CS232336B1 - Method of inoculating - Google Patents

Abstract

Spdseb olefinically unsaturated vaccination monomer at 0 to 200 ° C to macromolecular substrate exposed prior to vaccination Enhancing radiation, even better oxygen or its oligomer (0) is carried out so that the components of the initiation system at least one nitrogen is in the vaccination environment (NH 3, NH 4 QH, pyridine, di- to polyamines) and at least the inorganic compound created with at least two transient WITH The Church (H, Li. Na. K, Mg, Ca, Ba, C, O, S, . P, Sb, F, Cl, Ér, J), e.g. HCl, HNO 3. In the vaccination environment they usually also use active substances (regulators pH and mol. weight, surface-active substances etc.).

Description

(54) Method of vaccination

The method of inoculating an olefinically unsaturated monomer at 0 to 200 ° C on a macromolecular substrate exposed to radiation prior to inoculation, more preferably oxygen or its oligomer (0 ^), is accomplished such that at least one nitrogen (NH ₃₎ component of the initiator system in the inoculation environment. , NH ₄ QH, pyridine, di- to polyamines) and at least a inorganic compound formed with at least two non-transient

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

HCl, HNO 4. Inoculation environments usually also use surfactants (pH and molecular weight regulators, surfactants, etc.).

The present invention relates to a method of seeding synthetic and natural macromolecular materials with elefinically unsaturated monomers, in conjunction with an initiation system made of technically readily available organic and inorganic compounds.

It is known that sputtering with monomers of solid macromolecular materials can be carried out in diaperions in a suitable solvent, optionally in the inoculating monomer itself in the presence of peroxide initiators. For example, vinyl chloride can be seeded to polyethylene by heating the mixture of polyethylene and monomer to 95 ° C (French Pat. No. 1,445,350) or after dissolution in benzene and co-treating with benzoyl peroxide as the initiator (U.S. Pat.

814,393). Similar can be grafted vinyl chloride, polyethylene, dissolved in the monomer at 80 ^e C (Belgian Pat. No. 657762), and the vinyl chloride copolymer, ethylene vinyl acetate [Macho, V. et al ;: Chem. prftm. 27, 131 (1977): c. author's certificate 169 972,, 74 542]. A drawback, however, is the need to transfer the inoculated substrate to the solution and not a very high degree of vaccination.

However, significant progress has been made in this regard by using an inorganic-organic redox system to initiate 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): Citovicky et al., Chem. Ann. 36, 231 (1982); Coll. Czech. Chem. Comm. 45, 2319 (1980)]. A disadvantage, however, is the use of transition metal salts in high concentrations, which, after insufficient removal from the products, impair their stability. Although this deficiency is partially addressed by the use of polyethylene amines as activators of the breakdown of hydroperoxide groups bound to polymer chains [Natta et al., J. Polym. Sci. 34, 685 (1959)], but low conversion rates are achieved.

Significant progress is in the method of grafting irradiated or oxidized substrates with monomers using an initiation system formed with at least one nitrogenous and / or at least one organic reducing compound (cf. the author's certificate 231 123), but does not exhaust all possibilities of initiating the vaccination.

According to the present invention, the method of seeding the olefinically unsaturated monomer or monomer mixture is carried out at a temperature of 0 to 200 ° C on a macromolecular substrate exposed to radiation and / or oxygen and / or oxygen oligomers prior to vaccination such that at least one nitrogen component of the initiator system. the substance and at least one inorganic compound formed from at least two of the transient elements selected from hydrogen, lithium, sodium, potassium, alkoxide, calcium, barium, carbon, nitrogen, phosphorus, antimony, oxygen, sulfur, fluorine, chlorine, bromine and iodine, is generally carried out in the presence of excipients.

The advantages of the vaccination method of the present invention are the broad raw material and technical availability of the inorganic and organic components of the initiation system, high seeding and low homepolymerization efficiency. The advantage is also the ease of carrying out the inoculation at any scale, the easy removal of the residues of the initiation system from the crude inoculation products, and thus the high stability of the obtained products and of the dinellum products based thereon.

Last but not least, it is possible to carry out the inoculation process over a wide range of temperatures on conventional polymerization devices.

