CN1206332C

CN1206332C - Biodegradable lubricating grease

Info

Publication number: CN1206332C
Application number: CN 02153367
Authority: CN
Inventors: 姚智勤; 杨玮; 孙洪伟
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2002-11-29
Filing date: 2002-11-29
Publication date: 2005-06-15
Anticipated expiration: 2022-11-29
Also published as: CN1504552A

Abstract

The present invention relates to biodegradable lubricating grease which comprises (the total weight of a composition is used as a reference) 70 to 94% of vegetable oil with the dynamic viscosity of 100 to 250mm <2> /sec at the temperature of 40DEG C, 6 to 30% of thickener which is bentonite, or monomeric soap or complex soap generated by the reaction of organic acid of C1 to C20 and calcium hydroxide, calcium oxide, lithium hydroxide or lithium oxide and 0 to 2% of amine anti-oxidant or mixed anti-oxidant of phenol and amine. The lubricating grease has good conventional physical and chemical performance and good ecological characteristics. Even if the biodegradable lubricating grease is leaked in use, the biodegradable lubricating grease can also be naturally degraded into water and carbon dioxide as time flows away, and the biodegradable lubricating grease conforms to environmental protection requirement. The lubricating grease provided by the present invention is suitable for lubricating positions which are suitable for being lubricated by the ordinary lubricating grease.

Description

A kind of biodegradable lubricating grease

Technical field

The invention belongs to industrial lubricants, exactly, is a kind of grease composition.

Technical background

Industrial lubricants causes the pollution to soil, water and air easily owing to reasons such as permeating, leak, overflow and deal with improperly, destroys the ecotope and the eubiosis, has become very important realistic problem.According to the material report, general mineral generation can reach 100 years to phreatic influence.The lubricant of trace not only hinders the growth of plant, also can poison aquatic organism, and about 0.1 μ g/g Dormant oils can make aquatic shell class biology subtract the longevity 20%.Germany classifies the lubricant that contains additive to the deleterious material of water as, does not contain the also classified objectionable impurities that is as the criterion of lubricant of additive.Everything makes traditional industrial lubricants be faced with extremely stern challenge.

Europe, the United States, day etc., state carried out the research of environmentally friendly lubricant, some famous producers have developed the lubricant with biodegradation character successively, general main is base oil with vegetables oil, Dormant oils and synthetic ester, with lithium soap, calcium soap, compound lithium soap, wilkinite etc. is viscosifying agent, with amine, aldehydes matter is additive, makes the lubricating grease that can adapt to various power lubrication needs.

For example, CN 1120577 discloses a kind of special lubricating grease for automotive hydraulic brake leather cup, is by 12-oxystearic acid 10%, stearic acid 1%, and lithium hydroxide 4%, refined caster oil 85% and pentanoic are formulated.What the grease making process of this lubricating grease adopted is direct saponification method.US 5595965 discloses a kind of biodegradable vegetables oil lubricating grease, and its base oil is the triglyceride level in the vegetables oil, and thickening material is the reaction product of basic metal or alkaline-earth metal and carboxylic acid or carboxylicesters.JP 8020788A2 discloses a kind of biodegradable grease composition, and its base oil is a rapeseed oil, and the dynamic viscosity in the time of 40 ℃ is 25-80mm ²/ sec contains polymethyl acrylate thickening material, rust-preventive agent, extreme pressure agent etc. in addition.

Summary of the invention

The objective of the invention is on the basis of existing technology, a kind of lubricating grease with biodegradability is provided.

Biodegradable lubricating grease provided by the invention is benchmark with the composition gross weight, and its composition comprises:

(A) 70-94%, the vegetables oil of preferred 75-90%, 40 ℃ dynamic viscosity is 100～250mm ²/ sec;

(B) 6-30%, the viscosifying agent of preferred 10-25%, said viscosifying agent is a wilkinite, or C ₁-C ₂₀Organic acid and the reaction of calcium hydroxide (calcium oxide) or lithium hydroxide (Lithium Oxide 98min) the single soap or the compound soap that generate;

(C) 0-2%, amine antioxidants or the phenols and amine mixing oxidation inhibitor of preferred 0.5-1.0%.

The mixing oil of the preferred Viscotrol C of said vegetables oil or Viscotrol C and rapeseed oil, the blending ratio of the two are 1: 0-1.2, preferred 1: 0-1.

Said C ₁-C ₂₀Organic acid is selected from formic acid, acetate, propionic acid, phenylformic acid, diprotic acid, n-caprylic acid, boric acid, ten dihydroxystearic acids, stearic acid etc.

Said amine antioxidants can be di-iso-octyldiphenylamine, dioctyl diphenylamine or with the pentanoic of other alkyl, phenolic antioxidant can be 2,6 toluene di-tert-butyl phenols, 2,6 di-tert-butylphenols etc.The blending ratio of amine and phenolic antioxidant is 1: 0-2, preferred 1: 0.5-1.5.

Lubricating grease provided by the invention can prepare in accordance with the following methods:

1) single soap or the compound soap with calcium or lithium is viscosifying agent: with vegetables oil and calcium hydroxide (calcium oxide) or lithium hydroxide (Lithium Oxide 98min), water and C ₁-C ₂₀Organic acid mixes, and is warming up to 210-220 ℃, adds quenching oil, and cooling is ground, and gets final product.

Concrete steps are: at first the vegetables oil of 40-60% and calcium hydroxide (or calcium oxide) or lithium hydroxide (Lithium Oxide 98min) and water are mixed in system fat still at normal temperatures, add C then respectively ₁-C ₂₀Organic acid can be one or more acid, whenever add a kind of acid after, preferably reaction earlier adds another kind of acid after about 5-15 minute again, after whole acid all adds, is warming up to 210-220 ℃, adds the surplus vegetables oil, adds oxidation inhibitor as required, cooling is ground.

Usually preparation anhydrous calcium base grease multiselect is with ten dihydroxystearic acids or stearic acid.Compound calcium or complex lithium viscosifying agent are selected two kinds or two or more acid for use, generally select a kind of low molecular acid and a kind of polymer acid at least for use, select a kind of middle molecule acid (perhaps boric acid) in case of necessity again for use, it is generally acknowledged that the following acid of C6 is low molecular acid, the acid of C6-C12 is middle molecule acid, the above acid of C12 is polymer acid, and wherein the mol ratio of polymer acid, middle molecule acid and low molecular acid is 1: 0.1-1: be advisable in the 1-8 scope.

2) with the wilkinite viscosifying agent: the 40%-60% base oil is mixed with wilkinite, be heated to about 40-50 ℃, add a little acetone, add residue base oil (containing additive) while stirring, be cooled to room temperature, grind evenly.

The existing good conventional physicochemical property of biodegradable lubricating grease provided by the invention, the incomparable ecological characteristics of common lubricating grease is arranged again, even in use leak, can natural degradation be water and carbonic acid gas also as time goes by, for example, in 21 days, degradation rate can reach more than 80%, therefore do not pollute the environment and destroy the eubiosis, compliance with environmental protection requirements.

Embodiment

Embodiment 1

Form:

Viscotrol C: 75Wt%

Compound calcium viscosifying agent: 25Wt%

In the viscosifying agent: organic acid: calcium hydroxide=2: 1;

12-oxystearic acid: n-caprylic acid: Glacial acetic acid=1: 0.5: 5

Preparation:

Dissolve attitude calcium hydroxide with adding in 1/2 base oil, to add Glacial acetic acid under the room temperature, to be heated to about 50 ℃ and to add n-caprylic acid, add the 12-oxystearic acid near 80 ℃, to be warmed up to 210 ℃ after metalling run out and to add remaining 1/2 base oil, grind three times the cooling back.

Embodiment 2:

Form:

Viscotrol C: 79.5Wt%

Compound calcium viscosifying agent: 20Wt%

(SIBA's alkylated diphenylamine refines, L-57): 0.5wt%

In the viscosifying agent: 12-oxystearic acid: n-caprylic acid: Glacial acetic acid=1: 0.29: 5;

Organic acid: calcium hydroxide=2: 1.

Preparation:, just when cooling, add oxidation inhibitor with embodiment 1.

Embodiment 3:

Form

Viscotrol C: 89Wt%

Anhydrous calcium viscosifying agent: 11Wt%

In the viscosifying agent: the 12-oxystearic acid: calcium hydroxide=2: 1, calcium hydroxide excessive 5%

Preparation:

12-oxystearic acid and base oil are mixed, be warming up to 80-85 ℃, the molten back of acid adds calcium hydroxide alkali lye, and saponification finishes and is warming up to 135 ℃, and cooling is ground three times.

Embodiment 4:

Form:

Mixing oil (rapeseed oil: Viscotrol C=1: 1): 87.5Wt%

Anhydrous calcium viscosifying agent: 12Wt%

(SIBA's alkylated diphenylamine refines, L-57): 0.5wt%

Preparation:, just when cooling, add oxidation inhibitor with embodiment 3.

Embodiment 5:

Form:

Mixing oil (rapeseed oil: Viscotrol C=4: 6): 87Wt%

Complex lithium viscosifying agent: 12Wt%

(SIBA's alkylated diphenylamine refines, L-57): 0.5wt%

2,6 toluene di-tert-butyl phenols (T501): 0.5wt%

In the viscosifying agent: the 12-oxystearic acid: sebacic acid=3: 1

Organic acid: lithium hydroxide=1: 1, lithium hydroxide excessive 5%

Preparation:

2/3 oil is mixed with 12-oxystearic acid and sebacic acid, and it is molten entirely to be heated to acid, and temperature rises to more than 90 ℃, slowly add lithium hydroxide alkali lye about 95 ℃, saponification is metalled run out, and is warmed up to 205 ℃, add 1/3 quenching oil (containing additive), stir, be cooled to grinding at room temperature three times.

Embodiment 6:

Form:

Mixing oil (rapeseed oil: Viscotrol C=4: 6): 88.5Wt%

Complex lithium viscosifying agent: 11Wt%

(SIBA's alkylated diphenylamine refines, L-57): 0.5wt%

In the viscosifying agent: the 12-hydroxystearic acid: sebacic acid=3: 1

Organic acid: lithium hydroxide=1: 1, lithium hydroxide excessive 5%

Preparation: with embodiment 5.

Embodiment 7

Form

Mixing oil (rapeseed oil: Viscotrol C=4: 6): 79Wt%

Wilkinite: 20Wt%

(SIBA's alkylated diphenylamine refines, L-57): 1wt%

Preparation:

1/3 base oil is mixed with wilkinite, be heated to about 40-50 ℃, add a little acetone, add residue 2/3 oil (containing additive) while stirring, be cooled to room temperature, grind three times.

Embodiment 8:

Form

Mixing oil (rapeseed oil: Viscotrol C=2: 8): 84Wt%

Wilkinite: 15Wt%

(SIBA's alkylated diphenylamine refines, L-57): 1wt%

Preparation: with embodiment 7.

The PERFORMANCE OF GREASES of table 1 embodiment 1-4

The PERFORMANCE OF GREASES of table 2 embodiment 5-8

^*Weighting method:

Present method is with reference to CEC L-33-A-82 method, by selecting for use active sludge in the sewage work as thalline, determine that concentration of substrate is 1%, in the mineral salt nutrient solution of 150ml, add the inoculation bacterium of 2ml and the lubricating grease of about 1g, cultivated 21 days down at 25 ℃, characterize the biological degradability of lubricating grease with the consumption of lubricating grease in biodegradation process.Wherein mineral salt solution consists of:

KH ₂PO ₄ 0.6g/l Na ₂HPO ₄?2.0g/l MgSO ₄ 0.1g/l

(NH ₄) ₂SO ₄?0.4g/l NH ₄NO ₃ 0.3g/l CaCl ₂ 0.1g/l

Trace element 0.005g/l

Claims

1. a biodegradable lubricating grease is benchmark with the composition gross weight, comprising:

(A) vegetables oil of 70-94%, 40 ℃ dynamic viscosity are 100～250mm ²/ sec;

(B) viscosifying agent of 6-30%, said viscosifying agent are wilkinite, or C ₁-C ₂₀Organic acid and calcium hydroxide, calcium oxide, lithium hydroxide or Lithium Oxide 98min the reaction single soap or the compound soap that generate;

(C) amine antioxidants of 0-2% or blending ratio are 1: 0-1: 2 amine and phenolic antioxidant.

2. according to the described lubricating grease of claim 1, it is characterized in that content of vegetable oil is 75～90%.

3. according to the described lubricating grease of claim 1, it is characterized in that said vegetables oil is selected from the mixing oil of Viscotrol C or Viscotrol C and rapeseed oil, the blending ratio of the two is 1: 0-1: 1.2.

4. according to the described lubricating grease of claim 1, it is characterized in that viscosifying agent content is 10-25%.

5. according to the described lubricating grease of claim 1, it is characterized in that said C ₁-C ₂₀Organic acid is selected from formic acid, acetate, propionic acid, phenylformic acid, diprotic acid, n-caprylic acid, boric acid, ten dihydroxystearic acids and stearic acid.

6. according to the described lubricating grease of claim 1, it is characterized in that antioxidant content is 0.5-1.0%.

7. according to the described lubricating grease of claim 1, it is characterized in that said amine antioxidants is a dialkyl diphenylamine, phenolic antioxidant is 2,6 toluene di-tert-butyl phenols or 2,6 di-tert-butylphenols.

8. according to the described lubricating grease of claim 1, it is characterized in that the lubricating grease that is viscosifying agent with the single soap or the compound soap of calcium or lithium prepares in accordance with the following methods: with vegetables oil and calcium hydroxide, calcium oxide, lithium hydroxide or Lithium Oxide 98min and water and C ₁-C ₂₀Organic acid mixes, and is warming up to 210-220 ℃, adds quenching oil, adds oxidation inhibitor as required, cooling, grinding.

9. according to the described lubricating grease of claim 1, it is characterized in that, is that the lubricating grease of viscosifying agent prepares in accordance with the following methods with the wilkinite: vegetables oil is mixed with wilkinite, be heated to 40-50 ℃, add acetone and residue vegetables oil, add oxidation inhibitor as required, cooling, grinding.