CS218602B1 - Method of fixation of the low-molecule substances to the polymeres - Google Patents

Description

3

BACKGROUND OF THE INVENTION The present invention relates to a method for fixing low molecular weight polymers to polymers of polypropylene, polyethylene and polyvinyl chloride films, to spinning poly- [2,3-epoxypropyl methacrylate-bound powder in such a way that epoxide groups are reacted with mobile hydrogen.

In the prior art, the use of epoxide compounds to react with acids, amines, acid anhydrides, the reaction proceeded in a homogeneous phase with pure substances or in an organic solvent solution. The reaction was catalyzed by tertiary amines, quaternary ammonium salts, metal and organometallic compounds, complexes and ion exchangers. Isotactic polypropylene, polyethylene and polyvinyl chloride are bound by epoxides and epichlorohydrol esterified as well as carboxyl groups. Some of the above processes have disadvantages in that they operate in a homogeneous phase of influence, and the product needs to be more expensive and expensive to separate and clean. A good defined modified polymer can usually be worked up only in a loss in yield. The reaction system is unusable for further use. Esterification of the carboxylic acid groups of polyacid-bound polymers by epoxies has some limitations due to the lack of suitable substances with epoxy groups which may be specially synthesized. A preferred modification of the solid organic epoxy group carrier with mobile hydrogen in the heterogeneous phase has not been described.

Disadvantages of the prior art are eliminated according to the invention describing the method of fixing molecular substances to polymers of polypropylene, polyethylene and polyvinylchloride films, fibers and powder containing from 9.3 to 14.2 wt% bound polyol-2,3-epoxypropyl-tacrylate by compounds containing 1 to 4 reactively hydrogen atoms bound to oxygen, primary and secondary nitrogen or sulfur which - CH - CH 2 --H - R '

O

The reaction is catalyzed in particular by tertiary amines which mediate the transport of hydrogen or by acids. If R-H is the primary, but secondary secondary amine the reaction proceeds with sufficient speed without the support of the activator. Two or more reactive hydrogen-reactive moieties cause crosslinking of the product. The reaction is carried out using organic liquids which, in turn, wet the solid phase, the solubilized substances, and thus mediate their contact with epoxies on the surface of the polymer. The organic solvents do not dissolve both the aqueous seed polymer and the reaction product, since a characteristic of this method of polymer modification is the course of the reaction in the heterogeneous sub-218602 located in the aliphatic or alicyclic chain or on the carbon-containing aromatic nucleus. by weight of poly ([beta] 2-epoxypropyl methacrylate) bound by 12 to 55% by weight of poly (propylene, polyethylene or polyvinylchloride) containing from about 100 to about 14.2% by weight. parts of the compound with reactive hydrogen from the group consisting of dichloroacetic acid, 3-bromopropionic acid, adipoic acid, 3-phenylthiopropionic acid, 3- (4-hydroxy-3,5-di-tert-butyl) phenylpropionic acid, p-cyclohexylphenyl acetic acid; o-chlorophenol, 7,15-diazadispiro [5,1,5,3] hexadecane, NN-bis- (3-aminopropyl-) piperazine, 2,2,6,6-tetramethyl-4-aminopiperidine, morpholine, diethanolamine and target. dodecyl mercaptan in the presence of 70 to 2080 parts by weight of organic organic solvents such as heptane, hexane, toluene, o-xylene, m-xylene, p-xylene, dimethylformamide, dimethylsulfoxide or mixtures thereof, wherein the reaction can be carried out without catalyst or 0.4. up to 6.4 parts by weight of the catalyst, which may be triethylamine, tributylamine, trihydroxylamine, benzyldimethylamine or pyridine, further isolating the product by filtration.

Polypropylene, polyethylene and polyvinyl chloride in the form of powder, foil or poly [2,3-epoxypropyl methacrylate] fibers are prepared by seeding low-oxidized polymers with 2,3-epoxypropyl methacrylate at 30 ° C in water emulsion in the presence of an activator initiator, a chelate composed of FeSO 4 and disodium salt of the acid. ethylenediaminetetraacetic acid. The low reaction temperature of the polymerization system alone guarantees the integrity of the bound epoxy groups at the polymerization time of the polymerization. These groups can be used as reactive centers for further polymeric polymer conversions. They use their ability to bind substances with moving hydrogen according to the scheme:

--- CH — CH2 — R

OH mienkach. The use of solvents makes it possible to dispense the non-fixed substances in a minimum amount. With their presence in the system, approximately one to two orders of magnitude are associated with a higher catalyst requirement compared to reactions under homogeneous conditions. This is due to the fact that the catalyst is predominantly dispersed in the solution outside the surface of the polymer and thus out of reaction centers. The reaction is preferably carried out in an inert atmosphere, with respect to both the polymeric nature of the material and the possibility of oxidizing the components of the system. The materials used need to dispose of the admixture, especially water, thereby limiting the clear reactions leading to the unproductive reaction of a portion of the epoxide, possibly creating a 4 undesirable product. By appropriately selecting the reaction conditions, undesirable reactions can be avoided which cause disruption of the solid polymeric material, its darkening or cleavage of the low molecular weight moiety, or disruption of the structure of the liquified substance. Considerable importance for some substances is the possibility of reducing the temperature of the reaction, even at the expense of its duration, or of its duration. Also, the possibility of shortening the time of exposure to higher temperatures. Working in heterogeneous conditions has the major advantage of allowing rapid, unambiguous quantitative separation of the product from other system components by filtration and purification by simple elution.

By introducing reactive groups into the polymers, the catalysts change their properties and, on the other hand, create the conditions for subsequent polymeric analogs. These possibilities lead to the fixation of substances with a distinct effect on the polymer. This process has the advantage of undemanding conversion over the polymerization process of polymer modification, since these reactions occur with a non-radical mechanism. It is preferred to have a polymer-bound group having the ability to react with as many different structures as possible. This appears to be an epoxy group which is relatively easy to react with substances possessing a mobile hydrogen group, including carboxylic acids and amines, and heterocyclic-bonded secondary nitrogen. The advantage of these reactions is that they tend to lead to high yields and that they are the most unproductive product. For this reason, some primary amines and strong carboxylic acids are also suitable for the determination of epoxides. Since the polymeric conversion of the graft polymer is an increase in operation, its target should be significant changes in polymer quality. Polymers containing fixed stabilizers, biologically active or flame-retardant substances, antistatic agents, adhesives, catalytically, coloring agents and other specific agents may be considered as such. Substances can be bonded with relatively stable bonds (amines, alcohols), or with the possibility of their cleavage and release of the fixed substance in a not very aggressive environment (carboxylic acids), while there are still possibilities of crosslinking the polymer with two-functional substances (not only simultaneously but also through the groups formed by the reaction or introduced by fixed substance). It is believed that such modified powder materials would be added as the active ingredient concentrate to the polymer prior to processing. It is not contemplated that the formed bonds by the intermediate polyoxide and the fixed substance will be disrupted by the processing temperatures of the polymers. The key importance of such a polymer modification is that the polymer-fixed substances do not migrate during processing or use, migrate to the surface Comparison with low molecular weight ingredients does not confine to their possible loss and consequences 218602 resulting from the quality of the polymer, but the importance of fixing certain substances can be seen in the protection of health and safety at work and the wider application of polymers in such fields, such as healthcare or the food industry. For the economics of synthesizing such modified polymers, it is a serious fact that after separation by filtration of the solid phase as a single product, a liquid reaction can be used to supplement the depleted component. In doing so, the introduction of the invention does not involve costly investment in the manufacturing sector, nor does it require substantial changes in the field of production modes used in the production of commercial polymers.

The method for chemically modifying polypropylene, polyethylene and polyvinyl chloride films, fibers and poly- [2,3-epoxy-propyl methacrylate] -bonded powder is described in the following examples, which are not intended to be limiting. Example 1

Components in the order of 100 wt.% Are metered into the reaction vessel in an inert atmosphere. d. polypropylene powder containing 14.2 wt. % Na-linked pol- [2,3-epoxypropyl methacrylate], 33 wt. d. 7,15-Diazadispiro [5,1,5,3] hexadecane, 4.1 wt. d. benzyldimethylamine and 350 wt. d. toluene. After closing, the reaction vessel is rotated in a thermostat.

The polymer modification takes place at 110 ° C. At the end of the reaction, the reaction mixture is cooled, quenched with diethyl alcohol, and a solid phase containing a modified polymer is collected on a glass filter, washed and dried. The result of the modification, determined by the weight gain of the polymer after the reaction, is expressed as% of the reacted epoxide groups in its polar amount in the polymer used to fix the low molecular weight substance. After a 6-hour reaction, a solid phase was isolated in which 87.3% of the polar epoxy groups of the polymer were used to bind 7,15-diazodispiro [5,1,5,3] hexadecane. Example 2

Components in the order of 100 wt.% Are metered into the reaction vessel in an inert atmosphere. d. Poly-propylene film (0.17 mm thick) containing 12.2% bound poly- [2,3-epoxypropylme-acrylate], 17 wt. d. p-cyclohexylphenylacetic acid, 3.8 wt. d. tributylamine, 515 wt. d.p-xylene and 590 wt. d. dimethylformamide. Closing the reaction vessel is statically placed thermostate.

Modification of the polymer takes place at 110 ° C. The reaction mixture is worked up in the same manner as in Example 1. After a 7-hour reaction, a solid phase is isolated in which 95.2% of the polymeric epoxide groups are used to bind β-cyclohexylphenylacetic acid. -lazy. 5 218602 Example 3

Components in the order of 100 wt.% Are metered into the reaction vessel in an inert atmosphere. d. Polypropylene fiber (2.5 days / 38 mm) with 9.3% bound poly [2,3-epoxypropyl methacrylate], 14 wt. diethanolamine and 2080 wt.d. dimethylsulfoxide. Once closed, the reaction vessel is placed in a thermostate. Modification of the polymer takes place at 110 ° C. The reaction mixture is worked up in the same manner as in Example 1. After 8 hours of reaction, a solid phase is isolated in which 83.7% of the polymeric polyoxide moieties have been used for the binding of diethanolamine. Example 4

Components in the order of 100 wt.% Are metered into the reaction vessel in an inert atmosphere. d. Polypropylene powder containing 14.2% bound poly- [2,3-epoxypropyl methacrylate], 30 wt. d. 3-bromopropionic acid and 330 wt. d. hexane. After closing, the reaction vessel is rotated in thermo-state.

The polymer modification proceeds at 100 ° C. The reaction mixture is worked up in the same manner as in Example 1. After 6 hours of reaction, a solid phase is isolated in which 89.7% of the polyoxide epoxy groups are used for the binding of 3-bromopropionic acid. Example 5

Components in the order of 100 wt.% Are metered into the reaction vessel in an inert atmosphere. d. Polypropylene powder containing 14.2% bound poly- [2,3-epoxypropyl methacrylate], 55 wt. d. 3- (4-Hydroxy-3,5-di-tert-butyl) -phenylpropionic acid, 6.4 wt. d. Trihexalamine, 85 wt. d.m-xylene and 195 wt. d. dimethylformamide. Closing, the reaction vessel rotates in the thermostate.

Modification of the polymer takes place at 110 ° C. The reaction mixture is worked up in the same manner as in Example 1. After 6 hours of reaction, a solid phase is isolated in which 91.1% of the polar epoxide groups of the polymer are used for acid binding of 3 - (4 -hydroxy-3,5-di-tert-butyl) -phenyl-propionic acid Example 6

Components in the order of 100 wt. of polypropylene powder containing 14.2% bound poly- [2,3-epoxypropyl methacrylate], 20 wt. d.N-N-bis- (3-aminopropylpiperazine and 300 wt.% d.dimethylformamide. After closing, the reaction vessel was rotated in a thermostate).

The modification takes place at temperatures ranging from 25 to 90 ° C. The treatment of the reaction mixture is carried out by the same procedure as in Example 1. The following table shows the% utilization of the polar epoxide groups for the binding of N-N-bis- (3-aminopropyl) piperazine from the reaction temperature and the duration of the reaction: Reaction Time Temperature Zreag. epoxide hour ° C% 1 90 100.0 10 40 79.9 24 25 76.9 Example 7

Components in the order of 100 wt.% Are metered into the reaction vessel in an inert atmosphere. d. Polypropylene powder containing 14.2% bound poly- [2,3-epoxypropyl methacrylate], 40 wt. tert-dodecylmercaptan, 3 wt. d. triethylamine and 295 wt.d. dimethylformamide. After closing, the reaction vessel rotates in the thermostate.

The polymer modification proceeds at 110 ° C. The reaction mixture is worked up in the same manner as in Example 1. After 6 hours of reaction, a solid phase is isolated in which 83.4% of the polar epoxide groups are used to bind tert-decyl mercaptan. Example 8

Components in the order of 100 wt.% Are metered into the reaction vessel in an inert atmosphere. d. Polypropylene powder containing 14.2% bound poly- [2,3-epoxypropyl methacrylate], 26 wt. d-chlorophenol, 3 wt. d. triethylamine and 350 wt. doxyoxy. After closing, the reaction vessel is rotated thermostate.

The polymer modification proceeds at 110 ° C. The reaction mixture is worked up in the same manner as in Example 1. After 6 hours of reaction, a solid phase is isolated in which 91.0% of the polymeric polyoxide moieties are used for the binding of chlorophenol. Example 9

Components in the order of 100 wt.% Are metered into the reaction vessel in an inert atmosphere. d. Polypropylene powder containing 14.2% bound poly- [2,3-epoxypropyl methacrylate], 23 wt. d, 2,2,6,6-tetramethyl-4-aminopiperidine and 450 wt. dimethylsulfoxide. After closing, the reaction vessel is rotated in a thermostate.

