CN1037356A - Components of anti-icing liquor - Google Patents
Components of anti-icing liquor Download PDFInfo
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- CN1037356A CN1037356A CN 88102325 CN88102325A CN1037356A CN 1037356 A CN1037356 A CN 1037356A CN 88102325 CN88102325 CN 88102325 CN 88102325 A CN88102325 A CN 88102325A CN 1037356 A CN1037356 A CN 1037356A
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- icing
- liquor
- water
- corrosion protection
- rust protection
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Abstract
The invention belongs to cooling system anti-freeze cooling liquid constituent manufacturing technologies such as explosive motor cooling water tank.Replace ethylene glycol as the deicing fluid principal constituent with the glycol ether that accounts for total alcohol amount 80～95%, make antifreeze temperature reach below-70 ℃ and greatly reduce cost.The new triazole of a class or the double salt corrosion protection material of thiazole compound, organic acid and multiethylene polyamine have also been synthesized for this reason.They can form balanced corrosion protection system and mate dissolving well with the deicing fluid system based on glycol ether with habitual corrosion protection component, have improved the corrosion protection effect of deicing fluid to the multiple metal that comprises aluminium and aluminium alloy.
Description
The invention belongs to cooling system anti-freeze cooling liquid constituent manufacturing technologies such as explosive motor cooling water tank.Engine coolant requires to have good heat-conducting and thermostability, and do not freeze, do not boil, not corrosion, characteristic such as non-foaming.Current many based on ethylene glycol, the high boiling point water-soluble polyol that adds ethylene glycol amount 1～10% is auxiliary antifreeze composition.But the minimum antifreeze temperature of this class deicing fluid has only about-40 ℃, and because of ethylene glycol at industrial extensive use, price is also very high.Can reduce antifreeze temperature and cheap with the glycol ether for the deicing fluid composition, someone did this class work and had included ASTM's standard (ASTM D 3585-77(1983) in), in recent years also there is similar work in Japan, as (JP61-21176A) etc., but because of the balanced system of its corrosion protection is insoluble in reasons such as glycol ether, its consumption is all at below 10% of system total amount.In addition, as the rust protection component, for to multiple metal particularly aluminium and aluminium alloy have the corrosion protection performance, current except that with the phosphoric acid salt of hydroxyalkyl amine, as inorganic salt have Sodium orthomolybdate,
Acid sodium etc., as organic acid salt, the most noticeable is the trolamine of thyroidan sodium salt and benzotriazole or ethanolamine salt etc.These novel salts are easily molten and stable in the deicing fluid of main body at ethylene glycol, but are that the system of main body is almost insoluble at glycol ether, thereby are difficult to utilize.1987, have the human multiethylene polyamine to add antifreeze system as sequestrant and suppress the spot corrosion (JP62-74985A) that aluminium alloy takes place because of forming local galvanic cell, to be used to solve with the glycol ether be the problem of deicing fluid master composition but do not make a series of double salt.
The objective of the invention is to utilize domestic glycol ether cheap and easy to get to be frostproofer master composition, obtain freezing temperature and be lower than-60 ℃ components of anti-icing liquor.And the composite salt of for this reason seeking the new triazole of a class or thiazole compound, phenylformic acid or other organic acid and multiethylene polyamine, make it form balanced corrosion protection system and to mate dissolving well, thereby form a new components of anti-icing liquor system with practical value with habitual corrosion protection component with deicing fluid system based on glycol ether.
The invention is characterized in 100 parts of (weight) glycol ethers, to add 0～100 part (weight) other auxiliary alcohols, add 0.5～10 part of rust protection novel substance (weight) as following formula (1):
N=1～4 wherein, p+q≤n+2, p≤q, R is
N-caproic acid base, bay acidic group, hexanodioic acid base, Succinic Acid base, sebacic acid base, phthalic acid base, winestone acidic group, oxyacetic acid base etc.Add 1～14 part (weight) corrosion protection material commonly used and 5～200 parts of (weight) water again, adjust system pH=7.5～8.5 and constitute the balanced components of anti-icing liquor of a kind of new antifreeze inhibition.
From above proportioning as seen, the present invention is deicing fluid master composition with the glycol ether, and it accounts for 50～100% in the alcohols total content.Experiment showed, that the usage quantity of working as glycol ether is big more, the antifreeze ability of deicing fluid is strong more, so use it to allow separately.But consider the improvement of some performance of deicing fluid, need to add a kind of of other auxiliary alcohols or several.The glycol ether consumption is preferably 80～95% of total alcohol amount.
