DE2065417A1 - PROCESS FOR THE MANUFACTURING OF ACRYLIC ACID POLYESTERS - Google Patents

Description

PATENT AGENCY OFFICE TlEDTKE - Bühling -

TEU (0811) 539Θ 53-56 TELEX: 524845 tipat CABLE ADDRLSS: Germeniapa'Mlt Miinchon

8000 Munich 2

Bavariaring 4 P.O. Box 202403 <9 ^ ^ι8ΓΖ

Nippon Oil Seal Industry Co., Ltd.
Kanagawa (Japan)

Process for the manufacture of acrylic acid polyesters

The invention relates to a process for the production of acrylic acid polyesters from monomer units which in the side chain the group:

-R-OCO- (C = CH) - (CH-CH).-Ra ρ &

have, in which R is an aliphatic chain, R. What-

is hydrogen or a nitrile group, R _{2 is} a substituted or unsubstituted aromatic group, and
a and b are O or 1, characterized in that a polyacrylate of the formula:

?1

-H29-C-

COOR ₂
in which R is hydrogen, a low molecular weight alkyl group,

is a nitrile group or halogen, and R ^ is an aliphatic " Radical with a hydroxyl group, with an acid halide the formula:

309827/0917

XCO- (C = CH) _a - (CH = CH) _b -R ₂ ,

in which X is halogen, R ₁ , R ₂ , a and b have the meanings given above, to react.

These esters have photosensitive properties.

_. Examples of R- .. the polyacrylate unit are hydrogen,

Methyl, ethyl, nitrile groups, chlorine, etc., and examples of Rp are 2-hydroxyä: fchyl, 2-hydroxypropyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, 2 - (^ - hydroxyethoxy) ethyl groups etc. Exemplary polyacrylates are homopolymers of. Aorylates: such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl-OC -... _L. chloroacrylate, 2-hydroxyethyl- ° (cyanoaorylate, 2-hydroxypropylöC-chloroacrylate, diethylene glycol monoacrylate, diethylene glycol

P monomethacrylate and 2,3-dihydroxypropyl acrylate, copolymers of these acrylates with other vinyl compounds such as acrylic acid, alkyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, ⁰ ^ -Methyl styrene, p-methoxystyrene, isobutyl vinyl ether, ...

309827/09 17

2-chloroethyl vinyl ether, phenyl vinyl ether and aryl glycidyl ether, or copolymers of these acrylates with diolefin compounds such as butadiene, isoprene and chloroprene. . ■

Examples of R are the groups mentioned above with respect to Rp of the formula (2).

When a polyacrylate reacts with an acid halide one generally uses a slight excess of the acid halide over the hydroxyl group of the polyacrylate, i.e., acid halide to hydroxyl group in the chemical equivalent ratio of about 1.1 to 1.3. The esterification of the Hydroxyl group becomes almost complete under such a condition carried out. The partial esterification of the hydroxyl group can also be done and in this case can to use acid halide in a lower chemical equivalent.

The esterification can be carried out in a homogeneous or heterogeneous system. Homopolymers and copolymers of acrylate with a hydroxyl group are insoluble in general organic solvents, but in aprotic polar ones Solvents such as dimethylformamide, diethylformamide, diethylacetoamide, Dimethyl sulfoxide.,. Hexamethyl-phosphoramide and N-methylpyrrolidone soluble. A reaction in a homogeneous system

309827/0917

2Ö65A17 - 4 -

can be done by taking a polyacrylate and a Acid halide dissolves in one of these aprotic polar solvents * Or an acid halide can be added directly to the Polyacrylate added, which is dissolved in the solvent or a tertiary amine such as pyridine, whichever the latter substances can also be used as agents that split off hydrogen chloride. Reactions in heterogeneous Systems are, for example, those in which a polyacrylate is added to pyridine, etc. for the purpose of swelling, whereupon the Addition of an acid halide for the purpose of reaction with the polyacrylate takes place, or a Schotten-Baumann reaction takes place, in which an acid halide, which is in a water-immiscible solvent such as toluene, methyl ethyl ketone, Monochlorobenzene and cyclohexanone are dissolved to form an aqueous solution of a polyacrylate in the presence of a basic Substance is added. An aqueous polymer solution can also be used for the Schotten-Baumann reaction the polymerization of the acrylate was obtained without using its special treatment.

The properties of these new polymer esters vary with the type of newly substituted ester group, but are im generally soluble in solvents such as acetone, methyl ethyl ketone, Dimethylformamide, hexamethyl-phosphoramide and tetrahydrofuran, and are insoluble in solvents such as alcohol

309827/0917

pick up and hydrocarbons. The polymer esters obtained also have pilling properties. For example, if a. Acetone solution of a cinnamic acid ester of poly-2-hydroxyethyl acrylate on mercury is flowed to acetone solvent to distill off, you get a flexible, solid PiIm.

