CN110218604A - A kind of stable type tail seal grease of shield and preparation method thereof - Google Patents

A kind of stable type tail seal grease of shield and preparation method thereof Download PDF

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Publication number
CN110218604A
CN110218604A CN201910552048.6A CN201910552048A CN110218604A CN 110218604 A CN110218604 A CN 110218604A CN 201910552048 A CN201910552048 A CN 201910552048A CN 110218604 A CN110218604 A CN 110218604A
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China
Prior art keywords
grease
seal grease
shield
tail seal
fiber
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Granted
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CN201910552048.6A
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CN110218604B (en
Inventor
孔恒
郭飞
姜瑜
张丽丽
任斌
张旭光
尹丽艳
徐霖
扬伏川
郑青
赵晨阳
高胜雷
田治州
王凯丽
林雪冰
王璐
户迁迁
杨斌
刘雷廷
李振坤
邢建平
胡海波
张学军
车青森
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Beijing Sunnyway Dingxin Municipal Engineering Testing Technology Co
Xinda Chemical Technology Co Ltd
Beijing Municipal Construction Co Ltd
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Beijing Sunnyway Dingxin Municipal Engineering Testing Technology Co
Xinda Chemical Technology Co Ltd
Beijing Municipal Construction Co Ltd
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Application filed by Beijing Sunnyway Dingxin Municipal Engineering Testing Technology Co, Xinda Chemical Technology Co Ltd, Beijing Municipal Construction Co Ltd filed Critical Beijing Sunnyway Dingxin Municipal Engineering Testing Technology Co
Priority to CN201910552048.6A priority Critical patent/CN110218604B/en
Publication of CN110218604A publication Critical patent/CN110218604A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/24—Epoxidised acids; Ester derivatives thereof
    • C10M2207/243—Epoxidised acids; Ester derivatives thereof used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/102—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/04—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/26—Waterproofing or water resistance
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/34—Lubricating-sealants

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Sealing Material Composition (AREA)
  • Lubricants (AREA)

Abstract

The invention discloses a kind of stable type tail seal grease of shield and preparation method thereof, belong to shield machine sealing material technical field.The High-efficiency stable tail seal grease of shield is using LDH compound anti-oxidation stabilizer as inorganic filler, it can intercalation assemblability using LDH, heat stabilizer and oxidant guest molecule intercalation are assembled into LDH interlayer, overcome the defect of seal grease inoxidizability difference and storage stability difference.It introduces silicone coupling agents to be used to eliminate the difference between organic material and inorganic material, improves the interaction between interface, improve the water resistant intensity and globality of seal grease.Be used cooperatively using biomass fiber and polymer fiber, improve single creature fiber do not have lubrication make, wear away higher and single polymers fiber be relatively difficult to biodegradable defect.Also, used preparation method is simple, environmental-friendly, is convenient for industrialized production.

Description

A kind of stable type tail seal grease of shield and preparation method thereof
Technical field
The present invention relates to a kind of High-efficiency stable tail seal grease of shield and preparation method thereof, belong to shield machine sealing technique Field.
Background technique
For shield construction due to high degree of automation, speed of application is fast, safety and stability, the small feature of effect on environment, more It is used both at home and abroad come more.When shield driving, shield shell plays a protective role to section of jurisdiction, but shield shell and exists between tubulature piece Opposite sliding process, existing gap causes shield shell external water and silt particle etc. to be easily accessible shield body between shield shell and outer wall, causes The accidents such as land subsidence, water logging tunnel.Therefore, it is necessary to be sealed processing to shield shell-and-tube piece gap.Most of shield Machine is all using the tail sealing mode for filling seal grease between multiple tracks wire brush, when driving, by grease filling system to shield tail Tail seal grease of shield is injected between wire brush, by the sky inside the extruding force filling sealing wire brush of grease and between wire brush Gap prevents muddy water and soil sand from penetrating into so that shield tail be made to form firm sealant together.By seal grease and steel plate and section of jurisdiction Good adhesion, play sealing, antifriction and antisepsis.
Since shield machine involves great expense, technology is complicated, therefore the requirement to seal grease is very high, at present mainly by France The imported product monopolization of the companies such as CONDAT, Degussa-Admix-tures inc, Mitsubishi business production.Domestic development Relatively slow, product is very different, and leakproofness and pumping especially resistant to pressure are far below same kind of products at abroad.Simultaneously by shield machine, Shield-tunneling construction stratum, ambient temperature effect are big, harmful to underground water, soil property.Chinese patent CN106244299a discloses one Tail seal grease of shield is planted, introduces adhesion promoter in the present invention, effectively increases and the interaction force of substrate surface enhances The adhesive ability and stability of product.But since the compatibility between inorganic filler and organic matter is poor, water resistant means of press seals Property is still poor, and water swash of wave vector is higher.Chinese patent CN107384526A discloses a kind of tail seal grease of shield, introduces sheet Object improves its water-resistance as Drain Resistance agent, but platelet size is difficult to control, and the oversized tablet that will increase is to sealing The abrasion of grease pump.In addition, tail seal grease of shield is easily degraded by thermo-oxidative ageing, and lose its service performance.
Layered composite metal hydroxides (Layered Double Hydroxides, LDH) are a kind of widely used yin Ionic inorganic functional material is formed by two-dimentional laminate and interlayer anion ordered arrangement.Since LDH has the Nomenclature Composition and Structure of Complexes Various function objects are inserted into LDH using intercalation assembling means by the characteristic of Modulatory character and interlayer anion interchangeability Interlayer has obtained the nanosized supramolecular material with different function, such as selective ultraviolet blocking material, selective infrared absorption material Material, thermal stability, environmentally friendly catalyst, fire retardant, biocide mildewcide etc., these supermolecular intercalation structure functional materials are not But the original performance of function object is remained, while also showing LDH and new features that guest species do not have, is widely used in The various fields such as construction material, function additive, petrochemical industry.
Functional guest molecule intercalation with thermal stability and antioxygenic property is assembled into LDH interlayer system by the present invention The LDH compound anti-oxidation stabilizer of standby supermolecular intercalation structure.LDH compound anti-oxidation stabilizer is added to shield as inorganic filler Tail seal grease is absorbed heat since LDH has a large amount of-OH by thermal decomposition, thus greatly reduce seal grease thermal decomposition and Burn rate, LDH are covered in seal grease surface after being thermally decomposed, and then have cut off the entrance of thermal energy and oxygen, form layer of charcoal Protective film, to improve seal grease in high temperature section thermal stability.By interlayer guest molecule (antioxidant and thermostabilization Agent) and LDH main layer board between supermolecule interact, protective effect of the main layer board to interlayer object, inorganic layer plate The blocking effect of layer structure, can increase substantially stability, and less guest molecule external migration increases the persistence that performance plays. In addition, present invention introduces silicone coupling agents for improve organic principle in seal grease (fiber, thickener, preservative etc.) and The compatibility of inorganic host agent filler (LDH compound anti-oxidation stabilizer, bentonite etc.) is eliminated between organic material and inorganic material Difference, improve interface between interaction, improve inorganic filler in organic matter dispersibility and bonding force, improve Seal Oil The water resistant intensity and globality of rouge.LDH is also known as hydrotalcite, is the supermolecule layer structure of Nano grade, particle size is smaller, energy The lubricity and pumping of seal grease are significantly improved, while fine and close sealant can be formed when compressive sealed, is shown excellent Different sealing performance.The present invention is used cooperatively using biomass fiber with polymer fiber, improves single creature fiber and does not have Lubrication is made, the higher and single polymers fiber of abrasion is relatively difficult to biodegradable defect.
Summary of the invention
The object of the present invention is to provide a kind of High-efficiency stable tail seal grease of shield and preparation method thereof.Tail sealing oil Rouge has good storage stability, leakproofness resistant to pressure, pumping, inoxidizability and mechanical performance.
The invention is realized by the following technical scheme:
A kind of stable type tail seal grease of shield, is formed by the material combination of following weight: 10~20 parts of base oil, 7~15 parts of thickener, 0.2~2 part of preservative, 15~30 parts of inorganic filler, 2~5 parts of bentonite, 5~25 parts of composite fibre, silicon 0.1-1 parts of oxygen alkane coupling agent and 2~7 parts of lubricant.
The base oil is mechanical-hydraulic oil, isooctanol modified colza, isooctanol modified soybean oil, epoxidized soybean oil Or one of mineral oil or a variety of.
The thickener is one in rosin resin, polyacrylamide, polymethacrylates, polyisobutene or C5 resin Kind is a variety of, preferably polyisobutene.
The preservative is one of benzimidazole, organic sulfur or organic ammonium or a variety of, preferably organic sulfur.
The inorganic filler is excellent to be one or more in calcium carbonate, lime stone, barium sulfate, mica powder or hydrotalcite powder Hydrotalcite powder, in particular LDH composite material are selected, it, can be compound for LDH composite flame-retardant agent, LDH by being inserted into different function objects Antioxidative stabilizer, LDH composite thermal stabilizer are one or more, further preferred LDH compound anti-oxidation stabilizer.
The bentonite be one of sodium bentonite, calcium-base bentonite, potassium base bentonite or organobentonite or It is a variety of, preferred sodium bentonite.
The composite fibre is the compound of biological fiber and polymer fiber, and composite fibre has reticular structure, energy Enough reduce wears away grease pump.Biological fiber is one of wood fibre, cotton fiber, flax fiber or a variety of, and preferably cotton is fine Dimension.Polymer fiber is one or more in poly- third fiber, polyester fiber and polypropylene fiber, preferred polyester fiber.
The silicone coupling agents are γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy Silane, γ-(methacryloxypropyl) propyl trimethoxy silicane, one in N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane Kind is a variety of, preferably γ-glycidyl ether oxygen propyl trimethoxy silicane.
The lubricant is that lithium base grease, calcium-base grease, mixed base grease, urea-base grease or aluminium base are multiple Close one or more in lubricating grease, preferred lithium base grease.
A method of stable type tail seal grease of shield being prepared, specific preparation process is as follows: step A: using coprecipitation Prepare LDH compound anti-oxidation stabilizer.M will be contained2+、M3+Nitrate be configured to mixing salt solution, M2+For bivalent metal ion Mg2+、Zn2+、Ni2+、Ca2+、Fe2+Or Cu2+In any one or two kinds, preferably Mg2+Or Zn2+；M3+For trivalent metal ion Al3+、Co3+、Ti3+、Fe3+Or Cr3+In any one or two kinds, preferably Al3+；
Step B: the aqueous slkali that molar concentration is 0.05-2mol/L is prepared, aqueous slkali is NaOH, KOH or ammonia spirit；
Step C: antioxidant activity component (AO) and thermostabilization component (MO) are configured to certain density mixed solution, AO Amount with the substance of MO is M3+0.5-10 times of the amount of substance.Antioxidant activity component (AO) for intercalation is containing hindered phenol The organic acid or its sodium salt of group or phosphite group, be preferably obstructed phenates.Thermostabilization active component (MO) for intercalation It is metal mixture, 2 ethyl hexanoic acid salt, stearate, phenyl hydrochlorate, phenates, preferably stearate.
Step D: the mixing salt solution that step B preparation aqueous slkali is added drop-wise in step A, the preparation in step C mixing It in solution, stirs 2-10 hours under nitrogen protection, it is 7- that reaction product centrifuge separation and wash cycle, which are washed to mother liquor pH value, 8, filter cake is dried in vacuo 12-24 hours, obtains the compound antioxidant stabilizer of supramolecular structure LDH.
Step E: silicone coupling agents, base oil, inorganic filler and thickener are mixed in by corresponding weight In reaction kettle, 100 DEG C are reacted 2~4 hours, until thickener is completely dissolved；
Step F: and then sequentially add bentonite, preservative and lubricant by corresponding weight, constant temperature (25- 50 DEG C) it stirs to being uniformly mixed, it is eventually adding composite fibre, heat preservation continues stirring 2~4 hours, obtains paste tail sealing oil Rouge.
Compared with prior art, High-efficiency stable tail seal grease of shield of the present invention and preparation method thereof has the advantage that The present invention using LDH can intercalation assemblability, heat stabilizer and oxidant guest molecule intercalation are assembled into LDH interlayer, overcome The defect of seal grease inoxidizability difference and storage stability difference.Silicone coupling agents are introduced for eliminating organic material and inorganic Difference between material improves the interaction between interface, improves the water resistant intensity and globality of seal grease.LDH is smaller Particle size (50-500nm) significantly improve the lubricity and pumping of seal grease, solve grease pump and wear big disadvantage End.Be used cooperatively using biomass fiber and polymer fiber, improve single creature fiber do not have lubrication make, abrasion it is higher Biodegradable defect is relatively difficult to single polymers fiber.Also, used preparation method is simple, environmental-friendly, is convenient for Industrialized production.
Detailed description of the invention
Fig. 1 is the change curve of embodiment 1 and comparative example 1-5 pumping with ageing time.
Fig. 2 is that embodiment 1 and comparative example 1-5 water rush vector with the change curve of ageing time.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
Step a: 2.46kg Mg (NO is weighed3)2·6H2O and 1.72kg Al (NO3)3·9H2O, which is dissolved in 60L ionized water, to be matched At mixing salt solution.
Step b: it weighs 1.44kg NaOH and is dissolved in 160L deionized water and be made into aqueous slkali.
Step c: weighing 2.5kg β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid and 100L is added in 2.5kg odium stearate Deionized water.
Step d: solution prepared by step a and step c mixes, the alkali for preparing step b under nitrogen protection and stirring Solution is added drop-wise in the mixed solution of a and c, is added dropwise in 30min, and pH=9 is controlled, then anti-under room temperature and nitrogen protection It should be filtered through 6 for 24 hours and wash cycle is handled, last mother liquor pH value is in neutrality, and filter cake is dried in vacuo for 24 hours, and it is multiple that LDH is made Close antioxidative stabilizer.
Step e: by 0.5g γ-glycidyl ether oxygen propyl trimethoxy silicane, 15kg base oil 150SN mineral oil, 20kg inorganic filler LDH compound anti-oxidation stabilizer and 9kg thickener polyisobutene are mixed in reaction kettle, and 100 DEG C of reactions 3 are small When, until thickener is completely dissolved；
Step f: and then sequentially add 5kg sodium bentonite, 1kg preservative benzimidazole and 5kg lubricating oil lithium base lubrication Rouge, constant temperature are stirred to being uniformly mixed, are eventually adding 20kg composite fibre (cotton fiber and polyester fiber are compound), and heat preservation continues to stir White paste tail seal grease of shield is made after 4 hours.
Comparative example 1
This comparative example provides a kind of tail seal grease of shield preparation method, and step is substantially the same manner as Example 1, different It is: 20kg calcium carbonate is used to replace LDH compound anti-oxidation stabilizer as inorganic filler.
Comparative example 2
This comparative example provides a kind of tail seal grease of shield preparation method, and step is substantially the same manner as Example 1, different It is: 10kg LDH compound anti-oxidation stabilizer is added as inorganic filler.
Comparative example 3
This comparative example provides a kind of tail seal grease of shield preparation method, and step is substantially the same manner as Example 1, different It is: 40kg LDH compound anti-oxidation stabilizer is added as inorganic filler.
Comparative example 4
This comparative example provides a kind of tail seal grease of shield preparation method, and step is substantially the same manner as Example 1, different It is: 60kg LDH compound anti-oxidation stabilizer is added as inorganic filler.
Comparative example 5
This comparative example provides a kind of tail seal grease of shield preparation method, and step is substantially the same manner as Example 1, different It is: replaces the composite fibre of cotton fiber and polyester fiber with the cotton fiber of 20kg.
The performance test of the embodiment of the present invention 1 and comparative example 1-5 are all made of identical method: being tested using ASTM D1092 Pumping tests leakproofness resistant to pressure using Malsumara, vector is rushed using ASTM D4049 test water, using ASTM D4048 tests metal protection, and test result is as follows:
Table 1 is the performance test results of the embodiment of the present invention 1 and comparative example 1-5.
As shown in Table 1, LDH compound anti-oxidation stabilizer can significantly improve the pumping of seal grease, leakproofness resistant to pressure, Water rushes vector.Composite fibre can dramatically increase the pumping of seal grease instead of cotton fiber and water rushes vector.
Fig. 1 and Fig. 2 is that tail seal grease of shield increases pumping with ageing time and water rushes the change curve of vector, Cong Tuzhong It is found that seal grease (comparative example 1) pumping of LDH compound anti-oxidation stabilizer is not added after tail seal grease of shield stores December Property and water rush vector significant decrease, illustrate that LDH compound anti-oxidation stabilizer can improve the storage stability of tail seal grease of shield.
Embodiment 2
Step a: 6.4kg Mg (NO is weighed3)2·6H2O、7.4kg Zn(NO3)2·6H2O and 3.9kg Al (NO3)3· 9H2O, which is dissolved in 60L ionized water, is made into mixing salt solution.
Step b: it weighs 15kgNaOH and is dissolved in 180L deionized water and be made into aqueous slkali.
Step c: weighing 15kg 2,8- di-tert-butyl-4-methy phenol and 100L deionized water is added in 20kg odium stearate.
Step d: solution prepared by step a and step c mixes, the alkali for preparing step b under nitrogen protection and stirring Solution is added drop-wise in the mixed solution of a and c, is added dropwise in 30min, and pH=9 is controlled, then anti-under room temperature and nitrogen protection It should be filtered through 6 for 24 hours and wash cycle is handled, last mother liquor pH value is in neutrality, and filter cake is dried in vacuo for 24 hours, and it is multiple that LDH is made Close antioxidative stabilizer.
Step e: by 0.8g γ-glycidyl ether oxygen propyl trimethoxy silicane, 15kg base oil 150SN mineral oil, 20kg inorganic filler LDH compound anti-oxidation stabilizer and 9kg thickener polyisobutene are mixed in reaction kettle, and 100 DEG C of reactions 3 are small When, until thickener is completely dissolved；
Step f: and then 5kg sodium bentonite, 1kg preservative and 5kg lubricating oil are sequentially added, constant temperature stirs equal to mixing It is even, it is eventually adding 20kg composite fibre, paste tail seal grease of shield is made after continuing stirring 4 hours in heat preservation.
Embodiment 3
Step a: 6.4kg Mg (NO is weighed3)2·6H2O、7.4kg Zn(NO3)2·6H2O and 3.9kg Al (NO3)3· 9H2O, which is dissolved in 60L ionized water, is made into mixing salt solution.
Step b: it weighs 15kgNaOH and is dissolved in 180L deionized water and be made into aqueous slkali.
Step c: weighing 15kg 2,8- di-tert-butyl-4-methy phenol and 100L deionized water is added in 20kg odium stearate.
Step d: solution prepared by step a and step c mixes, the alkali for preparing step b under nitrogen protection and stirring Solution is added drop-wise in the mixed solution of a and c, is added dropwise in 30min, and pH=9 is controlled, then anti-under room temperature and nitrogen protection It should be filtered through 6 for 24 hours and wash cycle is handled, last mother liquor pH value is in neutrality, and filter cake is dried in vacuo for 24 hours, and it is multiple that LDH is made Close antioxidative stabilizer.
