CN104649913B - N-alkylaminomethyl aniline and synthesis, its polymer and for Metal surface anti-corrosion - Google Patents
N-alkylaminomethyl aniline and synthesis, its polymer and for Metal surface anti-corrosion Download PDFInfo
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Abstract
The invention discloses N alkylaminomethyl aniline and synthesis, its polymer and for Metal surface anti-corrosion.After utilizing amine inhibitor to protonate in acid condition, water solublity strengthens; aniline is in the feature that metal surface absorption affinity is strong and alkyl chain hydrophobicity is strong; synthesize N alkylaminomethyl aniline; polymerisation in solution by N alkylaminomethyl aniline; obtain the corrosion inhibiter of the superior performance of series of new; N alkylaminomethyl aniline is carried out in metal surface in-situ polymerization, forms the polymer coating of densification at metal material surface, thus protect metal material surface not corrode.The present invention is with environmentally friendly MOLECULE DESIGN as theory, its principle is reliable, easy and simple to handle, productivity is higher, environmental protection, the problem solving other Polymer corrosion inhibitor dissolubility being poor, adhesive force is more weak, and make the polymerization process of amino benzenes derivates and metal material anticorrosion occur in the same time in acid condition, it is achieved that effective antiseptical purpose in metal surface.
Description
Technical field
The present invention relates to N-alkylaminomethyl aniline and synthetic method, the preparation of its Polymer corrosion inhibitor, and at metal
The application of (carbon steel) surface anticorrosion, belongs to inhibition field of new.
Background technology
Metal erosion refers to that metal occurs chemistry or electrochemical reaction with the medium in environment about, thus causes metal
Surface or nexine destruction in various degree.Metal erosion phenomenon is widely present the every field of productive life, and its harm is the tightest
Weight.Because of corrosion, non-serviceable metallic article accounts for 1/4th of metal annual production then every year in the world.According to authoritative department report
The economic loss that the road U.S. causes because of corrosion every year is 3 $ 100 billion, and this is equivalent to its gross national product (Gross
National Product, GNP) 1-5%.Britain and Germany account for the 3.5% and 3% of GNP respectively because corroding economic loss.And
China GNP is 1,071,000,000,000 dollars, and corrosion loss accounts for the 6% of GNP.The corrosion loss not only caused economically also results in
Waste on the energy.Ageing equipment is caused not only to cause because of corrosion in the commercial production such as machinery, oil, chemical industry, pesticide
Economic loss is also possible to make hazardous material situations, even causes casualties.Metal erosion and dirt can be substantially reduced the thermal efficiency,
Cause a large amount of wastes of fire coal.China consumes 17,500,000 tons of standard coals much because of metal erosion or dirt reason.And coal is in burning
During can generate the harmful gass such as substantial amounts of fine coal and sulfur dioxide.This Resources for construction economizing type currently proposed with China,
Friendly environment society runs in the opposite direction.Therefore a kind of effective corrosion inhibiter is used to become a kind of imperative trend.
Corrosion inhibiter is a kind of to be present in environment with suitable concentration and form, can stop and slow down the chemicals of corrosion
Matter or the mixture of several chemical substance.It has with low cost, simple to operate, convenient and antiseptic property excellent, therefore it
Become one of focus of Chinese scholars research.Due to the fast development of petroleum industry, it is to the requirement of corrosion inhibiter the most increasingly
High.Therefore the long-acting corrosion inhibiter developing a kind of high temperature peracid becomes one of researcher difficult problem urgently to be resolved hurrily.
