GB2156359A - Composition for heat and light stabilisation of polymers - Google Patents
Composition for heat and light stabilisation of polymers Download PDFInfo
- Publication number
- GB2156359A GB2156359A GB08502426A GB8502426A GB2156359A GB 2156359 A GB2156359 A GB 2156359A GB 08502426 A GB08502426 A GB 08502426A GB 8502426 A GB8502426 A GB 8502426A GB 2156359 A GB2156359 A GB 2156359A
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- GB
- United Kingdom
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- type
- compound
- composition
- carbon atoms
- heat
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a composition for heat and light stabilisation of polymers based upon a phosphite antioxidant and a 2,2,6,6-tetramethyl piperidine derivative, and containing a mixture of from 0.01 to 0.3% by weight of 4,8-di-substituted-phenoxy-3,4,8,10-tetraoxa-4,9-diphospha spiro (5,5)-undecane and from 0.05 to 1% by weight of 2,2,6,6-tetramethyl piperidine.
Description
1
GB 2 156 359 A
1
Composition for heat and light stabilisation of polymers
The invention relates to a composition for heat and light stabilisation of polymers. The composition is particularly designed for stabilizing polypropylene.
5 As it is known in general, polymers, including polypropylene, have to be heat and light stabilized dur- 5 ing both the production and application thereof, in order to maintain their inherent advantageous mechanical, physical and chemical characteristics as long as possible. In technical practice and patent literature there are known many processes of polypropylene heat and light stabilization, thus, for example, in accordance with the Czechoslovak Inventor's Certificate No. 211,116, polypropylene is preferably 10 stabilized not only during processing but also in application thereof at relatively high temperatures by 10 means of diphenylpentserythrite diphosphite derivatives. Derivatives of 2,2,6,6-tetramethyl piperidine are well known as the most effective light stabilizers. Esters of 2,2,6,6-tetramethyl-4-piperidinol have been referred to in a plurality patent specifications such as U.S.P. No. 3,640,928, DE-OS No. 2,500,314, Czechoslovak Patent Application PV 7009-81 etc.
15 As results from the above mentioned prior art, these compounds can be applied either alone, or in 15
combination with other stabilizers, fillers and pigments.
Further it is known to preferably combine pentaerythrite diphosphite derivatives with benzophenone UV-absorbers as disclosed in the Czechoslovak Inventor's Certificate No. 190,837 and British Patent Specification No. 1,380,449.
20 Japanese Patent Specification No. 66,551/77 discloses the use of a combination of substituted piperi- 20 dine together with a triorganophosphite and a secondary organophosphite. The latter constitutes the essential component of the stabilizing composition.
Finally, the DE-OS No. 3,001,114 has referred to a combination of piperidine derivatives with pentaerythrite polyphosphites such as, for instance, distearyl pentaerythrite diphosphite with tripentaerythrite te-25 traphosphite. The hitherto known combinations of pentaerythrite with piperidines and UV-absorbers 25
based on benzophenone, or 2-phenylbenzotriazol can be preferably employed to improve the light stability of polypropylene or, optionally, other polymer types.
A drawback of all of the agents as above mentioned, however, consists in that they are practically incapable to protect the polymer substance against thermal destruction and oxidation which occur during 30 the heat treatment of polypropylene. To prevent the polymer from such a destruction, it is necessary to 30 add thereto some other stabilizers, usually from the group of stericaily hindered phenolic antioxidants.
This brings about not only a complication of the multicomponent system but also raises the cost of the stabilizing system.
Phosphorus containing antioxidants based upon pentaerythritol form subject matters of the US Patent 35 Nos. 3,047,269, 3,281,381, 3,576,918 and the Czechoslovak Inventor's Certificates Nos. 190,762, 190,248. 35 However, it is only derivatives of 4,9-dialkyl-3,5,8,10-tetraoxa-4,9-diphospha spiro(5,5)-undecane described in the US Patent No. 3,047,269 that have found a practical application.
It is an object of the present invention to eliminate all the disadvantages of prior art as hereinabove set forth, by providing an improved composition for heat and light stabilisation of polymers.
40 According to the invention, the composition contains from 0.1 to 0.3 % by weight of 4,9-di-substituted- 40 phenoxy-3,5,8,10-tetraoxa-4,9-diphospha spiro(5,5)-undecane of the general formula I
/I/
45
50
50
wherein R1, R2 and R3 stand each for a straight, or branched alkyl group having from 1 to 18 carbon atoms, an aralkyl group having from 7 to 9 carbon atoms, a cycloalkyl group having from 6 to 7 carbon atoms, respectively, and m, n, r are integers from 0 to 3; and from 0.05 to 1.0 % by weight of a 2,2,6,6-tetramethyl piperidine derivative of the general formula II
55
55
60
/II/
60
65
65
2
GB 2 156 359 A
2
wherein X stands for a hydrogen atom, or a methyl group, and A stands for an acyl group derived from a carboxylic acid or mixtures thereof having from 5 (or 6) to 18 carbon atoms. The carboxylic acid is preferably saturated but can contain, optionally, unsaturated components.
