US3654178A - Partial fatty esters of glycerol and polyglycerol stabilized with organic phosphites - Google Patents
Partial fatty esters of glycerol and polyglycerol stabilized with organic phosphites Download PDFInfo
- Publication number
- US3654178A US3654178A US853532A US3654178DA US3654178A US 3654178 A US3654178 A US 3654178A US 853532 A US853532 A US 853532A US 3654178D A US3654178D A US 3654178DA US 3654178 A US3654178 A US 3654178A
- Authority
- US
- United States
- Prior art keywords
- glycerol
- polyglycerol
- esters
- compositions
- partial fatty
- 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 - Lifetime
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title abstract description 60
- 229920000223 polyglycerol Polymers 0.000 title abstract description 19
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 title description 6
- 150000002194 fatty esters Chemical class 0.000 title 1
- 239000000203 mixture Substances 0.000 abstract description 42
- -1 HYDROXYL GROUP Chemical group 0.000 abstract description 24
- 150000002148 esters Chemical class 0.000 abstract description 22
- 239000003381 stabilizer Substances 0.000 abstract description 11
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 9
- 229930195729 fatty acid Natural products 0.000 abstract description 9
- 239000000194 fatty acid Substances 0.000 abstract description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 9
- 150000004665 fatty acids Chemical class 0.000 abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 abstract description 7
- 229910052740 iodine Inorganic materials 0.000 abstract description 5
- 239000011630 iodine Substances 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract 1
- 125000005456 glyceride group Chemical group 0.000 description 13
- 125000002877 alkyl aryl group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 150000005690 diesters Chemical class 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 150000005691 triesters Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 description 2
- TXSWGTOCTHQLJU-UHFFFAOYSA-N CCCCCCCCCC(C=C1)=C(CCCCCCCCC)C(CCCCCCCCC)=C1P(O)(O)O Chemical compound CCCCCCCCCC(C=C1)=C(CCCCCCCCC)C(CCCCCCCCC)=C1P(O)(O)O TXSWGTOCTHQLJU-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 2
- 150000002314 glycerols Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- ARIWANIATODDMH-AWEZNQCLSA-N 1-lauroyl-sn-glycerol Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)CO ARIWANIATODDMH-AWEZNQCLSA-N 0.000 description 1
- HMFPLNNQWZGXAH-UHFFFAOYSA-N 2-hexacosenoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCCCC=CC(O)=O HMFPLNNQWZGXAH-UHFFFAOYSA-N 0.000 description 1
- IBWJWZHGBDSCKC-UHFFFAOYSA-N C(CCCCCCCC)C=1C(=C(C=CC=1)P(O)(O)O)CCCCCCCCC Chemical compound C(CCCCCCCC)C=1C(=C(C=CC=1)P(O)(O)O)CCCCCCCCC IBWJWZHGBDSCKC-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- ARIWANIATODDMH-UHFFFAOYSA-N Lauric acid monoglyceride Natural products CCCCCCCCCCCC(=O)OCC(O)CO ARIWANIATODDMH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VZMCXGGUXGZNGT-UHFFFAOYSA-N bis(2,6-ditert-butylphenyl) hydrogen phosphite Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1OP(O)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C VZMCXGGUXGZNGT-UHFFFAOYSA-N 0.000 description 1
- HDXWXCVNEMSMKF-UHFFFAOYSA-N bis(4-nonylphenyl) hydrogen phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(O)OC1=CC=C(CCCCCCCCC)C=C1 HDXWXCVNEMSMKF-UHFFFAOYSA-N 0.000 description 1
- DBLFQTDPPZZDGX-UHFFFAOYSA-N bis(6-methylheptoxy)-oxophosphanium Chemical compound CC(C)CCCCCO[P+](=O)OCCCCCC(C)C DBLFQTDPPZZDGX-UHFFFAOYSA-N 0.000 description 1
- BDXLTGHNJUYTQE-UHFFFAOYSA-N bis[2,3-di(nonyl)phenyl] (2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=C(CCCCCCCCC)C=CC=1)CCCCCCCCC)OC1=CC=CC(CCCCCCCCC)=C1CCCCCCCCC BDXLTGHNJUYTQE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- OGVJEUDMQQIAPV-UHFFFAOYSA-N diphenyl tridecyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCCCCC)OC1=CC=CC=C1 OGVJEUDMQQIAPV-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- UHUSDOQQWJGJQS-UHFFFAOYSA-N glycerol 1,2-dioctadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCCCCCCCCCCC UHUSDOQQWJGJQS-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ILGYWHOGBUPIIQ-UHFFFAOYSA-N octan-3-yl dihydrogen phosphite Chemical compound CCCCCC(CC)OP(O)O ILGYWHOGBUPIIQ-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
