CA1202640A - Stabilizers for synthetic resins - Google Patents
Stabilizers for synthetic resinsInfo
- Publication number
- CA1202640A CA1202640A CA000433044A CA433044A CA1202640A CA 1202640 A CA1202640 A CA 1202640A CA 000433044 A CA000433044 A CA 000433044A CA 433044 A CA433044 A CA 433044A CA 1202640 A CA1202640 A CA 1202640A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- methyl
- butyl
- synthetic resins
- alkyl group
- 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.)
- Expired
Links
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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
Abstract
Abstract A stabilizer for synthetic resins such as polyolefins, styrene synthetic resins, polyacetals, polyamides, and polyurethanes, which is a mixture of a phenolic compound II) of the general formula:
(I) wherein R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 5 carbon atoms; and n is an integer from 1 to 4, and a sulfur-containing compound (II) of the general formula:
(II-1) wherein R2 is an alkyl group having 4 to 20 carbon atoms,
(I) wherein R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 5 carbon atoms; and n is an integer from 1 to 4, and a sulfur-containing compound (II) of the general formula:
(II-1) wherein R2 is an alkyl group having 4 to 20 carbon atoms,
Description
:12~Z~4~) The present invention relates to stabilize~ for synthetic resins which provide excellent stability to synthetic resins.
Various synthetic resins including polyolefins such as polyethylene, polypropylene, etc., styrene synthetic resins such as polystyrene, impact resistant polystyrene, ABS, etc., engineering plastics such as polyacetal, polyamide, etc., and polyurethane, are widely used in various fields. However, it is well known that when these synthetic resins are used singlely, they are not stable enough, that is to say, they deteriorate upon processing or upon use, by the action of heat, light and oxygen, to impair their mechanical properties remarkably, becoming soft, brittle, discolored, and forming cracks on the surface.
To solve this problem it is also well known to use various phenolic, phosphite-type or sulfur-containing antioxidants.
For example, it is known to use singlely phenolic type antioxi-dants such as 2,6~di-t-butyl-4-methylphenol; 2,2'-methylenebis(4-methyl-6-t-butylphenol); 4,4'-butylidenebis(3-methyl-6-t-butylphenol); n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate; 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)-butane; tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxymethyl~methane; etc., or to use these phenolic antioxidants together with phosphite-type antioxidants such as tris(nonyl-phenyl)phosphite; distearylpentaerythritol diphosphite; etc., or to use the above-mentioned phenolic antioxidants in combina-tion with sulfur-containing antioxidants such as dilauryl thio-dipropionate; dimyristyl thiodipropionate: distearyl thiodi-propionate; etc.
~' ~.
- :i21~26~
Xowever, these methods are also not yet satisfactory enough in respect of stability to heat and oxidation, discol~ration by heat, and vaporization.
In order to solve these problems~ we made an intensive studyO As a result~ we have found that, by mixing synthetic resins with a particular phenolic compound and a ~ t~u~r su~ur-containing compound9 it is possible to obtain a surprising synergetic effect Which can never be~anticipated from conventional techniques of combining antioxidants together, and this mixing provides excellent stability to heat and oxidation to the ~ynthe-tic resinsO
~he present invention has been accomplished on the basis of this discoveryO
~ 'he present invention provides a stabilizer ~or synthetic resins, of which the effective component is a mixture composed of a phenolic compound (I) represented by the general formula (I):
H3~ CH2cH2c-o-cH2 ~ c~ 2R1)4-n (I) (H3C)3 wherein R1 ~is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or ~n acyl group havin~ 1 to 5 carbon atoms~ and n is an integer from 1 to 4, and at least one sulfur-containing compound (II) selected from com-pounds represented by the general formulas (II-1) and (II-2):
(R2-S_CH2CX2C_O_CH2 ~ C (II-1) wherein R2 is an alkyl group haYing 4 to 20 carbon atoms, and :~2(;~Z~i4(~
l4l5 ~ -CH2~ / CH2_o ~ ~5l4 R SGHCH-CH C CH-CHCHSR (II-2) 3 \ O CH ~ ~ CH O / 3 wher~in R~ is an alkyl group having 3 to 18 carbon atoms and R4 and R5 each independently is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in the ratio (X):(II) of 1: 005-15 by weightO
In the phenolic compound (I)~ n and R1 mean as mentioned aboveO However, in respect of the performance as the stabilizer for synthetic resins9 n is preferably 2-4, especially 3-4, and R1 is preferably a hydrogen atom7 or C1 2 alkyl or acyl such as methyl~ ethyl J acetylO
Examples of such phenolic compounds (I) include te-trakis ~3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl~methane;
Various synthetic resins including polyolefins such as polyethylene, polypropylene, etc., styrene synthetic resins such as polystyrene, impact resistant polystyrene, ABS, etc., engineering plastics such as polyacetal, polyamide, etc., and polyurethane, are widely used in various fields. However, it is well known that when these synthetic resins are used singlely, they are not stable enough, that is to say, they deteriorate upon processing or upon use, by the action of heat, light and oxygen, to impair their mechanical properties remarkably, becoming soft, brittle, discolored, and forming cracks on the surface.
To solve this problem it is also well known to use various phenolic, phosphite-type or sulfur-containing antioxidants.
For example, it is known to use singlely phenolic type antioxi-dants such as 2,6~di-t-butyl-4-methylphenol; 2,2'-methylenebis(4-methyl-6-t-butylphenol); 4,4'-butylidenebis(3-methyl-6-t-butylphenol); n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate; 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)-butane; tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxymethyl~methane; etc., or to use these phenolic antioxidants together with phosphite-type antioxidants such as tris(nonyl-phenyl)phosphite; distearylpentaerythritol diphosphite; etc., or to use the above-mentioned phenolic antioxidants in combina-tion with sulfur-containing antioxidants such as dilauryl thio-dipropionate; dimyristyl thiodipropionate: distearyl thiodi-propionate; etc.
~' ~.
- :i21~26~
Xowever, these methods are also not yet satisfactory enough in respect of stability to heat and oxidation, discol~ration by heat, and vaporization.
In order to solve these problems~ we made an intensive studyO As a result~ we have found that, by mixing synthetic resins with a particular phenolic compound and a ~ t~u~r su~ur-containing compound9 it is possible to obtain a surprising synergetic effect Which can never be~anticipated from conventional techniques of combining antioxidants together, and this mixing provides excellent stability to heat and oxidation to the ~ynthe-tic resinsO
~he present invention has been accomplished on the basis of this discoveryO
~ 'he present invention provides a stabilizer ~or synthetic resins, of which the effective component is a mixture composed of a phenolic compound (I) represented by the general formula (I):
H3~ CH2cH2c-o-cH2 ~ c~ 2R1)4-n (I) (H3C)3 wherein R1 ~is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or ~n acyl group havin~ 1 to 5 carbon atoms~ and n is an integer from 1 to 4, and at least one sulfur-containing compound (II) selected from com-pounds represented by the general formulas (II-1) and (II-2):
(R2-S_CH2CX2C_O_CH2 ~ C (II-1) wherein R2 is an alkyl group haYing 4 to 20 carbon atoms, and :~2(;~Z~i4(~
l4l5 ~ -CH2~ / CH2_o ~ ~5l4 R SGHCH-CH C CH-CHCHSR (II-2) 3 \ O CH ~ ~ CH O / 3 wher~in R~ is an alkyl group having 3 to 18 carbon atoms and R4 and R5 each independently is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in the ratio (X):(II) of 1: 005-15 by weightO
In the phenolic compound (I)~ n and R1 mean as mentioned aboveO However, in respect of the performance as the stabilizer for synthetic resins9 n is preferably 2-4, especially 3-4, and R1 is preferably a hydrogen atom7 or C1 2 alkyl or acyl such as methyl~ ethyl J acetylO
Examples of such phenolic compounds (I) include te-trakis ~3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl~methane;
2,2,2-trls~3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl~
ethyl acetate; 2 9 2 9 2-tris¦3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxymethyl3-1-methoxyethane, etc~
Among these phenolic compounds (I), those wherein n is 1 to 3 are new compounds~ and these can be produced by reacting a
ethyl acetate; 2 9 2 9 2-tris¦3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxymethyl3-1-methoxyethane, etc~
Among these phenolic compounds (I), those wherein n is 1 to 3 are new compounds~ and these can be produced by reacting a
3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionic acid represented by the general formula (III):
HO ~ ~ CH2CX2COOR (III) (H3C~3C
wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms with a pentaerythritol represented by the general formula (IY):
~ -:
lZ(~2~i~0 (H3CH2 ~ C--~~CH2R1)4-n (IV) wherein n and R1 have the same meaning as mentioned above, in the molar ratio of 0~5--4 : 1, in the presence of an acid or alkaline catalyst~
Example of such catalysts include proton acids such as p-toluenesulfonic acid, sulfuric acid, hydrochloric acidg methanesulfonic acid, etcO, ~ewis acids such as aluminum chloride9 zinc chloride, titanium tetrachloride 9 boron trifluoride, etcO~
and basic cataly~ts such as potassium hydroxide~ ~odium hydroxide9 lithium hydroxide 9 lithium aluminum hydride~ sodium boron hydride, sodiurn hydrideg lithum hydride, sodium amide 9 sodium-t-butoxide~
potassium-t-butoxide~ sodium methoxide~ potas~ium ~ethoxide, sodium phenoxide, potassium phenoxide, metallic sodium, metallic potassium, etc, Among others, the use of potassium-t-butoxideg sodium ~ethoxide, sodium phenoxide or sodium hydroxide is preferableO
These catalysts are used in an amount of OOOO1 to 2 mol equivalents for the pentaerythritol (IV).
