CN1940037A - Thermal roll-oil composition of dispersing oily clay wear-resistant anti-skid agent - Google Patents
Thermal roll-oil composition of dispersing oily clay wear-resistant anti-skid agent Download PDFInfo
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Abstract
A hot-pressed oil composition containing oily-dispersing clay antifriction anti-slip agent has excellent dispersing ability, abrasion resistance and lubricity. The composition consists of 0.1-15wt% sulfur-contained extreme pressure agent from alkyl polysulfide, mineral oil sulfide and thiopoly alcohol ester, 0.1-20wt% phosphor-contained anti-scuff agent from organic phosphate, phosphonate ester, phosphate ester, acid amine salt organic phosphate, amine salt phosphate ester, phosphoamidster, dialkyl phosphateodithioate, dimercaptothioliazole phosphorodithioate and acid phosphate imidazoline salt and 0.01-1wt% oil-soluble clay anti-scuff lubricant of organic modified clay and C4-C24 hydroxy-acid compound or C13-C64 hydroxy-acid contained condensate. It has excellent dispersibility, abrasion resistance and lubricity.
Description
Technical field
The present invention relates to a kind of hot-rolled oil composition.
Background technology
The use hot-rolling oil is a new technology in the modern steel rolling field, early stage hot rolling need not oil and use water lubricating, directly adopted hot-rolling oil to lubricate roll afterwards, and its composition has mineral oil, animal-plant oil and based on the ucon oil of synthetic fatty acid, the pollution that causes is big.Hot-rolling lubricating obtains very big development in recent ten years, at present many large-scale hot continuous rolling units adopt the lubricating process that water oil sprays altogether to replace pure oil lubrication, in rolling process, the hot-rolling oil of minute quantity is mixed with a large amount of water (more than 99.5%) by oil-water mixer, force emulsification, be ejected into work roll surface, rotation by roll is brought emulsion into distorted area, not only cool off roll effectively, and at high temperature divide oily rapidly, between roll and stocking surface, form one deck oil film as thin as a wafer, improved texturizing condition, reduce the friction of stocking metal and roll crown, reducing the wearing and tearing of rolling load and roll, improve the surface quality of steel that produces, is a new technology that realizes good quality and high output.
The friction duty of roll is very harsh in the course of hot rolling, and relative sliding velocity can reach more than the 20m/s between roll and the stocking, and rolling pressure reaches 100kg/cm
2According to a preliminary estimate, the stocking temperature that first and second road roll is contacted is more than 1000 ℃, even at the 6th, seven road rolls, temperature is also more than 800 ℃, the hydrogen embrittlement effect of heating and cooling repeatedly and water makes roller surface easily produce be full of cracks, inordinate wear, scaling, roll surface roughen, not only directly influence the surface quality of the steel that produce, and roll is scrapped in advance.
Address this problem mainly from improving roll material and strengthening lubricant effect two aspects and start with.Adopting more attrition resistant material on the one hand, make working roll as tool steel, improve work-ing life, is improve roll lubricated on the other hand, comprises mode and the processing condition of improving fuel feeding and develops hot-rolling oil prescription efficiently.Require hot-rolling oil to have following characteristics: the lower concentration emulsion of formation at high temperature oilness is good, can reduce the roll wear that the friction of distorted area and roll banding or corrosion cause effectively, can cause that again milling train skids and causes nipping bad but oilness is very good, influence is produced; Hot-rolling oil is easily disperseed in water at ambient temperature, and at high temperature dried up plate-out ability is good, easily is adsorbed on roller surface and lubricate; Residual few after the stocking surface combustion of heat, can not shorten work-ing life of oil feed pump because of corrosion; Modest viscosity and is easy to spraying after water mixes; Nontoxic or low toxicity own, odorless or low odor, combustionmaterial is few to the pollution of air, the oil residues readily biodegradable; The hot-rolling oil cost of material is cheap, aboundresources etc.
US5,437,802 (1995) have introduced the hot-rolling oil with lubricating grease (lithium saponify, composite calcium-base fat and areidofat), inorganic insulation agent and solid lubricant (graphite, molybdenumdisulphide, sodium-chlor, water glass etc.) multiviscosisty, the high-content of lubricating grease reaches 90% in the prescription, and the content of inorganic insulation agent is also in the 10-35% scope.Use heavy-gravity, contain solid lubricant or other high ash content material the hot-rolling oil prescription also have JP102314939, US5,352,373, JP2004256630, EP04553565 etc.
