DD232057A1 - PROCESS FOR PREPARING ALPHA, OMEGA DUFINCTIONAL PREPOLYMERS WITH TWO GLYCIDYLENE GROUPS - Google Patents

Abstract

The invention relates to a process for preparing a, v-difunctional prepolymers having two glycidyl end groups with glycidyl end groups, which is characterized in that diglycidyl compounds with dithiol compounds in a molar ratio of between 10: 1 and 10: 9.5, preferably between 10: 5 and 10 : 9, in melt or solution, if appropriate in the presence of catalysts are reacted. The result is a, v-difunctional prepolymers having two glycidyl end groups, which contain b-hydroxy-thioether groups in the molecular strain. Because of the reactive glycidyl end groups, the prepolymers according to the invention can be used as intermediates for the preparation of linear polymers, networks, cast resins, composites, laminates, coatings, paints, adhesives, photoresists, light-curing printing or staining paints. u. a. be used.

Description

HS-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ Ch ₂ -SH

HS-CH ₀ CH ₀ -SH

HS-CH ₂ -CH (SH) -Ch ₂ OH

HS- (CH ₂ ) _n -SH η = 5, 8

HS-CH ₂ COOCH ₂ CH ₂ OCH ₂ CH ₂ OCh ₂ CH ₂ OOCCH ₂ -SH

HS-CH ₂ COO (CH ₂ ) 00CCH ₂ -SH n = 6, 8

HS-CH ₂ COO-C ₆ H ₄ -OOCCH ₂ -Sh HS-CH ₂ COO-C ₆ H ₄ CH ₂ CgH ₄ -OOCCH ₂ -SH

Field of application of the invention

The invention relates to a process for the preparation of a, ω-difunctional prepolymers having two glycidyl end groups, which can serve as versatile intermediates for the production of linear polymers, networks, casting resins, composites, photoresists, light-curing printing or staining paints, etc. due to the reactive glycidyl end groups ,

These are connections of the following type ->

- CH - CH ₀ - A - CH ₀ --CH - CH,

Due to the process occur mixtures of prepolymers with different intermediate chain length (A). Dependent on

_wjijd ^^ hem | _schen_Struktur and the average weight or length of A can characteris tics which Thermis chen e ig

(Glass transition temperature, flow temperature) of the prepolymers and the thermal properties of secondary products are influenced.

The use of prepolymers for the preparation of polymer products has the advantage over the use of monomers that the toxicity or odor intensity of the reaction components is reduced or eliminated, already a significant amount of heat of reaction is dissipated and in polymerization a much lower

Volume coughing occurs. Compared to the high polymers, the prepolymers have the advantage of lower viscosity, lower melting and flow ranges, improved solubility and just preserved functional end groups in a still usable concentration.

Characteristic of the known technical solutions

Prepolymers with / 3-hydroxy thioether groups in the molecule and two glycidyl end groups are not known. As α , ω-difunctional prepolymers with glycidyl end groups, so-called phenoxy resins or higher molecular weight epoxy resins are known, which are prepared for example by US 2602075, US 2615007 and US 2615008. These processes are characterized in that bisphenol A and epichlorohydrin are reacted in different molar ratios. These higher molecular weight epoxy resins carry the characteristic 2 (hydroxy) propylene group

- CH ₀ - CH - CH ₀ -2 ι d,

OH.

in the molecule trunk. DD-210915 describes a process for the preparation of prepolymers having two glycidyl end groups which have / 3-hydroxy-amine groups of the following type in the parent molecule and which are prepared from diglycidyl compounds and amines.

R '

- CH ₀ -CH-CH ₀ -N-CH ₀ -CH-Ch ₀ -

* ι ^ d ι 2

OH OH , ' '

R "R",

CH-CH-CH ₀ -NR "'- N-CH ₀ -CH-CH ₀ -

£ιd d2

OH OH

In contrast, the process according to the invention makes it possible to prepare prepolymers which differ characteristically from the abovementioned ones by virtue of the fact that the / 3-hydroxythioether moiety is contained in the molecular strain, which gives the prepolymers new and different properties.

- CH ₀ - CH - CH ₀ -SR * -S - CH ₀ - CH - CH ₀ -

^ Id <L .d

OH OH

Object of the invention

The object of the invention is the preparation of prepolymers bearing two reactive glycidyl end groups in the average molecule and thus opening up a large field of use as an intermediate for the preparation of new polymer products. Furthermore, it is desired to work out prepolymers with / 3-hydroxy-thioether groups in the molecular weight and with number-average molecular weights of about 500 to 6000 by an easily manageable, running in high yields synthesis.

Explanation of the essence of the invention

The process for the preparation of α , ω-difunctional prepolymers having two glycidyl end groups is characterized in that diglycidyl compounds are reacted with dithiol compounds in a molar ratio between 10: 1 and 10: 9.5, preferably in a molar ratio of between 10: 5 and 10: 9, to form prepolymers of Structure A will be implemented.

CH ₀ -CH-CH ₀ -Pr-CH ₀ -CH-CH-SRS-CH ₀ -CH-CH ₀ - ^ - R-CH ₀ -Ch-CH \ < d / d ^L d \ 2 2j ZJ d < j

^X CT OH OH o

OH OH - . ο

where χ is an average value dependent on the molar ratio used, and R and R 'are substituted or unsubstituted aliphatic, araliphatic, aromatic, cycloaliphatic or other difunctional radicals, including ethers (-O-), esters (-CO-O-) or amine groups ( -NR "-) representing the two glycidyl groups

(-CH ₀ -CH-CH ₀ )

or two thiol groups (-SH) can connect to each other. ,

It has further been found that the reaction according to the invention proceeds according to equation (1) and the prepolymers have in most cases an average degree of polymerisation P _n which follows the formula (2), provided that the

Implementation is led to virtually complete consumption of thiol groups. Equation (1):

η is GHo-GH-CH ₉ -R-CH ₀ -CH-CH ₀ + m HS-R'-3H ^

\ ^{2 _0/2 2} \ _^0/2

CH ₀ -CH-CH _o ~ PR-CH _o CHCH _o -3-R'-3-CH ₀ CHCH ₀ IR-Ch ₀ -CH-CH O OH .OH- ^X O ⁷

Equation (2):

^P n = H-7 ^r = £ 0.1 <rj 0.95

For example, in the reaction according to the invention of 10 mol of a diglycidyl compound with 5 mol of a dithiol, a prepolymer of structure A having an average degree of polymerisation of P _n = 3 and χ = 1 is formed

Suitable diglycidyl compounds which are particularly suitable for the preparation process are: diglycidyl ethers of dihydroxyaromatics, aliphatic diglycidyl ethers, diglycidyl esters, diglycidylamines. Preferably used are:

Bisphenol A diglycidyl ether

γ ¥ \ yO-CHg-CH-CH

- High molecular weight epoxy resins derived from bisphenol-A, z. As the commercial products of the Fa. Ciba-Geigy, Switzerland under the trade names Araldite, such as Araldite GT 6071, GT 7071

Bisphenol F diglycidyl ether, isomeric mixture

CH ₀ -CH-CH ₂ -OC ₆ H ₄ -CH ₂ -CgH ₄ -O-CH ₂ -CH-CH ₂

- aliphatic diglycidyl ethers

-CH-CH₀-O-CH₀CH₀OCH₀CH-CH2 2 2 2 /

z. For example, CH ₀ -CH-CH ₀ -O-CH ₀ CH ₀ OCH ₀

\ 2 y 2 2 2 2 \ /

^N 0 0

Diglycidyl ester e.g.

0 0

ü 11

CH ₀ -CH-CH ₀ -OC-R "-CO-CH ₀ -CH-CH ₀ s2 / 2 2/2

0 0

₀ 2

^Rtt " ^C 6 ^H 4 'W' ^CH 2 ^CH 2 - diglycidyl amines, eg.

CHP-CHCH ₀ -N (R "*) - CH ₀ CH-CH ₀ R"'= C _K H _K

0 ^ O

Dithiol compounds used for the preparation process according to the invention correspond to the formula

HS-FT-SH Particularly suitable dithiol compounds are:

HS-CH _O C _Ä H, CH ₀ -SH, HS-CH _o -f 7- ₀

HS-CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -Sh

HS- (CH ₂ CH) _n SH η = 2-10, especially η = 2, S, 8

HS-CH ₂ CH (SH) -Ch ₂ OH

HS-CH ₂ COOCH ₂ CH ₂ OCH ₂ CH ₂ OCh ₂ CH ₂ OOCCH ₂ -SH

HS-CH ₀ COO- (CH ₀ ) 0OCCH ₀ -SH η = 6, 8

HS-CH ₂ COO-C ₆ H ₄ -OOCCH ₂ -Sh HS-CH ₂ COO-C ₅ H ₄ -CH ₂ -C ₅ H ₄ -OOCCH ₂ -Sh

The reaction is advantageously carried out without solvent or diluent by heating the homogeneous mixture of the two components and at a temperature of 0 <T <14O ⁰ C, preferably at 60-120 ⁰ C. Namely, heated until the thiol groups have reacted , The prepolymers prepared by this procedure have a certain number-average molecular weight, which is predetermined by the molar ratio r of the reaction components. The prepolymers consist of a series of oligomers (x = 1,2,3,4, ...), which often also diglycidyl starting compound remains (x = 0). This is especially the case for r between 0.1 and 0.75. The prepolymers according to the invention are thus mixtures of diglycidyl compounds of different chain lengths, in a further embodiment of the invention it has appeared advantageous to carry out the reaction according to the invention in a solvent or diluent, preferably in monomethylglycol, ethylene diglycol, toluene, chlorobenzene, benzyl alcohol and / or in the presence of reaction catalysts to work. Tertiary amines, peroxides (such as benzoyl peroxide), alcoholates are particularly suitable for this purpose.

The breadth of variation of the method according to the invention proves to be extraordinarily large. This applies both with regard to the usable diglycidyl and dithiol components, as well as with regard to the achievable average molecular weights of the prepolymers.

example 1

10.0 g of bisphenol A diglycidyl ether (29.38 mmol) and 2.5 g of xylylenedithiol (HSCH ₂ C ₆ H ₄ CH ₂ SH) (14.69 mmol) are intimately mixed with one another while heating to 80 ° C. until a homogeneous mixture is formed is and then reacted without stirring at 100-120 ⁰ C for 50-70 hours. The result is a glassy amorphous prepolymer which is soluble in THF and contains two glycidyl end groups per average molecule.

Example 2

11.475 g of bisphenol A diglycidyl ether (33.71 mmol) and 3.073 g (16.86 mmol) of 3.6-dioxaoctane-dithiol-1.8 (HSCH ₂ CH ₂ OCH ₂ CH ₂ OCh ₂ CH ₂ SH) are mixed homogeneously by heating and stirring and heated at 8O ⁰ C for 85 hours. A viscous, clear, colorless prepolymer is soluble in THF, CHCl3 / CH3OH, dioxane, toluene, among other things, has a number average molecular weight M _n (VPO) of 785 and has two glycidyl group per average molecule.

Claims (6)

Invention claim: A process for the preparation of α , ω-difunctional prepolymers having two glycidyl end groups, characterized in that diglycidyl compounds are reacted with dithiol compounds in a molar ratio between 10: 1 and 10: 9.5, preferably in a molar ratio of between 10: 5 and 10: 9 and prepolymers of structure A are formed, wherein χ is an average value and R and R 'substituted or unsubstituted aliphatic, aromatic, araliphatic, cycloaliphatic or other difunctional radicals such as ethers, esters orertert. Amines that can connect two glycidyl groups or two thiol groups. A CH ₀ -CH-ChJr-CH ₀ -CH-CH ₀ -SR * -S-CH ₀ -CH-CH-CH ₀ -IR-CH-CH ₀ ^ g P ^{H 0H} X ° 2. The method according to item 1, characterized in that the mixtures of different diglycidyl compounds and / or different dithiol compounds are used. 3. The method according to item 1 and 2, characterized in that the reaction is carried out in the presence of solvents or diluents and / or reaction catalysts, preferably in the presence of methyl glycol, diglycol, benzyl alcohol, small amounts of tertiary amines, peroxides, alcoholates. 4. The method according to item 1 to 3, characterized in that the reaction in the melt, respectively without solvent or diluent is carried out. 5. The method according to item 1 to 4, characterized in that as diglycidyl bisphenol A diglycidyl ether, higher molecular weight epoxy resins having two glycidyl end groups, bisphenol F diglycidyl ether, aliphatic diglycidyl ethers, diglycidylamines or diglycidyl esters are used. 6. The method according to item 1 to 5, characterized in that as dithiol compounds, aliphatic, aromatic, araliphatic or cycloaliphatic dithiols are reacted, preferably HS-CH ₀ CcH ₇₁ CH ₀ -SH