~ he reaction is proceeds in an organic solvent such as toluene9 xylene, dimethyl~ormamide9 dimethyl ~ulfoxide, etcO, though it proceeds without u~ing any ~olventO
The reaction is carried out at a temperature between 100 and ~00CO~ preferably between 130 and 200Co Preferably~ the reaction is completed at a reduced pressure of 60-0~1 mm Hg at the terminal stageO
In the compounds repre~ented by the gsneral ~ormula tII~
:
HO ~ ~ CH2CX2COOR (III) (H3C~3C
wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms with a pentaerythritol represented by the general formula (IY):
~ -:
lZ(~2~i~0 (H3CH2 ~ C--~~CH2R1)4-n (IV) wherein n and R1 have the same meaning as mentioned above, in the molar ratio of 0~5--4 : 1, in the presence of an acid or alkaline catalyst~
Example of such catalysts include proton acids such as p-toluenesulfonic acid, sulfuric acid, hydrochloric acidg methanesulfonic acid, etcO, ~ewis acids such as aluminum chloride9 zinc chloride, titanium tetrachloride 9 boron trifluoride, etcO~
and basic cataly~ts such as potassium hydroxide~ ~odium hydroxide9 lithium hydroxide 9 lithium aluminum hydride~ sodium boron hydride, sodiurn hydrideg lithum hydride, sodium amide 9 sodium-t-butoxide~
potassium-t-butoxide~ sodium methoxide~ potas~ium ~ethoxide, sodium phenoxide, potassium phenoxide, metallic sodium, metallic potassium, etc, Among others, the use of potassium-t-butoxideg sodium ~ethoxide, sodium phenoxide or sodium hydroxide is preferableO
These catalysts are used in an amount of OOOO1 to 2 mol equivalents for the pentaerythritol (IV).
~ he reaction is proceeds in an organic solvent such as toluene9 xylene, dimethyl~ormamide9 dimethyl ~ulfoxide, etcO, though it proceeds without u~ing any ~olventO
The reaction is carried out at a temperature between 100 and ~00CO~ preferably between 130 and 200Co Preferably~ the reaction is completed at a reduced pressure of 60-0~1 mm Hg at the terminal stageO
In the compounds repre~ented by the gsneral ~ormula tII~
:
-4-26~0 the substituent R2 is preferably an alkyl group having 6 to 18 carbon atoms in respect of stability to heat and oxidat~on~
and most preferred is dodecyl groupO
Representative examples of such compound~ are shown in Table lo Table 1 ( R2-~-CH2c1l2c---CH2 Compound noO R2 ~ 3 C18H37 In the compound~ represented by t~e general ~ormula (II-2), lt l~ pr~f~rabl~ that the substituent R3 i5 an alkyl group having l2 to 18 carbon atoms9 and R4 and R5 is a hydrogen ato~ or an alkyl group having 1 to 3 carbon atoms, in respect of stability to heat and oxidation~
Representative example~ of such compounds are shown ln Table 20 Table 2 lR4lR5 /O-CH~\ / CH2-0\ R~5l4 R SCXCH~CH C ~H-CE HSR~
3 ~0~ / \CX -0 ~Z~2640 Compound No. R3 R4 R5 II-2-2 12 25 c4 9 -H
sII-2-4 C18 37 -CH3 -H
The stabilizer for synthetic resins of the present inven-tion is composed of a mixture of a phenolic compound (I) repre-sented by the general formula (I) and at least one sulfur-containing compound (II) selected from the compounds represented by the general formulas (II-l) and (II-2), and the mixing ratio (I):(II) by weight is l:O.S-lS, preferably 1:1-10, and more prefera~ly 1:2-6.
lS When the sulfur-containing compound (II) is less than O.S
times by weight for the phenolic compound (I), the desired effect cannot be fully attained. Also, even when it exceeds 15 times by weight, the effect obtained does not ~ecome correspond-ingly large, which is unfavourable economically.
The mixing amount of the stabilizer for synthetic resins of the present invention with synthetic resins is usually 0.01-
and most preferred is dodecyl groupO
Representative examples of such compound~ are shown in Table lo Table 1 ( R2-~-CH2c1l2c---CH2 Compound noO R2 ~ 3 C18H37 In the compound~ represented by t~e general ~ormula (II-2), lt l~ pr~f~rabl~ that the substituent R3 i5 an alkyl group having l2 to 18 carbon atoms9 and R4 and R5 is a hydrogen ato~ or an alkyl group having 1 to 3 carbon atoms, in respect of stability to heat and oxidation~
Representative example~ of such compounds are shown ln Table 20 Table 2 lR4lR5 /O-CH~\ / CH2-0\ R~5l4 R SCXCH~CH C ~H-CE HSR~
3 ~0~ / \CX -0 ~Z~2640 Compound No. R3 R4 R5 II-2-2 12 25 c4 9 -H
sII-2-4 C18 37 -CH3 -H
The stabilizer for synthetic resins of the present inven-tion is composed of a mixture of a phenolic compound (I) repre-sented by the general formula (I) and at least one sulfur-containing compound (II) selected from the compounds represented by the general formulas (II-l) and (II-2), and the mixing ratio (I):(II) by weight is l:O.S-lS, preferably 1:1-10, and more prefera~ly 1:2-6.
lS When the sulfur-containing compound (II) is less than O.S
times by weight for the phenolic compound (I), the desired effect cannot be fully attained. Also, even when it exceeds 15 times by weight, the effect obtained does not ~ecome correspond-ingly large, which is unfavourable economically.
The mixing amount of the stabilizer for synthetic resins of the present invention with synthetic resins is usually 0.01-
5 weight parts and preferably 0.05-1 weight part for 100 weight parts of synthetic resin. Upon use, the phenolic compound (I) and the sulfur-contair.ing com2ound (II) may be mixed separately with the synthetic resin, without previously preparing a mix-ture of the compounds.
~, 4~) Upon use of the sta~ilizer for synthetic resins of the present invention, other additives, for example, ultraviolet absorber, light stabilizer, antioxidant, metal deactivator, metallic soap, nucleating agent, lubricant, antistatic agent, flame retardant, pigment, filler, etc. may be used in combination.
The resistance to light of the synthetic resin can be improved by using the stabilizer of the present invention together with ultraviolet absorbers, hindered amine type light-stabilizers, etc. for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2(2-hydroxy-5~methylphenyl)-benzotriazole, 2(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chloro-benzotriazole, 2(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzo-triazole, 2(2-hydroxy-3,5-di-amylphenyl)benzotriazole, [2,2'-: 15 thiobis(4-t-octylphenolate)]-butylamine nickel salt, 2,2,6,6-tetramethyl-4-piperidinyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl-malonate, l-~2-(~-(3,5-di t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-4-~3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetra-methylpiperidine, and dimethyl succinate/l-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensation product.
By using the stabilizer of the present invention together with other phosphite-type antioxidants, the color of the synthetic . .
, . . .
~z~z~o resin can be improved. Such phosphite-type antioxidants include, for example~ distearylpentaerythritol diphosphite, tris(2,4-di-t-butyl phenyl)phophite~ bis(2,4-di-t-butylphenyl)penta-erythritol diphosphite, tetrakis(2,4-di~t buty~phenyl)-4,4'-biphenylene diphosphite, e-tc.
By using the stabilizer for synthetic resins of the present invention9 the stability of synthetic resins is greatly improved~
Example 3f such synthetic resins include low density polyethylene, high density polyethylene~ linear low density polyethylene, chlorinated polye-t~ylene~ EVA resin, polypropylene 9 polyvinyl chloride, methacrylic resin, polystyrene, impact re3istant polystyrene, ABS resin, A~S resin, MBS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide~
polyimide, polycarbonate, polyacetal, polyurethane, unsaturated polyester resint etcO Among others, the stabilizer is e~fectiv~
for polyprQpylene~
Example of production 1 Production of tetra~is(3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxymethyl~methane (Compound I-1) 30.04 g (0012 mol) of ~ethyl 3-(3-t-butyl-5-methyl-4- -hydroxyphenyl)propionate and 2.72 g (0002 mol) of pentaerythrltol were mixed. ~o this mixture~ 0.135 g (0.0025 mol) of sodium methoxide was added~ and the reaction system was heatod. After reaction at 140Co ~or o~e hour, the pressure of the reaction system was reduced, and at a pressure between 30 and 20 mm Hg and at a temperature between 140 and 150~, the system was reacted for an additional period o~ 20 hours4 During this reaction9 each 113 portion of 0O405 g (0~0075 mol) sodium methoxide was added with the progress of the reaction~
~%6~0 After the completion of the reaction~ the internal temperaturewas cooled to 80C., and after neutralization of the catalyst with hydrochloric acid9 200 g toluene was added to separate the solutionO
After washing the toluene phase with water, toluene was distilled away under reduced pressureO The thus-obtained crude product (30O07 g; yield 96~/o) was of 91~o purityO ~his was purified by silica gel column chromatography to obtain 15 0 9 g of a glass-like product with a purity of 98~o Melting point: 45-55Co Elemental analysis for C61 H84012 Calculated: C 72 o 6~/o~ H 8~4~
~ 'ound: C 72 4 3~) H 8.6 Mass analysis (FD-mass) Molecular ion peak 1008 Proton-NMR
1039 (36 H s) 2D 18 (12 H s) 2071 (16 H m) 3O93 (8 ~ s) 4D7 (4 H brO s) J 6085 (4~ s) -~.