Chemical composition according to corrosion inhibiter can be divided into inorganic inhibitor, organic inhibitor, polymerization species to delay corrosion inhibiter
Erosion agent.Inorganic inhibitor application relatively early, it be generate in metal surface passive oxidation film or formed on cathode chamber, metal surface heavy
Shallow lake film thus reach antiseptic effect, such as cadmate, nitrite, Quadrafos, silicate, borate, tungstates and molybdate
Deng.But along with the reinforcement of environmental consciousness, some poisonous and harmful substances are limited even to prohibit the use of.As phosphorus-containing compound can make water
Body eutrophication thus cause red tide, this will bring the disastrous effect that cannot retrieve to rivers and lakes.Chromate, arsenate, stannate
Although having a preferable antiseptic property with inorganic inhibitors such as mercury salts, but its toxicity will be our a great problem that cannot evade.
Rare earth compound is applied to corrosion-resistant field by people recently, but its cost is high, and complex process processes the time long.
Organic inhibitor such as aldehydes, amine, carboxylic acid, heterocyclic compound etc. may be used to corrosion-resistant field, and it is of a great variety,
Excellent performance.It mainly does center polar group by atoms such as bigger P, S, N, the O of electronegativity and C, H etc. are former molecular non-
Polar group is constituted.This kind of corrosion inhibiter has multiple adsorption site.It can be adsorbed in metal surface firmly by adsorption, with
Time molecule in hydrophobic group can orient be arranged in metal surface.And intramolecular or intermolecular easily form substantial amounts of hydrogen
Key is so that adsorption layer thickens.The most effectively retardance H+ ion is close to metal surface.Ambient temperature and pH change are to this kind of slow
Erosion agent impact is less, and this kind of corrosion inhibiter typically has the features such as hypotoxicity.
Along with the development in epoch, the proposition of national sustainable strategy, people start that sight is transferred to low toxicity and plant efficiently
On thing extract.People extract the effective ingredient of corrosion inhibiter from the natural plants such as Folium Camelliae sinensis, Pericarpium Zanthoxyli, peel, phragmites communis.This kind of slow
Erosion agent has turns waste into wealth, with low cost, low toxicity is the most nontoxic, it is achieved the feature such as make full use of of resource.But ground by actual
Studying carefully level to be limited, it is far away away from large-scale application.
Polymer is applied to inhibition field and has the longest history.People are by starch, syrup, Ovum Gallus domesticus album in early days
Be applied to pickling iron and steel corrosion inhibiter etc. various natural polymers, by arabic gum, soluble starch, the contour molecular application of agar in
Aluminium corrosion inhibiter in alkali liquor.New polymers corrosion inhibiter continues to bring out in recent years, demonstrates its superior performance.This is because
Polymer is easy to be formed single or multiple lift densification protecting film in metal surface, and has corrosion inhibition rate height, persistent, the most dirty
The advantages such as dye environment.The heat-resisting ability of general polymerization thing is better than general Organic substance, and this is also that polymer becomes corrosion inhibiter weight
Want a major reason of one of developing direction.At present in high-temperature corrosion inhibitor field, premier is alkynol compound.
This is because three keys are destroyed, and multilayer polymeric film occurs will produce during polymerization, and hydrophobic group has good shielding and makees
With, the two jointly acts on and has been greatly reinforced its corrosion inhibiting ability.But the toxicity of alkynol own is relatively big, and in souring operation easily
Produce volatile toxic gas.
The present invention has synthesized N-alkylaminomethyl aniline and polymer thereof from molecular design theory, makes polymer inhibition
Predicament has been broken away from agent.First, N-alkylaminomethyl aniline polar group centered by the atom N that electronegativity is bigger；Second, N-alkane
Base aminomethyl aniline contains benzene ring structure, i.e. there is big π key；3rd, polyaniline contains non-polar group, alkyl chain.Wherein
One and Article 2 it can be made to form the adsorbed film of densification with metal surface.And Article 3 can make it produce preferably in metal surface
Screen effect, the two produces synergism and has been greatly reinforced its corrosion inhibiting ability.And this Polymer corrosion inhibitor toxicity relatively monomer whose
Toxicity is much lower, and resistance to elevated temperatures is the most higher.
