DE2065417C3 - Process for the preparation of photosensitive polymeric esters - Google Patents

Description

—C — CH, -

COOR,

(1)

in which Ri is a hydrogen or a chlorine atom, a lower alkyl group or a nitrile group and R _{2 is} an aliphatic radical with a hydroxyl group, with an acid halide of the formula

T '

XC- \ C = CH / "- (CH = CH) _h -R ₄ (II)

in which X is a halogen atom, R _{3 is} a hydrogen atom or a nitrile group and α and b are 0 or I, with the proviso that for the case α = I and b = 0, R _{4 is} the remainder

There is already a process for producing photosensitive polymers known in which one initially a maleic anhydride-vinyl acetate copolymer for the purpose of introducing hydroxyl groups in alcoholic solution with an inorganic base treated and thereby converted polymers containing OH groups with cinnamic acid chloride. at In this way of working, a copolymer free of OH groups must first be produced and then only then form the hydroxyl groups by saponification (Japanese Auslegeschrift 17 063/1964).

It is also known. Copolymers of vinyl cinnamate and viral acetate thereby produce by subjecting polyvinyl acetate to an ester interchange reaction with methyl cinnamate. In this transesterification, however, no hydroxyl group-containing is formed Copolymer (J. Chem. Soc. Japan, Ind. Chem. Sect., 67 [1964], 472 to 474: Zentralblatt, 1966 [18], 2654).

There has now been a method of making light-sensitive polymeric esters by reacting hydroxyl group-bearing polymers found with acid halides, which is characterized in that polymers carrying hydroxyl groups Acrylic ester homo- or copolymers of the formula

- C — CH, —COOR ₂

in which R _{1 is} a hydrogen or chlorine atom, a lower alkyl group or a nitrile group and R _{2 is} an aliphatic radical with a hydroxyl group, with an acid halide of the formula

η ii_

in the event that a - I and b - 1, R _{4 is} a phenyl group and in the event that α and h - O, R _{4 is} the remainder

mean to be implemented.

X -C-I C = CH

"- (CH = CHh-R ₄ (II)

in which X is a halogen atom, R _{3 is} a hydrogen atom or a nitrile group and α and b are O or I, with the proviso that for the case a = 1 and b = O, R _{4 is} the remainder

NO,

in the event that a = I and b = I, R _{4 is} a phenyl group and in the event that α and b = O, R _{4 is} the remainder

mean to be implemented.

The preparation of these esters does not require treatment with alcoholic alkali. The received Esters have photosensitive properties and show good strength and adhesion.

Examples of R _{1 of} the polyacrylate unit are hydrogen, methyl, ethyl, nitrile groups, chlorine; Examples of R are 2-Hydroxyälhyl-, 2-Hydroxypropyl-, 3-Hydroxypropyl-, 2 - (/ i-Hydroxyäthoxy) -äthylgruppen. Exemplary polyacrylates are: homopolymers of 2-hydroxyethyl acrylate. 2 - hydroxypropyl acrylate. 3-Hydroxypropyl acrylate, 2-Hydroxyäthyimethacrylat, 2-Hydroxypropylmelhacrylat, 3-Hydroxypropylmethacrylat, 2-Hydroxyäthyl-n-ChluracryIat, 2-Hydroxyäthyl- u -cyanoacrylat, 2-Hydroxypropyl- «- - Chloracrylat, Diethyleneglykolmonongacrylat, Diethyleneglykolmonongacrylat; Copolymers of these acrylates with other vinyl compounds, such as acrylic acid, Al-kylacrylal, Methylmelhacrylat, acrylonitrile. Acrylamide. Vinyl chloride, vinylidene chloride, vinyl acetate, styrene, (t-methyl styrene, p-methyl styrene, isobutyl vinyl ether, 2-chloroethyl vinyl ether, phenyl vinyl ether and aryl glycidyl ether, or copolymers of these acrylates with diolefin compounds such as culinary isoprene and chloroprene.

In the reaction of this polyacrylate with the acid halide, a light one is generally used Excess of the acid halide over the hydroxyl group of the polyacrylate. d. H. Acid halide / u Hydroxyl group in chemical equivalent ratio of about 1.1 to 1.3. The esterification of the hydroxyl group is carried out almost completely under such a condition. The partial esterification of the hydroxyl group can also be carried out, and in this case one can use acid halide in lesser amounts apply chemical equivalent.