Further, it has been ascertained that as the phosphite antioxident there can be preferably used 4,9-di(tert.butyl-4-dimethylbenzyl)phenoxy-3,5,8,10-tetraoxa -4,9- diphosphaspiro(5,5)-undecane of the formula III
" (OHKO)-" - X - 0 -^OH-(o)/III/10
The preferred 2,2,6,6-tetramethyl piperidine derivative is a compound of the general formula II in which X stands for a hydrogen atom and A stands for an acyl group derived from a carboxylic acid having from
15 16 to 18 carbon atoms. 15
The composition for heat and light stabilisation according to the invention exhibits a remarkably high stabilizing efficiency and can be used for stabilizing polymeric products, preferably products from polypropylene, including polypropylene fibres. The final product stabilized by means of this composition is characterised, apart from its heat and light stability during the processing thereof, by a stability to discol-
20 ouration. It is also possible to add some other admixtures to the composition, such as fillers, pigments, 20 or, optionally, further stabilizers as calcium stearate, anti-static agents, or the like.
The stabilized product can be prepared by using conventional polypropylene stabilizing processes.
The concentration of phosphite antioxidant varies within the range of from 0.01 to 0.3 % by weight, depending upon the desired processing stability degree. The concentration of piperidine derivatives
25 ranges between 0.05 and 1 % by weight, more preferably between 0.1 and 0.3 % by weight. 25
Apart from some technical advantages (stability during the processing and heat stability), the application of the composition according to the invention is also economically effective, provided such a concentration of the composition is used to cause the same light stability of the product as by applying a derivative of 2,2,6,6-tetramethyl piperidine alone. Thus it is possible to replace, for example, up to 50 per
30 cent of piperidine derivatives by cheaper diphenylpentaerythrite diphosphites without decreasing the 30 light stability while simultaneously, on the contrary, the processing stability and the heat stability in application rise.
The following examples are given as illustrative only without, however, limiting the invention to the specific details thereof.
35 In the introduction of each of the examples the process of preparing the respecitve composition will be 35 described. The compositions were worked to foils of 0.5 mm thickness by pressing at the temperature of 260°C for 10 minutes. Such foils were then tested to ascertain the following characteristics thereof:
- processing stability of Brabender plastograph at the temperature of 190°C in air by checking the time till the viscosity drops to a half of its original value, or by working it in an extruder at temperatures 200, 275,
40 260°C respectively, and by determining the melt flow index after individual passages; 40
- heat stability in a drier (Chirana 39) at the temperature of 140°C by checking the time till as degradation of five parallel samples begins;
- light stability in a Xenotest (Original Hanau) by checking an increment of carbonyls by the value of 0.3 per hour under the following conditions: 45°C black panel temperature, 60 % relative himidity, sparying
45 for 9 minutes, 51 minutes dry run, rotating of frames. 45
The checked stabilizers:
- phenolic antioxidant: 2,6-di-tert.butyl-4-
methylphenol;
50 - compounds of the type I: tetraoxa-4,9-diphospha- 50
spiro/5,5/undecanes;
- compounds of the type II: esters of carboxylic acids and 2,2,6,6-tetra-methyl piperidinol.
55 55
All the stabilizing systems, except for example 2, contained 0.15 % of calcium stearate.
60 60
65
65
3
GB 2 156 359 A
3
Example 1
To non-stabilized powdered polypropylene HPF type, melt flow index IT23() = 8-11 g/10 min., isotactic fraction 96.6 %, components of the following stabilizing system were being admixed in a Brabender plas-tograph under nitrogen atmosphere for 5 minutes at the temperature of 190°C:
Heat
Light
Stabilizing System
Stability
Stability
(hours)
(hours)
non-stabilized polypropylene
4
250
C.1 % phenolic antioxidant
22
1 150
0.1 % phenolic antioxidant
0.1 % compound of the type 1-1
116
1 400
10
Example 2 15 Stabilizing System non-stabilized polypropylene 0.15 % compound of the type 1-1 20 0.15 % compound of the type 11-1
0.15 . compound of the type 1-1 0.15 % compound of the type II
-1
Processing Stability 112 (min)
5
100 16
280
Example 3
25 To non-stabilized powdered polypropylene (IT230 = 5.3 g/10 min), components of the following stabilizing system were being admixed in the Brabender plastograph under nitrogen atmosphere for 10 minutes at the temperature of 220°C:
Heat
Light
30
Stabilizing System
Stability
Stability
(hours)
(hours)
C.2 % compound of the type 11-1
5
2 800
C.1 % phenolic antioxidant
C.2 % compound of the type 11-1
5
4 000
35
0.1 % compound of the type 1-1
0.2 % compound of the type 11-1
22
4 500
10
15
20
25
30
35
Example 4
The following stabilizing system was prepared in a CAMIL-type extruder and the results were estimated 40 after the 1st, 5th, 10th and 15th passages:
40
45
50
55
Stabilizing System non-stabilized polypropylene 0.1 % of compound of the
12
0.25 % of compound of the type 11-1
0.1 % compound of the type 1-1 0.25 % compound of the type 11-1
Processing Stability IT 230 (g!10 min)
1.
22
24
23
5.
289
55 196 13
10.
15
127
300
27
36
66
Heat
Stability
(hours)
1.
24
22
160
15.
2
1200
12
40
Light
Stability
(hours)
1.
260
15 45 200
50
700
8000
8700
8000
55
8700
4 GB 2 156 359 A
4
Example 5
To non-stabilized powdered polypropylene (HPF type, IT230 = 8 g/10 min), components of the following stabilizing system were being admixed in a Brabender plastograph under nitrogen atmosphere for 5 minutes at the temperature of 190°C:
10
15
20
Heat
Light
Stabilizing System
Stability
Stability
(hours)
(hours)
0.2 % compound of the type
1-1
24
4000
0.1 % compound of the type
-1
0.2 % compound of the type
1-1
230
5500
0.1 % compound of the type
-2
0.1 % compound of the type
1-1
200
4900
0.1 % compound of the type
-3
0.2 % compound of the type
1-1
120
5100
0.1 % compound of the type
-4
0.2 % compound of the type
1-1
400
4300
0.1 % compound of the type
-5
0.2 % compound of the type
1-1
140
5000
0.1 % compound of the type
-6
0.2 % compound of the type
1-1
320
3000
(AAC0 = 0.04)
which means the absorption of the carboryl groups measured by infra red spectrometer 'specord IR 71'. 25 The value 0.04 thus means that the sample has not substantially degraded.
10
15
20
25
Example 6
The non-stabilized powdered polypropylene (HPF type, IT230 = 8 g/10 min), components of the following stabilizing system were being admixed in a Brabender plastograph under nitrogen atmosphere for 5 min-30 utes at the temperature of 190°C: 30
Stabilizing System
35
40
45
50
0.1 % 0.1 % 0.2 % 0.1 % 0.2 % 0.1 % 0.2 % 0.1 % 0.2 % 0.1 % 0.2 % 0.1 % 0.2 % 0.1 % 0.2 %
compound compound compound compound compound compound compound compound compound compound compound compound compound compound compound of the type of the type of the type of the type of the type of the type of the type of the type of the type of the type of the type of the type of the type of the type of the type
-1 -1 1-1 -1 I-2 -1 I-3 -1 I-4 -1 I-5 -1 I-6 -1 7
Heat
Stabilization
(hours)
210
230
240
190
220
200
225
195
Light
Stabilization (hours)
900
5 500
5 200
5 300
4 900
5 000
4 800
5 150
35
40
45
50
Stabilizers:
55
60
r - o - p,
p - O - R
55
60
65
65
'"'ft*
5
GB 2 156 359 A
5
Compound of the type 1-1
R - 0
Compound of the type I-2
10
15
Compound of the type I-3
20 Compound of the type I-4
25
Compound of the type I-5
30
35
Compound of the type I-6
0 -
o -
0+
O
O
/
<2>-K°> —
0 > - o ~
10
15
20
25
30
35
40
40
45
50
60
X -
< 1
O !
45
X
o in
<
0
Compound of the type 11-1
H;
-C-C5.17-
H31-H35
0
Compound of the type II-2
CH3;
-C-C517-
h33-h37 gg
0
Compound of the type II-3
h;
-C- c17
h35
0
Compound of the type II-4
CH3;
-c- c,7
h35
0
60
Compound of the type II-5
CH3;
-c- c7
h„
0
Compound of the type II-6
CH3;
-c- c8
h„
0
Compound of the type II-7
h;
-c- c„
^23 65
6
GB 2 156359 A
6
Claims (4)
1. A composition for heat and light stabilisation of polymers, based on a phosphite antioxidant and a derivative of 2,2,6,6-tetramethyl piperidine, the composition being characterised in that it contains from 0.1 to 0.3 % by weight of 4,9-di-substituted-phenoxy-3,5,8,10-tetraoxa-4,9-diphospha spiro(5,5)-undecane of the general formula I
10
15
20
/Y°x
\o_yv_o-^
P - 0 -
/I/
wherein R1, R2 and R3 stand each for a straight, or branched alkyl group having from 1 to 18 carbon atoms, an aralkyl group having from 7 to 9 carbon atoms, a cyclo-alkyl group having from 6 to 7 carbon atoms, respectively, and m, n, r are integers from 0 to 3; and from 0.05 to 1.0 % by weight of a 2,2,6,6-tetramethyl piperidine derivative of the general formula II
X - IT
25
0 - A
/II/
wherein X stands for a hydrogen atom, or a methyl group, and A stands for an acyl group derived from a carboxylic acid or mixtures thereof having from 5 (or 6) to 18 carbon atoms.
2. A composition as claimed in Claim 1, wherein the phosphite antioxidant is 4,9-di(tert.butyl-4-dime-thylbenzyl)phenoxy-3,5,8,10-tetraoxa -4,9-diphospha spiro(5,5)-undecane of
30
35
0 - P.
0
0
o-
P - 0
3. A composition as claimed in Claim 1, wherein the 2,2,6,6-tetramethyl piperidine derivative is a compound of the general formula II in which X stands for a hydrogen atom and A stands for an acyl group derived from a carboxylic acid having from 16 to 18 carbon atoms.
4. A composition as claimed in Claim 1 substantially as described in any one of the examples disclosed herein.
10
15
20
25
30
35
Printed in the UK for HMSO, D8818935, 8/85, 7102.
Published by The Patent Office, 25 Southampton Buildings, London, WC2A 7AY, from which copies may be obtained.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08407547A GB2156358A (en) | 1984-03-23 | 1984-03-23 | Composition for heat and light stabilisation of polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8502426D0 GB8502426D0 (en) | 1985-03-06 |
| GB2156359A true GB2156359A (en) | 1985-10-09 |
Family
ID=10558558
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08407547A Withdrawn GB2156358A (en) | 1984-03-23 | 1984-03-23 | Composition for heat and light stabilisation of polymers |
| GB08502426A Withdrawn GB2156359A (en) | 1984-03-23 | 1985-01-31 | Composition for heat and light stabilisation of polymers |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08407547A Withdrawn GB2156358A (en) | 1984-03-23 | 1984-03-23 | Composition for heat and light stabilisation of polymers |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB2156358A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5023285A (en) * | 1988-07-25 | 1991-06-11 | G E Specialty Chemicals | Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes |
| US5308901A (en) * | 1988-07-25 | 1994-05-03 | General Electric Company | 3-9-diphosphaspiroundecane-stabilized polymer compositions |
| AU3788189A (en) * | 1988-07-25 | 1990-01-25 | Borg-Warner Specialty Chemicals, Inc. | 3, 9-diphosphaspiroundecanes and process for making3, 9-diphosphaspiroundecanes |
| US5364895A (en) * | 1993-01-20 | 1994-11-15 | Dover Chemical Corp. | Hydrolytically stable pentaerythritol diphosphites |
| CN1048019C (en) * | 1993-08-30 | 2000-01-05 | 多弗化学公司 | Hydrolytically stable pentaerythritol diphosphites |
| US10891708B1 (en) | 2019-11-25 | 2021-01-12 | Arm Limited | Shader program execution in graphics processing |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110306A (en) * | 1975-12-01 | 1978-08-29 | Argus Chemical Corporation | Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, a triphosphite, and an acid phosphite or salt thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6017299B2 (en) * | 1977-11-21 | 1985-05-02 | アデカ・ア−ガス化学株式会社 | Light stabilizer for synthetic resins |
| JPS5578033A (en) * | 1978-12-08 | 1980-06-12 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin composition |
| CA1118139A (en) * | 1979-01-15 | 1982-02-09 | Elyse M. Bullock | Light-stable polypropylene compositions |
-
1984
- 1984-03-23 GB GB08407547A patent/GB2156358A/en not_active Withdrawn
-
1985
- 1985-01-31 GB GB08502426A patent/GB2156359A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110306A (en) * | 1975-12-01 | 1978-08-29 | Argus Chemical Corporation | Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, a triphosphite, and an acid phosphite or salt thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8502426D0 (en) | 1985-03-06 |
| GB2156358A (en) | 1985-10-09 |
| GB8407547D0 (en) | 1984-05-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |