DE2264991B2 - SYNTHETIC POLYMERS COMPOSITION STABILIZED AGAINST PHOTO AND THERMAL DECOMPOSITION - Google Patents

Description

R ₁ O OR ₁

H ₃ C

(1)

and

(11)

The invention relates to a synthetic polymer stabilized against photo- and thermal decomposition Composition, which is characterized in that • ie 0.01 to 5.0 percent by weight, based on the amount the synthetic polymer, a compound selected from the group consisting of the 4-piperidone ketal derivatives of the formulas

wherein Ri represents an alkyl group having 1 to 8 carbon atoms, and wherein Ri represents an alkylene group having 2 or 3 carbon atoms or O-phenylene group.

2. Synthetic polymeric composition according to claim 1, characterized in that the 4-piperidone ketal derivative is selected from the group consisting of 4,4-di-n-butoxy-2,2,6,6-tetramethylpeperidine, l ^ -Di-oxa-e-aza-ZJ. ^ - tetramethyl-spiro- [4,5] -decari and 4,4- (0-phenylenedioxy) -2,2,6,6-tetramethylpiperidine.

R ₁ O

(D

CH,

contains incorporated, wherein Ri is an alkyl group with 1 represents up to 8 carbon atoms and wherein R2 represents an alkylene group having 2 or 3 carbon atoms or Represents O-phenylene group.

In the above formulas (I) and (II), Ri can represent Methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl, hexyl, heptyl and octyl; and R: can mean, for example, ethylene, trimethylene. Propylene and O-phenylene.

The term "synthetic polymer" as used herein is intended to encompass polyolefins, including Homopolymers of olefins such as polyethylene, polypropylene, polystyrene, polybutadiene, polyisoprene and the like of low or high density, and copolymers of olefins with other ethylenically unsaturated Monomers, such as ethylene-propylene copolymer, ethylene-butene copolymer, Ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene-butadiene copolymer and the like; Polyvinyl chlorides and polyvinylidene chlorides, including homopolymers of each Vinyl chloride and vinylidene chloride, vinyl chloride-vinylidene chloride copolymers, and copolymers of each of vinyl chloride and vinylidene chloride with vinyl acetate or other ethylenically unsaturated monomers; Polyacetals, such as polyoxymethylene and polyoxyethylene; Polyesters such as polyethylene terephthalate: polyamides such as 6-nylon, 6,6-nylon, and 6,10-nylon; and polyurethanes.

Synthetic polymers are widely used because of their excellent properties found in various shapes and designs, for example as threads, fibers, yarns, films, Sheets and other molded objects, latex and foam. However, these polymers have some disadvantages, such as low light and heat stabilities and the like. For example, polyolefins and polyurethane elastomers tend to be often cause severe decomposition when exposed to light, such as sunlight or ultraviolet rays, and polyvinyl chloride and polyvinylidene chloride tend to decompose and become common discolored by the action of light and heat with simultaneous excretion of hydrogen chloride. Polyamides are also often subject to photodecomposition. For the purpose of stabilizing this A number of stabilizers have already been proposed for synthetic polymers against such degradation been; for example, for polyolefins, benzotriazole compounds and benzophenone compounds; for polyurethanes Phenolic compounds and benzophenone compounds; and for polyvinyl chloride and polyvinylidine chloride Lead salts such as basic lead silicate and tribasic lead maleate. and organic tin compounds, such as dibutyl tin laurate and dibutyl tin maleate.

While such known stabilizers have generated considerable satisfaction, they are still some problems remained to be improved. Therefore

Numerous attempts have been made in the art to find new and more effective stabilizers and develop.

As a result of extensive studies, it has now been found that the new 4-piperidone ketal derivatives (I) and (II) according to the present invention have a high stabilizing effect against photo and thermal Exercise decomposition of synthetic polymers.

Representative examples of the 4-piperidone ketal derivatives of the above formulas (I) and (II) are as follows:

Connection no.

Chemical name

1 4,4-diethoxy-2,2,6,6-tetramethy ¹ piperidine

2 4,4-di-n-butoxy-2 ^, 6,6-f; tramethylpiperidine

3 4,4-di-n-octoxy-2,2,6,6-tetramethylpiperidine

4 l ^ Dioxa-e-aza-yjAg-tetramethyl-spiro- [45} -decane

5!, S-Dioxa ^ -aza-S & 10.10-tetramethyl-spiro- [55] -undecane

6 4,4- (o-phenylenedioxy) -2,2,6,6-tetramethy! -
piperidine

The inventively used 4-Piperidonke- ₂ $ talderivate accordance with the procedure described (22 03 533 DT-OS) are produced in the parent application.

The 4-piperidone ketal derivatives (I) and (II), which are used according to the invention as stabilizers, can be incorporated into the synthetic polymers by any of several standard methods which are conventionally used can be conveniently incorporated. The stabilizer can be used in the synthetic polymers any desired stage prior to the manufacture of articles made therefrom. For example, the stabilizer can be in the form of a dry powder with the synthetic polymer be mixed, or a suspension or emulsion of the stabilizer can be mixed with the solution, suspension or Emulsion of the synthetic polymer are mixed.

The amount of the 4-piperidone ketal derivatives (I) and (II) which according to the invention in the synthetic Polymer used can vary widely depending on the types, properties and the particular uses of the synthetic polymers to be stabilized. In general the 4-piperidone ketal derivatives of the formulas (1) and (II) can be used in an amount ranging from 0.01 to 5.0 Percent by weight based on the amount of synthetic polymer added is practical Range depends on the type of synthetic polymer and is 0.01 to 2.0 weight percent, preferably 0.02 to 1.0 percent by weight for polyolefins; 0.01 to 1.0 percent by weight, preferably 0.02 to 0.5 percent by weight for polyvinyl chloride and polyvinylidene chloride; and 0.01 to 5.0 percent by weight, preferably 0.02 to 2.0 percent by weight for polyurethanes and polyamides.