- A61K47/14—Esters of carboxylic acids, e.g. fatty acid monoglycerides, medium-chain triglycerides, parabens or PEG fatty acid esters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/24—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing atoms other than carbon, hydrogen, oxygen, halogen, nitrogen or sulfur, e.g. cyclomethicone or phospholipids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/55—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/905—Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
- Y10S516/917—The agent contains organic compound containing oxygen
- Y10S516/918—The compound contains carboxylic acid ester group
Definitions
- compositions comprising (A) a member selected from the group consisting of aliphatic monocarboxylic, particularly fatty acid monoesters and diesters of glycerol and mixtures thereof, mixtures of aliphatic monocarboxylic, particularly fatty acid mono-, diand triesters of glycerol, said mixtures containing at least about 40% by weight monoester and less than about 25% by weight triester and partial aliphatic monocarboxylic, particularly fatty acid esters of polyglycerols having from 2 to 12 glycerolunits and said partial polyglycerol ester having at least one free hydroxyl group, said esters of glycerol and polyglycerol being further characterized as being substantially saturated and having an iodine number up to about 15 and (B) from about 0.1% to 5% by weight based on the weight of conwhere R is selected from the group consisting of hydrogen and alkyl radicals containing at least about 4 carbon atom
- Glycerol esters suitable for use in the compositions of the present invention include aliphatic monocarboxylic, particularly fatty acid monoand diesters of glycerol and mixtures thereof and preferably C to C saturated fatty acid esters as well as partial polyglycerol esters of the aforesaid acids, said polyglycerol esters having at least one free hydroxyl group.
- mixtures of aliphatic monocarboxylic, particularly fatty acid and preferably C to C saturated fatty acid mono-, diand triesters of glycerol said glycerol ester mixtures containing at least 40% by weight monoester and not more than about 25% by weight tnester.
- partial polyglycerol esters of the aforesaid acids said polyglycerols having between about 2 and 12 recurring glycerol units. It is essential that the esterified polyglycerol be a partial ester, i.e. it must contain at least one free hydroxyl group.
- glycerides and polyglycerides suitable for use in preparing the compositions of the present invention must be substantially saturated and, therefore, such suitable esters are further characterized as having an iodine number up to about 15, thus indicating the tolerable extent of unsaturation.
- the fatty acid portion of the ester may contain from about *6 to 30 carbon atoms.
- the acyl group will be derived from a long chain, straight chain, substantially saturated, aliphatic monocarboxylic acid containing from about 12 to 18 carbon atoms.
- esters of saturated fatty acids suitable for use in the compositions of the present invention are glycerol monolaurate, glycerol monopalmitate, glycerol monostearate and mixtures of same, mono and di-esters of caproic, caprylic, capric, myristic, arachidic and other higher fatty acids and the polyglycerol esters thereof.
- esters of acids such as caproleic, lauroleic, myristoleic, palmitoleic, oleic, eicosenoic, docosenoic and hexacosenoic acids will be stabilized at high temperatures provided that the degree of unsaturation is such that the iodine number of the glyceride mixture does not exceed about 15.
- the glycerides and glyceride mixtures which are eliectively employed in the compositions of the present invention may be prepared, for example, by the direct esterification of glycerol with the aforesaid acids so as to produce a mixture of mono-, diand triglycerides.
- glycerolysis of a triglyceride may be prepared by molecular distillation of commercial monoglyceride mixtures.
- Organic phosphite stabilizers suitable for use in the compositions of the present invention may be mono-, dior triesters of phosphorous acid or mixtures thereof, said esters containing at least one phenyl group and may be represented by the general formula R1 -t s R] J b where R is selected from the group consisting of hydrogen and alkyl radicals having at least 4 carbon atoms and preferably a C to C alkyl radical, R and R each may be a member selected from the group consisting of hydrogen and radicals such as alkyl, aryl, aralkyl, aralkyl having a phenolic hydroxy group, alkaryl, and alkaryl having a phenolic hydroxyl group, a is an integer from 1 to 3 and b is an integer equal to 3-a.
- R or R may each be hydrogen, straight or branched chain alkyl radicals, preferably containing up to about 20 carbon atoms including, for instance, methyl, ethyl, butyl, hexyl, octyl and dodecyl radicals, among others aryl and aralkyl radicals, such as, for instance, phenyl, benzyl, methylbenzyl, nonylphenyl, diisobutyl benzyl, phenylethyl, phenylpropyl, phenyloctadecyl radicals, and the like as well as napthyl and alkyl substituted napthyl radicals, aralkyl radicals having a phenolic hydroxyl group such as is exemplified by a p-hydroxycumenyl radical.
- Suitable organic phosphites useful in the compositions of the present invention are isooctyl dinonylphenyl phosphite, butylated Bisphenol A phosphites and others as disclosed in US. Pat. No.
- tris-nonylphenylphosphite tris di-nonylphenylphosphite, bis-dinonylphenyl nonylphenyl phosphite, bis-nonylphenyl di-nonylphenylphosphite and mixtures of same.
- the proportions of the organic phosphites utilized in the compositions of the present invention should be from about 0.1% to 5% by weight and preferably about 0.5 to 2% by weight based upon the weight of the glyceride component. No beneficial efiect is obtained by using more than about 5% by weight of organic phosphite, however, greater quantities of stabilizer may be utilized if so desired. Conventional techniques may be employed to prepare the compositions of the present invention. Preferably the organic phosphite will be added to the thoroughly intermixed with glyceride at a temperature slightly in excess of the melting point of the glycerol ester or mixture of esters.
- Test compositions employed (A) Glyceride consisting of approximately 40% glycerol monostearate, 45% glycerol distearate and glycerol tristearate (B) Composition A containing 1% stabilizer (C) A polyglycerol monostearate containing about 75% by weight stearic acid with a saponification number of 150 5 (D) Composition C containing 1% stabilizer TABLE 1 Degree of discoloration 10 Time (minutes) A B C D d Complete..- do do EXAMPLE 2 TABLE 2 30 Degree of discoloration Time (minutes) A B C D Slight None.
- a composition having color stability at temperatures in excess of about 200 C. consisting essentially of (A) a member selected from the group consisting of C to C aliphatic monocarboxylic acid monoesters and diesters of glycerol and mixtures of same, mixtures of aliphatic monocarboxylic acid mono-, di-, and triesters of glycerol, said mixtures containing at least about 40% monoester and up to about by weight triester and C to C aliphatic monocarboxylic acid partial esters of a polyglycerol having between about 2 and 12 glycerol units, said partial ester having at least one free hydroxyl group, said ester of glycerol and polyglycerol being further characterized as having an iodine number of up to about 15, and (B) from about 0.1% to 5% by weight based on the weight of the (A) component of an organic phosphite stabilizer of the formula liD l where R, is selected from the group consisting
- composition according to claim 1 wherein said aliphatic monocarboxylic acid is a substantially saturated long chain fatty acid containing from 12 to 18 carbon atoms.
- composition according to claim 1 wherein the composition contains from about 0.5% to 2% by weight of the said phosphite stabilizer.
- composition according to claim 1 wherein the phosphite is a member selected from the group consisting of tris-nonylphenylphosphite, tris-dinony1pheny1phosphite, bis-dinonylphenyl nonylphenylphosphite and mixtures of same.
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- Chemical & Material Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Birds (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Emergency Medicine (AREA)
- Dermatology (AREA)
- Dispersion Chemistry (AREA)
- Biophysics (AREA)
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Abstract
COMPOSITIONS COMPRISING (1) PARTIAL FATTY ACID ESTERS OF GLYCEROL CONTAINING AT LEAST 40% BY WEIGHT MONOESTER OF GLYCEROL AND/OR PARTIAL FATTY ACID ESTERS OF POLYGLYCEROL WHEREIN THE POLYGLYCERIDE HAS AT LEAST ONE FREE HYDROXYL GROUP AND SAID ESTERS BIENG SUBSTANTIALLY SATURATED AS INDICATED BY HAVING AN IODINE NUMBER LESS THAN ABOUT 15 AND (2) SMALL AMOUNTS OF AN ORGANIC PHOSPHITE STABILIZER ARE RESISTANT TO DETERIORATION AT TEMPERATURES IN EXCESS OF ABOUT 200*C. THE COMPOSITIONS ARE WIDELY USED AS SURFACTANTS AND DISPERSING AGENTS.
