CS232336B1 - Vaccination method - Google Patents

Abstract

The process of grafting an olefinically unsaturated monomer at a temperature of 0 to 200 °C onto a macromolecular substrate exposed before grafting to pOabenium radiation, even better oxygen or its oligomers (O^), is carried out in such a way that the components of the initiation system in the grafting environment are at least one nitrogenous substance (NH3, NH4QH, pyridine, di- to polyamines) and at least one inorganic compound formed at least with two non-transitional S rvkev (H, Li. Na. K, Mg, Ca, Ba, C, O, S, . P, Sb, F, Cl, Er, J), e.g. NaCl, CO, HCl, HNO^ ati. In the vaccination environment, surfactants are also usually used (pH and molecular weight regulators, surfactants, etc.).

Description

(54) Vaccination method

The method of grafting an olefinically unsaturated monomer at a temperature of 0 to 200 °C onto a macromolecular substrate exposed to radiation before grafting, even better oxygen or its oligomers (O^), is carried out in such a way that the components of the initiation system in the grafting environment are at least one nitrogenous substance (NH ₃ , NH ₄ QH, pyridine, di- to polyamines) and at least one inorganic compound formed with at least two impermeable

Srvkev (H, Li. Na. K, Mg, Ca, Ba, C, O, S, . P, Sb, F, Cl, Er, J), e.g. NaCl, CO,

HCl, HNO^ etc. In the inoculation medium, surfactants (pH and molecular weight regulators, surfactants etc.) are usually also used.

The invention relates to a method of grafting synthetic and natural macromolecular materials with olefinically unsaturated monomers in combination with an initiator system formed from technically readily available organic and inorganic compounds.

It is known that grafting of solid macromolecular materials with monomers can be carried out: in dispersions in a suitable solvent, or in the grafting monomer itself in the presence of peroxide initiators. For example, vinyl chloride can be grafted onto polyethylene by heating a mixture of polyethylene and monomer to a temperature of 95 °C (French Pat. No. 1,445,350) or after dissolution in benzene and with the co-incorporation of benzoyl peroxide as an initiator (British Pat. No.

814 393). Similarly, polyethylene dissolved in monomer at a temperature of 80 ^e C can be grafted with vinyl chloride (Belgian Pat. No. 657 762), as well as vinyl chloride to the ethylene-vinyl acetate copolymer [Macho V. et al.: Chem. prftm. 27. 131 (1977): Czechoslovak author's certificate 169 972, ,74 542]. However, the disadvantage is the need to transfer the grafted substrate into the solution and not too high a degree of grafting.

In this direction, however, significant progress has been achieved by using an inorganic-organic redox system for initiating grafting of polypropylene and other polymers with monomers at temperatures up to 30 °C [Citovický P., Mikulášová D., Chrástová V.: Europ. Polym. J. ,2. 627 (1976): Citovický et al.: Chem.zvěsti 36, 231 (1982); Coll. Czech. Chem. Comm. 45, 2319 (1980)]. However, the disadvantage is the use of transition metal salts in high concentrations, which, after insufficient removal from the products, reduce their stability. This disadvantage is partly solved by the use of polyethyleneamines as activators of the decomposition of hydroperoxide groups bound to polymer chains [Natta et al.: J. Polym. Sci. 34, 685 (1959)], but only low conversions are achieved.

A significant advance is represented by the method of grafting irradiated or oxidized substrates with monomers using an initiation system formed by at least one nitrogenous and/or at least one organic reducing compound (Czech Patent No. 231,123), but it does not exhaust all possibilities of graft initiation.

According to the present invention, the method of grafting an olefinically unsaturated monomer or a mixture of monomers is carried out at a temperature of 0 to 200 °C onto a macromolecular substrate exposed to radiation and/or oxygen and/or oxygen oligomers before grafting, such that the components of the initiation system in the grafting medium are at least one nitrogenous substance and at least one inorganic compound formed from at least two non-transitory elements from the group of hydrogen, lithium, sodium, potassium, hydrogen, calcium, barium, carbon, nitrogen, phosphorus, antimony, oxygen, sulfur, fluorine, chlorine, bromine and iodine, the grafting being carried out generally in the presence of auxiliaries.

The advantage of the grafting method according to this invention is the wide raw material and technical availability of inorganic and organic components of the initiation system, further high grafting and low homopolymerization efficiency. Another advantage is the simplicity of performing the grafting on any scale, easy removal of the remnants of the initiation system from the raw grafting products, and thus also the high stability of the obtained products and derivative products based on them.