J 6098 (4 H s) Example of production 2 Production of 2,2,2-tris ~-(3-methyl~5-t-butyl-4-hydroxyphenyl)l Propionyloxymethyllethanol (Compound I-2) 12052 g (0O050 mol) of methyl 3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propio-nate and 2~72 g (~020 mol) of pentaer~thritol were mixedD To thi~ mixture, OD 135 g(0.0025 mol) of sodium methoxide _g_ ~Z~640 was added~ and the reaction system was heatedO After reaction at 140Co for one hour~ the pressure o~ the reaction system was reduced, and at a pressure between 25 and 20 mm Hg and at a temperature between 140 and 1 50Co 9 the system was reacted for an additional period of 30 hoursv During this reaction, each 1/3 portion of 00405 g (00 0075 mol~ sodium methoxide was added with the progress of the reaction.
After the.~ompletion of the reaction9 the internal temperature was cooled to 80Co ~ and after neutrali~.ation of the catalyst with hydrochloric acid, 200 g toluene was added to separa~e the ~olution4 After washing the toluene phase with water, toluene was distilled away under reduced pressure~
~he thus-obtained crude product ~3.0 g; yield 99~) was of 78 purityO ~hi~ was purified by silica gel chromatography to obtain a 607 g colorless glass-like product with a purity of 96U/oO Melting point: 40-50Co Elemental analysis for C47H6601o Eound: C 71~ 6a/o ~ H 8~1%
Calculated: C 71.4a~9 H 804a~0 ~ass analysis (ED~mass) A;
Molecular ion peak: 790 Proton-N~R
c~ 1039 (27 H s) 2018 ~9 H s) 2070 (12H m) 3026 (2 H s~
c~ 3095 (6 H s) ~ 4097-(4 H br~ s) J 6~79 (3 H s~
6092 (3 H s) . .
~Z,0%640 Example of production 3 Production of 2 9 2 ? 2-tris~3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxy~e-thyl~ethyl acetate (Compound I-3) By acetylat~ng in the usual way the compound (I-2) obtained in Example of production 2, a reddish brown viscous product was obtainedO
Elemental analysis ~o:r C49H68011 Found: C 70o2~9 X 708~/o Calculated: C 70, 7~ H 802 ~ass analy~is (FD-mass) l~olecular ion peak: 832 Proton-NMR
1039 (27 H s) 2017 (3 ~ s) 2019 (9 ~ s) 2~71 (12 H m) 3092 (8 H ~) J 4075 (3 ~ br~ s) ~ 6083 (3 H s) J 6097 (3 H s~
Example of production 4 Production of 2~2,2-tris~3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxymet~yl ~ 1-methoxyeth~ne (Compound I-4) In place of pentaerythritol in the Example of production 2, pentaerythrltol monomethyl ether was usedO By reacting under the sa~e reaction condition, a reddish brown viscous product was obtainedO
:1~026~0 . ~
Elemental analysis for C48H680lo Found: C 7102~, H 801~
Calculated: C 7106~9 H 8~5~o Mass analyqis (~D-masY) Molecular ion peak: 804 Proton-NMR
1039 (27 H s) 2018 (9 H s) 2~70 (12 H m) 3015 (3 H s) 3u2~ (2 H 8) 3094 (6 H 9) 4095 (3 H brO s)
~, 4~) Upon use of the sta~ilizer for synthetic resins of the present invention, other additives, for example, ultraviolet absorber, light stabilizer, antioxidant, metal deactivator, metallic soap, nucleating agent, lubricant, antistatic agent, flame retardant, pigment, filler, etc. may be used in combination.
The resistance to light of the synthetic resin can be improved by using the stabilizer of the present invention together with ultraviolet absorbers, hindered amine type light-stabilizers, etc. for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2(2-hydroxy-5~methylphenyl)-benzotriazole, 2(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chloro-benzotriazole, 2(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzo-triazole, 2(2-hydroxy-3,5-di-amylphenyl)benzotriazole, [2,2'-: 15 thiobis(4-t-octylphenolate)]-butylamine nickel salt, 2,2,6,6-tetramethyl-4-piperidinyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl-malonate, l-~2-(~-(3,5-di t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-4-~3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetra-methylpiperidine, and dimethyl succinate/l-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensation product.
By using the stabilizer of the present invention together with other phosphite-type antioxidants, the color of the synthetic . .
, . . .
~z~z~o resin can be improved. Such phosphite-type antioxidants include, for example~ distearylpentaerythritol diphosphite, tris(2,4-di-t-butyl phenyl)phophite~ bis(2,4-di-t-butylphenyl)penta-erythritol diphosphite, tetrakis(2,4-di~t buty~phenyl)-4,4'-biphenylene diphosphite, e-tc.
By using the stabilizer for synthetic resins of the present invention9 the stability of synthetic resins is greatly improved~
Example 3f such synthetic resins include low density polyethylene, high density polyethylene~ linear low density polyethylene, chlorinated polye-t~ylene~ EVA resin, polypropylene 9 polyvinyl chloride, methacrylic resin, polystyrene, impact re3istant polystyrene, ABS resin, A~S resin, MBS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide~
polyimide, polycarbonate, polyacetal, polyurethane, unsaturated polyester resint etcO Among others, the stabilizer is e~fectiv~
for polyprQpylene~
Example of production 1 Production of tetra~is(3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxymethyl~methane (Compound I-1) 30.04 g (0012 mol) of ~ethyl 3-(3-t-butyl-5-methyl-4- -hydroxyphenyl)propionate and 2.72 g (0002 mol) of pentaerythrltol were mixed. ~o this mixture~ 0.135 g (0.0025 mol) of sodium methoxide was added~ and the reaction system was heatod. After reaction at 140Co ~or o~e hour, the pressure of the reaction system was reduced, and at a pressure between 30 and 20 mm Hg and at a temperature between 140 and 150~, the system was reacted for an additional period o~ 20 hours4 During this reaction9 each 113 portion of 0O405 g (0~0075 mol) sodium methoxide was added with the progress of the reaction~
~%6~0 After the completion of the reaction~ the internal temperaturewas cooled to 80C., and after neutralization of the catalyst with hydrochloric acid9 200 g toluene was added to separate the solutionO
After washing the toluene phase with water, toluene was distilled away under reduced pressureO The thus-obtained crude product (30O07 g; yield 96~/o) was of 91~o purityO ~his was purified by silica gel column chromatography to obtain 15 0 9 g of a glass-like product with a purity of 98~o Melting point: 45-55Co Elemental analysis for C61 H84012 Calculated: C 72 o 6~/o~ H 8~4~
~ 'ound: C 72 4 3~) H 8.6 Mass analysis (FD-mass) Molecular ion peak 1008 Proton-NMR
1039 (36 H s) 2D 18 (12 H s) 2071 (16 H m) 3O93 (8 ~ s) 4D7 (4 H brO s) J 6085 (4~ s) -~.
J 6098 (4 H s) Example of production 2 Production of 2,2,2-tris ~-(3-methyl~5-t-butyl-4-hydroxyphenyl)l Propionyloxymethyllethanol (Compound I-2) 12052 g (0O050 mol) of methyl 3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propio-nate and 2~72 g (~020 mol) of pentaer~thritol were mixedD To thi~ mixture, OD 135 g(0.0025 mol) of sodium methoxide _g_ ~Z~640 was added~ and the reaction system was heatedO After reaction at 140Co for one hour~ the pressure o~ the reaction system was reduced, and at a pressure between 25 and 20 mm Hg and at a temperature between 140 and 1 50Co 9 the system was reacted for an additional period of 30 hoursv During this reaction, each 1/3 portion of 00405 g (00 0075 mol~ sodium methoxide was added with the progress of the reaction.
After the.~ompletion of the reaction9 the internal temperature was cooled to 80Co ~ and after neutrali~.ation of the catalyst with hydrochloric acid, 200 g toluene was added to separa~e the ~olution4 After washing the toluene phase with water, toluene was distilled away under reduced pressure~
~he thus-obtained crude product ~3.0 g; yield 99~) was of 78 purityO ~hi~ was purified by silica gel chromatography to obtain a 607 g colorless glass-like product with a purity of 96U/oO Melting point: 40-50Co Elemental analysis for C47H6601o Eound: C 71~ 6a/o ~ H 8~1%
Calculated: C 71.4a~9 H 804a~0 ~ass analysis (ED~mass) A;
Molecular ion peak: 790 Proton-N~R
c~ 1039 (27 H s) 2018 ~9 H s) 2070 (12H m) 3026 (2 H s~
c~ 3095 (6 H s) ~ 4097-(4 H br~ s) J 6~79 (3 H s~
6092 (3 H s) . .