Description
United States Patent 3,654,178 PARTIAL FATI'Y ESTERS 0F GLYCEROL AND POLYGLYCEROL STABILIZED WITH ORGANIC PHOSPHITES Otto S. Kauder, Jamaica, N.Y., assignor to Argus Chemical Corporation, Brooklyn, NY. No Drawing. Filed Aug. 27, 1969, Ser. No. 853,532 Int. Cl. B011? 17/36 US. Cl. 252-356 4 Claims ABSTRACT OF THE DISCLOSURE This invention relates to improved esters of glycerol and polyglycerol. More particularly this invention relates to improved partial glycerol and polyglycerol esters that resist discoloration and deterioration at elevated temperatures.
Various monoand diesters of glycerol as well as partial esters of polyglycerol with saturated fatty acids have long been known in the art and have been found useful in numerous applications. They are widely used as surfactants and dispersing agents in food, pharmaceutical and cosmetic products. Other applications include lubricating compositions and as plasticizers and emulsifiers for polymers and polymer coating compositions. It has been observed that at elevated temperatures, in the order of 200 C. and above, these predominately saturated fatty glycerides tend to undergo discoloration. These higher temperatures are encountered, for example, when fatty glycerides are used as lubricants in the molding or extrusion of plastics. The use of certain esters of phosphorous-containing acids as stabilizers has been disclosed in the prior art and organic phosphates, phosphites and various derivatives thereof have been employed to prevent deterioration and degradation caused by exposure to oxygen and/ or excessive temperatures in a number of materials as, for example, to stabilize soap and soap products, lubricating oils, resins, synthetic rubber, various fats and oils, synthetic lubricants and the like. Examples of the prior art usage of organic phosphite stabilizers may be found in US. Pats. Nos. 2,234,379; 2,612,488; 2,717,902; 3,115,- 463; 3,115,464; 3,115,465 and 3,115,466.
However, there is nothing in the prior art that teaches or even suggests the preparation of partial glycerol esters that are stable at temperatures in excess of 200 C.
In accordance with this invention it has been discovered that compositions comprising (A) a member selected from the group consisting of aliphatic monocarboxylic, particularly fatty acid monoesters and diesters of glycerol and mixtures thereof, mixtures of aliphatic monocarboxylic, particularly fatty acid mono-, diand triesters of glycerol, said mixtures containing at least about 40% by weight monoester and less than about 25% by weight triester and partial aliphatic monocarboxylic, particularly fatty acid esters of polyglycerols having from 2 to 12 glycerolunits and said partial polyglycerol ester having at least one free hydroxyl group, said esters of glycerol and polyglycerol being further characterized as being substantially saturated and having an iodine number up to about 15 and (B) from about 0.1% to 5% by weight based on the weight of conwhere R is selected from the group consisting of hydrogen and alkyl radicals containing at least about 4 carbon atoms and R and R each may be selected from the group consisting of hydrogen and radicals such as alkyl, aryl, alkaryl containing a phenolic hydroxy group, alkaryl and alkaryl containing a phenolic hydroxy group, a is an integer from 1 to 3 and b is an integer equal to 3-a, are color stable at temperatures in excess of about 200 C.
Glycerol esters suitable for use in the compositions of the present invention include aliphatic monocarboxylic, particularly fatty acid monoand diesters of glycerol and mixtures thereof and preferably C to C saturated fatty acid esters as well as partial polyglycerol esters of the aforesaid acids, said polyglycerol esters having at least one free hydroxyl group.
Also suitable are mixtures of aliphatic monocarboxylic, particularly fatty acid and preferably C to C saturated fatty acid mono-, diand triesters of glycerol, said glycerol ester mixtures containing at least 40% by weight monoester and not more than about 25% by weight tnester. Also suitable are partial polyglycerol esters of the aforesaid acids, said polyglycerols having between about 2 and 12 recurring glycerol units. It is essential that the esterified polyglycerol be a partial ester, i.e. it must contain at least one free hydroxyl group. It has been found that glycerides and polyglycerides suitable for use in preparing the compositions of the present invention must be substantially saturated and, therefore, such suitable esters are further characterized as having an iodine number up to about 15, thus indicating the tolerable extent of unsaturation.
