CN106350036A - Alkyl tetramine synthesis method, alkyl tetramine product and shale inhibitor thereof - Google Patents
Alkyl tetramine synthesis method, alkyl tetramine product and shale inhibitor thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/12—Formation of amino and carboxyl groups
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Abstract
The invention relates to an alkyl tetramine synthesis method, an alkyl tetramine product and a shale inhibitor thereof. The synthesis method comprises the following steps of S1, amino acid synthesis; S2, esterification reaction; S3, ammonia transesterification; S4, Hofmann degradation reaction; S5, BOC removal protection. The alkyl tetramine product prepared by the method has the molecular structural formula shown as the accompanying drawing; the alkyl tetramine product and clear water are prepared into the shale inhibitor according to the proportion of 1 to 3 percent. The synthesis method provided by the invention is reliable; the synthesis yield is high; the raw material price is low; the production cost is low; the product is safe, achieves the environment-friendly effects, and is suitable for large-scale industrial production. The alkyl tetramine product is nontoxic and harmless and has good water solubility; the inhibition performance is obviously improved through being compared with that of similar products; meanwhile, the temperature-resistant capability reaches 240 DEG C; the product is particularly suitable for ultra-high-temperature deep well drilling.
Description
Technical field
The invention belongs to oilfield drilling technical field is and in particular to a kind of a kind of alkyl being applied to complicated shale drilling well
Synthetic method of tetramine shale control agent and products thereof, and the shale control agent using the configuration of alkyl tetramine.
Background technology
At present at home with external drilling well in, be frequently present of borehole instability problems.Hole instability may result in well
Wall caves in, undergauge, bit freezing the problems such as, increased drilling time and drilling cost.75% hole instability occurs mainly in mud
Shale formation, particularly water-sensitive strata.
China's shale gas resources exploration is in full swing, and for the accumulation feature of shale gas, horizontal well has become page
The main drilling mode of rock gas exploitation.Compared with conventional horizontal well, shale horizontal well horizontal segment is longer, it is typically in the range of 500～
2500m, the time that drilling fluid is contacted with stratum increases, and Shale Hydration is more serious.Drilling fluid filtrate enters layer reason gap, shale
Interior clay mineral water-swellable, the bulbs of pressure make tension force increase, and lead to shale formation (locally) tensile fracture, the borehole wall and collapse
Collapse, the down hole problem such as undergauge.60～70% external shale gas horizontal wells adopt oil base drilling fluid system, domestic complete
Shale gas horizontal well is most to adopt oil base drilling fluid system, oil base drilling fluid has that borehole wall stability is good, rejection ability is strong,
Lubricity is good, be conducive to protect reservoir advantage, but exist not environmentally, cost of a relatively high the shortcomings of.Water-base drilling fluid is proper
The shortcoming that oil base drilling fluid can be overcome well.
Inorganic salt is mainly adopted on oil field as inhibitor at this stage, but the inorganic salt of high concentration not only has a strong impact on
The rheological characteristic of drilling fluid, and underground environment is caused with serious pollution, widely used water-base drilling fluid pair at this stage simultaneously
Mud stone or strong retraction shale formation wellbore stability aspect yet suffer from problem, it is desirable to have pointedly further investigate.And with
The development of ultradeep well exploration and development, the research and development to shale control agent are put forward higher requirement.Due to using water-based drilling liquid
Shale gas horizontal well bores in system, and water is contacted with stratum at first, leads to the clay hydration swelling on stratum, and the aquation in order to suppress clay is swollen
Swollen, shale control agent must be rapidly inserted into clay interlayer, the hydrone of extrusion clay interlayer, reduces interlamellar spacing.Research finds, tool
There is multiple primary amine group inhibitor can increase the water solublity of inhibitor, and multiple primary amine group can make inhibitor brilliant with clay
It is more firm that layer adsorbs.The inhibition that alkyl chain improves inhibitor as hydrophobic chain is increased by portion in the molecular structure
Energy.And different alkyl hydrophobic chains has different performances for the effect of inhibitor, find and to synthesize performance more preferably more suitable
Close the alkyl hydrophobic chain product of complex hole condition, for raising shale drilling efficiency, ensure that drilling safety makes great sense.