Summary of the invention
It is an object of the invention to provide N-alkylaminomethyl aniline and synthetic method thereof, with environmentally friendly MOLECULE DESIGN
For theory, taking full advantage of water solublity after amine inhibitor protonates in acid condition and strengthen, aniline adsorbs in metal surface
The feature that power is strong and alkyl chain hydrophobicity is strong, has synthesized alkyl benzene amine, and its principle is reliable, and easy and simple to handle, productivity is higher, green ring
Protect.
Another object of the present invention is to provide the polymer of N-alkylaminomethyl aniline, by N-alkylaminomethyl aniline
Polymerisation in solution and obtain, be the corrosion inhibiter of a kind of novel superior performance, solve other Polymer corrosion inhibitor dissolubilities poor,
The problem that adhesive force is more weak, has excellent corrosion inhibition and wide market prospect.
Another object of the present invention also resides in offer and N-alkylaminomethyl aniline is used for Metal surface anti-corrosion, is by N-alkane
Base aminomethyl aniline carries out in-situ polymerization on metal (carbon steel) surface, thus realizes in metal surface effective antiseptical purpose.
For reaching above technical purpose, the present invention provides techniques below scheme.
N-alkylaminomethyl aniline, its structural formula is as follows:
N=6,8,10,12,14,16 or 18.
The polymer of N-alkylaminomethyl aniline, its structural formula is as follows:
R be carbon number be the alkyl of 6,8,10,12,14,16 or 18, k and k ' is polymer chain joint number.
In the present invention, when n is 6,8,10,12,14,16,18, N-alkylaminomethyl aniline is respectively designated as m-6, m-
8, m-10, m-12, m-14, m-16, m-18, the polymer of its correspondence is then p-m-6, p-m-8, p-m-10, p-m-12, p-m-
14、p-m-16、p-m-18。
The synthetic method of N-alkylaminomethyl aniline, comprises the following steps successively:
(1) in round-bottomed flask, add the 6.7g 3-methylol carbanilic acid tert-butyl ester and 17.4g carbon tetrabromide, use
120mL absolute ether makees solvent, is subsequently adding 11.1g triphenylphosphine, stirs 30 minutes, be filtered to remove precipitation, use ether under room temperature
Washing, is so carried out for several times, decompression distillation, solvent evaporated, and residue is crossed post and purified (dichloromethane: normal heptane=1:1), obtains
White powder 3-bromotoluidine base t-butyl formate；
(2) in three-neck flask, add a certain amount of alkylamine and 10-30mL acetonitrile stirred for several minute under the conditions of 80 DEG C,
Then 3-bromotoluidine base t-butyl formate is dissolved in 10-30mL acetonitrile, and it is added dropwise in 30min three
In neck flask, the mol ratio of alkylamine and 3-bromotoluidine base t-butyl formate is 1:1-5:1, reacts 8-14 hour, passes through
TLC monitors reaction, and solvent is evaporated after terminating by reaction, by column chromatography (200-300 mesh silica gel, oil mystery: ethyl acetate=
10:1-40:1 and dichloromethane: MeOH=10:1-40:1 carries out gradient elution) isolated and purified obtain faint yellow solid powder 3-
Alkylaminomethyl anilino-t-butyl formate；
(3) 3-alkylaminomethyl anilino-t-butyl formate is joined in flask, adds 20-50mL ethyl acetate,
Be rapidly added after stirring into homogeneous system a certain amount of HCl, 3-alkylaminomethyl anilino-t-butyl formate and HCl mole
Ratio is 1:2-1:5, by TLC monitoring reaction, reacts 3-8 hour, with NaOH, solution is adjusted to alkalescence, then with 3 × 20mL
Ethyl acetate extracts three times, uses anhydrous Na2SO4It is dried overnight, by column chromatographic isolation and purification (dichloromethane: methanol=5:1-
20:1) obtaining N-alkylaminomethyl aniline, productivity is 91.8%.
