CN1923989A - Hot-rolled oil composition containing organosilicon antiwear slip-proofing agent - Google Patents
Hot-rolled oil composition containing organosilicon antiwear slip-proofing agent Download PDFInfo
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Abstract
The invention discloses a hot-rolled composition with organic silicon anti-friction antilubricant, which comprises the following parts: (I) lubricant basic oil with viscosity at 5-300mm2/s at 40 deg.c, (II) 0.1-20wt% sulphur extreme pressure agent with one or more material from alkyl polysulfide, sulfur ore oil and sulfur polyol ester, (III) 0.05-15wt% phosphorus antiwear agent with one or more material from phosphate, phosphonate, phosphite ester, acid phosphate ester, phosphite ester amine salt, phosphamide ester, dialkyl dithiophosphate, dimercaptothiodiazole dithiophosphate ester and acid phosphate imidazoline salt, (IV) 0.001-25% organosilicon abrasion resistance antilubricant with silicon chloride, C2-16 aliphatic amine, disperser and non-ionic surface activator.
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 30-90wt% high base number alkylphenol 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 0.1～15.0 heavy % in the hot-rolled oil composition, preferred 0.2～13.0 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:
Deng, R
4-R
8Be H or C
1-C
8Alkyl.
R in the formula
1And R
2=C
3-C
12Alkyl, alkaryl and amido,
R
5=H ,-CH
3,-OCH
3
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 0.1～15.0 heavy % in the hot-rolled oil composition, preferred 0.2～8 heavy %.
(IV) organosilicon wear-resistant anti-skid agent
Described organosilicon wear-resistant anti-skid agent prepares in accordance with the following methods:
In the presence of organic solvent, with silicon tetrachloride and C
2-C
16Aliphatic amide reacts under the condition of 0.01～0.1MPa at 0～100 ℃, obtains intermediate product; Intermediate product is mixed with lubricating oil dispersant, nonionogenic tenside and lubricant base, and stirring reaction under 50 ℃～180 ℃, 0.01～0.1MPa becomes translucent thickness state up to product, promptly obtains containing organosilyl wear-resistant anti-skid agent.
Specifically, can prepare in accordance with the following methods:
1) silicon tetrachloride is dissolved in the non-polar solvent, under agitation adds C
2-C
16Aliphatic amide is 0～100 ℃ in temperature, and preferred 25～70 ℃, pressure is 0.01～0.1MPa, reacts under the condition of preferred 0.05～0.08MPa 1～8 hour, preferred 2～4 hours, obtains intermediate product.Wherein, the mol ratio of silicon tetrachloride and aliphatic amide is 1: 3～1: 10, preferred 1: 4～1: 8.The consumption of solvent is 5～30 times of silicon tetrachloride weight, preferred 10～25 times.
2) lubricating oil dispersant, nonionogenic tenside and carrier oil are mixed with intermediate product, at 50 ℃～180 ℃, preferred 75～150 ℃ were stirred 0.5～6 hour down, preferred 1～4 hour, reaction pressure 0.01～0.1MPa, preferred 0.05～0.08MPa obtains the additive of translucent thickness state.
Wherein, be 100% in the weight of intermediate product, dispersant dosage is 1～10%, preferred 2～6%; The nonionogenic tenside consumption is 1～10%, preferred 2～6%; The consumption of carrier oil is 20～70%, preferred 30～50%.
Said C
2-C
16Aliphatic amide is C
2-C
16Alkylamine or polyamines polyene, preferred ethylamine, n-butylamine, n-hexyl amine, dodecyl, diethylenetriamine, triethylene tetramine etc.It also can be one or more mixture wherein.
Said organic solvent is a non-polar solvent, preferred benzene,toluene,xylene, hexanaphthene, sherwood oil or their mixture.
Said lubricating oil dispersant is allyl butyrate imide, petroleum sodium sulfonate, calcium mahogany sulfonate or their mixture.
Said nonionogenic tenside is the single, double fatty acid ester of glycerine, as the single, double ester of the glycerine of citric acid, succsinic acid, lactic acid; The Sorbitol Powder fatty acid ester is as sorbityl monododecanoate, Sorbitol Powder monopalmitate, sorbitol monooleate; And the Soxylat A 25-7 of Sorbitol Powder fatty acid ester,, polyoxyethylene (20) Sorbitol Powder monostearate sorbityl monododecanoate etc. as polyoxyethylene (20).
Said carrier oil is mineral oil, ucon oil, vegetables oil or their mixture, and 40 ℃ of viscosity are 5～50mm
2/ s, preferred 10～30mm
2/ s.Ucon oil is ester class oil, polyethers, alkylbenzene, synthetic hydrocarbon or their mixture.