Content of the invention
For the problems referred to above, it is an object of the invention to provide a kind of synthetic method of alkyl tetramine shale control agent, its
The drilling fluid additive of obtained product configuration can fully meet the drilling well demand of various complex hole condition, effectively reduce by
The problem disperseing in shale hydration hole instability；Synthetic method provided by the present invention is reliable, synthetic yield is higher,
Cost of material is cheap, low production cost, product safety environmental protection, suitable large-scale industrial production.
Technical scheme is as follows:
A kind of synthetic method of alkyl tetramine, step is as follows:
S1, the synthesis of aminoacid
S1.1, the metallic sodium of 0.2～0.21mol is taken to be dissolved in absolute ethanol (purity be more than 99.99%), by Sodium ethylate
Solution is added dropwise in the ethanol solution of the diethyl acetamido of 0.2mol, at the uniform velocity stirs 1～1.5h；
S1.2, the alkyl dibromide of 0.1～0.11mol is added dropwise in the solution obtained by step s1.1, backflow is anti-
Answer 5.5～7h, after completion of the reaction, filter, revolving；
S1.3, the solution being obtained in step s1.2 add 46～49% hydrogen bromide solution 100ml, and back flow reaction 7～
8h；
S1.4, revolving remove the hydrogen bromide solution in obtained solution in s1.3, by crude product dissolving in ethanol, according still further to
Volume ratio adds the ethanol pyridine solution no less than 50% ratio, stands 12h, sucking filtration, obtains amino acid products；
S2, esterification
S2.1, take in 5mmol step s1 be obtained amino acid products add 250ml single-necked flask in, then successively plus
Enter 100ml ethanol and 4～6ml concentrated sulphuric acid, back flow reaction 5～7h, revolving falls solvent；
S2.2, the crude product amino ethyl ester hydrochlorate that step s2.1 is obtained put into dissolving stirring in 100ml dichloromethane,
Then weigh Bis(tert-butoxycarbonyl)oxide 10～20mmol, same dissolving stirring, in dichloromethane, dropwise adds under condition of ice bath
Enter in aminoethyl, be subsequently added into 0.08～0.15mmol dmap (DMAP), then even at ambient temperature
Speed stirring 16h；Continue the Bis(tert-butoxycarbonyl)oxide of 15mmol is dissolved in dichloromethane, add 0.09～0.12mmol
Dmap, continues at the uniform velocity to stir 48h at ambient temperature；
S2.3, add saturated sodium bicarbonate solution and saturated nacl aqueous solution to solution obtained by step s2.2, separating has
Machine layer, is dried with anhydrous magnesium sulfate, then passes through to filter, distills the amino ethyl ester obtaining the double protection of boc；
S3, urethane exchange reaction
The amino ethyl ester of double for the 5mmol boc being obtained in step s2 protections is dissolved in 50ml thf (oxolane),
Add 100ml methanolic ammonia solution, add 0.5g Feldalat NM, stoppered with flanging rubber plug, acutely stir under 50 DEG C of water bath condition
Mix 24h, vacuum distillation removes solvent, obtain the amino amides product of the double protection of boc；
S4, hofmann degradation reaction
Take 8mmol sodium hydroxide to be dissolved in 100ml pure water, add 2.1～2.3mmol bromine under condition of ice bath, stir
Mix 10min, the amino amides of double for the boc being obtained in step s3 protections is added reactant liquor, even under 25～35 DEG C of room temperature environments
Speed stirring 2h, is warming up to 80 DEG C of reaction 30min, filtrate chloroform extraction, extraction phase evaporation crystallizes after removing partial solvent.
