DE2038630A1 - Divinyl compounds and processes for their preparation - Google Patents

Description

DR. A. KÖHLER M. SCHROEDER PATENT LAWYERS

TELEPHONE: 374742 TELEGRAMS: CARBOPAT

θ MUNICH FRANZ-JOSEPH-STRASSE UB

US-43 - Dr. N / A

FORD-Werke Aktiengesellschaft Cologne-Deutz

Divinyl compounds and processes for their preparation

The divinyl compounds according to the invention, which are used for coating compositions and "in other processes for polymer formation Are used by reacting a diepoxide with acrylic acid and / or methacrylic acid and subsequent Implementation of the ester condensation product obtained with a saturated acyl halide.

The invention relates to new divinyl compounds and methods for their production. The compounds according to the invention are obtained by first applying a molar Share of a diepoxide with two molar fractions of acrylic acid and / or methacrylic acid to form one Divinyl compound with two free hydroxyl groups due to the opening of the epoxy ring is reacted and then the ester condensation product obtained with two molar proportions of a saturated acyl halide is implemented. In the reaction scheme below are the two reaction stages as reaction stage I and reaction stage II designated. The remainders R are in each

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Pall alkyl radicals with 2-18, preferably 4-10 carbon atoms.

The reaction of a molar proportion of a diepoxide with two molar proportions of acrylic acid and / or methacrylic acid and subsequent reaction of the divinyl ester condensation product obtained with two molar proportions of a saturated aliphatic acylhalogen oil Divinyl compounds formed are particularly useful for radiation curable paints. she on the one hand result in good adhesion and on the other hand can correspond to the molecular weight be "tailor-made" for the intended use.

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As starting materials for the preparation of the divinyl compounds Diepoxides used according to the invention can be of the epichlorohydrin-bisphenol, epichlorohydrin-polyalcohol type be or they can be by reacting diolefins with peracids, for example peracetic acid, or can be established by other measures. Diepoxyde and their manufacture are detailed in Modern Surface Coatings, Paul Nylen and Edward Sunderland, 1965, Science Publishers, a division of John Wiley & Sons Ltd., London-New York - Sydney, Library of Congress Catalog Card Number 65-28344, pages 197-208.

Examples of diepoxides include, but are not limited to to be the following links:

(1) 3,4 - epoxy - 6 - methyl - cyclohexylmethyl 3,4 - epoxymethyl - cyclohexanecarboxylate.

(2) 1 - epoxyethyl - 3,4 - epoxycyclohexane.

(3) Dipentene Dioxide (Limonene Dioxide).

(4) dicyclopentadiene dioxide.

(5) Dioxides with the following structural formulas:

/ ν HHH H HHH

^(a) III i III

H-C-C-C-O (-C-L O-C-C-C-H

wi I ⁿ r \ /

OHHHO

H H

i i

HH C-C HHH

(b) Il '/ \ III HCCOC COCCCH

0 C = C HO

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HH HH

HCHH OH 0 HHCH

0 ^ c-C-O-C (-C-) C-O-C-C ^ C

1 III ⁿ II

CH HH I

A "" 3 H 'HCH

^HH HH

Other suitable diepoxides are disclosed in U.S. patents 2,890,202, 3,256,226, 3,317,465 and 3,373,221 and in other literature references.

The diepoxides usually have molecular weights below about 2000, preferably in the range from about 140 to about 500. Usually they consist essentially of carbon, hydrogen and oxygen. You can get saturated or unsaturated, aliphatic, cycloaliphatic or heterocyclic and they can optionally be with non-interfering substituents, such as halogen atoms, ether radicals and the like. Be substituted. They can be monomeric or polymeric.

The preferred acyl halides are the chlorides of saturated aliphatic monocarboxylic acids with 2 to 1Θ, preferably 4 to 10 carbon atoms, but other compounds can also be used, for example the corresponding bromides.

The divinyl compounds obtainable according to the invention are Homopo | nneri egg bar and with vinyl monomers, for example

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Styrene, vinyltoluene, α-methylstyrene, divinylbenzene, Methyl methacrylate, ethyl acrylate, butyl methacrylate, Hydroxypropyl methacrylate, glycidyl methacrylate and the like, by reacting a monoepoxide with acrylic acid or methacrylic acid and reacting the ester condensation product obtained obtained with an acyl halide with vinyl unsaturation divinyl reaction product, the by reacting a diepoxide with two molar proportions of acrylic acid or methacrylic acid and then Implementation of the ester condensation product obtained with two molar proportions of an aromatic substituted saturated acyl halide, for example Benzoyl chloride, obtained divinyl reaction product, the dby reacting a diepoxide with two molar proportions of acrylic acid or methacrylic acid and subsequent reaction of the ester condensation product obtained with two molar proportions of one in the α, β-position olefinically unsaturated acyl halides with one on the ß-carbon atom bonded aromatic radical, for example cinnamic acid chloride, obtained reaction product by reaction of a diepoxide with two molar proportions of

^ Acrylic acid or methacrylic acid and subsequent conversion of the ester condensation product obtained with two molar proportions of an acyl halide with vinyl unsaturation formed tetravinyl compound, olefinic in α, β-position unsaturated polymers and the like. copolymerizable. The term "vinyl compound" as used herein denotes Compounds with one or more terminal radicals X H in which X is a hydrogen atom or the group

i 1
-C = CH

CH, means.

