CA2136373A1 - Ethoxylated acetylenic glycols having low dynamic surface tension - Google Patents
Ethoxylated acetylenic glycols having low dynamic surface tensionInfo
- Publication number
- CA2136373A1 CA2136373A1 CA002136373A CA2136373A CA2136373A1 CA 2136373 A1 CA2136373 A1 CA 2136373A1 CA 002136373 A CA002136373 A CA 002136373A CA 2136373 A CA2136373 A CA 2136373A CA 2136373 A1 CA2136373 A1 CA 2136373A1
- Authority
- CA
- Canada
- Prior art keywords
- surface tension
- ethoxylated
- ethoxylated acetylenic
- composition
- surfactants
- 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.)
- Abandoned
Links
- 150000002334 glycols Chemical class 0.000 title description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 alkyl phenol Chemical compound 0.000 claims description 6
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 3
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 3
- 229960000878 docusate sodium Drugs 0.000 claims 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 150000002009 diols Chemical class 0.000 abstract description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 17
- 239000000049 pigment Substances 0.000 description 9
- 229940117927 ethylene oxide Drugs 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000009736 wetting Methods 0.000 description 7
- RHRRUYIZUBAQTQ-UHFFFAOYSA-N 2,5,8,11-tetramethyldodec-6-yne-5,8-diol Chemical class CC(C)CCC(C)(O)C#CC(C)(O)CCC(C)C RHRRUYIZUBAQTQ-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- VQUXVWMAXIQKTQ-UHFFFAOYSA-N 3-methylnon-1-yn-3-ol Chemical compound CCCCCCC(C)(O)C#C VQUXVWMAXIQKTQ-UHFFFAOYSA-N 0.000 description 1
- HCKFFIBKYQSDRD-UHFFFAOYSA-N 4,7-dimethyldec-5-yne-4,7-diol Chemical compound CCCC(C)(O)C#CC(C)(O)CCC HCKFFIBKYQSDRD-UHFFFAOYSA-N 0.000 description 1
- SBJGYMAFEJLGIL-UHFFFAOYSA-N 5,5,6-trimethyltridec-3-yne-2,2-diol Chemical compound CCCCCCCC(C)C(C)(C)C#CC(C)(O)O SBJGYMAFEJLGIL-UHFFFAOYSA-N 0.000 description 1
- WDWJDXFFWSXMBZ-UHFFFAOYSA-N 7,10-dimethylhexadec-8-yne-7,10-diol Chemical compound CCCCCCC(C)(O)C#CC(C)(O)CCCCCC WDWJDXFFWSXMBZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/027—Dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Abstract
This invention relates to ethoxylated acetylenic glycol compositions represented by the formula:
wherein m and n are integers and the sum is from 4-12.
These ethoxylated acetylenic diols are excellent as surfactants alone or admixed with other surfactants for use in water borne coatings.
wherein m and n are integers and the sum is from 4-12.
These ethoxylated acetylenic diols are excellent as surfactants alone or admixed with other surfactants for use in water borne coatings.
Description
ETHOXYLATED ACETYLENIC GLYCOLS
HAVING LOW DYNAMIC SURFACE TENSION
FIELD OF THE INVENTION
This invention relates to ethoxylated acetylenic glycols suitability as a surfactant for aqueous coating systems.
BACKGROUND OF THE INVENTION
The waterborne coatings and ink industries require surfactants that provide excellent surface tension reducing capabilities for substrate wetting. Equilibrium surface tension performance is important when the system is at rest. End-users also need surfactants with good dynamic performance which is a measure of a surfactant's ability to provide wetting under high speed application such as when coatings are spray applied or inks are printed.
Traditional nonionic surfactants such as alkylaryl or alcohol ethoxylates, and ethylene oxide (EO)-propylene oxide (PO) copolymers have excellent equilibrium surface tension performance but are generally characterized as having poor dynamic surface tension reduction. In contrast, certain anionic surfactants such as sodium dialkyl sulfosuccinates can provide good dynamic results, but these are very foamy and impart water sensitivity to the finished coating.
Surfactants based on acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol and its ethoxylates are known for their good balance of equilibrium and dynamic surface tension reducing capabilities with little of the negative features of traditional nonionic and anionic surfactants. The molecules, however, may not provide the very low surface tension reduction needed for the wetting of contaminated surfaces or low surface energy substrates. In those cases, end-users may require silicone or fluorocarbon based surfactants which may be costly, foamy, exhibit poor dynamic performance and often cause adhesion problems.
