Secondary Alkane Sulfonate (SAS) is an anionic surfactant, also called paraffine sulfonate. It was synthesized for the first time in 1940 and has been used as surfactant since the 1960ies. Alkane sulfonate is one of the major anionic surfactants used in the market of dishwashing, laundry and cleaning products. The European consumption of Alkane sulfonate in detergent application covered by HERA was about 66.000 tons/year in 2001.
ALKANE SULFONATE
CAS No. : 68037-49-0/85711-69-9
EC No. : 288-330-3
Synonyms:
Secondary Alkane Sulfonate (SAS)(CAS 68037-49-0); Sulfonic acids, C10-18-alkane, sodium salts; SAS; n-alkyl(C10-C18) sulfonic acids, sodium salts (C10-C18); alkylsulfonic acid, sodium salt; sodium C14-17 alcohol sulfonate; volgonat; SODIUM C14-17 ALKYL SEC SULFONATE; Softifloc; SECONDARYALKANESULFONATE; ALKYL(C10-C18)SULPHONICACIDS; C10-18ALKANESULFONICACIDS,SODIUMSALTS; sek.Alkan(C-C17)-sulfonate; Sulfonsauren, C10-18-Alkan-, Natriumsalze; Sulfonic acids, C13-17-sec-alkane, sodium salts; Sulfonates, C13-17-sec-alkanesulfonates, sodium salts; Sulfonic acids, C13-17-sec-alkane, sodium salts; Emulsogen EP; Hostapur SAS 30; SAS 30; Sodosil RM 02; Sulfonic acids, C10-18-alkane, sodium salts; Sodium 1-tetradecanesulfonate; 6994-45-2; sodium tetradecane-1-sulfonate; Sodium myristylsulfonate; 1-Tetradecanesulfonic acid sodium salt; (C10-C18)Alkylsulfonic acid, sodium salt; 27175-91-3; 68037-49-0; Volgonat; Sulfonic acids, C10-18-alkane, sodium salts; Sodium C14-17 alcohol sulfonate; EINECS 248-288-9; EINECS 268-213-3; 1-Tetradecanesulfonic acid, sodium salt; sodyum alkane sülfonat ; ; SODYUM ALKAN SÜLFONAT ; sodyumalkan sülfonat ; sodyum alkan sülfonat ; sodiumalkane sulphonate , sodium alkane sulphonate; sodium alkanesulfonate ; Sulfonic acids, C13-17-sec-alkane, sodium salts ; hostapur SAS 60, alkan sülfonat, sekonder, parafin sülfonat ; Parafin Sülfonat ; Hostapur SAS 60 ; Secondary alkane sulphonate, sodium salt ; Sulfonates , C13-17-sec-alkanesulfonates , sodium salts ; Sulfonic acids , C13-17-sec-alkane , sodium salts ; Alkanesulfonates, C13-17-sec , sodium salts ; Emulsogen EP ; Hostapur SAS 30 ; SAS 30 ; Sulfonates , alkanesulfonates , C13-17-sec , sodium salts ; Sulfonic acids, C13-17-sec-alkane, sodium salts ; SOFTIFLOCK NF2 ; Alkyl C13-C17 -sulfonate, Sodium salt ; SODIUMC13-C17SECONDARYALKANESULPHONATE ; C13-C17SEC-ALKANESULPHONICACID , SODIUMSALT ; Sulfonsauren , C13-17-sec-Alkan-, Natriumsalze ; sec-Alkane-(C13-C17)-sulfonic acid sodium salt ; Einecs 288-330-3 ; Sulfonic acids, C13-17-sec- ; SAS, Hostapur SAS 60, Alkane Sulfonate, Hostapur SAS 93, Sodium Alkane Sulfonate, Sulfonic acids, C14-17-sec-alkane, sodium salts; Secondary Alkane Sulfonate Sodium Salt; Alkyl C14-17 Sulfonate ; Hostaphur SAS 60 ; Hostapur SAS 30 ; alkan sulfonat ; alkansülfonat ; alkansulfonat ; alkane sulphonate ; alkan sulphonate ; HOSTAPUR SAS 60 ; HOSTAPHUR SAS 60 ; SECONDARY ALKANE SULPHONATE ; secondary alkane sulphonate ;HOSTAPUR SAS 30 ; SULFONİC ACİDS, C13-17-SEC-ALKANE, SODİUM SALTS; sodium tetradecyl sulfonate; n-Alkyl(C10-C18)sulfonic acids, sodium salts; Sodium1-Tetradecanesulfonate; Secondary Alkane Sulfonate (SAS)(CAS 68037-49-0); Sulfonic acids, C10-18-alkane, sodium salts; SAS; n-alkyl(C10-C18)sulfonic acids, sodium salts (C10-C18); alkylsulfonic acid, sodium salt; sodium C14-17 alcohol sulfonate; volgonat; SODIUM C14-17 ALKYL SEC SULFONATE; Softifloc; SECONDARYALKANESULFONATE; ALKYL(C10-C18)SULPHONICACIDS; C10-18ALKANESULFONICACIDS,SODIUMSALTS; sek.Alkan(C-C17)-sulfonate; Sulfonsauren, C10-18-Alkan-, Natriumsalze; Sulfonic acids, C13-17-sec-alkane, sodium salts; Sulfonates, C13-17-sec-alkanesulfonates, sodium salts; Sulfonic acids, C13-17-sec-alkane, sodium salts; Emulsogen EP; Hostapur SAS 30; SAS 30; Sodosil RM 02; Sulfonic acids, C10-18-alkane, sodium salts; Sodium 1-tetradecanesulfonate; 6994-45-2; sodium tetradecane-1-sulfonate; Sodium myristylsulfonate; 1-Tetradecanesulfonic acid sodium salt; (C10-C18)Alkylsulfonic acid, sodium salt; Sodium 1-tetradecanesulphonate; CHEMBL551089; Sodium C10-18 alkyl sulfonate; CTK4F9218; DTXSID70892954; Tetradecylsulfonic Acid Sodium Salt; KS-000012NK; Sodium C14-17 alkyl sec sulfonate; ANW-35800; Tetradecane-1-sulfonic acid, sodium salt; Tetradecanesulfonicacid, sodium salt (1:1)
