DD257435A1 - METHOD FOR THE PRODUCTION OF ACID CLEANED EPOXY ADDITION POLYMERS - Google Patents

Abstract

The process according to the invention relates to the preparation of epoxide addition polymers which contain the following structural group in the polymer main chain: ... CH 2 CH 2 O CHOCH 2 CH 2... R The polymers are acid-cleavable. They can be used as adhesives, passivation materials in electrical engineering / microelectronics, resists and the like. a. m. be used.

Description

HS-CH ₂ CH ₂ O-CH-OCH ₂ CH ₂ -Sh II

, IiS-Z-CH ₀ CH ₀ O-CH-OCH ₀ CH ₀ -S 4 CH ₀ CH ₀ O-CH-OCH ₀ CH ₀ -Sh III

IC.C. C. d X. I ddIdd

^X R ⁷ . ^a R

where a can take averages of 1 to 20, NHR 'is a secondary amino group, e.g. B. NHC ₆ H ₅ , NHCH ₂ C ₆ H ₅ , NHCH ₃ , NHCH ₂ CH ₂ OH, NHCH ₂ CH = CH ₂ , and R is a monofunctional radical, such as. B. H, CH ₃ -, CH ₂ = CH-, C ₆ H ₅ , C ₆ H ₅ -CH = CH- represent.

2. The method according to claim 1, characterized in that the diepoxide and acetal in a molar ratio of 0.98: 1 to 1.02: 1 at 20-140 ⁰ C, preferably at 60-120 ° C are reacted.

3. The method according to claim 1 and 2, characterized in that the addition polymerization in solution or in substance (melt) is optionally carried out with the addition of catalysts or accelerators.

4. The method according to claim 1 to 3, characterized in that are used as diepoxide bisphenol A diglycidyl ether and acetal N, N'-dibenzyl-3,5-dioxaheptandiamin-1.7 and formed a high molecular weight soluble addition polymer of the following structural formula becomes.

1OCH ₀ CHCH ₀ N-CH ₀ CH ₀ O-CH ₀ -OCH ₀ CH ₀ -NCH ₀ CHCh ₀ O

d \ d \ d d d d dId \ d

OH CH ₂ C ₆ H ₅ C ₆ H ₅

5. The method according to item 1 to 3, characterized in that the diepoxide bisphenol A diglycidyl ether and acetal used as 1,7-dithio-3,5-dioxaheptan and a high molecular weight soluble addition polymer of the following structural formula is formed.

1OCH ₂ CHCH ₂ S-CH ₂ CH ₂ O-CH ₂ -OCH ₂ CH ₂ -SCH ₂ CHCh ₂ O- ^

^ Oh 6h ~

6. The method according to claim 1, characterized in that the diepoxide and acetal in a molar ratio 2: 1 to 1.07: 1 or 0.5: 1 to 0.93: 1 to form prepolymers having glycidyl end groups or amino or thiol end groups be implemented.

7. The method according to claim 1 to 6, characterized in that a part of the Diaminoacetalverbindung is replaced by a Dithiolacetalverbindung and so copolyadducts are prepared.

Field of application of the invention

The process for preparing acid-cleavable epoxide addition polymers relates to polymers containing the following structural units in the parent molecule.

CH ₂ CH ₂ -O-CH-O-CH ₂ CH ₂ -...

R wherein R = H-, CH ₃ -, CH ₂ = CH-, C ₆ H ₅ -, C ₆ H ₆ -CH = CH-.

Polymers according to the invention can be cleaved by subsequent chemical or photochemical reactions. Furthermore, such Etheramin- or thiolether-acetal polymers as adhesives, passivation materials for electrical engineering / electronics, extractants for metal ions and resist materials usable.

Characteristic of the known technical solutions

High molecular weight soluble epoxide-amine or epoxide-thiol addition polymers have been prepared by Hörhold and coworkers (DD 141677, DD 149534, DD 232058, Z. Chem. 22 [1982] 166). These polymers are hydrolysis-stable and acid not fissile. By reaction with acids rather high molecular weight, stable ammonium salts (polycations) were obtained (DD 211573, DD 146056). , ,

Object of the invention

The object of the invention is to produce acid-cleavable high molecular weight, soluble epoxide-amine or epoxide-thiol addition polymers which are readily accessible from DDR intermediates.

Presentation of the solution according to the invention

Acid-cleavable epoxide-amine addition polymers 1 and epoxide-thiol addition polymers 2 are obtained by reaction

OH R ' H ₂ O R H ₂ R ¹ OH CHCI OH J ₂ SC R OH ITT Π

'J-j

₀ -R "J-2a

2 years

OH ^V R ^'a R

SCH ₀ CHCH ₀ -R '' J- '2b

of diepoxides, preferably of digiycidyl ethers, diglycidyl esters or diglycidylamines, with acetal compounds of the formula 3 or 4, where

HIi-CH ₀ CH ₀ O-CH-OCH ₀ CH ₉ -NH

R 'RR'

HS-f-CH ₂ CH ₂ O-CH-OCH ₂ CH ₂ -S _z 4-

¹ R ^{/ a} R

a = 0,1,2 ... 20is,

HNR '= a secondary amino group. NHC ₆ H ₆ NHCH ₂ C ₆ H ₅ , NHCH ₃ , NHCH ₂ CH ₂ OH, NHCH ₂ CH = CH ₂ , NHC ₆ H ₄ -X

(X = substituent Cl, Br, OCH ₃ ),

R = a monofunctional radical, e.g. B. H, CH ₃ -, CH ₂ = CH-, C ₆ H ₆ , C ₆ H ₆ -CH = CH-

R "= a difunctional radical, eg

-OC ₆ H ₄ -C (CH ₃ ) 2 -C ₆ H ₄ O-, -OCO COO-, -N-

-OC ₆ H ₄ -CH ₂ -C ₆ H ₄ O-

° 6 ^H 5

represent.

To prepare high molecular weight soluble addition polymers, diepoxide and acetal compounds are used in a molar ratio of 0.98: 1 to 1.02: 1, catalysts or accelerators optionally being used. The addition polymerization can be carried out in solution or in bulk (melt) at 20-140 ⁰ C, preferably at 60-120 ⁰ C.

A part of the aminoacetal compound can be replaced by thiol acetal compound so that copolyadducts can be produced.

If diepoxide and acetal compound are used in a molar ratio of 2: 1 to 1.07: 1, prepolymers with glycidyl end groups are formed. On the other hand, the use of diepoxide and acetal in the molar ratio of 0.5: 1 to 0.93: 1 leads to prepolymers having amino or thiol end groups.

By using commercially available polyacetals (eg Thioplast G4 Chemiewerk Greiz-Dölau) it is possible to produce epoxide polymers with up to 20 average acetal groups in the molecule.

The acetal-containing addition polymers according to the invention are cleavable under acidic reaction conditions.

embodiments

Step Example! 1

86.5 g (0.5 mol) of 1,7-dichloro-3,5-dioxaheptane (Diformal-VEB Chemiewerk Greiz-Dölau) and 535.8 g (5.0 mol) of benzylamine are heated together for 2 hours at reflux. After cooling, it is shaken with 300 ml of 40% potassium hydroxide solution, the amine phase is separated off and dried over solid KOH. Subsequently, the excess benzylamine is distilled off in vacuo and the crude amine fractionated in an oil pump vacuum

 Bp 210-211 ° C / 0.6 torr. Yield: 106.8 g (67.9% of theory)

C ₁₉ H ₂₆ N ₂ O ₂ 314.4 Ber.C72.58 H8.34 N 8.91

Gef. C 72.42 H 8,19 N 8,98

5,000 g (14.69 mmol) of bisphenol A diglycidyl ether and 4.618 g (14.69 mmol) of N, N'-dibenzyl-3,5-dioxaheptanediamine-1,7 are homogeneously mixed with gentle heating and at 60 ° for 24 hours C reacted. The result is a slightly yellowish-colored, rubber-elastic polymer, which is soluble in CHCl ₃ / CH ₃ OH (vol. Ver. 4: 1), THF, pyridine, etc., and is cleavable by acid, eg alcoholic hydrochloric acid

M _n (VPO) 11,500, Tg 23 ° C

Q ₀ H ₆₀ N ₂ O ₆ 654.9 Ber.C73.37 H 7.70 N 4.28. .

C 73.81 H 7.60 N 4.87

Example 2

5,000 g (14.69 mmol) of bisphenol A diglycidyl ether and 2.309 g (7.34 mmol) of N, N'-dibenzyl-3,5-dioxaheptanediamine-1.7 are homogeneously mixed with gentle warming and stirred at 60 ° C. for 24 hours ⁰ C reacted. The result is a viscous prepolymer which is soluble in CHCl3 / CH3OH (vol. Ratio 4: 1), THF and others. C ₆₁ H ₇₄ N ₂ O ₁₀ 995.3 Ber.C73.62 H 7.49 N 2.81

Gef. C 74.51 H 7.33 N 2.45

The prepolymer has epoxide end groups.

Example 3

5,000 g (14.69 mmol) of bisphenol A diglycidyl ether and 2.472 g (14.69 mmol) of 3,5-dioxaheptanedithiol-1.7 are homogeneously mixed with gentle heating and reacted at 100 ° C for 40 hours. The result is a high molecular weight polymer which is cleavable by heating in dioxane / HCl / HiO.

Example 4

Representation of the polyadduct of DGEBA and Thioplast G4

3.444 g (10 mmol) of DGEBA and 10.500 g of Thioplast G4 (Greiz-Dölau) are weighed in a Schlenk flask. Thioplast G4 contains the following dithiol:

HS- (CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ -S _x -) -, CH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ Sh (a = 5)

The Schlenk vessel is seked several times in a dry ice / acetone mixture and the reaction mixture is homogenized with gentle heating with a magnetic stirrer.

Thereafter, the reaction mixture is reacted for 40 hours at 100 ° C in a metal bath.

The addition polymer thus obtained can be cleaved with dilute HCl.

Claims (1)

1. A process for the preparation of acid-cleavable Epoxidadditionspolymeren, characterized in that diepoxides, preferably diglycidyl ether, diglycidyl esters or diglycidylamines, with acetal compounds of the formulas I, II or III HN-CH ₀ CH ₀ O-CH-OCH ₀ CH ₀ -NH ι f dd ι dd , ' R 'R. , R '