DE2065418A1 - PROCESS FOR THE PRODUCTION OF POLYESTERS WITH A CHLOROMETHYL GROUP IN THE ALIPHATIC SIDE CHAIN - Google Patents

Description

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

-R-OCO- (C = CH) - (CH-CH) .- R,

a ■ D e.

have, in which R is an aliphatic chain, Ry is hydrogen or a nitrile group, R _{2 is} a substituted or unsubstituted aromatic group and a and b are 0 or 1, characterized in that a polymer with a chloromethyl group in its aliphatic Side chain, with a carboxylic acid salt of the formula:

MOOC- (C = CH) _a - (CH = CH) JjR ₂

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condensed, where in the formula M ammonium or alkali

is metal, R., R ₃ , a and b have the meanings given above, the condensation being carried out in an aprotic polar solvent.

These esters are sensitive to light.

For polymers, the chlorine of the chloromethyl group is in the aliphatic side chain, such as the homopolymers or copolymers of epichlorohydrin, vinyl chloroacetate, of 2-chloroethyl vinyl ether, of 2-chloroethyl acrylate and the 3,3-bis (chloromethyl) oxycetane, less than that Bromine of the bromomethyl groups and also less than the chlorine of the chloromethyl group of the p-chloromethylstyrene polymers, which, in contrast, has high activity. For this reason, the chlorine in the chloromethyl groups is the aliphatic Side chain of polymers, generally almost chemically inert, which leads to unsatisfactory results, when the chlorine of chloromethyl groups is used as a functional group in the reaction with such substances.

It has now been found that when d = m, methods according to the invention the condensation reaction proceeds very smoothly and polymer esters form, most of which are photosensitive are.

3 0 9 8 2 7/0918. ^Bad Ori _G i _NAl

Examples of IU of a carboxylic acid salt of the formula (8), are substituted or ■ unsubstituted aromatic groups such as phenyl, nitrophenyl, chlorophenyl, hydroxyphenyl, acetoxyphenyl or styrylphenyl, where the substituted groups of the above phenyl rings in the ortho, meta or para position stand, 1-haphthyl, 2-naphthyl, 9-anthoryl, 2-? urfuryl, 2-thienyl, 4-pyridil, p-azidophenyl and p-sulfonazidophenyl, ■ Examples of carboxylic acids which form ammonium salts or alkali salts used according to the invention are benzoic acid, p-nitrobenzoic acid, p-aaidobenzoic acid, cinnamic acid, m-nitrocinnamic acid, p-chlorocinnamic acid, p-methoxycinnamic acid, o (, - cyano cinnamic acid, cinnamilideneacetic acid, C ^ -Cyanocinnamilidenessigsäure, ß- (1) -haphthylacrylic acid, ^ - (2) -liaphthylacryl-

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acid, (3 - (^ - anthorylacrylic acid, (3 - (2) -i ¹ urfurylaeric acid, 0 (-Cyano-ß- (2) -furfurylaeric acid, j§- (2) -thienylacryic acid, β- (4) -pyridyl acrylic acid) and p-sulfonazidobenzoic acid. These acids are used "in the condensation reaction in the form of ammonium salts, sodium salts, potassium salts, etc."

A chloromethyl group in the side chain of the polymer, which is condensed with a carboxylic acid salt is generally a mono-malomethyl group, but the remainder can Hydrogen in the methyl group is also substituted by a halogen atom, an alkyl group, a hydroxyalkyl group, and so on be.

A condensation reaction of a polymer which Contains chloromethyl group in the aliphatic side chain, with a carboxylic acid salt, is performed by the carboxylic acid salt to those found in aprotic polar solvents such as hexamethyl-phoephoramide, dimethylformamide, diethylformamide, Dimethylformamide, dimethylacetamide, dimethyl sulfoxide and adding I-methylpyrrolidone to dissolved polymers. the Condensation reaction proceeds smoothly without a catalyst depending on the type of solvent, but it proceeds generally with high yield and a high degree of esterification by using a quaternary ammonium salt, for example Methyl triethylammoniumgodid, added. If

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. on the other hand, if a generally used inert organic solvent, with the exception of aprotic polar solvents, is used, the esterification reaction does not take place at all, even if the solvent dissolves the polymer having a chloromethyl group.

In general, a slight excess of the carboxylic acid salt is used in the reaction chemical equivalent of the chlorine of the polymer, but one useful for a photosensitive resin is also obtained Polymer ester at a chemical equivalent of not less than 0.3 x 2 polymeric ester obtained is in commonly used solvents such as acetone, benzene, toluene, Chloroform, dimethylformamide, tetrahydrofuran and hexamethylphosphoramide, soluble.

If, in turn, as mentioned above, the cinnamic acid ester of polyvinyl alcohols as the photosensitive resin uses which is a known photosensitive resin, it has a poor film-forming capacity, is very brittle in the form of films, in solvents such as methyl ethyl ketone and cyclohexane, but its solubility in the important solvent acetone is poor. In contrast for this purpose, the polymer ester obtained according to this embodiment of the concept of the invention, because of its film-forming ability, its flexibility in the form of films and

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its aeetone solubility, used with advantage.

When in a method of preparing polymer ester according to the invention, the chemical equivalent of the carboxylic acid salt is less than that of the chlorine in the chloromethyl group of the polymer to be esterified »this is how one achieves. a Esters with a low degree of esterification. It forms such a type of copolymer that a polymer ester with the necessary physical properties can be achieved by controls the degree of esterification.

Further examples that illustrate this embodiment, are the following:

Examples 1 to 19

A carboxylic acid salt and, if necessary, methyltriethylammonium iodide as a catalyst, become a polymer with a chloromethyl group in the aliphatic side chain, which is dissolved in an aprotic polar solvent is added and the mixture is left in react for a given number of hours at a given temperature. After the reaction, the reacted mixture is added added to water to precipitate the product. The precipitate is dissolved in methyl ethyl ketone and the solution to Reprecipitation and purification again added to water.

3 09827/0918

«T'flifprilillll, | Ι | Ι" ΙΙΡ; η "Ί-'Ί. ,; ■ ι -μ. · Ι ι. ,,.,.

7 -

The polymer ester obtained is determined by observations of the I.R. spectrum and N.M.R. spectrum confirmed and be Degree of esterification is observed by quantitative analysis of the unreacted chlorine that remains in the product, and is contained in each monomer unit. Be there applied the methods of microanalysis for halogen.

The results of the analysis are in the table below shown:

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!Tabel

co ο co co

σ cc

at
game Polymer δ Mole carboxylic acid salt G - Mol solvent cnr Kata
lysa
gate Reaction
condition Hours. product G Vereste
guessing
Degree 1 away
kür
tongue 6.73 0.05 link 9.3 0.05 High school diploma 70 G ⁰ C 10 ■ 11.0 0.98 2 PCEA 6.73 0.05 Potassium-
cinnamat 10.1 0.05 HMPA 70 1.0 100 10 10.5 0.93 3 PGEA 4.63 0.05 Ainmonium
cinnamat 11.2 0.06 HIiPA 40 1.0 100 10 7.3 0.96 4th BAD LUCK 18.5 0.20 Potassium-
oinnamat 41.0 0.22 HMPA 350 1.0 100 5 34.0 0.84 5 BAD LUCK 9.25 0.10 Potassium-
cinnamat 18.7 0.11 HMPA 150 4.0 100 8th 17.8 0.87 6th BAD LUCK 9.25 0.10 Sodium-
cinnamat 21.5 0.11 HIVIPA ' 150 2.0 100 '5 18.3 0.81 7th BAD LUCK 9.25 0.10 Sodium-
° * ~ oyano-
cinnamat 21.2 0.11 IMPA 150 2.0 60 6th 20.5 0.88 BAD LUCK Potassium-
cinnamili-
denacetate HMPA 2.0 80

Tabel

co ο co

to

• χ «. O (O

at
game Polymer G Mole carboxylic acid salt G Mole. solvent cm kata
lysa
gate Reaction
condition" Hours. product G Yereste-
guessing
Degree 8th away
kür
tongue 9.25 0.10 link 17.6 0.10 abbreviation 150 G ⁰ G 8th 18.1 0.91 9 PSCH 9.25 0.10 Kalitua-
furfuryl
acrylate 20.1 0.10 HMPA 150 2.0 70 7th 13.8 0.74 10 BAD LUCK 6.35 0.05 Potassium p-
azido
benzoate 10.25 0.055 HMPA 50 2.0 50 10 10.6 0.91 11 POETS 5.35 0.05 Potassium-
cinnamat 10.75 0.055 HMPA 50 1.0 80 5 5.2 0.63 12th PGETS 5.35 0.05 IJatriun-
c ^ -cyano-
oinnamat 11.2 0.055 HIvIPA 50 1.0 50 10 11.2 0.90 13th PGE ^- VE 5.35 0.05 Potassium-
cinnamili-
denacetate 9.7 0.055 HLiPA 50 1.0 80 10 10.1 0.91 y PGETE ZaIium-
furfuryl
acrylate HUPA ' 1.0 80

