CN1041324C - Double-component efficient anti-bubbling agent and its application - Google Patents

Double-component efficient anti-bubbling agent and its application Download PDF

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CN1041324C
CN1041324C CN 91101663 CN91101663A CN1041324C CN 1041324 C CN1041324 C CN 1041324C CN 91101663 CN91101663 CN 91101663 CN 91101663 A CN91101663 A CN 91101663A CN 1041324 C CN1041324 C CN 1041324C
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oil
formula
acrylate copolymer
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kilfoam
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CN1064884A (en
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王开毓
潘丽君
周嘉祥
魏依君
竺关妹
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REFINERY OF GAOQIAO PETROCHEMIAL CORP SHANGHAI
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REFINERY OF GAOQIAO PETROCHEMIAL CORP SHANGHAI
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Abstract

The present invention is characterized in that the two components of a dimethylsiloxane polymer and an acrylate copolymer are used in the same lubricating oil product; the compounding of the application performance of the two substances enhances the quality of the lubricating oil products, such as internal combustion engine oil, gear oil, hydraulic oil steam turbine oil, etc., and improves the disadvantages of poor foaming resistance or poor air release performance at the time of the single use of the dimethylsiloxane polymer or the acrylate copolymer.

Description

Two component efficient anti-bubbling agents and application thereof
The present invention relates to efficient anti-bubbling agent and application method thereof, specifically, the present invention relates to two component kilfoams, and it is used for the method for oil product dimethylsiloxane polymer (abbreviation silicone oil) and the compound composition of a kind of acrylate copolymer (being called for short last 902); And dimethylsiloxane polymer and a kind of acrylate copolymer solution added respectively in the oil product, as efficient anti-bubbling agent.The complex effect of the application performance by above-mentioned two kinds of kilfoams is to improve I. C. engine oil, gear oil, hydraulic efficiency oil and steam turbine wet goods lubricating oil product quality and to improve when using silicone oil or acrylate copolymer separately anti-bubble property difference or the shortcoming of gas release performance difference.
In order to reduce or eliminate the foaminess of lubricating oil, generally used following three class methods both at home and abroad:
1. use efficient anti-bubbling agent silicone oil and anti-bubble ability and anti-bubble persistence for improving silicone oil, adopted various dispersion addition method, promptly adopt means machinery or solvent cut, equably be scattered in oil product with nano sized particles (particle diameter<10 μ) silicone oil; Add in the lubricating oil again after perhaps silicone oil being made emulsion with various dispersion agents.
2. with silicone oil and the compound use of low molecular polarity compound (as alcohol, amine, aldehyde, acid etc.), as at U.S. Patent number 2,972,579 and 3,235,498 are disclosed.
3. the development structure is different from acrylate or the methacrylate polymers or the multipolymer of the efficient anti-bubble property of having of silicone oil, and as at U.S. Patent number 3,166,508 are disclosed.
But above the whole bag of tricks is not that the foaming problem of all lubricating oil or gas release performance problem can both finely be solved.For example I. C. engine oil, gear of vehicle wet goods oil product, gene basis oil source variations sometimes, production technique adjustment, operational condition fluctuation and cause the trace change of oil base stock composition; Or changed the surface property of oil product because of the use of multiple additives, so that cause the variation of oil product lathering property, make the existing dimethyl silicone oil kilfoam of independent employing or adopt the polyacrylate kilfoam separately, all be difficult to make the anti-bubble performance of lubricating oil product to get a desired effect.
Other oil products, as hydraulic efficiency oil, turbine oil and lathe wet goods oil product, sometimes the refining depth of gene basis oil is not enough, or because of the adding of some additive, make these oil products when using the non-silicon kilfoam of acrylate type separately or using silicone oil type kilfoam separately, the air release property of lubricating oil product and anti-bubble property are difficult to get a desired effect simultaneously.
Anti-bubble problem or air release property problem when above-mentioned situation occurring in order to solve oil product the invention provides a kind of pair of component efficient anti-bubbling agent, comprise have formula (I) dimethylsiloxane polymer (1) and have the acrylate copolymer (2) of formula (II):
Figure C9110166300051
This polymkeric substance is in the time of 25 ℃, and kinematic viscosity is 100-100000mm 2/ s is preferably 500-20000mm 2/ s,
Figure C9110166300052
In the formula, R 1=C 1-C 6Alkyl, R 2=C 6-C 18Alkyl,
R=C 2-C 10Alkyl,
X, y, z are 〉=0 positive integer, and x, y, z can not be 0 simultaneously.
The number-average molecular weight of this multipolymer is 2000-50000, is preferably 7000-15000.Weight with lubricating oil in the described efficient anti-bubbling agent is benchmark, the amount ranges of the acrylate copolymer of the dimethylsiloxane polymer of formula (I) and formula (II) is respectively: dimethylsiloxane polymer: 0.1-150ppm, acrylate copolymer: 2-500ppm.
When described kilfoam is used, after the acrylate copolymer of the dimethylsiloxane polymer of formula (I) and formula (II) can being mixed, become composite anti-foam agent to add in the oil product again with solvent cut.Also can be with the acrylate copolymer of the dimethylsiloxane polymer of formula (I) and formula (II) respectively with adding in the oil product behind the solvent cut.
Described solvent is other solvent that No. 200 solvent oils or aviation kerosene maybe can dissolve above-mentioned two kinds of kilfoams.
When mixing the back application, the concentration of described composite anti-foam agent is 20-1%, is preferably 10-2%; When two kinds of components are diluted the back application respectively, the concentration of the dimethylsiloxane polymer of formula (I) after with solvent cut is 20-1% (weight), be preferably 10-2% (weight), the concentration of the acrylate copolymer of formula (II) after with solvent cut is 50-2% (weight), is preferably 20-10% (weight).
The application method of described efficient anti-bubbling agent is characterized in that (1) and (2) is made an addition to lubricating oil product simultaneously, comprises I. C. engine oil, gear oil, hydraulic efficiency oil and steam turbine oils.In the above-mentioned application method, the solution that will use solvent cut respectively with composite anti-foam agent (3) or (1) and (2) of solvent cut makes an addition in the lubricating oil product with certain proportion.Perhaps using the concentration of the composite anti-foam agent (3) of solvent cut is 20-1%, is preferably 10-2%; And (1) and (2) be respectively 20-1% with the concentration of the solution of solvent cut respectively, is preferably 10-2% and 50-2%, is preferably the solution of 20-10%.And the solvent that it is characterized in that being used to diluting composite anti-foam agent (3) and (1) and (2) is No. 200 solvent oils or aviation kerosene or other solvent.Further, the solution that it is characterized in that making an addition to (3) or (1) and (2) in the lubricating oil product makes the concentration of in lubricating oil product (1) and (2) reach 0.05-200ppm and 1-500ppm respectively.Again further, it is characterized in that making an addition to (3) or (1) and the solution of (2) in the lubricating oil product, make the concentration of (1) and (2) in the lubricating oil product reach 0.1-30ppm and 3-25ppm respectively.
The Application of composite of above-mentioned kilfoam has following two kinds of methods.
1 method: be made into recombiner and be used for oil product.
Earlier silicone oil kilfoam (1) and acrylate copolymer kilfoam (2) are mixed into two component composite anti-foam agents by usage quantity, use solvent (200# solvent oil, aviation kerosene etc.) dilution again, be made into composite anti-foam agent solution (3), making the concentration of composite anti-foam agent in (3) is 20-1% (preferably 10-2%).During preparation, kilfoam and solvent is under 20 ℃ of-50 ℃ of temperature, even with machinery or hand mixing, and fully dissolving promptly makes (3), during use, (3) of requirement is directly added in the lubricating oil, and stirring gets final product.