~Z,0%640 Example of production 3 Production of 2 9 2 ? 2-tris~3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxy~e-thyl~ethyl acetate (Compound I-3) By acetylat~ng in the usual way the compound (I-2) obtained in Example of production 2, a reddish brown viscous product was obtainedO
Elemental analysis ~o:r C49H68011 Found: C 70o2~9 X 708~/o Calculated: C 70, 7~ H 802 ~ass analy~is (FD-mass) l~olecular ion peak: 832 Proton-NMR
1039 (27 H s) 2017 (3 ~ s) 2019 (9 ~ s) 2~71 (12 H m) 3092 (8 H ~) J 4075 (3 ~ br~ s) ~ 6083 (3 H s) J 6097 (3 H s~
Example of production 4 Production of 2~2,2-tris~3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxymet~yl ~ 1-methoxyeth~ne (Compound I-4) In place of pentaerythritol in the Example of production 2, pentaerythrltol monomethyl ether was usedO By reacting under the sa~e reaction condition, a reddish brown viscous product was obtainedO
:1~026~0 . ~
Elemental analysis for C48H680lo Found: C 7102~, H 801~
Calculated: C 7106~9 H 8~5~o Mass analyqis (~D-masY) Molecular ion peak: 804 Proton-NMR
1039 (27 H s) 2018 (9 H s) 2~70 (12 H m) 3015 (3 H s) 3u2~ (2 H 8) 3094 (6 H 9) 4095 (3 H brO s)
6~18 (3 ~ s) J 6093 (3 H s~
Example of execution l The following components were mixed for 5 minutes with a mixer~ and melt-k~eaded wi-th a mi ~; n~ roll at 180Co The compound thus obtained was formed by a heated press of 210C~ into a heet of 1 mm in thick~essO .A test.piece of the dimensi.ons of 40x40x1~mm ~as produced. The time until 30~ of the area of the test piece becomes brittle in a gear oven of 160C, was measured~ This time period was determined as the induction period to embrittlement, by which the stability -to heat and oxidation was evaluatedO
The results are shown in Table 30 264~
Components:
Non-stabilized polypropylene resin 100 weight parts Calcium stearate 0~1 weight part ~est compound variable In ~able 3, the signs of the test compounds show the following compounds:
AO-1 n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propio~ate 9 A0-2 tetrakis~3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxymethyl~methane, A0-3 1,3 9 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxy-benzyl)benzene, A0-4 1,1 9 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, ~0-5 dilauryl thiodipropionate, A0-~ distearyl thiodipropionate.
~ ` ~''7 lZ~;~64[) ~able 3 (1) Example of the Invention .. I
~est compound 1 2 3 4 5 6 7 8 9 I-1 0.05 0,05 0.05 0,05 0,05 0.05 0.05 0.05 0.05 .
A0-~
II-1-1 0.2 II-1-2 0.1 0.2 0.3 1-3 . 0.2 II-'2-1 0.2 :`~ II-2-2 0.2 II-2-3 0~2 II-2-4 0.1 c, .h II-2-5 .-: ,.~
II~2-6 `period to 1290 1190 1600 1990 1420 1310 1440 1500 1170 ;embrittlement (hours) . .
12(~6~0 ~able 3 (2) Example of the Invention ~est compound 10 11 12 13 14 i5 16 17 18 I-1 O.OL 0.05 0.050.05 I-2 0.05 0.05 5 0-05 '5 Ao-4 II-1-1 0.2 II-1-2 0.1 0.2 0.3 ` II-1-3 0.2 Il-2-1 ;.......~ II-2-4 0~2 0.3 .~. !h II-2-5 0.2 ~ 2-6 0,2 .. ,, c~
. A0-5 : ~0-6 .:: Induction periotd to 15801920 1500 1570 1260 1070 1570 1750 1390 (hours) ~ -15-''."' .. , . . , ~
~Z~Z6~0 ~able 3 (3) Example of the Inventi-on ~est compound 19 20 21 22 2~ 24 25 26 27 I-2 0.050.05 5 0.05 0.050-05 5 0 05 : I-3 P~ A0-~
II-1-1 0.2 II-2-1 0.2 b~
'~ ' ,5 II-2-2 0.2 c II-2-3 0.2 ~ o II-2-4 0.1 0.2 0.3 .~ ~ II-2-5 0.2 q~
II-2-6 0.2 ., Ao-s . ~ Induction - period to 12701400 1460 1050 1540 1710 1470 1480 1270.~ Pmbrittlement (hours) lZ~;264~
~able 3 (4) - Exa~ple of the invention.
~est compound 28 29 30 31 32 33 34 35 36 : I-3 0,05 0,05 0.05 O.Q50.05 0.05 0.05 0.05 I-4 0.05 .~ A0-1 -~ . .
II-1-2 0.2 0.2 3 0.2 II-2-1 0.2 ., II-2-2 0.2 ~ II-2-3 ~ 0.2 ... ,~ II-2-4 0.2 . ~ II-2-5 0.2 q~
II-2-6 0.2 . A0-5 Induction I period to 1590 1400 1300 1420 1490 1560 14.80 1490 1600.~ embrittlement (hours) .~
..:
~able 3 ~5) Example of Example of ~ompari~on Inventi on Test compound 37 38 39 40 41 42 43 44 45 I-1 0~05 I-Z 0,05 I-3 0.05 I-4 0.05 0.05 ' 5 A0-1 0.05 A0-3 0.05 ., ~: ~ II-2-4 0,2 h II-2-5 0.2 . .
A0-6 ~ ~ -~: Induction period to 1570 1490 150 120 130 130 30 50 40 embrlttl ement (hours) .
. -18-' ~æ~64r) ~able 3 (63 . ~xample of co~pari~on ~e~t compound 46 47 48 49 50 51 52 53 54 :: I-3 : I-4 .~ A0-1 r--A0-4 ~-5 II-1-1 0.2 . .
II-1-2 0.2 II-1-3 0.2 - II-2-1 0.2 ... ~
2-2 0.2 ~ II-2-3 0.2 .. ~ II-2-4 ~ 0.2 h II-2-5 :. ~ ..
. A0_5 :~ Induction : period to 25 30 30 20 20 20 20 20 20 .: embrittlement ~ (hours) :.
. ., .. .
. ~
~L2~ 0 ~able 3 (7) Example of comparison ~e~t compound 55 56 5758 59 60 L. -63 I-1 -5 0~05 `~ I-3 0.050.05 ~ ~0--1 ` t1 II-2-1 ..... ~
: ' II-2-2 ~ I~-2-3 ; . ~ II-2-4 ~ 2-6 0~2 .. ~ Ao-5 0.2 0.2 0.2 0.2.
`:. A0-6 0.2 0.2 0.2 0.2 ~ Induction : period to 20 15 15 460 620 430 580 440 600 : embrittlement ~ (hours) .~".`
.
' '~', 12~,26~0 ~able 3 (8) Example of o~mp~ri ~on ~e~t compound S4 65 66 67 68 69 - 70 71 72 : I-3 I-4 0.05 0.05 . A0-1 0.05 0.05 0.05 ~0-2 0,05 0~05 5 0 05 ~0-3 II-1-2 0.2 0.2 0.3 ~ s II-2-2 0.2 : ~ II-2-3 .. ~ II-2-4 0.2 0.2 ~ II-2-5 .. ~
~ 2-6 ` .:
:: A0-5 0.2 `.~ A0-6 0.2 0.2 Inductio~
period to 440 610 310 320 330 400 480 390 440 .i embrittlement :. (hours) :.
~ ~?n~
Table 3 (9) Example of co~pari~on ~e~t compound 73 74 75 76 77 78 79 80 81 A0-2 0.05 0.05 0.05 0.05 0.05 A0-~ 0.05 0.05 0.05 0.05 II-1-2 0.2 .
' ' G II-2-4 0-3 0,2 `. ~ II-2-5 . A0-5 0.2 0.3 0.2 :~, A0-6 0.2 0.3 0.2 ~
., Induction period to 530 450 500 750 820 490 460 380 670 embrittlement ; (hour 9 ) .
-22~
,::
':
:
:12~ 0 Table 3 (10) Example of comparison Te~t compound 82 83 84 85 .: I-4 , ~0-1 5 ~Q-2 A0 4 0~050.05 0.05 II-1-2 0.2 , II-Z-3 ~ -II-2-4 0.2 A0-6 0,2 .;;; Induction period to 510 430 390 5 - embrittlement .. (hours) .. ..
.,. l .:.
124~;~64~
Example of Execution 2 ~ o a graft ABS latex, suspensions, produced by bead-pepti~ation with an anionic surface-actlve agent, of the test compounds shown in Table 4 were added in a~ounts shown in ~able 4.
In the usual way~ the mixture was salted out with an aqueous magnesium sulfate s~lution~ and the resulting precipitate was flltered, washed with water and dried. The stability to heat and oxidation was evaluated by the following methods, using the ABS resin powder thus obtained as the test materialO ~he resul-ts are sho~n in ~able 4O
1b After heat-ageing in a gear oven at 180C., the degree of discoloratio~ of the ABS resin was observed, 2O ~he oxygen absorption inductlon period (I.P-) was measured in an oxygen atmosphere at 170Co ~ using an oxyg~n absorption induction period measuring apparatus, 3~ '~he ~BS resin powder was extruded repeatedl~ using a small .
extruder (screw D = 20 mm ~, L/D = 25, strand die D = 3 mm ~, L/D = 10) under the following condition~ ~he degree of the discolora-. tion of:the ABS pellets of the forth extrusion was evaluated by ... .
