Derivatives of dihydropyridines and stabilized polymer composition

 

(57) Abstract:

Use: stabilization of polymers. Essence: polyvinyl chloride and polypropylene stabilizing effective amount of derivatives of dihydropyridines of General formula:

[(CH3)2(R1)NC5H5(CH3)2XOC(CH3)2NC5HOCX(CH3)2NC5H5(R1)(CH3)2]nX

where

n = 1, 2; R1= H, CH3; x = 0, N-R2, R2-H, C4H9; and if n = 1, y = H, if n = 2, y = -/CH2/6. 2 S. p. f-crystals, 10 PL.

The invention relates to new derivatives of dihydropyridines including substituted piperidinyloxy group. It relates also to the use of these compounds for thermal and light stabilization of polymers.

In the patent FR-A-2239496 described 2,6-dimethyl-3,5-in primary forms- -1,4-dihydropyridines as stabilizers of polyvinyl chloride (PVC).

In the patent EP-A-0005678 described synergism 2,6 - dimethyl-3,5-in primary forms-1,4-dihydropyridines with-diketones in relation to thermal stabilization of PVC.

These derivatives of 1,4-dihydropyridines have good efficiency for thermal stabilization of PVC. However, for some premeability to the light.

The invention relates to new compounds with 1,4 dihydropyridine group of General formula (I):

< / BR>
where:

n is 1 or 2,

R1represents a hydrogen atom or a methyl radical,

X represents an oxygen atom or a radical N-R2in which R2represents a hydrogen atom or botilony radical; and when n is 1, Y represents a hydrogen atom when n is 2, Y represents -(CH2)6-.

The compounds of formula (I) can be obtained by the method of Chance [Hantzsch, CHEM. Rew. 72, 1 (1972)] by carrying out the reaction of acetoacetic ester or acetoacetamide formula (II):

< / BR>
with an aldehyde of formula (III):

< / BR>
and an amine of the formula (IV):

< / BR>
where the symbols n, X, R1and Y in formulas (II), (III), (IV) have specified values for the formula (I). You can, for example, to apply the terms of the transactions described in Organic Synthisis, volume XIV, page 30, 1934.

If X represents a hydrogen atom, it is easier to use hexamine than a mixture of formaldehyde/ammonia. The exercise of this option is described in the patent of the USSR N 300465.

Acetoacetic esters and acetamide formula (II) can be obtained by reaction of diketene 4-hydroxypiperidine or with the corresponding 4-aminopiperidine FOIA, above for compounds of formula (I).

Among the compounds of formula (I) can be named as examples:

2,6-dimethyl-bis-3,5-[(1,2,2,6,6-pentamethyl-4 - piperidinyl)-oxycarbonyl] -1,4-dihydropyridines,

2,6-dimethyl-bis-3,5-[(2,2,6,6-tetramethyl-4 - piperidinyl)-oxycarbonyl] -1,4-dihydropyridines,

2,6-dimethyl-bis-3,5-[(2,2,6,6-tetramethyl-4 - piperidinyl)-aminocarbonyl] -1,4-dihydropyridines,

2,6-dimethyl-bis-3,5-[(2,2,6,6-tetramethyl-4 - piperidinyl)-N-butylaminoethyl]-1,4-dihydropyridines,

1,6-bis[2,6-dimethyl-3,5-bis[(1,2,2,6,6-pentamethyl-4 - piperidinyl)-oxycarbonyl]-1,4-dihydro-4-pyridinyl]-hexane.

The compounds of formula (I) can be used as thermal stabilizers and stabilizers to light in organic polymers. So, they can be used as anti-UV additives in polyolefins, polystyrenes, polyalkalene, polyurethanes, polyamides, polyesters, polycarbonates, polysulfone, polyethersulfone, polyetherketone, acrylic polymers, halogenated polymers, their copolymers and their mixtures.