It was found that when the tensile strength was observed of the PiIms obtained on the copper surface using the Erichsen Pilm tester on the Kupferblech ™ at D = 8.5 mm cracks occur, while the PiIm showed neither cracks nor fractures, but sufficient resistance to it the applied tensile strength showed this value without peeling off the copper surface.

Perner owns the ester obtained, with the exception of the Non-substituted benzoate (a = b = 0) photosensitivity and is useful in photosensitive resins, lacquers, paints, etc. because it is insoluble in the presence of light | will.

In contrast to the use of the cinnamic acid ester des Polyvinyl alcohols as a photosensitive resin which, as mentioned above, have a softening point of not less than

309827/0917

10O ⁰ C, is very brittle and soluble in solvents such as methyl ethyl ketone and cyolohexane, but is sparingly soluble in acetone, which is an important solvent, the polymeric ester of the invention is used with advantage because its softening point is not more than 100 ⁰ C, is flexible in the form of films and dissolves in acetone. The photosensitivity of the polymeric ester obtained tends to become higher in the presence of ot-nitrile groups, cinnamilidene groups, furan rings, thiophene rings, etc., which are generally introduced into ester groups.

In the case where a photosensitive film obtained from the polymers of the acrylic acid esters of the present invention When applied to a non-metallic base such as a polyether film or polypropylene film, it exhibits a very high level of performance interesting appearance, the photosensitive film being lightly on a metallic base like copper sheet, aluminum sheet and zinc sheet can be piled up. The photosensitive film layer on the non-metallic base namely, can be easily coated on the metallic base by placing the metallic base on the Surface of the film3 brings and the layering at a higher temperature than the glass transition temperature. The bond between the photosensitive film and the metallic base is made without the use of an adhesive

3098 2 7/0917

substance while the bond between the light-sensitive PiIm and the non-metallic base is loose to such an extent that the non-metallic base is easily peeled off the film layer by hand can be but retained unless the base is deliberately peeled from the layer will.

Such a photosensitive laminate from a metallic base, a photosensitive film and a non-metallic basis has a very important one Usefulness. The non-metallic base acts as a protective base if the laminate is used as a light-sensitive Plate is used and further in the case of a shading non-metallic base is photosensitization difficult to protect the laminate. Therefore, the consumer can be in the form of a photosensitized Plate a quality laminate with stable Ia.ch.t- " sensitivity. The photosensitive one Laminate has good light sensitivity both with and without a non-metallic protective base, although such a protective base is preferred to protect the laminate. It comes in handy when the photosensitive laminate is shipped to the consumer with the protective base on top of the film. The reason-

309827/0917

layer is then peeled off if necessary.

When using the layer, st off it with a light-sensitive layer PiIm, which was formed on the metallic or non-metallic base, becomes a negative the PiIm applied. Then using a chemical lamp etc. exposed and after exposure you dissolve the unexposed areas of the pilm and wash them with a Solvents such as monochlorobenzene, which dissolves the polyacrylate used for the transformation. As a result the exposed areas leave an inverted image of the negative, because the exposed areas become cross-linked and insoluble in the solvent. Perner can work with the Use of a metal sheet as a basis, the metallic The base can be etched with an etchant such as an aqueous Perri-Chloride solution, the exposed areas are sufficiently resistant to the etchant so that clear images are obtained.

Other examples of this embodiment of the inventive concept are as follows:

Example A.

0.08 g of azobisisobutyl nitrile become 75 g of 2-hydroxy

309827/0917

. ■! ;; ■; ■■ - ■■■■. - -: ■! - -; ■ = ι · | -:. :: - ¹¹ J "

ethyl acrylate (HBA) dissolved in 150 cm hexamethyl phosphorus amide, added thereto and the mixture was polymerized in nitrogen gas for 1 hour at 60 ⁰ O, and an additional 2 hours bei.8O ⁰ C. are thus obtained poly-2-hydroxyethyl acrylate (PHEA ). (/ q / = 0.60). ■

Example B.

0.9 g Ka he liump sulfate are added to 90 g of 2-hydroxy-ethyl acrylate (HBA), dissolved in 900 cm of water, was added and the mixture is polymerized in nitrogen gas for 1 hour at 60 ⁰ C. Mach of the reaction is the product is to precipitate the polymer in 3 l of acetone. 81 g of poly-2-hydroxyethyl acrylate (PHEA) are then obtained. (/ ft / = 0.93).

Example C

0.05 g of azobisisobutylonitrile are added to 50 g of 2-hydroxyethyl acrylate (HEA), dissolved in 200 cnr dimethylformamide, was added and the mixture is polymerized in nitrogen gas for 3 hours at 65 ⁰ C and another 2 hours at 80 ⁰ C. It then obtains Poly-2-hydroxyethyl aorylate (PHEA). (Zt) Z = 0.43)

example D.

0.15 g of azobisisobutyl nitrile become 150 g of 2-hydroxypropyl acrylate (HPA), dissolved in 150 cnr hexamethyl phosphorus

309827/0917

.- 10 -

amide, added thereto and the mixture was polymerized in nitrogen gas for 1 hour at 60 ⁰ C and an additional hour at 8O ⁰ C. are thus obtained poly-2-hydroxypropyl acrylate (PEPA). (/ 5 / = 0.77).

Example B.

0.5 g AzoMsisobutylnitril are added to 50 g of 2-hydroxy ~ propyl methacrylate, dissolved in 180 cnr hexamethylphosphoramide, added thereto, and polymerizing the mixture in nitrogen gas for 3 hours at 6O ⁰ C. are thus obtained poly-hydroxypropyl methacrylate 2. (/ ^ / = 0.43).

Example ff

0.2 g of azo msisobutyl nitrile become 75 g of 2-hydroxyethyl acrylate and 25 g of n-butyl acrylate, both dissolved in 7.

300 cm ^v hexamethylphosphoramide, and added to the Gremisch polymerized in nitrogen gas for 3 hours at 60 ⁰ C and another 2 hours at 8O ⁰ C. This gives 2-hydroxyethyl acrylate · so-n-Butylaerylat copolymer.

Example S ._

0.5 g of azolyisisobutyl nitrile becomes 40 g of 2-hydroxy7 ethyl acrylate and 10 g n-butyl acrylate, both dissolved in 40 cm of dimethyl sulfoxide, added and polymerized the mixture, in nitrogen gas for 3 hours at 60 ° and more

309827/0917

2 hours at 8O ⁰ G. thus obtained 2-Hyaroxyathylacryl £ tn-Butylaerylat-Oopolymeres. -

, Example H

0.1 g of azobisisobutyl nitrile are added to 75 g of 2-hydroxyethyl acrylate and 75 g of styrene, both dissolved in 150 cm of hexamethylphosphoramide, and the mixture is polymerized in nitrogen gas for 3 hours at 60 ^° C. and a further 2 hours at 80 ^° C. "Man This gives 2-hydroxyethyl acrylate · styrene copolymer (/ P) / = 0.62).

example 1

3 12.9 g cinnamoyl chloride, dissolved in 50 cur hexamethyl

phosphoramide, are added with stirring to 7 _f 5 g PHBA from Example A, dissolved in 100 cm ^ hexamethylphosphoramide was added and the mixture allowed to react for 5 hours at 50 G. After the reaction, the product is added to 1.5 l of water to precipitate the polymer. The obtained polymer I

• z.

is again dissolved in 200 cnr acetone and the solution added to 1.5 l of water for reprecipitation. Man. thus obtained 9.0 g of the ester of PHEA-cinnamic acid.

From the results of an elemental analysis and the Observations of the I.R. spectrum and the N.M.R. spectrum the polymeric ester obtained is found to be

309827/0 917

is completely esterified, i.e. there is no absorption a hydroxyl group in the I.R. spectrum between 3500-3400 cm, there is still a chemical shift of an alcoholic hydroxyl group in the W.M.R. spectrum.

Element ar analysis of this product (C ^ H ^ .O.) S

■ Calculates G 68.2'9 #; H 5, Found C $ 66-98; H 5.675 ^.

Example 2

1.5 g of the oinnamate ester obtained in Example 10

■ z.

des PHEA dissolved in 7.5 cnr cyclohexanone are by means of a vortex applicator applied to the surface of a sheet of glass. Receives after drying a 1 / u thick film is placed on the surface of the glass.

A step wedge Ur. 2 (the Kodak Company) with 21 graded Images are placed on the photosensitive film produced on the surface of the glass plate and it is turned on for a period of 21 minutes at a distance of 10 cm with a 40 watt chemical lamp exposed. After exposure, the unexposed areas of the photosensitive film are dissolved and with Washed away monochlorobenzene. As a result, the

30 9 827/0917

-is -

Images traced on the glass plate, with those Images up to the third level are distinguishable.

Example 3

1.5 g of the cinnamic acid ester of PHEA obtained in Example 10 and 0.12 g of 5-nitroacenaphthene as a sensitizer, both dissolved in 7.5 cnr cyclohexanone, are applied to the surface of a glass plate by means of a vortex application device. After drying, a film with a thickness of less than 1 Ai is obtained on the surface of the glass pane.

A step wedge Fr. 2 (from Kodak Company) with 21 steps Illustrations, is then applied to the on the glass surface formed, photosensitive PiIm placed and exposed 4 minutes at a distance of 10 cm with a 40 watt chemical lamp. Make the exposure the unexposed ones Areas of the photosensitive film dissolved and washed away with monochlorobenzene. As a result, are on the Glass pane traced the images, of which those f up to the 17th level are distinguishable.

The same result is achieved if N-acetyl-4-nitro-1-naphthylamine is used as the sensitizer instead of 5 ~ Mtroa0enaph.th.en or the 4,4 '- (bisdimethylamino) benzophenone is used.

309827/0917

- H ₁ - 20S5417

Example 4

A copper sheet is coated with 3.0 g of the cinnamic acid ester of PHEA obtained in Example 10 and with 0.24 g of 5-haloacenaphthene, both dissolved in 15 cm of cyclohexanone, a film with a thickness of If the film formed in this way is dried at 50 ^° C. for one hour, a film with a thickness of 12 μm is obtained on the copper surface.

A negative is then applied to the photosensitive film obtained on the copper surface and exposed for 4 minutes with a 40 watt chemical lamp at a distance of 10 cm. Subject to ^: Exposure, the unexposed areas of the film are dissolved and washed with monochlorobenzene. Then this film is treated with an aqueous solution of ferric chloride for etching. · 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 yes thickness on the copper surface by means of of the Eriohsen film tester. Cracks on the copper sheet D = 8.5 mm occur, while the film shows no cracks, but shows sufficient resistance to the applied pull of this value.

309827/0917

Example 5

A polyester film is made with 3.0 g of the cinnamic acid ester of PHSA obtained in Example 10, and 0.24 g of 5-Hitroacenaph-

• 7.

then as a sensitizer, both dissolved in 15 cm cyclohexanone, coated with a doctor blade, resulting in a film thickness of 100 / u. Wax hour drying the coating thus formed at 5O ⁰ C, to obtain a film of 12 ai · thickness on the surface of the polyester film.

The photosensitive film layer on the polyester film surface is made using heated pressure rollers in the case of ■ a temperature of 100 ° 0 on the surface of a copper sheet well coated and the polyester film can peel lightly from the photosensitive film layer.

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

Example 6

20 cur of pyridine are dissolved to 10.0 g of PHEA from Example C- in 100 cmr dimethylformamide, added. 17.2 g

■ z

Cinnamoyl chloride dissolved in 50 cm of dimethylformamide, one adds under stirring and allowing for 5 hours at 50 ⁰ G with the mixture react. After the reaction, the product is added to 2 l of methanol to precipitate the polymer. Man

309827/09 17

holds 13.5 g of the cinnamic acid ester from PHEA.

example

50 cm of methyl ethyl ketone and 50 cm of aqueous sodium hydro xyd solution (concentration 2 mol per 1), become 3.64 g of PEDEA from Example B, which are dissolved in 50 cm of water, added and the mixture is cooled to -3 ° C. 7.0 g Ginnamoyl chloride, which dissolved in 50 cm methyl ethyl ketone are added with stirring and allowed to react with the mixture at -5 to 4 ° G for 1 hour. After Reaction, the organic phase of the product is added to 1 l of methanol to precipitate the polymer. You get so 5.8 g of the cinnamic acid ester of PHEA.

Example 8

3 11.5 g of cinnamoyl chloride, which in -50 cm of hexamethyl

phosphoramide are dissolved, 7.5 g of that in Example D

■ χ

PHEA obtained, which are dissolved in 100 enr hexamethylphosphoramide added and the mixture allowed to react for 5 hours at 50 ⁰ C. After the reaction, the product is added to 1.5 l of water to precipitate the polymer. The polymer is redissolved in 2oo cm of tetrahydrofuran and the solution is added to 1.5 l of water for reprecipitation. 11.3 g of the cinnamic acid ester of PHPA are thus obtained.

309827/0917

- ₁₇ , 2055417

From the results of the elemental analysis and the observations of the I, R. spectrum and the NMR spectrum of the polymeric ester obtained, it is found that the ester is completely esterified, that is, there is no absorption of a hydroxyl group in the IE, spectrum between 3500 -3400 cm, chemical shifting of an alcoholic hydroxyl group in the 'SM * R. spectrum.

Elemental analysis of this product (C ^ gH ^ gO *):

Calculated C $ 69.23 »H 6.153 ^ Found C $ 67.98 * H 5.99 #.

' Example 9

13.9 g of cinnamoyl chloride, which are dissolved in 50 cm hexamethylphosphoramide are added to 10.0 g of poly-2-hydroxypropyl methacrylate obtained in Example E, dissolved in 100 cm hexamethylphosphoramide, and it is added the mixture for 4 hours at ⁰ C 6Q around. After the reaction, the product is added to 2 liters of water to precipitate the polymer.

• 7.

added · The polymer is redissolved in 200 cm of acetone and the solution is added to 2 l of methanol for reprecipitation. 6.0 g of the cinnamic acid ester are obtained in this way of poly-2-hydroxypropyl methacrylate.

309827/0917

Elemental analysis of this product Cö- * cH-aQ *.} _N ;

Calculated C 70.10g; H 6.57g Found G $ 68.03; H -.6.87g.

Example IO

9.8 g of m-nitrocinnamoyl chloride, dissolved in 30 cm of hexamethylphosphoramide, are added to 4.5 g of the PHEA obtained in Example A, dissolved in 30 cm of hexamethylphasphaltide, and the mixture is allowed to react at 50 ° for 5 hours, the reaction is carried out the product was added to 2 liters of water to precipitate the polymer. The polymer is redissolved in 300 cm of acetone and the solution is added ZVtX Wieäerausfällung to 2 l of methanol.

Elemental analysis for this product (^ 14 ^ 13 ^ g) ₁₁ ^s

. Calculated G 57.72 ^; H. 4.479 * i K 4.81g Found G 56.56g i H 4.21g. ; K 4.79g.

Example I I

9 _f 7 g p-Chlorcinnajaoylchlorid dissolved in 20 cnr_ hexamethylphosphoramide, to be 4 "64 g of the _n I Example A PHEA obtained, dissolved in 60 cm ^J Hexamethylphospharamid,

982 7/09 1 7

206541?

added and the mixture allowed 5 hours "at 5O ⁰ G react After the reaction, adds the product to from precipitation of ^the;.. .Polymeren to 2 1 of methanol added, the polymer is redissolved in 100 cnr methyl ethyl ketone and the solution are added to the Reprecipitation and purification are added to 2 liters of methanol, giving 5.7 g of the p-chlorocinnamate of PHIiA.

Elemental analysis for this product (G _{1 .H 1} , ( _n

Calculated C $ 59.89; H $ 4.63; Cl $ 12.66

Found G $ 57.96; H $ 4.38; Cl $ 12.43.

' Example "12

14.8 g ^ -Cyanocinnamoylchlorid dissolved in 50 cnr hexamethylphosphoramide, to be 7.5 g obtained in Example A PHEA dissolved in 100 cm hexamethylphosphoramide, added with stirring and the mixture allowed 5 hours at 50 ⁰ G react. After the reaction, the product is added to 2 liters of water to precipitate the polymer. The poly

mere is dissolved in 200 cm acetone and the solution to be renewed Precipitation poured into 1 l of methanol. 9.0 g of the cyanocinnamic acid ester of PHEA are obtained in this way.

Elemental analysis for this product

309827/091 7

_ 20 _

Calculated C .66.42 ° / »; H $ 4.80; N 5 Found C 64.84%; H 4.96%; Έ 4.99%.

Example 13

13.3 GOI Gyanocinnamoylchlorid dissolved in 100 cm hexamethylphosphoramide, to be 7.5 g obtained in Example D PHPA dissolved in 100 cm ⁵ hexamethylphosphoramide, added with stirring and the mixture allowed 5 hours at 5O ⁰ G react. After the reaction, the product is added to 2 l of water to precipitate the polymer. The polymer is redissolved in 200 cm of acetone and the solution is added to 2 l of methanol for precipitation. 8.2 g of: of the oC-oyantinnamic acid ester of PHPA are obtained:

Elemental analysis for this product ί ⁰ -] ^ ¹¹

Calculated C 67.37% i H 5.2: 6%; H 4.91% Found G 67.56%; H 5.84%; I 4.26%.

Example ^ ⁴

9.0 g Cinnamilidenacetylchlorid dissolved in 30 hexamethylphosphoramide, obtained in Example A PHEA, dissolved in 60 cm hexamethylphosphoramide, · are added under stirring and it läßt-, the mixture reacted for 5 hours at 50 ^p g to 4.5 G. After the reaction , the product becomes too

309 8 27/0917

2 1 water added, the polymer do precipitate. The polymer is redissolved in 200 cnr acetone and the Reprecipitation solution added to 2 liters of methanol. 5.4 g of the Cinnamilidenessigsäureester des are obtained in this way

Elemental analysis for this product

Calculated C $ 70.60; H 5, Vv g

Found C $ 68.72; H 5,

Example 1 5

3.0 g of the cinnamilidene acetate ester obtained in Example 23 des PHEA and 0.24 g of 5-mitroacenaphthene as a sensitizer, both dissolved in 15 cm cyclohexanone are by means of a vortex application device. applied to the surface of a glass pane. After drying, one obtains a film with a thickness on the surface of the glass sheet less than ί / α. "

The exposure leads to 2 minutes at a chemical lamp in a similar way like in Example 12. As a ^result-1 nis be traced on the glass sheet, the images of the step wedge, of which those to the third stage

309827/0917

are distinguishable.

Example 16

10.1. g ^ -Cyanocinnamilidene acetyl chloride dissolved in

30 cm hexamethylphosphoramide, 4.5 g of the in both

• 2

Game A obtained PHEA, dissolved in 60 cm of hexamethylphosphoramide, added with stirring and the mixture is allowed to ^{react at 50 0} O for 5 hours. After the reaction, the product is added to 2 liters of water to precipitate the polymer. The polymer is redissolved in 200 cubic centimeters of acetone and then the solution is added to 2 liters of methanol for reprecipitation. 9.0 g of deso-cyanocinnamilideneacetic acid ester of PHEA are obtained in this way.

Element ar analysis for this product (Ο ^ γΗ ^ Ο J

Calculated C. $ 68.69; H $ 5.05 i N $ 4.71 Found C $ 67.43 »H $ 5.73; ' N $ 4.25.

10j7 gp -. (L) -Iaphthylaoryloylohlorid, dissolved in

30 cm of hexamethylphosphoramide becomes 4.5 g of the one in Bex's game A obtained PHEAj, dissolved in 60 cm hexamethylphosphorus

j is added with stirring and the mixture is allowed to ^{react at 50 °} C. for 5 hours. Add the subject to the reaction

309827/0917

Add product to 2 liters of water to precipitate the polymer. The polymer is redissolved in 200 cm ^ acetone and the solution was added to 2 l of methanol for reprecipitation. 7.1 g of the | 5- (1) -naphthylacrylic acid ester are obtained in this way of the PHEA.

Elemental analysis for this product

Calculates C. $ 71.19 ', H $ 5.19 Found C $ 69.98; H 5,

Example 18

11.1 g | 5- (2) -i ¹ urfurylaoryloylchloride, dissolved in 50 cm ⁵ hexamethylphosphoramide, are added with stirring to 7.5 g of the PHEA obtained in Example A, dissolved in 100 cm hexamethylphosphoramide, and the mixture is allowed to 5 Hours "react at 50 ° 0. After the" reaction, the product is added to 2 l of water to precipitate the polymer. The polymer is redissolved in 300 cc acetone and the solution is added to 2 l of methanol for reprecipitation. This gives 5.8 g of the (2) -furfurylaerylic acid ester of PHEA.

Elemental analysis of the product ^^^ - Λ ^^ - η *

Calculated C $ 61.01; H $ 5.09 Found C $ 61.15; H $ 4.83.

309827/09 17

Example 19

14.0 go (-Cyano-j5- (2) -furf-urylacryloylclilorid, dissolved in 50 cm hexamethylphosphoramide, are added to 7.5 g of the PHEA obtained in Example A, dissolved in 100 cm ⁵ hexamethylphosphoramide "Added with stirring" and the mixture is allowed to ^{react for 5 hours at 50 °} C. After the reaction, the product is added to 2 liters of n-hexane to precipitate the polymer

• 7.

added. The polymer is redissolved in 100 cubic centimeters of acetone and the solution was added to 5 liters of water for reprecipitation. 9.1 g of the o (-Cyano-β- (2) -furfurylacrylic acid ester are obtained in this way of the PHEA.

Elemental analysis of the product (Cj, H ₁₁ OcN) _n :

Calculated C $ 59.79; H $ 4.22; N 5.56% Found G $ 58.67 i H $ 4.54} N $ 5.11.