More than with the hot-rolling oil or the ointment of panoramic material preparation, cause is thickness and the existence that a large amount of suspended solidss are arranged too, generally be directly to use as hot-rolling oil, mix the technology that spray the back and be not suitable for profit, because adopt emulsion lubrication to be very different with adopting oil lubrication, use above-mentioned prescription not only to spray difficulty, also easily stifled nozzle.Use these prescriptions must use special spraying equipment, not only increase the equipment cost of lubrication in heat-rolling process, also increase with oily cost (because of oiling is difficult for, oily consumption is also big).Contain a large amount of inorganic materials or putty material is arranged, residual ash content is big in the operation of rolling, easily cause skid and nip bad.Some hot-rolling oil raw material can produce the toxic gas polluted air as petroleum pitch, cyanurate etc. in volatilization under the hot-rolled high with after decomposing, and does not meet environmental requirement.A large amount of inorganic materials of using because of hardness ratio steel height, easily are pressed into stocking and influence surface quality of products in the operation of rolling.
Other patents are introduced the nano titanium oxide that contains the dialkyl dithiophosphoric acid modification as CN1435472 (2003), but from structure own, can not have withstand voltage resistance to elevated temperatures good as sulphur, phosphorus extreme pressure agent.
Also there are some patents to adopt full oil soluble prescription, introduced the generation that the hot-rolling oil that adds the lipophilic carboxylic acid of 0.05-20wt%, sulfonic acid and acid anhydrides, part ester, acid amides and salt can suppress casting skin (iron scale) as JP8041486 (1996), reduce roll wear, JP8143881 (1996) employing adds the high-alkali alkylphenol of 30-90wt% and improves tackiness, but these additives can not have very high extreme pressure property, and the high-temperature decomposition product of phenol is also poisonous.
Summary of the invention
The present invention overcomes the above-mentioned shortcoming of prior art, and a kind of hot-rolled oil composition unlike the prior art is provided.This composition is by base oil, sulfur-containing extreme-pressure additive, phosphorous anti-wear agent, wear-resistant anti-skid agent and other auxiliary agent, as compositions such as antioxygen, anti-bubble, rust-preventive agent, it has good adhesivity, profit dispersiveness, extreme-pressure anti-wear antifriction quality, storage stability and environmental compatibility evidence, and is nontoxic, biodegradable.
Hot-rolled oil composition provided by the invention comprises:
(I) lubricant base
Said lubricant base is mineral oil or ester class oil.40 ℃ of viscosity are 5～300mm
2/ s, preferred 10～200mm
2/ s.Preferably contain a kind of ester class oil at least.
Mineral oil can be the mineral lubricating oils of being produced by paraffinic crude and naphthenic base crude, as 150SN, and 500SN, 650SN, 120BS, 150BS etc.
The mixture of ester class grease separation one or two or more kinds in synthetic ester, vegetable and animals oils, hot polymerization polyunsaturated vegetable oil and Viscotrol C ethylene oxide condensate.
Wherein synthetic ester can be C
8～C
12The diester of alcohol is as diisooctyl sebate, didecyl adipic acid ester; And C
8～C
24The polyol ester of lipid acid as trihydroxymethylpropanyl ester and pentaerythritol ester, can be monoesters, dibasic acid esters, three esters or full ester, as the trimethylolpropane tris monooctyl ester, and tetramethylolmethane dioleate, tetramethylolmethane vegetable fatty acid esters etc.; Also comprise the multiple ester that diprotic acid and dibasic alcohol (or polyvalent alcohol) esterification forms.
Hot polymerization polyunsaturated vegetable oil (as soya-bean oil, rapeseed oil, cottonseed wet goods) is prepared by heated polymerizable.The preparation method is referring to " rolling technology is lubricated " (Li Xiaoyu etc., metallurgical technology press, 1981).
The Viscotrol C ethylene oxide condensate can be castor oil polyoxyethylene (5～a 90) ether, preferably castor oil polyoxyethylene (5～40) ether.The Viscotrol C ethylene oxide condensate is to be raw material with the Viscotrol C, in the presence of alkaline catalysts with the oxyethane polycondensation after, through acid neutralization, hydrogen peroxide bleaching and making.This method is conventionally known to one of skill in the art.
(II) sulfur-containing extreme-pressure additive
Sulfur-containing extreme-pressure additive is selected from alkyl polysulfide, sulfuration Dormant oils, thio polyol ester etc.Alkyl polysulfide such as dialkyl group pentasulfide, two nonyl trisulphide, uncle's dodecyl trisulphide, dodecyl tetrasulfide, dinonyl disulphide, dilauryl tetrasulfide, uncle's dodecyl pentasulfide etc.The sulphide ores wet goods of sulfuration Dormant oils such as sulfur-bearing 20～40 heavy %.Thio polyol ester such as xanthogenic acid glycol ester, sulfuration neat's-foot oil, sulfuration lard, sulfuration soya-bean oil, sulfuration sunflower seed oil, sulfuration cottonseed wet goods.Preferred sulfuration lard, dialkyl group pentasulfide, two nonyl trisulphide, uncle's dodecyl trisulphide, dodecyl tetrasulfide etc.It can be one or more mixture.The content of sulfur-containing extreme-pressure additive is 0.1～15 heavy % in the hot-rolled oil composition, preferred 0.2～10 heavy %.