Broadlyspeaking, the fatty acid portion of the ester may contain from about *6 to 30 carbon atoms. Preferably the acyl group will be derived from a long chain, straight chain, substantially saturated, aliphatic monocarboxylic acid containing from about 12 to 18 carbon atoms.
Illustrative esters of saturated fatty acids suitable for use in the compositions of the present invention are glycerol monolaurate, glycerol monopalmitate, glycerol monostearate and mixtures of same, mono and di-esters of caproic, caprylic, capric, myristic, arachidic and other higher fatty acids and the polyglycerol esters thereof. Also suitable are mixtures of the aforesaid saturated fatty glycerides with various unsaturated fatty acid esters of glycerol and polyglycerol, as for example esters of acids such as caproleic, lauroleic, myristoleic, palmitoleic, oleic, eicosenoic, docosenoic and hexacosenoic acids will be stabilized at high temperatures provided that the degree of unsaturation is such that the iodine number of the glyceride mixture does not exceed about 15. The glycerides and glyceride mixtures which are eliectively employed in the compositions of the present invention may be prepared, for example, by the direct esterification of glycerol with the aforesaid acids so as to produce a mixture of mono-, diand triglycerides. Thus by heating equimolar quantities of stearic acid and glycerol a mixture of monoglycerides and diglycerides with minor amounts of triglyceride is formed. Similar mixtures may be prepared by glycerolysis of a triglyceride. Products with a very high monoglyceride content may be prepared by molecular distillation of commercial monoglyceride mixtures.
Organic phosphite stabilizers suitable for use in the compositions of the present invention may be mono-, dior triesters of phosphorous acid or mixtures thereof, said esters containing at least one phenyl group and may be represented by the general formula R1 -t s R] J b where R is selected from the group consisting of hydrogen and alkyl radicals having at least 4 carbon atoms and preferably a C to C alkyl radical, R and R each may be a member selected from the group consisting of hydrogen and radicals such as alkyl, aryl, aralkyl, aralkyl having a phenolic hydroxy group, alkaryl, and alkaryl having a phenolic hydroxyl group, a is an integer from 1 to 3 and b is an integer equal to 3-a. R or R may each be hydrogen, straight or branched chain alkyl radicals, preferably containing up to about 20 carbon atoms including, for instance, methyl, ethyl, butyl, hexyl, octyl and dodecyl radicals, among others aryl and aralkyl radicals, such as, for instance, phenyl, benzyl, methylbenzyl, nonylphenyl, diisobutyl benzyl, phenylethyl, phenylpropyl, phenyloctadecyl radicals, and the like as well as napthyl and alkyl substituted napthyl radicals, aralkyl radicals having a phenolic hydroxyl group such as is exemplified by a p-hydroxycumenyl radical.
Specific examples of suitable organic phosphites useful in the compositions of the present invention are isooctyl dinonylphenyl phosphite, butylated Bisphenol A phosphites and others as disclosed in US. Pat. No. 3,112,286, phenyl nonylphenyl dinonylphenol phosphites, p-t-butylphenyl di-isodecyl phosphite, bis(a'lphamethylbenzylphenyl) 2 ethylhexyl phosphite, Bisphenol A di-isooctylphosphite, di(hexadecylphenyl) lauryl phosphite, tridecyl diphenyl phosphite, di(2,6 di-t-butylphenyl) phosphite and 2-t-butyl-2(3-t-butyl 4 hydroxyphenyl) bis(p-nonylphenyl) phosphite. Especially suitable and preferred are tris-nonylphenylphosphite, tris di-nonylphenylphosphite, bis-dinonylphenyl nonylphenyl phosphite, bis-nonylphenyl di-nonylphenylphosphite and mixtures of same.
The proportions of the organic phosphites utilized in the compositions of the present invention should be from about 0.1% to 5% by weight and preferably about 0.5 to 2% by weight based upon the weight of the glyceride component. No beneficial efiect is obtained by using more than about 5% by weight of organic phosphite, however, greater quantities of stabilizer may be utilized if so desired. Conventional techniques may be employed to prepare the compositions of the present invention. Preferably the organic phosphite will be added to the thoroughly intermixed with glyceride at a temperature slightly in excess of the melting point of the glycerol ester or mixture of esters.
The invention is further illustrated by the following examples which are not to be considered as limitative of its scope. All percentages stated are by weight.
