DE1694923A1 - Polymers containing molding compounds, cyclic esters of hydroxycarboxylic acids and stabilizers - Google Patents

Description

description to the patent application

SHELL IM ¹ EHNASIOIiALE EESSAECH IvLAATSGEiIPPIJ N. 7. 30, Garel Tan Bylandtlann, Hague, The Netherlands

concerning

Molding compositions containing polymers of cyclic esters of hydroxycarboxylic acids and stabilizers

The invention relates to the stabilization of polymers based on cyclic esters of hydroxycarboxylic acids or, in other words, molding compositions consisting essentially of 'polymers of cyclic esters of hydroxycarboxylic acids exist.

The stabilization to which the present description relates, can be defined as the prevention or reduction of by the action of ultraviolet rays such as of sunlight, caused decomposition, degradation or discoloration of the polymer molecules _e

Contain the esters to be stabilized according to the invention

109833/1848

BATH

the group E ¹
1 O
. ti -O- E ³
ι -G-
■ ϊ O G -
ι

wherein R, R, R and R are usually hydrogen or a hydrocarbon radical, but in some cases. represent an atom other than hydrogen (e.g. halogen) or a group other than a hydrocarbon radical (e.g. an alkoxy group or a type of aryloxy group). The various hydrocarbon radicals can be the same or different. In addition, one or more hydrogen atoms in these hydrocarbon radicals can be substituted by other atoms or groups. The number of carbon atoms in each of the groups R, R, R and R is usually not more than 10 _e

The chain shown in the structural formula above is part of a ring. The part of this ring not shown may be a carbon chain connecting the terminal carbon atoms shown in the picture to one another; in in this case the cyclic ester is a lactone. This carbon chain usually contains 2 to 5 carbon atoms. The cyclic compound is also a lactone, namely a β-lactone if the terminal carbon atoms shown are directly connected to each other. aside from that

= ■. '■ - - 3 »»

109833/184 »

BATH ORIGINAL

can be the terminal carbon atoms of the Formula also by a second carbonyloxy group with one another be connected. This is the "pail" for glycolide and lactides, which is represented by the general formula

ir.. "■" _

r1 JJ - q, έ?

be played back _c

The term used in the present specification, "polymers ^u .schließt both homopolymers and copolymers a _c The copolymers may be copolymers of various cyclic esters" inter se be of hydroxycarboxylic acids or copolymers of one or by copolymerization of one or more cyclic esters of hydroxycarboxylic acids with more Compounds that can take part in this polymerization, such as epoxy compounds, are obtained «

Very suitable polymers are ^s_: ölche whose polymer chains consist of linear polyester chains "These polymers can äurch ring opening of the cyclic ester

ORIGINAL

while forming a linear structure that is at least contains a carbonyloxy group, and subsequent polymerization of the linear structure obtained can be obtained. Of course, you can take part in this polymerization again one or more comonomers participate ",

The invention is of particular importance for the stabilization of linear polyesters obtained by polymerizing lactones, especially β-lactones. Preferred β-lactones are L., -Dialkyl-β-propiolactones, in which each of the alkyl groups contains at most 4 carbon atoms . In these compounds, the two alkyl groups can be linked together with the ** ¹ · carbon atom to form a cyclic structure; this is the pail for example with 2-0xa-4-spiro _< / 3,67 ~ decanon-1. The simplest and at the same time the most important representative of the dexifi , <h -dialkyl-ß-propiolactone group is "- pi-dimethyl-ß-propiolactone.

The invention thus relates to preparations which essentially consist of polymers of cyclic esters of hydroxycarboxylic acids exist and is characterized by the fact that these connections have one or more phemical connections contain, in which two aromatic rings inter se by a carbonyl group, a garbonyloxy group or a ..

109833/1848 - ■ ^ 8Of

. , ■ --.-- '"" -Ο BAD ORIGINAL

■ - 5, -

ö group of 3 nitrogen atoms, one with one of the aromatic rings condensed 1, 2, 3 - triazole configuration belong, are connected »The term" ring "in this context means both individual rings as well as ring systems of at most two confused individuals Understand wrestling. Be with the term "aromatic" in the present description denotes rings or ring systems of an aromatic nature, i.e. planar cyclic structures with fluctuating "^ electrons"

In addition to one or more phemical hydroxyl groups, the aromatic rings can also contain one or more contain several other substituents in the ring. These hydroxyl groups and other substituents can be the same Ring or belong to different rings. Examples for other substituents are alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy and aryloxy groups

Very suitable phenolic compounds according to the invention as light stabilizers which can be used are those containing a 2-hydroxyphenyl group, the may contain other substituents in addition to the hydroxyl group.

Examples of the compounds having a 2-hydroxyphenyl group are the alkylphenyl esters of salicylic acid,

- 6 109033/1848

OBlGtNAL

e.g. 4-tert-butylphenyl salicylate and 4-n-dodecylphenyl salicylate and further in particular the 2-hydroxy-4-alkoxybenzophenones and 2,2'-dihydroxy-4-alkoxybenzophenones including, for example, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-n-octoxybenzophenone and 2,2'-dihydroxy-4-nmethoxybenzophenone include »

Excellent representatives of the light stabilizers with a 2-hydroxyphenyl group are in particular also the

φ 2- (2'-hydroxyphenyl) -benzotriazoles, including, for example, 2- (2 ^f -H $ idroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5 ^! -tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5'-amylphenyl) benzotriazole, 2- (2'-hydroxy-5'-n-nonylphenyl) benzotriazole, 2- (2'-hydroxy-5 ' -cyclohexylphenyl) benzotriazole, 2- (2'-hydroxy-4-carboxymethoxyphenyl) -benzotriazole, 2- (2'-hydroxy-5-carboxyniethyl-phenyl) benzotriazole, 2- (2 '^' - dihydroxyphenylobenzotriazole, 2- (2 ', 4-dihydroxy-5-chlorophenyl) benzotriazole, 2- (2'-hydroxy-3'»5'-

^ dimethylphenyl) -5-methyl-benzotriazole, 2- (2'-hydroxy-4-noctoxyphenyl) benzotriazole and 2- (2'-Hydroxy-5-n-octoxyphenyl) -benzotriazole *

Examples of the phenolic compounds which are also effective in the present process are the phenyl esters of sterically hindered phenols with 3,5-di-tert-alkyl-4-hydroxybenzoic acids, such as the 2-tert-butylphenyl ester, 2,6-] i-tert -butylphenyl ester and the

109833/1848

2,4-Di-tert-butylphenyl ester of 3 »5-di-tert-butyl-4-hydroxybenzoic acid called"

Suitable light stabilizers are also salts or complex compounds of the phenolic compounds mentioned with certain metals. The metals in the salts or complex compounds are preferably the metals of group 8 of the periodic table, in particular nickel and cobalt. However, copper, manganese, tin, zinc and cadmium are also suitable. In the process of this invention such metal salts or complex compounds are also within · the term "phenolic compounds" _β

The amount in which the said Lichtstahilisatoren be used is usually 0.001 to 1 wt _e - $, based on the total weight üer Formmasseν

The effect of the light stabilizers according to the invention can often be increased by adding other known stabilizers. Compounds suitable for this purpose are one or more heat stabilizers such as amines, for example phenyl-β-naphthylamine; Phenols, in particular sterically hindered phenols, such as 2,6-Diiäopropy! Phenol, 2,6-DJrfcert-butyl-4-methylphenol _t 2,2-bis (3 ', 5'-di-t§rt-' butyl-4 ¹ -hydroxyphenyl) propane and 1,3,5-iris- (3 ' ^r -5'— ^: ' ^: ""

- O -

di-tert-butyl-4 ^f -hydroxybenzyl) -2,4,6-trimethylbenzene; organic sulfur compounds, for example thiuram sulfides such as the tetraalkylthiuram disulfides; as well as dilauryl ßthiodipropionat and especially organic phosphites, ζ.Bο tri (nonylphenyl) phosphite.

The other stabilizers are usually in an amount of 0.01 to 1 wt .- ^, calculated on the total weight who uses masses according to the invention »

The stabilizers according to the invention and the other stabilizers can be mixed with the polymers with the aid of any known method. The ^ e-. wished preparation may for example by mixing d> _it: in the form of dry powders who <d.en components. Since, in general, very little stabilizer is needed, it is advisable to obtain a homogeneous distribution of the required amount of stabilizer -First with a small 'percentage of the to be stabilized polymer ψ' and then to mix the premix obtained with the major portion of the polymer. If appropriate, the stabilizers can also be added to the polymer in the form of a solution. Aromatic hydrocarbons, for example, can be used as solvents. Other suitable solvents

10 9 833/1848

BATH

are alcohols, ethers and ketones ,, - The! solvent becomes Usually after mixing the solution with 'the polymer evaporates and therefore becomes volatile solvents "preferred." '

The homogeneity of the preparation can continue through mechanical treatment can be increased, e.g. by a mill treatment at temperatures close to the Softening point. Another possibility is the stabilizers before or during the polymerization to add the cyclic ester · The advantage of this process is that the added stabilizers very homogeneous even during the formation of the polymer be mixed with this, so that a subsequent Mixing or kneading is not required »■

The stabilized preparations can in known Way to threads, fibers, fabric, strips, foils, webs, Pipes, bottles and numerous other objects of abuse are processed ■■ .---. ■

Example ; ■ '■

A linear polyester was produced from '& _T & -dimethyl-β-propiolactone using triphenyl phosphine as a catalyst. The intrinsic viscosity (IV).

- to -

OR / Qf _NAL

was determined with a solution, the polymer in Trtfluoroacetic acid "at 25 ⁰ C and was 10 dl / g»

A series of clay searches were then carried out by adding certain amounts of stabilizer and / or antioxidants to the polymer in the form of TοIuα! Solutions. The solvent was evaporated and the preparations were then processed into foils or plates the surface temperature of the mill was 255 ⁰ G and the mill time was 1 min.

The rolled plates were in a hydraulic · Press at a temperature of 270 ° 0 to a 0.5 mm strong foil. Hit these slides was the decrease the intrinsic yiscosity with the help of a xenon ester (described by P. Dubais in Kunststoffe 49 (1959) 632 - 645) determined. In the following lab el Ie are the; after an irradiation time of 1000, 2000, 5000 or 4000 h results obtained.

Tabel

- -11 -

Tabel

req. Stabilizer 0.5 #

known Stabilizer I.V. after irradiation. H

Weight # 0 1000 2000 3000 4000

- 6.0 1.5 - ■ -

Tetramethyl 7.2 4.5 2.2 1.5 thiuram disulfide
(Rod. A). 0.05

Tri (nonylphenyl) ~ 6.8 3.2 1.6 ~

phosphite

(Bar. B) 0.5

0.05 A +0.5 B 8.3 6.5 4.5 2.5 1.5

2- (2'-hydroxy
phenyl) benzotriazole 0.05 ·· 5 B 6.0 6.6 3.4 2.6 1.8 U 0.5 A. 7.1 6.3 5.9 4.2 Il 0.05 B. 6.9 7.7 5.4 4.6 3.8 M. 0.05 A + 0, 5 B 8.3 6.0 7.1 6.3 5.8 2.2 ^I -dihydroxy-
4'-methoxybenzo-
phenone 0.5 A. 6.8 5.9 5.2 4.6 H 0.05 B. 6.6 7.7 5.0 ^, 5 3.9 N A + 0, 7.9 7.2 6.5 6.0

2-hydroxy-4-noctoxybenzophenone

0.05 A + 0.5 B

8.3 7.3 6.7 5.8 4.9

The first four attempts without the addition of the invention Stabilizers are comparative tests.

Claims

721

BAD ORIOINAL

Claims (3)

r a t e η "t a η s ρ r Ü c h e 1 . Molding compositions containing cyclic lolyciferisates Lister von Hydro: ·, "/ carboxylic acids and stabilizers, marked by" a content on an or several pheno! compounds as light stabilizers, in two aromatic rings are linked by a carbonyl group, a carbonyloxy group or a group of three Nitrogen atoms belonging to a 1,2,3-triazole configuration condensed with an aromatic ring, connected o 2. Molding compositions according to claim 1, characterized by a linear polyester obtained by polymerizing lactones, preferably ß-lactones » 3. Molding compositions according to claim 1 and 2, characterized by a linear obtained by polymerization of fc , A. -Bialkyl-ß-propiolactones, wherein each of the alkyl groups contains at most 4 carbon atoms, preferably from (L, α, -dimethyl-üS-propiolactone Polyester" BATH ORIGINAL 109833 / 1841- Ί3 4c molding compounds. Claims 1 to 3, g e k e η η draws due to a content of phenolic compounds that contain a 2-hydroxyphenyl group « 5 * Molding compositions according to claim 4, g ^e characterized by a content of 2-hydroxy'-4-alkoxybenzophenone. 6 »Molding compounds according to requirements. 4, boiled ö η η ζ ~ calibration net by a content of 2.2 ^l -3Dihydroxy-'4-alkoxy'benzophenon * · 7 * molding compounds according to. Claims 1 to 6, g e k e η η draws due to a content of 2- (2'-hydroxyphenyl) benzotriazole " 80 molding compositions according to claims 1 to 7 »characterized by an additional content of at least another -St 9p Fornn & asen according to claim Q ₁ g ek s. Η η ζ calibration η e ^! , au.'ci. a content of organic rhospnites, ^ sv <eiiie- · & χ, i'ri (no ^: nylpnenyl) piiospnit _o 10 «forinia breeds according to claim 8, aeke η r. η et durct. a 'iefxalt- an Thiuramsuliii ₀ ¹²¹ ORIGINAL BATHROOM 109833- / Ί848 '