CS232123B1 - Method of vaccination iniciation - Google Patents

Description

The present invention relates to a method of initiating seeding of an olefinically unsaturated monomer or monomer mixture onto a macromolecular substrate by the interaction of readily available organic compound components.

It is appreciated that seeding with monomers of solid macromolecular compounds can be carried out in dispersions in a suitable co-solvent, optionally in the inoculating monomer itself in the presence of peroxide initiators. For example, vinyl chloride can be seeded to polyethylene by heating a mixture of polyethylene and monomer to 95 ° C (frainc. Pat. 1,445,350) or after dissolution in benzene and with the involvement of benzoyl peroxide as the initiator (V. Brit. Paten number 814,393). polyethylene dissolved in monomer at 80 ° C (Belgian Pat. 657 762) as well as vinyl chloride to ethylene-vinyl acetate copolymer can be grafted with vimyl chloride [Macho V. et al., Chem., 27, 131 (19'77); automotive certification 169 972;

174,542). However, the disadvantage is that the inoculated substrate must be transferred to the solution and not a very high degree of inoculation.

Seeding monomers into polymers using thermomechanical action is rarely used. Vaccination-induced reactions in this manner are relatively easy to carry out, but lead to the formation of "modified" (hydride) copolymers. Thus, in the extruder, zimes of acrylic acid and butyl acrylate can be continuously grafted onto polyethylene (Belgian Pat. No. 864 187), and the number of initiation centers can be further increased by using a peroxide initiator, as is the case with vinyl acetate grafting on polyethylene. 70 243). However, vaccination yields are not high. Radiation methods are used in techinical practice, but predominantly only to modify surface properties, such as fibers and foils [Polikarpov et al .: Vysokomoil. sojed. B21,916 (1979); Kurilenko et al .: Vysokomol. sojed. A22,1107 (1980); Lodes et al .: Radiochem. Radioanal. Lett. 32, 327 (1978)], thereby increasing their colorability, hydrophilicity, and the like. However, such vaccination requires more energy and efficiency in relation to energy consumption is relatively low.

The use of a redox system to initiate homopolymerization and copolymerization is also known [Vanderberg et al., Ind. Eng. Chem. 40, 932 (1948); US Pat. 4,261,870; 4,269,960; NSR pat. No. 2,929,485], but the results of the vaccination or resp. cleavage of polymers. 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., Ohrastová V .: Europ. Polym. J. 12, 627 (1976); Citovický et al .: Chem. rumors 36, 231 (1982); Ooll. Czeoh. Chem. Comm. 45, 2319 (1980)]. However, the disadvantage is the use of transition metal salts in high concentrations, which are difficult to remove from the products and reduce their stability. Although this deficiency is partly addressed by the use of polyethylene amines as activators of the breakdown of polymeric hydroperoxides [Natta et al., J. Polym. Sci. 34, 685 (1959)], but only low conversions are achieved. However, these and other technical problems are solved by the method of the present invention.

According to the present invention, the method of initiating seeding with an olefinically unsaturated monomer or monomer mixture onto a macromolecular substrate exposed to radiation and / or oxygen and / or oxygen oligomers prior to seeding is generally carried out in the presence of adjuvants in the presence of at least one nitrogenous substance among the compounds: ammonia, ammonium hydroxide, ammonium bicarbonate, aliphatic diamines to polyamines, hexamethylenetetramine, cyclic amines, heterocyclic nitrogen compounds, alkoholamines, mixtures of alkolamines in an amount of 0.1 to 35% by weight, calculated on the grafting monomer or monomers and / or at least one organic reducing agent of the compounds: reducing sugars, dienols, aldehyde alcohols, aliphatic aldehydes, hydroxy acids, and optionally at least one compound rnedl in an amount of 1.10 ^-5 to 1.10 ^-1 % by weight;

The advantage of the vaccination initiation method of the present invention is the wide raw material and technical availability of the organic components of the initiator system, its high inoculation and low homopolymerization efficiency. Furthermore, the ease of carrying out the process on any scale, the easy removal of the initiation system residues from the crude inoculation products, and thus the high stability of the products obtained and the finished products based thereon.

Last but not least, the possibility of carrying out the inoculation process over a wide range of temperatures and on conventional polymerization equipment.