The following patents and articles describe various acetylenic alcohols and their ethoxylates as surface active agents:
..
US 3,268,593 discloses ethyleneoxide adducts of tertiary acetylenic alcohols represented by the structural formula H(OCHzCH2)yO O(lH2cH2)xH
wherein R1 and R4 are alkyl radicals having from 3-10 carbon atoms and R2 and R3 are methyl or ethyl and x and y have a sum in the range of 3 to 60, inclusive. Specific ethyleneoxide adducts include the ethyleneoxide adducts of 3-methyl-1-nonyn-3-ol; 7,10-dimethyl-8-hexadecyne-7,10-diol;
HAVING LOW DYNAMIC SURFACE TENSION
FIELD OF THE INVENTION
This invention relates to ethoxylated acetylenic glycols suitability as a surfactant for aqueous coating systems.
BACKGROUND OF THE INVENTION
The waterborne coatings and ink industries require surfactants that provide excellent surface tension reducing capabilities for substrate wetting. Equilibrium surface tension performance is important when the system is at rest. End-users also need surfactants with good dynamic performance which is a measure of a surfactant's ability to provide wetting under high speed application such as when coatings are spray applied or inks are printed.
Traditional nonionic surfactants such as alkylaryl or alcohol ethoxylates, and ethylene oxide (EO)-propylene oxide (PO) copolymers have excellent equilibrium surface tension performance but are generally characterized as having poor dynamic surface tension reduction. In contrast, certain anionic surfactants such as sodium dialkyl sulfosuccinates can provide good dynamic results, but these are very foamy and impart water sensitivity to the finished coating.
Surfactants based on acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol and its ethoxylates are known for their good balance of equilibrium and dynamic surface tension reducing capabilities with little of the negative features of traditional nonionic and anionic surfactants. The molecules, however, may not provide the very low surface tension reduction needed for the wetting of contaminated surfaces or low surface energy substrates. In those cases, end-users may require silicone or fluorocarbon based surfactants which may be costly, foamy, exhibit poor dynamic performance and often cause adhesion problems.
The following patents and articles describe various acetylenic alcohols and their ethoxylates as surface active agents:
..
US 3,268,593 discloses ethyleneoxide adducts of tertiary acetylenic alcohols represented by the structural formula H(OCHzCH2)yO O(lH2cH2)xH
wherein R1 and R4 are alkyl radicals having from 3-10 carbon atoms and R2 and R3 are methyl or ethyl and x and y have a sum in the range of 3 to 60, inclusive. Specific ethyleneoxide adducts include the ethyleneoxide adducts of 3-methyl-1-nonyn-3-ol; 7,10-dimethyl-8-hexadecyne-7,10-diol;
2,4,7,9-tetramethyl-5-decyne-4,7-diol; and 4,7-dimethyl-5-decyne-4,7-diol. Preferably, the ethyleneoxide adducts range from 3 to 20 units. The patentees point out that these ethyleneoxide adducts have outstanding wetting property and that the presence of the acetylenic bond in the hydrophobic chain increases water solubility and improves surfactant properties. As the oxyethylene chain link increases, both detergency and amount of foam increase, and the wetting times decrease with increasing polyoxyethylene chain length.
US 4,117,249 discloses acetylenic glycols represented by the structural formula CH3-C~CH-CH2-CH2-CIC-C-l-CH2-R
OH OH
wherein R is hydrogen or an alkenyl radical. The acetylenic glycols are acknowledged as having utility as surface active agents and they can be 3~ used as wetting agents, dispersants, antifoaming nonionic agents and viscosity stabilizers.
In an article, Schwartz, The Importance of Low Dynamic Surface Tension in Waterborne Coatinqs, Journol of Coct~ngs Technology (1992), there is discussion of surface tension properties in waterborne coatings and a discussion of dynamic surface tension in such coatings.