Last but not least, it is possible to carry out the grafting process in a wide range of temperatures on conventional polymerization equipment.

The grafting of monomers according to the present invention is carried out at temperatures of 0 to 200 °C in a block, in a solution, in a suspension or in an emulsion, continuously, semi-continuously or intermittently. The olefinically unsaturated monomer or mixture of monomers are generally known vinyl (vinyl chloride, vinylidene chloride, styrene, acrylonitrile, vinyl acetate, etc.), acrylic (alkyl acrylates, acrylates, etc.), methacrylic and other monomers and comonomers, including olefins and dienes.

The grafted macromolecular substrate consists of synthetic homopolymer, copolymer, polyaddition and polycondensation products, as well as natural polymers such as natural fibers.

The entire macromolecular substrate or part of it is treated with irradiation, mainly with gamma rays, ultraviolet rays, low-temperature plasma, etc., before inoculation, in the presence of air or oxygen, or an oxygen-containing gas, especially with atomic oxygen and especially its known oligomers [Ytezumovskij S. D.: Kislorod - elementaryje formy i svojstvo, Izdatelstvo Chiaije, Moscow (1979); Ozone .i ego reakcii s orgahičeakimi soedinenijami, Izdatelstvo Nauka (1974) J . From a technical and economic point of view, the most suitable methods include ozonation of the substrate with ozone-containing oxygen.

The nitrogenous substances according to this invention include organic nitrogenous substances, such as ethylenediamine, diethylenetriamine and other aliphatic diamines to polyamines, cyclic amines such as cyclohexylamine, other heterocyclic nitrogenous compounds such as pyridine and alkylpyridines, alcoholimines, azines, etc. This also includes ammonia as such, but also in the form of an aqueous solution, i.e. ammonium hydroxide and ammonium carbonate and bicarbonate.

Inorganic compounds are understood to be compounds formed from at least two non-transitory elements of the periodic table, e.g. sodium chloride, magnesium oxide formed from two elements, ammonium chloride, sodium thiosulfate formed from three elements, etc.

Auxiliary substances include solvents, water, molecular weight regulators, pH regulators, surfactants, mainly emulsifiers, dispersants, as well as dyes, pigments, fillers, copper compounds in amounts of 1.10~ ² to 1.10' ¹ % by weight calculated on the monomer.

Further details of the method as well as further advantages are apparent from the examples, which, however, do not limit the method according to the present invention.

Example 1

Into thick-walled glass test tubes with a volume of 125 cm ^{3 each} , placed in a stainless steel case with a brass cap, 50 g of distilled water and 0.25 g of an emulsifier based on the sodium salt of alkyl sulfonic acids (Mersolat H) are dosed in the form of an aqueous solution with a conc.

% by weight, further 10 g of oxidized or ozonized powdered polyethylene with a grain size of 1.10 ^-3 to 3.10 ^-1 mm with a content of peroxide or hydroperoxide groups of 6.0.10 ^-3 mol/kg of polyethylene.

Then an inorganic compound formed from impermeable elements is added and after removing the air, ammonia or ammonium hydroxide is added, usually at a concentration of 26% by weight, and also 20 g of vinyl chloride. Then the test tubes are placed in a special rotating frame immersed in a water bath heated to a temperature of 50 ± 0.5 °C. The rotation speed is 35 min ^-1 and the polymerization or seeding time is 20 h. After this time, the test tubes are removed, cooled, the unconverted vinyl chloride is degassed and the obtained crude product is suctioned off on a filter crucible, where it is washed with distilled water and then dried to constant weight in an oven at a temperature of 60 °C. Despite the fact that an emulsifier is used, but in a lower concentration, there is practically no emulsion in the crude product and also in the filtrate.

The conversion of vinyl chloride is calculated from the weight gain of the polymer and the grafting yield from the converted vinyl chloride is determined by extraction of the dried product in cyclohexanone for 30 h at room temperature. For comparison, as a reference experiment, grafting of polyethylene is also carried out under otherwise similar conditions, but with the exclusion of both ammonia and ammonium hydroxide and other inorganic compounds. The results obtained are summarized in Table 1.

