GB1580207A - Resistance of compositions to oxidation - Google Patents
Resistance of compositions to oxidation Download PDFInfo
- Publication number
- GB1580207A GB1580207A GB42426/76A GB4242676A GB1580207A GB 1580207 A GB1580207 A GB 1580207A GB 42426/76 A GB42426/76 A GB 42426/76A GB 4242676 A GB4242676 A GB 4242676A GB 1580207 A GB1580207 A GB 1580207A
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- United Kingdom
- Prior art keywords
- compound
- compositions
- composition
- antioxidant
- resin
- 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
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- 239000000203 mixture Substances 0.000 title claims description 31
- 230000003647 oxidation Effects 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 16
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000003963 antioxidant agent Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 11
- 229940126062 Compound A Drugs 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- -1 hydrocarbon radical Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 229920000180 alkyd Polymers 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 description 2
- UBMXAAKAFOKSPA-UHFFFAOYSA-N [N].[O].[Si] Chemical compound [N].[O].[Si] UBMXAAKAFOKSPA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002976 peresters Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FHRAKXJVEOBCBQ-UHFFFAOYSA-L 2-ethylhexanoate;manganese(2+) Chemical compound [Mn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O FHRAKXJVEOBCBQ-UHFFFAOYSA-L 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 235000004347 Perilla Nutrition 0.000 description 1
- 244000124853 Perilla frutescens Species 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YOEYNURYLFDCEV-UHFFFAOYSA-N tert-butyl hydroxy carbonate Chemical compound CC(C)(C)OC(=O)OO YOEYNURYLFDCEV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- MXODCLTZTIFYDV-UHFFFAOYSA-L zinc;1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Zn+2].C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O.C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O MXODCLTZTIFYDV-UHFFFAOYSA-L 0.000 description 1
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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/005—Drying oils
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
(54) IMPROVING RESISTANCE OF
COMPOSITIONS TO OXIDATION
(71) We, DOW CORNING LIMITED, a British Company of 12 Whitehall,
London, SWIA 2DZ do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be performed to be particularly described in and by the following statement:- This invention relates to coating and other compositions having improved resistance to oxidation.
It has long been known that the resistance of organic compounds to deterioration can be significantly improved by the addition of antioxidants. Thus the addition to rubbers and plastics of substances, such as phenols and amines, which function as antioxidants is now commercially practised on a large scale.
There are, however, certain applications where it has not been possible to obtain the benefits which could arise from antioxidant addition. For example certain film forming compositions based on unsaturated oils rely on an oxidation (or free radical) reaction for their drying properties. Degradation of the film during subsequent exposure to the atmospheric elements cannot be reduced or eliminated by the prior incorporation of an antioxidant because the antioxidant would
interfere with the drying process. Similarly, problems arise with the incorporation of antioxidants into resins, for example polyester laminating resins, which are crosslinked under the action of an organic peroxide or per-ester.
According to this invention there is provided a composition comprising (1) an unsaturated oil or resin which is crosslinkable by an oxidative (free radical) process and (2) an organic substance having in the molecule at least one hydrolysable -SiR3 group attached to a carbon atom through a silicon-oxygen-carbon linkage or to a nitrogen atom through a silicon to nitrogen linkage or a silicon-oxygen-nitrogen linkage each R in said -SiR3 group independently representing a monovalent hydrocarbon radical, an alkoxy radical, an alkoxyalkoxy radical or an alkaryloxy radical, and the -SiR3 group being replaceable on hydrolysis by an active hydrogen atom to provide a substance having antioxidant properties with respect to the composition.
The crosslinkable unsaturated oils and resins which comprise component (1) of the compositions of this invention include the unsaturated "drying" oils and "semi-drying" oils for example linseed oil, tung oil, perilla oil, soyabean oil, dehydrated castor oils, and resins, for example oxidising alkyds obtained by the
modification of a synthetic resin with the natural oil or the acid derived therefrom.
Also operative as component (1) are unsaturated organic resins, for example
polyesters, which are curable by an oxidative process and which can be employed
in such applications as surface coating, moulding and laminating.
Component (2) is an organic substance having in the molecule at least one
hydrolysable -SiR3 group which is replaceable by hydrolysis by an active
hydrogen atom to form a substance having the desired antioxidant properties with
respect to the composition. Such compounds may be regarded as antioxidants
wherein the antioxidation capability has been reduced or removed by replacing at
least one of its active hydrogen atoms by an -SiR3 group.