The esterification can be carried out in a homogeneous or heterogeneous system. Homopolymers and copolymers of the acrylate having a hydroxyl group are insoluble in general organic solvents, but in aproiischcn polar solvents like dimethylformamide. Diethylformamide. Diethyl acetoamide. Dimethyl sulfoxide. Soluble hexamylphosphoramide and N-methylpyrrolidone. Fine reaction in the homogeneous system can be carried out by making a polyacrylate and dissolves an acid halide in one of these aproiischcn polar solvents. Or an acid halide can be / ugesct / t directly to the polyacrylate, which is dissolved in a solvent or a tertiary amine such as pyridine, which latter substances Can also be used as a hydrogen chloride-releasing agent, reactions in heterogeneous Systems are, for example, those in which a polyacrylate is added to pyridine, etc. for the sake of swelling is, whereupon the addition of an acid halide takes place for the purpose of reaction with the polyacrylate or a Schotten-Baum inn-reaction takes place, in which an acid halide, which in one with water Dissolved immiscible solvents such as toluene, methyl ethyl ketone, monochlorobenzene and cyclohexanone is added to an aqueous solution of a polyacrylate in the presence of a basic substance wild. For the Schotten-Baumann reaction, an aqueous polymer solution, which by the Polymerization of the acrylate was obtained without

ίο whose special treatment is used.

The properties of these new polymer esters vary with the type of ester group that is substituted but generally soluble in solvents such as acetone, methyl ethyl ketone, dimethylformamide, hexa-

methyl - phosphoramide and tetrahydrofuran, and are insoluble in solvents such as alcohols and hydrocarbons. The polymeric esters obtained also have film-forming properties. For example, if an acetone solution of a cinnamic acid ester of the poly-2-hydroxyäthyiacryIats on Mercury is flowed to distill off acetone solvent. so you get a flexible, solid one Movie.

It was found that when the tensile strength of the film obtained was observed on the copper surface by means of the Erichse η film tester, cracks occurred on the copper sheet at D = 8.5 mm, while the film still showed cracks, but had sufficient resistance to the at-

applied tensile strength of this value without peeling from the copper surface.

Further, the obtained ester has photosensitivity and is useful in photosensitive resins. Lacquers or paints because it becomes insoluble in the presence of light.

In contrast to the use of the cinnamic acid ester of polyvinyl alcohol as a photosensitive Resin, which has a softening point of not less than 100 ° C, is very brittle and in Solvents such as methyl ethyl ketone and cyclohexane are soluble, but in acetone, which is an important one Is solvent. is sparingly soluble, the polymeric ester prepared according to the invention is advantageous 'applied because its softening point is no longer

than 100 ° C is flexible in the form of films and dissolves in acetone. The photosensitivity of the resulting polymeric esters tends to occur when they »-Nitrile groups. (contain family groups, furan rings or thiophene rings, become higher / 11.

In the case where a photosensitive film obtained from the polymers of the acrylic acid esters of the present invention is coated on a non-metallic base such as a polyester film or polypropylene film, it shows a very interesting appearance. the photosensitive film being lightly on a metallic base such as copper sheet. Aluminum sheet and zinc sheet can be stacked. Namely, the photosensitive film layer on the non-metallic base can be easily coated on the metallic base by placing the metallic base on the surface of the film and pressing the sheet at a temperature higher than the glass transition temperature. The bond between the photosensitive film and the metallic base is maintained without the use of an adhesive, while the bond between the photosensitive film and the non-metallic base is maintained

OH RR AM

is loose to such an extent that the non-metallic However, the base can be easily peeled off by hand from the film layer remains unless the base is deliberately peeled from the layer.

Such a photosensitive laminate made of a metallic base, a photosensitive Film and a non-metallic base has very important utility. The non-metallic Foundation acts as a protective foundation when the to Laminate used as a photosensitive plate vnrd, and further, in the case of a shading non-metallic The basis of photosensitization of the laminate while protecting it is difficult. Therefore, the consumer can have a quality laminate in the form of a photosensitized plate stable photosensitivity can be delivered. The photosensitive laminate has both with good photosensitivity even without a non-metallic protective base, albeit one protective base to protect the laminate is preferred. It comes in handy when de photosensitive Laminate is shipped to the consumer with the protective base on top of the film. the The base is then peeled off if necessary.