VO

Tabel

(O

to

\ O

CO

at
game Polymer S. Mole carboxylic acid salt G Mole solvent cm kata
lysa
gate Reaction
condition Hours. product Vereste
tion s-
Degree 14th away
kür
tongue 5.35 0.05 link 11.1 0.055 abbreviation 50 S. ⁰ C 8th G 0.75 15th PCEVE 6.03 0.05 Potassium p-
azido
benzoate 10.25 0.055 HMPA 50 1.0 70 5 10.3 0.97 16 PVGA 6.03 0.05 Potassium-
cinnamat 10.75 0.055 IMPA 50 1.0 70 5 10.3 0.96 17th PVCA 6.03 0.05 Sodium-c (-
oyano-
cinnamat 11.2 0.055 HIdPA 50 0.5 50 5 10.1 0.93 18th PVCA 6.03 0.05 Potassium-
oinnamili-
denaeetat 9.7 0.055 HMPA 50 1.0 50 • 5 11.3 0.96 19th PVCA 6.03 0.05 Potassium-
furfuryl
acrylate 11.1 0.055 HMPA 5.0 1.0 50 6th 9.8 0.92 Yerglj-
bspl » PVCA 9.25; 0.1 Potassium p-
azido
benzoate 20.5 0.11 HMPA 150 50 8th 9.3 - BAD LUCK. Potassium-
cinnamat glyme 2.0 60 0.

O I

ω in

QO

^r m ' ^{Ιί! Γ} ' * ■

- 11 -

Abbreviations of the polymers;

PCEA: poly- (2-chlorätiiylacryla-fc) \ PECH: poly (epichlorohydrin)

(with the exception of the oligomer in Example 42, which is described in Form of a rubber-like material)

PCEVE: poly (2-chloroethyl vinyl ether) PVCA: poly (vinyl chloroacetate)

Abbreviations of the solvents ; HMPA ί Hexamethylphosphoramid glyme: ethylene glycol dimothyl ether.

Example 2Q

1.5 g of the cinnamate ester of the poly obtained in Example 4. Mers, dissolved in 7.5 cirr of cyclohexanone, are applied to the surface of a glass pane using a vortex application device. After drying, a film with a thickness of 1 Ai is obtained on the glass surface.

A step wedge, a so-called "step tablet" No. 2 (from the Kodak Company) with 21 stepped images, is brought in onto the photosensitive film layer formed on the surface of the glass pane and exposed to a for 21 minutes chemical 40 watt lamp at a distance of 10 cm. Subject to

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light, the unexposed areas of the photosensitive film are dissolved and washed away with monochlorobenzene. as As a result, the images are traced on the glass pane, from which those up to the third level can be distinguished.

Example 21 '

3.0 g of the cinnamate ester obtained in Example 40 0) polymers and 0.24 g of 5-nitroacenaphthene as a sensitizer, both dissolved in 15 cm cyclohexanone, using a vortex ringing device applied to the surface of a pane of glass. After drying you get on the surface of the glass pane a PiIm with a thickness of less than 1 / u.

A step wedge ITr. 2 (the Kodak Company) with 21 graded Images are then brought to the on the glass surface formed photosensitive film and exposed it For 4 minutes with a 40 watt chemical lamp at a distance

of 10 cm. After exposure, the non-exposed ones become grounded Areas of the photosensitive film dissolved and washed away with mono- chlorobenzene. As a result, are on the glass the pictures traced, of which those up to the 17th stage are distinguishable.

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- 13 -

Example 22

A sheet of copper is coated with 3.0 g of the cinnamate ester of the polymer obtained in Example 40 and with 0.24 g of 5-Nitroaeenaphthen, both dissolved in 15 cm cyclohexanone, using a doctor blade, a PiIm with a thickness of 100 yes results. After one hour of drying the thus created coating at 50 ⁰ G, one obtains a film with a thickness of 12yu on the Eupferoberfläche.