Equilibrium surface and dynamic surface tension are evaluated for several surface active agents including the ethyleneoxide adducts of acetylenic glycol, e.g., the 4,7-ethyleneoxide the 3.5 mole adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol where the number of ethyleneoxide units ranges from about 1.3 to 30, as well as the acetylenic glycols themselves, and ethyleneoxide adducts of other aromatic and aliphatic alcohols, e.g., nonylphenol and lauryl alcohol. At a concentration of 0.1% in distilled water, the dynamic surface tension ranges from a low of about 32 to a high of 72 dynes per centimeter.
SUMMARY OF THE INVENTION
This invention pertains to an ethoxylated 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol. The ethoxylated acetylenic glycol is represented by the formula:
lCH3 CH3 ~CH3 ~CH3 CH3-cH-cH2-cH2-c-c-- C-C-CH2-CH2-CH-CH3 O O
/¢H~ ~CH~
~CH2 m ~ H~ n H H
wherein m and n are integers and the sum is from 2-50, preferably 4-10.
There are significant advantages associated with the ethoxylated acetylenic glycol of this invention and these advantages include:
an ability to formulate water borne coatings and inks ha~ing excellent resistance to water;
an ability to produce water borne coatings and inks which may be applied to a variety of substrates with excellent wetting of substrate surfaces including contaminated and low energy surfaces;
an ability to provide a reduction in coating or printing defects such as orange peel and flow/leveling deficiencies;
an ability to produce water borne coatings and inks which have low volatile organic content thuS making these surfactants environmentally favorable; and an ability to formulate coating and ink compositions capable of high speed application.
DETAILED DESCRIPTION OF T~E INVENTION
The surfactants of this invention are ethoxylates of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol. These ethoxylates, because of their ability to decrease the surface tension of aqueous systems, have wide utility in formulating coating and ink formulations. The moles ethoxylate per mole of acetylenic glycol range from 2-50, preferably 3-10 and most preferably 4-7. When the moles ethoxylate ranges below the lower end of the scale, and when the ethoxylate ranges above the upper end of the scale, properties of the aqueous system may deteriorate.
The ethoxylates may be applied to a variety of substrates and these include metals, organic (e.g. oil) contaminated surfaces, plastics, composites, wood, glass, ceramics and other substrates that are printed or require a protective/decorative coating.
The ethoxylates may be combined with other surface active agents, e.g., dioctylsodium sulfosuccinate and ethoxylated alcohols, e.g., ethoxylated C5 l2 alkyl phenols and higher (8-16) alkanols. Surfactant levels typically range from 50-90 parts ethoxylated acetylenic glycol composition per 10-50 parts conventional surfactant.
Representative water based coating and ink formulations to which the ethoxylated acetylenic glycols may be added are as follows:
Typical Water Based Coatinq Formulation --O to 50 wt% Pigment Dispersant/Grind Resin 0 to 80 wt% Coloring Pigments/Extender Pigments/Anti-Corrosive Pigments other pigment types 5 to 99.9 wt% Waterborne/Water Dispersible/
Water-soluble Resins 0 to 30 wt% Slip Additives/Antimicrobials Processing Aids/Defoamers O to 50 wt% Coalescing or Other Solvents 0.01 to 10 wt% Surfactant/Wetting Agent/Flow and Leveling Agents Typi cal Water Based Coatinq Formulation O to 50 wt% Pigment Dispersant/Grind Resin O to 80 wt% Coloring Pigments/Extender Pigments other pigment types 5 to 99.9 wt% Waterborne/Water Dispersible/
Water-soluble Resins O to 30 wt% Slip Additives/Antimicrobials Processing Aids/Defoamers O to 50 wt% Coalescing or Other Solvents 0.01 to 10 wt% Surfactant/Wetting Agent/Flow and Leveling Agents The ethoxylated derivatives of this invention may be prepared in a manner similar to that used in producing the corresponding ethoxylated tertiary acetylenic glycols which are homologs and analogs to the derivatives described herein. Typically these involve the reaction of an aliphatic ketone with acetylene in the presence of potassium hydroxide followed by reaction with preselected molar levels of ethylene oxide. The outstanding surface tension reduction performance and other properties of the tetramethyldodecynediol ethoxylates are illustrated in the following examples.