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

The grafted macromolecular substrate comprises a synthetic homopolymer, copolymer, polyaddition and condensation products, as well as natural polymers such as starch, cellulose and its derivatives, ground wood, natural fibers, and the like.

All or part of the inoculated macromolecular sub232123 losses are treated with radiation, in particular gamma-rays, ultraviolet rays, low-intensity plasma, etc., prior to vaccination, in the presence of air or oxygen, respectively. an oxygen-containing gas, in particular atomic oxygen and in particular its oligomers (O2, O3, O4, etc.). From a technical-economic point of view, the most suitable methods are ozonization of the substrate with air containing ozone.

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, heterocyclic nitrogen compounds such as pyridine and alkylpyridines, alkoholamines, aziines 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.

Organic reducing components include organic dienols (ascorbic acid, dihydroxymaleinic acid and the like), aldehyde alcohols, aldehyde acids, especially reducing sugars, glycoldehyde, aliphatic aldehydes, polyhydric organic hydroxy acids and the like.

This group of reducing agents also includes irazadine and its derivatives, in particular the products of its addition with water and acids as well as organic polyamines.

The nitrogenous or reducing agent may even be a seeding monomer or comonomer.

Excipients include, in addition to the compounds, medium in an amount of 1.10 ^-5 to 1.10 ^-1 % by weight, calculated on the monomer, solvents, water, molecular weight regulators, pH regulators, surfactants, especially emulsifiers, dispersants, colorants, pigments, fillers and .

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

Example 1

A 50 g distilled water, 0.25 g of an alkylsulfonic acid sodium salt emulsifier (Mersolat Hj in the form of an aqueous solution at a concentration of 1%) was charged into a 0.125 dm ³ thick-walled glass tube placed in a stainless steel housing with a brass cap. 10.0 g of oxidized powdered polyethylene with a melt index of 7 g / 10 min and a density of 919 kg.ran ³ (type RA-7-23 / P3) with a content of peroxide groups of 6,10.10 ⁵ mol / kg polyethylene In addition, 0.3 g of glucose as a reducing agent and 1.0 g of 28% by weight ammonium hydroxide (i.e. 0.28 g of NH3) were charged with 20.0 g of vinyl chloride after 3 minutes of nitrogen purge. is placed in a swivel frame in a water bath at 50 ± 0.5 ° C. Rotation speed is 35 min ^-1 After 20 hours of polymerization, the tube is cooled in cold water, the non-polymerized vinyl chloride is degassed and the reaction product is transferred to a filter crucible where it is Despite the presence of the homopolymer, the crude product obtained practically does not remain in the emulsion. The filtered water is almost pure, despite the use of an emulsifier, the crude product obtained is visually similar to the polymer prepared by a typical suspension by polymerization or copolymerization. The conversion of vinyl chloride is calculated after drying the product in an oven at 60 ° C to reach 76.7%. To determine the vaccination extract, respectively. A portion of the grafted vinyl chloride from the total co-polymerized amount is extracted in cyclohexanone for 30 h at room temperature. The vaccination yield obtained was 74.4%. In the absence of glucose as a reducing agent, the conversion of vinyichloiride after 15 hours of polymerization is 0.5%, and if neither ammonia nor ammonia is used. ammonium hydroxide, conversion is only 0.1%.

Examples 2 to 14

The procedure of Example 1 is followed to inoculate vinyl chloride to oxidized powdered polyethylene under otherwise similar conditions but using other reducing agents. The results obtained are summarized in Table 1.

Table 1

Example Reducing agent number stabilizer (G) Polymerization time (H) Vinyl Chloride Conversion (%) yield vaccinations (%) 2 ascorbic acid 0.25 20 78.0 65.4 3 galactose 0.25 20 78.5 70.5 4 citric acid 0.25 17 20.8 41.8 5 fructose 0.25 20 74.0 59.7 6 dihydroxymaleinic acid 0.25 20 66.4 66.9 7 tocopherol 0.25 22 39.4 88.0 8 dietyléintriamín 0.25 17 78.8 51.6 9 triethylenetetramine 0.25 20 48.2 40.7 10 hexamethylenetetramine 0.25 20 18.6 55.7 11 hydírazínsulfát 0.25 17 20.1 50.8 12 hydrazine hydrate 0.25 20 19.6 55.0 13 benzoin 0.25 20 25.1 74.7 14 acetaldehyde 0.25 22 21.9 67.8

Examples 15 to 18

The procedure is similar to that in Example 1, but instead of polyethylene, ozonated synthetic polymers and copolymers in the form of powders are used as macromolecular substrates. Table 2 shows both the types of macromolecular substrates, as well as the content of peroxide groups therein, the vinyl chloride conversion achieved and the yield of grafted vinyl chloride from celto-converted.