Obtaining the polymer of N-alkylaminomethyl aniline by the polymerisation in solution of N-alkylaminomethyl aniline, process is such as
Under: a certain amount of N-alkylaminomethyl aniline is joined in round-bottomed flask, dissolves with methanol, be subsequently adding HCl, N-alkyl ammonia
Monomethylaniline. is 1:4 with the mol ratio of hydrochloric acid, is sufficiently stirred for, is added dropwise in round-bottomed flask by Ammonium persulfate. saturated solution,
N-alkylaminomethyl aniline is 0.5:1-1:1.5 with the mol ratio of Ammonium persulfate., reacts 10-14 hour, uses CH2Cl2Extraction, washes
Washing, decompression distillation for several times, obtains poly-N-alkylaminomethyl aniline.
Preparation N-alkylaminomethyl aniline and polymer thereof, reaction equation is as follows:
(R=C6H13C8H17C10H23C12H25C14H29C16H33C18H37)
(R=C6H13C8H17C10H23C12H25C14H29C16H33C18H37)
N-alkylaminomethyl aniline is used for Metal surface anti-corrosion, is on metal (carbon steel) surface by N-alkylaminomethyl aniline
Carry out in-situ polymerization, form the polymer coating of densification at metal material surface, thus protect metal material surface that corruption does not occur
Erosion, comprises the following steps successively:
(1) by smooth for metal material surface sand papering, rinse with water, acetone and dehydrated alcohol respectively, oil removing defat
And be dried；
(2) in the reactor N-alkylaminomethyl aniline methanol is dissolved, add metal material, be subsequently adding
The HCl of 100mL1-5M, stirring, subsequently the saturated solution of Ammonium persulfate. is added dropwise over reactor, N-alkylaminomethyl aniline with
The mol ratio of Ammonium persulfate. is 0.5:1-1:1.5, reacts 1～5d, after reaction terminates, at metal material surface at 30～90 DEG C
Form uniform black polymer thin film, be drawn off hanging, vacuum drying.
The series polymer corrosion inhibiter corrosion inhibition that the present invention provides is superior, preparation method simple possible, it is easy to operation, produces
Rate is higher, and makes the polymerization process of amino benzenes derivates and metal material anticorrosion occur in the same time in acid condition.
Result shows that amino benzenes derivates at metal material surface generation in-situ polymerization, can form the thin polymer film of even compact, for
Metal material provides preferably protection, relative to rubbing method, greatly reducing the usage amount of corrosion inhibiter.
Compared with prior art, the method have the advantages that
(1) low cost, easy to use.Corrosion inhibiter is the poly-N-alkylaminomethyl aniline that solution polymerization obtains, or former
The N-alkylaminomethyl aniline coating that position polymerization obtains, anil monomer preparation process is simple, and cheaper starting materials is easy to get, poly-
Conjunction reaction is susceptible to；Under acid condition, form the coating of densification at metal material surface in-situ polymerization, and can ensure that gold
Belong to material not corrode, can be widely applied to the anticorrosion of metal material under acid condition.
(2) green non-pollution, environmental friendliness.Corrosion inhibiter in the present invention is organic polymer, nontoxic, after using not
Can be a kind of green corrosion inhibitor to human body and environmental pollution.
(3) consumption is low, and corrosion inhibition is high and stable.Experiment proves to add the corrosion inhibiter in a small amount of present invention, at high temperature or
In the environment of person's peracid, effective protection of long period can be provided for metal material.Example hydrochloric acid concentration 1-5M, temperature 30-
90 DEG C, 1-5 days persistent period.
Accompanying drawing explanation
Fig. 1 is the infared spectrum of m-6
Fig. 2 is m-61HNMR collection of illustrative plates
Fig. 3 is m-613CNMR collection of illustrative plates
Fig. 4 is the mass spectrum of m-6
Fig. 5 is the mass spectrum (low molecular weight part) of P-m-6
Fig. 6 is the mass spectrum (high molecular weight moieties) of P-m-6
Fig. 7 is that in-situ polymerization thing corrosion inhibition rate is with temperature and the variation relation figure (concentration of hydrochloric acid 1M) of different soak time
Fig. 8 is that in-situ polymerization thing corrosion inhibition rate is with concentration of hydrochloric acid and the variation relation figure (30 DEG C) of different soak time
Fig. 9 is 90 DEG C, 12 hours, and in-situ polymerization thing corrosion inhibition rate is with the variation diagram of monomer consumption
Figure 10 is that the corrosion inhibition rate of polymer is with temperature and the variation relation figure (concentration of hydrochloric acid 5M) of different soak time
Figure 11 is the thermogravimetric analysis comparison diagram of m-8 and p-m-8
Figure 12 is the difference quotient thermogravimetric analysis comparison diagram of m-8 and p-m-8
Detailed description of the invention
Being specifically described the present invention below by embodiment, the present embodiment is served only for carrying out the present invention further
Illustrate, but it is not intended that limiting the scope of the invention, those skilled in the art makes according to foregoing
Nonessential improvement and adjustment fall within the scope of protection of the invention.
One, N-alkylaminomethyl aniline and the preparation of polymer thereof
Embodiment 1 3-((n-hexyl amino) methyl) aniline (brief note m-6) and the preparation of polymer (brief note p-m-6) thereof
In 200mL round-bottomed flask, add 6.7g tert-butyl group 3-hydroxy carbamate and 17.4g carbon tetrabromide, use
120mL absolute ether makees solvent, is subsequently adding 11.1g triphenylphosphine, stirs 30 minutes, be filtered to remove precipitation, use ether under room temperature
Washing, is so carried out for several times, decompression distillation, solvent evaporated, and residue is crossed post purification (dichloromethane: normal heptane=1:1) and obtained
White powder tert-butyl group 3-bromo carbamate.
2.77mL n-hexylamine and 10mL acetonitrile, stirred for several minute under the conditions of 80 DEG C is added in 50mL round-bottomed flask.So
After 2g tert-butyl group 3-bromo carbamate and 20mL acetonitrile are joined in constant pressure funnel.By the tert-butyl group in 30min
3-bromo carbamate is added drop-wise in round-bottomed flask.By TLC monitoring reaction, solvent is spin-dried for after terminating by reaction.Use 200-
300 mesh silicagel columns, eluant is petroleum ether: ethyl acetate=20:1 and dichloromethane: methanol=20:1 carries out gradient elution) point
Pressed powder is obtained from purification.Pass through1HNMR、13CNMR carries out sign and determines its structure, and its productivity is 87%.
1.25g product after purification is joined in 50mL round-bottomed flask, is subsequently adding 30mL ethyl acetate.When stirring into
The dense HCl of 2.4mL it is rapidly added after homogeneous system.By TLC monitoring reaction, react addition 10mL tri-in complete backward reaction system
Secondary distilled water.Then with 5M NaOH, solution is adjusted to alkalescence, then extracts three times by 3 × 20mL ethyl acetate.With anhydrous
Na2SO4 is dried overnight, and with dichloromethane: methanol=10:1 carries out column chromatography, its productivity is 85%.
Prepared by metal material: use X70 carbon steel, and other metal material processes by same method.By size be 3cm ×
The X70 carbon steel of 1.5cm × 0.3cm, successively with 200#, the sand papering of 800#, 1200# is smooth, rinses well, so with three water
Afterwards with acetone and dehydrated alcohol defat, after hot blast drying, it is placed in vacuum drying oven standby.