Step e: by 0.5g γ-(methacryloxypropyl) propyl trimethoxy silicane, 17kg base oil epoxidized soybean oil, 22kg inorganic filler LDH compound anti-oxidation stabilizer and 10kg thickener polyisobutene are mixed in reaction kettle, 100 DEG C of reactions 3 Hour, until thickener is completely dissolved；
Step f: and then sequentially add 6kg calcium-base bentonite, 1kg preservative benzimidazole and 5kg lubricating oil lithium base lubrication Rouge, constant temperature are stirred to being uniformly mixed, are eventually adding 20kg composite fibre (cotton fiber and polyester fiber are compound), and heat preservation continues to stir White paste tail seal grease of shield is made after 4 hours.
Embodiment 4
Step a: 6.4kg Mg (NO is weighed3)2·6H2O and 7.4kg Al (NO3)3·9H2O, which is dissolved in 60L ionized water, to be made into Mixing salt solution.
Step b: it weighs 15kgNaOH and is dissolved in 180L deionized water and be made into aqueous slkali.
Step c: weigh 15kg 2,8- di-tert-butyl-4-methy phenol and 20kg2- Sodium Ethylhexanoate be added 100L go from Sub- water.
Step d: solution prepared by step a and step c mixes, the alkali for preparing step b under nitrogen protection and stirring Solution is added drop-wise in the mixed solution of a and c, is added dropwise in 30min, and pH=9 is controlled, then anti-under room temperature and nitrogen protection It should be filtered through 6 for 24 hours and wash cycle is handled, last mother liquor pH value is in neutrality, and filter cake is dried in vacuo for 24 hours, and it is multiple that LDH is made Close antioxidative stabilizer.
Step e: 0.6g gamma-aminopropyl-triethoxy-silane, 17kg base oil isooctanol modified colza, 22kg is inorganic Filler LDH compound anti-oxidation stabilizer and 10kg thickener polyisobutene are mixed in reaction kettle, and 100 DEG C are reacted 3 hours, until Thickener is completely dissolved；
Step f: and then sequentially add 6kg organobentonite, 1kg preservative benzimidazole and 5kg lubricating oil lithium base lubrication Rouge, constant temperature are stirred to being uniformly mixed, are eventually adding 20kg composite fibre (cotton fiber and polyester fiber are compound), and heat preservation continues to stir White paste tail seal grease of shield is made after 4 hours.
Table 2 is the performance test results of 2-4 of the embodiment of the present invention.
Project Testing standard Embodiment 2 Embodiment 3 Embodiment 4
Pumping (25 DEG C, 1MPa, g/min) ASTM D1092 42 40 45
Leakproofness (25 DEG C, 3.5MPa) resistant to pressure Malsumara It is water-tight It is water-tight It is water-tight
Water rushes vector (0.28MPa, 5min ,/%) ASTM D4049 0 0 0
Metal protection (copper sheet, 100 DEG C, for 24 hours) ASTM D4048 It is corrosion-free It is corrosion-free It is corrosion-free
The technical principle of the invention is described above in combination with a specific embodiment, is only the preferred embodiment of the present invention.This The protection scope of invention is not limited merely to above-described embodiment, and all technical solutions belonged under thinking of the present invention belong to the present invention Protection scope.Those skilled in the art, which does not need to pay for creative labor, can associate other specific realities of the invention Mode is applied, these modes will fall within the scope of protection of the present invention.

Claims (10)

1. a kind of stable type tail seal grease of shield, which is characterized in that formed by the material combination of following weight: base oil 10~20 parts, 7~15 parts of thickener, 0.2~2 part of preservative, 15~30 parts of inorganic filler, 2~5 parts of bentonite, composite fibre 5 ~25 parts and 2~7 parts of lubricant.
2. a kind of stable type tail seal grease of shield according to claim 1, which is characterized in that the base oil is machinery One of hydraulic oil, isooctanol modified colza, isooctanol modified soybean oil, epoxidized soybean oil or mineral oil are a variety of.