S5, de- boc protection
By the mixed solution of the trifluoroacetic acid of 18mmol and 20ml dichloromethane be added in 4mmol step s4 be obtained
In the alkylamine of boc protection, 1h is stirred at room temperature, reaction stops, rotary evaporation.Surplus materialss are added appropriate ethyl acetate
Middle dissolving, using the na of 5% concentration2co3It is 8～9 that solution washs to ph, removes solvent, obtains final products alkyl tetramine.
Further, the molecular structural formula of the alkyl dibromide in described step s1.2 is:
Wherein, n is 2～10.
Further, in described step s1.2, alkyl dibromide is glycol dibromide, 1,3- dibromopropane Isosorbide-5-Nitrae-dibromo fourth
Any one in alkane.
Further, in described step s1.4, it is 60% according to the ethanol pyridine solution that volume ratio adds.
Further, the synthesis technique flow process of the present invention is shown below:
According to the technique of described step, the yield rate of final product is 65～73%.
Molecular structural formula using the alkyl tetramine synthesized by this method is:
Alkyl four amine product of gained is colourless liquid, needs to preserve using vacuum mode after producing.
Further, described alkyl four amine product and clear water are configured to shale control agent, alkyl four amine product in its proportioning
The ratio of weight ratio is 1～3%.
It is an advantage of the current invention that:
1st, the synthetic method of the present invention consistent reliable, yield is higher, the low in raw material price needed for sinteticses, fit
Preferably industrialized production；
Alkyl four amine product of the method synthesis the 2nd, being provided using the present invention is nontoxic, water solublity is good, rejection
It is obviously improved compared to like product, temperature resistance ability reaches 240 DEG C simultaneously, be particularly suitable for the drilling well of superhigh temperature deep-well.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but does not constitute any limit to the present invention
System.
If unspecified, the percentage sign " % " being related in embodiment is mass percent.
If unspecified, the chemical article being related in embodiment is technical grade articles for use, and can obtain from conventional meanses
?.
Embodiment 1
Using following ratio and step, synthesis of alkyl tetramine, step is as follows:
S1, the synthesis of aminoacid
S1.1, take the metallic sodium of 0.2mol to be dissolved in absolute ethanol, alcohol sodium solution is added dropwise to 0.2mol's
In the ethanol solution of diethyl acetamido, at the uniform velocity stir 1h；
S1.2, the glycol dibromide of 0.1mol is added dropwise in the solution obtained by step s1.1, back flow reaction
5.5h, after completion of the reaction, filters, revolving；
S1.3, the solution being obtained in step s1.2 add 46% hydrogen bromide solution 100ml, back flow reaction 7h；
S1.4, revolving remove the hydrogen bromide solution in obtained solution in s1.3, by crude product dissolving in ethanol, according still further to
Volume ratio adds the ethanol pyridine solution of 55% ratio, stands 12h, sucking filtration；
S2, esterification
S2.1, take in 5mmol step s1 be obtained aminoacid add 250ml single-necked flask in, then sequentially add
100ml ethanol and 4ml concentrated sulphuric acid, back flow reaction 5h, revolving falls solvent；
S2.2, the crude product amino ethyl ester hydrochlorate that step s2.1 is obtained put into dissolving stirring in 100ml dichloromethane,
Then weigh Bis(tert-butoxycarbonyl)oxide 10mmol, same dissolving stirring, in dichloromethane, is added dropwise under condition of ice bath
In aminoethyl, it is subsequently added into 0.08mmol dmap, then at the uniform velocity stir 16h at ambient temperature；Continue the two of 15mmol
Dimethyl dicarbonate butyl ester is dissolved in dichloromethane, adds 0.09mmol dmap, continues at the uniform velocity to stir 48h at ambient temperature；
S2.3, add saturated sodium bicarbonate solution and saturated nacl aqueous solution to solution obtained by step s2.2, separating has
Machine layer, is dried with anhydrous magnesium sulfate, then passes through to filter, distills the amino ethyl ester obtaining the double protection of boc；
S3, urethane exchange reaction
The amino ethyl ester of double for the 5mmol boc being obtained in step s2 protections is dissolved in 50ml thf, adds 100ml ammonia
Methanol solution, adds 0.5 Feldalat NM, is stoppered with flanging rubber plug, is stirred vigorously 24h under 50 DEG C of water bath condition, and decompression is steamed
Evaporate and remove solvent, obtain the amino amides product of the double protection of boc；
S4, hofmann degradation reaction
Take 8mmol sodium hydroxide to be dissolved in 100ml pure water, under condition of ice bath, add 2.1mmol bromine, stirring
10min, the amino amides of double for the boc being obtained in step s3 protections is added reactant liquor, at the uniform velocity stirs 2h at 25 DEG C, be warming up to 80
DEG C reaction 30min, filtrate chloroform extraction, extraction phase evaporation remove partial solvent after crystallize.