By 3.4mM m-6 after purification, dissolve with 2mL ethanol, join in the reactor of 200mL, add standby
X70 steel disc, stands 10min, is subsequently adding the HCl of 100mL variable concentrations, stirring, subsequently saturated molten by the Ammonium persulfate. of 4mM
Liquid is added dropwise over reactor, at 30-90 DEG C, reacts 1-5 days, after reaction terminates, is formed the most black at metal material surface
Color thin polymer film, is drawn off hanging, vacuum drying.CH is added in reactant liquor2Cl2Extract black liquor, revolve further
Dry obtain polyaniline corrosion inhibiter.
In said method, the thin film of metal surface and the polymer extracted are N-alkylaminomethyl aniline corrosion inhibiter,
If being not added with standby X70 steel disc, m-6 can also direct polymerization, obtain p-m-6.
In kind obtain m-8, p-m-8 etc..
Two, the structural characterization (as a example by m-6 and p-m-6) of N-alkylaminomethyl aniline and polymer thereof
Fig. 1 is the infared spectrum of m-6, infrared (KBr, the cm of m-6-1) spectrum analysis is shown in Table 1.
Fig. 2 is m-61HNMR collection of illustrative plates, the hydrogen spectrum parsing of m-6 is shown in Table 2.
Fig. 3 is m-613CNMR collection of illustrative plates, the carbon spectrum parsing of m-6 is shown in Table 3.
Infrared (KBr, the cm of table 1 m-6-1) spectrum analysis
| cm-1. | Ownership |
| 3439,3354 | NH2 |
| 2926,2854 | CH3,CH2 |
| 1620,1590 | Phenyl ring |
| 1297 | C-N |
| 760,687 | Phenyl ring |
The hydrogen spectrum of table 2 m-6 resolves
The carbon spectrum of table 3 m-6 resolves
| δppm | Ownership |
| 146.68,139.76,129.40,118.69,115.09,114.13 | Phenyl ring C |
| 53.41 | The C that phenyl ring is ined succession |
| 48.89 | First C that secondary amine is ined succession |
| 31.68,29.26,26.94,22.60 | Four C on alkyl chain |
| 14.04 | Terminal methyl group C |
Fig. 4 is the mass spectrum of m-6, and wherein vertical coordinate is the relative intensity of fragment ion, and abscissa is molecular ion peak
Position, i.e. molecular weight.Being 207.1836 by analyzing the molecular weight understanding m-6 in figure, what we calculated with reality differs minimum.
Above-mentioned spectral data analysis, the product synthesized by explanation is target product m-6.
Fig. 5-6 is the mass spectrum of P-m-6, analyzes collection of illustrative plates and understands, and recording molecular weight 613.4673 is trimer, 814.8044
For the tetramer.
According to mass spectrum and ir data analysis result, the polymer synthesized by explanation is target product.
Three, the performance evaluation (as a example by m-6 and p-m-6, m-8 and p-m-8) of N-alkylaminomethyl aniline and polymer thereof
The present invention, according to GB10124-88 " metal material laboratory homogeneous corrosion soaks experimental technique entirely ", uses dynamic weight loss
In weight-loss method detection in-situ polymerization corrosion process, the polymer coating of the formation corrosion inhibition to X70 steel disc.
Etchant solution used by the present invention is obtained with three water dilutions by the concentrated hydrochloric acid of 37%, and concentration is 1M, 3M, 5M.
Experimental technique is following (weight-loss method):
1, in-situ polymerization corrosion experiment
The preparation of metal material
The metal material of this experiment uses X70 steel disc, and other metal material processes by same method.X70 steel disc is successively
With 200#, the sand papering of 800#, 1200# is smooth, rinses well with three water, then with acetone and dehydrated alcohol defat, and heat
After wind is dry, accurately measures its size with slide gauge, more accurately weigh up its weight with electronic balance, be placed in vacuum drying oven
Standby.