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The vinyl compounds according to the invention are used in thermally curable resins for various fields of application and are particularly important for those polymerizable by radiation, in particular ionizing radiation Paints that are crosslinked by exposure to an electron beam. In such an application they can represent the only polymerizable component of the film-forming binder of the coating material, where their viscosity allows application by conventional paint application methods, or after dilution with non-polymerizable solvents which can be evaporated quickly after application · Preferred However, in this application they are used together with a or more of the above materials are used with which they are copolymerizable.

The divinic adducts according to the invention have lower values Viscosities than the corresponding divinyl compounds, those in the first reaction step of the present "process are formed. In paints, they result in films of greater flexibility than in corresponding quantities is achieved by tetravinyl compounds, which by reacting a diepoxide with two molar proportions of Acrylic acid or methacrylic acid and subsequent reaction of this divinyl product with two molar proportions of one Acyl halides with vinyl unsaturation were formed.

The following examples further illustrate the invention.

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example 1
The divinyl compound was prepared in the following way:

(1) In a reaction vessel equipped with a condenser, stirrer, nitrogen inlet and thermometer, the following Materials brought in:

Starting materials parts by weight

Diepoxyd (a) 192

Methacrylic acid 96

Toluene (solvent) 500

Dimethylbenzylamine (catalyst) 1

HH HH

Ii Il

0 H G-C CH, G-G H 0

HCGGOC C - GG COCCCH I ti \ / i \ / iii HHK G = C OH, C = C HHH

i! > ! I HHHH

(2) The diepoxide, the methacrylic acid and the DImethylben- zylamine were intimately mixed and in parts of the air

Toluene added "-which 'was kept at ^ CR- with nitrogen P".

(3) I'as R ea k t: i: ia sg ER * i ■: ■. .... -, ^: ; ' K ■: ■ ■ -na 1, teη »bis dIe

Reaction, the Epaxygriippei :: ρ ·,: - ίKt; λ ..- ·; α l ¹ ) '- ends what was indicated by an acid number of the product: · ■' .-- ■ ·! ls fenite e: r than 10 determines

became,

(4) Since the solution was 111 e 1 was ei e; ι ■ ν ^c · r V a I um e η tf er η t and ei η

fixed reaction pro ei tic wi !: ;;; ^:; α the awakening point of η

45 ⁰ C won.

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(5) The solid reaction product according to. (4) was dissolved in an amount of 280 parts by weight in 500 parts by weight of toluene and thereto 95 parts by weight of butyric acid thus added dropwise, the reaction mixture was maintained at 65 ⁰ C until the HGL evolution ceased.

(6) The solvent was removed under vacuum and the Divinyl compound obtained.

Example 2

A film-forming solution was made from 75 parts by weight of the after Example 1 prepared divinyl compound and 25 parts by weight Toluene produced and applied to a Mfcallunterlage. After the solvent was evaporated, the film was made by exposing the elm to an electron beam cured until tack free. The conditions of the irradiation were:

Radiation potential 275 KV

Amperage 25 milliamps

Atmosphere nitrogen

Example 3

The procedure of Example 1 was repeated, however Acetyl chloride used instead of butyric acid chloride.

Example 4

A film-forming solution was made from 9 parts by weight of the Example 3 obtained divinyl compound and two parts by weight of methyl methacrylate. The film-forming solution was as PiIm on a metal base and on a Plastic base made of polypropylene is applied. The film

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was cured with an electron beam according to Example 2.

This process was repeated, but with styrene, ethyl acrylate, butyl acrylate in the respective operations or butyl methacrylate is used instead of methyl methacrylate became. The amounts of these materials were from 1.5 Ms 5 parts by weight of the monovinyl monomer to 9 parts by weight the divinyl compound varies.

κ 'Excellent coatings were obtained.

Example 5

The process according to Example 1 was repeated, but using acrylic acid instead of methacrylic acid.

Example 6

The procedure according to Example 1 was repeated, but using hexanoic acid chloride instead of the butyric acid chloride.

Example 7

The procedure according to Example 1 was repeated, but capric acid chloride (decanoic acid chloride) instead of butyric acid chloride used.

Example 8

The procedure of Example 1 was repeated, but with lauric acid chloride (dodecanoic acid chloride) instead of butyric acid chloride used.

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Example 9

The procedure of Example 1 was repeated, however

chlprid
Stearic acid / (octadecanoic acid chloride) used instead of butyric acid chloride.

Example 10.

