DE10010856A1 - Polymer network, is prepared by condensation of an aldehyde with an amine containing component prepared by amination of polymeric ethers of 1,4-butanediol and having at least two free amine groups. - Google Patents

Abstract

A polymer network is prepared by condensation of an aldehyde or mixture of aldehydes or corresponding precursor with an amine containing component (A), optionally in the presence of a solvent whereby (A) is at least one amine prepared by amination of polymeric ethers of 1,4-butanediol and having at least two free amine groups. A polymer network (I) is prepared by condensation of an aldehyde or mixture of aldehydes or corresponding precursor with an amine containing component (A), optionally in the presence of a solvent whereby (A) is at least one amine (II) prepared by amination of polymeric ethers of 1,4-butanediol and having at least two free amine groups; optionally at least one amine of formula (1) and optionally at least one amine of formula (2). Y1>(-NH2)n (1) (Z-)(q-r)Y2>(-NH2)r (2) Y1>n-valent organic group; Y2>q-valent organic group; Z : functional monovalent group; n : 1-20; q : 2-20; r : 1-19 but is less than q.

Description

The invention relates to polymeric aldehyde / poly (THF) amine 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 areas 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. As an aliphatic diamine preferably ethylenediamine or propylenediamine. The one used Aldehyde is preferably formaldehyde.

No. 3,461,100 relates to condensation products of aldehydes or ketones Diamines and monoamines. The water-insoluble, but in aliphatic Hydrocarbon-soluble polymer materials are used as protective coatings, especially for metals, are used. You will get through Condensation of an aldehyde or ketone with a diamine in one organic reaction medium. Water produced as a by-product continuously removed. For example, formaldehyde and hexamethylene diamine implemented.  

JP-A-63 192 750 relates to the preparation of polymeric tertiary amines which Have hexahydrotriazine 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 are used.

US 5,830,243 relates to fuel compositions which are N-substituted Perhydro-s-triazine compounds included. These are made by Reaction of an aldehyde with at least one ether amine. The connections serve to reduce the formation of deposits in injection engines.

Most of the reaction products described are not about polymeric networks but about hydrocarbon-soluble ones Links. The formation of networked products by using Diamines and triamines are mentioned.

The object of the present invention is to provide polymers Networks whose properties can be set in a wide range. In addition, materials based on aldehydes and amines are provided that have novel properties.

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 amine (I) which is obtainable by amination of polymeric ethers of 1,4-butanediol and has at least two free amino groups,
optionally at least one amine of the formula (II)

Y ¹ (-NH ₂ ) _n (II)

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

(Z-) _(qr) 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 from 1 to 19 with the proviso that 1 ≦ r <q.

Formaldehyde or a mixture of is preferably used as the aldehyde Aldehydes containing formaldehyde are used. Corresponding forerunners these connections can be used. Such precursors are in for example the cyclic trimer form, the 1,3,5-trioxane or polymeric forms of formaldehyde, the so-called paraformaldehyde. Even acetals like Diethoximethane can 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 up to 20 mol%, preferably up to 10 mol% can also lead to usable polymer networks.

Component A contains at least one amine (I), which is obtained by amination of polymeric ethers of 1,4-butanediol is available and via at least two free Amino groups.

The amines (I) preferably have an average molecular weight (M _n ) of 150 to 20,000 g / mol, particularly preferably 400 to 10,000 g / mol, in particular 800 to 5000 g / mol.

The amine (I) can be branched or unbranched. In the simplest case become 1,4-butanediol available by condensation terminal Polyether diols aminated so that two terminal primary amino groups available. The 1,4-butanediol-based polyether diols (poly-THF) can be produced by known methods. The amination takes place preferably with ammonia in the presence of an inorganic catalyst. The Amination can be carried out in a solvent such as cyclohexane become.

In addition to the linear products, two poly-THF molecules with one Ammonia molecule to be condensed. It becomes one after the amination Obtained polyetheramine, the two terminal primary amino groups and one or has several internal secondary amino groups. The secondary Like the primary amino groups, amino groups can be combined with other poly-THF Molecules are condensed. In this case there are at least in the molecule primary and tertiary amino groups. Connections can also be obtained be in which primary, secondary and tertiary amino groups side by side available. The products obtained are predominantly by the Quantity ratio of the starting materials and the reaction conditions are determined. This can also be done via the molecular weight of the poly-THF used  Ratio of ether units to amino groups can be set. Poly-THF with a molecular weight of 150 is preferably used for the synthesis up to 20,000 g / mol, particularly preferably 400 to 10,000 g / mol, in particular 800 to 5000 g / mol used.

Crosslinked structures are already obtained when the diamines are used by condensing the amino groups with an equivalent amount of aldehyde to give a triazacyclohexyl structure, see for example EM 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 diamino ether can be components of two different ring systems, so that three-dimensional networks are formed:

If there are secondary amino groups or if there are branched ones Compounds with, for example, three primary amino groups can correspondingly more complex three-dimensionally networked products are obtained.

The reaction of amines (I) with the aldehydes, especially formaldehyde, can be carried out solvent-free or in the presence of a solvent (S) become. Water-miscible solutions, for example, are used as the solvent (S) medium used.

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

Acetone, dioxane, polyether glycols, Alcohols such as n-propanol and similar solvents are considered, provided that miscible, may 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 with Formaldehyde in solid or gaseous or preferably in dissolved form transferred. Acetals can also be used in liquid form. The If desired, the reaction can be carried out in the presence of basic Catalysts are carried out.

In addition to the amines (I), amines of the formula (II) can also be used. Compounds in which Y ¹ denotes n-valent organic radicals which are derived from C _2-3000 alkylene radicals, preferably C _2-1000 alkylene radicals, in particular C _2-100 alkylene radicals, in which non-adjacent CH ₂ groups can be replaced by oxygen, sulfur, -NH-, -N (C _1-4 -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.

In addition, amines of the formula (III) can also be used. These are preferably compounds in which Y ² denotes q-valent organic radicals which are derived from C _2-3000 alkylene radicals, preferably C _2-1000 alkylene radicals, in particular C _2-100 alkylene radicals, in which non-adjacent ones CH ₂ groups can be replaced by oxygen, sulfur, -NH-, -N (C _1-4 -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-C _1-12 -alkyl, -SO ₃ -C _1-12 -alkyl and -PO (OC _1-13 - 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.

The invention is illustrated by the examples below.

Examples

The number behind the poly-THF amine indicates the molecular weight. In poly THF amine 1700, the total amine number is about 85 to 90 mg KOH / g, the secondary amine number about 18 to 22 mg KOH / g and the tertiary amine number 0.5 to 2 mg KOH / g.  

In Examples 1 to 7, different concentrations were set example 1

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formalin (37% aqueous Formaldehyde solution). Both mixtures were combined and mixed well, then poured into a mold.

Poly-THF amine / formaldehyde ratio 1/1.

The product solidified after about 2 hours, remained slightly sticky, the color was yellowish.

Example 2

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

The product became firm and elastic after about 30 minutes and the color was light yellow transparent.

Example 3

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.  

After about 30 minutes the product became firm, elastic, the color was green yellowish. Significant shrinkage was observed.

Example 4

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

The product became firm after about 15 minutes, elastic, green-yellowish, somewhat Shrinkage.

Example 5

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

The product became firm after about 10 minutes, elastic, green-yellowish, somewhat Shrinkage.

Example 6

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.  

The product became firm, elastic after approx. 3 to 5 minutes, the color was green yellowish. Little shrinkage was observed.

Example 7

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

The product is difficult to mix because the polymerization starts immediately.

In Examples 8 to 12 was polymerized 50% Example 8

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/3.

The product became solid after about 3 to 5 minutes, slightly yellowish and somewhat brittle.

Example 9

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Ratio of poly-THF amine / formaldehyde ½.

The product became solid, green-yellowish, elastic after about 5 to 10 minutes.  

Example 10

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

The product became firm, milky, cloudy, somewhat sticky after about 15 minutes.

Example 11

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Ratio poly-THF-amine / formaldehyde 1 / 0.5.

The product became solid, milky, cloudy, somewhat sticky after about 2 hours.

Example 12

A mixture of poly-THF amine 1700 and acetone was prepared. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Ratio poly-THF-amine / formaldehyde 1 / 0.5.

The product became solid, milky, cloudy, somewhat sticky after about 3 to 4 hours.