The compounds of formula (I) are especially used in polyolefins and polyalkaline, such as polypropylene, polyethylene of low or high density, linear polyethylene is tsya composition of organic polymer, stabilized against the harmful effects of light and to ultraviolet radiation through effective amount of one or two compounds of formula (I).

Typically, these compositions contain from 0.004 to 20 milliequivalents group 2,2,6,6-tetramethyl-piperidinyl per 100 g of polymer. Preferably, the stabilized polymer compositions in accordance with the invention contain from 0.020 4 milliequivalents group 2,2,6,6-tetramethyl-piperidinyl per 100 g of polymer.

As an example, the stabilized polymer compositions contain from 0.01 to 5% by weight of compounds of formula (I). The addition of compounds of the formula (I) may be performed while receiving or after receiving the polymers. These compositions are organic polymers containing the compounds of formula (I) may contain other additives and stabilizers that are commonly used, for example:

antioxidants, as alkylated monophenol, alkylated hydrochinone, hydroxyl diphenyl sulfides, alkylidene-bis-phenols, benzyl compounds, aceraminophen, esters of 3-(3,5-ditretbutyl-4 - hydroxyphenyl)-propionic acid, esters of 3-(5-tetrabutyl-4-hydroxy-3 - were)-propionic acid, esters of 3-(3,5-dihydroxy-4-hydroxytryptophol radiation and stabilizers to light such as 2-(2'-hydroxyphenyl)-benzotriazole, 2-hydroxybenzophenones, esters of benzoic acid, possibly substituted, acrylic esters, compounds of Nickel, oxolamine,

the decontamination officers metals,

the phosphites and phosphonites,

connection-destroyers peroxides,

reagents okleinowania,

fillers and reinforcing agents,

plasticizers,

lubricants

emulsifiers,

pigments,

optical asurance,

protivovospalitel,

antistatic substances,

progeny.

The stabilized polymer compositions can be used in various forms, for example, in the form of molded articles, films, fibers, porous materials, profiles, or coatings, or as binders (binders) for paints, varnishes, adhesives or cements.

The compounds of formula (1) can also be used as stabilizers, for example, chlorinated polymers. In particular, in these polymers, they play the role of UV stabilizers and thermal stabilizers.

They can be used alone or in combination with other stabilizers, such as, for example, organic tin compounds. The compounds of formula (1) is also commonly used chlorine is their primary stabilizers are organic derivatives of zinc, calcium, barium, magnesium and strontium, and if hydrotalcite. Thus, compositions on the basis of stable chlorinated polymers may contain:

a) an effective amount of at least one organic zinc compounds;

b) an effective amount of at least one organic compounds of calcium, barium or strontium and/or hydrotalcite;

C) an effective amount of at least one compound from the group of 1,4-dihydropyridines of formula (1).

Chlorinated polymers are, in particular, polyvinyl chloride (PVC), polyvinylidenechloride, copolymers containing mostly parts of vinyl chloride derived from vinyl chloride and other monomers; mixtures of polymers or copolymers, in which the major part is derived from vinyl chloride.

Generally, any suitable type PVC, regardless of how you obtain it: polymerization in bulk, in suspension, in dispergirovannom state or another type, and regardless of its characteristic viscosity.

The homopolymers of vinyl chloride can also be modified chemically, for example by chlorination.

Copolymers of vinyl chloride can be copolymers obtained by copolymerization of visitengland maleic or fumaric acid and their esters: olefins, as for example, ethylene, propylene, hexene, acrylic or methacrylic esters, styrene, vinyl esters, such as finaldecision. Typically, these copolymers contain at least 50% by weight of vinyl chloride units and preferably at least 80% by weight of these links.

Preferred organic compounds of zinc are the carboxylates and the reaction zinc.

Most commonly used, for example, zinc salts of maleic acid, acetic acid, dvuhokonny, propionic, hexenoic, 2-ethylhexanol, decanoas, undecanoic, lauric, myristic, palmitic, stearic, oleic, ricinoleic, beganovic, hydroxystearates, hydroxyoctanoic, benzoic, phenylacetic, paratriathletes and salicylic acid; acids, the reaction of zinc phenol and phenols substituted by one or more alkyl radicals, such as, for example, nonylphenols.

