NL8100072A - COPOLYMERS OF ETHERIMIDS AND AMIDE IMIDES. - Google Patents

Description

s 2348-1111 * -¾ ’.

* P&C

Copolymers of etherimides and amide imides.

The invention relates to copolymers containing amide-imide (AI) units and etherimide (EI) units, which copolymers are suitable for coating and molding purposes. More particularly, the invention relates to a copolymer containing: (1) 5-95 mol% 5 AI units of formula (1) of the formula sheet, and (2) 95-5 mol% EI units of formula ( 2) of the formula sheet, in which formulas R is selected from: (a) bivalent organic groups of formulas (3), (4), (5), (6), (7) and (8) of the formula sheet, and (b) bivalent organic groups according to the general formula (9) of the formula sheet, wherein X represents a group -CL -, in which last group y is an integer yyj with a value of 1 - 5? and R represents a divalent organic group, namely (a) an aromatic group of 6-20 carbon atoms or a halogenated derivative thereof, and (b) an alkylene group or cycloalkylene group of 2-20 carbon atoms, (c) a polydiorganosiloxane having C15 alkylene groups, or (d) a divalent group according to formula (10) of the formula sheet, wherein Q represents: -O-, -C (O} -, -SC ^ -, -S- or - CxH2x “'^ which last group x is an integer value 1-5.

The combined randomly distributed units or block copolymers can be assigned the general formula (11) of the formula sheet, in which formula R and R * have the meanings given above, m and n independently integers with a value of ten at least 1 represent (for example 5-5000 or more), and p represents an integer with a value greater than 1 (for example 5-10,000 or more and 25 preferably 10-1000).

Before imidization, the copolymers are in the amide form which can be represented by the general formula (12) of the formula sheet, e.g. copolymers of formula (13) of the formula sheet, in which formulas R, R ', m, n and p are the have meanings given above.

Polyamide imides are known to have good chemical resistance and moderate thermal resistance. Although these polyamide imides for coating applications can be dissolved in suitable solvents, these polyamide imides are very difficult to mold into articles and require very high temperatures and pressures in the molding operation. It is known that polyetherimides have good properties at high temperatures and are more suitable for practical molding operations; however, it would be advantageous to improve the chemical resistance of these polyetherimides and reduce their costs for shaping and coating applications.

8100072. * - 2 -

Surprisingly, it has been found that copolymers containing chemically bonded units of formulas (1) and (2) over a wide range of molar concentrations can be prepared with properties modified from the properties of homopolymers of these 5 units. In some cases, the improvements in properties are particularly surprising given the amount of AI units or EI units present in the copolymer. By preparing the above-described copolymers, the suitability of the latter can be greatly expanded. Furthermore, by combining these two units in the copolymer, products can be obtained which are cheaper than polyetherimides alone, without deteriorating or significantly deteriorating physical properties.

A preferred group of copolymers of formula (11) are copolymers containing about 2 - 5000 or more and preferably 5 - 100 EI units according to formula (14) of the formula sheet, in which formula R * has the 2 meanings given above and R represents a group of the formula (15) of the formula sheet.

Examples of etherimide units of formula (14) as part of the copolymer molecules are the units of formulas (16), (17) and 20 (18) of the formula sheet and combinations thereof, in which formulas R * and 2 R have the meanings given above.

The copolymers of formula (14) can be prepared by reacting an aromatic bis (ether anhydride) of the general formula (19) of the formula sheet with tretate acetyl chlorine of the formula (20) of the formula sheet and an organic diamine of the general formula ( 21) of the formula sheet, in which formulas R and R1 have the meanings given above.

A total of 0.95 - 1.05 moles of the anhydrides of formulas (19) and (20) can be used per mole of organic diamine of formula (21). It is preferred to use substantially equal molar amounts of (a) the anhydrides of formulas (19) and (20) and (b) the organic diamine. The copolymers according to the invention may contain 10-5000 or more units according to formulas (1) and (2) and p in formula (11) has a value of 5 or more, for example 10-1000.

