CN1077708A - The stable composition of the aldehyde that sulphur replaces, be used for stablizing the method for aldehyde and stable aldehyde - Google Patents
The stable composition of the aldehyde that sulphur replaces, be used for stablizing the method for aldehyde and stable aldehyde Download PDFInfo
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- CN1077708A CN1077708A CN 92115231 CN92115231A CN1077708A CN 1077708 A CN1077708 A CN 1077708A CN 92115231 CN92115231 CN 92115231 CN 92115231 A CN92115231 A CN 92115231A CN 1077708 A CN1077708 A CN 1077708A
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- C07C319/26—Separation; Purification; Stabilisation; Use of additives
Abstract
The present invention relates to be used to have the stable composition of the aldehyde that the sulphur of the following general formula (I) of 4-15 carbon atoms replaces:
Description
The present invention relates to the aldehyde that sulphur replaces such as the stable composition of Beta-methyl sulfo-propionic aldehyde (MTPA), go bad down at all temps, humidity condition (be included in carbon steel exists or not down) to prevent this class product.The invention still further relates to the stabilising method of the stable composition that use provides and stable aldehyde.
Usually, the aldehyde through storing will absorb oxygen, thereby makes the series reaction of product degradation.Proposed to be used for stablizing the many adoptable method of aldehyde in the prior art, as adding following substances:
A) aromatic amine or aliphatic amine such as pyridine, quinoline, dialkylamine, add-on is preferably 2000ppm(and comprises MTPA).Trace back to nineteen twenty-nine, U.S.P.1736749 has proposed to add 1 as 1 by the amount of 0.25-1.0%, and 2-two (phenyl amino) ethane is stablized aldehyde, with anti-oxidation.Japanese Patent JP7232963 has disclosed adding pyridine, quinoline, collidine or lutidine and has stablized MTPA, and its consumption is 0.1%.Another Japanese Patent JP49116017(1974 November 27) propose to use N, the amine stabilized MTPA of N-dialkyl benzene, consumption is 0.2%, at last, in 1945, propose to use quinoline among the U.S.P.2381771, particularly with the antioxidant of the quinol that replaces as rubber, binding agent, petroleum products and derivative (gasoline, aldehyde).
B) alkanolamine
Author Sagarin E. and H.M.(be referring to Perfumer, 46(7), 33-5,1944) mention and use alkanolamine stablize aldehyde, they also propose to use the phenol of alkyl replacement to reach identical purpose.It is that the trolamine of 0.25-0.5% comes stabilized oxymethylene to prevent to form formic acid and methyl alcohol that patent SU568626 has disclosed by add-on.
C) unsaturation four substitution compounds
At GB075285(1952) in mentioned this class stablizer.
D) based on the composition of phenolic compound (phenol, naphthalene etc.) and amine (pyridine, picoline, lutidine, collidine or its mixture), preferably, under 1000ppm, be used for the aldehyde of sulphur replacement such as stablizing of MTPA based on the system of 4-methoxyphenol and pyridine.Above-mentioned composition is described in the U.S.P.4546205(PI8301502 that gives PENWALT CORP.) in.The stable composition of being recommended has many shortcomings in the prior art, for example in fact they contain deleterious amine, its boiling point is also lower than aldehyde, and this based composition even the distillation of before synthetic route product being carried out also have interference, and this annoyance level will depend on the scope of the relative molecular weight (and boiling point) of product and stablizer.
Generally speaking, the decomposition of aldehyde is owing to absorb oxygen, carries out the condensation of autoxidation, 3-acetaldol and thermolysis in some cases subsequently.
The dominant mechanism that the aldehyde that sulphur replaces decomposes is:
A), increase thereby make it radical owing to the autoxidation that absorbs oxygen and take place with metallic contact.
B) condensation of the 3-acetaldol in acidic medium; Cyclic trimerization effect and polymerization.
C) by metal catalytic or non-catalytic pyrolysis.For unstabilized MTPA, the reaction of methyl mercaptan, propenal, water and ethene can take place to be formed by MTPA itself and its degradation production.
D) nucleophilic addition(Adn) and replacement.With regard to MTPA, this situation be because the degradation production methyl mercaptan, thereby due to product mercaptal and the thioesters.
E) decarboxylation is promptly eliminated CO, thereby forms the organic sulfide of non-carboxylic acid.
This reaction of five types may concur, and prove by chain processes, with recommended as vegetables oil (Journal Amer.Oil Chem.Soc., 1977,54, P.4-7) other carboxylic compounds of antioxidant are compared, and it has the ability of the oxygen that very strong absorption causes for the aldehyde that is replaced by sulphur such as MTPA.Should be emphasized that, for the decomposition of the aldehyde that replaces for sulphur, oxygen and metal contact and hot factor plays decisive role separately or jointly.
Show that according to gas-chromatography and mass spectroscopy under the following conditions, the possible approach that MTPA decomposes is shown in following diagram.
