CS214394B1 - Method of chemical modification of oxidized isocyclic polypropylene - Google Patents

Description

Disadvantages of the prior art are eliminated according to the invention and to the chemical modification of oxidized isotactic polypropylene in the form of powder, foil or fiber with polar aonomers such as methyl to pantylacrylate or aatyl to pantylaetacrylate in water and emulsion systems at a temperature of about 20 ° C. 30% for 3 to 9 hours does not modify vaccination · 70 to 100 wt. d. oxidized isotactic polypropylene and both 0.02-0.08 wt. % hydroperoxide oxygen and in the presence of 100 wt. d. aononere convened from honological series, containing methyl to pantylacrylate, reap. nyl to pantylaatacrylate in anulznon ayethene, created from 2 to 7 ha. d. of a tone emulsifier, 460 to 1780 wt. d. water, with the addition of a water-insoluble organic phase such as benzene, n-haxane and ethyl acetate in an amount of 130-1250 ha. d., wherein the reaction is activated with 0.6 to 2.8 wt. d. ferrous sulfate heptahydrate and 0.5 to 2.2 wt. d. and that upon completion of the polymerization, the product is isolated from the emulsion by filtration.

The isotectic propylene of the invention is oxidized at room temperature with oxygen-containing ozone. The oxidized polymer is present in the polymerisone system as a heterogeneous polymerization initiator in an aqueous emulsion. The use of low temperatures in the reaction allows the presence of an initiator activator composed of FeSO4 and triethytenatramine in a molar ratio of 2: 3. Its task is to decompose peroxides impregnated on polypropylene, solid-phase radicals formed by sludge, and through the inclusion centers of modification. It is advantageous to use the low emulsifier concentrate required to mediate the contact of the reactants on the surface of the polypropylene with the modification reaction. Even under these conditions, the system produces an initially 1 unbound homopolymer. The acrylic and methacrylic esters can be reduced to below 10% monomer conversion by adding some organic substances to the system. They are water-soluble polar 1 non-polar solvents such as atyl acetate, benzene and n-hexane, which are able to reduce the homopolymer 1 by 50 56 relative to the desired yield of the modification (as with acrylic esters) or 1% monomer, under certain conditions. forming a bound polymer of 10-15% (as is the case with methacrylic esters). Such a polymer already undergoes a high rate of conversion to high conversion and a large predominance of modified polypropylene formation. The solid phase containing unchanged polypropylene and modified polypropylene can be separated from the emulsion by filtration. Otherwise, the components of the system, including homopolymar, are cast in the filtrate. At the end of the polymerization, a beading agent is added to the system to creep the iron into the solid salt and allow the debris to be removed from the surface of the modified polymer by simple washing.

The process for the chemical modification of the isotactic polypropylene in the form of powder, foil and fiber by the acrylic and methacrylic esters of the invention is described in more detail in the following examples, but is not limited to these examples.

214 394

Example 1

In an inert atmosphere, the following components are metered into the polymerization vessel:

100 hm.d. Polypropylene powder (0.04% active oxygen), lie. iron sulphate, FeSO heptohydrátu | · 7H ₂ O, 0.8 weight parts triethylenetetramine, 4.3 wt. H,

460 wt.% Water, 630 wt. benzene and 100 wt. by distillation of purified methyl methacrylate. After sealing, the polymerization vessel is rotated in an aqueous thermostat.

The polymerization takes place at 30 ° C. After a specified polymerization time, 3.4 wt. The disodium salt of ethylenediaminetetraacetic acid (Chelaton III) and the eclened filter retain a solid phase, circulate unchanged polypropylene and methyl methacrylate modified polypropylene, then dry with water and dry. A homopolymer precipitates from the frit-passed emulsion with methanol. The result of the polymerization is expressed as% of the reacted monomer, calculated on the weight of the parent monomer, separately for the polymer not loaded on the polypropylene, especially for the homopolymer. After 6 hours of polymerization, 87.2% of the float monomer is bound to polypropylene and 3.4% forms a homopolymer.

Example 2

In the polymerization vessel and in an inert atmosphere, the components are dosed in the following order:

pbw polypropylene fiber (2.5 days / 38 mm, 0.06% active oxygen), 1.7 wt. FeSC ₄ .7H ₂ O, 1.4 wt. triethylenetetramine, 4.4. Mersol H emulsifier, 1780 wt. water, 840 wt. benzene and 100 wt. deetillary of purified ethyl methacrylate.

The polymerization and treatment of e is carried out in the same manner as in Example 1, except that at the end of the polymerization a e a 4.8 wt. D is added to the reaction mixture. Chelatonu III. After 9 hours of polymerization, 71.5% of the float monomer is bound to polypropylene and 6.1% forms a homopolymer.

Example 3

Into the polymerization vessel and in an inert atmosphere, the components are dosed in the following order:

pbw polypropylene powder (0.02% active oxygen), 0.7 wt. FeS0 ₄ «7H ₂ 0

0,6 hm.d. triethylenetetramine, 3.3 wt. Mersol H emulsifier, 580 wt. water, 300 wt. ethyl acetate and 100 wt. by distillation of purified propyl methacrylate.

Polymerization and processing e were carried out in the same manner as in Example 1 except that ea per conol polymerization added 2.5 wt. D to the reaction mixture. Chelatonu III. After 6 hours of polymerization, 85.6% of the float monomer ea binds to polypropylene a

7.7 9 forms a homopolymer.

Řríkleů 4

The components in the order of:

214 394 hm.d. polypropylene powder (0.04% active oxygen), 0.7 wt. sulphate. heptohydrátu .7HgO _FeSO4, 0.6 weight parts triethylenetetramine, 2 wt. Lieraol H emulsifier, 640 wt. water, 130 wt. n-hexane and 100 wt. by the distillate of the purified butyl methacrylate

Polymerization and epraoating aa is done in the same manner as in Example 1 and by adding aa at the end of the polymerization to 2.5 wt. Chelatonu III.

After 3 hours of polymerization, 79.8% of the parent monomer aa is bound to polypropylene a

7.7% create homopolymar.

Example 5

The components are dosed into the polymerization vessel and under an inert atmosphere:

pbw polypropylene powder (0.04% active oxygen), 0.7 wt. sulphate. heptohydrátu pES0 ₊ 7H ₂ 0, 0.6 weight parts triethylenetetramine, 3.5 wt. Mersol H emulsifier, 560 wt. water, 280 wt. benzene and 100 wt. by the distillate of the purified pentyl methacrylate.

The polymerization and processing is carried out in the same manner as in Example 1, with the difference that 2.5 a.d. is added to the reaction mixture at the end of the polymerization. Chelatonu III. After 4 hours of polymerization, 69.0% of the parent monomer aa is bound to polypropylene a

9.3% will create a homopolymar.

Example 6

In the polymerization vessel and in an inert atmosphere, the components are dosed in the following order:

pbw polypropylene film (0.16 mm thick, 0.08% active oxygen), 2.8 wt. FeSO ₄ .7HgO, 2.2 wt. triethylenetetramine, 7 wt. Ifersol H emulsifier, 1670 wt. water, 1250 wt. ethyl acetate and 100 wt. methylated acrylate with de-ethyl.

The polymerization and apparatus was carried out in the same manner as in Example 1, except that 9.4 wt.% Was added to the reaction mixture at the end of the polymerization. Chelatonu III. After 7 hours of polymerization, 68.4% of the parent monomer aa binds to polypropylene a

6.7% create homopolymar.

Řríkled 7

In the polymerization vessel and in an inert atmosphere, the components ▼ add:

100 hm.d. polypropylene powder (0.04% active oxygen), 1.1 wt. FeS0 ₄ «7H ₂ 0

0,9 hm.d. triethylantetramine, 5 wt. Meraol H emulsifier, 560 wt. water, 770 wt. ethyl acetate and 100 wt. by de-purification of the purified ethyl acrylate.

The polymerization and processing was carried out in the same manner as in Example 1, except that 3.8 wt.% Was added to the reaction polymer. Chelatonu III. After 6 hours of polymerization, 86.0% of the parent monomer aa is bound to polypropylene a

8.8% Tylvarí. homopolymár.

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Example 8

The components of the polymerization vessel are dosed in an inert atmosphere in the order of:

pbw polypropylene powder (0.04% active oxygen), 1 wt. FeSO .THgO,

0,8 hm.d. trlethylenetetramine, 2.5 wt. emulsifier liersol H, 530 wt. water, 330 wt. n-hexane and 100 wt. by purification of purified propyl acrylate.

The polymerization and the refinement were carried out in the same manner as in Example 1 and by the separation, at the end of the polymerization, 3.4 wt.% Was added to the reaction mixture. Ghelatonu III. After 5 hours of polymerization, 83.4% of the float monomer is bound to polypropylene and

8.8% will form a honopolymer.

Example 9

The containers are started into the polymer and the components are dosed in an inert atmosphere in the order:

pbw polypropylene powder (0.04% active cyanide), 0.6 wt. FeSO 4 .7H ₂ 0,

0.5 wt.d. triethylantetramine, 3.9 wt. d. Meraol H emulsifier, 590 wt. water, 220 wt. n-hexane and 100 wt. by distillation of the purified butyl acrylate.