The acyl halide derivative of formula (20) which is derived from trimellitic anhydride (1,3,4-benzene tricarboxylic anhydride) may have at least one acyl halide group in the 4-membered ring, and ....... includes derivatives such as the 4-acid chloride, the 1,4-diacid chloride and the 2,4-diacid chloride. The bromide derivatives and other reactive halide 8100072 f 4 - 3 - * derivatives are also suitable.

Chainstoppers such as aniline or organic monoacid derivatives or monoanhydrides can be used to prepare the copolymers.

In general, the copolymers of the invention can be obtained by the selected diamine and the selected dianhydride and monoanhydride, respectively. of formulas according to formulas (19) and (20) in the presence of a dipolar aprotic organic solvent under ambient conditions to obtain a copolymer of amide acid.

Upon further heating, the amide acid is imidized and the resulting copolymer contains randomly distributed units of formulas (1) and (2). Depending on the solids content of the polyamic acid solution, the conversion can be completed in 0.5-2 hours or a longer period. After completion of the conversion, the solution can be poured onto a substrate so that the organic solvent evaporates. By heating at temperatures of 150® - 200¾ or higher temperatures, the copolymeric polyamic acid is converted into a polylmide, so that the final polymer obtained has good thermal resistance, good resistance to chemicals (e.g. good resistance to solvents) and good formability. . These materials are particularly suitable as wire coating coatings and impart solvent resistance and thermal resistance to various substrates.

The aromatic bis (ether anhydride) of formula (19) can be prepared by hydrolyzing the reaction product of nitro-substituted phenyldinitrile 25 followed by dehydration and reacting with a dialkali metal salt of an aryl compound with two hydroxy groups in the presence of a dipolar aprotic solvent; the alkali metal salt has the general formula (22) of the formula sheet, wherein R * has the meanings given above and preferably has the same meaning as R, and Alk represents an alkali metal ion. Several known methods can be used to convert the obtained tetranitriles to the corresponding tetraacids and dianhydrides.

Examples of the alkali metal salts of the above divalent phenols are the sodium and potassium salts of the following divalent phenols: 2,2-bis (hydroxyphenyl) propane; 2,4'-dihydroxydiphenylmethane; ______ bis- (bis- (2-hydroxyphenyl) methane; 2,2-bis- (4-hydroxyphenyl) propane, hereinafter also referred to as "bisphenol-A" or 8f00072 ► -4 - 4 - "BEA"; 1.1-bis- ( 4-hydroxyphenyl) ethane; 1,1-bis- (4-hydroxyphenyl) propane; 3,3-bis-r (4-hydroxy phenyl) pentane; 4,41-dihydroxybiphenyl; 4,4- 'dihydroxy-3,3r, 5.51 -tetramethylbiphenyl; 2,4-dihydroxybenzophenone; 4,41-dihydroxydiphenyl sulfone; 2,4'-dihydroxydiphenyl sulfone; 4,4'-dihydroxydiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfide; etc.

Examples of organic diamines of formula (21) are: m.phenylenediamine; p-phenylenediamine; 4,4'-diaminodiphenylpropane; 4,4'-diaminodiphenylmethane; benzidine; 4,4'-diaminodiphenyl sulfide; 4.41-diaminodiphenylsulfone; 4.41 diaminodiphenyl ether; 1.5-diaminona-talene; 3,3'-dimethylbenzidine; 3,3'-dimethoxybenzidine; 2.4-diaminotoluene; 2,6-diaminotoluene; 2,4-bis (β-amino-1-butyl) toluene; bis (p.β-methyl-o-aminopentyl) benzene; 1,3-diamino-4-isopropylbenzene; 1.2-bis (3-aminopropoxy) ethane; m.xylylendiamine; 30 p.xylylendiamine; bis (4-aminocyclohexyl) methane; 3-methylheptamethylenediamine; 4.4-dimethylheptamethylenediamine; 2,11-dodecanediamine; 2,2-dimethylpropylenediamine; octamethylenediamine; 3-methoxyhexamethylenediamine; 2.5-dimethylhexamethylenediamine; 3-methylheptamethylenediamine; 40 5-methylnonamethylenediamine; 8100072 * * - 5 - 1,4-cyclohexanediamine; 1,12-octadecane diamine; bis (3-aminopropyl) sulfide; N-methyl-bis (3-aminopropyl) amine; Hexamethylenediamine; nonamethylenediamine; 2,6-diaminotoluene; bis- (3-aminopropyl) tetramethyldisiloxane; etc-

The copolymeric material can be reinforced with various particulate fillers such as glass fibers, silica and carbon-10 "whiskers" in an amount of up to 50% by weight or more of the copolymer.

The invention is further illustrated in the following non-limiting examples.

EXAMPLE I

A copolymer with Al units and EI units was prepared by converting 2 g of 4,4'-methylenedianiline, 1.56 g of 4,4'-BFA dianhydride and 3 1.47 g of 4-chloroformylphthalic anhydride. cm N-methylpyrrolidone. The mixture was stirred at room temperature until it became clear, the temperature of the mixture rising to 40 ° C by the exothermic reaction.

After cooling, the copolymer material was cast as a film on glass 20 at a temperature of about 150 ° - 28 ° C to imidize the amide acid groups. This polymer, containing 30 mol% EI units and 70 mol% AI units, had a softening point of about 300 ° C.

EXAMPLE II

This example describes the preparation of a homopolyetherimide which is compared below with a copolymer material containing the same organic diamino compound. Methods for preparing these homopolyetherimides are described in U.S. Pat. No. 3,847,867. 5.2 g (0.01 mol) 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride (hereinafter referred to as "BFA dianhydride") and 1.08 g (0, 01 mol) 3 30 m.phenylenediamine were dissolved in 30 cm N-methylpyrrolidone. The mixture was stirred, the temperature rising to 42¾ by the exothermic reaction, to obtain a clear solution of homopolymeric amide acid. This this solution was cast a film at 280®-300®C, to obtain an imidized polymeric film.

35 'EXAMPLE III

This example describes the preparation of a homopolymer amide imide. 2.1 g (0.01 mol) of trimellitic acid chloride (TMZC, formula (20)) and 3 _____ 1.08 g (0.01 mol) of m.phenylenediamine were dissolved in 30 cm of N-methylpyrrolidone. The mixture was stirred, whereby the temperature of the solution rose to about 43 ° C by the exothermic reaction, to obtain a clear polymer amide acid amide. Part of this solution was cast on a flat surface at 280®-300®C to obtain an imidized homopolymer AI film.

5 - EXAMPLE IV

A copolymer was prepared by mixing 1.89 g (0.009 mole) TMZC, 0.52 g (0.001 mole) BPA dianhydride and 1.08 g (0.01 mole) m.phenylene diamine in 3 cm N- methylpyrrolidone to give a solution. After stirring at room temperature, the temperature of the mixture rose to about 47 ° C by the exothermic reaction, at which point a clear solution of polymeric amide acid amide was obtained, from which this solution was film, to obtain an imidized copolymer film.

EXAMPLE V

Using the conditions and reaction components of

Example IV, TMZC, bisphenol-A-dianhydride and m.phenylenediamine were similarly reacted to form copolymer materials which were cast into films at elevated temperatures of 280®-300®C, to give imidized copolymer films having good resistance to abrasion. Table A below shows the amounts of the various components and the temperatures to which the solutions of the three reactants rose due to the exothermic reaction after stirring. In each case, 30 cm N-methylpyrrolidone was used to prepare the original solution of the three reaction components. _

TABLE A

TMZC BFA dianhydride m.phenylene dianrine Temp.