When using the laminate with a photosensitive film which has been formed on the metallic or non-metallic base, a negative is applied to the film. Mercury vapor lamp exposure, and after exposure is dissolved the unexposed areas of the film to wash and ¹ it with a solvent such as monochlorobenzene continued, which dissolves the used film forming polyacrylate - then with low pressure chemical. As a result, the exposed areas leave a reverse image of the negative because the exposed areas become crosslinked and insoluble in the solvent. Furthermore, when using a metal sheet as the base, the metal base can be etched with an etchant such as an aqueous ferric chloride solution, the exposed areas being sufficiently resistant to the etchant so that clear images are obtained.

Further examples of this embodiment of the concept of misunderstanding are the following:

Example A.

0.08 g of azobisisobulyronitrile become 75 g of 2-hydroxyethyl acrylal! HIiAl. dissolved in 150 cm ^{3 of} hexamethyl phosphoramide. hin / ugcscl / t. and the mixture is polymerized in nitrogen gas for 1 hour at 60 ° C. and for a further 2 hours at 80 ° C. This gives poly-2-hydroxyethyl acrylate (PHI-A) ([,,] = 0.601. The mixture is acidified in nitrogen gas for 3 hours at 65 'C and ^J for a further 2 hours at 80 ° C. It is then poly-2-hydroxyäthylacrylal obtained (PHEA) ([/] = 0.43).

at

Example B.

0.9 g of potassium persulfate / 90 g of 2-hydroxyethyl acrylate (HKA), dissolved in 900 cm 'of water, are added, and the mixture is polymerized in nitrogen gas for 1 hour at 60 ° C. After the reaction, the product is poured into the polymer in 31 Acetone. 81 g of poly-2-hydroxyethyl acrylate (PHEA) are then obtained ([i /] = 0.93).

Example C

0.05 g of Aiob'sisobutyronilril are added to 50 g of 2-Hydroxyäthylacrylal (HEA), dissolved in 200 cm ^{3 of} dimethylformamide, and one polymcri-

spat!

0.15 g of azobisisobutyronitrile are added to 150 g of 2-hydroxypropyl acrylate (HPA) dissolved in 150 cm ^{3 of} hexamethyl phosphoramide, and the mixture is polymerized in nitrogen gas for 1 hour at 60 ° C. and for a further hour at 80 ° C. This gives poly-2-hydroxypropyl acrylate (PHPA) ([(, J = 0.77).

Example E.

0.5 g of azobisisobutyronitrile are added to 50 g of 2-hydroxypropyl methacrylate dissolved in 180 cm ^{3 of} hexamethyl phosphoramide, and the mixture is polymerized in nitrogen gas for 3 hours at 60 ° C. This gives poly-2-hydroxypnopyl methacrylate ([ ,,] = 0.43).

B c i s ρ i f F

0.2 g of azobisisobutyronitrile are added to 75 g of 2-hydroxyethyl acrylate and 25 g of n-butyl acrylate, both dissolved in 1X) cm ^{3 of} hexamethylphosphoramide, and the mixture is polymerized in nitrogen gas for 3 hours at 60 ° C. and for a further 2 hours at 80 ° C. This gives 2-hydroxyethyl acrylate-n-butyl acrylate copolymer.

Example CJ

0.5 g of azobisisobutyronitrile are added to 40 g of 2-hydroxyethyl acrylic and 10 g of n-bulyl acrylic, both dissolved in 40 cm ^{3 of} dimethyl sulfoxide. added, and you polymerize there? Mixture in nitrogen gas for 3 hours at 60 ° C. and a further 2 hours at 80 ° C. This gives 2-hydroxyethyl acrylal-n-butyl acrylate copolymer.

Example H

0.1 g of azobisisobutyronilril are added to 75 g of 2-hydroxyethyl acrylate and 75 g of styrene, both dissolved in 150 cm ^{3 of} hexamethylphosphoramide, and the mixture is polymerized in nitrogen gas for 3 hours at 60 ° C. and for a further 2 hours at 80 ° C. This gives 2-hydroxyethyl acrylate-styrene copolymers ([/,] = 0.62).

example 1

12.9 g of cinnamonyl chloride dissolved in 50 cm of hexamethylphosphoramide. are added with stirring to 7.5 g of PHKA from Example A. dissolved in 100 cm ^{3 of} hexamethylphosphoramide, and the mixture is allowed to react for 5 hours at 50 ° C. After the reaction, the product becomes 1.5 l to precipitate the polymer water added to the polymer obtained v / ith turn <n 200 cm ³ of acetone dissolved and the solution was added for re-precipitation to 1.5 1 Wasstr are thus obtained 9.0 g of ^L;.. slers of PHEA-Zimtsäurc.

