SU721008A3 - Polymeric composition - Google Patents

Description

Enuda Leni of two hydroxyl JES hydroxy acids, alkylene group, yryl group OR or arylendialkylene group.

If n is 3, then R means triatsilovuyu group derived from an aliphatic, aromatic or heterocyclic tricarboxylic acid, trikarbamoilgruppu, proish d extending from trikarbaminovoy acid tristiokarbamoilgruppu derived from an tristiokarbaminovoy acid mE ehvapentnuyu group derived coup removal of three hydroxyl groups of oksikisl : ata, alkantriylgroup, areentriylgroup or areentriyltrialkylenegroup.

However, the resistance of the composition to combustion is not high enough

The purpose of the invention is to increase the resistance of the composition to thermo-oxidative degradation.

This goal is achieved in that the polymer composition comprising a polymer selected from the group comprising a polyolefin, an acrylonitrile butadiene styrene copolymer and a poly urethai and a piperidine derivative contains a compound as a piperidine derivative

2 I

 Vo-f-R

W,

J1

not

HH,

3

 -or 2 ;

15, acetyl, phenylcarbamoyl,

butylcarbamoyl, acryloyl, - metacryloyl or cyclohexylcarbamoyl; . with acetyl, benzoyl, stearoyl, phenylcarbamoyl, butylcarbamoyl or cyclohexylcarbamoyl,:; . - t - CH- (1 -

II o

II o

or

- C 1CH.17r with II 0 II,

wow

in the following ratio of components, wt.% :.

Polymer 98-99.95

Derivative piper- 0.05-2

Dina

Examples of compounds used according to the invention are the following:. .

1-Acetyl-2,2,6, b-tetramethyl-4-acetyl xypiperidine

1-Acetyl-2,2,6, b-tetramethyl-4-benzyloxypipe Tridine

1-Acyl-2,2, b, b-tetrameth11L-4ggstearoyloxypiperidine

1-Acetyl-2,2,6, b-tetramethyl-4-benzoyloxypiperidine

1-Atsvtil-2, 2,6, 6-tetrag "1-methyl-4-butyl bamoyloxypiperidine

1-Acetyl-2,2,6,6-tetramethyl-4- (4-methoxyphenyl) -carbamoyloxypiperidine

1-Acetyl-2,2,6,6-tetramethyl-4-cyclohexylcarbamoyloxypiperidine 5 1-Lcryloyl-2,2,6,6-tetramethyl-4-benzoyloxypiperidine

1 - (- phenylpropionyl) -2,2,6,6-tetramethyl-4-phenylcarboxylic piperidine

"L 1-methylcarbamoyl-2,2,6,6-tetra-. methyl 4-stearloxypiperidine

1-Cyclohexylcarbamoyl-2,2,6,6-tetramethyl-4-cyclohexylcarbamoyloxypiperidine

1-Phenylcarbamoyl-2,2,6,6-tetra 5 methyl-4-benzoyloxypiperidine

Bis- (1-aietil-2,2,6,6-tetramethyl-4-piperidinyl) oxalate,

Bis (1-a1: ethyl-2,2,6,6-tetramethyl-4-piperidinyl) -isophthalate 20 Bis (1-methacryloyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate

Bis- (1-methylcarbamoyl-2,2,6,6-tet.;., Ramethyl-4-piperidinyl) succinate

Diphenylmethane-4,4-bis (1-acetyl25 -2,2,6,6-tetramethyl-4-carbamoyloxypiperidine)

The compounds used according to the invention can be prepared by known methods. For example, 2,2,6,6-tet30 ramethyl-4-hydroxy-piperidine is first substituted in position 1 with a residue previously defined as RI and the N -substituted 4-hydroxy-piperidine thus obtained, then by a known esterification method into an ether or ester or by reaction with isocyanate, in each case, the ester, ether, or urethanes are converted.

Alternatively, 2,2,6,6-tetramethyl-4-hydroxypiperidine can be replaced first in the hydroxyl group and then replaced with the NH-ppine. For the replacement of the spatially hindered NH-groups in this case, they are primarily suitable for reactions with chlorides or carboxylic acid hydrides, on the one hand, and reactions with isocyanates, on the other. If R and RU are the same. It is possible for both 0 substituents to enter into one reaction stage. The conduct of such substitution reactions is described in more detail in the examples.

The compounds of formula I give polyolefins a high degree of stabilization against decomposition by heat or photochemical decomposition, especially against UV rays. Thus, the method of the invention is suitable primarily for protecting 0 polyolefins from light. . The compounds of the formula I, not only in comparison with conventional commercial heat stabilizers, but also in comparison with the known compound 1, 5, are distinguished by an improved solubility in polymers, especially in polyolefins with the same or superior effect.

Another advantage of the compounds of formula 1 is that they: do not stain the substrate, but, vice versa, protect it from color by exposure to light and heat.

Examples of polyolefins are polyethylene, polypropylene and high-density and low-density polystyrene, polymers butene-1, 3-methylbutene, pentene-1, and co-and terpolymers of olefins, in particular, ethylene or propylene.

