DD154985A1 - PROCESS FOR PREPARING HIGH-MOLECULAR, N-SUBSTITUTED POLY (3.7-DIHYDROXY-1.9-DIOXA-5-AZA-NONAMETHYLENARYLENEES) - Google Patents

Abstract

The invention relates to a process for the preparation of high molecular weight, N-substituted poly (3,7-dihydroxy-1,9-dioxa-5-aza-nonamethylene-arylenes), wherein Ar = arylene radical, for example -C deep 6 H deep 4 -C (CH deep 3) deep 2 -C deep 6 H deep 4-, The task of producing formula-pure, linear and soluble addition polymers, by melt polymerization or solvent-free polyaddition at a temperature above the glass transition temperature of aromatic diglycidyl ethers, such as formula-pure bisphenol A diglycidyl ether (DDGE) , with primary monoamines (RN H deep 2), where R can be an aryl, aralkyl, alkyl, or cycloalkyl radical. The polymers are amorphous, thermoplastic and form films from solutions. The glass transition temperature of the polyadduct of DDGE with aniline is 96 degrees C.

Description

Process for the preparation of high molecular weight, N-substituted poly (3,7-dihydroxy-1,9-dioxa-5-aza-nonamethylenarylenes)

Field of application of the invention

The invention relates to a process for the preparation of high molecular weight, N-substituted poly (3,7-dihydroxy-l9-dioxa-5-aza-nonamethylene-arylenes), polyhydroxypolyetherpolyamine compounds of the following structure:

0-CH ₀ -CH-CH ₀ -N-CH ₀ -CH-CH ₀ -O-Ar OH OH

High molecular weight polymers of this type have valuable technically useful properties as polyfunctional compounds due to their reactive hydroxyl groups and the numerous imine and ether groups, such as excellent adhesion to glass, metal, plastic, wood, stone and other materials, and excellent complexing ability for metal ions. They are soluble in various solvents, such as in mixtures of chloroform / methanol, in dimethyl sulfoxide, dimethyl acetamide, dioxane and the like and form from solution easily applied protective and insulating layers, which can be replaced if necessary by suitable solvents again. They are therefore particularly suitable for the preservation of sensitive optical, electrical or mechanical components.

_r. rrn η ^ ^η * <; is OTiQ. "

- 2 - 2 18 888

Due to the thermoplasticity and solubility of these polymers is also a use as a melt or solution adhesive given. The bonds can be thermally or by solvents solve again, which is also 'beneficial for the processing of optical components and for the processing of other materials.

In addition, the novel polymers are processible by thermoplastic or solution to threads, films, layers and bodies or as chemical intermediates for novel polymer combinations and for the production of numerous functional polymers (reactions of the hydroxyl or / and imino groups). As ion-free film and laminating agents, they are primarily important as electrical insulating layers.

Characteristic of the known technical solutions

While networks of epoxy resins and primary diamines are widely used as thermosets technically, high molecular weight linear epoxy-amine polyadducts of primary monoamines and well-defined molecular structure have not yet been produced by technically advantageous methods. Although the implementation of epoxy resins having more than one epoxide group and primary monoamines has often been reported, only products have ever been obtained which either achieve only low average molecular weights (less than M 10,000) or / and considerable deviations or Sorokin, KA Lyalynshko, Khim, i Khim, Tekhnol, 1959, 358-62, CA 54, 373d, L. Canonica et al., Macromolecular Chemistry 116 , 158-172 (1968); P. Schlack DRP 676 117). The optical, electrical, mechanical and chemical properties of these products are usually unsatisfactory and do not reach the limits that can be achieved for formula-pure polymers with relative average molecular weights above 10,000 (M).

2 1 8 888

Next comes the process of the invention, a process for the preparation of high molecular weight thermoplastic epoxy-amine polyadducts according to WP 211 599. Such polyad ^; However, diepoxides and di-secondary diamines have a different molecular structure, which is characteristically differentiated by the different ratio of hydroxyl and imino groups from the polymers made by the present process. In the case of the polymers according to the invention, the ratio HO: RN = 2: 1, while in the case of the polymers according to WP 211 599 this ratio amounts to 1: 1. This has considerable consequences for the physical and chemical properties of the polymers according to the invention. In particular, it is not foreseeable that the melt polymerization according to the invention leads to high molecular weight polyadducts and that consequently both cyclization reactions (to oligocycles) and crosslinking reactions which endanger this target can be suppressed.

Object of the invention

The object of the invention is to disclose a generally applicable process for the preparation of N-substituted formula-pure, high molecular weight poly (Sy-dihydroxy-1-dioxa-S-aza-nonamethylene-arylenes) which has a favorable polymerization technology (solvent-free reaction , simple reaction, no expenses for isolation and purification of the products).

Explanation of the essence of the invention

According to the invention, high molecular weight, N-substituted poly (3,7-dihydroxy-1,9-dioxa-5-aza-nonamethylene-arylenes) are prepared by a process of polyaddition of aromatic diglycidyl ethers with primary monoamines, which is characterized

- 4- 2 18 888

characterized in that formula-pure diglycidyl ethers of dihydroxyaromatics, preferably diandiglycidyl ether (DDGE, 2.2-bis [4- (2.3-epoxypropoxy) -phenyl] propane), with primary monoamines in the molar ratio of 1.0: 1.0 by melt polymerization at temperatures of 30 to 200 ⁰ C, optionally in the presence of 0.1 to 2.0 percent by mass of an alcohol or phenol as accelerator, are reacted.

The process is described by the following reaction equation:

η is CH ₀ -CH-CH ₀ -O-Ar-O-CH ₀ -CH-CH ₀ + η NH ₀ ^

V ² . ² ν

R.

-R 0-CH ₀ -CH-CH ₀ -N-CH ₀ -CH-CH ₀ -O-Ar -

¹ 'η

OH OH

Ar = bifunctional mononuclear or polynuclear aromatic radical, such as -C ₅ H ₄ -, -C ₁₀ H ₆ -. -C ₅ H ₄ -C (CH ₃ J ₂ -CgH ₄ -

R β is an aryl, aralkyl, alkyl, cycloalkyl or substituted radical derived therefrom

The diglycidyl dihydroxyaryl compound used is preferably the diglycidyl ether of bisphenol A (DDGE; 2,2-bis [4- (2,3-epoxypropoxy) -phenyl] propane). Suitable primary monoamines are, for example, aniline, p-methoxyaniline, p-chloroaniline, benzylamine, phenethylamine, butylamine and cyclohexylamine. The N-substituent R may therefore be both a substituted or unsubstituted aryl radical, an aralkyl radical, an alkyl radical or a cycloalkyl radical.

Formula-pure DDGE can be obtained relatively easily by repeated fractional distillation of epoxide resins from bisphenol A and epichlorohydrin. Optionally, the product is crystallized. Instead of DDGE, other formula-pure aromatic diglycidyl ethers, such as hydroquinone diglycidyl ether or diglycidyl ether of 1.5-Di =

- 5 - 2 18 888

hydroxynaphthalene be used. The aromatic diglycidyl ether is intimately mixed with the gleichmolareri amount of the relevant primary monoamine, optionally by heating to 30 to 100 ⁰ C and thorough stirring. Then, the mixture is heated in a reaction vessel, which is embedded in a suitable heating bath, between 10 and 150 hours to reach rel, average molecular weights over M _n = 10,000 to 30 to 200 ⁰ C. Preferably, a temperature of 100 - 120 ⁰ C is set. Is one of the components at this temperature volatile, the reaction starts at 30-100 ⁰ C, she runs to the oligomerization, and then raising the reaction temperature to 100-150 ⁰ C. It is expedient in particular cases, the reaction temperature gradually into the To increase the glass transition temperature of the polyadduct, here longer time to hold and finally to a temperature which is 10 to 50 ⁰ C above Tg, increase. Optionally, the melt polymerization under an inert gas and optionally with the addition of 0.1 to 2 percent by mass of an alcohol or phenol as an accelerator, for example phenethyl alcohol. Benzyl alcohol, carried out. In general, however, an addition of an accelerator is not required. After a sufficiently long reaction time, the optimum is determined by sampling and molecular weight determination, generally gives a homogeneous glassy amorphous mass, which consists quantitatively of the corresponding polymers. Occasionally, a slight discoloration of the polymerization batch occurs.

At the end of the reaction time, the polymer produced can be used without further purification operations for thermoplastic processing or dissolution in suitable solvents. If necessary, a cleaning by dropping done.

From 1.0 mole and 1.0 mole of benzylamine DDGE the glassy amorphous poly (3.7-dihydroxy-5- arises, for example according to the invention by melt polymerization at 105 ⁰ C 60stündige

2 18 888

ben2yl-1.9-dioxa ~ 5-aza-nonamethylene-phen-1,4-ylene-prop-2.2- ^ ylene phen-1,4-ylene) (1) with a relative average molecular weight of 18,000 and a glass transition temperature of 68 ⁰ C. The nearly colorless polymer dissolves in a mixture of chloroform / methanol (4: 1) and forms from this solution excellent transparent films adhering to glass, metal or plastic. «

Similarly, for example, from aniline and anisidine polymers 2 and 3, which are suitable with glass transition temperatures of about 85 ⁰ C and their excellent adhesion to metal, preferably as an electrical insulating.

Polymers produced by the process according to the invention, preferably those having aliphatic N-3 substituents, such as 4 and 5, are suitable as hot melt adhesive or as intermediates for the production of thermoplastically shaped bodies or of novel polymer combinations (blends).

6 ^H 5 CH ₀

- 0 ₀ CH-CH-CH ₀ - N - CH -CH-CH _{o o} -0-f \

2, OH

M_ 18 000

2, OH

2 "

Tg 68 ^U C

0-CH ^ -CH-CH ₀ - Ν - CH ₂ ^ CH-CH ₂ -O- / ~~ \ - C - / ^

OH ~ CH ₃

₀ CHCH ₀ 2 ι d.

OH

10,500

Tg 96

° 6 ^H 4 " ^W " 3

0-CH ₀ -CH-CH ₀ -N- 'CH ₀ -CH-CH ₀ -O- ^ VC

2 ι 2 2 j 2 \ - /, \ / /

OH OH

CH ₃

M _n 12 000

0-CH ₀ -CH-CHOH

Tg 89 ⁰ C

-N-

CH ₀

CH ₀ -CH-CH ₀ -O- /  \ y C ^{2 2} ^

CH ₃

0-CH ₀ -CH-CH d. .

-N-

CH ₀ -CH-CH ₀ -O

2 18 888

Copolymers can be obtained with the mixture of two or more primary monoamines, if it is ensured that the molar ratio of the diglycidyl ether compounds and the primary monoamines is always 1.0: 1.0. For example, 1.0 mole of DDGE can be reacted with a mixture of 0.5 mole of aniline and 0.5 mole of benzylamine to give a high molecular weight copolymer of glass transition temperature greater than 80 ^° C.

' Example 1

5.00 g of diandiglycidyl ether, colorless crystals of melting point 42 - 44 ⁰ C are mixed with 1.57 g of benzylamine until a homogeneous mixture is formed. This mixture is heated at 105 ^° C. for 60 hours. The result is a glassy amorphous polyadduct of structure 1.

M 18,000 (by vapor pressure osmometry in chloroform / methanol) Tg 68.5 ⁰ C (DSC-I Perkin Elmer)

Elemental analysis:

( ^C 28 ^H 33 ^N0 4> n ( ⁴⁴⁷ < ⁶ > _n

Calc .: C 75.14 H 7.43 N 3.13

Found: C, 75.15, H, 7.66, N, 3.64

The polymer is soluble in dimethylacetamide, N-methylpyrrolidone, and CHClo / CH 2 OH mixture and forms well adhering films from solution to glass.

Example 2

5.00 g of diandiglycidyl ether, colorless crystals of melting point 42-44 ° C, are mixed with 1.36 g of aniline by gentle warming and then polymerized at 105 ⁰ C for 50 hours. The result is a pale brown colored amorphous glassy mass consisting of the polymer 2.

M _n 10 500, Tg 96 ° C

2 18 888

Elemental analysis: .6) η C 74 80 H 7 , 21 N 3 .23 (C ₂₇ H ₃₁ NO ₄ J _n (433 * C 74 60 H 7 .20 N 2 99 Ber. * Ge f.

The product dissolves in chloroform / methanol mixture, toluene / cyclohexanone mixture, dimethylacetamide or IM-methylpyrrolidone and forms films which adhere well to water or metal.

Example 3.

5.00 g of diandiglycidyl ether, colorless crystals of melting point 42 - 44 ⁰ C, are well mixed with 1.80 g of p-anisidine by gentle warming and stirring and then polymerized at 105 ⁰ C for 64 hours. The result is an amorphous, glassy mass consisting of the polymer 3.

M _n 12 000, Tg 89 O C C 72 , 55 H 7 .18 Elemental analysis: C 72 .17 H 7 , 09 ( ^C 28 ^H 33 ^N0 5) n < ⁴⁶³ ' 6) η Ber. : Gef .:

N 3.02 N 3.38

The polymer is thermoplastic and is soluble in a mixture of chloroform / methanol (4: 1) as well as in dimethylacetamide, dimethyl sulfoxide, dioxane, etc.