(III) phosphorous anti-wear agent
Phosphorous anti-wear agent is selected from phosphoric acid ester, phosphonic acid ester, phosphorous acid ester, acid phosphate amine salt, phosphorous acid ester amine salt, phosphoramidate, dialkyl dithiophosphate, dimercaptothiodiazole phosphorodithioate and acid phosphoric acid ester imidazoline salt etc.
The preferred tricresyl alkaliine of phosphoric acid ester, two-ethylhexyl dihydrogen phosphate, dilauryl phosphoric acid ester, n-hexadecyl phosphoric acid ester, two Octadecane base phosphoric acid ester, thiophosphoric acid phenyl ester, O, O '-diethyl eicosane ketone group phosphoric acid ester (formula 1), dilauryl two polyoxypropylene phosphoric acid ester (formula 2) etc.
Phosphonic acid ester can be phosphonate ester, aryl phosphate ester, preferred two dodecyl phosphonic acid esters, O, O-di-n-butyl dodecyl phosphonic acid ester, O, O '-di-isopropyl benzylphosphonic acid ester (formula 3), O, O '-two (neighbour) nitrophenyl phosphonic acid ester (formula 4) etc.
Phosphorous acid ester such as di-n-octyl phosphorous acid ester or two-(2-ethylhexyl) phosphorous acid ester etc.The amine salt of acid phosphate amine salt and phosphorous acid ester is suc as formula shown in (5) and (6), can be primary amine salt, secondary amine salt, tertiary ammonium salt, diamine salt and ether amine salt, preferred di-n-butyl phosphorous acid ester stearylamine salt, two-(2-ethylhexyl) phosphorous acid ester hexahydroaniline salt, diethyl phosphorous acid ester tallow amine salt, dioctyl phosphoric acid ester-N-tallow base-1,3-Pn salt, di-isopropyl phosphoric acid ester-N-oil base-1,3-propenyl two amine salt, DHP dihexylphosphoric acid METH 124 Triazole oleyl amine salt, n-hexyl phosphorous acid ester tripropyl amine salt, dioctyl phosphoric acid ester-five polytrimethylene ether propylamine salt (formula 7).
Phosphoramidate comprises the phosphoramidate of sulfur-bearing not and single thiophosphoryl monoamine ester (formula 8), two thiophosphoryl monoamine ester (formula 9), and single thiophosphoryl diamine ester (formula 10).The phosphinylidyne monoamine ester and the phosphinylidyne diamine ester that also comprise monoamine and diamine.Preferred N-dodecyl-di-n-hexyl phosphoramidate, N, N-diallyl-di-n-butyl phosphoramidate (formula 11), two (to) butylbenzene base thio-phosphamide ester (formula 12), O-octyl group-N-sec.-propyl-N ' p-methoxyphenyl thioureido thiophosphoryl diamines ester (formula 13), O, O '-two (2-ethylhexyl)-N, N-di-n-butyl-dithio phosphoramidate (formula 14) etc.
R in the formula
1And R
2Be C
8-C
12Alkyl, alkaryl and amido, R
3And R
4Can be H or C
1-C
8Alkyl.
R in the formula
1And R
2Be C
8-C
12Alkyl, alkaryl and amido, R
3For:
R in the formula
1And R
2=C
3-C
12Alkyl, alkaryl and amido,
Dialkyl dithiophosphate can be zinc salt or molybdenum salt.As the di-n-butyl zinc dithiophosphate, di-n-octyl zinc dithiophosphate, O-butyl, O '-octyl group zinc dithiophosphate, dioctyl phosphorodithioic acid oxygen molybdenum etc.
Dimercaptothiodiazole phosphorodithioate (formula 15) can be 2,5-(O, the two diisooctyl phosphorodithioic acid of O ' base)-1,3,4-thiadiazoles, 2,5-(O, the two di-n-butyl phosphorodithioic acid of O ' base)-1,3,4-thiadiazoles etc.
The acid phosphoric acid ester imidazoline salt can be O, O '-two 1-isobutyl-3,5-dimethylhexylphosphoric acid-1-(triamine ethyl)-2-17 alkenyl imidazoline salt (formula 16).
Phosphorous anti-wear agent can be a kind of in above a few class, can be several mixtures also, and the content of phosphorous anti-wear agent is 0.05～12 heavy % in the hot-rolled oil composition, preferred 0.1～6 heavy %.
(IV) clay wear-resistant anti-skid agent
Described clay wear-resistant anti-skid agent prepares in accordance with the following methods:
With organo-clay and C
4-C
24Carboxylic acid compound or C
13-C
64The condenses that contains carboxylic acid carries out esterification under 100-160 ℃ in the presence of organic solvent, the separated and collected product promptly gets clay wear-resistant anti-skid agent then.
Organo-clay and C
4-C
24Carboxylic acid compound or C
13-C
64The weight ratio that contains the condenses of carboxylic acid is 1: 0.1～1: 100, preferred 1: 0.2～1: 50.Temperature of reaction is 100-160 ℃, and preferred 100-130 ℃, the reaction times can be 4-40 hour, preferred 6-30 hour.Steam solvent after reaction is finished, promptly get the oil soluble clay wear-resistant anti-skid agent.
For the ease of subsequent operations, can in product, add lubricant base, be mixed with unit for uniform suspension.Also can add tensio-active agent and improve the dispersiveness of wear-resistant anti-skid agent in hot-rolling oil.Tensio-active agent can be Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate etc., the heavy % of the 0.1-0.5 of surfactant comprise clay wear-resistant anti-skid agent gross weight.
Said clay is selected from wilkinite, polynite, attapulgite etc.Organically-modified is the ion such as the Na that can be exchanged with between ion such as ammonium, phosphine, oxygen, sulfonium etc. and clay seam
+, K
+, Mg
2+Deng carrying out ion-exchange, give the clay parent organic property.Organo-clay can be the commercial goods, also can be according to conventional method of modifying self-control.Comparatively general method of modifying is that clay and alkylamine or aminocarboxylic acid, hydrochloric acid are added in the distilled water, is warmed up to 30-90 ℃, fully stir, with muddy liquid centrifugation, with the distilled water repetitive scrubbing to no Cl
-Detect,, obtain organo-clay isolate vacuum-drying at room temperature.By organically-modified, the clay layer edge contains great amount of hydroxy group, can with organism generation esterifications such as carboxylic acid, acid anhydrides.
Said carboxylic acid compound is selected from C
4-C
24, preferred C
12-C
22Carboxylic acid, acid anhydrides and carboxylic acid and the adduction product of acid anhydrides, can be monoprotic acid, also can be diprotic acid, preferred fatty acid, for example oleic acid, sebacic acid, Succinic Acid, hexosamine, lauric acid (C
12), tetradecanoic acid (C
14), palmitinic acid (C
16) and erucic acid (C
22).
Said C
13-C
64The condenses that contains carboxylic acid can be C
9-C
48Polyoxyethylene ester or multi-hydroxy ester and C
4-C
16The monoesters that the diprotic acid condensation forms, it has the free carboxyl.C
9-C
48Preferred polyoxyethylene lauric acid ester (the C of polyoxyethylene ester
11H
23COO (CH
2CH
2O) polyoxyethylene stearic acid ester (C nH),
17H
35COO (CH
2CH
2O) polyoxyethylene oleate (C nH),
17H
33COO (CH
2CH
2O) nH), n is 1～30, preferred 2～10 integer; C
9-C
48The preferred Xylitol monoleate of multi-hydroxy ester (C
23H
44O
5), Protanal Ester SD-LB (C
9H
14O
7), rosin triglyceride (C
23H
36O
4), 9,10-dihydroxyl methyl behenate, 15,16-dihydroxyl tetracosane acetoacetic ester, 9,14-dihydroxyl-10,12-octadecadienoic acid ester glyceryl ester etc.; C
4-C
16Diprotic acid is fumaric acid (HOOCCH=CHCOOH), sebacic acid, Thapsic acid etc. preferably.The condensation mol ratio of polyoxyethylene ester or multi-hydroxy ester and diprotic acid is 0.1: 1～1.9: 1, preferred 0.8: 1～1.2: 1.
Organic solvents such as selected solvent can toluene, dimethylbenzene, benzene, ethanol, ethylene glycol, methyl-phenoxide and dioctyl sebacate, preferably reflux temperature is at 100-160 ℃ organic solvent.
Described clay wear-resistant anti-skid agent accounts for the heavy % of 0.01-1 of hot-rolling oil gross weight, the preferably heavy % of 0.03-0.08.
Can also add other additive as required in the hot-rolled oil composition provided by the invention, as viscosity index improver, metal passivator, oxidation inhibitor, kilfoam, rust-preventive agent etc.
Hot-rolled oil composition provided by the invention has the following advantages:
1) has oil-soluble group, various additives dispersed fine in oil;
2) utilize the complex effect of sulphur phosphorus extreme pressure anti-wear additives to make hot-rolling oil have good lubricity.
3) the oil soluble clay wear-resistant anti-skid agent that utilizes the inventive method to prepare can significantly reduce the frictional coefficient under the harsh operating mode of boundary lubrication, reduces rolling load; And can regulate the frictional coefficient that relaxes under the operating mode (elastohydrodynamic lubrication and mixed lubrication) by changing dosage, play anti-skidding effect.
