Abstract

Polymeric networks can be obtained by condensing an aldehyde or a mixture of aldehydes or precursors thereof with a component A containing amines, optionally in the presence of a solvent S. Component A contains at least one polyetheramine (I) which can be obtained by alkoxylation of polyols of general formula Y<3>(-OH)s, wherein Y<3> means an s-valent organic radical and s means an integral value from 4 to 20, with 1 to 100 mol per mol hydroxyl groups or one or more C1-8-alkylene oxides, and subsequent amination with ammonia, so that 50 to 100 % of the hydroxyl groups are aminated and there are at least two primary amino groups per molecule; optionally, at least one amine of formula (II) Y<1>(-NH2)n and optionally, at least one amine of formula (III) (Z-)(q-r)Y<2>(-NH2)r, wherein Y<1> means n-valent organic radicals, Y<2> means q-valent organic radicals, Z means functional monovalent radicals, n means an integral value from 1 to 20, q means an integral value from 2 to 20 and r means an integral value from 1 to 19 on the condition that 1 </= r < q.

Description

Polymeric aldehyde polyetheramine networks

The invention relates to polymeric aldehyde / polyetheramine networks.

Reaction products of aldehydes such as formaldehyde and amines such as monoamines and aliphatic diamines have been known for a long time and are used in different fields of application.

DE-A-26 45 170 relates to a vulcanization accelerator for rubbers. The accelerator comprises a reaction product of an aldehyde with phenylenediamine or an aliphatic 1,2- or 1,3-diamine. Ethylene diamine or propylene diamine are preferably used as the aliphatic diamine. The aldehyde used is preferably formaldehyde.

US 3,461,100 relates to condensation products of aldehydes or ketones with diamines and monoamines. The water-insoluble, but soluble in aliphatic hydrocarbons polymer materials are used as protective coatings, especially for metals. They are obtained by condensing an aldehyde or ketone with a diamine in an organic reaction medium. As a by-product, water is continuously removed. For example, formaldehyde and hexamethylene diamine are implemented.

JP-A-63 192 750 relates to the preparation of polymeric tertiary amines which have hexahydrotriazm units. The connections are obtained by

Implementation of primary and secondary amines with formaldehyde. You can as Catalysts for urethane foams and as hardeners for epoxy resins and rubber latices can be used.

US 5,830,243 relates to fuel compositions which contain N-substituted perhydro-s-triazine Nerbindungen. These are produced by reacting an aldehyde with at least one ether amine which has a maximum of three primary amino groups. The Nerbindungen serve to reduce the formation of deposits in injection engines.

Most of the reaction products described are not polymeric networks but Nerbindungen soluble in hydrocarbons. The formation of cross-linked products using diamines and triamines is mentioned.

The object of the present invention is to provide polymeric networks whose properties can be adjusted over a wide range. In addition, materials based on aldehydes and amines that have novel properties are to be made available.

The objects are achieved according to the invention by polymeric networks which can be obtained by condensing an aldehyde or a mixture of aldehydes or precursors thereof with an amine-containing component A, optionally in the presence of a solvent S, component A comprising at least one polyetheramine (I ), obtainable by alkoxylation of polyols of the general formula

Y ^J (-OH) _s

in what mean

Y ³ s-valent organic residue

s integer value from 4 to 20 with 1 to 100 mol per mol of hydroxyl groups, one or more C ₈ alkylene oxides and subsequent amination with ammonia, so that 50 to 100% of the hydroxyl groups present are aminated and at least two primary amino groups are present per molecule,

optionally at least one amine of the formula (II)

and optionally at least one amine of the formula (III)

(Z-) _(q - _r) Y ² (-NH ₂ ) _r (III)

contains what mean

Y ¹ n-valent organic radicals,

Y ² q-valent organic radicals,

Z functional monovalent residues,

n is an integer from 1 to 20,

q an integer value from 2 to 20 and

r is an integer value from 1 to 19 with the proviso that 1 <r <q.

Formaldehyde or a mixture of aldehydes containing formaldehyde is preferably used as the aldehyde. Corresponding precursors to these compounds can also be used. Such precursors are, for example, the cyclic trimer form, 1,3,5-trioxane or polymeric forms of formaldehyde, the so-called paraformaldehyde. Acetals such as diethoximethane can also be used. The aldehydes are condensed with component A.

The ratio is preferably chosen so that stoichiometric amounts of reactive aldehyde groups and amino groups are present. Deviations from the stoichiometry of up to 20 mol%, preferably up to 10 mol%, can also lead to usable polymer networks.

Component A contains at least one polytheramine (I), obtainable by alkoxylation of polyols of the general formula

Y ³ (-OH) _s

in what mean

Y ³ s-valent organic residue

s integer value from 4 to 20

with 1 to 100 mol per mol of hydroxyl groups, one or more C ₈ alkylene oxides and subsequent amination with ammonia, so that 50 to 100% of the hydroxyl groups present are aminated and at least two primary amino groups are present per molecule.