From the results of an ElcmcriUlrähälysc And the observations of the IR spectrum and the NMR spectrum the resulting polymeric ester is found to be fully esterified; h "it shows there is neither absorption of a hydroxyl group in the IR spectrum between 3500-3400 cm ", still shows

chemical shift of an alcoholic hydroxyl group in the NMR spectrum.

Elemental analysis of this product (C ₁₄ H ₁₄ O ₄ J _n :
Calculated ... C 68.29, H 5.69%; ,

ginning .... C 66.98, H 5.67%.

a) To demonstrate advantageous properties, 1.5 g of the Cinfianialcsler des PHEA obtained in Example 1, dissolved in 7.5 cm ^{3 of} cyclohexanone, are applied to the surface of a glass pane by means of a vortex application device. After drying, a film 1 μm thick is obtained on the oil surface.

A # 2 step wedge (from Kodak Company) with 21 stepped images is placed on the surface the photosensitive film produced on the glass plate, and it is for a period of Exposed for 21 minutes at a distance of 10 cm with a 40-wall chemical lamp. After exposure the unexposed areas of the photosensitive film are dissolved and treated with monochlorobenzene washed away. As a result, the images are traced on the glass plate, with those Images up to the third level are distinguishable.

b) 1.5 g of the cinnamic acid ester obtained in Example I. des PHEA and 0.12 g of 5-nitroacenanhthene as a sensitizer, both dissolved in 7.5 cm of cyclohexanone, are by means of a vortex application. rrichlung applied to the surface of a glass plate. After drying, it is obtained on the glass pane surface a film with a thickness of less than 1 μ.

A # 2 step wedge (from Kodak Company) with 21 stepped images is then placed on top of the The photosensitive film formed on the glass surface is applied and the exposure is carried out for 4 minutes at a Distance of 10 cm with a 40 watt chemical lamp. After exposure, the unexposed Areas of the photosensitive film dissolved and washed away with monochlorobenzene. As a result the images are traced on the glass, from which those up to the 17th level can be distinguished are.

The same result can be achieved. if you use the as a sensitizer instead of 5-nitroacenaphthene N-acetyl-4-nitro-1-naphthylamine or 4.4 '- (bisdimethylamino) benzophenone used.

c) A copper sheet is coated with 3.0 g of the cinnamic acid ester of PHEA obtained in Example 1 and with 0.24 g of 5-nitroaccnaphthene. both dissolved in 15 cm ³ of cyclohexanone, which results in using a doctor blade to a film mil Löerziehen a thickness of 100 μ. After drying the film formed in this way at 50 ^° C. for one hour, a film with a thickness of 12 μ is obtained on the copper surface.

On the photosensitive ones obtained on the copper surface A negative is then applied to film and exposed for 4 minutes with a 40 watt chemical lamp at a distance of 10 cm. After exposure, the unexposed areas of the film are dissolved and washed away with monochlorobenzene. Then this film is used for etching with an aqueous solution of Treated ferric chloride. The insoluble areas of the film are sufficiently resistant to the etching solution, and clear images are obtained on the copper.

It is found that by observing the strength of the film of 12 μm thickness on the copper surface using the Erichsen film lester, cracks appear on the copper sheet at D = 8.5 mm. While the film shows no cracks, but shows sufficient resistance to the applied pull of this value.

d) A polyester film is coated with 3.0 g of the cinnamic acid ester of PI-IEA obtained in Example I and 0.24 g of 5-Nitföaccnaphlhen as a sensitizer, both dissolved in 15 cm ^{3 of} cyclohexanone, using a doctor blade, a film thickness of 100 μ yields. After cinslündigem drying the coating thus formed at 50 ⁿ C to obtain a film of 12 μ thickness on the surface of the Polycslerfilms.

The photosensitive film layer on the polymer film surface c will roll using heated pressure at a temperature of 100 'C on the surface a copper sheet is well stacked, and the polyester film can be removed from the photosensitive Slightly peel off the film layer.

A polypropylene film used in place of the polypropylene film also shows a successful result.

Example 2

20 rm ³ pyridine are added to 10.0 g PHEA from Example C, aurgclöst in 100 cirr ⁵ dimethylformamide. 17.2 g of cinnamoyl chloride. dissolved in 50 cm ^{3 of} dimethylformamide, added with stirring and allowed to react with the mixture at 50 ° C. for 3 hours. After the reaction, the product is added to 2 l of methanol to precipitate the polymer. In this way 13.5 c of desiccic acid from PHEA are obtained.