Other auxiliary alcohols comprises carboxyl alcohols, amido alcohols such as Triethylene glycol, polyoxyethylene glycol, ethylene glycol, butyleneglycol, dipropylene glycol, polypropylene glycol, tartrate and oxyacetic acid.Different alcohol can make the performance based on the deicing fluid aspect of glycol ether improve.For example, add boiling point and the corrosion resistance that Triethylene glycol and poly-ethanol can improve deicing fluid; Adding ethylene glycol, sulfydryl alcohols can improve the solubility property of salt and make the pH value of system be unlikely to too high.Auxiliary alcohols consumption is 0～50% of total alcohol amount, and the auxiliary alcohols consumption of generalized case is 5～20% of total alcohol amount.
Antirust corrosion protection material shown in top (1) formula is 0.4～2.4% of a system content.According to the requirement of different metal to provide protection, R can be different substituting groups in the formula.
Auxiliary corrosion protection material has the phosphoric acid salt or the organic acid salt of alkyl alcoholamines such as inorganic salt such as borax, SODIUMNITRATE, Sodium Nitrite, SODIUM PHOSPHATE, MONOBASIC (potassium) Sodium phosphate dibasic (potassium), water glass and trolamine, can use separately, also can mix use, consumption is 0.9～3.3% of a system total amount.A kind of or several mixtures of SODIUMNITRATE that the present invention is preferred, Sodium Nitrite, Sodium Tetraborate, SODIUM PHOSPHATE, MONOBASIC, trolamine are complementary corrosion protection material.
In order to adjust system pH, can select organic acids such as trolamine, phthalic acid, phosphoric acid, tartrate, Succinic Acid, sebacic acid, oxyacetic acid, hexanodioic acid, Thiovanic acid for use.
For making color eye-catching, can add the blue look of 10～30ppm water-pure solubility, yellow, blue green or green colouring material, dyestuffs such as for example alkaline gorgeous orchid, methylene blue, pure molten orchid, water soluble fluorescence Huang.
For preventing the concussion foaming, can add 10～50ppm organosilicon water miscible liquid.For increasing the delicate fragrance sense, also can in refrigerating fulid, add a small amount of spices.
Institute's water is deionized water such as distilled water preferably, but use tap water and cleaning spring or well water also to allow, because it is the used multiethylene polyamine of the present invention has the effect that prevents the fouling of calcium, magnesium ion precipitation, more reliable when using alcohol acid such as tartrate, citric acid in the double salt especially.Consumption is 4.7～47.2% of a system total amount.
The such double salt of the used formula of the present invention (1) is generally answered prepared beforehand, is particularly using under the situation of Sodium Nitrite, and necessary prepared beforehand is in order to avoid amino and nitrite anions reaction generation nitrosamine or the side reaction of generation diazotization.The preparation of double salt is generally taked load weighted multiethylene polyamine is dissolved in the ethylene glycol or glycol ether of 5～10 times of weight, the triazole or thiazole compound and the organic acid that add specified amount again, stirring at normal temperature, by its exothermic heat of reaction heat up naturally and accelerated reaction till the whole solubilizing reactions of solid obtain transparent mucus.Multiethylene polyamine Diethylenetriaminee (DETA), triethylenetetramine and tetraethylenepentamine generally commonly used, its performance is approximate, with low cost is to select foundation.Triazole or thiazole compound have benzotriazole, toluene a pair of horses going side by side triazole, mercapto benzothiazole etc., its add mole number (p) general with multiethylene polyamine etc. mole.Organic acid mole number (q) can be greater than triazole or thiazole compound, be q 〉=p, but both mole number sums (p+q) should be not more than the amido summation (n+2) in the multiethylene polyamine, otherwise high and low temperature stability is not good enough after adding auxiliary composition difficulty of other corrosion protection or adding; If add-on is very little, also bad when (p+q)＜1/2(n+2), at this moment can not give full play to its corrosion protection proportionality action, system pH is also easily higher.Organic acid can be used phenylformic acid, right-tert-butylbenzene formic acid, n-caproic acid, lauric acid, Succinic Acid, hexanodioic acid, sebacic acid, phthalic acid, m-phthalic acid, tartrate, oxysuccinic acid, oxyacetic acid, ricinolic acid etc.Use phenylformic acid, phthalic acid and tert-butylbenzene formic acid that scolding tin and aluminium etc. is had good protective action; Use lauric acid, ricinolic acid and sebacic acid that copper, brass, scolding tin are had the better protecting effect; And the hydroxyl acids helps improving the stability of deicing fluid and improves boiling point.In addition, when adding strong organic acid, mole number (q) can be a little bit smaller, do not influence the add-on of other auxiliary corrosion protection composition so that total system pH is controlled between 7.5～8.5.
The present invention is the anti-freeze ability that deicing fluid master composition has improved deicing fluid because of adopting glycol ether.With main composition is that the deicing fluid of ethylene glycol is compared, and under spissated situation, the former zero pour is below-70 ℃ and the latter is-16 ℃; When concentration was 60%, the former zero pour was-42～-48 ℃ for-65～-72 ℃ of latter.The raising of this freezing tolerance further enlarges the deicing fluid scope of application and region.On the other hand; owing to used the double salt of novel multiethylene polyamine; particularly it and benzotriazole (or toluene a pair of horses going side by side triazole) and the formed double salt of organic acid; deicing fluid is had the following advantages: first; even use separately, when consumption be frostproofer 1% the time to the existing quite satisfied protection effect of metals such as aluminium, ferrous metal, brass, scolding tin.The second, very easily dissolving in glycol ether, thermostability and low-temperature stability are good.The 3rd; make Sodium Nitrite, Sodium Tetraborate; particularly phosphoric acid salt is to obtain the hydrotropy effect in the deicing fluid of leading at glycol ether; thereby and help the pH value is transferred between 7.5～8.5 and do not precipitate the disadvantage of separating out the balanced system of many components rust protection is established, and the multiple metal that comprises aluminium and aluminium alloy all there is good provide protection.
(synthesis example 1～16)
In the beaker of 2000ml, add 1000g ethylene glycol (also can use glycol ether), the Diethylenetriaminee (DETA) of 103g (1mol), the phenylformic acid (1mol) of the benzotriazole of 119g (1mol) and 122g fully stirs, and obtains the product DBA-1 of example 1 in 1 hour in reaction below 50 ℃.Because of reaction is thermopositive reaction, the initial stage need not heating, and the later stage suitably heats, and temperature is controlled at 40～50 ℃.Benzotriazole answers porphyrize to add earlier, and the phenylformic acid porphyrize adds after a while.
Use same quadrat method, can synthesize other 15 products by the ratio of components of example 2～16 in the subordinate list 1, code name as shown in Table.
(embodiment 1～16)
Press subordinate list 2 listed proportioning raw materials (weight percent) at first with water and inorganic salt dissolving, add the solution of ethylene glycol, glycol ether and the corresponding sequence number of synthesis example then, regulating the pH value is 8.0 ± 0.2.Add dyestuff and also fully mix thoroughly, add the product that defoamer can get embodiment 1～16 again.
Products therefrom surveyed its performance by the method for subordinate list 3 and subordinate list 4 and compare with the performance of ASTM (ASTM) reference formulation that provides, the result also example in subordinate list 3 and subordinate list 4.From these contrasts as can be seen, the antifreeze corrosion protection of 16 components of anti-icing liquor of embodiment 1～16 and the general equal conformance with standard of physical and chemical performance, performance is good.
(embodiment 17～21)
According to the composition of subordinate list 5, adopt the compound method of embodiment 1～16, can allot 5 kinds of glycol ethers components of anti-icing liquor different of embodiment 17～21 with the ethylene glycol relative content.After tested, their general physical properties and no significant difference, the anti-corrosion performance excellence, just freezing point is significantly different, and glycol ether content is low more, and freezing point is high more.Subordinate list 5 is also listed the comparative example of embodiment 17～21 and some documents.Resistance to frost of the present invention as can be seen obviously is better than prior art.
Note deicing fluid metal corrosion test method
Dissolving sodium sulfate 148mg in 1 liter of distilled water, sodium-chlor 165mg, sodium bicarbonate 138mg, to concentrate deicing fluid with this aqueous solution, to be diluted to volume 30%(be that deicing fluid is got 300ml, and above-mentioned solution is got 700ml), feed the speed ventilation of dry air 100 ± 10ml/min with per minute, maintain the temperature at 88 ± 2 ℃, make the test piece dipping after 336 hours, survey its dipping front and back quality change, formula is as follows:
U= (m
2- m
1)/(S) (mg/cm
2)
U: mass change, i.e. every square centimeter quality change
m
1: the quality (mg) of print before the test
m
2: the quality (mg) of test back print
S: the total surface area (cm of print before the test
2)
Wherein:
Aluminium is generally used (AU-2A)
The sample area is generally according to the ASTM method
The volume of test solution is generally taken.
Claims (6)
1, a kind of components of anti-icing liquor of forming by alcohols, rust protection material and water, wherein rust protection novel substance structure is suc as formula shown in [1]:
Hexanodioic acid base, Succinic Acid base, sebacic acid base, phthalic acid base, winestone acidic group, oxyacetic acid base etc. is characterized in that containing (weight ratio):
100 glycol ethers
0～100 auxiliary alcohol
0.5～10 rust protection materials [1]
1～14 auxiliary rust protection material
5～200 distilled water or tap water
And system pH=7.5～8.5.
2, according to the described components of anti-icing liquor of claim 1, it is characterized in that the auxiliary preferred SODIUMNITRATE of rust protection material, Sodium Nitrite, Sodium Tetraborate, SODIUM PHOSPHATE, MONOBASIC, diethanolamine is a kind of or several mix and use, constituent is preferably formed (weight ratio) and is:
100 glycol ethers
5～25 auxiliary alcohol
0.5～6 rust protection materials (1)
1～8.5 auxiliary rust protection material
5.5～125 distilled water or tap water.
3, according to claim 1 or 2 described components of anti-icing liquor, certain is characterised in that with organic acid adjusts system pH.
4, according to claim 1 or 2 described components of anti-icing liquor, it is characterized in that adding 10～50ppm organosilicon water miscible liquid.
5, according to claim 1 or 2 described components of anti-icing liquor, it is characterized in that adding 10～30ppm water-pure soluble dye.
6,, it is characterized in that adding 10～30ppm water-pure soluble dye according to the described components of anti-icing liquor of claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102325 CN1037356A (en) | 1988-05-03 | 1988-05-03 | Components of anti-icing liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102325 CN1037356A (en) | 1988-05-03 | 1988-05-03 | Components of anti-icing liquor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1037356A true CN1037356A (en) | 1989-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88102325 Pending CN1037356A (en) | 1988-05-03 | 1988-05-03 | Components of anti-icing liquor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082991C (en) * | 1998-04-02 | 2002-04-17 | 姚明忠 | Scale-inhibiting flame-retardant corrosion-free boiling-preventing anti-freezing solution and preparation method thereof |
| CN102421867A (en) * | 2009-05-08 | 2012-04-18 | 雪佛龙美国公司 | Antifreeze concentrate and coolant compositions and preparation thereof |
| CN102605374A (en) * | 2012-01-19 | 2012-07-25 | 张颖 | Corrosion inhibitor for engine coolant |
| CN106905932A (en) * | 2016-11-27 | 2017-06-30 | 青岛康普顿科技股份有限公司 | A kind of organic engine cooling liquid of carboxylated Graphene and preparation method thereof |
| CN110028933A (en) * | 2019-05-14 | 2019-07-19 | 煤炭科学技术研究院有限公司 | A kind of no chlorine Railway Coal transport antifreezing agent |
| CN115975737A (en) * | 2022-12-13 | 2023-04-18 | 新疆金雪驰科技股份有限公司 | Multifunctional environment-friendly aromatic glass water composition and preparation method thereof |
-
1988
- 1988-05-03 CN CN 88102325 patent/CN1037356A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082991C (en) * | 1998-04-02 | 2002-04-17 | 姚明忠 | Scale-inhibiting flame-retardant corrosion-free boiling-preventing anti-freezing solution and preparation method thereof |
| CN102421867A (en) * | 2009-05-08 | 2012-04-18 | 雪佛龙美国公司 | Antifreeze concentrate and coolant compositions and preparation thereof |
| CN102605374A (en) * | 2012-01-19 | 2012-07-25 | 张颖 | Corrosion inhibitor for engine coolant |
| CN102605374B (en) * | 2012-01-19 | 2013-09-11 | 宁波市瑞通新材料科技有限公司 | Corrosion inhibitor for engine coolant |
| CN106905932A (en) * | 2016-11-27 | 2017-06-30 | 青岛康普顿科技股份有限公司 | A kind of organic engine cooling liquid of carboxylated Graphene and preparation method thereof |
| CN110028933A (en) * | 2019-05-14 | 2019-07-19 | 煤炭科学技术研究院有限公司 | A kind of no chlorine Railway Coal transport antifreezing agent |
| CN115975737A (en) * | 2022-12-13 | 2023-04-18 | 新疆金雪驰科技股份有限公司 | Multifunctional environment-friendly aromatic glass water composition and preparation method thereof |
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