Table 2

Example Macromolecular substrate Peroxide groups content in substrate .IQ ³ (mol. Kg ^-1 ) Conversion of vinyl chloride (%) Vaccination yield (%) 15 suspension poles vinyl chloride o K 70 35.2 89.9 74.3 16 polypropylene 16.2 29.3 75.7 17 a vinyl chloride-propylene slurry copolymer having a K value of 58 and a copolymerized propylene content of 3.6 wt. 53.8 87.9 74.0 18 vinyl-suspension suspension copolymer 25.7 13.8 77.2

chloride-vinyl acetate containing 15% of copolymerized vinyl acetate

Example 19

The procedure is similar to Example 1, but the oxidized polyethylene is grafted with vinyl chloride using nitrogen bases other than ammonia or ammonium hydroxide. Thus, using 1 g of ethylenediamine for 20 h results in a conversion of vinyl chloride of 92.6% and a seeding yield of 84.5%. With pyridine (1 gram) a conversion of vinyl chloride of 11.8% and a seeding yield of 61.8% was achieved under similar conditions.

Example 20

The effect of the amount of ammonia on the inoculation of ozonated polyethylene (10 g, using ascorbic acid as a reducing agent (0.3 g) in an emulsion formed from 50 g of an aqueous solution of Mersolat H of 0.5% by weight and 20 g of vinyl chloride is monitored. After 4 hours of copolymerization or seeding, the results summarized in Table 3 are obtained, depending on the amount of ammonia.

0.0013 0.078 0.26

Table: 3

Amount of NH3 added (as 0

100% j (g) ____________________ pH of the aqueous phase 7.4

Conversion of vinyl chloride (% j 7.5

Vaccination yield (%) 23.2

Example 21

The procedure is similar to that of Example 21, but the amount of ammonia used is 1.3 g and the polymerization time, respectively. vaccination is 20 h. The aqueous phase has a pH of 11.8; a vinyl chloride conversion of 78.4% and a seeding yield of 72.2 were achieved.

From this is evident positive effect of increased amount of ammonia, respectively. ammonium hydroxide for conversion as well as seeding yield.

Example 22

The procedure is similar to Example 1, but the composition of the batch is different, respectively. suspension polymerization and seeding are performed. Typical dispersants are also used instead of emulsifiers. Using methylhydroxypropylcellulose (Metocel 50 Fj in an amount of 0.5 g / 10 g of oxidized polyethylene, 0.3 g of ascorbic acid, 0.26 g of ammonia (as 100%), 50 g of water and 20 g of vinyl chloride at 50 ° C over 20 h the conversion of vinyl chloride reached 67.7% and the seeding yield 48.2%.

Using 0.25 g of cetyl alcohol polyaddition product with 20 moles of ethylene oxide instead of methylhydroxypropylcellulose under similar conditions yielded a conversion of 33.9% and a seeding yield of 54.9%.

Again, using a 0.25 g of a polyaddition product of lanrylalcohol with 4 moles of ethylene oxide, a conversion of 23.3% and a seeding yield of 44.6% was achieved.

Example 23

The procedure is similar to that of Example 1, but styrene is inoculated for oxidized polyethylene instead of vinyl chloride. The amount of emulsifier used was 0.1 g, the weight of ozoneized polyethylene 5.0 g and styrene 5.0 g. The amount of glucose 0.3 g and ammonia is (calculated to 100%) 0.26 g. After 17 hours of polymerization at 50 ° C, the solid phase is isolated by suction on a glass filter crucible. The product obtained contained 33.9% of converted styrene. Extraction in benzene revealed 59.0% of the converted styrene bound to polyethylene.

Example 24

The initiation system used also allows

10.8 11.3 11.5 5.8 19.1 24.2 22.4 64.5 66.0 inoculation methyl methacrylate Peroxidizo-

polymers. According to Example 1, 0.1 g of an emulsifier, 10.0 g of an oxidized suspension polyvinyl chloride having a K value of 70 (Slovinyl S-701) was metered into a glass tube, the peroxide content being 15.0. . 10-3 _Mo i _ kg ^"1 PVC. Furthermore, 10.0 g of methyl methacrylate; glucose and ammonia, respectively. ammonium hydroxide as in Example 1. After 17 hours of polymerization, a solid phase containing 38.4% converted methyl methacrylate is isolated. Extraction in benzene shows that 91.9% of the converted methyl methacrylate is bound to polyvinyl chloride. Example 25

The procedure is similar to that in Example 1, but instead of the polyethylene substrate prepared by ozonization, a polymer prepared by irradiating the polyethylene powder with χ-rays in the presence of air is used. The polyethylene powder thus prepared has a peroxide group content of 1.5-10 ^-3 mol. . kg ' ¹ . Using it similar to Example 1, a conversion of vinyl chloride of 16.2% and a seeding yield of 83.9 percent is achieved in 20 h.

Example 26

The procedure is similar to that of Example 1, but instead of vinyl chloride alone, a mixture consisting of 10 g vinylidene chloride and 10 g vinyl chloride, 10 g ozonized polyethylene, 50 g water, 0.26 g ammonia, 0.3 g ascorbic acid and 0.1 g is used. 25 g Merzolate. At a seeding temperature of 50 + 0.5 ° C for 20 h, the conversion of the monomer mixture was 91.0% and from this amount it was bound to polyethylene 71.3%. Example 27

The procedure is similar to that of Example 1, but a 390 cm ³ stainless steel cuvette is used instead of a metal tube with a brass cap. The batch consists of 10 g of ozonated polyethylene (type RA 7-23), 100 g of an aqueous solution of Mersolat H with conc. 0.2 wt. Furthermore, 0.6 g of glucose and 0.52 g of ammonia (as 100%) in the form of an aqueous solution with conc. 33% wt. and optionally adding hydrated copper sulfate. After sealing and removing air, g of vinyl chloride is metered in and polymerized for 20 hours at 50 + 0.1 ° C. The results obtained for the conversion of vinyl chloride and the vinyl acetate seeding yield of vinyl chloride are shown in Table 4.

Table 4

Quantity CuSOá. 5HzO (g) Vinyl Chloride Conversion (%) Vaccination yield (%) 0.0000 n, i 18.5 0.0005 32.2 53, q 0.0051 57.6 67.2 0,0163 74.5 66.9 Examples 28 to 33 the difference that other nitrogenous substances are used

or organic reducing agents. Dosiah-

The procedure as in the example 1, p forcing it the results are listed in Table 5. table 5 Example Crude protein species quantity (G) Organic reducing compound kind of quantity (G) conversion of vinyl chloride (%) yield vaccinations (%) 28 ammonium carbonic acid 0.5 glucose 0.3 76.0 69.2 29 ammonium hydroxide 0.3 acid guilty. 0.3 78.2 70.1 30 cyclohexylamine + ammonia 0.3 0.2 galactose 0.3 72.5 68.5 31 bicarbonate ammonium 0.4 fructose 0.4 77.3 65.8 32 monoethanol amine 0.4 glucose 0.3 57.3 62.3 33 mixture of diethanolamine with butanolamine 0.5 glucose 0.5 59.8 67.9

SUBJECT

Claims (2)

A method of initiating seeding with an olefinically unsaturated monomer or monomer mixture onto a macromolecular substrate exposed to radiation and / or oxygen and / or oxygen oligomers prior to vaccination as a rule in the presence of adjuvants, characterized in that the component of the initiation system in the seeding environment is at least one nitrogenous substance Ammonia, ammonium hydroxide, ammonium bicarbonate, aliphatic diamines to polyamines, hexamethylenetetramine, cyclic amines, heterocyclic nitrogen compounds, alkoholamines, mixtures of alkoholamines in amounts We claim: 0.1 to 35% by weight, based on the inoculum monomer or monomers and / or at least one organic reducing agent spomeidii of the compounds: reducing sugars, dienols, aldehyde alcohols, aliphatic aldehydes, hydroxy acids and optionally at least one medium compound in an amount of 1. . 10 ~ ⁵ to 1.10 ^_1 wt. 2. A method according to claim 1, wherein the organic reducing agent is dienol, preferably ascorbic acid, dihydroxymaleic acid and / or hydroxy acid, preferably citric acid and tartaric acid.