DE1179376B - Process for the preparation of copolymers from esters of unsaturated acids - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C08f

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German class: 39 c -25/01

M 53747 IVd / 39 c
July 31, 1962
October 8, 1964

It is already known to use acrylic acid esters with esters of the formula

R ₄ - (CH = CR ₅ ) _m COO (CH ₂ ) J, CR ₆ = CR ₇ -X

to polymerize in the presence of catalysts. With these catalysts, however, you only get Products that cannot be cross-linked.

There has now been made a method of copolymerizing one or more esters of unsaturated acids the general formula

R ₁ - (CH = CR ₂ ) "- COOR ₃

(A)

in which R ₁ and R _{2 are} hydrogen atoms, alkyl, aryl or cycloalkyl groups having 1 to 10 carbon atoms, R _{3 is} an alkyl, aryl or cycloalkyl group having 1 to 10 carbon atoms, η = 1 or 2 and R _{2 is} im If η = 2 is a hydrogen atom, with one or more esters of unsaturated acids with unsaturated alcohols of the general formula

= CR ₅ ) ^ COO (CH ₂ V

(B)

in which R ₄ , R ₅ , R ₆ and R _{7 are} hydrogen atoms or alkyl, aryl or cycloalkyl groups with 1 to 10 carbon atoms, X is a hydrogen or halogen atom, m = 1 or 2, ρ is an integer between 0 and 6 and R ₅ in the case of m = 2 is a hydrogen atom, found in the presence of catalysts, optionally inert solvents, which is characterized in that the polymerization is carried out at a temperature between -100 and +20 ⁰ C, preferably between - 70 and -2O ⁰ C, is carried out in the presence of an anionic catalyst, 'ler is selected from one of the following groups:

a) organometallic compounds of metals from Group I of the Periodic Table of the Elements, in particular lithium alkyls and lithium aryls, for example lithium butyl or lithium fluorenyl;

b) organometallic compounds of metals of Group II of the Periodic Table, including organometallic monohalides, especially magnesium aryl halides, for example Phenylmagnesium chlorides, bromides or iodides, p-toluylmagnesium bromide or magnesium diethyl halides;

c) Compounds with metal-nitrogen bonds according to the general formula

MeiMe ⁿ [N (R'R ")], Xr

in which R 'and R "are both identical and different from one another and are alkyl, cycloalkyl,

Process for the preparation of copolymers
from esters of unsaturated acids

Applicant:

Montecatini Societä Generale per l'Industria

Mineraria e Chimica, Milan (Italy)

Representative:

Dr.-Ing. A. v. Kreisler, Dr.-Ing. K. Schönwald,

Dr.-Ing. Th. Meyer,

Dipl.-Chem. Dr. rer. nat. J. F. Fues

and Dipl.-Chem. Dr. H.-G. Eggert,

Patent attorneys, Cologne 1, Deichmannhaus

Named as inventor:

Giulio Natta,

Mario Donati,

Mario Farina, Milan (Italy)

Claimed priority:

Italy of August 3, 1961 (14 326)

Aryl or alkylaryl groups with a maximum of 10 carbon atoms, which optionally also form a heterocyclic ring with the nitrogen, Me ^{1 is} an alkali metal, Me ^{n is} a metal from Group I, II or III of the Periodic Table, X is hydrogen or halogen, r 0 or an integer, s and t also an integer and the sum s + t is equal to the sum of the valences of Me ¹ and Me ¹¹ ;

d) Complexes obtained by combining the compounds listed under a), b) and c) with Lewis Bases have been obtained, especially ethers and tertiary amines, anisole, triphenylphosphine or pyridine.

The polymerization can be carried out either in the presence or in the absence of solvents where the solvents can be inert with respect to the catalytic system, such as Hydrocarbons such as toluene or

Heptane. However, an excess of complexing agent can also be used as a solvent be, for example diethyl ether.

409 690/356

These copolymers have a linear structure due to a random repetition of monomeric units, depending on the reactivity ratio between the two monomers, which are derived from (A) and (B) by addition to the double bond or to the system of conjugated double bonds of the acid radical of the monomer. In addition to the unsaturation in the main chain that is present when η and m in the formulas of the two monomers = 2, there is also unsaturation in the side chain due to the presence of an unsaturated alkoxycarbonyl group derived from the monomer (B). This unsaturation, which can be determined by infrared investigations, shows that the monomeric units of the copolymer which are derived from the monomer (B) do not have a cyclic structure according to the polymerization process described, which, on the other hand, often occurs in the generally known polymerization processes.

As monomers of type (A) for the process according to the invention, the methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, benzyl and cyclohexyl esters, for example the acrylic, methacrylic, crotonic, cinnamon, pentadiene, sorbic, / ί-styrylacrylic acid is used will.

As monomers of type (B), the esters of the acrylic, methacrylic, croton, cinnamon, pentadiene, Sorbic or / I-styrylacrylic acid with, for example the following alcohols: vinyl, allyl, methallyl, 3-chloroallyl, 3-butenol-l, 4-pentenol-l, in question.

According to the invention, it is also possible to use more than one monomer of type (A) and / or more than one To polymerize monomer of type (B), terpolymers or even more complex polymers being obtained will.

The mixture of monomers may include, with the exception of the extreme proportions of any composition from 0 to I00 ° / _0th In the case of very small amounts of the comonomer used, the resulting copolymer is to be regarded as a modified polymer which has the basic characteristics of the polymer of the monomer, the proportion of which predominates. In general, this is a monomer of type (A), but the polymer also has certain properties, in particular side chain unsaturation of considerable reactivity, which are due to the presence of monomeric units from the second monomer, for example those of type (B).

The copolymers made by the process of the invention are characterized by the presence of a highly reactive unsaturated side chain characterized.

As a result of this property, it is possible to carry out crosslinking using the usual methods. In this way one obtains insoluble products or products that are caused by solvents at most be swollen.

The following examples illustrate the invention.

Examples 1 to 19

For each of Examples 1 to 19 compiled in the table below, a solution of the monomers is used (A) and (B) in 50 ml of anhydrous toluene filled into a dry test tube under nitrogen.

After cooling to -70 ° C, a solution of lithium butyl (about 2 moles) is added. The mixture is vigorously stirred, and the temperature of the bath then at - 50 ⁰ C increases. The reaction is interrupted by adding methanol, which destroys the catalyst, and the polymer coagulates. After decanting or filtering off, the polymer is then dried in vacuo in the cold.

Infrared examination of the samples shows an unsaturated side chain.

at Monomer A G Monomer B Allyl sorbate G Time 48 12th yield game 2.5 Allyl sorbate 0.3 h / min 48 18th G 1 Methyl sorbate 1.4 Metallylsorbate 1.4 2.30 ' 16 16 0.46 2 Methyl sorbate 1.9 4-pentenyl sorbate 0.9 50 5 16 0.17 3 Methyl sorbate 1.9 Allyl acrylate 0.9 2.30 ' 48 16 0.60 4th Methyl sorbate 6.7 Allyl acrylate 0.5 40 ' 16 48 0.85 5 Methyl sorbate 3.4 3-chloroallyl acrylate 0.4 16 4.60 6th Methyl sorbate 1.0 4-pentenyl acrylate 0.5 2.30 ' 0.70 7th Methyl sorbate 1.9 Allyl methacrylate 0.9 40 ' 0.10 8th Methyl sorbate 1.9 Methallyl crotonate 0.9 0.50 9 Methyl sorbate 1.9 Allyl sorbate 0.9 0.73 10 Methyl sorbate 0.9 Methallyl sorbate 0.5 0.17 11 Methyl acrylate 1.9 4-pentenyl sorbate 0.9 0.15 12th Methyl acrylate 1.9 Allyl acrylate 0.9 0.50 13th Methyl acrylate 1.9 4-pentenyl acrylate 0.9 0.50 14th Methyl acrylate 1.9 3-chloroallyl acrylate 0.9 1.05 15th Methyl acrylate 0.9 Methallyl crotonate 0.5 0.57 16 Methyl acrylate 1.9 3-chloroallyl acrylate 0.9 0.40 17th Methyl acrylate 0.9 Allyl methacrylate 0.5 0.25 18th Methyl methacrylate 1.9 0.9 0.25 19th Methyl methacrylate 0.30

Example 20

65 of 3 mmol of lithium diethylamide Li [N (C ₂ H ₆ ) ₂ ] in 10 ml of heptane were added. The whole is while a solution of 1.9 g Methylsorbat and 0.9 g for 1 hour at - 50 ⁰ C maintained. 0.65 g of allyl methacrylate is obtained at -7O ⁰ C to form a suspension of copolymer.

Example 21

When working as in Example 20, but with 1.9 g of methyl acrylate and 0.9 g of allyl methacrylate one 1.2 g of copolymer after 30 minutes.

Example 22

To a suspension of 0.5 g of phenyl magnesium bromide in toluene, a solution of 1.9 g Methylsorbat and 0.9 g of allyl methacrylate (total toluene = ml) is added at -7O ⁰ C.

After 16 hours at -50 ° C., 0.05 g of copolymer is obtained.

B is ρ ie 1 23 ^1S

When working as in Example 1, but using 1.5 mmol of a complex of Lithium butyl and tetrahydrofuran in a ratio of 1: 1 as a catalyst and 0.4 g of allyl methacrylate and 0.9 g Methyl sorbate as monomers in 8 ml of toluene is obtained after 12 hours at -50 ° C. 0.32 g of copolymer.

Example 24

When working as in Example 23, but using 1.5 mmol of a complex of Lithium butyl and tributylamine in a ratio of 1: 1 as a catalyst, after 12 hours at -50 ° C Obtained 0.20 g of copolymer. Example 25

When working in accordance with Example 1, but using 0.9 g butyl-ß-styryl, 0.9 g Methylsorbat and 0.9 g allyl methacrylate, 1.2 g of terpolymer are obtained after 12 hours at -5o C ^0.

Substantially analogous results are achieved if one of the following compounds is used as the catalyst is used: lithium amyl, lithium ethyl, lithium phenyl, triethyllithium aluminum, magnesium diethyl, Magnesium diphenyl chloride or iodide, p-toluyl magnesium bromide; triphenylphosphine, pyridine, anisole or dimethylaniline can also be used as complexing agents be used.

Claims (1)

Claim: Process for the copolymerization of one or more esters of unsaturated acids of the general formula R ₁ - (CH = CRa) _n - COOR ₃ in which R ₁ and R _{2 are} hydrogen atoms, alkyl, aryl or cycloalkyl groups having 1 to 10 carbon atoms, R _{3 is} an alkyl, aryl or cycloalkyl group having 1 to 10 carbon atoms, η = 1 or 2 and R _{2 is} im If η = 2 is a hydrogen atom, with one or more esters of unsaturated acids with unsaturated alcohols of the general formula (CH = CR ₅ ) _m - COO - CR ₆ = CR ₇ - X in which R ₄ , R ₅ , R ₆ and R _{7 are} hydrogen atoms or alkyl, aryl or cycloalkyl groups with 1 to 10 carbon atoms, X is a hydrogen or halogen atom, m = 1 or 2, ρ is an integer between 0 and 6 and R ₅ in the case of m = 2 is a hydrogen atom, in the presence of catalysts, optionally of inert solvents, characterized in that the copolymerization is carried out at a temperature between -100 and + 2O ⁰ C in the presence of an anionic catalyst consisting of one of the following groups is selected: a) Organometallic compounds of metals belonging to Group I of the Periodic Table of the Elements; b) organometallic compounds of metals from Group II of the Periodic Table, including organometallic monohalides; c) compounds with metal-nitrogen bonds according to the formula MeiMe ^u [N (R'R ") LX, in which R 'and R "are both identical and different from one another and are alkyl, cycloalkyl, aryl or alkylaryl groups with a maximum of 10 carbon atoms, which optionally form a heterocyclic ring with the nitrogen atom, Me ¹ an alkali metal, Me ³³ a metal of Group I, II or III of the Periodic Table means, X is hydrogen or halogen, r is 0 or an integer, s and t is also an integer and the sum s + t is equal to the sum of the valencies of Me ¹ and Me ¹¹ ;
d) Complexes which have been obtained by combining the compounds mentioned under a), b) and c) with Lewis bases. Considered publications:
French Patent No. 859,548;
British Patent No. 496 276. 409 690/356 9.64 © Bundesdruckerei Berlin