S5, de- boc protection
The mixed solution of the trifluoroacetic acid of 18mmol and 20ml dichloromethane is added to the alkylamine of 4mmolboc protection
In, 1h is stirred at room temperature, reaction stops, rotary evaporation.Surplus materialss are added dissolving in appropriate ethyl acetate, using 5%
Na2co3It is 8 that solution washs to ph, removes solvent, obtains final products 1, Isosorbide-5-Nitrae, 4- fourth tetramine (c4h14n4), structural formula is such as
Under:
Obtained product is colourless liquid, and its yield is 65%.
Performance characterization: by the alkyl tetramine (c to synthesis4h14n4) carry out molecular weight and mesh that LC-MS records product
The molecular weight of mark product is identical.Also confirm that product is exactly target product by the hydrogen spectrum and carbon spectrum measuring nuclear magnetic resonance, NMR.
1h nmr(dmso-d6)δ:3.97(s,2h,ch),1.75(s,4h,ch2),1.11(s,8h,nh2).13c nmr
(dmso-d6)δ:63.2(ch),35.4(ch2).lc-ms(esi):118.12[m+h]+.
Embodiment 2:
Using following ratio and step, synthesis of alkyl tetramine, step is as follows:
S1, the synthesis of aminoacid
S1.1, take the metallic sodium of 0.21mol to be dissolved in absolute ethanol, alcohol sodium solution is added dropwise to 0.2mol's
In the ethanol solution of diethyl acetamido, at the uniform velocity stir 1.5h；
S1.2,1, the 3- dibromopropane of 0.11mol is added dropwise in the solution obtained by step s1.1, back flow reaction
7h, after completion of the reaction, filters, revolving；
S1.3, the solution being obtained in step s1.2 add 49% hydrogen bromide solution 100ml, back flow reaction 8h；
S1.4, revolving remove the hydrogen bromide solution in obtained solution in s1.3, by crude product dissolving in ethanol, according still further to
Volume ratio adds the ethanol pyridine solution of 65% ratio, stands 12h, sucking filtration；
S2, esterification
S2.1, take in 5mmol step s1 be obtained aminoacid add 250ml single-necked flask in, then sequentially add
100ml ethanol and 4～6ml concentrated sulphuric acid, back flow reaction 7h, revolving falls solvent；
S2.2, the crude product amino ethyl ester hydrochlorate that step s2.1 is obtained put into dissolving stirring in 100ml dichloromethane,
Then weigh Bis(tert-butoxycarbonyl)oxide 20mmol, same dissolving stirring, in dichloromethane, is added dropwise under condition of ice bath
In aminoethyl, it is subsequently added into 0.15mmol dmap, then at the uniform velocity stir 16h at ambient temperature；Continue the two of 15mmol
Dimethyl dicarbonate butyl ester is dissolved in dichloromethane, adds 0.12mmol dmap, continues at the uniform velocity to stir 48h at ambient temperature；
S2.3, add saturated sodium bicarbonate solution and saturated nacl aqueous solution to solution obtained by step s2.2, separating has
Machine layer, is dried with anhydrous magnesium sulfate, then passes through to filter, distills the amino ethyl ester obtaining the double protection of boc；
S3, urethane exchange reaction
The amino ethyl ester of double for the 5mmol boc being obtained in step s2 protections is dissolved in 50ml thf, adds 100ml ammonia
Methanol solution, adds 0.5 Feldalat NM, is stoppered with flanging rubber plug, is stirred vigorously 24h under 50 DEG C of water bath condition, and decompression is steamed
Evaporate and remove solvent, obtain the amino amides product of the double protection of boc；
S4, hofmann degradation reaction
Take 8mmol sodium hydroxide to be dissolved in 100ml pure water, under condition of ice bath, add 2.3mmol bromine, stirring
10min, the amino amides of double for the boc being obtained in step s3 protections is added reactant liquor, at the uniform velocity stirs 2h at 35 DEG C, be warming up to 80
DEG C reaction 30min, filtrate chloroform extraction, extraction phase evaporation remove partial solvent after crystallize.
S5, de- boc protection
The mixed solution of the trifluoroacetic acid of 18mmol and 20ml dichloromethane is added to the alkylamine of 4mmol boc protection
In, 1h is stirred at room temperature, reaction stops, rotary evaporation.Surplus materialss are added dissolving in appropriate ethyl acetate, using 5%
Na2co3It is 9 that solution washs to ph, removes solvent, obtains final products 1,1,5,5- penta tetramine (c5h16n4), structural formula is such as
Under.
Obtained product is colourless liquid, and its yield is 68%.
Performance characterization: by the alkyl tetramine (c to synthesis5h16n4) carry out molecular weight and mesh that LC-MS records product
The molecular weight of mark product is identical.Also confirm that product is exactly target product by the hydrogen spectrum and carbon spectrum measuring nuclear magnetic resonance, NMR.
1hnmr(dmso-d6)δ:3.91(s,2h,ch),1.75(s,4h,ch2),1.31(s,2h,ch2),1.12(s,8h,
nh2).13c nmr(dmso-d6)δ:63.5(ch),36.0(ch2),20.4(ch2).lc-ms(esi):132.14[m+h]+.
Embodiment 3
Using following ratio and step, synthesis of alkyl tetramine, step is as follows:
S1, the synthesis of aminoacid
S1.1, take the metallic sodium of 0.202mol to be dissolved in absolute ethanol, alcohol sodium solution is added dropwise to 0.2mol
The ethanol solution of diethyl acetamido in, at the uniform velocity stir 1h；
S1.2, the Isosorbide-5-Nitrae-dibromobutane of 0.105mol is added dropwise in the solution obtained by step s1.1, backflow is anti-
Answer 6h, after completion of the reaction, filter, revolving；
S1.3, the solution being obtained in step s1.2 add 48% hydrogen bromide solution 100ml, back flow reaction 7h；
S1.4, revolving remove the hydrogen bromide solution in obtained solution in s1.3, by crude product dissolving in ethanol, according still further to
Volume ratio add 60% ratio ethanol pyridine solution, stand 12h, sucking filtration；
S2, esterification
S2.1, take in 5mmol step s1 be obtained aminoacid add 250ml single-necked flask in, then sequentially add
100ml ethanol and 5ml concentrated sulphuric acid, back flow reaction 6h, revolving falls solvent；
S2.2, the crude product amino ethyl ester hydrochlorate that step s2.1 is obtained put into dissolving stirring in 100ml dichloromethane,
Then weigh Bis(tert-butoxycarbonyl)oxide 15mmol and equally dissolve stirring in dichloromethane, under condition of ice bath, be added dropwise to amine
In base ethyl ester, it is subsequently added into 0.1mmol dmap, then at the uniform velocity stir 16h at ambient temperature；Continue two carbon of 15mmol
Sour di tert butyl carbonate is dissolved in dichloromethane, adds 0.1mmol dmap, continues at the uniform velocity to stir 48h at ambient temperature；
S2.3, add saturated sodium bicarbonate solution and saturated nacl aqueous solution to solution obtained by step s2.2, separating has
Machine layer, is dried with anhydrous magnesium sulfate, then passes through to filter, distills the amino ethyl ester obtaining the double protection of boc；
S3, urethane exchange reaction
The amino ethyl ester of double for the 5mmol boc being obtained in step s2 protections is dissolved in 50ml thf, adds 100ml ammonia
Methanol solution, adds 0.5g Feldalat NM, is stoppered with flanging rubber plug, is stirred vigorously 24h under 50 DEG C of water bath condition, and decompression is steamed
Evaporate and remove solvent, obtain the amino amides product of the double protection of boc；
S4, hofmann degradation reaction
Take 8mmol sodium hydroxide to be dissolved in 100ml pure water, under condition of ice bath, add 2.2mmol bromine, stirring
10min, the amino amides of double for prepared boc in step s3 protections is added reactant liquors, stirs 2h at 30 DEG C, be warming up to 80 DEG C instead
Answer 30min, filtrate chloroform extraction, extraction phase evaporation crystallizes after removing partial solvent.
S5, de- boc protection
The mixed solution of the trifluoroacetic acid of 18mmol and 20ml dichloromethane is added to the alkylamine of 4mmol boc protection
In, 1h is stirred at room temperature, reaction stops, rotary evaporation.Surplus materialss are added dissolving in appropriate ethyl acetate, using 5%
na2co3It is 8.5 that solution washs to ph, removes solvent, obtains final products 1,1,6,6- own tetramine (c6h18n4), structural formula is such as
Under.
Obtained product is colourless liquid, and its yield is 70%.
Performance characterization: by the alkyl tetramine (c to synthesis6h18n4) carry out molecular weight and mesh that LC-MS records product
The molecular weight of mark product is identical.Also confirm that product is exactly target product by the hydrogen spectrum and carbon spectrum measuring nuclear magnetic resonance, NMR.
1h nmr(dmso-d6)δ:3.96(s,2h,ch),1.75(s,4h,ch2),1.31(s,2h,ch2),1.18(s,
8h,nh2).13c nmr(dmso-d6)δ:63.5(ch),36.0(ch2),25.0(ch2).lc-ms(esi):146.15[m+h]+.
Embodiment 4
The inhibitor of the product obtained by embodiment 1～3 and clear water configuration (is selected with conventional shale control agent
Hexamethylene diamine class inhibitor and polyamine class inhibitor) carry out contrast experiment, using linear expansion rate and rolling rate of recovery, to evaluate
State the inhibitor performance of embodiment preparation, its concrete operation step is with reference to " sy-t5613-2000 mud shale physicochemical property test side
Method " and " sy/t5971-1994 water filling clay stabilizer method of evaluating performance ", linear expansion rate is lower, and inhibitor is described
Rejection is better；Rolling rate of recovery is higher, illustrates that the rejection of inhibitor is better.The data recording after test such as table 1 He
Shown in table 2:
Table 1 linear expansion rate
The impact to linear expansion rate for the table inhibitor 2 dosage
Table 3 rolling rate of recovery (rolls temperature and is 240 DEG C)
| Component | The response rate/% |
| Clear water | 19.58 |
| 1% hexamethylene diamine | 34.26 |
| 1% polyamine | 44.58 |
