GB2156358A - Composition for heat and light stabilisation of polymers - Google Patents
Composition for heat and light stabilisation of polymers Download PDFInfo
- Publication number
- GB2156358A GB2156358A GB08407547A GB8407547A GB2156358A GB 2156358 A GB2156358 A GB 2156358A GB 08407547 A GB08407547 A GB 08407547A GB 8407547 A GB8407547 A GB 8407547A GB 2156358 A GB2156358 A GB 2156358A
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- GB
- United Kingdom
- Prior art keywords
- type
- compound
- composition
- heat
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
Abstract
A composition for heat and light stabilisation of polymers, particularly polypropylene comprises a mixture providing 0.01 to 0.3% by weight of 4,9-di-substituted-phenoxy-3,4,8,1 0-tetraoxa-4,9-diphospha spiro (5,5)-undecane and 0.05 to 1% by weight of a 2,2,6,6-tetramethyl piperidine ester derivative
Description
SPECIFICATION
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.
As it is known in general, polymers, including polypropylene, have to be heat and light stabilized during 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 stabilized not only during processing but also in application thereof at relatively high temperatures by 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.
As results from the above mentioned prior art, these compounds can be applied either alone, or in combination with other stabilizers, fillers and pigments.
Further it is known to preferably combine pentaerythrite diphosphite derivatives with benzophenone
UV-absorbers as disciosed in the Czechoslovak Inventor's Certificate No. 190,837 and British Patent Specification No. 1,380,449.
Japanese Patent Specification No. 66,551/77 discloses the use of a combination of substituted piperdine 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 tetraphosphite. The hitherto known combinations of pentaerythrite with piperidines and UV-absorbers 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 the heat treatment of polypropylene. To prevent the polymer from such a destruction, it is necessary to add thereto some other stabilizers, usually from the group of sterically hindered phenolic antioxidants.
This brings about not only a complication of the multicomponent system but also raises the cost of the stablizing system.
Phosphorus containing antioxidants based upon pentaerythritol form subject matters of the US Patent
Nos. 3,047,269, 3,281,381, 3,576,918 and the Czechoslovak Inventor's Certificates Nos. 190,762, 190,248.
However, it is only derivatives of 4,9-dialkyl-3,5,8,l04etraoxa-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 the prior art as hereinabove set forth, by providing an improved composition for heat and light stabilisation of polymers.
According to the invention, the composition contains from 0.1 to 0.3 % by weight of 4,9-di-substituted phenoxy-3,5,8,1 O-tetraoxa-4,9-diphospha spiro(5,5)-undecane of the general formula I
wherein R1, RZ 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
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 16 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-3,5,8,1 0-tetraoxa -4,9-diphosphaspiro(5,5)-undecane of the formula Ill
The preferred 2,2,6,6-tetramethyl piperidine derivaxtive 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 hav
ing from 16 to 18 carbon atoms.
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 poly
propylene, 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 discolouration. It is also possible to add some other admixtures to the composition, such as fillers, pigments,
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
ranges between 0.05 to 1 % by weight, more preferably between 0.1 and 0.3 % by weight.
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 cent of piperidine derivatives by cheaper diphenylpentaerythrite diphosphites without decreasing the
light stability while simultaneously, on the contrary, the processing stability and the heat stability in ap
plication rise.
The following examples are given as illustrative only without, however, limiting the invention to the specific details thereof.
In the introduction of each of the examples the process of preparing the respective composition will be 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, 260"C respectively, and by determining the melt flow index after individual passages;
heat stability in a drier (Chirana 39) at the temperature of 140"C by checking the time till a 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: 450C black panel temperature, 60 % relative humidity, sparying for 9 minutes, 51 minutes dry run, rotating of frames.
The checked stabilizers:
phenolic antioxidant: 2,6-di-tert.butyl-4-methylphenol; compounds of the type I: tetraoxa-4,9-diphospha- spiro/5,5/undecanes;
compounds of the type II: esters of carboxylic acids and 2,2,6,6-tetramethyl piperidinoi.
All the stabilizing systems, except for example 2, contained 0.15 % of calcium stearate.