In General organic zinc compounds are 0.005% to 1% by weight, relative to the chlorinated polymer, and preferably from 0.01% to 0.6% by mass.

Preferably, the organic compounds of calcium, barium, magnesium and strontium are the carboxylates and the reaction of these metals.

Most often used is th, hexenoic, 2-ethylhexanol, decanoas, undecanoic, lauric, myristic, palmitic, stearic, oleic, ricinoleic, beganovic, hydroxystearates, hydroxyoctanoic, benzoic, phenylacetic, paratriathletes and salicylic acid; the reaction of calcium, barium, magnesium and strontium phenol and phenol substituted by one or more alkyl radicals, such as nonylphenols.

In General organic compounds of calcium, barium, mania and strontium or hydrotalcite range from 0,005 to 5% by weight relative to the chlorinated polymer, and preferably from 0.02 to 2% by weight. For food applications, in particular for food bottles PVC, apply organic compounds of calcium or a mixture of organic compounds of calcium with organic compounds of magnesium.

Hydrotalcite that can be entered in compositions based on chlorinated polymers in accordance with the invention, instead of the organic compounds of calcium, barium, magnesium and strontium, or together with these compounds, in particular, are compounds that are described in the French patent FR-A-2433934 and in the European patent EP-A-0063180.

In the General case of compositions based on chlorinity. Preferably, they contain from 0.01 to 2% by weight of compounds of formula (1) relative to the chlorinated polymer.

Compared with the 1,4-dihydropyridines of the prior art, which are used as stabilizers chlorinated polymers, the compounds of formula (1) have at least the same efficiency from the point of view of resistance to yellowing, with the same mass, i.e., with fewer 1,4-dihydropyridine links, but they also have an efficient protective effect against UV radiation.

In compositions based on chlorinated polymer in accordance with the invention, naturally you can enter and also other additives.

In particular, it-diketones or b-keto-aldehydes, which have a synergistic effect with the compounds with the dihydropyridine group.

As non-limiting examples of such b-diketones can be listed benzoylthiourea, dibenzoylmethane, benzoylacetone, benzoyl-3-methyl-butanolate, methoxycarbonylbenzyl-benzoylmethyl, bis-b-diketones such as 1,4-bis(acetylacetonato)butane, 1,8-bis(benzoylacetone)octane, 1,4-bis(acetylacetone)benzene.

If they are, b-diketones are 0.005 to 5% by weight of p is availa able scientific C with the invention can have other secondary stabilizers such as, for example, polyols, phosphites, epoxy compounds.

The advantage of polyols is that they extend the service life of chlorinated polymers that undergo heat treatment. In the General case, it is preferable that the polyols used had a boiling point above 150oC and preferably above 170oC, because of the use of chlorinated polymers at elevated temperatures.

As examples of such polyols can be called trioli, as for example, trimethylolpropane, gliderol, 1,2,6-hexanetriol, 1,2,4-butanetriol, trihydroxyacetophenone; thetruly, as, for example, pentaerythritol, diglycerol; pentitol, such as xylitol, tetramethyldisiloxane; hexitol, such as mannitol, sorbitol, dipentaerythritol, polyols, partially esterified carboxylic acid and in the formula of which at least 3 free hydroxyl groups; polyvinyl alcohols, particularly alcohols, in which there is less than 30 mol%. ester groups in relation to the total number of ether and hydroxyl groups and which have a viscosity at 20oC 4-Ohm aqueous solution by weight in the range from 410-3to 6010-3Pass.

Among the polyols are preferred xylitol, Manito is in accordance with the invention, it is usually used 0.005 to 1% by weight of the polyol relative to the chlorinated polymer, and preferably from 0.01 to 0.6 mass%.

The epoxides that can be used in the compositions in accordance with the invention, are usually complex compounds, it is usually epoxy polyglycolide, as, for example, epoxydecane soybean oil, which is used most often, epoxydecane linseed oil, epoxydecane fish fats, epoxydecane fat.

Compositions in accordance with the invention may also contain organic phosphites, for example, aliphatic phosphites or aromatic phosphites, or mixed aliphatic and aromatic phosphites.

Most preferred the following phosphites:

diphosphite of pentaerythritol and diphenyl,

diphosphite of pentaerythritol and bis(2,4-ditertbutyl),

diphosphite of tetraalkyl and bis(1,4-phenylene)dimethylmethane,

diphosphite of tetraalkyl and bis(2,5-dialkyl-1,4-phenylene)alkylamine,

the diphosphite of diphenyl, bis[2-(2-butoxy-ethoxy)-ethyl] and 4,4'-isopropylidenediphenol,

the diphosphite tetrakis[(2-butoxy-ethoxy)-ethyl] and 4,4'-isopropylidenediphenol,

triphosphate of diphenyl, Tris[2-(2-yutaki-ethoxy)-ethyl] bis(4,4'-isopropyl-Christ.

the diphosphite of diphenyl, bis[2-(2-butoxy-ethoxy)-ethyl] and 4,4'-isopropylidenediphenol,

the diphosphite tetrakis[2-(2-butoxy-ethoxy)-ethyl] and 4,4'-isopropylidenediphenol,

triphosphate of diphenyl, Tris[2-(2-butoxy-ethoxy)-ethyl] bis(4,4'-isopropylidenediphenol),

TETRAPHOSPHATE of diphenyl, tetrakis[2-(2-butoxy-ethoxy)-ethyl] and Tris(4,4'-isopropylidenediphenol),

pentaphosphate of diphenyl, pentakis[2-(2-butoxy-ethoxy)-ethyl] and tetrakis(4,4'-isopropylidenediphenol),

hexaphosphate of diphenyl, hexacis[2-(2-butoxy-ethoxy)-ethyl] pentakis(4,4'-isopropylidenediphenol),

triphosphate pentakis[2-(2-butoxy-ethoxy)-ethyl] bis(4,4'-isopropylidenediphenol).

If they are used, the phosphites in the range of from 0.05 to 5% by weight relative to the chlorinated polymer, and preferably from 0.1 to 2% by mass.

Compositions in accordance with the invention can also contain conventional additives such as, for example, phenolic antioxidants, anti-UV agents, as, for example, benzophenone or benzotriazole.

Compositions in accordance with the invention can be rigid, i.e., without plasticizer, or semi-rigid, i.e. with a reduced content of plasticizer, for example, for applications in the construction of plastifitsirovannoj condition, for example, for the production of films for agriculture.

As usual, the introduction of various stabilizers or additives for chlorinated polymer in a powdered state.

Of course, you can get a mixture of 2 or more components in accordance with the invention prior to their introduction into the chlorinated polymer.

You can apply all the usual methods of introduction of various stabilizers or additives in polymers. For example, the homogenization of the polymer composition can be conducted in a roller mixer at a temperature when the composition becomes fluid, usually from 150 to 200oC for PVC, in sufficient time, of the order of from several minutes to several tens minutes.

Compositions based on chlorinated polymers, especially PVC, can be conventional, for example, by extrusion, by injection, extrusion-blowing, calendering and molding during the rotation.

The compounds of formula (I) are particularly effective as antioxidants in organic polymers mentioned above, i.e., such as polyolefins, polystyrenes, polyalkalene, polyurethanes, polyamides, polyesters, polycarbonates, polysulfones, polyethersulfone, polyester-Kyo is emery, copolymers and blends of these polymers.

As antioxidants, the compounds of formula (I) used are from 0.01 to 5% by weight of compounds of formula (VI) with respect to the weight of the stabilized polymer, preferably from 0.05 to 2% by mass.

It was also found that the compounds of formula (I) favorable in the sense that is usually called "adaptability" when thermoformed polymer.

Found that a polymer containing one or more compounds of the formula (I), during thermoforming is not destroyed (or few breaks), and does not form (or not form) cross-linking, as opposed to only one polymer or polymer containing either one or known connection with sterically hindered amine group, or one known connection with dihydropyridines group, or a mixture of these two types of connections. This is for polyolefins and especially for propylene.

The following examples illustrate the invention.

Example 1. Obtaining 2,6-dimethyl-bis-3,5-[(2,2,6,6-tetramethyl-4-piperidinyl)oxycarbonyl]-1,4-dihydropyridines

1A. Getting 4-acetoacetate-2,2,6,6-tetramethylpiperidine.

In a three-neck flask with a capacity of pomeshaut:

of 31.4 g (0.2 mol) 4-hydroxy-2,2,6,6-piperidine, 200 cm3toluene, 1 cm3of triethylamine (catalyst).

Heated with stirring at 70oC, then gradually over 30 min heats up to 16.8 g (0.2 mol) of diketene, keeping the temperature 70oC. This temperature is kept for 2 h 30 min after the end of the fill.

All these operations are carried out in nitrogen atmosphere.

Then remove the toluene, triethylamine and traces of diketene under reduced pressure by gradual heating:

a pressure of 2000 PA gradually decreases to 65 PA,

temperature of 20oC increases to 65oC by the end of the operation.

Get 48,1 g orange homogeneous oil, which after analysis method acidimetry shows 393 milliequivalent (mEq) per 100 g of b-keto ester group (in theory 414.9 mEq/100 g), which corresponds to a purity of 95%

The proposed structure is confirmed by IR spectra and mass spectra.

1 b. Obtaining 2,6-dimethyl-bis-3,5- [(2,2,6,6-tetramethyl-4-piperidinyl)oxycarbonyl]-1,4-dihydropyridines.

As described in example 1 and the apparatus placed 4 acetoacetate-2,2,6,6-tetramethyl-piperidine, obtained in stage 1A (concentration 95%): 38.05 g (0.15 mol 3.

The homogeneous reaction mixture is stirred and heated at 72oC for 2 h 50 min in nitrogen atmosphere.

After cooling, the pH was adjusted to 11.4 by adding 5N. alkali sodium. Then add 700 cm3water with vigorous stirring; a precipitate, which is dewatered, washed with water and dried under reduced pressure at 80oC.

Get to 26.8 g of a yellow solid substance with a melting point 189 - 190oC, almost pure, its IR spectrum and mass spectrum are in agreement with the proposed structure.

The net output of selected product in relation to the entered connection 1a is 75%

Example 2.

2A. Getting 4-acetoacetate-1,2,2,6,6-pentamethyl-piperidine.

Repeat example 1A, using 4 - hydroxy-2,2,6,6-tetramethyl-N-methyl-piperidine.

Get a yellow-orange oil, which after analysis acidimetry shows 369 mEq/100 g (according to theory of 292 mEq/100 g): purity of about 94%

2B. Obtaining 2,6-dimethyl-bis-3,5-[(1,2,2,6,6-pentamethyl-4-piperidinyl)oxycarbonyl]-1,4-dihydropyridines.

Repeat example 1, but replacing 4-acetoacetate-2,2,6,6 - tetramethylpiperidine the same molar quantities of ametal-4-piperidinyl)oxycarbonyl] -1,4-dihydropyridines in the form of hard yellow substance with a melting point of 232oC, whose structure is confirmed by IR spectrum, the spectrum of nuclear magnetic resonance (NMR) and mass spectrum.

Example 3.

3A. Getting 4-acetoacetamide-2,2,6,6-tetramethylpiperidine.