Comparative Evaluation of Surfactant Systems A series of aqueous systems were prepared for determining the effect of various surfactants on equilibrium and dynamic surface tension. Aqueous systems containing 0.1% of active surfactant were evaluated. ~n preparing the ethoxylated acetylenic glycols, ethylene oxide was reacted with the surfactant base glycol. The moles EO
represents the number of moles ethylene oxide reacted per mole of base glycol. The results are as follows:
-0.1 wt% in Water Surface Tension, dynes/cm Surfactant Moles Equilibrium Dynamic Base Glycol Ethyleneoxide Per Mole G1YCO1 104* 1.3 32 35.1 104 3.5 34 37.3 104 10 43.1 46 104 30 48.2 50.2 124** 4 26.7 31.2 124 6 26.6 29.8 124 10 29.6 32.7 *104 is a designation for 2,4,7,9-tetramethyl-5-decyne-4,7-diol sold under the trademark Surfynol.
- **124 is a designation for 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.
The above comparative studies confirms the superior wetting capabilities of the ethoxylated dodecynediol surfactants, particularly at a level of about 6 moles (5-7) ethylene oxide over other high performance ethoxylated acetylenic glycol based surfactants. In contrast to the ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7=diol, the ethoxylated 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol surfactants imparted much lower equilibrium and dynamic surface tension at the lower ethoxylate levels.
To determine the effectiveness of the surfactant properties with other surfactant compositions, the ethoxylated derivatives of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol were mixed with other conventional surfactants. These included ethoxylated derivatives of nonyl phenol, acetylenic glycols and diocytlsodiumsulfosuccinate (DOSS). The results are shown in Table 2.
Table 2 0.1 wt% in Water;
Surface Tension, dynes/cm Surfactant Ratio Moles Equilibrium Dynamic Base Glycol Wt. Parts Ethyleneoxide Per Mole Glycol 124/CO-730a 75/25 6 25.5 30.2 124/DOSS 75/25 6 24.9 27.7 124/Surfynol 420b 90/10 - 6 24.4 27.3 124/CO-730 75/25 4 z5.4 30.7 124/DOSS 75/25 4 25.5 31.7 (a) Nonyl phenol ethoxylate.
(b) Surfynol 420 is a designation for the 1.3 mole ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol.
The above results show that favorable surfactant properties can be achieved by combinin~ the ethoxylated derivative of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol with conventional surfactants. The results appear to show some synergism in that considerably lower equilibrium and dynamic surface tension results were obtained with the admixture than were obtained obtained with the ethoxylated derivative alone.
E:\RL8\113PU505142.APE
US 4,117,249 discloses acetylenic glycols represented by the structural formula CH3-C~CH-CH2-CH2-CIC-C-l-CH2-R
OH OH
wherein R is hydrogen or an alkenyl radical. The acetylenic glycols are acknowledged as having utility as surface active agents and they can be 3~ used as wetting agents, dispersants, antifoaming nonionic agents and viscosity stabilizers.
In an article, Schwartz, The Importance of Low Dynamic Surface Tension in Waterborne Coatinqs, Journol of Coct~ngs Technology (1992), there is discussion of surface tension properties in waterborne coatings and a discussion of dynamic surface tension in such coatings.
Equilibrium surface and dynamic surface tension are evaluated for several surface active agents including the ethyleneoxide adducts of acetylenic glycol, e.g., the 4,7-ethyleneoxide the 3.5 mole adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol where the number of ethyleneoxide units ranges from about 1.3 to 30, as well as the acetylenic glycols themselves, and ethyleneoxide adducts of other aromatic and aliphatic alcohols, e.g., nonylphenol and lauryl alcohol. At a concentration of 0.1% in distilled water, the dynamic surface tension ranges from a low of about 32 to a high of 72 dynes per centimeter.
SUMMARY OF THE INVENTION
This invention pertains to an ethoxylated 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol. The ethoxylated acetylenic glycol is represented by the formula:
lCH3 CH3 ~CH3 ~CH3 CH3-cH-cH2-cH2-c-c-- C-C-CH2-CH2-CH-CH3 O O
/¢H~ ~CH~
~CH2 m ~ H~ n H H
wherein m and n are integers and the sum is from 2-50, preferably 4-10.
There are significant advantages associated with the ethoxylated acetylenic glycol of this invention and these advantages include:
an ability to formulate water borne coatings and inks ha~ing excellent resistance to water;
an ability to produce water borne coatings and inks which may be applied to a variety of substrates with excellent wetting of substrate surfaces including contaminated and low energy surfaces;
an ability to provide a reduction in coating or printing defects such as orange peel and flow/leveling deficiencies;
an ability to produce water borne coatings and inks which have low volatile organic content thuS making these surfactants environmentally favorable; and an ability to formulate coating and ink compositions capable of high speed application.