EXAMPLE I Heat stability tests were performed at 230 C. upon certain glycerides to which was added 1% stabilizer consisting of a mixture of tris (monoand dinonylphenyl) phosphites. The glycerides were heated in beakers with occasional stirring and samples were periodically removed and placed on a glass plate to cool and solidify. The degree of discoloration was visually observed. Control experiments were performed with glycerides containing no phosphite stabilizer. The results are tabulated below in Table 1.
Test compositions employed (A) Glyceride consisting of approximately 40% glycerol monostearate, 45% glycerol distearate and glycerol tristearate (B) Composition A containing 1% stabilizer (C) A polyglycerol monostearate containing about 75% by weight stearic acid with a saponification number of 150 5 (D) Composition C containing 1% stabilizer TABLE 1 Degree of discoloration 10 Time (minutes) A B C D d Complete..- do do EXAMPLE 2 TABLE 2 30 Degree of discoloration Time (minutes) A B C D Slight None.
Severe Do. Comp1ete. Slight.
60 Complete do What is claimed is:
1. A composition having color stability at temperatures in excess of about 200 C. consisting essentially of (A) a member selected from the group consisting of C to C aliphatic monocarboxylic acid monoesters and diesters of glycerol and mixtures of same, mixtures of aliphatic monocarboxylic acid mono-, di-, and triesters of glycerol, said mixtures containing at least about 40% monoester and up to about by weight triester and C to C aliphatic monocarboxylic acid partial esters of a polyglycerol having between about 2 and 12 glycerol units, said partial ester having at least one free hydroxyl group, said ester of glycerol and polyglycerol being further characterized as having an iodine number of up to about 15, and (B) from about 0.1% to 5% by weight based on the weight of the (A) component of an organic phosphite stabilizer of the formula liD l where R, is selected from the group consisting of hydrogen and alkyl radicals containing at least about 4 carbon atoms, R and R are members selected from the group consisting of hydrogen and radicals such as alkyl, aryl, aralkyl, aralkyl containing a phenolic hydroxy group, alkaryl and alkaryl containing a phenolic hydroxy group, a is an integer from 1 to 3 and b is an integer equal to 3a.
2. A composition according to claim 1 wherein said aliphatic monocarboxylic acid is a substantially saturated long chain fatty acid containing from 12 to 18 carbon atoms.
3. A composition according to claim 1 wherein the composition contains from about 0.5% to 2% by weight of the said phosphite stabilizer.
4. A composition according to claim 1 wherein the phosphite is a member selected from the group consisting of tris-nonylphenylphosphite, tris-dinony1pheny1phosphite, bis-dinonylphenyl nonylphenylphosphite and mixtures of same.
References Cited UNITED STATES PATENTS Re 21,322 1/1940 Harris 252--356 X 2,142,510 1/1939 Harris et a]. 252-356 X 3,112,286 11/1963 Morris et a1. 26029.7 3,493,387 2/1970 Swicklik 252356 X RICHARD D. LOVERING, Primary Examiner US. Cl. X.R.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US85353269A | 1969-08-27 | 1969-08-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3654178A true US3654178A (en) | 1972-04-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US853532A Expired - Lifetime US3654178A (en) | 1969-08-27 | 1969-08-27 | Partial fatty esters of glycerol and polyglycerol stabilized with organic phosphites |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3966632A (en) * | 1974-06-06 | 1976-06-29 | G. D. Searle & Co. | Vegetable oil emulsion |
| US6784226B2 (en) | 1999-07-28 | 2004-08-31 | Chi Mei Corporation | Process for producing a styrenic resin composition |
| US20050159320A1 (en) * | 2001-09-13 | 2005-07-21 | Saputra Asep H. | Oil composition for automatic transmission |
| US20050207433A1 (en) * | 2004-01-09 | 2005-09-22 | Camelot Technology Associates Ltd. | Video communication systems and methods |
-
1969
- 1969-08-27 US US853532A patent/US3654178A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3966632A (en) * | 1974-06-06 | 1976-06-29 | G. D. Searle & Co. | Vegetable oil emulsion |
| US6784226B2 (en) | 1999-07-28 | 2004-08-31 | Chi Mei Corporation | Process for producing a styrenic resin composition |
| US20050159320A1 (en) * | 2001-09-13 | 2005-07-21 | Saputra Asep H. | Oil composition for automatic transmission |
| US20050207433A1 (en) * | 2004-01-09 | 2005-09-22 | Camelot Technology Associates Ltd. | Video communication systems and methods |
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