Example 20

8.6 g of 2-Thienylacryloylchlorid dissolved in 30 cnr hexamethylphosphoramide, to be 4.6 g obtained in Example A PHEA dissolved in 60 cnr hexamethylphosphoramide, added with stirring and allowed the Gemisah-5 hours at 50 ⁰ O react. After the reaction, the product is added to 1.7 l of methanol to precipitate the polymer. This gives 5.7 g of the 2-thienyl acrylic acid ester of PHEA;

309 827/0917

:: i ι. ■: i .: ι !!! ' ■ ^■:; 11 i ": ■ ■ 111; 11 μ 11 i 11 ί ι ■,; ::, 111 j ι .: ι] 111 ti ι; ι '111! ::;:! 11111: ι; 11 i; i ;! ι; j 111 ;; i ■ '11 i 11: ■ ν.; ι;!: j! ': ;; ■ ■: 11: ,,,, i |: ■ ι i ;; i ι :::: ':: 111 μ :::! ■.:;, :: ":!. ::::

Elemental analysis of the product (C ^

Calculated $ 57.14; H $ 4.7 J S $ 12.70 Found C $ 57.03; H $ 4.52; S $ 12.54.

Example 21

14.8 g of cinnamoyl chloride, dissolved in 20 cm of hexamethylphosphoramide, are dissolved in 10.0 g of the 2-hydroxyethyl acrylate-n-butyl acrylate copolymer obtained in Example Έ in 50 cm of hexamethylphosphoramide, added with stirring and the mixture is allowed to 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 is redissolved in 100 cm of iceton and the solution was added to 1.5 l of methanol for reprecipitation, giving 9.5 g of the copolymeric n-butyl acrylate-2-hydroxyethyl acrylate ester of cinnamic acid.

Example 22

5 cm of pyridine are added to 5.0 g of the product obtained in Example G, 2-hydroxyethyl acrylate-butyl acrylate-n ~ Gopolymeren dissolved in 50 cm ^ dimethylsulfoxide, is added and is added with stirring 6.9 g Cinnamoylehlorid dissolved in 20 cm of chloroform added _f and leaves this with the mixture for 5 hours at 3O ⁰ C to react, laughing of the reaction, the product is

3098 27/09 17

1 V / water added to precipitate the polymer * One obtains so 5.8 g of the copolymer n-ButylaGrylat-2-hyäroxyäthyl-

acrylate esters of cinnamic acid. "- '

Example 23

• st

14 $ 8 g of cinnamoyl chloride, dissolved in 50 cm of hexamethyl »

phosphor amide, to 15 * 0 g of that obtained in Example H earth

2-HydroxyäthylaGryiat-Styröl-ööpplymeren, dissolved in 100 em Hexamethylphosphoramide, is added and the mixture is left React at 50 C for 5 hours. After the reaction you give that Product to precipitate the polymer into 2 liters of water * The polymer is dissolved in 200 g acetone and the Re-precipitation solution was added to 2 l of methanol. 40 g of the polymeric styrene-2-hydroxyethyl aylate star are obtained in this way of cinnamic acid »

Example 24 "

• 7.

7.1 g of benzyl chloride, dissolved in 50 cm of hexamethylphosphoramide, become 4 _? β4 S äes in Example A obtained PHEA ^ dissolved in 60 vs & r Hexamethylfhosphoramid, added Vüaä allowed the (Jeiaiooh 5 hours · respond, · wherein one holding a ßeaitionstamperatur at 50 ⁰ G "EFaah the Eeaktion ftigt allowing the product to precipitate, the polymer to 2 1 water

■ ■ - Ή
added. Las polymer is dissolved again in-· 100 a ^ Hethyläthylketoö wää the Itösumg- to "re Ausfillumg iit 2 '1 Water

0 i Ö 2 7 / Ö 9 ί 1 BAO

! Ί I! «! > «■" ■■ - '■ i>' ■

given. 3.6 g of the benzoic acid ester of PHEA are obtained in this way.

Element ar analysis of the product (^ ΐρ ^Η · ΐ2 ^ 4 ^ η ^:

Calculated C $ 65.45; H $ 5.45 Found C, 63.32; H $ 5.55.

Example 25

• 5

9.5 g of p-azidobenzoyl chloride dissolved in 50 cm of hexamethyl

phosphoramide, to be 5.8 g of the PHEA obtained in Example A, dissolved in 50 cnr hexamethylphosphoramide was added and the mixture is allowed to react 5 hours while maintaining the temperature at 30 ⁰ G. After the reaction, the product is added to 500 cm of methanol to precipitate the polymer. The polymer is redissolved in 50 em methyl ethyl ketone and the solution is poured into 500 cm of methanol for renewed precipitation. 9.4 g of the p-azidobenzoic acid ester of PHEA are obtained in this way.

Since the measurements of the 1.R ₄ spectrum and the NMR spectrum of the polymer obtained do not show the presence of an alcoholic hydroxyl group, it can be concluded that the esterification of the polymer has progressed to completion.