Other polymeric photosensitive materials whose properties are improved by the addition of the proposed compounds to them are, for example, natural and synthetic rubbers, the latter, for example, including the homo, co and terpolymers of acrylonitrile, butadiene and styrene.

In addition, polyvinyl chloride, copolymers of vinyldene chloride and vinyl chloride, polyvinyl acetate, as well as condensation polymers and addition polymers containing groups of ethers and esters (monocarboxylic acids, sulfonic acids or carbonic acids), amides or urethanes are suitable for carrying out the proposed method. These polymers can be the basis, for example, in paints and varnishes. Stabilizers are introduced into the polymer material by known methods. For example, it is possible to mix the stabilizer with the polymer in a closed mixer. The stabilizer can be introduced in the form of a solution or suspension. In a suitable solvent or dispersant, for example methanol, ethanol or acetone, into a powdered polymer, the mixture can be stirred in a mixer, and then the solvent is removed. The stabilizer can also be added to the polymers during their preparation, for example, at the latex stage, in which case a pre-stabilized polymeric material is obtained.

Other known substances that are common to polymer compositions, for example phenolic or amine antioxidants, UV absorbents and light stabilizers, emollients, lubricants and flame retardants, pigments, carbon black, asbestos, glass fiber, kaolin, talc can be added to the composition according to the invention. and other targeted supplements.

Below are examples that clarify the invention, but do not limit it.

Para and p 1. 3.14 g of 2,2,6,6-tetramethylpipteridinol-4- and 3.50 g of acetic anhydride are heated (1 hour in steam bath. Then add

20 ml of water and heated for another 1 hour. After neutralization with NaHCOj solution, the solution is extracted several times with ether, the ether solution is dried with sodium sulfate and evaporated. AT

1-acetyl-2, 2, 6,6-tetramethyl-4-acetoxypiperidine is obtained, which, after drying in vacuum, melts at 33-34 C.

Cleaned yono,%: C 64.73; H 9.45;

0

N 5.81

 Hti

Found,%: C 64.51; H 9.69;

N 5, 67. Examples 2-5. 130 g

5 2,2,6,6-tetramethyl-4-benzoyloxypiperidine is heated with 200 g of acetic anhydride for 12 hours ZZ-EO C. Then an excess of anhydride. And the resulting acetic acid is completely distilled off

0 in a vacuum. The oily residue is dissolved in 400 ml of hexane while still warm. During cooling, the product crystallizes out. It is filtered, washed first with cold.

5 hexane, and then with water and dried. Get 1-acetyl-2,2,6,6-tetramethyl-4-benzoyl-oxypiperidine with so pl.

If instead of 2,2,6,6-tetramethyl-4-benzoyloxypiperidine, the appropriate amount of 2,2,6,6-tetramethyl-4-kaprioyloxypiperidine, or 2,2,6,6-tetramethyl-4-stearoyloxypiperidine is used, or bis, (2,2,6,6-t. tetramethyl-4-piperidinyl) sebacate, and otherwise proceed as described in example 1, 1-acetyl-2,2,6,6-tetramethyl-4- is obtained caprinonexypiperidine or 1-acetyl-2, 2,6,6-tetramethyl-4-stearoyl 0 hydroxypiperidine with so pl. 52 f. Or bis

(acetyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate with m.p.

Examples 6-7. 39.2 g

5 2,2,6,6-tetramethyl-4-benzoyloxypiperidine is dissolved in 250 ml of toluene. To this solution is added dropwise, stirring the solution out at room temperature. 18 g of phenyl0 isocyanate in 50 ml of toluene. Then the reaction mixture was stirred for 5 hours at 80 ° C and another 5 hours under reflux. The reaction solution is evaporated in vacuo and the residue is crystallized from hexane. Phenylcarbamoyl-2, 2,6,6-tetramethyl-4-benzoyloxypiperidine is obtained. 1, which melts at a temperature of approximately 80 ° C with decomposition.

If an equivalent amount of bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate is used instead of 2,2,6,6-tetramethyl-40 f-benzoyloxypiperidine, 9 for the rest. Proceed as described in Example 1 get

5 bis (1-phenylcarbamoyl-2,2,6,6-tetra

Claims (1)

., Claim A polymer composition comprising a polymer selected from the group consisting of polyolefin, acrylonitrile copolymer and po20 liuretan and a piperidine derivative of r l and h and w u ¹ and I with I that, for the purpose, increases, the resistance of the composition to photochemical and tormookislitelnoy destruction, it contains 25 in. as a piperidine derivative, a compound of the formula Food Editor T, Ushakov a _n = 1 or 2; R ₍ - acetyl, phenylcarbamoyl, butylcarbamoylacryloyl, methacryloyl or cyclohexylcarbamoyl; P _g - with n = 1 - acetyl, benzoyl, stearoyl, phenylcarbamoyl, butylcarbamoyl or cyclohexylcarbamoyl, with η = 2 - and pi II o (CH _g ) _g 0 - II About the following ratio of components, wt.% Polymer '98 -9 9.9 5 Derivative 0.05-2 50 piperidine