2, in-situ polymerization experiment
By 3.4mM N-alkylaminomethyl aniline, dissolve with 2mL ethanol, join in the reactor of 200mL, add gold
Belong to material, stand 10min, be subsequently adding the HCl of 100mL variable concentrations, stirring, subsequently by the saturated solution of the APS of 4mM dropwise
Add reactor, at 30 DEG C, 60 DEG C, at 90 DEG C, react 1d, 3d, 5d.Doing blank experiment, blank experiment is identical simultaneously
Under the conditions of steel disc is immersed in HCl solution.
After experiment terminates, from solution, take out steel disc, with three distilled water flushings, then with washes of absolute alcohol, to remove
Remove to cover the polymer coating on steel disc surface, and corrosion product, place into oil removing in acetone, then dry up with warm braw and claim
Weight.According to the weight loss of X70 steel disc, its corrosion rate V (g/cm in hydrochloric acid can be calculated2And inhibition efficiency .d)
IE%.Do three groups of parallel tests simultaneously, average as test result.
According to previous experiments method, test in in-situ polymerization corrosion process, form the corrosion inhibition of corrosion inhibiter coating.
When Fig. 7 is to form N-alkylaminomethyl aniline coating, corrosion inhibiter inhibition efficiency is with temperature and different etching times
Variation relation figure (P-m-6).In figure, vertical coordinate is corrosion inhibition rate (IE%), and abscissa is temperature (DEG C), as can be seen from Figure, former
Position polymerization corrosion process in, formed N-alkylaminomethyl aniline corrosion inhibiter in higher temperature and in the longer time, Ke Yiwei
The protected effect that metal material provides, 90 DEG C, after 5 days, p-m-6 is 98% to the corrosion inhibition rate of X70 steel.
When Fig. 8 is to be formed in situ poly-N-alkylaminomethyl aniline coating, corrosion inhibiter inhibition efficiency is with concentration of hydrochloric acid and difference
The variation relation figure (P-m-8) of etching time.In in-situ polymerization corrosion process, form N-alkylaminomethyl aniline corrosion inhibiter relatively
Under strong acid condition, can provide preferably protection to metal material, in the hydrochloric acid solution of 5mol/L, after 5 days, p-m-8's is slow
Erosion rate is still up to 98%.
Fig. 9 is the corrosion inhibition rate of p-m-8 and the graph of a relation of monomer (m-8) consumption in 90 DEG C and 5M hydrochloric acid, is not difficult to find out at m-8
When consumption is 1g, soaking 12 hours in 5M hydrochloric acid, the corrosion inhibition rate of in-situ polymerization thing is 98%.
3, polymer solution corrosion experiment
In the conical flask of 100mL, load the hydrochloric acid of 100mL5mol/L, be subsequently added the corrosion inhibiter of variable concentrations so that it is
Concentration is 0-90ppm, by the size of vernier caliper measurement steel disc, accurately claims its quality subsequently with electronic balance, by steel disc with thin
Rope is put on, and is suspended from solution, and ensures solution submergence steel disc, uses water-bath constant temperature, soaks 3h at 30,60,90 DEG C.
Distilled water, dehydrated alcohol are used in experiment successively after terminating, acetone cleans steel disc, weighs, according to X70 steel after hot blast drying
Mass loss calculate corrosion inhibition rate (IE%) and corrosion rate V (g/cm2h), carry out three groups of parallel laboratory tests simultaneously, average
For end product.
Figure 10 illustrates polymer (p-m-8) the solution corrosion inhibition situation to X70 steel.It is not difficult to find out, along with polymer is dense
Degree increases, and corrosion inhibition rate increases, and soaks 3 hours in 90 DEG C and 5M hydrochloric acid, and corrosion inhibition rate is 94.9%.
These results suggest that p-m-n of the present invention can be metal material under higher temperature and stronger acid condition
Protection for a long time is provided.The polymeric film especially formed at steel in situ Polymerization shows more preferable resistance to higher than polymer
Gentle highly acidity and the ability of persistently suppression corrosion of steel.
Figure 11 and Figure 12 is m-8 and p-m-8 thermogravimetric analysis and difference quotient thermogravimetric analysis contrast respectively.As can be seen from the figure with
The speed raising monomer mass loss of temperature apparently higher than polymer.And monomer has damaged when temperature reaches 600 DEG C
Lose totally, and polymer still has the remnants of 16.15%.This also further illustrates the heat-resisting ability of poly-N-alkylaminomethyl aniline
It is better than monomer.
Claims (3)
- The synthetic method of 1.N-alkylaminomethyl aniline, comprises the following steps successively:(1) in round-bottomed flask, add the 6.7g 3-methylol carbanilic acid tert-butyl ester and 17.4g carbon tetrabromide, with 120mL without Water ether makees solvent, is subsequently adding 11.1g triphenylphosphine, stirs 30 minutes, be filtered to remove precipitation under room temperature, washs with ether, subtracts Pressure distillation, solvent evaporated, residue is crossed post and is purified, obtains 3-bromotoluidine base t-butyl formate；(2) in three-neck flask, a certain amount of alkylamine and 10-30mL acetonitrile stirred for several minute under the conditions of 80 DEG C is added, then 3-bromotoluidine base t-butyl formate is dissolved in 10-30mL acetonitrile, and it is added dropwise in 30min three necks burnings In Ping, the mol ratio of alkylamine and 3-bromotoluidine base t-butyl formate is 1:1-5:1, reacts 8-14 hour, will after terminating Solvent is evaporated, and obtains 3-alkylaminomethyl anilino-t-butyl formate by column chromatographic isolation and purification, and described alkylamine is RNH2, R=C6H13、C8H17、C10H23、C12H25、C14H29、C16H33Or C18H37；(3) 3-alkylaminomethyl anilino-t-butyl formate is joined in flask, add 20-50mL ethyl acetate, when stirring The mol ratio being rapidly added a certain amount of HCl, 3-alkylaminomethyl anilino-t-butyl formate and HCl after mixing homogeneous system is 1:2-1:5, reacts 3-8 hour, with NaOH, solution is adjusted to alkalescence, extraction, is dried, obtains N-by column chromatographic isolation and purification Alkylaminomethyl aniline, its structural formula is as follows:N=6,8,10,12,14,16 or 18.
- The preparation method of the polymer of 2.N-alkylaminomethyl aniline, process is as follows: by the side described in a certain amount of claim 1 The N-alkylaminomethyl aniline of method synthesis joins in round-bottomed flask, dissolves with methanol, is subsequently adding HCl, N-alkylaminomethyl Aniline is 1:4 with the mol ratio of hydrochloric acid, is added dropwise in round-bottomed flask by Ammonium persulfate. saturated solution, N-alkylaminomethyl benzene Amine is 0.5:1-1:1.5 with the mol ratio of Ammonium persulfate., reacts 10-14 hour, uses CH2Cl2Extraction, washing, decompression distillation, To poly-N-alkylaminomethyl aniline.
- 3. utilize the N-alkylaminomethyl aniline that the method described in claim 1 synthesizes for Metal surface anti-corrosion, be by N-alkane Base aminomethyl aniline carries out in-situ polymerization in metal surface, forms the polymer coating of densification at metal material surface, wraps successively Include following steps:(1) by smooth for metal material surface sand papering, rinsing with water, acetone and dehydrated alcohol respectively, oil removing defat is also done Dry；(2) in the reactor N-alkylaminomethyl aniline methanol is dissolved, add metal material, be subsequently adding 100mL1- The HCl of 5M, stirring, the saturated solution of Ammonium persulfate. is added dropwise over reactor, N-alkylaminomethyl aniline and Ammonium persulfate. Mol ratio is 0.5:1-1:1.5, reacts 1～5d, after reaction terminates, formed uniformly at metal material surface at 30～90 DEG C Black polymer thin film.
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