3. a kind of stable type tail seal grease of shield according to claim 1, which is characterized in that the thickener is rosin It is one or more in resin, polyacrylamide, polymethacrylates, polyisobutene or C5 resin.
4. a kind of stable type tail seal grease of shield according to claim 1, which is characterized in that the preservative is benzo One of imidazoles, organic sulfur or organic ammonium are a variety of.
5. a kind of stable type tail seal grease of shield according to claim 1, which is characterized in that the inorganic filler is carbon It is one or more in sour calcium, lime stone, barium sulfate, mica powder or hydrotalcite powder, it is LDH by being inserted into different function objects Composite flame-retardant agent, LDH compound anti-oxidation stabilizer, LDH composite thermal stabilizer are one or more.
6. a kind of stable type tail seal grease of shield according to claim 1, which is characterized in that the bentonite is sodium base One of bentonite, calcium-base bentonite, potassium base bentonite or organobentonite are a variety of.
7. a kind of stable type tail seal grease of shield according to claim 1, which is characterized in that the composite fibre is raw The compound of fibres and polymer fiber, composite fibre have reticular structure, can reduce and wear away to grease pump；Biological fiber For one of wood fibre, cotton fiber, flax fiber or a variety of；Polymer fiber is poly- third fiber, polyester fiber and polypropylene fibre It is one or more in fiber.
8. a kind of stable type tail seal grease of shield according to claim 1, which is characterized in that the silicone coupling agents For γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, γ-(methacryloxypropyl) propyl It is one or more in trimethoxy silane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, preferred γ-glycidol ether Oxygen propyl trimethoxy silicane.
9. a kind of stable type tail seal grease of shield according to claim 1, which is characterized in that the lubricant is lithium base It is one or more in lubricating grease, calcium-base grease, mixed base grease, urea-base grease or aluminum-base composite lubricating grease.
10. a kind of method for preparing stable type tail seal grease of shield, which is characterized in that specific preparation process is as follows: step A: adopting LDH compound anti-oxidation stabilizer is prepared with coprecipitation；M will be contained2+、M3+Nitrate be configured to mixing salt solution, M2+For divalent Metal ions M g2+、Zn2+、Ni2+、Ca2+、Fe2+Or Cu2+In any one or two kinds；M3+For trivalent metal ion Al3+、Co3 +、Ti3+、Fe3+Or Cr3+In any one or two kinds；
Step B: the aqueous slkali that molar concentration is 0.05-2mol/L is prepared, aqueous slkali is NaOH, KOH or ammonia spirit；
Step C: antioxidant activity component AO and thermostabilization component MO are configured to certain density mixed solution, the object of AO and MO The amount of matter is M3+0.5-10 times of the amount of substance；
Step D: the mixing salt solution that step B preparation aqueous slkali is added drop-wise in step A, the preparation in step C mixed solution In, it stirs 2-10 hours under nitrogen protection, it is 7-8, filter that reaction product centrifuge separation and wash cycle, which are washed to mother liquor pH value, Cake is dried in vacuo 12-24 hours, obtains the compound antioxidant stabilizer of supramolecular structure LDH；
Step E: silicone coupling agents, base oil, inorganic filler and thickener are mixed in reaction by corresponding weight In kettle, 100 DEG C are reacted 2~4 hours, until thickener is completely dissolved；
Step F: and then sequentially add bentonite, preservative and lubricant by corresponding weight, constant temperature (25-50 DEG C) Stirring is eventually adding composite fibre to being uniformly mixed, and heat preservation continues stirring 2~4 hours, obtains paste tail seal grease of shield；
Antioxidant activity component AO for intercalation is organic acid or its sodium salt containing hindered phenol group or phosphite group； Thermostabilization active component for intercalation is metal mixture, 2 ethyl hexanoic acid salt, stearate, phenyl hydrochlorate, phenates.
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CN113563949A (en) * 2021-06-25 2021-10-29 中铁第五勘察设计院集团有限公司 Flame-retardant hand-coating type shield tail sealing grease and preparation method thereof

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