Modification of the polymer takes place at 120 ° C. The reaction mixture is worked up in the same manner as in Example 1. After 6 hours of reaction, a solid phase is isolated in which 83.2% of the polymeric polyoxide moieties are used for 2.2.6. 6-tetramethyl-4-aminopiperidine. Example 10

In an inert atmosphere, the components in the order of 100 wt. d. Polyethylene powder containing 12.8% bound poly- [2,3-epoxypropyl methacrylate], 13 wt. d. Adipic acid, 0.4 wt. d. pyridine and 440 wt. d. dimethylformamide. After closing, the reaction vessel rotates in the thermostate.

The polymer modification takes place at 90 ° C. The reaction mixture was worked up in the same manner as in Example 1. After a 6-hour reaction,

Claims (1)

6 isolates the solid phase in which 98.3% of the polar epoxide groups of the polymer were used for adipic acid binding. EXAMPLE 11 Components in the order of 100 wt.% Are metered into the polymerization vessel in an inert atmosphere. d.polyethylene film (0.05 mm thick) containing 10.6% bound poly- [2,3-epoxypropylme-acrylate], 20 wt. d. 3-Phenylthiopropionic acid, 2.3 wt. d. triethylamine and 540 wt. d. dimethylformamide. Once closed, the reaction vessel is statically placed in a thermostate. The modification takes place at 110 ° C. The workup reaction is carried out in the same manner as in Example 1. After an 8-hour reaction, a solid phase is isolated in which 85.7% of the polymeric epoxy groups are used to bind 3-phenylthiopropionic acid. Example 12 In an inert atmosphere, the components in the order of 100 wt. polyvinyl chloride powder containing 13.5% bound poly- [2,3-epoxypropyl methacrylate], ARTICLE A method for fixing low molecular weight polymers to polypropylene, polyethylene and polyvinylchloride film, fiber and powder compositions containing from about 9.3% to about 0.5% by weight. 14.2% by weight of bound poly [2,3-epoxypropyl methacrylate] using compounds containing 1 to 4 reactive hydrogen atoms bound to oxygen, primary and secondary nitrogen or sulfur present in the aliphatic or alicyclic chain or to the aroma characterized in that 100 parts by weight of polypropylene, polyethylene or polyvinyl chloride containing from 9.5 to 14.2% by weight of bound poly- [2,3-epoxypropylmethacrylate] is modified with 12-55 parts by weight of a reactive hydrogen compound from the group consisting of dichloroacetic acid, 3-bromo-218602 15 wt. d. morpholine, 380 wt. d. hexane and 70 wt. dimethylformamide. After closing, the reaction period is rotated in the thermostate. The polymer modification takes place at 60 ° C. Treatment of the reaction mixture is carried out in the same manner as in Example 1. After a 6-hour reaction, a solid phase is isolated, of which 96.3% of the polymeric polysaccharide groups are used for morpholine binding. Example 13 In a polymerization vessel, components in the order of 100 wt. polyvinyl chloride film (0.04 mm thick) containing 10.9% bound poly [2,3-epoxypropyl methacrylate], 12 wt. d. dichloroacetic acid and 570 wt. d. heptane. Once closed, the reaction vessel is statically placed in a thermostate. The modification takes place at 60 ° C. The workup reaction is carried out in the same manner as in Example 1. After a 7-hour reaction, a solid phase is isolated in which 87.0% of the polymeric epoxide groups are used to bind the dichloroacetic acid. pionic, adipic, 3-phenylthiopropionic, 3- (4-hydroxy-3,5-di-tert-butyl) phenylpropionic acid, p-cyclohexylphenylacetic acid, o-chlorophenol, 7,5-diazadispiro [5,1,5,3 hexadecane, NN-bis- (3-aminopropyl-) piperazine, 2,2,6,6-tetramethyl-4-aminopiperazine, morpholine, diethanolamine and tert-dodecylmercaptan in the presence of 70-2080 parts by weight of organic solvents such as heptane, hexane, toluene , o-xylene, m-xylene, dimethylformamide, dimethyl sulfoxide or mixtures thereof, wherein the reaction may be carried out without a catalyst or with 0.4 to 6.4 parts by weight of a catalyst which may be triethylamine, tributylamine , trihexylamine, benzyldimethylamine or pyridine product formed is further isolated by filtration.