2 methods: add in the oil product respectively
Earlier use solvent (200# solvent oil or aviation kerosene etc.) to be mixed with kilfoam solution separately respectively silicone oil kilfoam and acrylate copolymer kilfoam, wherein the concentration of silicone oil kilfoam solution can be 20-1% (preferably 10-2%), and the concentration of acrylate copolymer kilfoam solution can be 50-2% (preferably 20-10%).During two kinds of kilfoam solution preparations, evenly get final product with machinery or hand mixing down at 20 ℃-50 ℃ respectively.Can these two kinds of kilfoam solution be added respectively in the same lubricating oil product by requirement separately during use.
Below, with the present invention is described in further detail with application examples in conjunction with specific embodiments, so that advantage of the present invention is more obvious.
Embodiment 1.
To have the silicone oil (1) of (I) formula and acrylate copolymer with (II) formula
Figure C9110166300071
This polymkeric substance is in the time of 25 ℃, and kinematic viscosity is 100-100000mm 2/ s is preferably 500-20000mm 2/ s and
Figure C9110166300072
In the formula, R 1=C 1-C 6Alkyl, R 2=C 6-C 18Alkyl,
R=C 2-C 10
X, y, z are 〉=0 positive integer, and x, y, z can not be 0 simultaneously.
The number-average molecular weight of this multipolymer is 2000-50000, be preferably 7000-15000, in the reactor that has stirring and chuck, above-mentioned silicone oil (1) is become two component composite anti-foam agents (3) with acrylate copolymer (2) by required mixed, 20 ℃ of-50 ℃ of temperature and under stirring, be diluted to (3) of 20-1% (being preferably 10-2%) concentration with solvent (for example: No. 200 solvent oils or aviation kerosene) to this composite anti-foam agent (3), during use, (3) of requirement are directly added in the lubricating oil.
Embodiment 2.
In the reactor that has chuck with machinery or hand mixing, respectively with the acrylate copolymer (2) of the silicone oil kilfoam (1) of said structure formula (I) and said structure formula (II) at 20 ℃-50 ℃ solution that are mixed with the acrylate copolymer (2) of silicone oil kilfoam (1) solution of 20-1% (being preferably 10-2%) concentration and 50-2% (being preferably 20-10%) concentration down with solvent (for example: No. 200 solvent oils or aviation kerosene).During use, can measure on demand above-mentioned two kinds of kilfoam solution are added respectively in the same lubricating oil.
Above-mentioned (3) or (1) and the solution of (2) that makes an addition in the lubricating oil product makes the concentration of (1) and (2) in the lubricating oil reach 0.05-200ppm respectively, preferably is 0.1-30ppm and 1-500ppm, preferably is 3-100ppm.
Below be the correlated actual effect of kilfoam Application of composite of the present invention:
1. the application test in CC level diesel engine oil
Composite anti-foam agent is that result of use in the 40-CC level diesel engine oil of base oil is listed in table-1 at the neutral oil with Daqing crude oil production:
Showing-1 pair of component kilfoam Application of composite effect in the 40-CC diesel engine oil compares
The main additive that contains in the oil product Kilfoam add-on ppm Anti-bubble property ml/ml Remarks
(1) (2) 24℃ 93℃ 24℃
Oxidation and corrosion inhibitor detergent-dispersant additive (the single agent of ECA11288-Exxon Co produces) etc. - - 25/0 360/140
30 - 40/0
20 30 15/0 15/0 10/0 2. method adds
20 30 15/0 10/0 10/0 1. method adds
ECA11218 recombiner-Exxon Co produces - - 60/0
20 - 45/0
- 40 30/0
20 20 25/0 10/0 20/0 2. method adds
20 30 15/0 10/0 15/0 2. method adds
Oxidation and corrosion inhibitor detergent-dispersant additive (T 106-homemade) 30 - 30/0 5/0 5/0
- 30 30/0 10/0 5/0
15 25 20/0 5/0 5/0 2. method adds
15 25 15/0 10/0 10/0 1. method adds
Annotate: anti-bubble character figureofmerit is: 24 ℃ ≯ 25ml/0ml.93 ℃ ≯ 150/0.