Example I
To non-stablized powdered polypropylene HPF type, melt flow index IT230 = 8 - 11 g/10 min., isotactic fraction 96.6 %, components of the following stablizing system were being admixed in a Brabender plastograph 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 entioxidant 22 1150 0.1 % phenolic antioxidant)
0.1 % compound of the type 1-1) 116 1 400
Example 2
Stabilizing System Processing Stability
1/2 (min)
non-stabilized polypropylene 5
0.15 % compound of the type 1-1 100 0.15 % compound of the type 11-1 16
0.15 % compound of the type In1 ) 0.15 % compound of the type 11-1) 280
Example 3
To non-stabilized powdered polypropylene (IT230 = 5.3 g/10 min), components of the following stabilizing system were being admixed in a Brabender plastograph under nitrogen atmosphere for 10 minutes at the temperature of 110 C::
Heat Light
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
0.1 % compound of the type l-1)
0.2 % compound of the type 11-1) 22 4 500
Example 4
The following stablizing system was prepared in a CAMIL-type extruder and the results were estimated after the 1st, 5th, 10th and 15th passages::
Processing Heat Light
Stabilizing Stability Stability Stability
System IT 230 (hours) (hours)
(g/10 min)
1. 5. 10. 15 1. 15. 1. 15
non-stabilized
polypropylene 22 289 - - 8 2 260 200 o.1% of com
pound of the
type 1-1 12 24 55 127 36 24 1200 700
0.25% of compound ofthethe type 11-1 23 196 300 - 22 12 8000 8000
0.1 % compound
of the type 1-1) 0.25 % com- ) 8 13 27 66 160 40 8700 8700
pound of the )
type Il-i) Example 5
To non-stabilized powdered polypropylene (HPF type, lT230 = 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 1900C:: Heat Light
Stabilizing system Stabilization Stabilitization
(hours) (hours)
0.2 % compound of the type 11-1 24 4000
0.1 % compound of the type l-1)
0.2 % compound of the type 11-1) 230 5500
0.1 % compound of the type 1-2 )
0.1 % compound of the type 11-1) 200 4900
0.1 % compound of the type 1-3 ) 0.2 % compound of the type 11-1) 120 5100
0.1 % compound of the type 1-4 )
0.2 % compound of the type 11-1) 400 4300
0.1 % compound of the type 1-5 )
0.2 % compound of the type 11-1) 140 5000
0.1 % compound of the type 1-6
0.2 % compound of the type 11-1) 320 3000
(A10 = 0.04)
Example 6
The non-stabilized powdered polypropylene (HPF type, lT230 = 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: Heat Light
StabilizingSystem Stabilization Stabilization
(hours) (hours)
0.1 % compound of the type 1-1 210 900
0.1 % compound of the type I-I) 0.2 % compound of the type 11-1) 230 5 500
0.1 % compound of the type l-1)
0.2 % compound of the type 11-2) 240 5 200
0.1 % compound of the type l-1) 0.2 % compound of the type 11-3) 190 5 300
0.1 % compound of the type l-1)
0.2 % compound of the type 11-4) 220 4 900
0.1 % compound of the type l-1)
0.2 % compound of the type 11-5) 200 5 000
0.1 % compound of the type l-1)
0.2 % compound of the type 11-6) 225 4 800
0.1 % compound of the type l-1)
0.2% compound of the type 11-7) 195 5150
Stabilizers:
Compound of the type I-1 R - 0
Compound of the type I-2
Compound of the type I-3
Compound of the type I-4
Compound of the type I-5
Compound of the type I-6
II.