Example 3

50 cm ^{3 of} methyl ethyl ketone and 50 cm ^{3 of} an aqueous sodium hydroxide solution (concentration 2 mol per liter) are added to 3.64 g of PHEA from Example B, which ^{are dissolved in 50 cm 3 of} water, and the mixture is cooled to -3 "C. 7.0 g of cinnamoyl chloride, dissolved in 50 cm ^{3 of} methyl ethyl ketone, are added with stirring and allowed to ^{react with the mixture for 1 hour at -5 to 4 °} C. After the reaction, the organic phase of the product is added to the precipitate of the polymer is added to I i methanol, giving 5.8 g of the cinnamic acid ester of PHEA.

Example 4

11.5 g of cinnamoyl chloride containing ³ Hexamcthylphosphoramid are dissolved in 50 cm, to be 7.5 g of the compound obtained in Example D PHEA containing ³ Hexamethylphösphoramid are aurgelöst in 100 cm, was added, and the mixture is allowed 5 hours at 50 ⁰ C to react . After the reaction, the product is added to 1.5 l of water to precipitate the polymer. The polymer is redissolved in 200 cm ^{3 of} tetrahydrofuran and the solution is added to 1.5 liters of water for reprecipitation. 11.3 g of the cinnamic acid ester of PHPA are thus obtained.

From the results of the elemental analysis and the observation of the IR spectrum and the NMR spectrum of the obtained polymeric ester, a test is made that the ester is completely esterified; hu there is no absorption of a hydroxyl group in the IR spectrum between 3500-3400 cm " ¹ nor

chemical shift of an alcoholic hydroxyl group in the NMR spectrum.

Detailed analysis of this product (Cj ₅ H ₁₆ O ₄ ) ,,:
Calculated .... C 69.23, H 6.15%;

found ..,. C 67.98, H 5.99%,

Example 5

9 g of cinnamonyl chloride, which ^{are dissolved in 50 cm 3 of} hexamethylphosphoramide, are added to 10.0 g of the poly-2-hydroxypropyl methacrylate obtained in Example E, dissolved in 100 cm of uexamethylphosphoramide, and the mixture is reacted at 60 ° C. for 4 hours . After the reaction, the product is added to precipitate the polymer to 21 Walser. the polymer is dissolved in 200 cm ³ of acetone au ^r, and the solution is added to the re-precipitation to 21 methanol. is thus obtained 6.0 g of the cinnamic acid ester of the poly

Elemental analysis of this product (C ₁₆ H | _g O ₄ ) ":
Calculated ... C 70.10, H 6.57%;
found .... C 68.03, H 6.87%.

^25th

B e i s ρ i e 1 6

9.8 g of m-nitrocinnamoyl chloride, dissolved in 30 cm ^{3 of} hexamethylphosphoramide, are added to 4.5 g of the PHEA obtained in Example A, dissolved in 30 cm ^{3 of} hexamethylphosphoramide, and the mixture is allowed to ^{react at 50 °} C. for 5 hours. After the reaction, the product is added to 2 liters of water to precipitate the polymer. The polymer is ^{redissolved in 300 cm 3 of} acetone, and the solution is added to 21% of ethanol for reprecipitation. 6.7 g of the m-nitrocinnamic acid ester of PHEA are obtained in this way.

Elemental analysis for this product (C ₁₄ H _U O ₆ ) “: Calculated ... C 57.72, H 4.47, N 4.81%;
found .... C 56.56, H 4.21. N 4.79%.

the solution was added to 1 l of methanol for reprecipitation. 9.0 g of the li-cyaiizirritic acid are obtained in this way of the PHEA.

Elemental analysis for this product (C ₁₅ H ₁ JO ₄ N) _n : Calculated ... C 66.42, H 4.80, N 5.17%;
rounded ,,,. C 64.84, H 4.96, N 4.99%.

Example 9

13,3gd-Cyanocinnamoylchlofici dissolved in 100cm ³ Hexarnelhylphosplioramid be about 7.5 g of the compound obtained in Example D PHPA dissolved in iÖÖ cm ³ hexamethylphosphoramide, added with stirring, and the mixture is allowed 5 hours at 50 ⁰ C to react. After the reaction, the product is added to 2 liters of water to precipitate the polymer. The polymer is redissolved in 200 cm ^{3 of} acetone and the solution is added to 2 1 of methanol for precipitation. This gives 8.2 g of the u-cyancinnamon

äciuiccMcia uca irirn.