4) belong to the very low hot-rolled oil composition of ash content, can not have a negative impact to rolling performance because of ash problems.
5) nontoxic, biodegradable, favourable to environmental protection.
Description of drawings
Fig. 1 is the comparison of the hot-rolled oil composition antifriction performance of Comparative Examples 3 and example 10 preparations.
Embodiment
The preparation of embodiment 1～7 explanation clay wear-resistant anti-skid agent.
Example 1
With 4.00 gram quaternary ammonium salt modified wilkinites of the U.S. and 4.00 gram oleic acid and maleic anhydride adducts, 200 gram toluene add in the there-necked flask, reflux 36 hours, and pressure reducing and steaming toluene is with 150SN base oil stripping product, numbering A.
Example 2
With 4.00 homemade quaternary ammonium salt modified wilkinites of gram and 11.12 gram oleic acid, 250 gram toluene refluxed 12 hours, and pressure reducing and steaming toluene is dissolved in the 150SN base oil with product, numbering B.
Example 3
Produce quaternary ammonium salt modified wilkinite and 4.00 gram sebacic acid with the 4.00 gram U.S., 250 gram toluene, back flow reaction 12 hours, pressure reducing and steaming toluene is dissolved in the 150SN base oil with product, numbering C.
Example 4
With 10.00 gram Ca base montmorillonites, 20 gram stearylamines, the hydrochloric acid of the 200ml of 1: 10 dilution proportion, normal temperature stirred 4 hours down, filtered, and was washed with distilled water to no Cl
-Detect, oven dry is pulverized, and obtains organically-modified clay.
Get 10 gram products and 3 gram Succinic Acid, reaction is 8 hours under refluxing toluene, and pressure reducing and steaming toluene is dissolved in the 150SN base oil with product, numbering D.
Get 10 gram products and 10 gram erucic acid reacts 6 hours under reflux in toluene, pressure reducing and steaming toluene is dissolved in the 150SN base oil with product, numbers E.
Example 5
Get 10 gram attapulgites, 10 gram hexosamines, 200ml are with the hydrochloric acid of dilution in 1: 10, and normal temperature stirred 4 hours down, filter, and washing, oven dry is pulverized.
Get the attapulgite of 3 gram modifications, 6 gram maleic acid anhydrides were reflux in toluene 6 hours, and pressure reducing and steaming toluene is dissolved in the 150SN base oil with product, numbering F.
Example 6
With the quaternary ammonium salt modified wilkinite of 5 grams, 10 gram sebacic acid, in ethylene glycol solution,, leave standstill after-filtration in 110 ℃ of reactions 8 hours, use distilled water wash, evaporate to dryness.Product is dissolved in base oil among the 150SN, numbering G.
Example 7
In being equipped with the 500ml three-necked bottle of water trap, add polyoxyethylene lauric acid ester 0.4mol, sebacic acid 0.4mol, toluene 160ml, dehydration catalyst tetrabutyl titanate 4g, stir down and reflux dewatering 3h at 12g-130 ℃, boil off toluene and filtered while hot again, obtain the condenses of polyoxyethylene lauric acid ester and sebacic acid.
Take out the above-mentioned condenses of 32.3g in another three-necked bottle, add 150ml toluene, 1g 325 order attapulgites, the 0.5g Sodium dodecylbenzene sulfonate at 120-135 ℃ of following stirring reaction 6h, boils off toluene, and product is dissolved in the dioctyl sebacate base oil, gets product H.
Example 8～10 explanation the present invention carry the hot-rolling oil group of arch and the composition of thing.
Comparative Examples 1
The hot-rolling oil HRO-A that China's hot rolling line uses is as reference oil.
Example 8
Preparation hot-rolled oil composition " HRO-1 " 100 grams, comprising base oil 92.4 grams (150SN mineral oil 46.2 gram+pentaerythritol esters 46.2 grams), sulfide mineral 1.0 grams, sulfuration oleum gossypii seminis 4.0 grams, N, N '-di-n-butyl-O, O '-diisooctyl dithio phosphoramidate 1.0g, acid phosphoric acid ester imidazoline salt 0.5 gram, zinc dialkyl dithiophosphate 0.8 gram, metal passivator 124 Triazole 0.3 gram is pressed wear-resistant anti-skid agent A 0.05 gram of embodiment 1 preparation, and performance data sees Table 1.Wear scar diameter D (mm) test condition is 392N, 60min, 1200rpm.
The oilness of table 1 hot-rolling oil
| Oil sample | V 40℃，mm 2/s | P B，N | P D，N | ZMZ | D(mm) |
| HRO-A HRO-1 | 83.80 79.10 | 1373 1472 | 1962 3090 | 51.72 61.76 | 0.36 0.35 |
Comparative Examples 2
Preparation hot-rolled oil composition " HRO-B " 100 grams are as reference oil, comprising base oil 90 grams (30# turbine oil 20 gram+sebates 60 gram+polymerization Oleum Gossypii semens 10 grams), sulfurized mineral oil 1.0 grams, O, O-two (2-ethylhexyl)-N, N '-di-n-butyl-dithio phosphoramidate 4 grams, phenyl tertiary butyl phosphoric acid ester 3 grams, O, O '-di-isopropyl benzylphosphonic acid ester 2 grams.
Example 9
Preparation hot-rolled oil composition " HRO-2 " 100 grams, comprising " HRO-B " 99.4 grams, and the wear-resistant anti-skid agent D0.6 gram of pressing embodiment 4 preparations, performance data is listed in table 2.Wear scar diameter D (mm) test condition is 392N, 75 ℃, and 1200rpm.
Table 2 wear-resistant anti-skid agent is to the influence of hot-rolling oil oilness
| Hot-rolling oil | P B，N | P D，N | D(mm) |
| HRO-B HRO-2 | 1059 1373 | 2453 3090 | 0.44 0.39 |
Comparative Examples 3
Preparation hot-rolled oil composition " HRO-C " 100 grams are as reference oil, comprising base oil 97.2 grams (pentaerythritol ester 90.0 grams, polymerization Yatall MA (refining tall oil) 4.7 grams, polyoxyethylenated castor oil 2.5 grams), dodecyl polysulfide 0.3 gram, N, N '-di-n-butyl-O, O '-di-n-octyl dithio phosphoramidate 1.0 grams, dimercaptothiodiazole phosphorodithioate 0.5 gram, di-n-octyl zinc dithiophosphate 1.0 grams, as a comparison case.
Example 10
Prepare hot two oil compositionss " HRO-3 ", " HRO-4 " and " HRO-5 " each 100 gram, the wear-resistant anti-skid agent H that wherein comprises by the preparation of the method for example 7 is respectively 0.06 gram, 0.1 gram and 0.2 gram, surplus is HRO-C.
At the curve of MTM test aircraft measurements The friction coefficient velocity variations, and contrast with HRO-C.Fig. 1 shows that the frictional behaviour of anti-skidding anti-wear agent changes with concentration, but the effect that significantly reduces frictional coefficient in boundary lubrication (low regime) is all arranged, HRO-3, HRO-4 and the HRO-5 frictional coefficient under 10 rev/mins is respectively 0.073,0.045 and 0.076, is starkly lower than contrast HRO-C (0.11).Lubricated then relevant at the plastic sulfur body with the content of wear-resistant anti-skid agent with the performance in mixed lubrication district.
Claims (25)
1. a hot-rolled oil composition is a benchmark with the composition gross weight, comprising:
(I) 40 ℃ of a large amount of viscosity are 5～300mm
2The lubricant base of/s;
(II) content is the sulfur-containing extreme-pressure additive that is selected from alkyl polysulfide, sulfuration Dormant oils, the thio polyol ester one or more of 0.1～15 heavy %;
(III) content is the phosphorous anti-wear agent that is selected from phosphoric acid ester, phosphonic acid ester, phosphorous acid ester, acid phosphate amine salt, phosphorous acid ester amine salt, phosphoramidate, dialkyl dithiophosphate, dimercaptothiodiazole phosphorodithioate and the acid phosphoric acid ester imidazoline salt one or more of 0.1～20 heavy %;
(IV) content is the oil soluble clay wear-resistant anti-skid agent of preparation in accordance with the following methods of the heavy % of 0.01-1: with organo-clay and C
4-C
24Carboxylic acid compound or C
13-C
64The condenses that contains carboxylic acid carries out esterification, separated and collected product then with 1: 0.1～1: 100 weight ratio under 100-160 ℃.
2. according to the described composition of claim 1, it is characterized in that lubricant base is mineral oil or ester class oil.
3. according to the described composition of claim 2, it is characterized in that, mineral oil is the mineral lubricating oils of being produced by paraffinic crude or naphthenic base crude, the mixture of ester class grease separation one or two or more kinds in synthetic ester, vegetable and animals oils, hot polymerization polyunsaturated vegetable oil and Viscotrol C ethylene oxide condensate contains a kind of ester class oil at least in the base oil.
4. according to the described composition of claim 3, it is characterized in that synthetic ester is C
8～C
12The diester or the C of alcohol
8～C
24The polyol ester of lipid acid.
5. according to the described composition of claim 3, it is characterized in that synthetic ester is diisooctyl sebate, didecyl adipic acid ester, trimethylolpropane tris monooctyl ester, tetramethylolmethane vegetable fatty acid esters.
6. according to the described composition of claim 1, it is characterized in that alkyl polysulfide is dialkyl group pentasulfide, two nonyl trisulphide, uncle's dodecyl trisulphide, dodecyl tetrasulfide, dinonyl disulphide, dilauryl tetrasulfide or uncle's dodecyl pentasulfide.
7. according to the described composition of claim 1, it is characterized in that the sulfuration Dormant oils is the sulfuration Dormant oils of sulfur-bearing 20～40 heavy %.
8. according to the described composition of claim 1, it is characterized in that the thio polyol ester is xanthogenic acid glycol ester, sulfuration neat's-foot oil, sulfuration lard, sulfuration soya-bean oil, sulfuration sunflower seed oil or sulfuration Oleum Gossypii semen.
9. according to the described composition of claim 1, it is characterized in that content 0.2～13 heavy % of sulfur-containing extreme-pressure additive in the hot-rolled oil composition.
10. according to the described composition of claim 1, it is characterized in that, phosphoric acid ester is tricresyl alkaliine, two-ethylhexyl dihydrogen phosphate, dilauryl phosphoric acid ester, n-hexadecyl phosphoric acid ester, two Octadecane base phosphoric acid ester, thiophosphoric acid phenyl ester, O, O '-diethyl eicosane ketone group phosphoric acid ester or dilauryl two polyoxypropylene phosphoric acid ester.
11., it is characterized in that phosphonic acid ester is two dodecyl phosphonic acid esters, O, O '-di-n-butyl dodecyl phosphonic acid ester, O, O '-di-isopropyl benzylphosphonic acid ester or O, O '-two (neighbour) nitrophenyl phosphonic acid ester according to the described composition of claim 1.
12., it is characterized in that phosphorous acid ester is di-n-octyl phosphorous acid ester or two-(2-ethylhexyl) phosphorous acid ester according to the described composition of claim 1; The amine salt of acid phosphoric acid ester and the amine salt of phosphorous acid ester are di-n-butyl phosphorous acid ester stearylamine salt, two-(2-ethylhexyl) phosphorous acid ester hexahydroaniline salt, diethyl phosphorous acid ester tallow amine salt, dioctyl phosphoric acid ester-N-tallow base-1,3-Pn salt, di-isopropyl phosphoric acid ester-N-oil base-1,3-propenyl two amine salt, DHP dihexylphosphoric acid METH 124 Triazole oleyl amine salt, n-hexyl phosphorous acid ester tripropyl amine salt or dioctyl phosphoric acid ester-five polytrimethylene ether propylamine salt.
13. according to the described composition of claim 1, it is characterized in that phosphoramidate is selected from the phosphinylidyne monoamine ester of not phosphoramidate, single thiophosphoryl monoamine ester, two thiophosphoryl monoamine ester, single thiophosphoryl diamine ester and the monoamine and the diamine of sulfur-bearing and in the phosphinylidyne diamine ester one or more.
14. according to the described composition of claim 13, it is characterized in that, phosphoramidate is N-dodecyl-di-n-hexyl phosphoramidate, N, N-diallyl-di-n-butyl phosphoramidate, two (to) butylbenzene base thio-phosphamide ester, O-octyl group-N-sec.-propyl-N p-methoxyphenyl thioureido thiophosphoryl diamines ester or O, O '-two (2-ethylhexyl)-N, N-di-n-butyl-dithio phosphoramidate.
15., it is characterized in that dialkyl dithiophosphate is zinc salt or molybdenum salt according to the described composition of claim 1.
16., it is characterized in that dialkyl dithiophosphate is di-n-butyl zinc dithiophosphate, di-n-octyl zinc dithiophosphate, O-butyl according to the described composition of claim 15, O '-octyl group zinc dithiophosphate or dioctyl phosphorodithioic acid oxygen molybdenum.
17., it is characterized in that the dimercaptothiodiazole phosphorodithioate is 2 according to the described composition of claim 1,5-(O, the two diisooctyl phosphorodithioic acid of O ' base)-1,3,4-thiadiazoles or 2,5-(O, the two di-n-butyl phosphorodithioic acid of O ' base)-1,3, the 4-thiadiazoles.
18., it is characterized in that the acid phosphoric acid ester imidazoline salt is O according to the described composition of claim 1, O '-two 1-isobutyl-3,5-dimethylhexylphosphoric acid-1-(triamine ethyl)-2-17 alkenyl imidazoline salt.
19., it is characterized in that the content of phosphorous anti-wear agent is 0.5～10 heavy % in the hot-rolled oil composition according to the described composition of claim 1.
20. according to the described composition of claim 1, it is characterized in that, in the preparation process of described clay wear-resistant anti-skid agent, organo-clay and C
4-C
24Carboxylic acid compound or C
13-C
64The weight ratio that contains the condenses of carboxylic acid is 1: 0.2～1: 50, and temperature of reaction is 100-130 ℃, and the reaction times is 4-40 hour.
21., it is characterized in that said clay is wilkinite, polynite or attapulgite according to the described composition of claim 1.
22., it is characterized in that said carboxylic acid compound is C according to the described composition of claim 1
12-C
22Lipid acid.
23., it is characterized in that said C according to the described composition of claim 1
13-C
64The condenses that contains carboxylic acid is C
9-C
48Polyoxyethylene ester or multi-hydroxy ester and C
4-C
16The monoesters that the diprotic acid condensation forms, the condensation mol ratio of polyoxyethylene ester or multi-hydroxy ester and diprotic acid is 0.1: 1～1.9: 1.
24., it is characterized in that C according to the described composition of claim 23
9-C
48Polyoxyethylene ester is polyoxyethylene lauric acid ester, polyoxyethylene stearic acid ester or polyoxyethylene oleate; C
9-C
48Multi-hydroxy ester is Xylitol monoleate, Protanal Ester SD-LB, rosin triglyceride, 9,10-dihydroxyl methyl behenate, 15,16-dihydroxyl tetracosane acetoacetic ester or 9,14-dihydroxyl-10,12-octadecadienoic acid ester glyceryl ester; C
4-C
16Diprotic acid is fumaric acid, sebacic acid or Thapsic acid.
25., it is characterized in that described clay wear-resistant anti-skid agent accounts for the heavy % of 0.03-0.8 of hot-rolling oil gross weight according to the described composition of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB200510105432XA CN100425681C (en) | 2005-09-28 | 2005-09-28 | Thermal roll-oil composition of dispersing oily clay wear-resistant anti-skid agent |
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| CNB200510105432XA CN100425681C (en) | 2005-09-28 | 2005-09-28 | Thermal roll-oil composition of dispersing oily clay wear-resistant anti-skid agent |
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| CN1940037A true CN1940037A (en) | 2007-04-04 |
| CN100425681C CN100425681C (en) | 2008-10-15 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717684B (en) * | 2009-11-20 | 2013-01-16 | 东莞市安默琳节能环保技术有限公司 | Spray supply mode cutting oil for metal material cutting processing |
| CN103261384A (en) * | 2010-12-20 | 2013-08-21 | 日本帕卡濑精股份有限公司 | Lubricant for plastic processing of metal material |
| CN105925348A (en) * | 2015-02-28 | 2016-09-07 | 印度石油有限公司 | Hot rolling oil for steel |
| CN107267259A (en) * | 2016-04-08 | 2017-10-20 | 雅富顿化学公司 | Lubricant additive and lubricant compositions with improved frictional behavior |
| CN108410543A (en) * | 2018-04-19 | 2018-08-17 | 翟琳 | A kind of fire-retardant preparation of greases method of concave convex rod soil matrix |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA84247B (en) * | 1983-02-18 | 1984-09-26 | Lonza Ag | Parting and lubricating agent in solid form |
| DD224332B1 (en) * | 1984-06-18 | 1987-08-12 | Bandstahlkombinat Matern Veb | LUBRICANT COMPOSITION BASED ON SODIUM SOAP FOR LUBRICATING THE ROLLERS ON PANEL ROLLERS |
| JP2001049275A (en) * | 1999-08-12 | 2001-02-20 | New Japan Chem Co Ltd | Lubricating oil for refrigerator |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101717684B (en) * | 2009-11-20 | 2013-01-16 | 东莞市安默琳节能环保技术有限公司 | Spray supply mode cutting oil for metal material cutting processing |
| CN103261384A (en) * | 2010-12-20 | 2013-08-21 | 日本帕卡濑精股份有限公司 | Lubricant for plastic processing of metal material |
| CN103261384B (en) * | 2010-12-20 | 2015-04-01 | 日本帕卡濑精股份有限公司 | Lubricant for plastic processing of metal material |
| CN105925348A (en) * | 2015-02-28 | 2016-09-07 | 印度石油有限公司 | Hot rolling oil for steel |
| CN107267259A (en) * | 2016-04-08 | 2017-10-20 | 雅富顿化学公司 | Lubricant additive and lubricant compositions with improved frictional behavior |
| CN107267259B (en) * | 2016-04-08 | 2021-02-12 | 雅富顿化学公司 | Lubricant additives and lubricant compositions having improved friction characteristics |
| JP2019517612A (en) * | 2016-06-03 | 2019-06-24 | クローダ インターナショナル パブリック リミティド カンパニー | Lubricant composition |
| US11697783B2 (en) | 2016-06-03 | 2023-07-11 | Equus Uk Topco Ltd | Lubricant composition |
| CN108410543A (en) * | 2018-04-19 | 2018-08-17 | 翟琳 | A kind of fire-retardant preparation of greases method of concave convex rod soil matrix |
| TWI774522B (en) * | 2021-08-19 | 2022-08-11 | 陳文祥 | Internal combustion engine oil improvement lozenges |
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