Example 4

5.00 g of diandiglycidyl ether, colorless crystals of melting point 42-44 C, are mixed with 1.07 g of n-butylamine by heating to about 35 C and kept at this temperature for 30 hours. Then an additional 48 hours at 45 C heated. It may also be so proceeded that after mixing for 6 hours is kept at room temperature and then the reaction temperature for 20 hours at 70 C is increased. The result is a clear, glassy mass which is soluble in N-methylpyrrolidone, N, N ^f -Dimethylacetamid, dimethyl sulfoxide and similar solvents. she consists

2 18 888

from poly (3,7-dihydroxy-5-butyl-1,9-dioxa-5-aza-nonamethylene-phen-1,4-ylene-prop-2,2-ylene-1,4-phenylene). M _n > 10 000, Tg 62 ⁰ C

Elementarana lysis: ^'57 > n 72 .61 H 8th , 53 N 3 , 39 ( ^C 25 ^H 35 ^N0 4> n (413 : C 72 .23 H B , 54 N 3 48 Ber. : C Gef. Example 5

5.00 g of diandiglycidyl ether, colorless crystals of melting point 42 - 44 ⁰ C, are mixed with 1.45 g of cyclohexylamine by heating to 60 ⁰ C and thorough stirring. This homogeneous mixture is heated at 105 ^° C. for 24 hours and at 140 ° C. for a further 60 hours. The result is the glassy, transparent poly (3.7-dihydroxy-5-cyclohexyl-1,9-dioxa-5-aza-nonamethylene-phen-l ^ -ylene-propyl-ylen-phen-1-ethylene), soluble in chloroform / Methanol (4: 1) and the aforementioned aprotic polar solvents.

M 6 000 - 10 000 η ' ⁵ > n 73 .77 H 8th 48 N 3 .19 Elemental analysis: : C 73 .71 H 8th .26 N 3 , 05 i ^C 27 ^H 37 ^N0 4 ^ n ^ ⁴²⁹ : C Ber. Gef.

Example 6

5.00 g of diandiglycidyl ether, colorless crystals of melting point 42 - 44 ⁰ C are mixed with 0.78 g of benzylamine and 0.68 g of aniline with heating. The homogeneous mixture is heated for 60 hours at 105 ⁰ C and gives after cooling a transparent, hard elastic glassy mass of the corresponding copolymer. It dissolves in the abovementioned solvents.

-40 -. 2 18 8 8 8

Example 7

5.00 g of diandiglycidyl ether, colorless crystals of melting point 42-44 C are mixed with 1.87 gp ~ chloroaniline by heating and stirring and the homogeneous mixture polymerized at 105 ⁰ C for 70 hours. The result is a glassy amorphous polyadduct of the structure

C ₆ ^H 4 ^C1 _r - _x ? ^H 3

C-CH ₀ -CH-CH ₀ -N-CH ₀ -Ch-CH ₀ -O- ^ V) -C- ^

C. i C- C- I C- \ f \

OH OH . CH ₃

M 15 500 (vapor pressure osmometry), Tg 111 ° C (DSC), soluble in chloroform / methanol (4: 1).

Elementarana analysis (468.0 ) H 6 , 46 N 2 99 Cl 7 , 58 (C ₂₇ H ₃₀ ClNO ₄ ) _n 69.29 H 6 , 66 N 3 , 31 Cl 7 , 52 Ber. : C 69.08 Gef. : C

Claims (1)

invention claim 1. Process for the preparation of high molecular weight, N-substituted poly (3,7-dihydroxy-1.9-dioxa-5'-aza-nonamethylene-arylenes) 0-CH ₉ -CH-CH ₉ -N-CHp-CH-CH ₉ -O-Ar OH OH aromatic diglycidyl ethers and primary monoamines, characterized in that they contain formula-pure diglycidyl ethers of dihydroxyaromatics, preferably fortelined diandiglycidyl ether (bisphenol A diglycidyl ether), with primary monoamines R-NH ₂ in a molar ratio of 1.0: 1.0
be reacted by melt polymerization at 30 - 200 ⁰ C, wherein R may be an aryl, aralkyl, alkyl or cycloalkyl radical or a substituted radical derived therefrom. 1,1 "Process according to item 1", characterized in that are used as the primary monoamine, aniline, anisidine, p-chloroaniline, benzylamine, phenethylamine, butylamine, cyclohexylamine or mixtures of these amines ,,