The polymerization and treatment were carried out in the same manner as in Example 1, except that the polymerization was carried out at 20 ° C and the polymerization slurry was added to the reaction mixture at 2.1 wt. Chelatonu III. After 9 hours of polymerization, 77.6% of the parent monomer ea binds to polypropylene and 7.6% forms a homopolymer.

Example 10

The components in the order of:

pbw polypropylene powder (0.04% active oxygen), 1 wt. FeSO 4 .7H ₂ O,

0,8 hm.d. triethylenetetramine, 3 wt. Meraol H emulsifier, 460 wt. water, 270 wt. ethyl acetate and 100 wt. by distillation of the purified pentylacrylate.

The polymerization and the process are carried out in the same manner in the same way as in Example 1, with the same difference being added to the reaction mixture at 3.4 wt. Chelatonu ni. After 6 hours of polymerization, 75.7% of the float monomer ea is bound to polypropylene a

9.3% will form a homopolymer.

The prepared modified polypropylene can be freed from the components of the polymerization system in a simple manner by simple washing, while maintaining a heterogeneous character during the reaction. Certain oxygen residues in the polymer can be reduced, if necessary, by lower oxidation of the float polymer and / or the polymer. additionally remove. It does not matter for foils and fibers where ea is not expected to be thermally-mechanical. The method of polypropylene oxidation is not lukewarm ozone, the polymerization rings can be formed by cooling the polymer in the cold, with oxygen at elevated temperature, and the like. In addition to the foregoing, a number of developments make reference to the possibility of using the invention in an intermediate technically and economically advantageous manner. First of all, a simple polymerization system and a relatively non-sensitive to traces of the metal in the polymerization feedstock at the beginning of the reaction due to its preferential reaction with the metal carbonate present. It achieves high polymerization rates at a low temperature by economically utilizing the monomer both from the point of view of its overall conversion as well as the formation of the product to which the polymer is bound predominantly. Separation of the product from the homopolymer by filtration is unambiguously. The bonded polyester branches on the surface of the polypropylene severely limit its hydrophobicity, thereby increasing its utilization. Ester groups such as reaction oentres on polypropylene provide! Salzle reaction options, e.g. polymer-analogous transformations, leading to the preparation of polymers with special properties. From the blend with unchanged polypropylene, the modified polypropylene can be obtained by a seperation method based on the process of first dissolving the polymer blend at 120 ° C in o-xylenes; upon cooling and then the unaltered polypropylene is separated from the solution, which aa is filtered off from the copolymer solution.

They are not associated with the introduction of the invention in the manufacture of costly investments, nor do they require or alter the manufacturing regimes used in the production of commercial polymers by emulsion polymerization.

Claims (1)

214 394 6 of the prior art technically and economically advantageous use of the invention, in addition to the aforementioned facts. First of all, it is a simple polymerization system with relative sensitivity to oxygen traces in the polymerization batch at the reaction time, preferably with a metal chelate present. It achieves high polymerization rates at low temperature and economical utilization of the monomer both from its overall conversion and product formation by which the polymer is largely bound. The separation of the product from the homopolymer by filtration is unambiguous. on the surface of the polypropylene sline limit its hydrophobicity, thereby increasing it! possibilities of its use. The ester groups provide the reaction centers on polypropylene! It offers the possibility of reacting, for example, polymeric conversion, leading to the preparation of polymers with special properties. The modified polypropylene can be recovered from the modified unopened polypropylene by a process-based separation method according to which the polymer composition first dissolves at 120 ° C in o-xylene; after cooling, unchanged polypropylene is precipitated out of the solution, which is filtered from the copolymer solution. 3 by the introduction of the invention, they are not involved in the manufacture of expensive plastics, and it is not required to change emulsion polymerization in the manufacture of commercial polymers. EXAMPLE The method of chemically modifying oxidized isotactic polypropylene in the form of a powder, film and fiber with polar monomer, such as methyl- to pentyl acrylate, respectively. with methyl to pentyl methacrylate in an aqueous emulsion system, characterized in that the temperature of 20 to 30 ° C is modified by inoculating 70 to 100 wt. oxidized isotactic polypropylene containing 0.02 to 0.08 wt. % of hydroperoxide oxygen and the presence of 100 wt. a monomer selected from homologous groups containing methyl to pentyl acrylate, respectively. methyl to pentyl methacrylate in an emulsion system formed by 2-7 wt.d. liner emulsifier 460 to 1780 wt.d. water, in the presence of a water-insoluble organic phase such as benzene, n-hexane and ethyl acetate in an amount of 130 to 1250 wt.%, wherein the reaction is activated with 0.6 to 2.8 wt. ferrous sulfate heptahydrate and 0.5 to 2.2 wt.d. trlethylenetetramine, and that upon completion of the polymerization, the product is isolated from the emulsion by filtration.