CS238940B1 - Processing of copolymeres propylene and polyesther - Google Patents

Abstract

Production of copolymers of propylene with polyethers. On the polypropylene chains in the environment do not inactivate ions oligomeric dicatlonates cationic centers, with which it is then reacted at temperature 250-350 K polyether solution or mixture polyethers.

Description

The present invention relates to the preparation of copolymers of propylene with polyethers by macroion reactions. Polypropylene, isotactic, syndiotactic and atactic, is one of the most hydrophobic polymers known.

This feature limits some applications. For example, it fails to dye, displaces stabilizers, and is not compatible with almost any other polymer or filler. Isotactic polypropylene is produced in considerable quantities and is relatively inexpensive.

Expanding the range of its applications is of considerable economic importance, as it will allow the replacement of some expensive special materials and / or the production of new quality items.

For a large number of polypropylene applications (and generally most polyalkenes), it would be desirable to introduce a degree of hydrophilicity into it, preferably controllable variable (controlled for a particular purpose).

The above disadvantages would thus be suppressed or eliminated. The hydrophilicity of the polymers is due to the presence of electronegative heteroatoms - such as nitrogen, oxygen and, to a lesser extent, fluorine - capable of forming hydrogen bonds.

OF

The introduction of such atoms into polypropylene chains is very difficult. Polypropylene is formed by coordination polymerization on Ziegler-Natta catalysts, whose activity ceases in the presence of nitrogen, oxygen, sulfur and partly fluorine containing substances.

Monomers with these atoms act as catalytic poisons and copolymerization with polar monomers is not possible. The hydrocarbon chain of the finished polyalkene is chemically stable, inert. The additional defined chemical modification of polypropylene is therefore also very difficult and requires special procedures.

For example, powdered polypropylene is ozonized. The resulting hydroperoxide groups can be used to initiate emulsion polymerization of hydrophilic monomers. Graft copolymers are formed.

In MS. AO No. 220422 describes a modification of polypropylene by the interaction of oligomeric dications with polypropylene and subsequent cationic polymerization of oxygen, nitrogen and fluorine-containing monomers.

Only copolymers of polypropylene with cationic polymerizing monomers can be obtained in this way. It has now been found that polypropylene-polyether copolymers can be obtained when a polyether solution is used in place of the monomer in the reaction.

SUMMARY OF THE INVENTION The present invention provides a process for producing propylene with polyethers, wherein polypropylene with cationic centers introduced via oligomeric dications is treated at a temperature of 250 to 350 K with a solution of a polyether or polyether blend, eliminating pollutant competitors competing with the cationic centers.

The object of the invention thus formulated is the most concise expression of the complex processes taking place in the modification process. Polypropylene reacts with a dication on the α-polymer bonds present as residues. coordination centers after propene polymerization), on chain defects (e.g., c bonds) and at other reactive sites of the chains to form cationic centers.

These centers undergo exchange reactions in contact with the polyether, represented schematically by the equations / wnnJ denoting the polypropylene chain; An oligomeric dication;

'0 half-strand chain; cation center; UVU> optionally —copolymer /:

η_! Τ_π_π_π_ + shaao® hjhjv vvvvv © * ® ντιη ^ ττίΓ

-LTirirír?

TJTJT_nJVV © + ABOUT U-LTLTIA /

About · ® ΈΓυννΟν ⁺ © / -v?

?

/ VO + ·

-LTLnjl_rL · ⁺ .rirv * - ίττιπ

Cation centers on polypropylene chains are formed by the interaction of polyalkene λ dications, such as the siloxonium type:

B® ^ i / CH _3/2 - O - Si / CH ₃ / - O-Si / CH _3/2 & B® wherein the counterion is as CIO®, Asi®, SBR ^, ^ Pl etc. n is 4 to 10 octamethylene-bis-dioxolenyl lithium eP:

ch ₂ -.0 °: _> ^c - / ° ¼ CH, -

- CH '

CH, bis / iP / p xylene - ·. <, Diyllium:

CH ² VJ

CH, and other dications of this type from alpha, omega dihalohydrocarbon and the corresponding silver salt of superacid / A ^ # (,

From dications formed from tetrahydrofuran or oxepane oligomerized with fluorosulfonic anhydrides: cf ₃ SO F S0 ₃ 'O CF, so / ^, F SO ₃ * ^ *

Also described in Polymer Preprints 13, 1, 66 (1972), J. Macromol. Sol 17 (7) (1399) (1973), or, optionally, dicons resulting from diazonium salt decomposition products in tetrahydrofuran polymerization (e.g. from 4-chlorophenyldiazonium hexafluorophosphate)

PIg is formed by Makrom visa. Chem. 177 3545 (1976)

Examples of modifying polyethers include poly (dimethylene oxide) (polyethylene oxide) and poly (1-methylethylene oxide); poly (chloromethylethylene oxide) i poly (trimethylene oxide) i poly (3,3 bis chloromethyloxetane) poly (tetramethylene oxide) (polytetrahydrofuran); poly (hexamethylene oxide) (polyoxepane) and substituted derivatives of these polyethers.

The degree of hydrophilicity can be controlled by the number of electronegative stors and the spacings between them in the copolymer, either by the length of the blocks or grafts with heteroatoms, or by the type of polyethers. The preparation of the copolymer according to the invention is particularly advantageous if the polyether is formed other than cationically.

The processes illustrated can be carried out technically relatively simply and with a good yield. The following examples illustrate the invention.

He did

To 1.5 g of polypropylene dried in the main branch of a high-vacuum twin-reactor was added 0.18 mmol of siloxonium dlions with vapor anionic C10 ions in a countercurrent of dry nitrogen.

In the meantime, 0.5 g of polydimethylene oxide / o molecular weight was dried in the side branch of the reactor

6.000 g in 20 cm &lt; 3 &gt; of tetrahydrofuran with sodium metal. After 24 hours of interaction of the polypropylene with the dication, the polyether solution was added thereto and the mixture was allowed to react at room temperature for 144 hours.

After cutting the reactor, the polyether homopolymer is extracted from the mixture with water. 1.74 g of product are obtained, which is wetted with water.

Example 2

The procedure was as in Example 1, but instead of polydimethylene oxide, polytetramethylene oxide (polytetrahydrofuran) having a molecular weight of 17,500 was used. After extraction in hot isopropaftol, 1.65 g of product was obtained, due to the less hydrophilicity of the water-wettable polytetramethynyl oxide.

More pronounced than the increase in hydrophilicity is a decrease in the melt viscosity caused by the presence of low temperature melting blocks of polytetramethylene oxide.

Example 3

The procedure was as in Example 1 except that poly (chloromethyloxirane) (polyepichlorohydrin), dried with CaH ₂ was used instead of polydimethylene oxide. After extraction in acetone, 1.8 g of product were obtained.

It was characterized both by increased hydrophilicity (compared to polypropylene) and by the content of C - Cl bonds, which allow further modification by polymer - analogous reactions with macroions.

Example 4

Following the procedure of Example 1, a solution of a mixture of polydimethylene oxide and polychloromethyloxirane was added to the cationic centers on the polypropylene. The product was well wettable with water and allowed further polymeranalogical reactions with macroanions.

Example 5

The procedure was as in Example 1, but bis-p-xylene was used in place of the siloxonium dication. , a diyl dikation with ClO 2 ® counterions. The wettability of the product was identical to that of Example 1.

Claims (1)

SUBJECT OF THE INVENTION A process for the preparation of copolymers of propylene with polyethers, characterized in that it is converted into polypropylene with cationic polymers. Centers introduced through oligomeric dications act at a temperature of 250 to 350 K with a polyether solution or a mixture of polyethers to eliminate competing polyethers in the reaction with the cationic centers.