Diagram 2
A.1.1-absorb oxygen and autoxidation: at O
2And forming addition compound between the MTPA, this compound is subjected to the restriction of institute's dissolved oxygen in organic medium.Based on this, perhaps form the MTPA peroxy acid, it produces MTPA acid again, and perhaps this reaction forms the radical with the thiolate form gradually, and it forms disulphide and heavier compounds again.
A.1.2-the condensation of the 3-acetaldol in acid medium: promotedly by the stability of MTPA enol form formed dipolymer, trimer and polymkeric substance by acid catalyzed reaction:
A.1.3-thermolysis: MTPA and its degradation production mainly carry out under＞65 ℃.Such reaction has been quickened in the existence of metal.A.1.1 this pyrolysis has replaced and balance A.1.2, and causes the A.1.4 reaction of type owing to discharging methyl mercaptan.
A.1.4-addition and replacement: methyl mercaptan causes the addition compound that forms mercaptal and half thioacetal type.By forming the compound of thioether type with the reaction of the carboxylic acid that exists.
A.1.5-decarboxylation: as the situation of MTPA, the existence of mercaptan has particularly at high temperature promoted the decarboxylic reaction of aldehyde, thereby has formed corresponding organic sulfide.
The initial step that MTPA decomposes comprises oxygen absorption, and to cause very strong stability by MTPA enol form be feature and promoted autooxidation.Carry out the acidity that causes by the peroxy acid that forms or its corresponding carboxylic acid subsequently and by the condensation reaction of catalytic 3-acetaldol in acid medium.By MTPA itself and/or the thermal control decomposition reaction that taken place by the MTPA peroxy acid, this decomposition reaction is because to form methyl mercaptan, propenal and ethene caused.
In inert atmosphere, the Study of Thermal Decomposition of MTPA is shown, being lower than under 90 ℃ the temperature, be few by the mercaptan that adds thermosetting.Yet more than 105 ℃ the time, thermolysis becomes the very important factor of the stability of this molecule.The applicant the results showed, in oxygen atmosphere, makes the decomposition that discharges methyl mercaptan much easier, this situation even also can take place at low temperatures, and this may be owing to there is peroxy acid to participate in this process.
The present invention relates to be used to have the stable composition of the aldehyde that the sulphur of the following logical formula I of 4-15 carbon atom replaces:
Wherein:
R1=C
1-5Alkyl, C
5-9Aryl, furfuryl group and benzyl,
R2＝H、R1，
R3＝H、R1，
It is characterized in that it is based on the prototropic agent (A) that combines with oxygen extraction agent (B).This class A and B compound can be selected from:
Table A/B
A.1: aromatic amine or heteroaromatic B.1: the phenol of replacement or quinhydrones, as right
Amine, as pyridine, diformazan tert.-butyl phenol (PTBP),
Base aniline, quinoline, 82,6-di-t-butyl-4-
But-hydroxyquinoline power methylphenol (BHT).
Fourth, picoline, Lu
Pick pyridine.
A.2: alkanolamine or non-fragrance B.2: sour or unsaturated antioxidant,
Cyclammonium, as trolamine such as ascorbic acid (AA),
(TEA), N-β-Hu Luobusu.
Methylmorpholine.
A.3: interior acyl class, as the N-first
The base pyrrolidone.
Except that following two pairs: A=pyridine/B=p-tert-butylphenol and the A=quinoline/B=p-tert-butylphenol, said stable composition is made up of A and B, preferably the stable composition of following expression:
| Composition | A | B |
| C1 | TEA | AA |
| C2 | Pyridine | AA |
| C3 | Quinoline | AA |
Or rather, composition A/B can be TEA/AA.The effect of prototropic agent A is the acid site of eliminating the condensation that causes addition 3-acetaldol, and reagent B competes O
2, therefore just avoided in the aldehyde that sulphur replaces, causing undesirable reaction.
The stable composition that is used to have the aldehyde that the sulphur of formula I replaces is characterised in that its amount is 500-1500ppm, is preferably 1000ppm.The mol ratio of A/B component is 5: 95 to 5: 50.In addition, preferred stable composition is to be the TEA/AA of 1000ppm with the amount, has 10-50%AA in TEA.As described in the prior art (referring to the table 1 of embodiment), for using isolating amine, pointed out the synergy of stable composition, it is existing distinctive faint yellow that the aldehyde that stable sulphur is replaced does not demonstrate degradation production.When stable aldehyde is carried out stratographic analysis, find almost not have the component aldehyde that formation itself exists by changing, therefore, stabilization is highly effective.This stable composition does not influence the postorder treatment process of stablizing aldehyde yet, and this is because A and B component remain in the distillation residue (referring to the table 4 of embodiment).
What obtain in addition proving is (referring to the table 2 of embodiment), and under different temperature, stabilization is effective.For example come stable MTPA with TEA/AA, kept 15 days down at 50 ℃, the amount that reduces because of loss at lay up period is less than 2%.
The present invention also relates to be used for the method for the aldehyde that stable sulphur with formula I replaces, as mentioned above, the method is characterized in that, the A/B stable composition has been joined in the said aldehyde.
