CN106146549A - Bio-based alkylthio phosphoric acid or derivatives thereof, its preparation method and application - Google Patents
Bio-based alkylthio phosphoric acid or derivatives thereof, its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of bio-based alkylthio phosphoric acid or derivatives thereof, its preparation method and application.This bio-based alkylthio phosphoric acid has a structure shown in formula (I):Wherein R1、R2, at least one in X, Y, Z, W, M be from organism-based raw material；R1、R2Independently be alkyl, hydroxyl, carbonyl or hetero atom；And at least one in X, Y, Z, W comprises sulphur atom, remaining is arbitrarily selected from O, S atom；And M be H or another there is the deriveding group of the molecule of structure shown in formula (I).The bio-based sulfur of the present invention at least one raw material sources in the building-up process of phosphoric acid or derivatives thereof in organism-based raw material, the most natural and reproducible raw material, have green, environmental friendliness, raw material is renewable, save the advantages such as the energy, can be widely used for the fields such as lubricating oil, grease, flotation agent, pesticide, fire retardant and rubber accelerator.
Description
Technical field
The present invention relates to a kind of alkylthio phosphoric acid and derivant thereof, particularly to a kind of bio-based alkylthio
Phosphoric acid or derivatives thereof, its preparation method and application, belong to machinery or material science.
Background technology
Along with minimizing, energy shortage problem and the progressively enhancing of people's environmental consciousness increasingly of fossil resources,
Replace petrochemical with bio-renewables to greatest extent, be applied to various types of materials and additive agent field,
It is increasingly becoming the emphasis of people's research.Bio-based materials is with Renewable resource as primary raw material, right reducing
While petrochemicals consume, also reduce the petroleum-based feedstock pollution in process of production to environment.
Bio-based materials refers to utilize renewable material, including crops, trees, other plant and residuum thereof and interior
Inclusion is raw material, the class new material manufactured by methods such as biological, chemistry and physics, bio-based materials
Product be generally of green, environmental friendliness, the renewable and biodegradable characteristic of raw material (Zhang Bo, 2011,
Bio-based materials development；Chen Hongzhang, 2010, biobased products process engineering；Zhan Guozhu, 2009,
The cruel resin of modified cyanate and the research of compound system thereof；Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences,
2011, what is bio-based materials), development bio-based materials contributes to solving current global economy society and sends out
Open up the problems such as the serious resource and energy shortage faced, and environmental pollution.Therefore, exploitation bio-based
Lubricating oil is also the important directions that current lubricating oil changes to energy-saving and environmental protection type.
Bio-based materials is mainly included bio-based macromolecular material by classification of chemical structure, and [plastics are (such as: poly-hydroxyl
Base fatty acid ester (PHA), poly butylene succinate (PBS), carbon dioxide copolymer (PPC),
Polyglycolic acid (PGA), polylactic acid (PLA), polyamide (PA), polyurethane (PUR), poly-ammonia
Base acid and starch-based material etc.), rubber (such as natural rubber), fiber (such as alginic acid fibre), coating,
Adhesive (such as rubber made from soybean cake), natural macromolecular material (such as cellulose, starch, chitosan etc.), high score
Subbase composite, functional high molecule material], bio-based monomer/fine chemicals (alcohol, phenol, hydrocarbon, ether,
The compounds such as amine, ester, acid, ketone, heterocyclic), bio-based oligomer, bio-based platform chemicals etc..
Classification by use mainly include biological plastics, bio-based ink, dyestuff and fuel, paint, adsorbent,
Buy clearly agent, industry adhesive, biological ployose and film, composite, starch and cellulose derivative,
Biological medicine material, lubricant, surfactant and various additive products etc., for people clothing,
Food, shelter, row etc..
In recent years, U.S. government and European Union promulgate bill in succession, are authenticated biological lubricants, classification,
Wish to promote the sale of biological lubricant, encourage enterprise to give priority to purchasing bio-based lubricating oil.Bio-based lubricating oil
Including bio-based base oil and bio-based oil dope, wherein bio-based base oil has animal oil and vegetable oil
(Adeps Sus domestica, Oleum Ricini etc.), Monsanto Chemicals is own through starting with the VIStite gold soybean oil of independent research
Carry out synthesising biological based lubricating oil.The raw material of the bio-based lubricating oil that dominant company of the U.S. produces is mainly vegetable oil.
And the bio-based oil dope reported at present includes dispersant, detersive, antioxidant, antiwear additive and friction
Modifier etc., but actual application is seldom.The additive of these bio-based petroleum base to be inferior in performance adds
Adding agent, structure is more complicated, complex manufacturing, and stability is poor, and practical application is the strongest.
Dialkyl dithiophosphoric acid slaine (ZDDP), as the wear-resistant anti-rotten multifunction additive of antioxygen, is used for
In lubricating oil more than 60 year, it is function admirable and the most comprehensive multifunction additive, prior art does not still have
There is a kind of additive can replace ZDDP completely.But the raw material of preparing of existing ZDDP is non-natural or non-
Renewable material, is a kind of consumable products due to ZDDP again, causes the loss of fossil resources.
Summary of the invention
For the deficiencies in the prior art, present invention is primarily targeted at a kind of bio-based alkylthio phosphorus of offer
Acid or derivatives thereof, its at least one raw material sources, in natural and renewable material, have green, environment friend
The advantages such as good, raw material is renewable, the saving energy.
For achieving the above object, the technical solution used in the present invention includes:
A kind of bio-based alkylthio phosphoric acid, has a structure shown in formula (I):
Wherein R1、R2, in X, Y, Z, W, M at least one from organism-based raw material,
R1、R2Independently be alkyl, hydroxyl, carbonyl or hetero atom,
And at least one comprises sulphur atom in X, Y, Z, W, remaining is arbitrarily selected from O, S atom,
And M be H or another there is the deriveding group of the molecule of structure shown in formula (I).
Among one more preferably case study on implementation, Z, W are O atom.
Further, appointing during described alkyl includes but not limited to alkyl, cycloalkyl, aralkyl, alkaryl
One and/or any one has any one basic alkyl of similar structures with this.
Further, described organism-based raw material be selected from but be not limited to include activity hydroxy, activity phenolic hydroxyl group,
One or more combination in active epoxy base, reactive amines/amino, active amide base natural and/or
Renewable raw materials.
Further, described activity hydroxy at least derives from and comprises C2-C40Alcohol and/or the biological base of saccharide
Material, wherein said alcohol includes any one in the primary, secondary, tertiary and quaternary alcohol of straight chain, side chain and isomerization or two
Plant above combination, and be not limited to this.
Further, described activity phenolic hydroxyl group at least derive from comprise alkyl, alkoxyl, ether, aldehyde, ketone,
The organism-based raw material of the substituted monophenols or polyphenols of at least one in carbonyl, and it is not limited to this.
Such as, described monophenols or polyphenols is at least selected from tea polyphenols, anthocyanidin, gallic acid, phenol, fennel
Any one or any one derivant in aromatic, cumic alcohol, zingiberone, thymol, eugenol, and not
It is limited to this.
Further, described active epoxy base at least derive from include bio-based expoxy propane, epoxy soybean oil,
In epoxy Colophonium, Galla Turcica (Galla Helepensis) epoxy, malic acid epoxy, citric acid epoxy, Oleum Verniciae fordii epoxy any one or appoint
A kind of organism-based raw material of derivant, and it is not limited to this.
Further, described reactive amines/amino can be mainly derived from the amino acids or fat comprising biogenetic derivation
The organism-based raw material of amine, and it is not limited to this.
Further, described active amide base can be mainly derived from the acrylamide or oleic acid comprising biogenetic derivation
The organism-based raw material of amide, and it is not limited to this.
The derivant of described bio-based alkylthio phosphoric acid, comprises the metal of described bio-based alkylthio phosphoric acid
Appointing in salt, metal complex, ionic compound, ammonia or amine salt, ammonium salt, ester or polyol ester derivant
One, and it is not limited to this.
Present invention also offers the preparation method of described bio-based alkylthio phosphoric acid or derivatives thereof, including:
Described bio-based alkylthio phosphoric acid is prepared by making phosphorus pentasulfide and described organism-based raw material react
Or the derivant of described bio-based alkylthio phosphoric acid；
Or, by by described bio-based alkylthio phosphoric acid or commercialization alkylthio phosphoric acid at least with biology
Any one in basic ring oxygen, bio-based amine, bio-based amide is reacted and is prepared described bio-based alkylthio
The derivant of phosphoric acid.
Present invention also offers the application of described bio-based alkylthio phosphoric acid or derivatives thereof.
Such as, as one of application scheme, the invention provides a kind of compositions, it comprises described bio-based
Alkylthio phosphoric acid or derivatives thereof.
Further, described compositions also can comprise diluent or solvent, and described diluent or solvent comprise base
Any one in plinth oil, alkane, aromatic hydrocarbons, halogenated hydrocarbons, alcohol, ether, ketones solvent or both above groups
Close, and be not limited to this.Wherein, addition opportunity of solvent or diluent can be described bio-based alkylthio
Before the preparation reaction of phosphoric acid or derivatives thereof, reaction carry out in or after having reacted.
The most such as, as one of application scheme, the invention provides a kind of antioxygen multi-functional interpolation of wear-resistant anti-corruption
Agent, it comprises described bio-based alkylthio phosphoric acid or derivatives thereof or described compositions.
The most such as, as one of application scheme, also can be by described bio-based alkylthio phosphoric acid or derivatives thereof
Or described compositions promotes for lubricating oil, grease, flotation agent, pesticide, fire retardant and rubber
The fields such as agent.
Compared with prior art, the invention have the advantages that provide based on natural and reproducible raw material
Sulfur is for phosphoric acid or derivatives thereof, and in its building-up process, at least one raw material sources is in bio-based.The present invention carries
The bio-based sulfur of confession has the advantages such as green, environmental friendliness, raw material be renewable for phosphorous acid and derivant thereof.
Detailed description of the invention
The present invention uses bio-based alcohol, phenol, epoxy, amine/ammonia and amide to replace petroleum-based feedstock, on the one hand exists
Lube oil additive reduces the consumption to fossil resources, on the other hand because introducing the carbon of bio-based source,
Have environmental friendliness, biodegradable, relatively low to marine organisms toxicity, will not in vivo gathering etc. excellent
Point.Furthermore, organism-based raw material is often polyfunctional compound, it ZDDP synthesized can be further
Strengthening its antioxygen, wear-resistant and antiseptic property, part biological base ZDDP low temperature viscosity is little, can save fuel.
One aspect of the present invention provides a kind of bio-based alkylthio phosphoric acid and/or the mixing of its derivant
Thing, at least one in its raw material derives from the material of biorenewable.
More specifically, the bio-based alkylthio phosphoric acid of present invention offer and/or the mixture of its derivant,
It is bio-based dialkyl dithiophosphoric acid and derivant thereof, it is characterized in that synthesising biological base dialkyl dithio phosphorus
The raw material of acid and derivant thereof contains based on natural and reproducible raw material.
The present invention uses based on natural and reproducible raw material, containing one or the activity hydroxy of mixing,
At least one in phenolic hydroxyl group, epoxy radicals, amidine functional group.
Specifically, described organism-based raw material, it is selected from arbitrarily by chemical method, physical method, biology side
The method that method converts from biomass obtains.
When described organism-based raw material is containing activity hydroxy, including C2-C18Monohydric alcohol, dihydroxylic alcohols, polyhydric alcohol and
Saccharide, described alcohol at least selected from straight chain, side chain and isomerization primary, secondary, tertiary and quaternary alcohol in any one or
Two or more combinations.
The alkyl of described biomass alcohol is selected from by any alkyl, cycloalkyl, aralkyl or alkaryl and has
The alcohol of the basic alkyl of similar structures；Described alcohol comprises the primary, secondary, tertiary and quaternary of straight chain and side chain and isomerization
Alcohol and mixture thereof.So-called basic hydrocarbon refers to containing substituent group, as ether, ester group, nitro and halogen this
A little groups the most do not affect that hydrocarbon of the hydrocarbon characteristic of this alkyl.
Described alkyl be selected from but be not limited to isopropyl, isobutyl group, normal-butyl, sec-butyl, various amyl group,
Heptyl, 2-ethylhexyl, double isobutyl group, iso-octyl, nonyl, docosyl, decyl, dodecyl, three
Decyl etc..The alkane phenyl enumerated includes butylbenzene base, penta phenyl, dodecylphenyl, phenyl in heptan etc..Ring
Alkyl is the most also useful, and they mainly include cyclohexyl and relatively low alkyl-cyclohexyl group.Many
Number substituted hydrocarbon radical can also use, such as chloro amyl group, dichloro-phenyl and dichloro-decyl.
Representative bio-based alcohol includes but not limited to following:
Saturated alcohols lower alcohol: ethanol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, isoamyl alcohol, positive third
Alcohol, Methylethyl methanol, hexanol, n-octyl alcohol, n-nonyl alcohol, Decanol, methyl-n-nonyl carbinol, osmanthus
Alcohol, dodecanol etc..
High alcohol class: positive tridecanol, n-tetradecanol, hexadecanol, stearyl alcohol, hexacosanol,
Octacosanol, triacontanol (peak flower alcohol), three undecylenic alcohols, n-Dotriacontanol, inearnatyl alcohol etc..
Unsaturated alcohols: leaf alcohol (beta, gamma-hexenol), matsutakealcohol (1-pentenol-3), cucumber alcohol, people
Ginseng alcohol, cicutexin, silkworm alcohol, linalool, hardship carry alcohol, geraniol, coriandrol, nerol, dance poison
Moth alcohol, terpene alcohols, pohytol (phytol) etc..
Polyalcohols: ethylene glycol, propylene glycol, three methylene glycols, symmetric dimethyl ethylene glycol, glycerol, sugar
Alcohols.
Specifically, described organism-based raw material containing activity phenolic hydroxyl group, be selected from arbitrarily including alkyl, alkoxyl,
Substituted single phenol and the polyphenol such as ether, aldehyde, ketone, carbonyl.Described bio-based phenol such as tea polyphenols, anthocyanidin, do not have
Gallate-based, phenol, anise alcohol, cumic alcohol, zingiberone, thymol, eugenol etc. and its derivant.
Specifically, when described organism-based raw material is containing active epoxy base, it is selected from the epoxy of any bio-based source
Propane, epoxy butane, oxepane, epoxy soybean oil, epoxy Colophonium, Galla Turcica (Galla Helepensis) epoxy, malic acid ring
Oxygen, citric acid epoxy, Oleum Verniciae fordii epoxy etc. and its derivant.
Specifically, when described organism-based raw material is containing reactive amines/amino, including amino acids, the amine of biogenetic derivation
Class etc..Wherein amino acids includes nonprotein amino acid and protein-based aminoacid.Nonprotein amino acid
Alkalescence, acidity and neutral amino acid, preferably neutral and basic amino acid, more preferably alkalescence can be included again
Aminoacid.Concrete neutrality and basic amino acid have: leucine, Cucurbitin, laminine etc..Egg
White matter aminoacid also includes alkalescence, acidity and neutral amino acid, preferably neutrality and basic amino acid, more preferably
Be basic amino acid.Concrete neutrality and basic amino acid have: glycine, alanine, valine, bright
Propylhomoserin, isoleucine, cysteine, methionine, cystine, arginine, lysine, serine, Soviet Union
Propylhomoserin etc..Amine for the present invention can be described generally as having the primary, secondary or tertiary of about 3-30 carbon atom
Amine, can be fatty amine, aliphatic cyclic amine, heterocyclic amine and arylamine.Such amine can also include hydroxyalkyl amine, ether
Amine.Particularly preferably primary amine, suitable amine include octyl amine, lauryl amine, lauryl amine, 13
Alkylamine, oil, coconut amine, primary t-alkyl-amine, octadecylamine etc..
Specifically, when described organism-based raw material is containing active amide base, it is selected from the fat of any bio-based source
Same clan's amide, fragrance same clan amide, beta-lactam amide.
More specifically, aliphatic amide includes spilanthol, α-sanshool, sanshoamide, stick shape pepper
Amide, neoherculin, acrylamide, oleamide etc..Fragrance same clan amide include capsaicin,
Oil of pepper amide, chavicin, piperyline, Fructus Piperis Longi amide, piperlonguminine, fagaramide etc..
Beta-lactam amide includes mainly including penicillin, cephalosporin etc..
Containing bio-based alkylthio phosphoric acid and/or the preparation method of the mixture of its derivant:
(1) P is made2S5The bio-based alkyl reacted with bio-based hydroxyl raw material (alcohol and/or phenol) and prepare
D2EHDTPA and slaine, metal complex or ionic compound, ammonia or amine salt, ammonium salt, ester, polynary
Ester derivative etc.；It typically relates to heat the mixed of phosphorus pentasulfide in suitable solvent or diluent
Compound is also added thereto to the mixture of alcohol and/or phenol, and continues heating until reaction completely, now removes and evaporates
Go out liquid and remaining mixture cooled down and filters to remove the phosphorus pentasulfide of any residual.Then two are reclaimed
Alkyl dithiophosphoric acid.Or, phosphorus pentasulfide can be slowly added in the mixture of alcohol and/or phenol.
The synthesis of the derivant of bio-based alkylthio phosphoric acid, can be by the alkylthio phosphoric acid in aforementioned generation
In, use lithium, sodium, potassium, zinc, copper, stannum, lead, ferrum, magnesium, calcium, nickel, chromium and the cobalt etc. of alkalescence
Slaine, hydroxide, oxide etc. neutralize this alkylthio phosphoric acid product.
(2) or, the synthesis of the derivant of bio-based alkylthio phosphoric acid, it is possible to use bio-based epoxy,
Bio-based amine, bio-based amides compound and product in (1) provide bio-based alkylthio phosphoric acid to spread out
Biological.
(3) or, the synthesis of the derivant of bio-based alkylthio phosphoric acid, it is possible to use bio-based epoxy,
Bio-based amine, bio-based amides compound and business-like alkylthio phosphatase reaction provide part raw
Thing base alkylthio phosphoric acid derivatives.
Aforementioned biological base dialkyl dithiophosphoric acid and/or the mixture of its derivant, it is also possible to comprise diluent
Or solvent, described diluent comprises in base oil, alkane, aromatic hydrocarbons, halogenated hydrocarbons, alcohol, ether, ketones solvent
The above combinations of any one or both, its add can be reaction before, reaction is neutralized reaction and carries out
After.
The mixture of bio-based alkylthio phosphoric acid of the present invention and/or its derivant can be applicable to lubricating oil, lubrication
The fields such as fat, flotation agent, pesticide, fire retardant and rubber accelerator, this bio-based compounds has green
Color, environmental friendliness, raw material are renewable, meet the advantages such as Sustainable development policies, can be as day by day reducing
The succedaneum of fossil energy based additive.
The present invention also provides for a kind of lubricant for internal combustion engine, it comprise lubricant base fluid and at least one
Bio-based alkylthio phosphoric acid and/or its derivant, and optionally comprise one or more selected from viscosity improver,
Oxidation retarder, pour-point depressant, detersive, dispersant, friction improver, antiwear additive, foam inhibitor,
Other additives of corrosion inhibiter and metal deactivator.
The present invention is described further by the following example: according to following embodiment, may be better understood
The present invention.But, as it will be easily appreciated by one skilled in the art that the concrete material ratio described by embodiment,
Process conditions and result thereof are merely to illustrate the present invention, and should also without limitation on institute in claims not in detail
The thin present invention described.
Illustrate: following all percentage compositions are weight/mass percentage composition, be to launch according to inductively coupled plasma
Spectrogrph draws with organic element analyzer test.
Embodiment 1 (comparative example)
The present embodiment uses dodecylphenol synthesis sulfur phosphoric acid and derivant thereof, and dodecylphenol is by phenol and four
Polypropylene (different laurylene) is alkylated reaction under cation exchange resin or active hargil catalytic action
Prepare.
The synthesis of sulfur phosphoric acid: by 22.23gP2S5Put in reaction bulb with 10.0g150N base oil, be heated to 70 DEG C
And dispersed with stirring, then 110.1g dodecylphenol is added drop-wise in mixture, because of exothermic heat of reaction, controls to drip
Acceleration makes temperature be less than 105 DEG C.Completion of dropwise addition after 105 DEG C of constant temperature 1h, is increased to temperature
125℃.After maintaining 1h, purge with nitrogen, make hydrogen sulfide gas Lead acetate paper in system detect in the moon
Property, reaction terminates.Filtering, in product, sulfur phosphorus acid content is 89%, and P is 4.3%, and S is 9.2%.
Neutralize reaction: joined by 1.51gZnO in 7.5g150N base oil, dispersed with stirring.It is heated to
45-50 DEG C, drip 25g sulfur phosphoric acid, control rate of addition, make reaction temperature be less than 75 degree.After completion of dropwise addition,
Adding catalyst acetic acid 0.025g, reactant liquor is heated to 100 DEG C, and after reaction 2h, decompression distillation is except water, then
Kieselguhr drainage obtains product.Test in product P be 3.2%, Zn is 1.8%.
Embodiment 2
The present embodiment uses phenol synthesis sulfur phosphoric acid and the derivant thereof of biogenetic derivation.
The synthesis of sulfur phosphoric acid: by 22.23gP2S5Put in reaction bulb with 10.0g150N base oil, be heated to 70 DEG C
And dispersed with stirring, then 63.0g thymol is added drop-wise in mixture, because of exothermic heat of reaction, controls dropping speed
Degree makes temperature be less than 105 DEG C.Completion of dropwise addition after 105 DEG C of constant temperature 1h, is increased to 125 DEG C by temperature.
After maintaining 1h, purge with nitrogen, make hydrogen sulfide gas Lead acetate paper detection in system be negative, reaction
Terminate.Filtering, in product, sulfur phosphorus acid content is 85.7%, and P is 6.7%, and S is 13.8%.
Neutralize reaction: 9.13gZnO is joined 30g150N base oil and 30g Herba thymi vulgaris phenolic group sulfur phosphoric acid,
Dispersed with stirring.It is heated to 45-50 DEG C, drips remaining 70g sulfur phosphoric acid, control rate of addition, make reaction temperature
Degree is less than 75 DEG C.After completion of dropwise addition, adding catalyst acetic acid 0.37g, reactant liquor is heated to 100 DEG C, reaction
After 2h, decompression distillation is except water, and then kieselguhr drainage obtains product.Test in product P be 4.9%, Zn is
11.2%.
Embodiment 3-10
Embodiment 3-10 uses the monohydric alcohol of biogenetic derivation and mixture thereof to synthesize sulfur phosphoric acid and derivant thereof, synthesis
Step changed according to different raw materials accordingly with embodiment 1 or 2, concrete sulfur phosphoric acid synthesis temperature and time,
Concrete rate of charge with the results are shown in Table 1 and table 2.
Table 1
| Embodiment | The kind of bio-based alcohol | P2S5(g) | Alcohol 1 (g) | Alcohol 2 (g) | 150N(g) | Sulfur phosphoric acid % | P% | S% |
| Embodiment 3 | N-butyl alcohol | 22.2 | 31.1 | - | 10.0 | 80.8% | 10.3% | 21.4% |
| Embodiment 4 | 2-butanol | 22.2 | 31.1 | - | 10.0 | 80.8% | 10.3% | 21.4% |
| Embodiment 5 | N-octyl alcohol | 22.2 | 54.7 | - | 10.0 | 84.9% | 7.4% | 15.4% |
| Embodiment 6 | 1-amylalcohol | 22.2 | 37.0 | - | 10.0 | 82.1% | 9.4% | 19.5% |
| Embodiment 7 | Sec-butyl alcohol, 2-amylalcohol | 22.2 | 13.8 | 20.7 | 10.0 | 81.6% | 9.8% | 20.3% |
| Embodiment 8 | N-octyl alcohol, 2-Ethylhexyl Alcohol | 22.2 | 16.4 | 38.3 | 10.0 | 84.9% | 7.4% | 15.4% |