The monomer seeding according to the invention is carried out at temperatures of 0 to 200 ° C in block, solution, suspension or emulsion, continuously, semicontinuously or in a continuous state. Vinyl (vinyl chloride, vinylidene chloride, styrene, acrylonitrile, vinyl acetate, etc.), acrylic (alkyl acrylates, acrylaid, etc.), methacrylic and other monomers and comonomers, including olefin dienes.

The grafted macromolecular substrate consists of a synthetic homopolymer, copolymer, polyaddition and polycondensation products, as well as natural polymers such as e.g. naturally fiber.

All or part of the macromolecular substrate is irradiated prior to vaccination, in particular by gamma rays, ultraviolet rays, low temperature plasma, etc., in the presence of air or oxygen, respectively. an oxygen-containing gas, in particular with atomic oxygen, and in particular its known oligomers [jtezumovskij S. D .: Kislorod - elementary forms and states, Izdatelstvo Chiaije, Moscow (1979); Ozon .i ego reaction with orgahičeakimi soedinenijami, Izdatelstvo Nauka (1974) J. From the technical-economic point of view, the most suitable methods are ozonization of the substrate with ozone-containing oxygen.

The nitrogen compounds of the present invention include organic nitrogen compounds such as ethylenediamine, diethylenetriamine, and other aliphatic diamines to polyamines, cyclic amines such as cyclohexylamine, further heterocyclic nitrogen compounds such as pyridine and alkylpyridines, alcoholymines, asines, and the like. This includes ammonia as such, but also in the form of an aqueous solution, i.e. ammonium hydroxide and ammonium carbonate and bicarbonate.

By inorganic compounds are meant compounds formed from at least two non-transient elements of the periodic system, e.g. sodium chloride, two-elemental magnesium oxide, ammonium chloride, three-element sodium thiosulfate, and the like.

Adjuvants include water-soluble, water molecular weight regulators, pH regulators, surfactants, especially emulsifiers, dispersants, other dyes, pigments, fillers, medium compounds in amounts of ^from about ¹⁰ % to about ¹⁰ % by weight, based on the monomer.

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

Example 1

Into 125 cm ³ thick-walled glass tubes placed in a stainless steel stainless steel case with a brass cap, 50 g of distilled water, 0.25 g of an alkylaulfonic acid sodium salt emulsifier (Mersolat H) in the form of an aqueous solution of conc.

10 g of oxidized resp. of ozonated powder polyethylene of the grain size 1.10 ^-3 to 3.10 ^-1 mm containing peroxide, resp. of hydroperoxide groups 6.0.10 ^-3 mol / kg polyethylene.

The inorganic compound formed from the transient elements is then added, and after removal of air, ammonia or ammonium hydroxide is usually added at a concentration of 26% by weight. as well as 20 g of vinyl chloride. Thereafter, the tubes are placed in a special rotating frame immersed in a thermostated water bath at a temperature of 50-1.5 ° C. The rotation speed is 35 min ^-1 and the polymerization time resp. vaccination 20 h. After this time, the tubes are removed, cooled, unconverted vinyl chloride and degassed and the crude product obtained is sucked off on a filter crucible, washed with distilled water and then dried to constant weight in an oven at 60 ° C. Although an emulsifier is used, but at 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 seeding yield from the converted vinyl chloride is determined by extracting the dried product in cyclohexanone for 30 h at room temperature. For comparison as reference experiments, the inoculation of polyethylene under otherwise similar conditions, but with the exclusion of ammonia and ammonia, is still carried out. ammonium hydroxide, as well as other inorganic compounds. The results obtained are summarized in Table 1.

Table 1

Quantity (as 100%) <Β> Inorganic Compound Conversion yield vaccinations (%) kind of quantity of vinyl- (g) percentage (%) 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 On-SJO, 0.30 19.7 45.2 0.26 Na ₂ N 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 The procedure is similar to Example 1 but excluding 0.26 g NH (calculated as pure 100%) as an inorganic compound formed from transient elements, use oxide carbon monoxide through which the contents are blown of the tube at room temperature and left to positive pressure 0.1 MPa. Conversion of vinyl chloride during 20 h of polymerization at 50 ° C ° C fades 41.0% and inoculated from the converted vinyl chloride to polyethylene (cleaves) 62%. Example 3 The procedure as in example 1, , but the content is changing ammonia and how inorganic compounds, inorganic acids are used. The results are summarized in Table 2. table 2

The amount of NH 4 Inorganic compound conversion yield (as 100%) kind of number of vinyl vaccinations ( «) ( «) % (%) (%)

0 hno ₃ 0.20 4.4 13.6 0.26 hno ₃ 0.20 22.4 75.7 0.26 HCl 0.10 29.6 79.0

Example 4

The procedure is similar to that of Example 1, but instead of emulsion polymerization, the grafting with vinyl chloride is carried out under suspension polymerization conditions. Methyl hydroxypropylcellulose (Metocel 50 F) was used as a dispersant in an amount of 0.25 g per 10 g of oxidized polyethylene, 0.30 g sodium chloride, 0.86 g ammonia (as 100%), 50 g water and 20 g. vinyl chloride. At 50 ° C, a conversion of 47.5% and a seeding 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 of NaCl and 1.0 g of pyridine, a conversion of vinyl chloride of 11.2% and a seeding yield of 75.9% are achieved within 20 h.

Example 6

The procedure is similar to that of Example 1, except that an oxidized suspension polyvinyl chloride having a K value of 35.2 and a peroxide group content of 35.2 is used as the macroinitiator of the grafting. ² 10 ~ ³ mol / kg of a polyvinyl chloride seeding 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 NH4 (as, 00%), 0.25 g of Mersolat H and 50 g of water, the solid phase is isolated after 5 hours of polymerization. from a homopolymer emulsion by aspirating the crude product onto a filter crucible. When using styrene as a monomer, 36.3% of the grafted or homopolymerized stytene is present in the product obtained. Extraction in benzene for 30 h at room temperature is 65.7% inoculated onto polyvinyl chloride. When methyl methacrylate is used, these values are 40.9 and 40.9%, respectively. 76.3%.

Example 7

The procedure is as in Example 6, but the macromolecular substrate used is an ozonated vinyl chloride-propylene suspension copolymer having a K value of 58 containing 3.6% by weight. of propylene. The amount of peroxide groups in the substrate is 53.8. 10 ~ ^J mol / kg copolymer. 5 g of the 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, the solid product is separated from the reaction product containing 50.2% of inoculated or homopolymerized styrene by suction on a filter crucible. Extraction in benzene for 30 h at room temperature revealed that -62.1% of this amount was bound to the substrate used.

Example 8

The procedure is similar to Example 1 except that a 300 cm ³ stainless steel cuvette is used instead of a glass tube fitted with a stainless steel housing and a brass cap. In the presence of 0.85 g of ammonia (100% pure), 1.6 g of ammonium chloride, 10 g of ozonated polyethylene powder, 20 g of vinyl chloride and 100 g of an aqueous solution of Mersolat c conc. 0.5 wt. A conversion of vinyl chloride of 14% and a seeding yield of 18% are achieved at a seeding temperature of 50 and 0.1 ° C for 20 h. On the other hand, under otherwise similar conditions, but in addition with the addition of 0.005 g of crystalline copper sulfate, a conversion of vinyl chloride of 58% and a seeding yield of 64% is achieved.

OBJECT OF THE INVENTION

Claims (4)

A method of seeding an olefinically unsaturated monomer or mixture of monomers at a temperature 0 to 200 ° C per macromellular substrate exposed to radiation and / or oxygen and / or oxygen oligomers prior to vaccination, characterized in that the components of the initiator system in the vaccination environment are at least one nitrogenous substance and at least one inorganic compound formed from at least two non-transient elements from the group of hydrogen, lithium, sodium, potassium, magnesium, calcium, barium, carbon, nitrogen, phosphorus, antimony, oxygen, sulfur, fluorine, chlorine, bromine and iodine, the inoculation being generally carried out in the presence of adjuvants. The method of inoculation according to claim 1, characterized in that the component of the initiation system in the inoculation environment is at least one organic nitrogenous substance, preferably organic diamines to polyamines and / or amines, preferably ammonium hydroxide, in an amount of 0.5 to 30%. % by weight, calculated as seeding monomer or monomers. 3. The method of inoculation according to claim 1 and 2, characterized in that the transient elements are formed from inorganic salts, metals, thiosulfates and ammonium salts. The method according to claim 1, wherein the inorganic compound, preferably alkali halides 4. A method according to claim 1, wherein the inorganic compound is carbon monoxide and / or inorganic acids, preferably nitric acid and hydrochloric acid.