See from table-1, when modulation CC level diesel engine oil, when ECA11288 detergent-dispersant additive that uses import or ECA11218 recombiner, the preceding 24 ℃ of anti-bubble property of oil product are defective when using (1) silicone oil or acrylate copolymer kilfoam (2) separately, after two kinds of compound uses of kilfoam, then can reach the quality index of regulation.
2. the application test in gear oil
The effect of two kinds of compound uses of kilfoam in the GL-5 automotive gear oil sees Table 2.
Show the Application of composite effect of-2 pairs of component kilfoams in automotive gear oil
The oil name Base oil Include main additive (1) ppm (2) ppm Anti-bubble property ml/ml
24℃ 93℃ 24℃
The GL-5 automotive gear oil Neutral oil, bright stock with Daqing crude oil production Oxidation inhibitor, rust-preventive agent, extreme pressure anti-wear additives etc. 60 - 65/0
- 150 40/25
100 20 15/0 25/0 12/0
The GL-5 automotive gear oil The neutral oil that grand celebration stock oil is produced Oxidation inhibitor, rust-preventive agent, extreme pressure anti-wear additives etc. 20 - >20/0 >50/0 >20/0
20 250 <20/0 <50/0 <20/0
Annotate: the qualified index of the anti-bubble of GL-5 is: 24 ℃ ≯ 20/0,93 ℃ ≯ 50/0.
From table-2 as can be known, in the gear oil GL-5 of high-end vehicle, if add silicone oil (1) or acrylate copolymer kilfoam (2) separately, when the anti-bubble property of oil product is defective, then two kinds of kilfoams are used for oil product simultaneously, the anti-bubble of oil product performance just can reach the quality index of regulation.
3. the effect in hydraulic efficiency oil.
In the hydraulic efficiency oil prescription, contain T 705During rust-preventive agent, use 902 kilfoams (2) on the non-silicon separately, the oil product gas release performance is qualified, but anti-bubble property is bad; Use silicone oil kilfoam (1) separately, anti-bubble property is good, but the venting value difference if add the silicone oil of minute quantity in non-silicon kilfoam, then can make anti-bubble property and gas release performance all can reach criterion of acceptability, sees Table-3.
Show the Application of composite effect of-3 pairs of component kilfoams in hydraulic efficiency oil
The oil name Base oil Include main additive (1) ppm (2) ppm The venting value (minute) Anti-bubble property ml/ml
24℃ 93℃ 24℃
HL-N 32Lathe hydraulic efficiency oil The neutral oil of grand celebration raw material production Oxidation inhibitor, rust-preventive agent (T 705) etc. 5 - 7′25″ 5/0 10/0 5/0
- 10 4′33″ 120/0 250/0 150/0
0.5 9.5 4′30″ 5/0 10/0 0/0
Annotate: HL-N 32Qualified index is:
Venting value ≯ 7 ' 00 "
24 ℃ 93 ℃ ≯ 100/0 of anti-bubble property
At the high viscosity lathe with the effect in the oil.
Because the high viscosity oil product is responsive especially to the silicone oil kilfoam, even very little consumption, disadvantageous effect to the oil product gas release performance is also very remarkable, at this moment adopt the silicone oil (1) and acrylate copolymer (2) Application of composite of trace, then the gas release performance of oil product and anti-bubble property all will reach the purpose of remarkable improvement, see Table-4.
The Application of composite effect of table 4. kilfoam in the high viscosity oil product
The oil name Base oil Include main additive (1) ppm (2) ppm The venting value (minute) Anti-bubble property ml/ml
24℃ 93℃ 24℃
HL-N 100Lathe is with oily The neutral oil that grand celebration stock oil is produced Oxidation inhibitor, rust-preventive agent etc. 2 - 18′15″ 5/0 10/0 5/0
- 5 13′01″ 35/0 40/0 50/0
0.1 4.9 13′03″ 0/0 0/0 0/0
Annotate: HL-N 100Qualified index:
Venting value: ≯ 15 ' 00 "
Anti-bubble property: 24 ℃ 93 ℃ ≯ 100/0.
Because silicone oil kilfoam (1) and acrylate copolymer kilfoam (2) differ from one another and advantage, in I. C. engine oil, gear oil and hydraulic pressure wet goods oil manufacture, can be with these two kinds of compound uses of dissimilar kilfoams, to bring into play their outstanding advantages separately, avoid shortcoming separately, improve the anti-bubble property of oil product or improve its purpose to the gas release performance to reach.
As mentioned above, the application method of two component kilfoams can adopt 1 method and 2 methods to make an addition in the oil product, all can reach above-mentioned same effect and purpose.