| 1,1,4,4- fourth tetramine obtained by 1% embodiment 1 | 67.85 |
| 1,1,5,5- penta tetramine obtained by 1% embodiment 2 | 75.63 |
| The own tetramine of 1,1,6,6- obtained by 1% embodiment 3 | 79.68 |
The impact (roll temperature and be 240 DEG C) to the response rate for the table 4 inhibitor dosage
| Component | The response rate/% |
| 1,1,4,4- fourth tetramine obtained by 1% embodiment 1 | 67.85 |
| 1,1,4,4- fourth tetramine obtained by 2% embodiment 1 | 71.53 |
| 1,1,4,4- fourth tetramine obtained by 3% embodiment 1 | 76.76 |
| 1,1,5,5- penta tetramine obtained by 1% embodiment 2 | 75.63 |
| 1,1,5,5- penta tetramine obtained by 2% embodiment 2 | 79.53 |
| 1,1,5,5- penta tetramine obtained by 3% embodiment 2 | 84.45 |
| The own tetramine of 1,1,6,6- obtained by 1% embodiment 3 | 79.78 |
| The own tetramine of 1,1,6,6- obtained by 2% embodiment 3 | 86.36 |
| The own tetramine of 1,1,6,6- obtained by 3% embodiment 3 | 89.24 |
The linear expansion rate result of table 1 shows, under conditions of identical dosage, 1, and Isosorbide-5-Nitrae, 4- fourth tetramine, 1,1,5,5- penta
Tetramine, 1,1,6,6- own tetramine all show excellent rejection, have more preferable suppression than like product hexamethylene diamine and polyamine
Performance processed, compared to having 2 primary amine hexamethylene diamines, the rejection with the 1 of four primary amine, 1,6,6- own tetramine is more preferable.
The impact to linear expansion rate for the inhibitor dosage of table 2 shows, with the increase of inhibitor dosage, linear expansion rate
Reduce, rejection more preferably, and the increase with long alkyl chains, rejection also improves therewith.
The rolling rate of recovery result of table 3 shows, 1, Isosorbide-5-Nitrae, and 4- fourth tetramine, 1,1,5,5- penta tetramine, 1,1,6,6- own tetramine
Rolling rate of recovery all higher than the rolling rate of recovery of hexamethylene diamine and polyamine, illustrate 1, Isosorbide-5-Nitrae, 4- fourth tetramine, 1,1,5,5- penta tetramine,
1,1,6,6- own tetramine has preferable rejection, and the increase with long alkyl chains, also make rejection further
Improve.
The impact to rolling rate of recovery for the inhibitor dosage of table 4 shows, with the increase of inhibitor dosage, rolling rate of recovery
Also accordingly increase, its rejection is more preferable.And the increase with long alkyl chains, so that rejection is improved further.
The experimental data of table 3 and table 4 shows, inhibitor provided by the present invention shows excellent at high operating temperatures, has
Fabulous high temperature resistant property, temperature resistance ability reaches 240 DEG C.
The alkyl tetramine raw material being configured using the method for alkyl tetramine provided by the present invention, can individually be configured with clear water
Become inhibitor, also can mix mutually, then be configured to inhibitor with clear water, in inhibitor the proportion of alkyl tetramine weight ratio be 1～
3%.
The above be only the preferred embodiment of the present invention it is noted that the invention is not limited in aforesaid way,
Without departing from the principles of the invention moreover it is possible to improve further, these improvement also should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of synthetic method of alkyl tetramine is it is characterised in that step is as follows:
S1, the synthesis of aminoacid
S1.1, the metallic sodium of 0.2～0.21mol is taken to be dissolved in absolute ethanol (purity be more than 99.99%), by alcohol sodium solution
In the ethanol solution of the diethyl acetamido being added dropwise to 0.2mol, at the uniform velocity stir 1～1.5h；
S1.2, the alkyl dibromide of 0.1～0.11mol is added dropwise in the solution obtained by step s1.1, back flow reaction 5.5
～7h, after completion of the reaction, filters, revolving；
S1.3, the solution being obtained in step s1.2 add 46～49% hydrogen bromide solution 100ml, back flow reaction 7～8h；
S1.4, revolving remove the hydrogen bromide solution in obtained solution in s1.3, crude product are dissolved in ethanol, according still further to volume
The ratio ethanol pyridine solution adding no less than 50% ratio, stands 12h, sucking filtration, obtains amino acid products；
S2, esterification
S2.1, take in 5mmol step s1 be obtained amino acid products add 250ml single-necked flask in, then sequentially add
100ml ethanol and 4～6ml concentrated sulphuric acid, back flow reaction 5～7h, revolving falls solvent；
S2.2, the crude product amino ethyl ester hydrochlorate that step s2.1 is obtained put into dissolving stirring in 100ml dichloromethane, then
Weigh Bis(tert-butoxycarbonyl)oxide 10～20mmol, same dissolving stirring, in dichloromethane, is added dropwise under condition of ice bath
In aminoethyl, it is subsequently added into 0.08～0.15mmol dmap (DMAP), then at the uniform velocity stirs at ambient temperature
Mix 16h；Continue the Bis(tert-butoxycarbonyl)oxide of 15mmol is dissolved in dichloromethane, add 0.09～0.12mmoldmap,
Continue at ambient temperature at the uniform velocity to stir 48h；
S2.3, add saturated sodium bicarbonate solution and saturated nacl aqueous solution to solution obtained by step s2.2, separate organic layer,
It is dried with anhydrous magnesium sulfate, then pass through to filter, distill the amino ethyl ester obtaining the double protection of boc；
S3, urethane exchange reaction
The amino ethyl ester of double for the 5mmol boc being obtained in step s2 protections is dissolved in 50ml thf (oxolane), adds
100ml methanolic ammonia solution, adds 0.5g Feldalat NM, is stoppered with flanging rubber plug, is stirred vigorously under 50 DEG C of water bath condition
24h, vacuum distillation removes solvent, obtains the amino amides product of the double protection of boc；
S4, hofmann degradation reaction
Take 8mmol sodium hydroxide to be dissolved in 100ml pure water, under condition of ice bath, add 2.1～2.3mmol bromine, stirring
10min, the amino amides of double for the boc being obtained in step s3 protections is added reactant liquor, at the uniform velocity stirs 2h at 25～35 DEG C, heat up
To 80 DEG C of reaction 30min, filtrate chloroform extraction, extraction phase evaporation crystallizes after removing partial solvent.
S5, de- boc protection
The mixed solution of the trifluoroacetic acid of 18mmol and 20ml dichloromethane is added in the alkylamine of 4mmol boc protection,
1h is stirred at room temperature, reaction stops, rotary evaporation.Surplus materialss are added dissolving in appropriate ethyl acetate, using 5% concentration
Na2co3It is 8～9 that solution washs to ph, removes solvent, obtains final products alkyl tetramine.
2. a kind of synthetic method of alkyl tetramine according to claim 1 is it is characterised in that alkane in described step s1.2
The molecular structural formula of base dibromo is:
Wherein, n is 2～10.
3. a kind of synthetic method of alkyl tetramine according to claim 2 is it is characterised in that described alkyl dibromide is 1,2-
Bromofume, any one in 1,3- dibromopropane Isosorbide-5-Nitrae-dibromobutane.
4. a kind of synthetic method of alkyl tetramine according to claim 1 is it is characterised in that in described step s1.4, press
It is 60% according to the ethanol pyridine solution that volume ratio adds.
5. a kind of alkyl tetramine according to any one in Claims 1 to 4 synthetic method it is characterised in that this
Bright synthesis technique flow process is shown below:
According to the technique of described step, the yield rate of final product is 65～73%.
6. a kind of synthetic method of alkyl tetramine according to claim 1 is it is characterised in that adopt synthesized by this method
Alkyl four amine product, its molecular structural formula is:
Alkyl four amine product of gained is colourless liquid, needs to preserve using vacuum mode after producing.
7. a kind of alkyl four amine product according to claim 6 is it is characterised in that described alkyl four amine product is joined with clear water
Make alkyl tetramine shale control agent, in its proportioning, the ratio of alkyl tetramine product weight ratio is 1～3%.
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