Table 1

Quantity (as 100%) <β> Inorganic Compound Conversion Inoculation Yield (%) species amount of vinyl chloride (g) (%) 0 0.1 0.26 - 0.5 - 0.86 - 2.2 - 0.86 NaCl 0.30 76.4 68.1 0.26 nh ₄ ci 0.80 31.4 75.9 0 NH^Cl 0.80 2.1 - 0.26 Na-SjO, 0.30 19.7 45.2 0.26 On ₂ S 0.30 14.1 55.4 0.26 KBr 0.60 10.7 55.2 0.26 KJ 0.80 25.8 54.8 Example 2 Progresses is similar to example 1, but except for 0.26 g NH, (calculated as pure substance- (100%) is an inorganic compound formed from non-transitory elements, uses oxide carbon, through which the contents are blown test tubes at room temperature and left to overpressure 0.1 MPa. Conversion of vinyl chloride during 20 h of polymerization at a temperature of 50 °C will reach 41.0% and from converted vinyl chloride it is grafted onto polyethylene (splits) 62%. Example 3 Progresses as in example 1, , but with the difference that the content changes ammonia and how inorganic compounds inorganic acids are used. The results obtained are summarized in table 2. Table 2

Amount of NH^ Inorganic compound Conversion Extract (as 100%) species quantity vinyl chloride vaccinations («) («) Ride (%) (%)

0 manure ₃ 0.20 4.4 13.6 0.26 manure ₃ 0.20 22.4 75.7 0.26 HCI 0.10 29.6 79.0

Example 4

The procedure is similar to that in Example 1, but instead of emulsion polymerization, the grafting with vinyl chloride is carried out under suspension polymerization conditions. As a dispersant, methylhydroxypropylcellulose (Metocel 50 F) is used in an amount of 0.25 g per 10 g of oxidized polyethylene, further 0.30 g of sodium chloride, 0.86 g of ammonia (as 100%), 50 g of water and 20 g of vinyl chloride. At a temperature of 50 ° C, a conversion of 47.5% and a grafting yield of 61.3% are achieved within 20 h.

Example 5

The procedure is similar to Example 1, but oxidized polyethylene is grafted with vinyl chloride using nitrogen bases other than ammonia or ammonium hydroxide. Thus, using 0.30 g NaCl and 1.0 g pyridine, a vinyl chloride conversion of 11.2% and a grafting yield of 75.9% are achieved within 20 h.

Example 6

The procedure is similar to that in Example 1, but with the difference that the macroinitiator of the grafting is oxidized suspension polyvinyl chloride with a K value of 70, a peroxide group content of 35.2 . 10~ ^{2 3} mol/kg polyvinyl chloride and the grafting monomers are methyl methacrylate or styrene. Using 10 g of oxidized polyvinyl chloride, 10 g of monomer, 0.30 g of NaCl, 0.26 g of NH^ (as a .00% substance), 0.25 g of Mersolate H and 50 g of water, after 5 h of polymerization, the solid phase is isolated from the homopolymer emulsion by suctioning off the crude product on a filter crucible. When styrene is used as the monomer, the product obtained contains 36.3% of grafted or homopolymerized styrene. By extraction in benzene for 30 h at room temperature, 65.7% of the above amount is grafted onto polyvinyl chloride. When methyl methacrylate is used, these values are 40.9 and 76.3%, respectively.

Example 7

The procedure is as in Example 6, but as macromolecular substrate an ozonized suspension copolymer of vinyl chloride-propylene with a K value of 58 and containing 3.6 wt. % copolymerized propylene is used. The amount of peroxide groups in the substrate is 53.8 . 10~ ^J mol/kg of copolymer. 5 g of macroinitiator, 0.25 g of Mersolate H, 0.30 g of NaCl, 0.86 g of NH^ (as 100%) and 10 g of styrene are used. After 18 h of polymerization at a temperature of 50 °C, a solid phase containing 50.2% of grafted or homopolymerized styrene is separated from the reaction product by suction on a filter crucible. Extraction in benzene for 30 h at room temperature shows that -62.1% of this amount is bound to the substrate used.

Example 8

The procedure is similar to that in Example 1, but instead of a glass tube equipped with a stainless steel sleeve and a brass cap, a stainless steel cuvette with a volume of 300 cm ³ is used. In the presence of 0.85 g of ammonia (as a substance of 100% purity), 1.6 g of ammonium chloride, 10 g of ozonized polyethylene powder, 20 g of vinyl chloride and 100 g of an aqueous solution of Mersolat c conc. 0.5% by weight, at a seeding temperature of 50 ± 0.1 °C for 20 h, a vinyl chloride conversion of 14% and a seeding yield of 18% are achieved. In contrast, under otherwise similar conditions, but with the addition of 0.005 g of crystalline copper sulfate, a vinyl chloride conversion of 58% and a seeding yield of 64% are achieved.

SUBJECT OF THE INVENTION

Claims (4)

Example 5 Poetup is similar to Example 1, but oxidized polyethylene is seeded with vinyl chloride using other nitrogen bases than ammonia or ammonium hydroxide. Thus, using 0.30 g of NaCl and 1.0 g of pyridine, a conversion of vinyl chloride of 11.2% and a seed yield of 75.9% is achieved for 20 h. EXAMPLE 6 A procedure similar to Example 1 was followed but with the exception that an oxidized suspension polyvinyl chloride of K value of 70, a peroxidic group content of 35.2 was used as the inoculation macroinitiator. 10 µmol / kg polyvinyl chloride and inoculating monomers sd methyl methacrylate but bostyrene. Using 10 g of oxidized polyvinyl chloride, 10 g of monomer, 0.30 g of NaCl, 0.26 g of NH4 (as, 00%), 0.25 g of Mersolat H and 50 g of water are isolated from the solid phase after 5 h of polymerization homopolymer emulsions by aspirating the crude product on the filter crucible. When used as a monomer, 36.3% of the obtained product is grafted or homopolymerized with the resin. Extraction in benzene for 30 h at room temperature is 65.7% inoculated onto polyvinyl chloride from this amount. When using methyl methacrylate sd these values of 40.9, respectively. 76.3%. EXAMPLE 7 The procedure is as in Example 6, but as the macromolecular substrate, the vinyl chloride-propylene suspension copolymer (K) of 58 is used with 3.6 wt. propylene. The amount of peroxidic groups in the substrate is 53.8. 10-mol mol / kg copolymer. 5 g of a macroinitiator, 0.25 g of Mersolate H, 0.30 g of NaCl, 0.86 g of NH4 (as 100%) and 10 g of styrene are used. After 18 hours of polymerization at 50 ° C, a solid phase containing 50.2% of inoculated or homopolymerized styrene is removed from the reaction product by aspiration of the filter crucible. Extraction in benzene for 30 h at room temperature reveals that 62.1% of this amount is bound to the substrate used. Example 8 A procedure similar to Example 1 is followed, except that a 300 cm stainless steel cuvette is used in place of a glass tube fitted with a stainless steel case and a brass closure in the presence of 0.85 g of ammonia. , 6 g of ammonium chloride, 10 g of ozonized polyethylene powder, 20 g of vinyl chloride and 100 g of aqueous Mersolat c conc. 0.5 wt. at a inoculation temperature of 50 ° C and 0.1 ° C for 20 hours, a conversion of vinyl chloride of 14% and a yield of inoculation of 18% is obtained. In contrast, under otherwise similar conditions, but with the addition of 0.005 g of crystalline copper sulfate, a conversion of vinyl chloride of 58% and a yield of inoculation of 64% is achieved. SUBJECT OF THE INVENTION A method for inoculating olefinically unsaturated monomer or a mixture of monomers at a temperature of 0 to 200 ° C to a macromelecular substrate subjected to inoculation with radiation and / or oxygen and / or oxygen oligomers, characterized in that the components of the inoculation system are at least one nitrogenous substance and at least one inorganic compound formed from at least two non-transition elements from the group of hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, carbon, nitrogen, phosphorus, antimony, oxygen, sulfur, fluorine, chlorine, bromine and iodine; The vaccination is usually carried out in the presence of excipients. 2. A method according to claim 1, wherein the component of the inoculation system is at least one organic nitrogen compound, preferably organic diamines 232336 6 to polyamines and / or amine, preferably 0.5% ammonium hydroxide. up to 30% by weight, calculated on the seed monomer or monomers. 3. The method of inoculation according to items 1 and 2, characterized by non-transition elements, is inorganic salts, metals, thiosulfates and ammonium salts. is an inorganic compound, preferably an alkali halide 4. The process according to claim 1, 2 and 3, wherein the inorganic compound is carbon monoxide and / or inorganic acids, preferably nitric acid and hydrochloric acid.