~"! the color difference ~ YI from the non-addition A~S peIlets of the first extrusion~
~: Extrusion condition: .
' Number of rotatior~: 40 rpm ~emperature: C1 C2 C D
220 240 260~ 280~.
4O The A~S..pelle~s after the forth extrusion obtained in the above-mentioned method of paragraph 3 vas compression molded at 180C. for 10 minutes to prspare a No, 1 ~est Piece specified _24-~ZV264~) in JIS K 7111u By using a Charpy impact testing machine 7 the Charpy impact value of the ~est Piece was measured, following JIS ~ 7111~
In ~able 4, AO-7 is the following compound:
AO-7 2,6-di-t-butyl-4-methylphnol.
. .:
....
:
., :,.;,. .
: ' "
,, '':' lZ~ '640 TABLE 4 (1) Example of the Invention Test Compound 1 2 3 4 5 6 7 I-l 0.5 0.5 0.5 0.5 0.5 0.5 u I-2 r I-3 ~0-7 II-1-2 0.5 1.0 0-5 2-4 0.5 1.0 II-2-5 0.5 1.0 ~ AO-5 Discoloration light light light light light light light After 30 min. yellow yellow yellow yellow yellow yellow yellow fter 60 min. yellow yellow yellow yellow yellow yellow yellow brown brown brown brown brown brown brown Oxygen aibSorplitlon 210 270 205 260 210 265 190 period (min) ~ YI 10.9 10.3 11.0 10.7 10.9 10.5 10.9 value 21.2 21.7 20.3 20.9 20.7 21.2 19.5 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
4iD
TABLE 4 (2) Example of the Invention Test Compound 8 9 10 11 12 I-l u I-2 0.5 0.5 0.5 0.5 0.5 II-1-2 1.0 r~
., II-2-4 0.5 1.0 I ~
, r II-2-5 0-5 1.0 ~ AO-5 Discoloration light light light light light After 30 min. yellow yellow yellow yellow yellow After 60 min. yellow yellow yellow yellow yellow brown brown brown brown brown Oxygen absorption 255 185 240 190 250 induction period (min) Q YI 10.6 11.0 10.8 11.2 10.6 Charpy impact value 20.0 19.0 19.4 19.3 19.7 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
~,-:12~2641D
TABLE 4 (3) Example of the Invention Test Compound 13 14 15 16 17 I-l ~ I-2 o I-3 0.5 0.5 0.5 I-4 0.5 0.5 II-1-2 0.5 0-5 II-2-4 0.5 0~5 h ~
II-2-5 0.5 ~ AO-S
Discoloration light light light light light After 30 min. yellow yellow yellow yellow yellow fter 60 min. yellow yellow yellow yellow yellow brown brown brown brown brown Oxygen 200 195 200 205 200 absorp tlon induction period (min) ~ YI 10.7 10.8 11.0 10.6 10.7 Charpy impact20.7 20.2 20.4 20.8 20.4 value (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
.....
~ `?
~Zl:~26~1~
TABLE 4 (4) tion Example of Comparison Test Compound 18 19 20 21 22 23 24 I-l 0.5 1.0 0.5 0.5 r I-3 I-4 0.5 ~ .
.' II-2-4 ., II-2-5 0.5 ~ AO-5 0.5 1.0 0.5 Discoloration light deep yellow yellow yellow deep yellow After 30 min. yellow brown- brown brown brown brown brown fter 60 min. yellow black deep black brown brown brown brown brown brown brown Oxygen iabsorption 205 140 165 145 170 130 135 period (min) ~ YI 10.9 14.2 14.0 14.6 14.7 14.2 14.1 Charpy impact value 20.5 11.9 13.0 12.1 13.2 11.3 11.6 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
1~;Z6~) TABLE 4 (5) Example of Comparison Test Compound25 26 27 28 29 30 31 I-l u I-2 r I-3 0.5 0.5 ,~ I-4 0.5 0.5 AO-2 0~5 1.0 0.5 II-2-5 0.5 0.5 u~ , AO-5 Discoloration deep yellow deep . yellow deep ybellow ybellow After 30 min. brown brown brown brown br wn rown rown After 60 min.black black ' black deep brownbrown brown brown brown brown brown Oxygen absorption 135 140 135 140 140 165 145 induction period (min) ~ YI 14.0 14.2 14.1 14.3 13.9 13.7 14.5 Charpy impact value 11.7 11.9 11.7 11.9 11.5 12.7 11.7 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
. . . ~.
:~Z(~%640 TABLE 4 (6) Test Compound 32 33 34 35 36 37 38 c I-3 AO-2 0.5 0.5 0.5 0.5 0.5 0.5 AO-7 1.0 II-1-2 1.0 _, ~, II-2-4 0.5 II-2-5 0.5 1.0 ~1 ~ , AO-5 0.5 1.0 Discoloration yellow yellow yellow yellow yellow yellow yellow After 30 min. brown brown brown brown brown brown brown After 60 min.
brown brown brown brown brown brown :brown Oxygen iabsorption 155 145 145 155 145 155 145 period (min) ~ YI 14.7 14.3 14.5 14.8 14.6 14.9 13.2 Charpy impact value 12.9 11.6 11.6 13.0 11.4 13.5 12.8 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
.. .
~` 'l 2~
TAB~E 4 (7) Example of Comparison Test Compound 39 40 41 42 43 ~ I-2 o I-3 N
O
s I-4 AO-7 0.5 0.5 0.5 0.5 D
II-1-2 0.5 T
., II-2-4 0.5 O
, N
r ~ II-2-5 r ~ j AO-5 0 5 Discoloration deep deep deep deep deep After 30 min. brown brown brown brown brown fter 60 min. black black black black black brown brown brown brown brown Oxygen absorption 150 150 150 140 10 induction period (min) 14.5 14.6 14.8 15.0 15.9 Charpy impact value 12.4 12.5 12.4 11.7 7.2 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
: `
iL;Z ~Z6~0 ExamPle of execution 3 ~ o a 25~ urethane dope (prepared from 25 parts of urethane resin, 3075 parts of dimethylformamide and 71~25 parts of tetrahydrofuran~, each of the test componds shown in ~able 5 was added in an amount by weight parts shown in Table 5 for 100 weight parts of the above-mentioned polyurethane. Thereafter, the resulting dope was coated in 1.2 mm thickness on a.polyester film, and was dried at 45C. for one hour in a drier~ The sheet thus obtained was punched out into test pieces by a No~ 3 Dumbbell J
After irradiated with light for 60 hours and 120 hours in a Fade-0-Meter (light sour~e: UV carbon arc; black panel temperature: 63 i 3C~)~ the test pieces ~ere subjected to a tensile test (tensile speed: 200 mm~min; measurement temperature:
25C~) to obtain the retension ratio of brea~ strength.
The results are shown in ~able 5~
: ~.
:.
-~33-'~
Table 5 (1) ~xample of the invention Test comp~ound 1 2 3 4 5 6 7 8 9 10 11 ~ 0.5 0.5 0.5 0.5 ~5 0 5 I-2 0.50.5 0,5 0.5 0.5 A0~1 a~
II-1-2 0.5 1.0 0.51.0 $
II-2-4 0.5 1.0 0.5 1.0 r II- -5 0.5 1.0 0.5 Break strength retension (~) -60 hour~57 61 55 57 56 59 5558 55 57 56 120 hours40 43 37 40 39 42 3639 35 38 36 r 1~ _~ .
i Table 5 (2) ~xa~ple of the invention ~xample of oo~parison , Test compound 12 ~ .--1-3 14 15 16- 17 18 19 20 21 22 I-1 r 0~ 5 1 ~0 0~ 5 0~ 5 I-2 0.5 I-3 0.5 - 0.5 0.5 I-4 . . 0,5 0,5 0.5 ~;
2 0.5 0.5 $
II-2-4 0.5 0.5 II-2-51.0 0.5 - 0.5 A0-5 , 5 1.0 : I
Break strength retension (~) 60 hours 58 56 55 55 55 56 55 35 38 36 37 120 hours 39 37 35 36 35 37 36 20 23 22 23 , "
I
Table 5 (3) Example of comparison Test compound 23 24 25 26 27 28 29 30 31 32 33 I-2 . 0.5 0.5 I-3 - 0.50.5 I-4 0.50.5 A0-1 0 5 5 5 0'5 5 2 5 ~a A0-5 0.5 0.5 0.5 ` Break stren th retension (~) 60 hourq 33 34 3~ 35 35 36 31 32 32 32 32 120 hours 18 20 19 21 20 22 17 18 17 18 1~
,;:
Table 5 ~4) Example of comparison q'est compound 34 35 36 37 38 39 40 41 42 A0-2 0.5 1.0 0.5 ~5 5 0.5 0.5 0.5 ~
s II-1-2 0.5 1.0 o II-2-5 0.5 1.0 reak strength ~-' retension (%) 60 hours35 38 36 37 36 36 37 36 30 120 hours20 22 21 21 20 21 22 20 16 .