Weight Mole Weight Mole Gewi'cfifwMol (exoth.) I; ra: ·) (gram) __ (gram) __ (gram) ___

30 Ex. IV 1.89 0.009 0.52 0.001 1.08 0.01 47®C

VA 1.68 0.008 1.04 0.002 1.08 0.01 48®C

Ex 1.26 0.006 2.08 0.004 1.08 0.01 46®C

V 0.84 0.004 3.12 0.006 1.08 0.01 44®C

VD 0.42 0.002 4.16 0.008 1.08 0.01 43®C

35 PU 0.21 0.001 ^ 4.68 0.009 1.08 0.01 44®C

1) VF 1.05 0.005 2.6 0.005 1.08 0.01 41®C

1) 15 cm 3 N-methylpyrrolidone used.

The Tg values (which are a measure of the degree of softening of the polymers) of all copolymers of Examples IV and VA to 40 and with VF were determined; the results are given in Table B below.

8100072 * / •.-7-

TABLE B

Taste Tg ®C

Example VA - "VB 223 5" VC 221 «VD 204.

"VE 212" VF 209 "II 193 10» m 241 IV 222

The copolymers of Examples IV and VA to VF can be represented by the formula (23) of the formula sheet, wherein m and n are integers with a value greater than 1 and substantially correspond to the originally used molar concentrations of the reaction components, p is an integer with a value greater than 1 and the units are randomly distributed.

EXAMPLE VI

Using the same conditions as in Example IV, 2.1 g (0.01 mole) of TMZC and 2.48 g (0.01 mole) of 4,4'-diphenyldiaminosulfon 3 of the formula (24) of the formula sheet dissolved in 15 cm N-methylpyrrolidone with stirring; the temperature of the mixture rose to 37% due to the exothermic reaction. The resulting clear solution of the polymeric amide acid amide was cast at 280®-300®C to obtain an imidized homopolymer film.

EXAMPLE VII

Under the conditions of Example IV, 5.2 g

(0.01 mole) of BFA dianhydride and 2.48 g (0.01 mole) of the in Example VI

3 used sulfone of the formula (24) dissolved in 15 cm N-methylpyrrolidone; After stirring, the temperature of the mixture rose to 38 ° C by the exothermic reaction and a clear solution of homopolymeric amide acid was obtained.

From this solution was added. 280®-300®C a film cast; an imidized homopolymeric film was obtained.

1 EXAMPLE VIII

In this example, copolymers were prepared from TMZC, BFA dianhydride and the sulfone of formula (24) by dissolving the reactants 3 in 15 cm N-methylpyrrodilone and stirring the mixture until a clear solution of polymeric amide acid amide was obtained. In all cases, films were cast at 280®-300®C to obtain imidized copolymer 8100072. ♦ · - ê - several films with good abrasion resistance. Table C below shows the weight and molar concentrations of the components, the temperature of the exothermic reaction, and the transition temperature to the glass state (Tg) for all materials listed in Examples VI-VIII.

TABLE C

TM2C BFA dianhydride 1) Sulfone

Weight Mole Weight Mole Weight Mole Temp.

Test (grams) __ (grams) ~~ (grams) (exoth.) Tg ° C

10 Ex. VI. --- 37 220 "VII --- 37 220" VIIIA 1.05 0.005 2.6 0.005 2.48 0.01 41 VIIIB 0.42 0.002 4.16 0.008 2.48 0.01 39 181 "VIIIC 1, 68 0.008 1.04 0.002 2.48 0.01 37 208 15 1) 4,4'-diaminodiphenylsulfone <

The imidized copolymers of Example VIII can be represented by the formula (25) of the formula sheet, wherein m, n and p have the meanings given above.

The examples below describe the preparation of homopolymers 20 from a dianhydride with 4,4'-ozydianiline of the formula (26) of the formula sheet or from TMZC and the same oxydianiline, as well as copolymers from a mixture of the oxydianiline, the BFA dianhydride and the TMZC.