In the -SiR3 group the R substituents may be the same or different and each
R may be, for example, methyl, ethyl, n-butyl, vinyl, phenyl, methoxy, hexoxy, methoxyethoxy or tolyloxy. For ease of hydrolysis preferably at least two of the R substituents are alkyl or alkoxy groups having less than about 4 carbon atoms, especially methyl, methoxy or ethoxy.
Operative as Component (2) therefore are silyl group-containing phenolic and amino compounds such as:
wherein Me=methyl, Et=ethyl and sBu=sec-butyl.
Preferred as Component (2) are phenolic compounds wherein at least one of the active hydrogen atoms has been replaced by the -SiR3 group.
The operative silyl group-containing compounds can be prepared by the silylation of the appropriate antioxidant compound for example by the reaction of hexamethyldisilazane or trimethylchlorosilane on p-cresol or hydroquinone.
Preferably the reaction employing the chlorosilane is carried out in the presence of an acid acceptor, such as pyridine. Methods for silylating organic compounds are now generally well known in the art.
Component (2) of the compositions of this invention can be employed in proportions which are conventional for antioxidant addition. In general proportions of from 0.1 to 5 parts by weight of (2) per 100 parts by weight of(l) are preferred.
The compositions of this invention can be crosslinked by an oxidative (free radical) mechanism but at the same time exhibit in the crosslinked state improved resistance to oxidative deterioration when compared with equivalent compositions from which component (2) is omitted. It is believed that such improvement is due to the conversion of the silyl-containing compound (2) to the active antioxidant during exposure of the crosslinked product to atmospheric or other moisture.
Depending on the nature of (I) the compositions of this invention may be, for example, coating materials, laminating resins or moulding resins: In addition to components (I) and (2) therefore the compositions may additionally comprise for example organic solvents, fillers, pigments, flame retardants and accelerators for the cross-linking process. Thus, for example, when component (1) is a drying or semi-drying oil or an alkyd resin the composition may contain metal salt "driers" such as cobalt naphthenate, lead naphthenate, manganese 2-ethylhexanoate and a zinc resinate. Such compositions, with the incorporation of a solvent carrier and suitable pigments, are useful as decorative and protective paints. Compositions comprising an unsaturated polyester, component (2) and an organic peroxide or perester as accelerator are useful as laminating and moulding resins.
The following examples illustrate the invention. Compound A referred to and employed in Examples 1 and 2 was prepared as follows.
MeSi(OMe)3 (136 g., 1 mole) was heated with p-cresol (108 g., 1.0 mole) in toluene (300 ml.). The toluene/methanol azeotrope was removed by means of a
Dean and Stark apparatus until gas-liquid chromatographic analysis indicated that all of the p-cresol had reacted. After distillation to remove toluene and low boiling products a residue was obtained which consisted of
in a ratio of approximately 5 parts by weight of I to one part by weight of II. This residue is referred to in the Examples as Compound A.
Example 1
Compound A (0.1 g.), styrene (10 g.) and t-butylperoxycarbonate (0.1 g.) were mixed and the mixture heated in an aluminium dish at 900C for 4 hours.
For comparative purposes the procedure was repeated twice except that in one repeat Compound A was omitted and in the other Compound A was replaced by p-cresol. It was found that the mixture containing p-cresol remained liquid while in the other two cases the mixture cured to a hard resin. This result illustrates that
Compound A did not interfere with the cure of the resin whilst a known silicon-free antioxidant prevented cure.
When the experiments were repeated with the styrene replaced by an equal amount of a polyester resin similar results were obtained.
Compound A (10 g.) was heated with water (20 ml.) and acetic acid (1 drop) for 20 minutes. The resulting mixture was extracted with diethyl ether and gle examination of the ether solution indicated the presence of p-cresol. When the ether was evaporated p-cresol (3.06 g.) was obtained, its structure being confirmed by its infra-red and nmr spectra.
Example 2
An alkyd resin (Plastyrol 99x) (10 g.) was mixed with Compound A (0.2 g.).
Thin films of this mixture and of the resin alone were painted on to an aluminium panel and a glass plate. No difference in the drying times of the films could. be detected, indicating that Compound A did not interfere with the oxidative cure of the resin.