The influence of water-content
In aldehyde or said composition that sulphur replaces, the stabilizing power of the A/B system that the existence influence of water is added mainly is when aldehyde contacts with metal or carbon steel, and under this condition, the component A of amine type makes release the OH of 3-acetaldol condensation
-Following reaction, for example, for TEA, in the presence of water, will take place in ion:
For MTPA, the 3-acetaldol condensation reaction that is taken place in alkaline medium (when especially having carbon steel in such medium) is as follows:
Therefore, the existing water yield must reach minimum value in the aldehyde that sulphur replaces or in said stable composition.The method that is used for stablizing the aldehyde of the sulphur replacement with formula I is characterised in that when equilibrium temperature was up to 50 ℃, contained water yield maximum value was 300ppm in the aldehyde, preferably is less than 100ppm.
The application of the aldehyde that replaces according to the sulphur in commercial run, suggestion when it is produced, it initial distillation and transfer to container after, before water formation, water is added as degradation production.
Carbon steel
Show that through experimental observation carbon steel produces different influences for the aldehyde that sulphur replaces:
During 1) in temperature＜50 ℃, for the effect of isolation from oxygen, carbon steel makes aldehyde stable, and this may be because steel surface has the ability of extracting oxygen from this medium.Or rather, for MTPA, the complexing of its enol can take place, this is undertaking the autooxidation that metal ion carries out.
2) in temperature＞50 ℃ amount, carbon steel helps the decomposition of aldehyde, particularly in the presence of oxygen.With regard to MTPA, formed methyl mercaptan salt or enol may corrode steel surface and discharge Fe
2+, Fe
3+And Mn
2+Metal ion, this metal ion plays katalysis to the oxygenolysis of aldehyde again.
The stabilising method of the aldehyde that the sulphur of described formula I replaces are characterised in that aldehyde contacts or is not in contact with it with carbon steel.In the presence of the carbon steel and under all test temperatures (referring to embodiment table 1A), described A/B stable composition has reduced the decomposition of the aldehyde of sulphur replacement.The temperature that these stabilising method are used for being stood is the aldehyde of 25-100 ℃ of scope.
Aldehyde with sulphur replacement of formula I is characterised in that and contains foregoing A/B stable composition.
Embodiment
Stabilising system
1) synergy of stabilising system
To stablize or unstabilized MTPA sample is packed into after weighing in glass narrow-necked bottle or " Pa Er pump " (being lined with the teflon narrow-necked bottle of carbon steel outward), capping, and in atmospheric air and unglazed down, in stove, be heated certain hour.Then, sample is analyzed, to check synergy at the stabilising effect and the composition A+B of material described in Table A/B with oximate and/or gas-chromatography.
In order to reach the purpose of comparison, each test all compares with the unstabilized MTPA sample that stands identical heat treated dynamic conditions.Each test and each sample all carry out secondary.
The preparation of sample is that the chemical reagent that is used to test as stablizer of appropriate amount is weighed with analytical balance or microbalance, and the amount ranges of stablizer is 1000 to 2500ppm in MTPA.This test is also carried out under 50 ℃, 80 ℃ and 120 ℃ except that at room temperature.
Analytical procedure:
Gas-chromatography
Measure the chromatogram situation of sample with gas chromatographic analysis, and measure MTPA content in order to 100% normalization method.
The dosimetry of oximate
Obtain MTPA content with potentiometric titration by the sense analysis.
The result
Following table I combines the test conditions (consumption of time, temperature, stablizer) of each sample and corresponding stablizer, and:
-MTPA initial content,
-through the MTPA content of certain hour after the heating phase,
-sample color,
-MTPA decomposes and steady rate.
-GC chromatogram situation focuses on formed impurity.Selecting molecular weight is 190(MTPA crotomer) the corresponding formation speed of the impurity feature of decomposing as expression MTPA.
-stability factor is defined as the merchant between the changing value of unstabilized MTPA content and stable MTPA content.
At first, add xitix separately,, do not demonstrate stabilization, because the in fact condensation reaction of acid meeting catalysis 3-acetaldol aldehyde although can absorb oxygen by intensive.Compare with the material of independent application, the synergy of the A/B composition in the MTPA stabilization is very clearly, particularly amine such as pyridine, quinoline and xylidine, and this had record in the prior art.In addition, the amount in the A/B stabilising system is lower than the amount of recommending in the prior art.
The mass ratio of the stablizer of testing for stabilized mixture is 1000,2000 and 2500ppm, and the mol ratio of the xitix in TEA is 10%, 20% and 50%.Known trolamine demonstrates low toxicity, and in fact it is tasteless, and has high boiling point (being 206 ℃ under 15mmHg), and its boiling point is higher than MTPA, so it is actively to recommend on the industrial treatment to use.
2) test with TEA/AA
Other more accurate tests have been carried out with the TEA/AA stabilising system.
The preparation sample uses the mass ratio and the mol ratio of following expression:
9.6mg xitix (0.055mmol) and 90.4mg trolamine (0.603mmol) are than 100ml MTPA, the actual mol ratio of using is that 8.4% mole of xitix is than 91.6% mole of triethanolamine.