Forming solutions were separated using 5 parts by weight of the divinyl compounds of Example 3,6,7, 8 and 9 each made with 3 parts by weight of methyl methacrylate. The film-forming solutions became a cross-section as a paint film on wooden substrates Depth · of about 25 / U applied. The films were made with a Electron beam cured as in Example 2, but electrons of the beam with an average energy of about 350,000 KV used.

Excellent coatings were obtained »

Example 11

The procedures of Examples 1, 3, 6, 7 »8 and 9 were repeated, however, as a diepoxide, 1 - epoxyethyl - 3,4-epoxycyclohexane used.

Example 12

The procedures of Examples 1, 3, 6, 7, 8 and 9 were repeated, but dipentene oxide is used as diepoxide "

Example 13

The procedures of Examples 1, 3, 6, 7, 8 and 9 were repeated, however, dicyclopentadiene dioxide is used as diepoxide.

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Example 14

The procedures of Examples 1, 3, 6, 7, 8 and 9 were followed repeated, but the diepoxide with the structural formula (5) (a) given above, in which "n" denotes the number 4, is used.

Example 15

The procedures of Examples 1, 3, 6, 7, 8 and 9 were repeated, but using the diepoxide having structural formula (5) (b) given above.

Example 16

The procedures of Examples 1, 3, 6, 7, 8 and 9 were repeated but the diepoxyd with the above Structural formula (5) (o), in which "n" means the number 4, used.

Example 17

The procedure of Example 1 was repeated, but using butyric acid bromide instead of butyric acid chloride.

Example 18

The process according to Example 1 was repeated, but using a mixture of acrylic acid and methacrylic acid instead of the methacrylic acid used in the first reaction stage.

1098ÜU / 2237

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The process according to the invention for the preparation of divinyl compounds consists in that first a molar proportion of a diepoxide with 2 molar proportions of acrylic acid and / or methacrylic acid is reacted and the divinyl ester condensation product obtained in this way is then reacted with two molar proportions of a saturated aliphatic acyl halide is reacted.

Preferably it becomes a diepoxide with a molecular weight used below about 2000, preferably in the range from about 140 to about 500, in particular with a molecular Weight from around I40 to around 350. Conveniently, it is called Acyl halide a chloride or a saturated bromide aliphatic monocarboxylic acid having 2 to 18 carbon atoms, preferably 4 to 10 carbon atoms, is used.

The reaction takes place at elevated temperatures between approximately 40 ^° C. and the boiling point of the most volatile constituent, advantageously between 50 and 100 ^° C. Alkaline catalysts, for example weak organic bases, are used.

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Claims (1)

ι υ yes 6 3 Claims Divinyl compounds, prepared by reacting a molar proportion of a diepoxide with two molar proportions of the α, β-olefinically unsaturated monocarboxylic acid, acrylic acid and / or methacrylic acid and subsequent reaction of the divinyl ester condensation products obtained with two molar proportions of a saturated aliphatic acyl halide _{or the like} * 2, divinyl compounds according to claim 1, characterized in that that a diepoxide has a molecular weight was used below about 2000. 3β divinyl compound according to claim 1 or 2, characterized in that that as acy! halide a chloride of a saturated aliphatic monocarboxylic acid with 2 to 8 carbon atoms was used » 4 divinyl compound according to claim 1 to 3, characterized in that that as acylnlogenid a chloride of a saturated aliphatic monocarboxylic acid with 4 to J) carbon atoms was used. 5 »divinyl compounds according to claim 1 or 2, characterized ge indicates that the acyl halide is the bromide of a saturated aliphatic monocarboxylic acid with 2 to 18 carbon atoms was used. 6. divinyl compound according to claim 1 or 2, characterized in that that the acyl halide is the bromide of a saturated aliphatic monocarboxylic acid with 4 to 109809/2237 2U38630 / τ 10 carbon atoms was used. 7. divinyl compounds according to claim 1 to 6, characterized in that that a diepoxide having a molecular weight in the range of about 140 to about 500 is used became. 8. divinyl compounds according to claim 1 to 7, characterized in that a diepoxide with a molecular weight in the range of about 140 to about 350 is used became" 9. A process for the preparation of divinyl compounds, characterized in that first a molar proportion of a Diepoxydβ with 2 molar proportions of acrylic acid and / or methacrylic acid is reacted and thus obtained Divinyl ester condensation product is then reacted with two molar proportions of a saturated aliphatic acyl halide. 10. The method according to claim 9 »characterized in that a diepoxide having a molecular weight below about 2000, preferably in the range from about 140 to about 500 is used. 11. The method according to claim 10, characterized in that a diepoxide with a molecular weight of about 140 to about 350 is used. 12. The method according to claim 9 to 11, characterized in that that the acyl halide is a chloride or a bromide saturated aliphatic monocarboxylic acid with 2 to 1 09809/2237 2U38630 Carbon atoms, preferably 4 "to 10 carbon atoms is used. 109809/2237