309827/0917

Elemental analysis of the product (^ pH-j-j O, N,):

Billed Έ $ 16.09
Found N $ 15.99.

Example 26

'4-, Og p-azidobenzoyl chloride, dissolved in 15 cnr dimethylformamide, become 2.3 g of that obtained in Example A.

• 5
PHEA dissolved in 40 cm of dimethylformamide is added and the mixture is allowed to react for 5 hours while keeping it at room temperature. After the reaction, the product is added to 300 enr methanol to precipitate the polymer. The polymer is redissolved in 20 cm of methyl ethyl ketone and the solution is added to 300 cm of methanol for reprecipitation. 1.1 g of the p-azidobenzoic acid ester of PHEA are obtained in this way.

Example 27

4.0 g of p-azidobenzoylechloride dissolved in 15 cm of hexamethylphosphoramide are added to 2.9 g of the poly-2-hydroxypropyl methacrylate obtained in Example E dissolved in 50 cm of hexamethylphosphoramide, and the mixture is allowed to react for 5 hours , the temperature being kept at ⁰ ° C. After the reaction, the product is treated as in

309827/0917

B. Example 35 and thus receives 3.5 g of the poly-2-hydroxypropyl methacrylate ester of p-azidobenzoic acid.

Elemental analysis for the product (^ .j JB ^ cO .B ^) _n :

¹ Billed Έ $ 14.53
Found Έ $ 14.45.

Example 28

4.0 g of p-azidobenzoylochloride, dissolved in 15 cnr hexa-, methylphosphoramide, are added to 3 »6 g of the 2-hydroxyethyl aorylate-n-butyl acrylate copolymer obtained ^{in Example I 1, dissolved in 25% hexamethylphosphoramide, and this is left} Gremisch- react for 2 hours while maintaining the temperature at 5O ⁰ G. After the reaction, the product is treated as in Example 35 and 2.0 g of the co-polymeric 2-hydroxyethyl acrylate-n-butyl acrylate ester of p-azidobenzoic acid are obtained. ■ '

In each of the above-mentioned examples, the proportion of acid chloride to the hydroxyl group contained in the polyacrylate is such that the former is slightly in excess. D _€ h. the chemical equivalent of the acid halide to that of a hydroxyl group is 1.04 in Example 34, 1.10 in Examples 27, 35, 36 and 37, 1.25 in FIGS

309827/0917

Examples 29 and 33, 1.30 in Example 16 and 1.20 in the other examples. , ■

Example 29

0.023 g of azobisisobutylonitrile to be 21.0 g of 2-hydroxyethyl acrylate and 1.7 g of vinyl acetate, both dissolved in 25 cnr hexamethylphosphoramide, were added and allowed the overall * mixture 4 hours at 6O ⁰ C to react. The copolymer of 2-hydroxyethyl acrylate - vinyl acetate (//} / = 1. »■ 3.5) is obtained.

Thereafter, 75 cnr hexamethylphosphoramide are added to the reacted solution, and the mixture is allowed to 5 hours at 50 ⁰ C to react. The converted solution is added to 3 l of methanol to precipitate the polymer. The polymer is redissolved in 150 cm x ⁵ methyl ethyl ketone for reprecipitation. Thus obtained 25.8 g of Oinnamatesters of copolymer 2-Hydroxyäthylacrylat-? Inylacetats (! Pg = 65 ⁰ G).

Example 30

The cinnamic acid ester of 2-hydroxyethyl acrylate-vinyl acetate copolymer, as obtained in Example 38 is treated in a manner similar to Example 12. As a result the images of the step wedge are traced on the glass pane, of which those images up to the 16th level are distinguishable.

309827/0917

Claims (1)

Claim Process for the production of acrylic acid polyesters from monomer units which have the group in the side chain: ? I -R-OCO- (C = CH) _a - (CH-CH) _b -R ₂ in which R is an aliphatic chain, R _{1 is} hydrogen or a nitrile group, R ^ is a substituted or unsubstituted aromatic group, and a and b are 0 or 1, characterized in that a polyacrylate of the formula: ?1 -H ₂ CC- COOR ₂ in which R _{1 is} hydrogen, a low molecular weight alkyl group, a nitrile group or halogen, and R _{2 is} an aliphatic radical with a hydroxyl group, with an acid halide of the formula: XCO- (C = CH) _a - (CH = CH) _b -R ₂ , in which X is halogen, R ,, R ₂ , a and b have the meanings given above, reacts, 309827/0917 ORIGINAL INSPECTEO