EXAMPLE IX

5.2 g (0.01 mol) of BFA dianhydride and 2 g (0.01 mol) of 4,4'-oxydianiline 3 were dissolved in 15 cm of N-methylpyrrolidone and stirred; after the temperature of the mixture had risen to 51 ° C by the exothermic reaction, a clear solution of polymeric amide acid was obtained. A film was cast from this solution at 280®-300®C; an imidized homopolymeric film was obtained.

EXAMPLE X

2.1 g (0.01 mol) TMZC and 2.0 g (0.01 mol) 4,4'-oxydianiline were dissolved in 15 cm N-methylpyrrolidone; the mixture was stirred vigorously after which the temperature of the mixture rose to 53 ° C by the exothermic reaction. A film was cast from the resulting clear solution of homopolymeric amide acid at 280 ° - 300 ° C; an imidized homopolymeric film was obtained.

EXAMPLE XI

In this example, TMZC, BFA dianhydride, and 4,4'-oxydianiline were copolymerized in the same manner as in Example IV by the reaction. ..... ...... '--- - dissolving 9-3 components in 15 cm N-methylpyrrolidone; then the polymer amide acid amide solution was cast into a film at 280®-300®C? an imidized copolymer film was obtained. Table D below shows the weight and molar concentrations of the reaction components and the temperature of the exothermic reaction achieved by stirring the reaction components for each mixture.

TABLE D

. . TMZC .1 EFA Dianhydride 4,41-Oxydianiline

Test Weight Mol Weight Mol Weight Mol Temp.

10 - (gram), ... (gram) _ (gram) _ (exoth.)

XIA .1.05 0.005: 2.6 0.005 1.98 0.01 41 ®C

XIB 1.68 0.008 1.04 0.002 2.0 0.01 50®C

The Tg values of the homopolymers and copolymer prepared in Examples IX, X, XIA and XIB 'were determined; the results are given in Table E.

15 TABLE E

Taste Tg

Example IX 213®C

"X 230®C

"XIA 205®C

20 "XIB 206®C

The copolymers obtained in Examples XIA and XIB have randomly distributed units and can be represented by formula (27) of the formula sheet, wherein m and n are values corresponding to the molar concentrations of the reactants used, and p is an integer -25 number with is a value greater than 1.

The examples below describe the preparation and properties of homopolymers and copolymers prepared using 4,4'-methylenedianiline of the formula (28) of the formula sheet as the organic diamine.

EXAMPLE XII

2.1 g (0.01 mol) TMZC and 1.98 g (0.01 mol) 4,4'-methylenedianiline 3 were dissolved in 15 cm N-methylpyrrolidone and stirred until the temperature of the mixture by the exothermic reaction reached a value of 54®C. The resulting clear solution of homopolymeric acid amide was cast into a film at 280 DEG-300 DEG C; an imidized homopolymeric film was obtained.

EXAMPLE XIII

5.2 g (0.01 mol) of EFA dianhydride and 1.98 g (0.01 mol) of 4,4'-methylene-dianiline were dissolved with stirring in 15 ml of N-methylpyrrolidone, whereby the temperature of the mixture rose to 49 ° C (exothermic reaction).

8100072 ♦ - * _. .-. . - 4 (. * ·.

. t "- ♦ <- - - WW.-.— · ^. - ^ ^ ^ • - 10 -

A film was cast from the resulting clear solution of homopolymeric amide acid at 280®-300®C; a homopolymeric imidized film was obtained.

example XIV

In this example, under the same conditions as in Example IV, TMZC, BFA dianhydride and 4,4'-methylenedianiline were mixed with 3 and dissolved in 15 cm N-methylpyrrolidone to give a solution of a copolymer amide acid amide . A film was cast from this solution at 280®-300®C; an imidized copolymer film was obtained. Table E below shows the weight and molar concentrations of the reactants as well as the temperatures reached by the exothermic reaction.

TABLE E

BFA dianhydride Methylene-15 dianiline

Test Weight Mold Weight Mol Weight Mol Temp.

• (grams) __ (grams) _ (grams) (exoth.)