Test under 50,80 and 100 ℃, its heat-up time is (15 days) up to 360 hours.
The gained data are shown in table 2, and wherein each numerical value all is the mean value of the quite high secondary revision test of tolerance range.Measure MTPA content with gas-chromatography and oximate.For data, wherein also be included in 50 ℃ and stabilising system exist or not in the presence of MTPA and the carbon steel data that contact and obtained.
Table 2
Basic test-MTPA-stablizer
Period
67 hours
Sample:: observe:: the result
::: aldehyde: GC:
:: appearance color: (%): (%): stable
::: (on average): (on average): coefficient
MTPA: 50: colourless: 95.73: 92.55: 1.00
MTPA+ trolamine: 50: colourless: 97.15: 94.26: 2.27
+AA : : : : :
MTPA: 80: faint yellow: 79.27: 80.11: 1.00
MTPA+ trolamine: 80: colourless: 93.87: 94.36: 4.54
+AA : : : : :
MTPA: 100: deep yellow: 58.91: 69.83: 1.00
MTPA+ trolamine: 100: faint yellow: 74.11: 82.94: 1.64
+AA : : : : :
MTPA+ carbon steel: 50: colourless: 95.55: 92.94: 1.00
MTPA+ carbon steel: 50: colourless: 97.58: 94.67: 5.83
Trolamine+AA:::::
Basic test-MTPA-stablizer
Period
144 hours
Sample:: observe:: the result
::: aldehyde: GC:
:: appearance color: (%): (%): stable
::: (on average): (on average): coefficient
MTPA: 50: colourless: 89.70: 90.07: 1.00
MTPA+ trolamine: 50: colourless: 97.59: 93.48: 8.30
+AA : : : : :
MTPA: 80: yellow: 68.39: 73.16: 1.00
MTPA+ trolamine: 80: colourless: 86.87: 88.80: 2.66
+AA : : : : :
MTPA: 100: faint yellow: 41.43: 55.00: 1.00
:: brown:::
:: (thickness):::
MTPA+ trolamine: 100: faint yellow: 61.15: 76.38: 1.54
+AA : : : : :
MTPA+ carbon steel: 50: colourless: 92.32: 93.05: 1.00
The MTPA+ carbon steel+: 50: colourless: 96.40: 94.08: 3.55
Trolamine+AA:::::
Basic test-MTPA-stablizer
Period
240 hours
Sample:: observe:: the result
::: aldehyde: GC:
:: appearance color: (%): (%): stable
::: (on average): (on average): coefficient
MTPA: 50: colourless: 86.02: 83.58: 1.00
MTPA+ trolamine: 50: colourless: 96.89: 94.07: 11.09
+AA : : : : :
MTPA: 80: yellow: 55.30: 63.13: 1.00
MTPA+ trolamine: 80: very light yellow: 79.55: 83.54: 2.31
+AA : : : : :
MTPA: 100: faint yellow: 30.22: 36.92: 1.00
:: brown:::
:: (thickness):::
MTPA+ trolamine: 100: faint yellow: 52.54: 71.58: 1.49
+AA
MTPA+ carbon steel: 50: very light yellow: 91.52: 92.21: 1.00
The MTPA+ carbon steel+: 50: colourless: 95.95: 93.00: 3.16
Trolamine+AA:::::
Basic test-MTPA-stablizer
Period
360 hours
Sample:: observe:: the result
::: aldehyde: GC:
:: appearance color: (%): (%): stable
::: (on average): (on average): coefficient
MTPA: 50: colourless: 80.29: 78.27: 1.00
MTPA+ trolamine: 50: colourless: 97.25: 92.98: 17.71
+AA : : : : :
MTPA: 80: deep yellow: 44.11: 59.26: 1.00
MTPA+ trolamine: 80: very light yellow: 72.51: 79.90: 2.11
+AA : : : : :
MTPA: 100: faint yellow: 24.46: 29.23: 1.00
:: brown:::
:: (thickness):::
MTPA+ trolamine: 100: yellow: 44.02: 56.39: 1.36
+AA : : : : :
MTPA+ carbon steel: 50: very light yellow: 89.56: 88.40: 1.00
The MTPA+ carbon steel+: 50: colourless: 93.66: 91.63: 1.95
Trolamine+AA:::::
Can find out the effective performance of stable composition from table 2.For the MTPA that initial amount is 98.01%, be to be noted that its content (measuring with oximate) in fact remained unchanged at 97% o'clock after heating 15 days, and do not having stablizer to have that (and under identical heat condition, above-mentioned content drops to 78%.
It is effective keeping the MTPA that contacts with carbon steel under composition of the present invention is used to be stabilized in 50 ℃.
Stable materialization data:
Fig. 1 represents the corresponding data in the table 2, wherein:
I is stable MTPA under 50 ℃,
II is unstabilized MTPA under 50 ℃,
III is stable MTPA under 80 ℃,
IV is unstabilized MTPA under 80 ℃,
V is stable MTPA under 100 ℃,
VI is unstabilized MTPA under 100 ℃.
Being to be noted that between for 50 and 80 ℃ MTPA content and time numerical value exists first order kinetics to change.Under 100 ℃, corresponding variation is not linear, and this thinks interference mechanism, particularly under this temperature, carry out and up to 80 ℃ of Decompositions of pass through to heat of a bit not carrying out.The initial velocity constant that calculates under three kinds of temperature for stable and unstable MTPA is listed in the table 3.
Table 3
Velocity constant (K) about the dynamics data of unstabilized and stable MTPA-under each temperature
Temperature: unstabilized: stable
(℃) : MTPA : MTPA*
: k (hour
-1): K (my god
-1): K (hour
-1): K (my god
-1)
50 :5.5×10
-1) :1.3×10
-2) :1.2×10
-5) :2.9×10
-4)
80 :2.2×10
-3) :5.3×10
-2) :3.7×10
-4) :8.8×10
-2)
100** :5.3×10
-3) :1.26×10
-1) :1.2×10
-3) :3.0×10
-2)
*Stablizer: 10% mole of AA-trolamine (1000ppm)
*The K value is to be the numerical value of the pseudo-first-order initial velocity constant that calculates between 0 and 67 hour the time in the table 2.
As shown in table 3, the activation energy that calculates under the both of these case just can obtain following numerical value:
Unstabilized MTPA decomposition activation energy: 10.5 kilocalories/mol,
Stable MTPA decomposition activation energy: 25.5 kilocalories/mol.
On kinetics and thermodynamics, stablize MTPA with the TEA/AA stable composition and just equal activation energy numerical value is increased by two sesquialters, this with regard to quantificational expression the existence by stablizer this decomposition is stoped this kind degree.
According to corresponding log K=f(1/T) (30 ℃), can calculate velocity constant K=1.15 * 10 of the stable aldehyde under this temperature by the deduction of the data in table 2 and the table 3
-5Hour
-1This numerical value means by speed can be predicted in envrionment conditions and in the presence of stablizer, stores MTPA through 1 month and reduces less than 1%.
3. stabilising system is to the distillatory influence of the aldehyde of sulphur replacement
This test shows that in the MTPA distillation, TEA/AA stablizes the mass distribution of component in lighting end, distillate and residual fraction.Since AA have high boiling point then allowed this imagination promptly this component remain in the distillatory resistates, therefore, the effect of the TEA by the back, the control that makes it stablizer is achieved.
This test is to be to be undertaken by batch distillation in 5cm, the high glass column that the teflon perforation plate is housed for 65cm at external diameter.
With 5.58g(990ppm) TEA and 0.62g(100ppm) AA(distillatory under 91 ℃ and 39mmHg) join 5.97 liters of (6210g) MTPA(90.0%, new distillatory) in.The lighting end that collection obtains is the continuous distillate cut of 18%, three time of total mass altogether 77.7%, and resistates is 3.4% of a total mass.
As titrating solution, each cut is carried out potentiometric titration to measure TEA with the acetic acid solution of the perchloric acid of 0.01N.Simultaneously, sample is carried out blank test, this test shows that the dose limit value of TEA is 10ppm with this understanding.Gained the results are shown in table 4.
Table 4
The dosimetry of trolamine in stable MTPA distillation fraction
: : : : :
::::: trolamine
: boiling range: quality: single quality: mass accumulation: content
Cut: 39mm Hg: (g): %: %: ppm
Lighting end: 84-91: 1104: 17.8: 17.8: 10 (ND)
*
I :91 :2094 :33.7 :51.5 :10(ND)
*
II :91 :2010 :32.6 :84.1 :10(ND)
*
III :91 :782 :12.5 :96.6 :10(ND)
*
Resistates :-: 220: 3.4: 100.0: 26150
Flash distillation:::::
Last running:::::
: : : : :
12/12/90 :- :- :- :- :<10(ND)
*Measure without the potentiometric titration dosimetry.
As can be seen from the above table, under this condition, all TEA remain in the distillation residue.Therefore, possible is, the component of the stable composition that precognition is provided even also will remain in the resistates in the operate continuously process.
Carbon steel
1) test of long duration of MTPA decomposition: at 37 ℃ and in the carbon steel existence with not, the stabilization in inert atmosphere.
Under 37 ℃, in the carbon steel existence with not, and stabilising system carries out 120 days test of long duration in inert atmosphere.
To have 100% initial content at N
2(and remain on N
2In) in three kinds of distillatory MTPA be enclosed in N
2In the glass narrow-necked bottle in the saturated atmosphere, it contains or does not contain the carbon steel test sample.Use has the stable composition of 900ppm TEA and 100ppm AA.By the result shown in the following table 3A as can be seen:
A) under this temperature, storing between 15 days and 1 month, be decomposed into the important stage, this situation thinks that the product itself that decomposes has strong self-catalysis.
B) stabilization of this system: on average be decomposed into 7% in 3 months storage, what compare with it is, on average is decomposed into 17% at identical lay up period for stable product not.
C) stabilization of the MTPA in the presence of carbon steel.
Table 3A
In the carbon steel existence with not, in inert atmosphere, the test of long duration of the decomposition of MTPA and stabilization-MTPA content %
Test under 37 ℃
: 3 days: 7 days: 15 days
: August/27: August/21: August/29
: narrow-necked bottle: HPLC: narrow-necked bottle: HPLC: narrow-necked bottle: HPLC
: No.: content: No.: content: No.: content
:1 :97.89 :9 :97.06 :17 :96.84
MTPA :2 :100.06 :10 :97.50 :18 :98.54
MTPA+ :3 :99.85 :11 :97.82 :19 :98.65
Carbon steel::::::
Carbon steel: 4: 98.24: 12: 101.77: 20: 95.81
MTPA+T.E.A.+ :5 :99.51 :13 :101.60 :21 :105.05
A.A. :6 :99.09 :14 :100.81 :22 :98.98
MTPA+T.E.A. :7 :99.18 :15 :97.69 :23 :99.50
A.A.+ carbon steel: 8: 99.74: 16: 101.18: 24: 97.60
Test under 37 ℃
: 30 days: 44 days: 62 days
: September/13: September/27: October/15
: narrow-necked bottle: HPLC: narrow-necked bottle: HPLC: narrow-necked bottle: HPLC
: No.: content: No.: content: No.: content
:25 :99.80 :33 :89.14 :41 :90.33
MTPA : :95.47 : : : :90.38
:26 :95.57 :34 :92.46 :42 :89.90
MTPA+ :27 :74.64 :35 :69.74 :43 :32.34
Carbon steel N::::::
STEEL :28 :90.37 :36 :67.42 :44 :71.96
MTPA+T.E.A. :29 :97.69 :37 :97.36 :45 :97.45
+A.A. :30 :97.33 :38 :95.62 :46 :96.08
MTPA+T.E.A.+ :31 :97.93 :39 :88.68 :47 :62.36
A.A.+ carbon steel: 32: 96.98: 40: 81.08: 48: 65.41
Test under 37 ℃
: 76 days: 97 days: 120 days
: September/29: November/12: December/12
: narrow-necked bottle: HPLC: narrow-necked bottle: HPLC: narrow-necked bottle: HPLC
: No.: content: No.: content: No.: content
MTPA :49 :94.50 :57 :78.73 :73 :54.66
:50 :90.62 :58 :88.26 :74 :-
MTPA+ :51 :56.36 :59 :40.66 :75 :15.93
Carbon steel STEEL: 52: 37.09: 60: 17.82: 76 :-
MTPA+ :53 :96.45 :61 :92.76 :77 :88.42
T.E.A.+A.A. :54 :Broken :62 :93.62 :78 :87.12
MTPA+T.E.A.+ :55 :52.33 :63 :51.51 :79 :44.66
The A.A.+ carbon steel | STEEL: 56: Broken: 64: 49.57: 80: 35.63
MTPA: distilled and redistillation the same day of test preparation.In nitrogen atmosphere-inert atmosphere, prepare sample.
Carbon steel: 1020.
The method that is used to measure MTPA content is to carry out with the dosimetry of liquid chromatography (HPLC) by outer stdn.
Instrument: HPLC-Varian 5010 or analogous instrument.
Pillar: Lichrosorb RP18, length=30cm, internal diameter=0.4cm.
Move section: acetonitrile/H
2O, 1: 9V/V.
Emission flow: 1.2me/ branch.
Measure: UV(200nm).
Measure the dilution of solution: the 0.1%(acetonitrile)
Volume injected: 10 μ l.
Retention time: about 8 minutes.
Totalizing instrument: HP3390.
Outer standardized dosimetry: the MTPA standard is to be kept in the refrigerator by vapor enrichment and under nitrogen atmosphere, and it comes stable with 900ppm TEA and 100ppm AA.
2) in common steel or stainless steel existence and the behavior of the MTPA under differing temps and the effect of stabilising system.
The same procedure of " kinetics function of stabilising system " use as above-mentioned 1).The dosimetry of MTPA is by oximate and also undertaken by gas-chromatography and liquid chromatography (referring to aspect of Chromatogram).
In the test of in the presence of carbon steel, being carried out, the test sample of this material is put into narrow-necked bottle, then capping and heat certain hour.The TEA/AA system of use under 1000ppm.
Data sheet among the above-mentioned table 1A understands that carbon steel has dual function to MTPA:
T＜50 ℃: MTPA compares with Individual existence, when it contacts with carbon steel, shows that by chromatogram the minimizing of MTPA content and the speed that impurity forms have reduced (absolute difference that at room temperature contains numerical quantity is 39.9%) significantly.
After 1080 hours (45 days), MTPA content at room temperature is with identical under the situation that does not have carbon steel under stabilizer function.
T＞50 ℃: carbon steel has very strong promoter action to the decomposition of aldehyde.Test shows, in the presence of carbon steel, is 6.4% at the MTPA content after 360 hours under 80 ℃.And the MTPA content of placing the identical time under identical heat condition is 65.5%.100 ℃ down this effects show in addition stronger.Under this condition under 80 ℃, the decomposition of stablizer is effective.When in the presence of carbon steel, stable MTPA content is than unstabilized MTPA content height.
Therefore, its conclusion is, in the presence of carbon steel, under differing temps, it is effective that stablizer is used to stop the decomposition of the aldehyde that sulphur replaces.
Water
1) in 50 and 80 ℃ down and in the presence of the ever-increasing water of content and the decomposition run of the MTPA in the presence of the mixture at the 90%TEAT-10%AA of 1000ppm.
Under these conditions, with high resolution liquid chromatography (HPLC) sample is carried out the MTPA analysis on Content.
Table 2A shows that under test temperature, water is to stable negative interaction.
Table 2A
In 50 ℃ and 80 ℃ down and the decomposition of the MTPA in the presence of ever-increasing water of content and mixture at the 90%TEAT-10%AA of 1000ppm
Content
: 7 days: 13 days: 28 days
MTPA+250ppm?H20 :99.6% :98.3% :98.65%
:98.7% :97.5% :96.7%
MTPA+250ppm?H20+TEA :96.5% :94.4% :89.4%
+A.A.(1000ppm) :97.8% :96.1% :91.0%
MTPA+350ppm?H20+T.E.A. :97.3% :79.6% :92.9%
+A.A.(1000ppm) :99.9% :- :91.5%
MTPA+1250ppm?H20+TEA :99.5% :95.8% :87.8%
+A.A.(1000ppm) :99.8% :92.4% :89.7%
MTPA+250ppm?H20 :93.3% :97.2% :64.3%
:85.9% :85.5% :59.4%
MTPA+250ppm?H20+TEA :65.0% :19.4% :32.2%
+A.A.(1000ppm) :71.5% :19.4% :21.9%
MTPA+350ppm?H20+TEA :65.0% :19.6% :24.4%
+A.A.(1000ppm) :58.0% :19.9% :22.6%
MTPA+1250ppm?H20+TEA :70.6% :18.1% :23.6%
+A.A.(1000ppm) :65.4% :23.5% :21.3%
-initial MTPA content: 100%.
-TEA-trolamine (900ppm); A.A.-xitix (100ppm).
-HPLC the dosimetry undertaken by outer stdn.
-test is at N
2In carry out.
This numerical value has been pointed out corresponding twice test of carrying out simultaneously.
2) in 50 ℃ down and the decomposition run of the MTPA in the presence of 1000ppm water and stabilized mixture at 90% pyridine-10% xitix of 1000ppm.
As previously mentioned, under these conditions, chromatographically carries out the MTPA analysis on Content to sample.Therefore, pointed out the influence (table 4A) of water and carbon steel to MTPA.
Table 4A
In 50 ℃ down and the decomposition of the MTPA in the presence of the mixture at 90% pyridine-10% xitix of 1000ppm water and 1000ppm
Content
: 14 days: 27 days: 43 days
MTPA sample: 92.6%: 93.1%: 84.6%
:99.5% :97.1% :82.2%
MTPA+py+A.A.(1000 :98.6% :92.9% :91.6%
ppm)+1000ppm H
2O :101.1% :95.2% :93.3%
MTPA+ carbon steel: 96.5%: 92.5%: 39.7%
:- :71.7% :39.1%
The MTPA+ carbon steel+: 98.8%: 54.1%: 16.5%
py+A.A(1000ppm)+ : : :
1000ppm H
2O :93.3% :- :-
-MTPA initial content (HPLC): 100.02%.
-PY(pyridine, 900ppm); The A.A.(xitix, 100ppm).
-at N
2In test.
The test several times accordingly that-test has been pointed out to carry out simultaneously.
Claims (10)
1, is used to have the stable composition of the aldehyde that the sulphur of the following logical formula I of 4-15 carbon atom replaces
Wherein:
R1=C
1-5Alkyl, C
6-9Aryl, furfuryl group, benzyl,
R2=H、R1，
R3=H、R1，
It is characterized in that it is based on the prototropic agent (A) that combines with oxygen extraction agent (B).
2, according to the stable composition that is used for the aldehyde that sulphur replaces of claim 1, it is characterized in that component except that composition A/B=pyridine/PTBP and quinoline/PTBP (A) is selected from:
Aromatic amine or heterocyclic aromatic amine are as pyridine, xylidine, quinoline, oxine;
The non-fragrant alkanolamine of alkanolamine or ring-type is as trolamine (TEA), N-methylmorpholine;
Lactan is as N-Methyl pyrrolidone;
And component (B) is selected from:
The phenol or the quinhydrones that replace are as p-tert-butylphenol (PTBP), 2,6 di tert butyl 4 methyl phenol (BHT);
Sour or unsaturated antioxidant is as xitix (AA) or β-Hu Luobusu;
3, according to the stable composition that is used for the aldehyde that sulphur replaces of claim 1 and 2, it is characterized in that said composition is preferably (A) TEA/(B) AA.
4, according to the stable composition that is used for the aldehyde that sulphur replaces of an above-mentioned claim, it is characterized in that said composition add-on is 500-1500ppm, be preferably 1000ppm.
5, according to the stable composition that is used for the aldehyde that sulphur replaces of claim 4, the mol ratio that it is characterized in that component (A)/(B) is 5/95-50/50.
6, be used for the stabilising method of the aldehyde that the sulphur of formula I replaces, it is characterized in that said stable composition (A)/(B) adds described in claim 1-5.
7, the stabilising method of the aldehyde that replaces according to the sulphur that is used for formula I of claim 6 is characterized in that being up to 50 ℃ for equilibrium temperature, and said aldehyde is anhydrous or water content is less than 300ppm, preferably is less than 100ppm.
8, the stabilising method of the aldehyde that replaces according to the sulphur that is used for formula I of claim 6 or 7 is characterized in that the temperature that stands of said aldehyde is 25-100 ℃.
9, the stabilising method of the aldehyde that replaces according to the sulphur that is used for formula I of claim 6 to 8 is characterized in that said aldehyde contacts with carbon steel.
10, have the aldehyde that the aliphatic sulphur of the following logical formula I of 4-15 carbon atom replaces:
Wherein:
R1=C
1-5Alkyl, C
6-9Aryl, furfuryl group, benzyl,
R2＝H、R1，
R3＝H、R1，
It is characterized in that said aldehyde contains just like the A/B stable composition described in the claim 1 to 5 or its stablizes by the method described in the claim 6 to 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR919105694A BR9105694A (en) | 1991-12-26 | 1991-12-26 | STABILIZING COMPOSITION FOR S-SUBSTITUTED ALDEHYDE, STABILIZATION PROCESS OF STABILIZED ALDEHYDE |
| BRPI9105694 | 1991-12-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1077708A true CN1077708A (en) | 1993-10-27 |
Family
ID=4053491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92115231 Pending CN1077708A (en) | 1991-12-26 | 1992-12-26 | The stable composition of the aldehyde that sulphur replaces, be used for stablizing the method for aldehyde and stable aldehyde |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH06506001A (en) |
| CN (1) | CN1077708A (en) |
| BR (1) | BR9105694A (en) |
| CA (1) | CA2103796A1 (en) |
| MX (1) | MX9207585A (en) |
| WO (1) | WO1993013059A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903197A (en) * | 2017-12-22 | 2018-04-13 | 蓝星安迪苏南京有限公司 | The stabilizer for preparing and storing for MMP |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19735332A1 (en) * | 1997-08-14 | 1999-02-18 | Degussa | Aliphatic alkanals with improved storage stability and process for improving storage stability |
| EP2813489A1 (en) * | 2013-06-11 | 2014-12-17 | Evonik Degussa GmbH | Method for the preparation of storage-stable 3-methylmercaptopropionaldehyde |
| EP3339290B1 (en) * | 2016-12-22 | 2019-06-19 | Evonik Degussa GmbH | Storage of 3-methylthiopropionaldehyde and methyl mercaptan |
| EP3656760A1 (en) | 2018-11-21 | 2020-05-27 | Evonik Operations GmbH | Storage stable form of 3-methylthiopropionaldehyde |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL302251A (en) * | 1963-01-28 | 1965-10-11 | ||
| US4414419A (en) * | 1979-02-12 | 1983-11-08 | Ruhrchemie Aktiengesellschaft | Stabilization of aldehydes |
| US4546205A (en) * | 1982-06-16 | 1985-10-08 | Pennwalt Corporation | Stabilization of aldehydes |
| EP0148648B2 (en) * | 1984-01-04 | 1995-01-18 | Shin-Etsu Chemical Co., Ltd. | A method for stabilizing aliphatic higher aldehyde compounds |
-
1991
- 1991-12-26 BR BR919105694A patent/BR9105694A/en not_active Application Discontinuation
-
1992
- 1992-12-22 JP JP5511322A patent/JPH06506001A/en active Pending
- 1992-12-22 WO PCT/BR1992/000020 patent/WO1993013059A1/en active Application Filing
- 1992-12-22 CA CA 2103796 patent/CA2103796A1/en not_active Abandoned
- 1992-12-26 CN CN 92115231 patent/CN1077708A/en active Pending
- 1992-12-28 MX MX9207585A patent/MX9207585A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903197A (en) * | 2017-12-22 | 2018-04-13 | 蓝星安迪苏南京有限公司 | The stabilizer for preparing and storing for MMP |
| CN107903197B (en) * | 2017-12-22 | 2018-12-14 | 蓝星安迪苏南京有限公司 | The stabilizer for preparing and storing for 3- methylthiopropionaldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06506001A (en) | 1994-07-07 |
| WO1993013059A1 (en) | 1993-07-08 |
| MX9207585A (en) | 1994-06-30 |
| CA2103796A1 (en) | 1993-06-27 |
| BR9105694A (en) | 1993-06-29 |
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