X - N # - O - A X A
Compound of the type II-1 Compound of the type II-2
Compound of the type II-3
Compound of the type II-4
Compound of the type II-5
Compound of the type II-6
Compound of the type II-7
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
wherein R', 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 2,2,6,6tetramethyl piperidine derivative of the general formula 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 16 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-3,5,8,1 0-tetraoxa-4,9-diphospha spiro(5,5)-undecane of
3. A composition as claimed in Claim 1, wherein tne 2-,2,b-,b-tetrametnyl 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.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08407547A GB2156358A (en) | 1984-03-23 | 1984-03-23 | Composition for heat and light stabilisation of polymers |
| GB08502426A GB2156359A (en) | 1984-03-23 | 1985-01-31 | Composition for heat and light stabilisation of polymers |
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 |
|---|---|
| GB8407547D0 GB8407547D0 (en) | 1984-05-02 |
| GB2156358A true GB2156358A (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 After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08502426A Withdrawn GB2156359A (en) | 1984-03-23 | 1985-01-31 | Composition for heat and light stabilisation of polymers |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB2156358A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0356687A1 (en) * | 1988-07-25 | 1990-03-07 | Ge Specialty Chemicals, Inc. | Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes |
| US5137950A (en) * | 1988-07-25 | 1992-08-11 | Borg-Warner Specialty Chemicals, Inc. | 3-9-diphosphaspiroundecanes and process for making 3-9-diphosphaspiroundecanes |
| US5308901A (en) * | 1988-07-25 | 1994-05-03 | General Electric Company | 3-9-diphosphaspiroundecane-stabilized polymer compositions |
| US5364895A (en) * | 1993-01-20 | 1994-11-15 | Dover Chemical Corp. | Hydrolytically stable pentaerythritol diphosphites |
| WO1995006651A1 (en) * | 1993-08-30 | 1995-03-09 | Dover Chemical Corporation | Hydrolytically stable pentaerythritol diphosphites |
| US10891708B1 (en) | 2019-11-25 | 2021-01-12 | Arm Limited | Shader program execution in graphics processing |
Citations (4)
| 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 |
| GB2039494A (en) * | 1979-01-15 | 1980-08-13 | Borg Warner | Light-stable polypropylene compositions |
| US4362831A (en) * | 1978-12-08 | 1982-12-07 | Adeka Argus Chemical Co., Ltd. | Synergistic light and heat stabilizer compositions for synthetic resins and resin compositions containing the same |
| US4396735A (en) * | 1977-11-21 | 1983-08-02 | Adeka Argus Chemical Co., Ltd. | Synergistic light stabilizer compositions for synthetic resins and resin compositions containing the same |
-
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 (4)
| 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 |
| US4396735A (en) * | 1977-11-21 | 1983-08-02 | Adeka Argus Chemical Co., Ltd. | Synergistic light stabilizer compositions for synthetic resins and resin compositions containing the same |
| US4362831A (en) * | 1978-12-08 | 1982-12-07 | Adeka Argus Chemical Co., Ltd. | Synergistic light and heat stabilizer compositions for synthetic resins and resin compositions containing the same |
| GB2039494A (en) * | 1979-01-15 | 1980-08-13 | Borg Warner | Light-stable polypropylene compositions |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0356687A1 (en) * | 1988-07-25 | 1990-03-07 | Ge Specialty Chemicals, Inc. | Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes |
| US5023285A (en) * | 1988-07-25 | 1991-06-11 | G E Specialty Chemicals | Bis (tri-tertiary-alkylphenoxy) diphosphaspiroundecanes |
| US5137950A (en) * | 1988-07-25 | 1992-08-11 | Borg-Warner Specialty Chemicals, Inc. | 3-9-diphosphaspiroundecanes and process for making 3-9-diphosphaspiroundecanes |
| US5308901A (en) * | 1988-07-25 | 1994-05-03 | General Electric Company | 3-9-diphosphaspiroundecane-stabilized polymer compositions |
| US5364895A (en) * | 1993-01-20 | 1994-11-15 | Dover Chemical Corp. | Hydrolytically stable pentaerythritol diphosphites |
| WO1995006651A1 (en) * | 1993-08-30 | 1995-03-09 | Dover Chemical Corporation | Hydrolytically stable pentaerythritol diphosphites |
| US5438086A (en) * | 1993-08-30 | 1995-08-01 | Stevenson; Donald R. | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8407547D0 (en) | 1984-05-02 |
| GB2156359A (en) | 1985-10-09 |
| GB8502426D0 (en) | 1985-03-06 |
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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) |