Elemental analysis for this product (C ₁₆ H ₁₅ O ₄ N) _n : Calculated ... C 67.37, H 5.26, N 4.91%;
found .... C 67.56, H 5.84, N 4.26%.

Example 10
9.0 g of cinnamilidene acetyl chloride of the formula

40

Example 7

9.7 g of p-chlorocinnamoyl chloride, dissolved in 20 cm ^{3 of} hexamethylphosphoramide, are added to 4.64 g of the PHEA obtained in Example A, dissolved in 60 cm ^{3 of} hexamethylphosphoramide, and the mixture is allowed to ^{react at 50 °} C. for 5 hours. After the reaction, the product is added to 2 l of methanol to precipitate the polymer. The polymer is ^{redissolved in 100 cm 3 of} methyl ethyl ketone, and the solution is added to 2 l of methanol for renewed precipitation and purification. 5.7 g of the p-cinnamic acid ester of PHEA are obtained in this way.

Elemental analysis for this product (C ₁₊ H ₁₃ O ₄ Cl) _n : Calculated ... C 59.89, H 4.63, Cl 12.66%;
found C 57.96, H 4.38, CI 12.43%.

Example 8

14.8 g of -cyanocinnamoyl chloride, dissolved in 50 cm ^{3 of} hexamethylphosphoramide, are added with stirring to 7.5 g of the PHEA obtained in Example A, dissolved in 100 cm ^{3 of} hexamethylphosphoramide, and the mixture is left at 50 ° C. for 5 hours react. After the reaction, the product is added to water to precipitate the polymer. The polymer is dissolved in 200 cm ^{3 of} acetone and

60

CH = CH - CH = CH - C

Cl

Aurelissolved in 30 cm ^{3 of} hexamethylphosphoramide are added with stirring to 4.5 g of the PHEA obtained in Example A, dissolved in 60 cm ^{3 of} hexamethylphosphoramide, and the mixture is allowed to ^{react at 50 °} C. for 5 hours. After the reaction, the product is added to 2 liters of water in order to precipitate the polymer. The polymer is redissolved in 200 cm ^{3 of} acetone and the solution is added to 2 1 of methanol for reprecipitation. 5.4 g of the cinnamilideneacetic acid ester of PHEA are obtained in this way.

Elemental analysis for this product (C ₁₆ H ₁₆ O ₄ ),:
Calculated ... C 70.60, H 5.88%;
rounded .... C 68.72, H 5.98%.

To demonstrate advantageous properties, 3.0 g of the PHEA cinnamic acetate ester obtained in Example 10 and 0.24 g of 5-nilroaccnaphline as a sensitizer, both dissolved in 15 cm ^{3 of} cyclohexanone, are applied to the surface of a pane of glass by means of a vortex applicator. After drying, a film with a thickness of less than 1 μ is obtained on the surface of the glass pane.

The exposure is carried out for 2 minutes with a chemical lamp in a manner similar to that in the example 12. As a result, the images of the step wedge are traced on the glass pane, of which those up to the third stubbornness are distinguishable.

Example II

10.1 g of ii-cyanocinnamilidene acetyl chloride, dissolved in 30 cm ^{3 of} hexamethylphosphoramide. are added to 4.5 g of the PHEA obtained in Example A, dissolved in 60 cm ^{3 of} hexamethylphosphoramide, with stirring

added and the mixture allowed to react for 5 hours at 5O ⁰ C. After the reaction, the product is added to 2 l of water to make up the polymer. The polymer is redissolved in 200 cm ^{3 of} acetone and then the solution is added to 21% of methanol for reprecipitation. 9.0 g of the 1-cyanocinnarnilideneacetic acid ester of PHEA are obtained in this way.

Elemental analysis for this product (Ci _{7 HiSO 4} N) _n : Calculated ... C 68.69, H 5.05, N 4.71%;
found .... C 67.43, H 5.73, N 4.25%.

- γϊ; ιι

iUaiailUIIg

η — ι- «- ..

I injllllllll £ IS

IO

Example 12

10.7 g / (- (l-NaphthyO-acryloyl chloride, dissolved in 30 cm ^{3 of} hexamethylphosphoramide, are added with stirring to 4.5 g of the PHEA obtained in Example A, dissolved in 60 cm ^{3 of} hexamethylphosphoramide, and the mixture is left React for 5 hours at 50 ^° C. After the reaction, this is added and the mixture is allowed to ^{react for 5 hours at 50 °} C. After the reaction, the product is added to 1.7 l of methanol to precipitate the polymer thus obtained 5.7 g of the 2-thienyl acrylic acid ester of PHEA.

Elemental analysis of the product (C ₁₂ H ₁₃ O ₄ S) _n :
Calculated ... C 57.14, H 4.7, S 12.70%;
found .... C 57.03, H 4.52, S 12.54%.

Example 16

14.8 g of cinnamoyl chloride, dissolved in 20 cm ^{3 of} hexamethylphosphoramide, are added with stirring to 10.0 g of the 2-hydroxyethyl acrylate-n-butyl acrylate copolymer obtained in Example F, dissolved in 50 cm ^{3 of} hexamethylphosphoramide, and the mixture is left React for 5 hours at 55 ° C. After the reaction, the product is added to 2 l of water to precipitate the polymer. The polymer

in I iV \ / * m ^ A ^ plnn \ u \ f * Aor ai \ tnt * \ i \ <it iinrl Hip

added. The polymer is redissolved in 200 cm ^{3 of} acetone and the solution is added to 21% of methanol for reprecipitation. 7.1 g of the / i- (l) -naphthyIacrylic acid ester of PHEA are obtained in this way.

Elemental analysis for this product (C ₁₆ H ₁₄ O ₄ J _n :
Calculated ... C 71.19, H 5.19%;
found .... C 69.98, H 5.41%.

Example 13

11.1 g / y- (2-furfuryl) -acryloyIchlorid, dissolved in 50 cm ^{3 of} hexamethylphosphoramide, are added to 7.5 g of the PHEA obtained in Example A, dissolved in 100 cm ^{3 of} hexamethylphosphoramide, with stirring, and this is left React mixture at 50 ^° C. for 5 hours. After the reaction, the product is added to 2 liters of water to precipitate the polymer. The polymer is redissolved in 300 cm ^{3 of} acetone and the solution is added to 2 1 of methanol for reprecipitation. This gives 5.5 g of the / <- (2) -furfuryl acrylic acid ester of PHEA.

Elementary analysis of the product (C ₁₂ H ₁₂ O ₅ ),:
Calculated ... C 61.01, H 5.09%;
found .... C 61.15, H 4.83%.

Example 14

14.0 g of cyano - // - (2-furfuryl) acryloyl chloride, dissolved in 50 cm ^{3 of} Hxamethylphosphoranrd, are added to 7.5 g of the PHEA obtained in Example A, dissolved in 100 cm ^{3 of} hexamethylphosphoramide, with stirring, and the mixture is allowed to react at 50 ° C. for 5 hours. After the reaction, the product is added to n-hexane to precipitate the polymer. The polymer is redissolved in 100 cm ^{3 of} acetone and the solution is added to 5 l of water for reprecipitation. 9.1 g of the (i-cyano- / i- (2) -furfurylacrylic acid ester of PHEA are obtained in this way.

Elemental analysis of the product (C ₁₃ H ₁₁ O ₅ N) _n :
Calculated ... C 59.79, H 4.22, N 5.36%;
found .... C 58.67, H 4.54, N 5.11%.

Example 15

8.6 g // - (2-thienyl) -acryloyIchlorid, dissolved in 30 cm ³ hexamethylphosphoramide, are added to 4.6 g of the PHEA obtained in Example A, dissolved in 60 cm ³ hexamethylphosphoramide, with stirring.

i \ j rr iiu solution for reprecipitation added to 1.5 l of methanol. 9.5 g of the copolymeric n-butyl acrylate-2-hydroxyethyl acrylate ester of cinnamic acid are obtained in this way.

Example 17

5 cm ^{3 of} pyridine are added to 5.0 g of the 2-hydroxyethyl acrylate-n-butyl acrylate copolymer obtained in Example G, dissolved in 50 cm ^{3 of} dimethyl sulfoxide,

added, and 6.9 g of cinnamoyl chloride are added with stirring. dissolved in 20 cm ^{3 of} chloroform, added and allowed to react with the mixture at 30 ° C. for 5 hours. After the reaction, the product is added to 1 liter of water to precipitate the polymer. 5.8 g of the copolymeric n-butyl acrylate-2-hydroxyethyl acrylate of cinnamic acid are obtained in this way.

Example 18

14.8 g of cinnamoyl chloride, dissolved in 50 cm ^{3 of} hexamethylphosphoramide, are added to 15.0 g of the 2-hydroxyäthylacrylal-styrene copolymer obtained in Example H, dissolved in 100 cm ^{3 of} hexamethylphosphoramide, and the mixture is left at 50 ° C. for 5 hours react. After the reaction, the product is added to 2 l of water to precipitate the polymer. The polymer is redissolved in 200 cm ^{3 of} acetone and the solution is added to 2 1 of methanol for reprecipitation. 40 g of the copolymeric styrene-2-hydroxyethyl acrylate ester of cinnamic acid are thus obtained.

Example 19

9.5 g of p-azidobenzoyl chloride, dissolved in 50 cm ^{3 of} hexainethylphosphoramide, are added to 5.8 g of the im

Example A PHEA obtained, dissolved in 50 cm ³ Hexamelhylphosphoramid, was added and the mixture is allowed to react 5 hours while maintaining the temperature at 30 ⁰ C. After the reaction, the product is added to precipitate the polymer

to 500 cm ^{3 of} methanol added. The polymer is ^{redissolved in 50 cm 3 of} methyl ethyl ketone and the

Solution for reprecipitation in 500 cm ^{3 of} methanol

poured. 9.4 g of the p-azidobenzoic acid ester are obtained in this way of the PHEA.

Since the measurements of the IR spectrum and the N'MR spectrum of the polymer obtained do not the presence of an alcoholic hydroxyl group

show it is to fail that the esterification of the polymer has progressed to completion.

Elemental analysis of the product (C ₁₂ Hi ₁ O ₄ N ₃ J _n :
Calculated ... N 16.09%; »

found .... N 15 _t 99%.

Example 20

4.0 g of p-Azidobcnzoylchlofid dissolved in 15 cm ^{3 of} dimethylformamide are added to 2.3 g of the PHEA obtained in Example A, dissolved in 40 cm 'of dimethylformamide, and the mixture is allowed to react for 5 hours, while it is Room temperature hall. After the reaction, the product is added to 300 cnr 'of methanol to precipitate the polymer. The polymer is ^{redissolved in 20 cm 3 of} methyl ethyl ketone and the solution is ^{added to 300 cm 3 of} methanol for reprecipitation. 1.1 g of the p-azidobenzocic acid ester of PH EA are thus obtained.

Example 21

4.0 g of azidobenzoyl chloride, dissolved in 15 cm ^{3 of} Hxamcthylphosphofamid, are added to 2.9 g of the poly-2-hydroxypropyl methacrylate obtained in Example E, dissolved in 50 cm ^{3 of} hexamethylphosphoramide, and the mixture is allowed to react for 5 hours, whereby the temperature is kept at 0 ^° C. After the reaction, the product is treated as in Example 35 and thus 3.5 g of the poly-2-hydroxypropyl methacrylate of p-azidobenzoic acid are obtained.

Elemental analysis for the product (C ₁₄ H _i; O ₄ N ₃ ) ":
Calculated ... N 14.53%;
found .... N 14.45%.

Example 22

4.0 g of p-azidobenzoyl chloride, dissolved in 15 cm ³ Hexamclhylphosphorarnid are to 3.6 g of the compound obtained in Example F 2-hydroxyethyl acrylate-n-butyl · äcfylat copolymers, dissolved in 25 erti Hexamelhylphosphoramid ^3, is added and allowed to the mixture react for 2 hours Läng, while maintaining the temperature at 50 ⁰ C. After the reaction, the product is treated as in Example 35, and 2.0 g of the copolymeric 2-hydroxyethyl acetylate-n-butyiacfyialeslef of p-azidoberizoesäüfe are obtained.

In each of the above-mentioned examples, the proportion of acid chloride is greater than that contained in the polyacrylate Hydroxyl group such that the first cre is present in a slight excess. That is, the chemical equivalent of the acid halide to that of a hydroxyl group is 1.04 in Example 19, 1.10 in Examples 13, 20, 21, 22, 1.25 in Example 15, 1.30 in example 3 and 1.20 in the other examples.

Claims (1)

Claim: Process for the preparation of photosensitive polymeric esters by reacting Polymers bearing hydroxyl groups with acid halides, thereby characterized in that polymers carrying hydroxyl groups Acrylic ester homo- or copolymers of the formula R ¹