XIVA 1.05 0.005 2.6 0.005 1.98 0.01 41 ®C

XIVB 1.68 0.008 1.04 0.002 1.98 0.01 49®C

Each of the polymers of Examples XII, XIII, XIVA and XIVB.

examined for Tg values; Table F gives the results of these analyzes; These copolymers can be represented by formula (29) of the formula sheet, wherein m, n and p have the meanings given above.

TABLE F

25 Tg

Example XII 215¾ XIII 187¾

"XIV A 220 ®C

"XIV B 229¾ '30" Of course, except for the preparation of the above described t.

copolymers, diamino compounds are also used, other diamino compounds are used, many examples of which have been mentioned above. Likewise, in addition to the bisphenol-A-dianhydride used in the examples, other dianhydrides can be used to prepare other types of copolymers, many of the other dianhydrides of which are given above. Finally, the molar amounts of the reactants can be varied within wide limits to obtain polymers with different molar amounts of the units.

To the present copolymers, other polymers and resins can be added in amounts of 1 - 50% by weight or more, based on the copolymer.

"8 1 0007 2 'Z

-line. Examples of polymers to be added are polyolefins, polystyrene, polyphenylene oxides, such as those disclosed in U.S. Patent 3,306,875, epoxy resins, polycarbonate resins, such as those disclosed in U.S. Patent 3,028,365, siloxane-5 resins, polyarylene polyethers, such as those disclosed in U.S. Patent 3,329,909, etc.

The materials of the invention can be used in a wide variety of physical forms, for example, as films, molding materials, etc. When used as films or when molded into articles, these copolymers, including the ones thereof Laminated products obtained not only have good physical properties at room temperature but also retain their strength and excellent load response at elevated temperatures for a long time.

Films formed from the copolymers of the invention can be used in applications where films have hitherto been used. These films are effective in a wide variety of packaging applications.

For example, the materials of the invention may be used for automotive and aircraft decorative and protective purposes, and as high temperature resistant electrical insulation for liners for 20 slots in motors, transformers and capacitors.

Also solutions of the present curable materials can be coated on electrical conductors such as copper, aluminum, etc., after which the coated conductor can be heated at an elevated temperature to remove the solvent and to cure (imidize) the standing resinous material. If desired, a further top layer can be applied to these insulated conductors, for example, a polymeric coating layer such as of polyamide, polyester, siloxane, polyvinyl formal resin, epoxy resin, polyimide, polyether fluorethylene, etc.

Recommended applications for these resins are those as binders for asbestos fibers, carbon fibers and other fibrous materials used to make brake linings. Furthermore, grinding wheels and other abrasive objects can be manufactured from these resins by incorporating grinding grains such as alundum, silicon carbide, silicon nitride, carborundum, diamond dust, cubic boron nitride, etc., and forming the mixture under heat and pressure to the desired configuration. and shape for grinding and sanding purposes.

8100072

Claims (5)