The polyetheramines (I) preferably have an average molecular weight (M _n ) of 200 to 20,000 g / mol, particularly preferably 500 to 10,000 g / mol, in particular 1000 to 5000 g / mol.

In the polyols of the general formula Y ³ (OH) _s , s preferably has an integer value from 4 to 10, particularly preferably from 4 to 6.

Y ³ is an s-valent organic radical. This can be any suitable s-valent organic residue that is suitable for alkoxylation and subsequent Amination is suitable. It is preferably derived from C ₄ - ₅ o-alkylene radicals, particularly preferably C ₄ - ₃ o-alkylene radicals, in particular C ₄ . ₂ o-alkylene residues, which can be linear, branched or cyclic. In addition, non-adjacent CH ₂ groups in the alkylene radicals can be replaced by oxygen groups, sulfur, -NH-, -N (-CC- ₄ -alkyl) -, CO, optionally substituted arylene and / or optionally substituted heteroarylene. Y is preferably an alkylene radical which is linear or branched and in which there is no more than one hydroxyl group on a carbon atom. These are preferably linear or single-branched aliphatic carbon backbones which have 4 to 10, in particular 5 to 6, carbon atoms.

The aliphatic polyols are particularly preferably selected from pentaerythritol and sugar alcohols with at least 4 hydroxyl groups, especially tetrites, pentites or hexites. Mixtures of these can also be used. Examples of suitable tetrites are erythritol and threitol. Preferred pentites are rebit, arabite and xylitol. Preferred hexites are dulcite, mannitol and sorbitol. Pentaerythritol and sorbitol, especially D-sorbitol, are particularly preferably used. All other alcohols derived from corresponding sugars by reduction can also be used. If appropriate, the sugars themselves can also be used, provided that they have the required number of hydroxyl groups.

The polyols are alkoxylated with 1 to 100 mol, preferably 1 to 80 mol, in particular 1 to 60 mol, per mol of hydroxyl groups, of one or more C ₈ alkoxides. Preferred alkoxides are ethylene oxide, propylene oxide and butylene oxide, especially ethylene oxide and propylene oxide. Ethylene oxide, propylene oxide or mixtures thereof are particularly preferably used. Statistically alkoxylated products can be obtained by using alkylene oxide mixtures. Block products can also be produced by first alkoxylation with an alkylene oxide and subsequent alkoxylation with another alkylene oxide, etc. Suitable alkoxylation processes are known.

After the alkoxylation, the alkoxylated polyols are aminated with ammonia, so that 50 to 100%, preferably 80 to 100%, of the hydroxyl groups present are aminated and there are at least 2, preferably at least 3 primary amino groups per molecule.

In the simplest case, the polyether polyols are aminated such that there are at least two terminal primary amino groups. The amination is preferably carried out with ammonia in the presence of an inorganic catalyst. The amination can be carried out in a solvent such as cyclohexane.

In addition to the simply aminated products, two polyol molecules can also be condensed with one ammonia molecule. After the amination, a polyetheramine is obtained which, in addition to terminal primary amino groups, has one or more internal secondary amino groups. Like the primary amino groups, the secondary amino groups can be condensed with further polyol molecules. In this case there are at least primary and tertiary amino groups in the molecule. Compounds can also be obtained in which primary, secondary and tertiary amino groups are present side by side. The products obtained are predominantly determined by the quantitative ratio of the starting materials and the reaction conditions. The ratio of ether units to amino groups can also be adjusted via the molecular weight of the polyol used.

Even when using the (primary) diamines, cross-linked structures are obtained by condensing the amino groups with an equivalent amount of aldehyde to a triazacyclohexyl structure, see for example E.M. Smolin, L. Rapoport: s-Triazines and derivatives, in: The Chemistry of Heterocyclic Compounds, Vol. 13, ed. By A, Weissberger, Interscience PubL, New York, 1959, pp. 473-544.

The amino groups of a di- or polyamino ether can be components of two or more different ring systems, so that three-dimensional networks are formed:

m [Y (-N = CH ₂ ) _n ]

If there are secondary amino groups or if there are branched compounds with, for example, four primary amino groups, correspondingly more complex three-dimensionally crosslinked products can be obtained.

The reaction of amines (I) with the aldehydes, in particular formaldehyde, can be carried out without solvent or in the presence of a solvent (S). For example, water-miscible solvents are used as the solvent (S).

Formaldehyde is used, for example, as an aqueous formalin solution.

Acetone, dioxane, polyether glycols, alcohols such as n-propanol and similar solvents can also be used as solvents, which, if miscible, can contain water.

The reaction is preferably carried out at temperatures in the range from 0 to 70 ° C., particularly preferably 10 to 50 ° C., in particular 15 to 30 ° C.

As a rule, the polyetheramine is placed in the solvent and then mixed with formaldehyde in solid or gaseous or preferably in dissolved form. Acetals can also be used in liquid form. If desired, the reaction can be carried out in the presence of basic catalysts. In addition to the amines (I), amines of the formula (II) can also be used. Compounds are preferably used in which Y ¹ denotes n-valent organic radicals which are derived from C ₂ -3ooo-alkylene radicals, preferably C -oooo-alkylene radicals, in particular C ₂ -oooo-alkylene radicals, in which non-adjacent CH ₂ -Groups can be replaced by oxygen, sulfur, -NH-, -N (-CC-4-alkyl) -, -CO-, optionally substituted arylene and / or optionally substituted heteroarylene.

Those amines of the formula (II) in which Y ¹ denotes n-valent organic radicals which are derived from oligomers or polymers of ethylene, propylene or mixtures of these monomers with an average number of 1000 of these monomer units are particularly preferably used.

Amines of the formula (III) can also be used. This is preferably Nerbindungen in which Y ² denotes q-valent organic residues derived from C, -, preferably _3-ooo alkylene C -ιooo-alkylene, especially C2-1 ₀₀ - alkylene radicals are derived, in which non-adjacent CH ₂ groups can be replaced by oxygen, sulfur, -ΝH-, -Ν (Cι- ₄ alkyl) -, - CO-, optionally substituted arylene and / or optionally substituted heteroarylene.

The q-valent organic radicals Y ^{2 are} preferably derived from oligomers or polymers of ethylene, propylene or mixtures of these monomers with an average number of up to 1000 of these monomer units.

The functional monovalent radicals Z can be selected from the group consisting of -OH, -SH, -COO-Cι-ι ₂ alkyl, -SO ₃ -C _M2 alkyl and PO (O-Cι-ι ₃ alkyl) ) ₂ . The Z radicals can also be selected from neutralized acid radicals, such as carboxyl or sulfonyl groups neutralized with alkali or amines or ammonia.

According to one embodiment of the invention, only the polytheramines (I) are used. The invention is illustrated by the examples below.

Examples

Three different polyetheramines were used in the examples. The polyetheramine 1 is derived from pentaerythritol and has a molecular weight of 5000 (number average). It is statistically alkoxylated with ethylene oxide and propylene oxide in a molar ratio of 4: 1 and subsequently aminated with stoichiometric amounts of ammonia. The polyetheramine 2 corresponds to the polyetheramine 1, but has a number-average molecular weight of 15,000.

The polyetheramine 3 is derived from sorbitol, which is propoxylated with 12 mol of propylene oxide and then stoichiometrically aminated. The amine number is about 350 mg KOH / g, the acetylation number about 400 mgKOH / g. The product has a melting point of -5 to -10 ° C and a boiling point above 200 ° C. The pH at 20 ° C in a concentration of 10 g / 1 is about 11.4.

!

example 1

A mixture of the polyetheramine 1 and acetone was produced. A mixture of formalin (37% formaldehyde in water) and acetone was also prepared. Both mixtures were combined at room temperature, mixed well and poured into a bowl. The molar ratio of polyetheramine 1 to formaldehyde was 1: 1.

After about 5 min. the reaction product became solid but remained sticky. It was yellow in color.

Example 2

A mixture of the polyetheramine 1 and acetone was produced. A mixture of formalin (37% formaldehyde in water) and acetone was also prepared. Both Mixtures were added at room temperature, mixed well and poured into a bowl. The molar ratio of polyetheramine 1 to formaldehyde was 1: 1.

Example 3

Example 4

A mixture of the polyetheramine 2 and acetone was produced. A mixture of formalin (37% formaldehyde in water) and acetone was also prepared. Both mixtures were combined at room temperature, mixed well and poured into a bowl. The molar ratio of polyetheramine 2 to formaldehyde was 1: 1.

Example 5

A mixture of the polyetheramine 2 and acetone was produced. A mixture of formalin (37% formaldehyde in water) and acetone was also prepared. Both mixtures were combined at room temperature, mixed well and poured into a bowl. The molar ratio of polyetheramine 2 to formaldehyde was 1: 1. After about 5 min. the reaction product became solid but remained sticky. It was yellow in color.

Example 6

In Examples 1 to 6 was polymerized 50%.

Example 7

A mixture of the polyetheramine 3 and acetone was produced. A mixture of formalin (37% formaldehyde in water) and acetone was also prepared. Both mixtures were combined at room temperature, mixed well and poured into a bowl. The molar ratio of polyetheramine 3 to formaldehyde was 1: 1.

After about 5 min. the reaction product became solid but remained sticky. The product turned yellow after three days.