| Embodiment 9 | 2-Ethylhexyl Alcohol, 2-butanol | 22.2 | 28.1 | 15.1 | 10.0 | 83.3% | 8.6% | 17.8% |
| Embodiment 10 | Hexanol, n-octyl alcohol | 22.2 | 21.9 | 26.8 | 10.0 | 84.1% | 8.0% | 16.6% |
Table 2
| Embodiment | Sulfur phosphoric acid (g) | Zinc oxide (g) | 150N(g) | Zn% | P% | S% |
| Embodiment 3 | 25.0 | 3.5 | 7.5 | 14.2% | 7.3% | 15.2% |
| Embodiment 4 | 25.0 | 3.5 | 7.5 | 14.2% | 7.3% | 15.2% |
| Embodiment 5 | 25.0 | 2.5 | 7.5 | 11.4% | 5.4% | 11.1% |
| Embodiment 6 | 25.0 | 3.2 | 7.5 | 12.7% | 6.7% | 13.9% |
| Embodiment 7 | 25.0 | 3.3 | 7.5 | 14.3% | 7.0% | 14.5% |
| Embodiment 8 | 25.0 | 2.5 | 7.5 | 10.4% | 5.4% | 11.1% |
| Embodiment 9 | 25.0 | 2.9 | 7.5 | 12.3% | 6.2% | 12.8% |
| Embodiment 10 | 25.0 | 2.7 | 7.5 | 11.3% | 5.8% | 12.0% |
Embodiment 11-15
Embodiment 11-15 uses the dihydroxylic alcohols of biogenetic derivation synthesize sulfur phosphoric acid with the mixture of monohydric alcohol and spread out
Biology, synthesis step is with embodiment 1 or 2, and concrete sulfur phosphoric acid synthesis temperature and time are according to different raw materials
Corresponding variation, concrete rate of charge with the results are shown in Table 3 and table 4.
Table 3
| Embodiment | The kind of bio-based alcohol | P2S5(g) | Alcohol 1 (g) | Alcohol 2 (g) | 150N(g) | Sulfur phosphoric acid % | P% | S% |
| Embodiment 11 | 1-hexanol, 1,3-propylene glycol | 22.2 | 40.1 | 2.1 | 10.0 | 83.1% | 8.7% | 18.1% |
| Embodiment 12 | 1-hexanol, 1,4-butanediol | 22.2 | 40.5 | 2.1 | 10.0 | 83.2% | 8.7% | 18.0% |
| Embodiment 13 | 1-hexanol, 1,5-pentanediol | 22.2 | 40.8 | 2.2 | 10.0 | 83.2% | 8.6% | 17.9% |
| Embodiment 14 | 1-hexanol, 1,6-HD | 22.2 | 41.1 | 2.2 | 10.0 | 83.3% | 8.6% | 17.8% |
| Embodiment 15 | 1-hexanol, 1,8-ethohexadiol | 22.2 | 41.4 | 2.2 | 10.0 | 83.3% | 8.6% | 17.7% |
Table 4
| Embodiment | Sulfur phosphoric acid (g) | Zinc oxide (g) | 150N(g) | Zn% | P% | S% |
| Embodiment 11 | 25.0 | 3.0 | 7.5 | 12.5% | 6.3% | 13.0% |
| Embodiment 12 | 25.0 | 2.9 | 7.5 | 11.8% | 6.2% | 12.9% |
| Embodiment 13 | 25.0 | 2.9 | 7.5 | 12.0% | 6.2% | 12.8% |
| Embodiment 14 | 25.0 | 2.9 | 7.5 | 12.3% | 6.2% | 12.8% |
| Embodiment 15 | 25.0 | 2.9 | 7.5 | 12.4% | 6.2% | 12.7% |
Embodiment 16-20
Embodiment 16-20 use in embodiment 2 gained sulfur phosphoric acid respectively with appropriate Zn (OH)2, CuO, propylene
Amide, dodecyl primary amine, 1,2-epoxy butane react.Step is reacted with the neutralization of embodiment 2, gained
In zinc salt derivant, zinc is 16.23%, and P is 6.80% (embodiment 16), and in mantoquita derivant, Cu is 16.03%,
P is 7.01% (embodiment 17), and in acrylamide derivative, P content is 6.87% (embodiment 18), ten
In dialkyl group primary amine derivatives, P content is 6.10% (embodiment 19), and in epoxides, P content is 6.89%
(embodiment 20).
Finally, in addition it is also necessary to explanation, term " includes ", " comprising " or its any other variant are intended to
Comprising of nonexcludability, so that include the process of a series of key element, method, article or equipment not only
Including those key elements, but also include other key elements being not expressly set out, or also include for this mistake
The key element that journey, method, article or equipment are intrinsic.
Claims (10)
1. a bio-based alkylthio phosphoric acid, has a structure shown in formula (I):
Wherein R1、R2, at least one in X, Y, Z, W, M from organism-based raw material,
R1、R2Independently be alkyl, hydroxyl, carbonyl or hetero atom,
And at least one in X, Y, Z, W comprises sulphur atom, remaining is arbitrarily selected from O, S atom,
And M be H or another there is the deriveding group of the molecule of structure shown in formula (I).
Bio-based alkylthio phosphoric acid the most according to claim 1, it is characterised in that: Z, W are O
Atom.
Bio-based alkylthio phosphoric acid the most according to claim 1, it is characterised in that: described alkyl bag
Include any one in alkyl, cycloalkyl, aralkyl, alkaryl or two or more combinations.
Bio-based alkylthio phosphoric acid the most according to claim 1, it is characterised in that: described bio-based
Raw material is selected from including activity hydroxy, activity phenolic hydroxyl group, active epoxy base, reactive amines/amino, active amide
Natural and/or the renewable raw materials of one or more the combination in base.
Bio-based alkylthio phosphoric acid the most according to claim 4, it is characterised in that:
Described activity hydroxy at least derives from and comprises C2-C40Alcohol and/or the organism-based raw material of saccharide, Qi Zhongsuo
State alcohol and include the group of any one or more in the primary, secondary, tertiary and quaternary alcohol of straight chain, side chain and isomerization
Close；
Described activity phenolic hydroxyl group at least derives from and comprises in alkyl, alkoxyl, ether, aldehyde, ketone, carbonyl extremely
The organism-based raw material of few a kind of substituted monophenols or polyphenols, described monophenols or polyphenols is at least selected from tea polyphenols, flower
Arbitrary in blue or green element, gallic acid, phenol, anise alcohol, cumic alcohol, zingiberone, thymol, eugenol
Kind or the derivant of any one；
Described active epoxy base at least derives from and includes bio-based epoxychloropropane, epoxy soybean oil, epoxy pine
In perfume, Galla Turcica (Galla Helepensis) epoxy, malic acid epoxy, citric acid epoxy, Oleum Verniciae fordii epoxy any one or any one
The organism-based raw material of derivant；
Described reactive amines/amino derives from the biological base of the amino acids comprising biogenetic derivation or fatty amines
Material；
Described active amide base derives from the biological base of the acrylamide comprising biogenetic derivation or oleamide
Material.
6. the derivant of bio-based alkylthio phosphoric acid as according to any one of claim 1-5, comprises described
Slaine, metal complex, ionic compound, ammonia or the amine salt of bio-based alkylthio phosphoric acid, ammonium salt,
Any one in ester or polyol ester derivant.
7. bio-based alkylthio phosphoric acid or as claimed in claim 6 as according to any one of claim 1-5
The preparation method of the derivant of bio-based alkylthio phosphoric acid, it is characterised in that including:
Described bio-based alkylthio phosphoric acid is prepared by making phosphorus pentasulfide and described organism-based raw material react
Or the derivant of described bio-based alkylthio phosphoric acid；
Or, by by described bio-based alkylthio phosphoric acid or commercialization alkylthio phosphoric acid at least with biology
Any one in basic ring oxygen, bio-based amine, bio-based amide is reacted and is prepared described bio-based alkylthio
The derivant of phosphoric acid.
8. a compositions, it is characterised in that comprise bio-based alkyl sulfide according to any one of claim 1-5
For the derivant of bio-based alkylthio phosphoric acid described in phosphoric acid or claim 6.
9. the wear-resistant anti-rotten multifunction additive of antioxygen, it is characterised in that comprise in claim 1-5 arbitrary
The derivant of bio-based alkylthio phosphoric acid described in described bio-based alkylthio phosphoric acid, claim 6 or
Compositions described in claim 8.
10. a lubricant oil composite, including the wear-resistant anti-rotten multifunction additive of the antioxygen described in claim 9.
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