1. Copolymer: 'V -: -: -. ., of the formula (11) or (12), wherein R represents: (a) a divalent organic group of the formula (3), (4), (5) .-, (6), (7) or ( 8); or (b) a divalent organic group according to the general formula (9), wherein X represents a group -C EL - and y is an integer> y t-x number having a value of 1 to 5; and R is a divalent organic group, namely: (a) an aromatic hydrocarbon group of 6-20 carbon atoms or a halogenated derivative thereof, (b) an alkylene or cycloalkylene group of 2-20 carbon atoms, (c) a polydiorganosiloxane 10 with C 2 -C 8 alkylene groups, or (d) a divalent group of formula (10), wherein Q represents -O-, -C (O) -, -SC ^ -, -S-, or a group -CXH2X- / * n we ^ ® last group x is an integer with a value from 1 - 5; m and n independently represent integers with a value of at least I; and b represents an integer with a value of 15 greater than 1. v 2.. Copolymer, characterized by (1) 5 - 95 mol% chemically bonded units of formula (1), and (2) 95 - 5 mol% chemically bonded units of formula (2), wherein R and R 1 are as claimed in claim 1 have given meanings. Copolymer of formula (23), wherein m, n and p have the meanings given in claim 1. Copolymer of formula (25), wherein m, n and p have the meanings given in claim 1. Copolymer of formula (27), wherein m, n and p have the meanings given in claim 1. 6. Copolymer according to formula (29), wherein m, n and p have the meanings given in claim 1. Copolymer of formula (30), wherein m, n and p have the meanings given in claim 1. . 30: \ 8100072 S 2348-1111 Ned. - Annex 4,. General Electric Company of Schenectady, New York, United States of America "... ..." o ·; ·. . u, -n-UO) ^. ri_ IV • O / ". .... · ·:. ? . O; ; ... · (2) - ïï YJvi Λ / 'γ \ · - ”. - ·· .y ~ R1- "" - 'V ^ 5 · v \ -: · -. -. o · £, / ;: / pv fh3. | (3) - €) / <4) '"7 * 3. F «3 (5) - (o) -V ° / ~ (6) V '': - f · \. . ·; tf | H3 BrCH,. v V> '. j ·. · .. "'5 Br Br (8) -C tCH3) -Br Br 8100072 -2.-. (9) ίΐω ~ ^ q \ q (oy ~ - * \ ft- o -ι ro 0 Ί '· * ** SfoT'Vs1- ^^ s3- ° -B-0-eCC> "Rl (11) *" Γ n *.. * · »· .- * *." O 0 OJ ·. Πι 1— '- r • J. P ,,, · Γ L! * JU; 5 ”;' d —n - · ':. J |' •. * * IH" - u «3" HO. O " O 0 * a P • '· · O' ö n '* .-- 11 - (14) --N Yo4 - OR20-40 I yiR1- *.. V:. S Y ·. (15) - (Ö) - Ï - ^ - (Ö) - * H3 .8 1 0007 2 '.. - 3 -, · ". • O. · - - O - f». - II (16) o r2 • . «'C -:; 0 O γ ooww“ / Vs / A: x: (17) / NR ± ~ "". _. · O. * O \ ff.' ML at. (18) "r R1 - 0 0-R2—0 oo. O - «»> · "" OO ·. O '. -' If '? Ι'ουΛ. (20)., C1 — c-iZ \ / - II o' (21) H2NR ^ 'H2 (22) Alk - 0. - R1 - 0 - Alk'! 8100072 '</ .. ·.. •. - 4 - r ": o 0 0 0” ”H (23) / -N- ci§ {^ - 0- -i (^ SXo - ^) - C (CH3)> H 1 .2 II _ 0 J 0 0 "m '1, VV v; -,:. ;; /;:; -: / X. · ·. Ί * - ·. (24) NH2 ~ \ Q ^ —S • Γ> ;. · .. o 2 0 Ί 2 V 0. (25, '- <^ SLo - ^ ( ca3, ^> 4 g) ^ - @. s ^). ° ° «. 2. S 0; -. si. .. ... · * v. . P (26) NH2 “^ 0 ^ —C- ^ 0 ^ -NH2 r. . : -j \. /. ο o · -. 0. . · · ’·· ..... . · "·· 1! ** o 0 O. ....... V. η - n • ·. </ ·. ·. ·. -'P. V" N> c - - '' 8100072 * · · V .. ·. .. ¢. * · · - ". ~ * "- '~ · -'.,. - --5-. - ·., -. <28) m2 ~ (oy-car (oy ^ ia2 0 r" ® (29) I js-βθ · ® ^ · ^ - [.. L 0 J 0 0 ^ & * ·.. · -... · ·. P · v * '. • *' · «IF" 0 - · O J2 CH * C w ς ||] '' 5 “2 Ï ', -, 1 A; * nj.' · -, - p; * .- '* ir' V« * v - jew \ '---.! · · Ν « *! - 8100072