Example 8

A mixture of the polyetheramine 3 and acetone was produced. A mixture of formalin (37% formaldehyde in water) and acetone was also prepared. Both Mixtures were put together at room temperature, mixed well and poured into a bowl. The molar ratio of polyetheramine 3 to formaldehyde was 1: 1.

Example 9

Example 10

A mixture of the polyetheramine 3 and acetone was produced. A mixture of formalin (37% formaldehyde in water) and acetone was also prepared. Both mixtures were combined at room temperature, mixed well and poured into a bowl. The molar ratio of polyetheramine 3 to formaldehyde is 1: 1.

Example 11

A mixture of the polyetheramine 3 and acetone was produced. A mixture of formalin (37% formaldehyde in water) and acetone was also prepared. Both mixtures were combined at room temperature, mixed well and poured into a bowl. The molar ratio of polyetheramine 3 to formaldehyde was 1: 1. After about 5 min. the reaction product became solid but remained sticky. The product turned yellow after three days.

In Examples 7 to 11, polymerization was carried out in various concentrations.

Example 12

Example 13

Example 14

In Examples 12 to 14 was polymerized 50%.

Claims

claims

1. Polymer networks, obtainable by condensing an aldehyde or a mixture of aldehydes or Norläufer thereof with an amine-containing component A, optionally in the presence of a solvent S, component

A

at least one polyetheramine (I), obtainable by alkoxylation of polyols of the general formula

Y ³ (-OH) _s

in what mean

Y s-valued organic residue

s integer value from 4 to 20

with 1 to 100 mol per mol of hydroxyl groups, one or more C ₈ alkylene oxides and subsequent amination with ammonia, so that 50 to 100% of the hydroxyl groups present are aminated and at least two primary amino groups are present per molecule,

optionally at least one amine of the formula (II)

Y ^ -ΝH ^ n (II)

and optionally at least one amine of the formula (III) (Z-) _(q - _r) Y ² (-NH ₂ ) _r (III)

contains what mean

Y ¹ n-valent organic radicals,

Y ² q-valent organic radicals,

Z functional monovalent residues,

n is an integer from 1 to 20,

q an integer value from 2 to 20 and

r is an integer value from 1 to 19 with the proviso that 1 <r <q.

2. Polymer networks according to claim 1, characterized in that formaldehyde or a mixture of aldehydes containing formaldehyde, or Norläufer of formaldehyde is used as the aldehyde.

3. Polymer networks according to claim 1, characterized in that formaldehyde is used as the aldehyde.

4. Polymer networks according to one of claims 1 to 3, characterized in that the polyether amines are derived from aliphatic polyols.

5. Polymer networks according to claim 4, characterized in that the aliphatic polyols are selected from pentaerythritol, tetrites, pentites, hexites or mixtures thereof.

6. Polymeric networks according to one of claims 1 to 5, characterized in that the amines of the formula (II) which are optionally present in component A are those N compounds in which Y ¹ denotes n-valent organic radicals which differ from C ₂ - Derive ₃ oo-alkylene radicals in which non-adjacent CH ₂ groups are replaced by oxygen, sulfur, -Ν (H) -, -N (Cι_4-alkyl) -, -CO-, optionally substituted arylene and / or optionally substituted heteroarylene can.

7. Polymer networks according to one of claims 1 to 5, characterized in that such as optionally contained in component A amines of formula (II)

Nerbindungen used, in which Y ¹ denotes n-valent organic radicals which are derived from oligomers or polymers of ethylene, propylene or mixtures of these monomers with an average number of up to 1000 of these monomer units.

8. Polymer networks according to one of claims 1 to 7, characterized in that

II as amines of the formula (III) which are optionally present in component A, those N compounds are used in which Y denotes q-valent organic radicals which are derived from C ₂ - ₃ 000 alkylene radicals and in which non-adjacent CH ₂ groups are caused by oxygen , Sulfur, -Ν (H) -, -N (Cι- ₄ alkyl) -, -CO-, optionally substituted

Arylene and / or optionally substituted heteroarylene can be replaced.

9. Polymer networks according to any one of claims 1 to 7, characterized in that such amines of the formula (III) optionally present in component A are those Nerbindungen in which Y denotes ² -valent organic radicals which are derived from oligomers or polymers derive from ethylene, propylene or mixtures of these monomers with an average number of up to 1000 of these monomer units.

10. Polymeric networks according to any one of claims 1 to 9, characterized in that such amines of formula (III) optionally present in component A are used in such compounds in which the functional monovalent radicals Z are selected are from the group consisting of -OH, -SH, -COO-Ci_ι ₂ alkyl, -SO ₃ -Cι_ι ₂ alkyl and -PO (O-Cι, ι ₂ alkyl) ₂ or neutralized acid residues.