.
Example of execution l The following components were mixed for 5 minutes with a mixer~ and melt-k~eaded wi-th a mi ~; n~ roll at 180Co The compound thus obtained was formed by a heated press of 210C~ into a heet of 1 mm in thick~essO .A test.piece of the dimensi.ons of 40x40x1~mm ~as produced. The time until 30~ of the area of the test piece becomes brittle in a gear oven of 160C, was measured~ This time period was determined as the induction period to embrittlement, by which the stability -to heat and oxidation was evaluatedO
The results are shown in Table 30 264~
Components:
Non-stabilized polypropylene resin 100 weight parts Calcium stearate 0~1 weight part ~est compound variable In ~able 3, the signs of the test compounds show the following compounds:
AO-1 n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propio~ate 9 A0-2 tetrakis~3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxymethyl~methane, A0-3 1,3 9 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxy-benzyl)benzene, A0-4 1,1 9 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, ~0-5 dilauryl thiodipropionate, A0-~ distearyl thiodipropionate.
~ ` ~''7 lZ~;~64[) ~able 3 (1) Example of the Invention .. I
~est compound 1 2 3 4 5 6 7 8 9 I-1 0.05 0,05 0.05 0,05 0,05 0.05 0.05 0.05 0.05 .
A0-~
II-1-1 0.2 II-1-2 0.1 0.2 0.3 1-3 . 0.2 II-'2-1 0.2 :`~ II-2-2 0.2 II-2-3 0~2 II-2-4 0.1 c, .h II-2-5 .-: ,.~
II~2-6 `period to 1290 1190 1600 1990 1420 1310 1440 1500 1170 ;embrittlement (hours) . .
12(~6~0 ~able 3 (2) Example of the Invention ~est compound 10 11 12 13 14 i5 16 17 18 I-1 O.OL 0.05 0.050.05 I-2 0.05 0.05 5 0-05 '5 Ao-4 II-1-1 0.2 II-1-2 0.1 0.2 0.3 ` II-1-3 0.2 Il-2-1 ;.......~ II-2-4 0~2 0.3 .~. !h II-2-5 0.2 ~ 2-6 0,2 .. ,, c~
. A0-5 : ~0-6 .:: Induction periotd to 15801920 1500 1570 1260 1070 1570 1750 1390 (hours) ~ -15-''."' .. , . . , ~
~Z~Z6~0 ~able 3 (3) Example of the Inventi-on ~est compound 19 20 21 22 2~ 24 25 26 27 I-2 0.050.05 5 0.05 0.050-05 5 0 05 : I-3 P~ A0-~
II-1-1 0.2 II-2-1 0.2 b~
'~ ' ,5 II-2-2 0.2 c II-2-3 0.2 ~ o II-2-4 0.1 0.2 0.3 .~ ~ II-2-5 0.2 q~
II-2-6 0.2 ., Ao-s . ~ Induction - period to 12701400 1460 1050 1540 1710 1470 1480 1270.~ Pmbrittlement (hours) lZ~;264~
~able 3 (4) - Exa~ple of the invention.
~est compound 28 29 30 31 32 33 34 35 36 : I-3 0,05 0,05 0.05 O.Q50.05 0.05 0.05 0.05 I-4 0.05 .~ A0-1 -~ . .
II-1-2 0.2 0.2 3 0.2 II-2-1 0.2 ., II-2-2 0.2 ~ II-2-3 ~ 0.2 ... ,~ II-2-4 0.2 . ~ II-2-5 0.2 q~
II-2-6 0.2 . A0-5 Induction I period to 1590 1400 1300 1420 1490 1560 14.80 1490 1600.~ embrittlement (hours) .~
..:
~able 3 ~5) Example of Example of ~ompari~on Inventi on Test compound 37 38 39 40 41 42 43 44 45 I-1 0~05 I-Z 0,05 I-3 0.05 I-4 0.05 0.05 ' 5 A0-1 0.05 A0-3 0.05 ., ~: ~ II-2-4 0,2 h II-2-5 0.2 . .
A0-6 ~ ~ -~: Induction period to 1570 1490 150 120 130 130 30 50 40 embrlttl ement (hours) .
. -18-' ~æ~64r) ~able 3 (63 . ~xample of co~pari~on ~e~t compound 46 47 48 49 50 51 52 53 54 :: I-3 : I-4 .~ A0-1 r--A0-4 ~-5 II-1-1 0.2 . .
II-1-2 0.2 II-1-3 0.2 - II-2-1 0.2 ... ~
2-2 0.2 ~ II-2-3 0.2 .. ~ II-2-4 ~ 0.2 h II-2-5 :. ~ ..
. A0_5 :~ Induction : period to 25 30 30 20 20 20 20 20 20 .: embrittlement ~ (hours) :.
. ., .. .
. ~
~L2~ 0 ~able 3 (7) Example of comparison ~e~t compound 55 56 5758 59 60 L. -63 I-1 -5 0~05 `~ I-3 0.050.05 ~ ~0--1 ` t1 II-2-1 ..... ~
: ' II-2-2 ~ I~-2-3 ; . ~ II-2-4 ~ 2-6 0~2 .. ~ Ao-5 0.2 0.2 0.2 0.2.
`:. A0-6 0.2 0.2 0.2 0.2 ~ Induction : period to 20 15 15 460 620 430 580 440 600 : embrittlement ~ (hours) .~".`
.
' '~', 12~,26~0 ~able 3 (8) Example of o~mp~ri ~on ~e~t compound S4 65 66 67 68 69 - 70 71 72 : I-3 I-4 0.05 0.05 . A0-1 0.05 0.05 0.05 ~0-2 0,05 0~05 5 0 05 ~0-3 II-1-2 0.2 0.2 0.3 ~ s II-2-2 0.2 : ~ II-2-3 .. ~ II-2-4 0.2 0.2 ~ II-2-5 .. ~
~ 2-6 ` .:
:: A0-5 0.2 `.~ A0-6 0.2 0.2 Inductio~
period to 440 610 310 320 330 400 480 390 440 .i embrittlement :. (hours) :.
~ ~?n~
Table 3 (9) Example of co~pari~on ~e~t compound 73 74 75 76 77 78 79 80 81 A0-2 0.05 0.05 0.05 0.05 0.05 A0-~ 0.05 0.05 0.05 0.05 II-1-2 0.2 .
' ' G II-2-4 0-3 0,2 `. ~ II-2-5 . A0-5 0.2 0.3 0.2 :~, A0-6 0.2 0.3 0.2 ~
., Induction period to 530 450 500 750 820 490 460 380 670 embrittlement ; (hour 9 ) .
-22~
,::
':
:
:12~ 0 Table 3 (10) Example of comparison Te~t compound 82 83 84 85 .: I-4 , ~0-1 5 ~Q-2 A0 4 0~050.05 0.05 II-1-2 0.2 , II-Z-3 ~ -II-2-4 0.2 A0-6 0,2 .;;; Induction period to 510 430 390 5 - embrittlement .. (hours) .. ..
.,. l .:.
124~;~64~
Example of Execution 2 ~ o a graft ABS latex, suspensions, produced by bead-pepti~ation with an anionic surface-actlve agent, of the test compounds shown in Table 4 were added in a~ounts shown in ~able 4.
In the usual way~ the mixture was salted out with an aqueous magnesium sulfate s~lution~ and the resulting precipitate was flltered, washed with water and dried. The stability to heat and oxidation was evaluated by the following methods, using the ABS resin powder thus obtained as the test materialO ~he resul-ts are sho~n in ~able 4O
1b After heat-ageing in a gear oven at 180C., the degree of discoloratio~ of the ABS resin was observed, 2O ~he oxygen absorption inductlon period (I.P-) was measured in an oxygen atmosphere at 170Co ~ using an oxyg~n absorption induction period measuring apparatus, 3~ '~he ~BS resin powder was extruded repeatedl~ using a small .
extruder (screw D = 20 mm ~, L/D = 25, strand die D = 3 mm ~, L/D = 10) under the following condition~ ~he degree of the discolora-. tion of:the ABS pellets of the forth extrusion was evaluated by ... .
~"! the color difference ~ YI from the non-addition A~S peIlets of the first extrusion~
~: Extrusion condition: .
' Number of rotatior~: 40 rpm ~emperature: C1 C2 C D
220 240 260~ 280~.
4O The A~S..pelle~s after the forth extrusion obtained in the above-mentioned method of paragraph 3 vas compression molded at 180C. for 10 minutes to prspare a No, 1 ~est Piece specified _24-~ZV264~) in JIS K 7111u By using a Charpy impact testing machine 7 the Charpy impact value of the ~est Piece was measured, following JIS ~ 7111~
In ~able 4, AO-7 is the following compound:
AO-7 2,6-di-t-butyl-4-methylphnol.
. .:
....
:
., :,.;,. .