The cured films were immersed in water containing 2 /n by weight of dibutyltin dilaurate for 5 hours. They were then removed, washed and dried, and extracted for one hour in refluxing dry diethyl ether. The ether extract, after concentration was shown by gas-liquid chromatography to contain p-cresol and Compound A in a weight ratio of approximately 3:1.
Example 3
Two silylated phenolic compounds designated Compound B and Compound C were prepared by the reaction of hexamethyldisilazane on respectively 2,t - butyl 4,6 - dimethylphenol and an antioxidant sold as Santowhite (Trade Mark). The silylated compounds had the following structures:
Compound B
Compound C
in which Me represents methyl and Bu represents t-butyl.
A coating composition was prepared by mixing by weight:
Linseed-pentaerythritol alkyd
resin (Paralac 10) 100 parts
TiO2 75 parts
Cobalt drier 0.05 parts
White Spirit 72 parts
To samples of this coating composition was added with stirring 20/ by weight, based on the weight of alkyd, of Compound B or Compound C and the resulting composition brushed on to aluminium panels. A control panel was also prepared using composition containing no silylated additive. The films were allowed to dry and gloss values for the coatings obtained before and after artifical weathering for 2,000 hours in accordance with British Standard 3900 F3.
The gloss values obtained were as follows:
Initial After 2000 hours
Control 99 18
Compound B 99 25
Compound C 99 31
WHAT WE CLAIM IS:
1. A composition comprising (1) an unsaturated oil or resin which is crosslinkable by an oxidative (free radical) process and (2) an organic substance having in the molecule at least one hydrolysable -SiR group attached to a carbon atom through a silicon-oxygen-carbon linkage or to a nitrogen atom through a silicon to nitrogen linkage or a silicon-oxygen-nitrogen linkage, each R in said -SiR3 group independently representing a monovalent hydrocarbon radical, an alkoxy radical, an alkoxyalkoxy radical or an alkaryloxy radical, and the -SiR3 group being replaceable on hydrolysis by an active hydrogen atom to provide an organic substance having antioxidant properties with respect to the composition.
2. A composition as claimed in Claim 1 wherein (2) is a phenolic compound in which at least one of the reactive hydrogen atoms has been replaced by a -SiR3 group.
3. A composition as claimed in Claim I or Claim 2 wherein (2) is present in an amount of from 0.1 to 5 parts by weight per 100 parts by weight of (1).
4. A composition as claimed in any one of the preceding claims wherein (1) is an unsaturated drying oil or semi-drying oil or an oxidising alkyd resin.
5. A composition as claimed in any one of Claims 1 to 3 wherein (1) is an unsaturated polyester resin.
6. A protective and/or decorative paint comprising a composition as claimed in
Claims (1)
- Claim 4.7. A composition as claimed in Claim 1 substantially as described with reference to the Examples.8. A process for coating a surface which comprises applying thereto a protective and/or decorative paint as claimed in Claim 6.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB42426/76A GB1580207A (en) | 1976-10-13 | 1976-10-13 | Resistance of compositions to oxidation |
| DE19772745546 DE2745546A1 (en) | 1976-10-13 | 1977-10-10 | DIMENSIONS BASED ON UNSATATURATED OIL OR RESIN |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB42426/76A GB1580207A (en) | 1976-10-13 | 1976-10-13 | Resistance of compositions to oxidation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1580207A true GB1580207A (en) | 1980-11-26 |
Family
ID=10424365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB42426/76A Expired GB1580207A (en) | 1976-10-13 | 1976-10-13 | Resistance of compositions to oxidation |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE2745546A1 (en) |
| GB (1) | GB1580207A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2823846A1 (en) * | 1978-05-31 | 1979-12-13 | Siemens Ag | METHOD FOR STABILIZATION OF POLYMERS |
| DE2823820A1 (en) | 1978-05-31 | 1979-12-06 | Siemens Ag | PROCESS FOR CROSSLINKING AND STABILIZATION OF RADICALLY CROSSLINKABLE POLYMERS |
| GB8600933D0 (en) * | 1986-01-15 | 1986-02-19 | Kodak Ltd | Organosilanes |
-
1976
- 1976-10-13 GB GB42426/76A patent/GB1580207A/en not_active Expired
-
1977
- 1977-10-10 DE DE19772745546 patent/DE2745546A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE2745546A1 (en) | 1978-04-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |