DD292918A5 - METHOD FOR THE PRODUCTION OF FUNCTIONALIZED SOLUBLE EPOXY-AMINE ADDITION POLYMERS - Google Patents

Abstract

The invention relates to a process for preparing functionalized soluble epoxy-amine polyadducts, wherein a-amino acid esters are used as the amine monomer. In addition to the possibility of synthesizing optically active polyadducts, the addition polymers have intermediate character due to the ester group in the side chain, which allows the preparation of specifically modified epoxy-amine polyadducts. By this change in the ester group by means of polymer-analogous reactions, polymeric hydrazides, anilides, carboxylic acid salts and carboxylic acid hydrochlorides are available. {Epoxide-amine addition polymers; a-Aminosaeureester; diepoxides; optically active polymers; Substanzpolyaddition; Film formation; Conversion to hydrazides; Conversion to carboxylic acid hydrochloride}

Description

For this 1 page formulas Field of application of the invention

The invention relates to a process for the preparation of functionalized, soluble epoxy-amine addition polymers, the valuable properties such. B. film or film formation and optical activity.

The addition polymers are novel reactive polymers and can be used as intermediates for the preparation of specific functionalized specialty polymers.

Characteristic of the known state of the art

A process for the preparation of functionalized, soluble addition polymers by reacting diepoxides with a-amino acid esters is not yet known.

Studies on the polyaddition of aniline derivatives with diepoxides have already used p-aminobenzoic acid ethyl ester (Acta Polymerica 38 [1987] 5). In B 620428 (1962) and GB 962 242 (1964), reaction products of amino acid residue with polyamides are used as curing agents for epoxy resins.

Object of the invention

The object of the invention is to produce functionalized, soluble epoxide-amine addition polymers from readily available monomers by a process which is relatively easy to implement industrially.

Explanation of the essence of the invention

The invention is based on the object by means of polymer-analogous reactions specially modified thermoplastic, high molecular weight and optically transparent epoxy-amine addition polymers with a large variability and valuable

Properties such as Schient- or film formation and optical activity to develop. According to the invention, this object is achieved in that Diepoxide with a-amino acid esters in a molar ratio of 1.0: 1.0 to Reaction are brought and the ester grouping is present unchanged in the side chain of the linear polymer formed. to Synthesis of the polymers according to the invention are compounds of general formula I as α-amino acid esters

used

2. 0

I 1 if

NMp-CI-I-C,

^ ^0R 2

where R2 is an aliphatic or araliphatic radical such as ζ. As methyl, ethyl, benzyl and Ri can assume the following meaning:

^ ₁ = -! I (glycine)

-CII ₃ (alanine)

" ^Cil 2" V7 (phenylalanine)

CIL / - ^ύ -CII (Valine)

-CII-CII ₉ -ChL (isoleucine)

CII ₃ ^ (leucine)

^N cii ₃

-CH ₂ -CII ₃ (norvaline)

As diepoxides preferably aromatic diglycidyl ether of the formula II can be used: CII ₉ -CN CII ₀ -O-Ii-O-Cn ₉ -CII-CII ₀ OO

- ^C1I 3 _

η ILN-CII-C + η C! l ₉ -CH-C! l ₉ -O-R- _O -CM _o -CII-CIL

K ₁ on 0

Cl-I-R

- / "- 0-CII ₀ -CII-CIi ₀ -N-CII ₉ -CII-CII ₉ -OR -; -

on on

The synthesis of the epoxide-amine polyadducts with ester groups in the side chain takes place by reacting stoichiometric amounts of diepoxide and a-amino acid esters in the melt. For this purpose, after weighing the monomers with additional heating a homogeneous, colorless reaction mixture is prepared, which is heated continuously over a longer period. Here, the temperature interval of 50-100 ⁰ C and a period of 70-80 h have been found to be particularly suitable. By varying these reaction parameters (T, t) it is possible on the one hand to prepare colorless, optically transparent, but on the other hand also discolored, but higher molecular weight addition polymers. Optimum reaction temperatures are specific to the individual amino acid esters. In general, they should not be too high in order not to favor the relevant side reaction of the formation of substituted piperazines from the free amino acid esters. Due to the known limited shelf life of the free amino acid esters, the required amounts of material must be liberated from the corresponding salts (hydrochlorides, tosylates) before the polymerization.

The polyaddition gives hard, crystal-clear polymer bodies which can be cast from solution into films or used for other surface-protecting or insulating purposes. From previous investigations it is known that the formation of soluble addition polymers of aliphatic amines and epoxides succeed only in exceptional cases, for. B. when using aliphatic amino alcohols. Thus, when n-heptylamine or n-propylamine is used, discoloration and crosslinking take place after a short time, while branched amines (t-butylamine, i-propylamine) do not achieve high conversions owing to steric hindrance and thus give products with relatively low Mn values ,

Experiments with amino acid esters brought the surprising result that the synthesis of linear and high molecular weight epoxy-amine addition polymers is possible with this class of substances. However, the applicability of the reaction to the limited

Use of α-amino acid esters. Experiments with β-, γ- or ε-amino acid esters (for example e-aminocaproic acid esters) gave crosslinked products after only a short reaction time.

For the purposes of the invention, the technically readily available racemates of the α-amino acids or the optically active D or L forms can be used. Upon reaction of optically active amino acid esters, optically active addition polymers are synthesized. Due to the polyfunctionality, the polyadducts also have intermediate character; With simple preparative means diverse polymer modifications are possible through which the properties, eg. As solubility can be changed. For example, solubility in water can be achieved by alkaline saponification of the epoxide-amine addition polymers of the invention. Thus, the synthesis of modified epoxy-amine addition polymers with free carboxylic acid groups or their salts, with quaternary ammonium groups, as well as those with hydrazide or amide groups becomes possible.

embodiments

1. 2.00 g (5.87 mmol) of bisphenol A diglycidyl ether and 0.687 g (5.87 mmol) of freshly distilled free L-alanine ethyl ester are homogenized and heated to 7O-75 ^{C for} 75 h. This gives a colorless, glassy polymer body which is soluble in THF, CH ₂ Cl ₂ , CHCl ₃ , CHCl ₃ / CH ₃ OH = 4: 1 or DMF.

M _n (VPO) 8500

(C ₂₆ H ₃₆ NO ₆ I _N Calc. C 68.29 H 7.65 N 3.06 Found. C 68.50 H 7.97 N 3.36

The measured specific rotation for a solution in THF at 2O ⁰ C / a / l ⁰ = - (15.0 ± 0.106) °.

2. 2.00 g (5.87 mmol) of bisphenol A diglycidyl ether and 0.9355 g (5.87 mmol) of freshly distilled, free L-leucine ethyl ester are homogenized and heated to 90-95 ° C for 75 h. The resulting colorless, glassy z. In THF, CH ₂ Cl ₂ , CHCl ₃ , CHCl ₃ / CH ₃ OH = 4: 1 or DMF-soluble polymer bodies is characterized as follows:

M _n (VPO) 10000

(C ₂₉ H ₄₁ NOe) _n Ber. C 69.71 H 8,27 N 2,80 Gef. C69,29 H 8,29 N 2,53

The measured specific rotation for a solution in THF at 20 ⁰ C / a / g ⁰ = - (30.9 ± 0.5) °.

3. 2.00g (5,87mmol) of bisphenol-A-diglycidyletherund0,8553g (5,87mmol) of freshly distilled, freierL-Leucinmethylesterwerden homogenized and 90 h at 90-95 ⁰ C heated. The result is a slightly yellowish solid, glassy polymer body in THF, CH ₂ Cl ₂ , CHCl ₃ , CHCl ₃ / CH ₃ OH = 4: 1 or DMF is soluble.

M _n (VPO) 8400

(C ₂₈ H ₃₉ NOg) _n Ber. C 69.25 H 8.09 N 2.88 Gef. C 69.68 H 8.26 N 2.70.

4. 2.00g (5,87mmol) of bisphenol-A-diglycidylotherund 1,131g (5,87mmol) of freshly distilled, freierL-phenylalanine ethyl ester are homogenized and heated to 105 ⁰ C 95h.

The resulting glassy polymer body is soluble in THF, CH ₂ Cl j, CHCl ₃ , CHCl ₃ / CH ₃ OH = 4: 1 or DMF. M _n (VPO) 10000

C ₃₂ H ₃₉ NOe) _n Ber. C 72.02 H 7.37 N 2.62 Vessel C 71..99 H 7.94 N 2.83.

5. 1.00 g (3.2 mmol) of bisphenol F diglycidyl ether and 0.62 g (0.0032 mol) of freshly distilled, free L-phenylalanine ethyl ester are homogenized and heated to 100 ° C for 95 h.

M _n (VPO) SOOO

6. 2.00g (5,87mmol) of bisphenol-A-diglycidyletherund0,687g (5,87mmol) of freshly distilled, freierDL-Alaninethylesterwerden homogenized and 75 h at 70-75 ⁰ C heated. This gives a colorless, glassy polymer body, which is soluble, for example, in methylene chloride, THF, DMF, chloroform, pyridine.

M _n (VPO) 9000

7. 2.00 g of the linear polymer of bisphenol A diglycidyl ether and L-Alaninethylester are dissolved in 20 ml of pyridine and an excess of commercially available hydrazine hydrate (2.0 g) was added with stirring. The mixture is heated for 10 h at 90 ° C and precipitated in water. The separated precipitate is dried, it is soluble in pyridine, DMF, DMSO.

(C ₂₄ H ₃₃ N ₃ Oe) _n Ber. C 65.00 H 7.50 N 9.47 Gef. C 64.69 H 7.70 N 9.43.

8. 1.00 g of the polyadduct of DGEBA and L-leucine ethyl ester and 0.05 g of tetrabutylammonium iodide are dissolved with stirring in 20 ml of methylene chloride and treated with a solution of 0.5 g KOH in 1 g of H ₂ O. The heterogeneous mixture is stirred for 5 h at room temperature and the precipitate separated. The potassium salt is dissolved in distilled water, filtered and precipitated in a hydrochloric acid aqueous solution. The precipitate is separated and dried, it is soluble, inter alia, in DMF, DMSO, pyridine, ethanol, methanol. The hydrochloride of the free acid of the corresponding polyadduct has the following elemental analysis:

C ₂₇ H ₃₈ NO ₆ CI Ber. C 63.90 H 7.54 N 2.75 Cl 7.01 Gef. C 64.42 H 7.84 N 2 .83 Cl 6.77.

Saponification e.g. KOH / H2O / Bu ^ NJ r

CH-R ₁

H ₂ O / HCl ρΗ = 1

V ⁰

CH-R _n 1®

H Q

he

-CH ₂ -CH-CH ₂ -O-Ar-O-CH ₂ -CH-CH ₂ OH OH

Modification of Ester Grouping in Linear Epoxide-α-Amino Acid Ester Addition Polymers

Claims (6)

A process for the preparation of functionalized, soluble epoxy-amine addition polymers, characterized in that the diepoxides are reacted with α-amino acid esters in a molar ratio of 1.0: 1.0 and the a-amino acid ester groups introduced in this way into a polymer chain either remain unchanged or further modified polymer analog in a second reaction stage. 2. The method according to claim 1, characterized in that are used as the a-amino acid ester compounds of the general formula I, il ^ NII ₀ -CII-C I I ₀ where R2 is an aliphatic or araliphatic radical such as ζ. Β. Methyl, ethyl, benzyl and R ₁ can assume the following meaning: R ₁ = -Il (glycine) -CH ₃ (alanine) -CH ₀ V _x \ (phenylalanine) ₃ CM (valine) ₃ -CH-CH ₀ -CIL (isoleucine) I ί. ν) CII ₀ (Leucine) -CH ₀ -CIL, (norvaline) 3. Process according to claims 1 and 2, characterized in that are preferably used as diepoxides aromatic diglycidyl ethers of the formula II. CH " R = - L /> -C-ClI 4. Process according to claims 1 to 3, characterized in that the reaction at a temperature of 20 to 150 ⁰ C, preferably from 50 to 100 ⁰ C is performed. 5. Process according to claims 1 to 4, characterized in that optically active linear polymers are produced by using optically active D or L-α-amino acid esters. 6. Process according to claims 1 to 5, characterized in that the inventively introduced into a polymer chain a-Aminosäureestergruppierungen be modified by saponification, transesterification, salt formation, amidation and the reaction with hydrazines.