: ' "
,, '':' lZ~ '640 TABLE 4 (1) Example of the Invention Test Compound 1 2 3 4 5 6 7 I-l 0.5 0.5 0.5 0.5 0.5 0.5 u I-2 r I-3 ~0-7 II-1-2 0.5 1.0 0-5 2-4 0.5 1.0 II-2-5 0.5 1.0 ~ AO-5 Discoloration light light light light light light light After 30 min. yellow yellow yellow yellow yellow yellow yellow fter 60 min. yellow yellow yellow yellow yellow yellow yellow brown brown brown brown brown brown brown Oxygen aibSorplitlon 210 270 205 260 210 265 190 period (min) ~ YI 10.9 10.3 11.0 10.7 10.9 10.5 10.9 value 21.2 21.7 20.3 20.9 20.7 21.2 19.5 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
4iD
TABLE 4 (2) Example of the Invention Test Compound 8 9 10 11 12 I-l u I-2 0.5 0.5 0.5 0.5 0.5 II-1-2 1.0 r~
., II-2-4 0.5 1.0 I ~
, r II-2-5 0-5 1.0 ~ AO-5 Discoloration light light light light light After 30 min. yellow yellow yellow yellow yellow After 60 min. yellow yellow yellow yellow yellow brown brown brown brown brown Oxygen absorption 255 185 240 190 250 induction period (min) Q YI 10.6 11.0 10.8 11.2 10.6 Charpy impact value 20.0 19.0 19.4 19.3 19.7 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
~,-:12~2641D
TABLE 4 (3) Example of the Invention Test Compound 13 14 15 16 17 I-l ~ I-2 o I-3 0.5 0.5 0.5 I-4 0.5 0.5 II-1-2 0.5 0-5 II-2-4 0.5 0~5 h ~
II-2-5 0.5 ~ AO-S
Discoloration light light light light light After 30 min. yellow yellow yellow yellow yellow fter 60 min. yellow yellow yellow yellow yellow brown brown brown brown brown Oxygen 200 195 200 205 200 absorp tlon induction period (min) ~ YI 10.7 10.8 11.0 10.6 10.7 Charpy impact20.7 20.2 20.4 20.8 20.4 value (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
.....
~ `?
~Zl:~26~1~
TABLE 4 (4) tion Example of Comparison Test Compound 18 19 20 21 22 23 24 I-l 0.5 1.0 0.5 0.5 r I-3 I-4 0.5 ~ .
.' II-2-4 ., II-2-5 0.5 ~ AO-5 0.5 1.0 0.5 Discoloration light deep yellow yellow yellow deep yellow After 30 min. yellow brown- brown brown brown brown brown fter 60 min. yellow black deep black brown brown brown brown brown brown brown Oxygen iabsorption 205 140 165 145 170 130 135 period (min) ~ YI 10.9 14.2 14.0 14.6 14.7 14.2 14.1 Charpy impact value 20.5 11.9 13.0 12.1 13.2 11.3 11.6 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
1~;Z6~) TABLE 4 (5) Example of Comparison Test Compound25 26 27 28 29 30 31 I-l u I-2 r I-3 0.5 0.5 ,~ I-4 0.5 0.5 AO-2 0~5 1.0 0.5 II-2-5 0.5 0.5 u~ , AO-5 Discoloration deep yellow deep . yellow deep ybellow ybellow After 30 min. brown brown brown brown br wn rown rown After 60 min.black black ' black deep brownbrown brown brown brown brown brown Oxygen absorption 135 140 135 140 140 165 145 induction period (min) ~ YI 14.0 14.2 14.1 14.3 13.9 13.7 14.5 Charpy impact value 11.7 11.9 11.7 11.9 11.5 12.7 11.7 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
. . . ~.
:~Z(~%640 TABLE 4 (6) Test Compound 32 33 34 35 36 37 38 c I-3 AO-2 0.5 0.5 0.5 0.5 0.5 0.5 AO-7 1.0 II-1-2 1.0 _, ~, II-2-4 0.5 II-2-5 0.5 1.0 ~1 ~ , AO-5 0.5 1.0 Discoloration yellow yellow yellow yellow yellow yellow yellow After 30 min. brown brown brown brown brown brown brown After 60 min.
brown brown brown brown brown brown :brown Oxygen iabsorption 155 145 145 155 145 155 145 period (min) ~ YI 14.7 14.3 14.5 14.8 14.6 14.9 13.2 Charpy impact value 12.9 11.6 11.6 13.0 11.4 13.5 12.8 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
.. .
~` 'l 2~
TAB~E 4 (7) Example of Comparison Test Compound 39 40 41 42 43 ~ I-2 o I-3 N
O
s I-4 AO-7 0.5 0.5 0.5 0.5 D
II-1-2 0.5 T
., II-2-4 0.5 O
, N
r ~ II-2-5 r ~ j AO-5 0 5 Discoloration deep deep deep deep deep After 30 min. brown brown brown brown brown fter 60 min. black black black black black brown brown brown brown brown Oxygen absorption 150 150 150 140 10 induction period (min) 14.5 14.6 14.8 15.0 15.9 Charpy impact value 12.4 12.5 12.4 11.7 7.2 (Kg f.cm/cm) NOTE: The amount of test compound added is by weight of solid matter for 100 weight parts of the solid matter of resin.
: `
iL;Z ~Z6~0 ExamPle of execution 3 ~ o a 25~ urethane dope (prepared from 25 parts of urethane resin, 3075 parts of dimethylformamide and 71~25 parts of tetrahydrofuran~, each of the test componds shown in ~able 5 was added in an amount by weight parts shown in Table 5 for 100 weight parts of the above-mentioned polyurethane. Thereafter, the resulting dope was coated in 1.2 mm thickness on a.polyester film, and was dried at 45C. for one hour in a drier~ The sheet thus obtained was punched out into test pieces by a No~ 3 Dumbbell J
After irradiated with light for 60 hours and 120 hours in a Fade-0-Meter (light sour~e: UV carbon arc; black panel temperature: 63 i 3C~)~ the test pieces ~ere subjected to a tensile test (tensile speed: 200 mm~min; measurement temperature:
25C~) to obtain the retension ratio of brea~ strength.
The results are shown in ~able 5~
: ~.
:.
-~33-'~
Table 5 (1) ~xample of the invention Test comp~ound 1 2 3 4 5 6 7 8 9 10 11 ~ 0.5 0.5 0.5 0.5 ~5 0 5 I-2 0.50.5 0,5 0.5 0.5 A0~1 a~
II-1-2 0.5 1.0 0.51.0 $
II-2-4 0.5 1.0 0.5 1.0 r II- -5 0.5 1.0 0.5 Break strength retension (~) -60 hour~57 61 55 57 56 59 5558 55 57 56 120 hours40 43 37 40 39 42 3639 35 38 36 r 1~ _~ .
i Table 5 (2) ~xa~ple of the invention ~xample of oo~parison , Test compound 12 ~ .--1-3 14 15 16- 17 18 19 20 21 22 I-1 r 0~ 5 1 ~0 0~ 5 0~ 5 I-2 0.5 I-3 0.5 - 0.5 0.5 I-4 . . 0,5 0,5 0.5 ~;
2 0.5 0.5 $
II-2-4 0.5 0.5 II-2-51.0 0.5 - 0.5 A0-5 , 5 1.0 : I
Break strength retension (~) 60 hours 58 56 55 55 55 56 55 35 38 36 37 120 hours 39 37 35 36 35 37 36 20 23 22 23 , "
I
Table 5 (3) Example of comparison Test compound 23 24 25 26 27 28 29 30 31 32 33 I-2 . 0.5 0.5 I-3 - 0.50.5 I-4 0.50.5 A0-1 0 5 5 5 0'5 5 2 5 ~a A0-5 0.5 0.5 0.5 ` Break stren th retension (~) 60 hourq 33 34 3~ 35 35 36 31 32 32 32 32 120 hours 18 20 19 21 20 22 17 18 17 18 1~
,;:
Table 5 ~4) Example of comparison q'est compound 34 35 36 37 38 39 40 41 42 A0-2 0.5 1.0 0.5 ~5 5 0.5 0.5 0.5 ~
s II-1-2 0.5 1.0 o II-2-5 0.5 1.0 reak strength ~-' retension (%) 60 hours35 38 36 37 36 36 37 36 30 120 hours20 22 21 21 20 21 22 20 16 .
.
Claims (12)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
10 A stabilizer for synthetic resins, of which the effective ingredient is a mixture composed of a phenolic compound (I) represented by the general formula (I):
(I) wherein R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 5 carbon atoms; and n is an integer from 1 to 4 and at least one sulfur-containing compound (II) selected from compounds represented by the general formulas (II-1) and (II-2):
(II-1) wherein R2 is an alkyl group having 4 to 20 carbon atoms, and (II-2) wherein R3 is an alkyl group having 3 to 18 carbon atoms, and R4 and R5 each independently is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in the ratio (I):(II) of 1: 0.5-15 by weight. - 2. The stabilizer for synthetic resins as claimed in Claim 1 wherein the phenolic compound (I) is tetrakis[3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, 2,2,2-tris [3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl]ethanol, 2,2,2-tris[3-(3-methyl-5-t-butyl-4-hydroxyphenol)propionyloxymethyl]
ethyl acetate, or 2,2,2-tris[3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxymethyl]-1-methoxyethane. - 3. The stabilizer for synthetic resins as claimed in Claim 1, wherein the sulfur-containing compound (II-1) is tetrakis(3-docdyl-thiopropionyloxymethyl)methane.
- 4. The stabilizer for synthetic resins as claimed in Claim 1, wherein the sulfur-containing compound (II-2) is 3,9-bis(2-dodcyl-thioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.