Alkane Sulfonate
Alkane sulfonates are esters of alkane sulfonic acids with the general formula R-SO2-O-R'. They act as alkylating agents, some of them are used as alkylating antineoplastic agents in the treatment of cancer, e.g. Busulfan.
Secondary Alkane Sulfonate (SAS) is an anionic surfactant, also called paraffine sulfonate. It was synthesized for the first time in 1940 and has been used as surfactant since the 1960ies. Alkane sulfonate is one of the major anionic surfactants used in the market of dishwashing, laundry and cleaning products. The European consumption of Alkane sulfonate in detergent application covered by HERA was about 66.000 tons/year in 2001.
Human Health
The presence of Alkane sulfonate in many commonly used household detergents gives rise to a variety of possible consumer contact scenarios including direct and indirect skin contact, inhalation, and oral ingestion derived either from residues deposited on dishes, from accidental product ingestion, or indirectly from drinking water. The consumer aggregate exposure from direct and indirect skin contact as well as from inhalation and from oral route in drinking water and dishware results in an estimated total body burden of 3.87 µg/kg bw/day.
The toxicological data show that Alkane sulfonate was not genotoxic in vitro or in vivo, did not induce tumors in rodents after two years daily dosing using both, the oral and dermal route of exposure, and failed to induce either reproductive toxicity or developmental or teratogenic effects. The critical adverse effects identified are of local nature mainly due to the irritating properties of high concentrated Alkane sulfonate. Comparison of the aggregate consumer exposure to Alkane sulfonate with a systemic NOEL of 180 mg/kg body weigh per day (assuming 90% absorption; adapted from Michael, 1968) which is based on a chronic feeding study, results in an estimated Margin of Exposure (MOE) of 46500. This is a very large Margin of Exposure, large enough to account for the inherent uncertainty and variability of the hazard database and inter species and intra species extrapolations (which are usually conventionally estimated at a factor of 100). Neat Alkane sulfonate is an irritant to skin and eyes in rabbits. The irritation potential of aqueous solutions of Alkane sulfonate depends on concentration. However, well documented human volunteer studies indicate that Alkane sulfonate up to concentrations of 60% active matter is not a significant skin irritant in humans. Local effects of hand wash solutions containing Alkane sulfonate do not cause concern given that Alkane sulfonate is not a contact sensitizer and that the concentrations of Alkane sulfonate in such solutions are well below 1% and therefore not expected to be irritating to eye or skin. Laundry pre-treatment tasks, which may translate into brief hand skin contact with higher concentrations of Alkane sulfonate, may occasionally result in mild irritation easily neutralized by prompt rinsing of the hands in water. Potential irritation of the respiratory tract is not a concern given the very low levels of airborne Alkane sulfonate generated as a consequence of cleaning spray aerosols or laundry powder detergent dust.
In view of the extensive database on toxic effects, the low exposure values calculated and the resulting large Margin of Exposure described above, it can be concluded that use of Alkane sulfonate in household laundry and cleaning products raises no safety concerns for the consumers.
Use applications summary
Most of the European consumption of Alkane sulfonate is in household cleaning. The far most important use is in dishwashing liquids, other minor applications are laundry detergents, household cleaners, cosmetics hair and body care products, industrial cleaners and special technical sectors (see 5.1.1).
Claims
1. Alkane sulfonic acid or alkane sulfonate composition, which composition comprises a monosubstituted alkane substituted by one sulfonic acid or sulfonate group and optionally a disubstituted alkane substituted by two sulfonic acid or sulfonate groups, wherein if the composition comprises said disubstituted alkane the molar ratio of the monosubstituted alkane to the disubstituted alkane is equal to or higher than 12:1 and is preferably in the range of from 12:1 to 10,000:1.
2. Alkane sulfonic acid or alkane sulfonate composition according to claim 1, wherein the molar ratio of the monosubstituted alkane to the disubstituted alkane is in the range of from 12:1 to 5,000:1, preferably 15:1 to 1,000:1, more preferably 20:1 to 500:1.
3. Alkane sulfonic acid or alkane sulfonate composition according to claim 1 or 2, wherein the alkanes have an average carbon number in the range of from 5 to 30, preferably 12 to 26, more preferably 14 to 24, more preferably 16 to 24, most preferably 18 to 22.
4. Alkane sulfonic acid or alkane sulfonate composition according to any one of the preceding claims, wherein one or more alkane sulfonic acids or alkane sulfonates are selected from the group consisting of C14-17 AS, C18-20 AS, C18-23 AS and C19-24 AS, preferably from the group consisting of C14-17 AS, C18-20 AS and C18-23 AS, wherein "AS" stands for "alkane sulfonic acid" or "alkane sulfonate".
5. Alkane sulfonic acid or alkane sulfonate composition according to claim 4, wherein one or more alkane sulfonic acids or alkane sulfonates are selected from the group consisting of C18-20 AS and C18-23 AS, preferably C18-23 AS.
6. Alkane sulfonic acid or alkane sulfonate composition according to any one of the preceding claims, which composition further comprises one or more surfactants selected from the group consisting of internal olefin sulfonates (IOS), alkoxylated alcohol sulfates, carboxylates and glycerol sulfonates, linear alkyl benzene sulfonates (LABS), and heavy alkyl benzene sulfonates (HABS).
7. Process for treatment of an alkane sulfonic acid or alkane sulfonate composition, which composition comprises a monosubstituted alkane substituted by one sulfonic acid or sulfonate group and a disubstituted alkane substituted by two sulfonic acid or sulfonate groups, in which process substantially all of the disubstituted alkane is removed or the disubstituted alkane is removed to such extent that the molar ratio of the monosubstituted alkane to the disubstituted alkane is increased to a value which is equal to or higher than 12:1 and is preferably in the range of from 12:1 to 10,000:1.
8. A method of treating a hydrocarbon containing formation, comprising the following steps:
a) providing an alkane sulfonic acid or alkane sulfonate composition, which composition comprises a monosubstituted alkane substituted by one sulfonic acid or sulfonate group and optionally a disubstituted alkane substituted by two sulfonic acid or sulfonate groups, wherein if the composition comprises said disubstituted alkane the molar ratio of the monosubstituted alkane to the disubstituted alkane is equal to or higher than 12:1 and is preferably in the range of from 12:1 to 10,000:1, or the composition as obtained by the process of claim 7, to at least a portion of the hydrocarbon containing formation; and
b) allowing the alkane sulfonic acid or alkane sulfonate from the composition to interact with the hydrocarbons in the hydrocarbon containing formation.
9. Method according to claim 8, wherein the molar ratio of the monosubstituted alkane to the disubstituted alkane is in the range of from 12:1 to 5,000:1, preferably 15:1 to 1,000:1, more preferably 20:1 to 500:1.
10. Method according to claim 8 or 9, wherein the alkanes have an average carbon number in the range of from 5 to 30, preferably 12 to 26, more preferably 14 to 24, more preferably 16 to 24, most preferably 18 to 22.
11. Method according to any one of claims 8-10, wherein one or more alkane sulfonic acids or alkane sulfonates are selected from the group consisting of C14-17 AS, C18-20 AS, C18-23 AS and C19-24 AS, preferably from the group consisting of C14-17 AS, C18-20 AS and C18-23 AS, wherein "AS" stands for "alkane sulfonic acid" or "alkane sulfonate".
12. Method according to claim 11, wherein one or more alkane sulfonic acids or alkane sulfonates are selected from the group consisting of C18-20 AS and C18-23 AS, preferably C18-23 AS.
13. Method according to any one of claims 8-12, which composition further comprises one or more surfactants selected from the group consisting of internal olefin sulfonates (IOS), alkoxylated alcohol sulfates, carboxylates and glycerol sulfonates, linear alkyl benzene sulfonates (LABS), and heavy alkyl benzene sulfonates (HABS).
Summary of the invention
Surprisingly, it was found that an alkane sulfonic acid or alkane sulfonate composition having such improved cEOR performance parameter(s) is a composition which comprises a monosubstituted alkane substituted by one sulfonic acid or sulfonate group and optionally a disubstituted alkane substituted by two sulfonic acid or sulfonate groups, wherein if the composition comprises said disubstituted alkane the molar ratio of the monosubstituted alkane to the disubstituted alkane is equal to or higher than 12:1 and is preferably in the range of from 12:1 to 10,000:1.
Accordingly, the present invention relates to an alkane sulfonic acid or alkane sulfonate composition as described above.
Further, the present invention relates to a process for treatment of an alkane sulfonic acid or alkane sulfonate composition, which composition comprises a monosubstituted alkane substituted by one sulfonic acid or sulfonate group and a disubstituted alkane substituted by two sulfonic acid or sulfonate groups, in which process substantially all of the disubstituted alkane is removed or the disubstituted alkane is removed to such extent that the molar ratio of the monosubstituted alkane to the disubstituted alkane is increased to a value which is equal to or higher than 12:1 and is preferably in the range of from 12:1 to 10,000:1.
Still further, the present invention relates to a method of treating a hydrocarbon containing formation, comprising the following steps:
a) providing the composition as described above or the composition as obtained by the process as described above to at least a portion of the hydrocarbon containing formation; and
b) allowing the alkane sulfonic acid or alkane sulfonate from the composition to interact with the hydrocarbons in the hydrocarbon containing formation.
Detailed description of the invention
In one aspect, the present invention relates to an alkane sulfonic acid or alkane sulfonate composition, which composition comprises a monosubstituted alkane substituted by one sulfonic acid or sulfonate group and optionally a disubstituted alkane substituted by two sulfonic acid or sulfonate groups, wherein if the composition comprises said disubstituted alkane the molar ratio of the monosubstituted alkane to the disubstituted alkane is equal to or higher than 12:1 and is preferably in the range of from 12:1 to 10,000:1.
Thus, the composition of the present invention is an alkane sulfonic acid or alkane sulfonate composition, which comprises an alkane sulfonic acid or an alkane sulfonate. An alkane sulfonic acid is an alkane substituted by one or more sulfonic acid groups. An alkane sulfonate is an alkane substituted by one or more sulfonate groups.
In the present invention, said alkane sulfonic acid or alkane sulfonate composition comprises a monosubstituted alkane substituted by one sulfonic acid or sulfonate group and optionally a disubstituted alkane substituted by two sulfonic acid or sulfonate groups. This means that the composition of the present invention either comprises both said monosubstituted alkane and said disubstituted alkane or comprises said monosubstituted alkane and substantially no disubstituted alkane.