DETAILED DESCRIPTION OF T~E INVENTION
The surfactants of this invention are ethoxylates of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol. These ethoxylates, because of their ability to decrease the surface tension of aqueous systems, have wide utility in formulating coating and ink formulations. The moles ethoxylate per mole of acetylenic glycol range from 2-50, preferably 3-10 and most preferably 4-7. When the moles ethoxylate ranges below the lower end of the scale, and when the ethoxylate ranges above the upper end of the scale, properties of the aqueous system may deteriorate.
The ethoxylates may be applied to a variety of substrates and these include metals, organic (e.g. oil) contaminated surfaces, plastics, composites, wood, glass, ceramics and other substrates that are printed or require a protective/decorative coating.
The ethoxylates may be combined with other surface active agents, e.g., dioctylsodium sulfosuccinate and ethoxylated alcohols, e.g., ethoxylated C5 l2 alkyl phenols and higher (8-16) alkanols. Surfactant levels typically range from 50-90 parts ethoxylated acetylenic glycol composition per 10-50 parts conventional surfactant.
Representative water based coating and ink formulations to which the ethoxylated acetylenic glycols may be added are as follows:
Typical Water Based Coatinq Formulation --O to 50 wt% Pigment Dispersant/Grind Resin 0 to 80 wt% Coloring Pigments/Extender Pigments/Anti-Corrosive Pigments other pigment types 5 to 99.9 wt% Waterborne/Water Dispersible/
Water-soluble Resins 0 to 30 wt% Slip Additives/Antimicrobials Processing Aids/Defoamers O to 50 wt% Coalescing or Other Solvents 0.01 to 10 wt% Surfactant/Wetting Agent/Flow and Leveling Agents Typi cal Water Based Coatinq Formulation O to 50 wt% Pigment Dispersant/Grind Resin O to 80 wt% Coloring Pigments/Extender Pigments other pigment types 5 to 99.9 wt% Waterborne/Water Dispersible/
Water-soluble Resins O to 30 wt% Slip Additives/Antimicrobials Processing Aids/Defoamers O to 50 wt% Coalescing or Other Solvents 0.01 to 10 wt% Surfactant/Wetting Agent/Flow and Leveling Agents The ethoxylated derivatives of this invention may be prepared in a manner similar to that used in producing the corresponding ethoxylated tertiary acetylenic glycols which are homologs and analogs to the derivatives described herein. Typically these involve the reaction of an aliphatic ketone with acetylene in the presence of potassium hydroxide followed by reaction with preselected molar levels of ethylene oxide. The outstanding surface tension reduction performance and other properties of the tetramethyldodecynediol ethoxylates are illustrated in the following examples.
Comparative Evaluation of Surfactant Systems A series of aqueous systems were prepared for determining the effect of various surfactants on equilibrium and dynamic surface tension. Aqueous systems containing 0.1% of active surfactant were evaluated. ~n preparing the ethoxylated acetylenic glycols, ethylene oxide was reacted with the surfactant base glycol. The moles EO
represents the number of moles ethylene oxide reacted per mole of base glycol. The results are as follows:
-0.1 wt% in Water Surface Tension, dynes/cm Surfactant Moles Equilibrium Dynamic Base Glycol Ethyleneoxide Per Mole G1YCO1 104* 1.3 32 35.1 104 3.5 34 37.3 104 10 43.1 46 104 30 48.2 50.2 124** 4 26.7 31.2 124 6 26.6 29.8 124 10 29.6 32.7 *104 is a designation for 2,4,7,9-tetramethyl-5-decyne-4,7-diol sold under the trademark Surfynol.
- **124 is a designation for 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.
The above comparative studies confirms the superior wetting capabilities of the ethoxylated dodecynediol surfactants, particularly at a level of about 6 moles (5-7) ethylene oxide over other high performance ethoxylated acetylenic glycol based surfactants. In contrast to the ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7=diol, the ethoxylated 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol surfactants imparted much lower equilibrium and dynamic surface tension at the lower ethoxylate levels.