A negative is then placed on the photosensitive PiIm obtained on the copper surface and it lasts for 4 minutes long with a chemical 40 watt lamp at a distance of 10 cm exposed. After exposure, the unexposed areas of the film are dissolved and washed away with monochlorobenzene. Then the PiIm is treated for etching with an aqueous ferric chloride solution, whereby the insoluble areas of the film are sufficiently resistant to the etching solution and are obtained clear etched images on the copper.

It is found that by observing the strength of the 12p thick film on the copper surface using the Erichsen Film Tester, cracks on the copper sheet at D = 8.5 mm occur while the film shows no cracks, but rather sufficient resistance to the applied pull of this value shows.

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Example 2 3

A polyester film is coated with 3.0 g of the cinnamate ester of the polymer obtained in Example 40 and with 0.24 g of 5-nitroene naphthene as a sensitizer, both dissolved in 15 cm of cyclohexanone, using a doctor blade for coating, a film thickness of 10Ou results. After one hour of drying the coating thus formed at 5O ⁰ C, is obtained on the polyester film surface of a film of 12 u Dioke.

The light-sensitive layer on the polyester film surface is easily coated using heated pressure rollers at a temperature of 100 ⁰ G on the copper sheet and the polyester film is easily from the photosensitive film layer to peel. .

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

Example 24

65.1 g of potassium cinnamonium and 2.0 g of methyltriethylairanonium iodide became 75.5 g Epichlorhydrinäthylenoxyd-Mischpolyraerem "(" HYDRIN 2OO "from the Good Rich Company, with a quantity - * - .. Ratio of epichlorohydrin: ethylene oxide = 65 mol% ■ · :. 35 mol%), dissolved in 500 ml of dimethylformamide, added and the mixture

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was reacted at 100 ° C. for 10 hours. After the reaction, the reacted mixture was added to 10 liters of water to obtain the Precipitate product. The precipitate was dissolved in methyl ethyl ketone and the solution was again used to precipitate in Given water. Then this precipitate was redissolved in methyl ethyl ketone and the solution was dissolved in 10 l of methanol given for precipitation.

93 g of polymeric ester were obtained in which 35% of the total amount of the monomer units was esterified.

The relative photosensitivity of the resulting polymeric ester to KPR (trade name for a Polyvinyl alcohol cinnamate photosensitive resin from Kodak) had a value of 650 compared to the sensitivity of KPR = 100.

Example 25

153 g of potassium cinnamate and 2.0 g of methyltriethylammonium iodide became 75.5 g of epichlorohydrin-ethylene oxide copolymers (the same as in Example 24) dissolved in 500 ml of dimethylformamide, and the mixture was added at 100 ° C implemented for 10 hours. After the reaction was the reacted mixture treated as in Example 24.

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113 g of polymeric ester were obtained in which 64% of the total amount of the monomer units was esterified.

The relative photosensitivity of the polymeric ester obtained to KPR showed a value of 1500, compared ^ equated with the sensitivity of KPR = * 100.

Example 26

83 g of ammonium cinnamate were converted into 75.5 g of epichlorohydrin-ethylene oxide copolymers (the same as in Example 24), dissolved in 500 ml of hexamethylphosphoramide, added, and the mixture was reacted at 100 ° C. for 10 hours. After the reaction, the reacted mixture became treated as in Example 24. It became a polymeric ester * obtained in which 47% of the total amount of the monomer units was esterified.

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Claims (1)

Claim Process for the production of polyesters from monomer units which have the group in the side chain: ?1 -R-OCO- (C = CH) _a - (CH-CH) _b -R ₂ have, in which R is an aliphatic chain, R. is hydrogen or a nitrile group, R _{0 is} a substituted or unsubstituted aromatic group and a and b are 0 or 1, characterized in that a polymer with a chloromethyl group in its aliphatic side chain, with a carboxylic acid salt of the formula: ?1
MOOC- (C = CH) _a - (CH = QI) _b -R ₂ condensed, where in the formula M is ammonium or alkali metal, R., R ₂ , a and b have the meanings given above, the condensation being carried out in an aprotic polar solvent. ORIGlMAL INSPECTED 309827/0918