These products are used for the following industries / applications
pharma, cosmetics
body care
textile & leather
industrial cleaners
A field study was conducted to determine the mass flow of secondary alkane sulfonate (SAS) surfactants in a municipal wastewater treatment plant. The concentration of SAS in samples of sewage (raw sewage, primary and secondary effluent) was determined using solid-phase extraction with C18 disks and injection port derivatization with gas chromatography/mass selective detection (GC/MS). The concentration of SAS in raw and anaerobically-digested sludge was determined by ion-pair/supercritical fluid extraction and injection-port derivatization GC/MS. The removal of SAS from the waste stream is efficient (99.7%) with approximately 16% (w/w) transferred to sludge. Given current Swiss sludge disposal regulations, a maximum of approximately 350 mg m−2 SAS are applied every three years to a given section of agricultural soil. Of the total SAS mass flow entering the treatment plant, an average of 0.3% (w/w) is discharged to the adjacent receiving water stream.
Secondary alkane sulfonate is an anionic surfactant, which is manufactured by sulfoxidation of n-paraffins. It provides good water solubility, excellent grease and soil dispersing properties, high wetting properties, and distinct foaming power. Therefore, secondary alkane sulfonate is an important surfactant ingredient in detergents, especially dishwashing detergents.
Secondary alkane sulfonate can be manufactured either through sulfochlorination or sulfoxidation process. Under the sulfochlorination process, n-paraffins are converted into alkylsulfochlorides with sulfur dioxide and chlorine in radical reaction. The sulfochlorination process is primarily used for non-detergent technical purposes. Under the sulfoxidation process, secondary alkane sulfonate is manufactured by reacting n-paraffins with sulfur dioxide and oxygen in the presence of water. Products produced through the sulfoxidation process are primarily used in household care.
Secondary alkane sulfonate is widely employed in household cleaning applications, especially in dishwashing liquids and laundry detergents, owing to its efficient and effective properties. It is also used in cosmetics such as hair and body care products, household cleaners, and industrial cleaners. Therefore, rising demand for household products, high standard of living in developing nations, and increasing demand for hygienic products in emerging economies are boosting the secondary alkane sulfonate market. However, secondary alkane sulfonate can cause environmental and health concerns. Therefore, government agencies have imposed various regulations to address these issues. These agencies monitor toxicity levels to ensure they are within the permitted limit. Thus, implementation of stringent regulations is hampering the secondary alkane sulfonate market.
Product Characteristics
Excellent detergent/wetting agent
Excellent solubility - electrolyte compatibility - hardness tolerance
Enzyme and bleach compatible
Mildness profile superior to LAS
Foam profile similar to LAS
Viscous liquid/paste with special handling/storage requirements
Product Status
Commercially available – TSCA registered / DSL listed
Readily biodegradable
On-going production in Europe
Applications - any liquid cleaning
product application
Many other potential application
areas yet to be explored
Based on application, the secondary alkane sulfonate market can be segmented into chemical processing, surface-active substances, emulsion polymerization, and others. Secondary alkane sulfonate is used primarily in the emulsion polymerization of acrylonitrile, butadiene, vinyl chloride, acrylates, styrene, and other monomers, as it is stable and offers outstanding emulsifying properties. It is also employed as an auxiliary for the production and maintenance of emulsions. Additionally, secondary alkane sulfonate is used in textile auxiliary applications such as Kier boiling, bleaching, post-saponification, washing, and wetting. It provides high wetting power and good stability features. Thus, it is an ideal raw material for textile processing chemicals, leather auxiliaries, detergents, and cleaning products.
In terms of end-use industry, the secondary alkane sulfonate market can be divided into textile, household care, personal care, industrial cleaners, construction, and others. The household care segment is expected to dominate the secondary alkane sulfonate market during the forecast period, as secondary alkane sulfonate products provide high chemical stability across a wide range of pH values; emulsifying and cleaning performance with strong surfactant features; and value added washing performance. Additionally, rise in demand for high-quality personal care products and industrial cleaners is boosting the global secondary alkane sulfonate market.