- 5. The stabilizer for synthetic resins as claimed in Claim 1, wherein the synthetic resins are polyolefin resins.
- 6. The stabilizer for synthetic resins as claimed in Claim 5, wherein the polyolefin resin is polypropylene.
- 7. Phenolic compounds represented by the general formula:
wherein n' is an integer from 1 to 3, and R1 stands for a hydrogen atom or an alkyl group having 1 to g carbon atoms or an acyl group having 1 to 5 carbon atoms. - 8. The compounds as claimed in Claim 7, wherein the phenolic compound is 2,2,2-tris[3-(3-methyl-5-t-butyl-4-hydroxyphenyl) propionyloxymethyl]ethanol, 2,2,2-tris[3-(3-methyl-5-t-buty-4-hydroxyphenyl)propionyloxymethyl]ethyl acetate, or 2,2,2-tris[3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionyloxymethyl]-1-methoxyethane.
- 9. A method of producing phenolic compounds repre-sented by the general formula:
wherein n' is an integer from 1 to 3, and R1 is a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 5 carbon atoms, characterized by reacting a 3-(3-methyl-5-t-butyl-4-hydroxy-phenyl)propionic acid represented by the general formula:
wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, with a pentaerythritol represented by the general formula:
wherein n' and R1 have the same meaning as previously mentioned. - 10. The method as claimed in Claim 9 wherein the molar ratio of the pentaerythritol to the 3-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionic acid is 1 : 0.5- 4.
- 11. The method as claimed in Claim 9 wherein the reaction is carried out in the presence of an acidic or basic catalyst.
- 12. The method as claimed in Claim 11 wherein the basic catalyst is potassium t-butoxide, sodium methoxide, sodium phenoxide or sodium hydroxide.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP130634/82 | 1982-07-26 | ||
| JP13063482A JPS5920337A (en) | 1982-07-26 | 1982-07-26 | Stabilized polyolefin resin composition |
| JP231293/82 | 1982-12-27 | ||
| JP23129382A JPS59120642A (en) | 1982-12-27 | 1982-12-27 | Stabilized polyolefin resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1202640A true CA1202640A (en) | 1986-04-01 |
Family
ID=26465721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000433044A Expired CA1202640A (en) | 1982-07-26 | 1983-07-22 | Stabilizers for synthetic resins |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4511491A (en) |
| EP (1) | EP0102193B1 (en) |
| CA (1) | CA1202640A (en) |
| DE (1) | DE3367236D1 (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4511491A (en) * | 1982-07-26 | 1985-04-16 | Sumitomo Chemical Co., Ltd. | Stabilizers for synthetic resins |
| CA1248747A (en) * | 1984-02-29 | 1989-01-17 | Sumitomo Chemical Co., Ltd. | Phenolic compounds and stabilizers containing the same |
| JPS60197747A (en) * | 1984-03-19 | 1985-10-07 | Sumitomo Chem Co Ltd | Stabilizer for synthetic resin |
| JPS60240745A (en) * | 1984-05-15 | 1985-11-29 | Sumitomo Chem Co Ltd | Stabilizer for polymer |
| JPH0655742B2 (en) * | 1985-02-13 | 1994-07-27 | 住友化学工業株式会社 | Acetylene carbamide derivative and stabilizer for organic substances containing the same as active ingredient |
| JPH0618926B2 (en) * | 1985-05-02 | 1994-03-16 | 住友化学工業株式会社 | UV absorber |
| JPH0653828B2 (en) * | 1985-07-16 | 1994-07-20 | 住友化学工業株式会社 | Butadiene-based polymer composition |
| US4734519A (en) * | 1986-06-05 | 1988-03-29 | Mallinckrodt, Inc. | Pentaerythritol co-esters |
| JPH0751536B2 (en) * | 1987-02-03 | 1995-06-05 | 吉富製薬株式会社 | Process for producing tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
| JPH0710807B2 (en) * | 1987-02-03 | 1995-02-08 | 吉富製薬株式会社 | Method for producing tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
| NL9101619A (en) * | 1991-09-25 | 1993-04-16 | Harcros Chemicals Bv | STABILIZERS FOR ORGANIC MATERIALS. |
| US5808108A (en) * | 1997-01-15 | 1998-09-15 | Chappelow; Cecil C. | Polymeric compositions and composites prepared from spiroorthocarbonates and epoxy monomers |
| US7595074B2 (en) * | 2002-04-05 | 2009-09-29 | University Of Massachusetts Lowell | Polymeric antioxidants |
| US7223432B2 (en) * | 2002-04-05 | 2007-05-29 | University of Massachusettes Lowell | Polymeric antioxidants |
| US7323511B2 (en) * | 2004-01-21 | 2008-01-29 | University Of Massachusetts Lowell | Post-coupling synthetic approach for polymeric antioxidants |
| JP2008507613A (en) * | 2004-07-23 | 2008-03-13 | ポルノクス コーポレーション | Antioxidant macromonomer and antioxidant polymer, and methods for making and using the same |
| WO2006060802A1 (en) * | 2004-12-03 | 2006-06-08 | Polnox Corporation | Synthesis of sterically hindered phenol based macromolecular antioxidants |
| WO2006060801A2 (en) * | 2004-12-03 | 2006-06-08 | Polnox Corporation | Process for the synthesis of polyalkylphenol antioxidants |
| US20060128939A1 (en) * | 2004-12-03 | 2006-06-15 | Vijayendra Kumar | One pot process for making polymeric antioxidants |
| EP1828104A1 (en) | 2004-12-03 | 2007-09-05 | Polnox Corporation | Synthesis of aniline and phenol-based antioxidant macromonomers and corresponding polymers |
| WO2006091705A2 (en) * | 2005-02-22 | 2006-08-31 | Polnox Corporation | Nitrogen and hindered phenol containing dual functional macromolecular antioxidants: synthesis , performances and applications |
| CA2606303A1 (en) * | 2005-03-25 | 2006-10-05 | Polnox Corporation | Alkylated and polymeric macromolecular antioxidants and methods of making and using the same |
| US20070106059A1 (en) * | 2005-10-27 | 2007-05-10 | Cholli Ashok L | Macromolecular antioxidants and polymeric macromolecular antioxidants |
| EP1966293A1 (en) * | 2005-10-27 | 2008-09-10 | Polnox Corporation | Stabilized polyolefin compositions |
| WO2007050985A2 (en) * | 2005-10-27 | 2007-05-03 | Polnox Corporation | Macromolecular antioxidants based on stξrically hindered phenolic phosphites |
| EP1963468A1 (en) | 2005-12-02 | 2008-09-03 | Polnox Corporation | Lubricant oil compositions |
| WO2008005358A2 (en) | 2006-07-06 | 2008-01-10 | Polnox Corporation | Novel macromolecular antioxidants comprising differing antioxidant moieties: structures, methods of making and using the same |
| US7767853B2 (en) | 2006-10-20 | 2010-08-03 | Polnox Corporation | Antioxidants and methods of making and using the same |
| WO2015077635A2 (en) | 2013-11-22 | 2015-05-28 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures methods of making and using the same |
| US20180251695A1 (en) | 2017-03-01 | 2018-09-06 | Polnox Corporation | Macromolecular Corrosion (McIn) Inhibitors: Structures, Methods Of Making And Using The Same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644482A (en) * | 1961-10-30 | 1972-02-22 | Geigy Ag J R | (4-hydroxy-5-alkylphenyl) alkanoic acid esters of polyols |
| US3285855A (en) * | 1965-03-11 | 1966-11-15 | Geigy Chem Corp | Stabilization of organic material with esters containing an alkylhydroxy-phenyl group |
| US3457286A (en) * | 1967-12-01 | 1969-07-22 | Geigy Chem Corp | Organic esters containing an alkylhydroxyphenyl group |
| DE1813316A1 (en) * | 1968-12-07 | 1970-07-02 | Merck Anlagen Gmbh | Tetraoxaspiro (5,5) undecane and process for their preparation |
| US3758549A (en) * | 1971-10-12 | 1973-09-11 | Ciba Geigy Corp | Poly alkanol esters of alkylthio-alkanoic acids |
| JPS5649372B2 (en) * | 1974-03-07 | 1981-11-21 | ||
| US4032562A (en) * | 1974-11-05 | 1977-06-28 | Ciba-Geigy Corporation | 3,5-dialkyl-4-hydroxyphenylalkanoic acid esters of polyalkylene glycols |
| US4511491A (en) * | 1982-07-26 | 1985-04-16 | Sumitomo Chemical Co., Ltd. | Stabilizers for synthetic resins |
-
1983
- 1983-07-15 US US06/514,021 patent/US4511491A/en not_active Expired - Lifetime
- 1983-07-22 CA CA000433044A patent/CA1202640A/en not_active Expired
- 1983-07-26 EP EP83304324A patent/EP0102193B1/en not_active Expired
- 1983-07-26 DE DE8383304324T patent/DE3367236D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0102193B1 (en) | 1986-10-29 |
| US4511491A (en) | 1985-04-16 |
| EP0102193A3 (en) | 1984-07-04 |
| DE3367236D1 (en) | 1986-12-04 |
| EP0102193A2 (en) | 1984-03-07 |
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