Repeat example 1A, but take 4-amino-2,2,6,6-tetramethyl - piperidine, the catalyst is not used, and prelivanje diketene carried out at 0 to 10oC, get 4 acetoacetamide-2,2,6,6-tetramethyl-piperidine in the form of a white solid with a melting point 115oC.

The output of the selected product in relation to the 4 - amino-2,2,6,6-tetramethyl-piperidine is 90%

3b. Obtaining 2,6-dimethyl-bis-3,5-[(2,2,6,6-tetramethyl-4-piperidinyl)aminocarbonyl]-1,4-dihydropyridines.

Into a flask of Erlenmeyer capacity of 100 cm3placed 1.50 g (0.05 mol) of formaldehyde, 21,3 g (0,089 mol) of 4-acetoacetamide-2,2,6,6-tetramethyl-piperidine, obtained in stage 3A, 20 cm3absolute ethanol, 5 drops of diethylamine.

The obtained homogeneous reaction mixture is left at 4oC for 24 h and then at room temperature for 48 hours

Then add to 4.6 cm3aqueous ammonia solution, with a content of NH3290 g/l (or 0,078 mol NH3).

In the distillation of the solvents under reduced pressure to obtain 23 g of orange solid, slightly pasty. This solid is dissolved in 200 cm3methanol and then precipitated by adding 500 cm3water with vigorous stirring. The precipitate is filtered, washed with water and dried under reduced pressure at 40oC.

Obtain 4.5 g of solid yellow substance with a melting point 170oC, which has the structure of 2,6-dimethyl-bis - 3,5-[(2,2,6,6-tetramethyl-4-piperidinyl)aminocarbonyl]-1,4-dihydro-pyridine confirmed by NMR spectra.

Example 4.

4A. Getting 4-N-n-butylacetoacetate - 2,2,6,6-tetramethyl-piperidine.

Conduct operations as in example 3A, but using 4-n-butylamino - 2,2,6,6-tetramethyl-piperidine and receive a 4-N - n-butylacetoacetate-2,2,6,6-tetramethyl-piperidine as a yellow viscous liquid with a purity of above 95%

4B. Obtaining 2,6-dimethyl-bis-3,5-[(2,2,6,6-tetramethyl-4-piperidinyl)n-butylaminoethyl]-1,4-dihydro-pyridine.

Repeat example 3, but using instead 4 - acetoacetamide-2,2,6,6-tetramethyl-piperidine substance obtained in stage 4A. Receive 2,6-dimethyl-bis-3,5-[(2,2,6,6-tetramethyl-4 - piperidinyl)n-butylaminoethyl]-1,4-dihydro-pyridine in the form of a white solid with a melting point of 172oC. IR system-3,5-(1,2,2,6,6-pentamethyl-4-piperidinyl-oxycarbonyl)-1,4-dihydro-4-pyridinyl]hexane.

Repeat example 3, but replacing formaldehyde on 3.55 g (0,025 mol) of octangula and using 4-acetoacetate-1,2,2,6,6-pentamethyl-piperidine, obtained in example 2A. Get (yield 70%) 19,7 yellow solid with a melting point of 110oC, its structure confirmed by NMR spectra.

Examples 6-11 and comparative tests A1 and A2.

Thermal stabilization of PVC.

Prepare the following basic composition:

PVC in powder form, obtained by polymerization or suspension, sold under the trademark LACOVYL SO 71 S (the viscosity index according to the standard NF T 51013:80) 1000 g, shockproof agent (copolymer of butadiene/styrene/methyl methacrylate): 80 g, grease, ester-based resin (wax E): 5 g, epoxy soybean oil: 30 g calcium stearate: 3 g zinc stearate: 2.5,

After homogenization in the cold in high-speed mixer to select 8 fractions of composition A. each of the fractions add some amount of the compounds obtained in example 2B (BPH/HALS, HALS light stabilizers containing blocked amines, approx. 2B), the compound of example 1B (BPH/HALS approx. 1B), example 5 (BPH/HALS approx. 5) or 2,6-dimethyl-bis-3,5-(dodecyloxybenzoyl)-1,4-dihydro-pyridine (BPH prior art) From the thus obtained compositions and from unmodified compositions And prepare sheets with a thickness of 1 mm, in the mixer with 2 cylinders for 3 min at 180oC.

From these sheets cut samples (1 cm x 2 cm) conduct test thermal ageing in a ventilated chamber at 180oC and observe the color change on Gardner.

In table. 1 shows the indices of the color on the Gardner that were measured at different duration of aging up to 30 minutes

Example 12 and comparative example B1.

Stabilization in UV-irradiated PVC

Prepare the base composition of the following composition:

PVC LACOVYL SO 71 S: 1000 g, the internal lubricant (mixture of hexadecanol and octadecanol): 14 g, grease wax E (based on the ester of rosin): 2 g, grease wax OP (on the basis of montanata propylene glycol, partially smilenov): 3 g, tiravanija stabilizer mixture of 75% by weight of dictyonema-bis (selfeducated of isooctyl) and 25% by weight of trioctylamine-(selfeducated of isooctyl).

After homogenization in the cold in mixer select 2 fraction of this composition Century. To each fraction or add 0,10 (100 g PVC) compounds of the formula (1) obtained in example 16 (BPH/HALS example 1B), or 0.10 g (Anna song get In the sheets with a thickness of 1 mm, by mixing in a mixer with 2 cylinders for 3 min at 180oC.

From these sheets get a film thickness of 200 μm using a disk press at 185oC.

Then these films are placed in a chamber for accelerated aging at 30oC, which includes a fluorescent lamp type 40 W, the emission spectrum of which 275 380 nm, with a maximum intensity of 310 nm.

In the visible spectrum observed optical density polyene chains (containing 10 conjugated double bonds) at a wavelength of 447 nm.

Over 750 hours of aging get listed in table. 2 values.

Anti UFJ 2-hydroxy-4-octyloxy-benzophenone (anti UV stabilizer is a benzophenone type, widely used for PVC) to the table. 2

You can see a very clear anti-UV action of the compounds of formula (1) obtained in example 1B, efficiency more than anti-UV effect widely used benzophenone. In addition, this efficiency has in the composition, thermally stable toolbarname the compound, which is known significant photosensitive effect.

Example 13. Photostabilization polypropylene (PP), type APPRYL 3030 R.

In a slow mixer prepare 300 g ka is:

the extruder brand THORET: screw diameter 20 mm,

screw length 400 mm,

the temperature profile: zone

200oC,

zone 2 220oC,

zone 3 220oC,

zone 4 230oC,

the head of the nozzle 215oC.

The resulting rod is granulated, and then the granules are pressed to a film thickness of 200 μm using a CARVER press under the following conditions:

temperature 200oC,

time 5 min,

the pressure of 20 MPa.

These films were placed in the chamber of accelerated aging type SAIRAM-SEAP 12 24. In this chamber the samples were placed on a cylindrical drum that rotates. The drum itself was located in the center of the camera in the form of a parallelepiped, the corners of which were mercury lamps "medium pressure" type MAZDA MA 400 watts.

The bulb pass only wavelengths greater than 300 nm (such a device is described in French patent 2430609). The temperature in the chamber was maintained 60oC using the control.

The aging of the films was measured by the IR-spectrometer: optical density of the carbonyl band at 1720 1740 cm-1shows the degree of photo-oxidation of polymeric material. The results are shown in table.4.

Example 14. Photostabilization levy antioxidant IRGANOX 1076 IRGANOX 1076 3-(4-hydroxy-3,5-ditretbutyl-phenyl)-propionate octadecyl 0.05 g

Calcium stearate 0.10 g

Investigational anti-UV (see tab. V) 0 or 0.15

Conduct dry homogenization in a slow mixer for 5 minutes these different mixtures.

Then produce sheets by passing for 5 min at 170oC through the mixer with two cylinders. These sheets are made of a film thickness of 200 μm using a press SHABESTAN, under the following conditions:

contact: 2 min at 220oC,

pressing: 1 min at 37 MPa (370 bar).

Then, the resulting film was placed in the chamber for artificial aging, which is equipped with fluorescent lamps of 400 W: spectrum in the range of 275 to 380 nm with a maximum of 310 nm. The temperature of the chamber 55oC with an atmosphere of saturated humidity.

Then, as in the previous example, monitoring changes in optical density of the carbonyl band 1720 1740 cm-1that shows the degree of aging of the polymer.

The following results were obtained (the length of aging, which is necessary for obtaining an optical density of 0.3).

Example 15. Thermomechanical stability of polypropylene mark VB 65 11 B company Neste

In the rapid mixer prepare each of the following mixtures, the composition of which is the VILLAGE. Temperature stirring was maintained 220oC.

Acting on the mixture of the moment of forces was measured over time. Thermomechanical stability was defined as the ratio of the moment of forces, acting on each of the mixtures from the N to the U to the moment of forces acting on the mixture of N, 15 min after the application of thermo-mechanical stress. The higher the ratio, the better thermomechanical stability.

In table.7 shows the values of the stability of various compositions.

Example 16. Thermo-mechanical stabilization of polypropylene mark VB 65 11 B company Neste

In the conditions of example 15 was measured thermomechanical behavior of the compositions, the composition of which is given in table.8.

In table.9 represents the magnitude of thermo-mechanical stability, measured for different compositions.

Example 17. The heatset polypropylene mark VB 65 II B.

Separately prepare 4 a mixture of the following composition polypropylene 100 g, antioxidant IRGANOX 1076 0.05 g, Ca stearate 0.1 g, the stabilizer (see table. 10) 0 or 0.15 g

Each of these mixtures are homogenized for 5 min in a high-speed mixer. Then produce leaves by mixing in the mixer with the cylinders when Yah:

contact: 40 s at 220oC

pressing: 2 min at 2.1 MPa.

Obtained under these conditions the plate had a thickness of 1 mm, Then these plates were placed in a ventilated chamber at a temperature of 150oC. Thermal degradation of the polymer was determined by the appearance of microcracks, which caused the fragility of the polymer.

1. Derivatives of dihydropyridines of General formula

< / BR>
where n=1 or 2;

R1hydrogen or methyl;

X is oxygen or a radical N R2in which R2hydrogen or butyl; moreover, if n=1, then Y is hydrogen; if n=2, then Y is the group - (CH2)6.

2. Stabilized polymer composition comprising polyvinyl chloride or polypropylene, and derivatives of dihydropyridines as a stabilizer, characterized in that as a derivative of dihydropyridine it contains an effective amount of the compounds on p. 1.0

 

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The invention relates to a filler with a modified surface for thermoplastics

Polymer composition // 2078104
The invention relates to the field of phenolic and refers in particular to compositions containing Novolac phenol-formaldehyde resin, filled with wood flour mixed with mineral filler

The invention relates to compositions of mixtures, processed by way of injection molding and can be used for the manufacture of products for General purposes

The rubber mixture // 2070900
The invention relates to rubber mixtures based on unsaturated rubber and can be used in the tire industry

The invention relates to a rubber mixture based on butyl rubber and can be used in the tire industry

The rubber mixture // 2068857
The invention relates to rubber mixtures based on unsaturated rubber and can be used in the rubber industry for the production of rubber products
The invention relates to methods for C-alkylimidazole, in particular 2-substituted imidazoles

The rubber mixture // 2044006
The invention relates to the rubber industry, in particular to the rubber mixtures, and can be used for gammirovanie shafts used in textile finishing machines of continuous action (plyaski, washing and impregnating bath and others)

The invention relates to new derivatives of pyridine and their salts, to a method for their herbicide composition containing a specified derivative as an effective ingredient, and to a method of controlling weeds
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