CAS No. EINECS No. NAME
85711-69-9 288-330-3 Sulfonic acids, C13-17-sec-alkane, sodium salts
68037-49-0 268-213-3 Sulfonic acids, C10-18-alkane, sodium salts (used in IUCLID)
97489-15-1 307-055-2 Sulfonic acids, C14-17-sec-alkane, sodium salts
85711-70-2 288-331-9 Sulfonic acids, C14-18-sec-alkane, sodium salts
75534-59-7 - Sulfonic acids, C13-18-sec-alkane, sodium salts
Benefits
Strong grease removal
Excellent wetting & emulsification properties
Good particle soil removal
High tolerance towards hard water
Stability over a wide pH range and high compatibility with enzymes, electrolytes and oxidizing agents, like chlorine
Viscosity depressing action
Benzene and ethylene oxide free
Good skin compatibility
Low aquatic toxicity with low impact on the environment
Based on region, the secondary alkane sulfonate market can be segregated into North America, Asia Pacific, Europe, Latin America, and Middle East & Africa. Rapid industrialization in Asia Pacific, led by government support to augment the manufacturing business, is estimated to drive the secondary alkane sulfonate market in the region. Increase in demand for sulfonation products in various applications such as dish washing liquids & cleaners, industrial cleaners, and personal care products in North America is anticipated to boost the secondary alkane sulfonate market during the forecast period. However, implementation of stringent government regulations on human & environment in Europe is projected hamper the market growth.
Liquid detergent containing secondary alkane sulfonate and cationic surfactants
The invention relates to liquid laundry detergents and cleaners for textiles containing secondary alkanesulfonate and one or more cationic surfactants.
In addition to the washing powders, liquid detergents are very important today
Detergents for textiles. Liquid detergents contain surfactants as their main constituent. As a rule, several surfactants are used simultaneously in modern detergents.
The combination of anionic and nonionic has proven to be useful here
Surfactants.
Usually anionic surfactants are linear alkylbenzenesulfonates (LAS), fatty alcohol sulfates (FAS), secondary alkane sulfonates (SAS) and, in part, also Fatty alcohol ether sulfates (FAES) used. Come as nonionic surfactants
Ethoxylates of long-chain synthetic alcohols, e.g. the oxo alcohols, or of native fatty alcohols used.
As further essential ingredients, builders such as e.g. Polycarboxylates and solubilizers such as e.g. Ethanol, glycerine or propanediol. >
In addition, additive ingredients which are generally grouped together under the term washing assistants and contain the substance groups which are as diverse as foam regulators, grayness inhibitors, soil release polymers, enzymes, optical brighteners,
Color transfer inhibitors and dye fixatives.
For laundry care, so-called fabric softeners or laundry conditioners are used after washing. These give the laundry a pleasant soft feel, reduce wrinkles and reduce the wear of the laundry, as they reduce the fiber-fiber friction. These products contain cationic surfactants, essentially quaternary ammonium salts such as so-called ester quats. Unfortunately, so far, liquid detergents containing anionic surfactants could not be combined with cationic surfactants in order to impart a laundry-conditioning effect to the detergent and thus render the use of a softener superfluous. The reason for this is the lack of compatibility of the anionic surfactants with the cationic surfactants, which leads to a flocculation, precipitation or phase separation of the components.
A new methodology has been developed for the determination of secondary alkane sulfonates (SAS), an anionic surfactant, in environmental matrices. Sediment and sludge samples were extracted using pressurized liquid extraction and sonication, whereas wastewater and surface water samples were processed using solid-phase extraction. Extraction recoveries were acceptable for both aqueous (78–120%) and solid samples (83–100%). Determination of Alkane sulfonate was carried out by high or ultra performance liquid chromatography – mass spectrometry using ion trap and time-of-flight detectors. The methodology was applied to samples from Guadalete River (SW Spain), where Alkane sulfonate concentrations below 1 μg L−1 were measured in surface water, and from 72 to 9737 μg kg−1 in sediments. Differential partitioning was observed for Alkane sulfonate homologues as those having a longer hydrocarbon chain which preferentially sorbed onto particulate matter. A preliminary environmental risk assessment also showed that Alkane sulfonate measured levels were not harmful to the aquatic community in the sampling area.
Application
Hand dishwashing liquids, all liquid laundry and cleaning agents, especially suited for highly concentrated products and industrial cleaning agents.
Storage
Hostapur alkane sulfonate 60 can be stored for at least to 2 years in original sealed containers at room temperature under the recommended conditions. Protect from exposure to cold during transport and storage. The properties of Hostapur alkane sulfonate 60 are reversibly altered by exposure to cold. If Hostapur alkane sulfonate 60 becomes turbid, thickens or freezes through exposure to cold, thaw slowly at room temperature and afterwards stir briefly.