In Examples 13 to 19 different concentrations were used set Example 13

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

After about 2 hours the product became solid, colorless, clear, somewhat sticky, elastic.

Example 14

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

The product became solid after about 30 minutes, colorless, clear, somewhat sticky, elastic.

Example 15

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

After about 20 minutes the product became solid, colorless, clear, somewhat sticky, elastic.  

Example 16

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

After about 10 minutes the product became solid, colorless, clear, somewhat sticky, elastic.

Example 17

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

The product became solid, colorless, clear, somewhat sticky, elastic after about 5 minutes.

Example 18

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

After about 3 minutes the product became solid, colorless, clear, somewhat sticky, elastic.  

Example 19

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

The product is difficult to mix because the polymerization starts immediately.

In Examples 20 to 24 was polymerized 50% Example 20

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/3.

The product becomes solid, colorless, clear, somewhat sticky after approx. 2 to 3 minutes, elastic.

Example 21

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Ratio poly-THF-amine / formaldehyde 1/2.

The product becomes solid, colorless, clear, somewhat sticky after approx. 10 to 15 minutes, elastic.  

Example 22

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1/1.

The product did not become solid, colorless clear.

Example 23

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Ratio poly-THF-amine / formaldehyde 1 / 0.5.

The product did not become solid, colorless clear.

Example 24

A mixture of poly-THF-amine 4000 and acetone was produced. A mixture of formaldehyde (37%) in water was also prepared. Both mixtures were combined and mixed well, then into one Form poured out.

Poly-THF amine / formaldehyde ratio 1 / 0.25.

The product did not become solid, colorless clear.

Claims (9)

1. Polymer networks, obtainable 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
at least one amine (I) which is obtainable by amination of polymeric ethers of 1,4-butanediol and has at least two free amino groups,
optionally at least one amine of the formula (II)
Y ¹ (-NH ₂ ) _n (II)
and optionally at least one amine of the formula (III)
(Z-) _(qr) 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 from 1 to 19 with the proviso that 1 ≦ r <q. 2. Polymer networks according to claim 1, characterized in that as Containing aldehyde formaldehyde or a mixture of aldehydes Formaldehyde, or a precursor to formaldehyde thereof. 3. Polymer networks according to claim 1, characterized in that as Aldehyde formaldehyde used. 4. Polymer networks according to one of claims 1 to 3, characterized records that amines (I) with an average molecular weight of 150 up to 2000 g / mol used. 5. Polymer networks according to any one of claims 1 to 4, characterized in that the compounds of formula (II) which are optionally present in component A are those compounds in which Y ¹ denotes n-valent organic radicals which differ from C ₂ Derive _-300 alkylene radicals in which non-adjacent CH ₂ groups by oxygen, sulfur, -N (H) -, N (C _1-4 alkyl) -, -CO-, optionally substituted arylene and / or optionally substituted heteroarylene can be replaced. 6. Polymer networks according to any one of claims 1 to 4, characterized in that such compounds in which Y ¹ denotes n-valent organic radicals which are derived from oligomers or polymers are used as amines of the formula (II) which are optionally present in component A. derive from ethylene, propylene or mixtures of these monomers with an average number of up to 1000 of these monomer units. 7. Polymer networks according to one of claims 1 to 6, characterized in that such compounds are used as amines of the formula (III) which are optionally present in component A, in which Y denotes ^2- valent organic radical which is derived from C _2- Derive ₃₀₀₀ alkylene radicals in which non-adjacent CH ₂ groups by oxygen, sulfur, -N (H) -, -N (C _1-4 alkyl) -, -CO-, optionally substituted arylene and / or optionally substituted heteroarylene can be replaced. 8. Polymer networks according to any one of claims 1 to 6, characterized in that such compounds in which Y denotes ^2- valent organic radicals which are derived from oligomers or polymers are used as amines of the formula (III) which are optionally present in component A. derive from ethylene, propylene or mixtures of these monomers with an average number of up to 1000 of these monomer units. 9. Polymer networks according to one of claims 1 to 8, characterized in that such compounds in which the functional monovalent radicals Z are selected from the group consisting of -OH, are optionally used as amines of the formula (III) contained in component A. -SH, -COO-C _1-12 alkyl, -SO ₃ -C _1-12 alkyl and -PO (OC _1-12 alkyl) ₂ or neutralized acid residues.