To determine the effectiveness of the surfactant properties with other surfactant compositions, the ethoxylated derivatives of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol were mixed with other conventional surfactants. These included ethoxylated derivatives of nonyl phenol, acetylenic glycols and diocytlsodiumsulfosuccinate (DOSS). The results are shown in Table 2.
Table 2 0.1 wt% in Water;
Surface Tension, dynes/cm Surfactant Ratio Moles Equilibrium Dynamic Base Glycol Wt. Parts Ethyleneoxide Per Mole Glycol 124/CO-730a 75/25 6 25.5 30.2 124/DOSS 75/25 6 24.9 27.7 124/Surfynol 420b 90/10 - 6 24.4 27.3 124/CO-730 75/25 4 z5.4 30.7 124/DOSS 75/25 4 25.5 31.7 (a) Nonyl phenol ethoxylate.
(b) Surfynol 420 is a designation for the 1.3 mole ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol.
The above results show that favorable surfactant properties can be achieved by combinin~ the ethoxylated derivative of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol with conventional surfactants. The results appear to show some synergism in that considerably lower equilibrium and dynamic surface tension results were obtained with the admixture than were obtained obtained with the ethoxylated derivative alone.
E:\RL8\113PU505142.APE
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An ethoxylated acetylenic glycol composition the formula:
wherein m and n are integers and the sum is from 2-50.
wherein m and n are integers and the sum is from 2-50.
2. The composition of Claim 1 wherein the sum of m plus n is from 3-10.
3. The composition of Claim 1 wherein the sum of m plus n is from 4-7.
4. The composition of Claim 1 wherein the ethoxylated acetylenic glycol composition is admixed with a surfactant selected from the group consisting of an ethoxylated derivative of a C5-12 alkyl phenol and dioctylsodiumsulfosuccinate.
5. The composition of Claim 4 wherein the ethoxylated acetylenic glycol composition is admixed with a C5-12 alkyl phenol in a weight ratio of from 50-90 weight parts ethoxylated acetylenic glycol composition per 10-50 weight parts to C5-12 alkyl phenol.
6. The composition of Claim 4 wherein the ethoxylated acetylenic glycol composition is admixed with dioctylsulfosuccinate in a weight ratio of from 50-90 weight parts ethoxylated acetylenic glycol composition per 10-50 weight parts dioctylsodiumsulfosuccinate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15867293A | 1993-11-29 | 1993-11-29 | |
| US08/158672 | 1993-11-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2136373A1 true CA2136373A1 (en) | 1995-05-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002136373A Abandoned CA2136373A1 (en) | 1993-11-29 | 1994-11-22 | Ethoxylated acetylenic glycols having low dynamic surface tension |
Country Status (5)
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| US (1) | US5650543A (en) |
| EP (2) | EP0897744B1 (en) |
| JP (1) | JPH07188087A (en) |
| CA (1) | CA2136373A1 (en) |
| DE (2) | DE69417356T2 (en) |
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| EP0618000B1 (en) * | 1992-08-06 | 1996-03-20 | Air Products And Chemicals, Inc. | Water soluble surfactant compositions |
-
1994
- 1994-11-22 CA CA002136373A patent/CA2136373A1/en not_active Abandoned
- 1994-11-23 EP EP98114923A patent/EP0897744B1/en not_active Expired - Lifetime
- 1994-11-23 DE DE69417356T patent/DE69417356T2/en not_active Expired - Lifetime
- 1994-11-23 EP EP94118433A patent/EP0655495B1/en not_active Expired - Lifetime
- 1994-11-23 DE DE69426678T patent/DE69426678T2/en not_active Expired - Lifetime
- 1994-11-28 JP JP6292619A patent/JPH07188087A/en active Pending
-
1995
- 1995-08-31 US US08/524,129 patent/US5650543A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69426678T2 (en) | 2001-05-23 |
| EP0897744B1 (en) | 2001-02-07 |
| EP0655495A1 (en) | 1995-05-31 |
| EP0897744A1 (en) | 1999-02-24 |
| DE69417356T2 (en) | 1999-07-15 |
| US5650543A (en) | 1997-07-22 |
| DE69417356D1 (en) | 1999-04-29 |
| JPH07188087A (en) | 1995-07-25 |
| DE69426678D1 (en) | 2001-03-15 |
| EP0655495B1 (en) | 1999-03-24 |
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