According to the invention, the stabilizer can be used alone or in combination with other known antioxidants, ultraviolet absorbers, fillers, Pigments and the like

Optionally, two or more of the 4-piperidone ketal derivatives of the formulas (1) and (II) can be used according to the invention with advantage.

For a better understanding, the invention is explained in more detail by the following examples. In the Examples are all parts, unless otherwise specified, parts by weight, and the number of The test connection used below is the same as the one given above.

example 1

In 100 parts of polypropylene (used after two Recrystallization from monochlorobenzene) were 0.25 parts of each of the inventions given below Test Compounds Incorporated The resulting mixture was mixed and melted and then formed into a plate 0.5 mm thick with the application of heat and pressure

As a control for comparison, a polypropylene plate was prepared in the same manner as the above described, but without any stabilizers, manufactured-

Then, all these plates to the embrittlement thus formed were (among which the one time, expressed in hours, is to be understood to the test plate brittle is) tested under ultraviolet irradiation at a temperature of 45 ⁰ C by means of a fade meter described in Japanese Industrial Standard JIS -1044 entitled "Testing Method of Color Fastness to Light of Dyed Textiles and Dyestuffs", Paragraph 3.8 (in English)

The results are shown in Table 1 below compiled.

Table 1

test Embrittling link Time No. (Hours) 2 620 3 860 4th 960 6th 1000 No 100

Example 2

In 100 parts of high density polyethylene (used after two recrystallization from toluene) were 0.25 parts of the test compounds according to the invention given below were incorporated. The resulting mixture became a plate with a thickness of 0.5 mm by the same procedure as in Example 1 above processed.

The panels thus formed were checked for the embrittlement time by the same method as in the above Example! 1 tested.

The results are compiled in Table 2 below.

Table 2

Test connection

No.

Embrittlement time
(Hours)

2 1400 4th 1580 6th 1920 No 400

Example 3

In 100 parts of 6-nylon (containing no stabilizer) was 0.25 parts of each of the below

test compounds according to the invention incorporated. The resulting mixture was heated and melted and then through a conventional injection molding machine Print formed into a film having a thickness of about 0.1 mm. The film thus formed was under the aged following aging conditions and then subjected to an ultimate tensile test to ensure the retentions the tensile strength and elongation due to tine Stand.-ydmelhode to be determined.

IO

Aging test

1. Exposure to ultraviolet radiation for 300 hours in the fadeometer described above 45 ° G

2. Aging at 160 ^° C. for 2 hours in Geers aging tester, described in Japanese Industrial Standard JIS-K-6301 with the title "Physical Testing Methods for Vulcanized Rubber", Paragraph 6.5 (in English).

The results are compiled in Table 3 below

Table 3 Table 4

Test- Fadeometei Retention Geers aging tester 160 ° C) ver ■ the (2 hours, Retention am- (after 300 hours) Tear Retention the manure Retention strength
(%) the Tear No. the 53 strain strength
(%) strain 55 (%) 67 2 (%) 67 64 68 3 65 67 69 71 4th 71 38 68 69 6th 72 example 70 52 No 74 7th 6th 4th

35

In 100 parts of polyurethane made from polycaprolactone, there were 0.5 parts of each of the below stated test compound according to the invention incorporated. The resulting mixture was heated and melted and then formed into a plate about 0.5 mm thick. The plate thus formed became at 45 ° C for 15 hours in the example above 1, the fadeometer illustrated was exposed to ultraviolet radiation and then applied to the retentions the elongation and tensile strength tested as in Example 3 above.

The results are shown in Table 4 below.

Tesa connection
No.

Retention of

strain

Retention of

Attrition wedge

2 85 92 4th 88 89 6th 95 94 No 75 53

Example 5

In 100 parts of polyvinyl chloride, 1.0 part of lead stearate was 0.5 part of dibasic lead phosphite, 0.5 Parts of barium stearate, 0.5 parts of cadmium stearate and 0.2 Portions of each of the test compounds of the present invention set forth below are incorporated into the obtained Mixture was mixed and kneaded on a kneading drum for 4 minutes to make a plate having a thickness of 0.5 mm. The panel was tested by the aging test method described below tested for their degree of discoloration

Aging test

1. exposure to the sunshine carbon arc apparatus for 600 hours, described in Japanese Industrial Standard JlS Z-0230 entitled "Accelerated Weathering Test of Rust Proofing Oils", Paragraph 2.

2. The plate was aged for 90 minutes at 170 ^° C. in the Geers aging tester described in Example 3 above.

The results are shown in Table 5 below.

Table 5

Test discoloration
Sunshine coal no. arc apparatus

(after 600 hours)

Geers aging tester (after 90 minutes,
170 ⁰ C)

2
4th
6th
No

pale yellow
pale yellow
light yellowish
dark brown

yellow
pale yellow
light yellowish
black

From the above results it can be seen that the 4-piperidone ketal derivatives according to the invention are based on synthetic Polymers exert a stabilizing effect against their decomposition to a high degree.

Claims (1)

and claims: 1. A synthetic polymer composition stabilized against Ph:> to- and thermal decomposition, characterized in that it is 0.01 to 5.0 percent by weight, based on the amount of the synthetic polymer of a compound from the group consisting of the 4-piperidone ketal derivatives of the formulas