Claims (6)

1. two component efficient anti-bubbling agent comprises dimethylsiloxane polymer (1) with (I) formula and the acrylate copolymer (2) with (II) formula:
This polymkeric substance is in the time of 25 ℃, and kinematic viscosity is 100-100000mm 2/ s,
Figure C9110166300022
In the formula,
R 1=C 1-C 6Alkyl, R 2=C 6-C 18Alkyl,
R=C 2-C 10Alkyl,
X, y, z are 〉=0 positive integer, and x, y, z can not be 0 simultaneously,
The number-average molecular weight of this multipolymer is 2000-50000, and the weight with lubricating oil in the described efficient anti-bubbling agent is benchmark, and the amount ranges of the acrylate copolymer of the dimethylsiloxane polymer of formula (I) and formula (II) is respectively:
Dimethylsiloxane polymer: 0.1-150ppm
Acrylate copolymer: 2-500ppm.
2. the application of kilfoam as claimed in claim 1 is characterized in that becoming composite anti-foam agent to add in the oil product with solvent cut the dimethylsiloxane polymer of formula (I) and the acrylate copolymer mixing back of formula (II) again.
3. the application of kilfoam as claimed in claim 1 is characterized in that acrylate copolymer with the dimethylsiloxane polymer of formula (I) and formula (II) is respectively with adding in the oil product behind the solvent cut.
4. as claim 2 or 3 described application, it is characterized in that described solvent is No. 200 solvent oils or aviation kerosene.
5. application as claimed in claim 2 is characterized in that the concentration with described composite anti-foam agent solution behind the solvent cut is 20-1% (weight).
6. application as claimed in claim 3, the dimethylsiloxane polymer that it is characterized in that formula (I) concentration after with solvent cut is 20-1% (weight), and the concentration of the acrylate copolymer of formula (II) after with solvent cut is 50-2% (weight).
CN 91101663 1991-03-15 1991-03-15 Double-component efficient anti-bubbling agent and its application Expired - Fee Related CN1041324C (en)

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KR100433332B1 (en) * 1995-07-10 2004-08-12 이데미쓰 고산 가부시키가이샤 Refrigerator oil and lubrication methods using it
CN1064268C (en) * 1996-04-10 2001-04-11 财团法人工业技术研究院 Composition of mixed silicon series defoaming agent
US5766513A (en) * 1996-09-10 1998-06-16 Exxon Research And Engineering Company Antifoaming agents for lubricating oils (law455)
CN102020769B (en) * 2010-11-24 2012-06-06 华东理工大学 Application of silica copolymer
CN104232246B (en) * 2013-06-07 2017-02-01 中国石油化工股份有限公司 Lubricating oil composite type antifoaming agent and application thereof
JP6695759B2 (en) 2015-08-19 2020-05-20 Jxtgエネルギー株式会社 Defoaming agent and lubricating oil composition
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CN105385484A (en) * 2015-10-19 2016-03-09 中国石油化工股份有限公司 Anti-foaming agent composition and application thereof
CN110290848B (en) 2017-02-22 2022-04-22 Jxtg能源株式会社 Defoaming agent and lubricating oil composition
FR3100816B1 (en) * 2019-09-12 2022-02-18 Total Marketing Services DEAERATION OF A LUBRICANT COMPOSITION
CN112646647A (en) * 2019-10-10 2021-04-13 中国石油化工股份有限公司 Anti-foaming composition, preparation method and application thereof
CN113088356A (en) * 2021-03-15 2021-07-09 安徽工程大学 Anti-corrosion petroleum additive containing anti-foaming agent and preparation method and application thereof

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