Wear-resistant anti-skid agent accounts for the heavy % of 0.001-25 of hot-rolling oil gross weight, the preferably heavy % of 0.005-18.Wear-resistant anti-skid agent wherein can be used as the hot-rolling oil component and adds at last, also can adopt the carrier oil component of hot-rolling oil to call in the hot-rolling oil as the preparing carriers slipproofing agent again.The used carrier oil of preparation wear-resistant anti-skid agent can be identical or different with the base oil in the hot-rolled oil composition.
Can also add other additive as required in the hot-rolled oil composition provided by the invention, as viscosity index improver, oxidation inhibitor and 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) add wear-resistant anti-skid agent, in friction process, on surface of friction, decompose and generate silicon nitride, the rubbing characteristics similar with the ceramic nano extreme pressure anti-wear additives to the clay extreme pressure anti-wear additives arranged, not only improve supporting capacity and oilness after adding hot-rolling oil, and adjusting hot-rolling oil frictional behaviour, play anti-skidding effect, under lower concentration, have than clay anti-wear agent, oxidate nano anti-wear agent and the better resistance to abrasion of silicate nano anti-wear agent.
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 that the hot-rolled oil composition abrasion resistance of Comparative Examples 1 and example 7 preparations compares.
Embodiment
The preparation of embodiment 1～3 explanation wear-resistant anti-skid agent.
Example 1
The 2.43g silicon tetrachloride is dissolved in the 35.58g benzene, under stirring, reducing pressure, adds the 8.6g di-n-butyl amine, under reduced pressure stir 2 hours (Heating temperature is 25 ℃, pressure 0.05MPa) again after adding finishes; (40 ℃ of viscosity are 22mm with 30g mineral oil
2/ s), the single succimide of hanging of sorbityl monododecanoate, the 2g of 1g mixes with above-mentioned substance, heated and stirred 4 hours (Heating temperature is 75 ℃, pressure 0.05MPa) reduces pressure; Add epoxy soybean oil 0.5g, get wear-resistant anti-skid agent A after stirring.
Example 2
The 3.15g silicon tetrachloride is dissolved in the 38.63g sherwood oil, under stirring, normal pressure, adds the 13.5g triethylene tetramine, under normal pressure, stir 4 hours (Heating temperature is 45 ℃) after adding finishes again; (40 ℃ of viscosity are 25.3mm with the 38g Oleum Gossypii semen
2/ s), the single succimide of hanging of 2g Sorbitol Powder monopalmitate, 2g mixes with above-mentioned substance, and normal pressure heated and stirred 5 hours (Heating temperature is 150 ℃), adding amido vinyl ether 1g must wear-resistant anti-skid agent B after stirring.
Example 3
The 4.23g silicon tetrachloride is dissolved in the 55.36g toluene, under stirring, normal pressure, adds 17.83g dodecyl amine, under normal pressure, stir 3.5 hours (Heating temperature is 30 ℃) after adding finishes again; (40 ℃ of viscosity are 20.6mm with the 38.7g rapeseed oil
2/ s), the Soxylat A 25-7 of 2g Sorbitol Powder fatty acid ester, the single succimide of hanging of 2g mix with above-mentioned substance, and normal pressure heated and stirred 4 hours (Heating temperature is 101 ℃), adding amido vinyl ether 1g must wear-resistant anti-skid agent C after stirring.
The composition and the performance of embodiment 4～12 explanations hot-rolled oil composition provided by the invention.
Example 4
Preparation hot-rolled oil composition " HRO-1 " 100 grams, comprising base oil 82.5 grams (42.5 gram 500SN mineral oil+40 gram plam oils), sulfuration lard 13.0 grams, two butylbenzene base thio-phosphamide esters, 1.0 grams, and embodiment 1 wear-resistant anti-skid agent A3.5 gram, performance data sees Table 1.
Example 5
Preparation hot-rolled oil composition " HRO-2 " 100 grams, comprising base oil 88.0 grams (44 gram 500SN mineral oil+44 gram pentaerythritol esters), dinonyl trisulphide 1.0 grams, sulfuration rapeseed oil 3.0 grams, phosphoric acid ester T451 1.0 grams, tricresyl alkaliine 0.5 gram, polyisobutene viscosity index improver 6.0 grams, and embodiment 2 wear-resistant anti-skid agent B0.5 gram, performance data sees Table 1.
Example 6
Preparation hot-rolled oil composition " HRO-3 " 100 grams, comprising base oil 81.5 grams (unsaturated rapeseed oil 10 grams of 150BS mineral oil 34.5 gram+dioctyl sebacates, 27 gram+castor oil polyoxyethylenes (10) ether 10 gram+hot polymerizations), dodecyl trisulphide 2.0 grams, acid dioctyl phosphite 1.0 grams, DHP dihexylphosphoric acid METH 124 Triazole oleyl amine salt 0.5 gram, di-n-butyl zinc dithiophosphate 1.0 grams, dilauryl phosphoesterase 30 .5 gram, and embodiment 3 wear-resistant anti-skid agent C13.5 gram, performance data sees Table 1.
Table 1 hot-rolled oil composition performance
| Example | Hot-rolled oil composition | Saponification value | Acid number (mgKOH/g) | V40℃ (mm 2/s) | P B (N) | P D (N) | ZM Z(N) | D 40kg 60min， (mm) |
| 4 | HRO- 1 | 101 | 6.0 | 52 | 1470 | 3087 | 605 | 0.40 |
| 5 | HRO- 2 | 80 | 5.0 | 72 | 1079 | 4905 | 617 | 0.45 |
| 6 | HRO- 3 | 92 | 11.0 | 222 | 1275 | 3924 | 679 | 0.32 |
Comparative Examples 1
Preparation hot-rolled oil composition HRO-A 100 grams are as reference oil, comprising base oil 99.65 grams (95.65 gram 200SN mineral oil+4 gram polymerization Oleum Gossypii semens), sulfuration Dormant oils 0.25 gram, O-octyl group-N-sec.-propyl-N '-p-methoxyphenyl thioureido thiophosphoryl diamines ester 0.10 gram, as a comparison case.
Example 7
Preparation hot-rolled oil composition " HRO-4 " 100 grams, comprising HRO-A 99.75 grams, and the wear-resistant anti-skid agent A0.25 gram of pressing embodiment 1 preparation, the result of four-ball test shows that the resistance to abrasion of " HRO-4 " is better than HRO-A (Fig. 1).
Example 8
Preparation hot-rolled oil composition " HRO-5 " 100 grams, comprising base oil 98.0 grams (75.0 gram 200SN mineral oil+20 gram trihydroxymethylpropanyl esters+1.0 gram polymerization Oleum Gossypii semens), 1.0 gram dodecyl trisulphide, 0.5 gram acid phosphoric acid ester imidazoline salt, 0.5 gram molybdenum dialkyl-dithiophosphate, press the wear-resistant anti-skid agent A2.0 gram of embodiment 1 preparation, record four ball oil film strength P
B1275N, sintering load P
B2453N.
Comparative Examples 2
Preparation hot-rolled oil composition HRO-B 100 grams are as reference oil, comprising base oil dioctyl sebacate 93 grams, sulfurized mineral oil 5.0 grams, di-n-butyl zinc dithiophosphate 1.0 grams, acid phosphate amine salt 0.5 gram, O, O '-n-octyl-N, N '-di-n-butyl-dithio phosphoramidate 0.5 gram.
Example 9
Preparation hot-rolled oil composition " HRO-6 " 100 grams, comprising HRO-B 99.95 grams, and the wear-resistant anti-skid agent A0.05 gram of pressing embodiment 1 preparation, performance data is listed in table 2.
The four-ball wear test result of table 2 hot-rolled oil composition
| Hot-rolling oil | Wear scar diameter, D 60min 30kg，mm | Wear scar diameter, D 60min 40kg，mm |
| HRO-B | 0.39 | 0.36 |
| HRO-6 | 0.36 | 0.33 |
Comparative Examples 3
Preparation hot-rolled oil composition HRO-C100 gram is 29.0mm as reference oil comprising V40 ℃
2150SN mineral oil 99.0 grams of/s, sulfuration sunflower seed oil 0.2 gram, phosphorous acid di-n-octyl 0.1 gram, trihydroxymethylpropanyl ester 0.70 gram.
Example 10
In reference oil HRO-C, add different wear-resistant anti-skid agents, carry out 15 hours one pin three post wearing tests, the results are shown in table 3.Under lower concentration, the resistance to abrasion of the hot-rolled oil composition HRO-7 of this examples preparation obviously is better than the resistance to abrasion of reference oil.
One pin, the three post endurance check results of table 3 hot-rolled oil composition
| Hot-rolling oil | Form | Test block total weightless (mg) up and down |
| HRO-C | - | 43 |
| HRO-7 | The wear-resistant anti-skid agent A of HRO-C+4 ‰ example 1 preparation | 5 |
Example 11
HRO-2 carries out test of small white mouse oral toxicity and skin toxicology test in Medical School of Peking University, belongs to actual nontoxic.HRO-3 proves to belong to biodegradable product in Peking University's biodegrade test.
In its mouse oral acute toxicity test, carried out 14 days experimental observation by small white mouse to the healthy ICR of 40 SPF levels.Finally reach a conclusion: the microemulsion its mouse oral is irritated the stomach maximum tolerated dose more than the 35.2g/kg body weight, and the true border of per os acute toxicity is nontoxic.
In acute skin irritation test, by to the observation in 1,24,48 and 72 hours after removal is tried thing of 4 healthy rabbits, smear position skin and there is no the obvious stimulation reaction, be judged to be the effect of animal skin nonirritant.
Example 12
With reference to the OECD301E method of ECDC development institution, the while is in conjunction with the ratio (BOD of five-day BOD and chemical oxygen demand (COD)
5/ COD) come the biological degradability of HRL-2 and import oil is done relatively.The result shows two kinds of oily biological degradation rates near 60%, illustrates that these two kinds of oil are can be biodegradable.
Claims (27)
1. a hot-rolled oil composition that contains organosilicon antiwear slip-proofing agent 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 0.1～20 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 0.05～15 heavy %;
(IV) content is the organosilicon wear-resistant anti-skid agent of preparation in accordance with the following methods of the heavy % of 0.001-25: in the presence of organic solvent, with silicon tetrachloride and C
2-C
16Aliphatic amide reacts under the condition of 0.01～0.1MPa at 0～100 ℃, obtains intermediate product; Intermediate product is mixed with dispersion agent, nonionogenic tenside and carrier oil, stirring reaction under 50 ℃～180 ℃, 0.01～0.1MPa, become translucent thickness state up to product, wherein, the mol ratio of silicon tetrachloride and aliphatic amide is 1: 3～1: 10, is 100% in the weight of intermediate product, and dispersant dosage is 1～10%, the nonionogenic tenside consumption is 1～10%, and the consumption of carrier oil is 20～70%.
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 0.3～15 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 0.1～6 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 of described organosilicon wear-resistant anti-skid agent, silicon tetrachloride and C
2-C
16The reaction conditions of alkylamine or polyamines polyene is 25～100 ℃ of temperature, pressure 0.05～0.08MPa; The reaction conditions of dispersion agent, nonionogenic tenside, carrier oil and intermediate product is 75～150 ℃, reaction pressure 0.05～0.08MPa.
21., it is characterized in that said C according to the described composition of claim 1
2-C
16Aliphatic amide is C
2-C
16Alkylamine or polyamines polyene.
22., it is characterized in that said C according to the described composition of claim 21
2-C
16Aliphatic amide is ethylamine, n-butylamine, n-hexyl amine, dodecyl, diethylenetriamine or triethylene tetramine, or one or more mixture wherein.
23., it is characterized in that said dispersion agent is allyl butyrate imide, petroleum sodium sulfonate, calcium mahogany sulfonate or their mixture according to the described composition of claim 1.
24., it is characterized in that said nonionogenic tenside is the Soxylat A 25-7 of single, double fatty acid ester, Sorbitol Powder fatty acid ester or the Sorbitol Powder fatty acid ester of glycerine according to the described composition of claim 1.
25., it is characterized in that said nonionogenic tenside is the single, double ester of the glycerine of citric acid, succsinic acid, lactic acid according to the described composition of claim 24; Sorbityl monododecanoate, Sorbitol Powder monopalmitate, sorbitol monooleate; Sorbityl monododecanoate or polyoxyethylene (20) the Sorbitol Powder monostearate of polyoxyethylene (20).
26., it is characterized in that said carrier oil is mineral oil, ucon oil, vegetable and animals oils or their mixture according to the described composition of claim 1,40 ℃ of viscosity are 5～50mm
2/ s.
27., it is characterized in that the organosilicon wear-resistant anti-skid agent accounts for the heavy % of 0.005-18 of hot-rolling oil gross weight according to the described composition of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100937918A CN100389184C (en) | 2005-08-31 | 2005-08-31 | Hot-rolled oil composition containing organosilicon antiwear slip-proofing agent |
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| CNB2005100937918A CN100389184C (en) | 2005-08-31 | 2005-08-31 | Hot-rolled oil composition containing organosilicon antiwear slip-proofing agent |
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| CN1923989A true CN1923989A (en) | 2007-03-07 |
| CN100389184C CN100389184C (en) | 2008-05-21 |
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| CN114574264A (en) * | 2020-12-02 | 2022-06-03 | 中国石油天然气股份有限公司 | Composite extreme pressure antiwear agent and preparation method and application thereof |
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