CN111410747A

CN111410747A - Dendrimer derivative and preparation and application thereof

Info

Publication number: CN111410747A
Application number: CN201910010854.0A
Authority: CN
Inventors: 罗霄; 韩午丽; 任晗; 庄庆佐
Original assignee: China National Petroleum Corp; CNPC Research Institute of Safety and Environmental Technology Co Ltd
Current assignee: China National Petroleum Corp; CNPC Research Institute of Safety and Environmental Technology Co Ltd
Priority date: 2019-01-07
Filing date: 2019-01-07
Publication date: 2020-07-14
Anticipated expiration: 2039-01-07
Also published as: CN111410747B

Abstract

The invention discloses a dendrimer derivative and preparation and application thereof. The dendrimer derivative can be used as a flocculant for treating the waste water-based drilling fluid, can realize high-efficiency flocculation of harmful solid phases in the waste water-based drilling fluid under a small addition amount, and still has good flocculation efficiency in a high-salinity environment. The dendrimer derivative is obtained by carrying out addition and condensation reactions in solution one by one, and the preparation method has the advantages of simple operation, mild conditions and high yield. The structural formula of the dendrimer derivative is shown in formula 1, wherein R is independently shown in formula 2 or formula 3.

Description

Dendrimer derivative and preparation and application thereof

Technical Field

The invention belongs to the field of petrochemical industry, and particularly relates to a dendrimer derivative, and preparation and application thereof.

Background

The waste water-based drilling fluid produced in the drilling process is a multiphase stable colloid suspension system containing clay, weighting materials, chemical treatment agents, sewage, oil stains and drill cuttings, wherein the multiphase stable colloid suspension system contains hydrocarbons, various polymers and certain heavy metal ions (such as mercury, arsenic, zinc, lead and the like) which are harmful to the environment, the components are difficult to naturally decompose and degrade, and if the drilling waste fluid is not effectively subjected to harmless treatment, the local ecological environment can be seriously damaged, and the life safety of organisms is endangered.

The method is characterized in that a specific flocculating agent such as a proper organic polymer is used for flocculating and settling settleable components in the drilling waste liquid, so that the high-efficiency separation of a solid phase and a liquid phase is realized, and the method is a main mode for performing harmless treatment on the waste liquid. However, most of the currently used organic high polymers are linear macromolecules with molecular main chains formed by C-C bonds, and due to the inherent internal rotation effect of the C-C bonds, molecular chain segments of the organic high polymers are relatively flexible, so that the organic high polymers are easy to curl and form clusters in a high-salinity waste liquid environment and further are wrapped by polymer components in the waste liquid, flocculant molecules are poisoned and ineffective due to the fact that substances to be flocculated are difficult to adsorb, and the problems of large dosage, poor flocculation effect and the like are presented as a result. The use cost is increased by simply increasing the addition of the flocculating agent, the waste liquid is obviously thickened, the spatial diffusion of flocculating agent molecules is limited, and the flocculation effect is also limited.

As a novel molecule different from the traditional linear macromolecule, the dendritic macromolecule has high space symmetry and accurate molecular structure, the surface of the molecule contains a large amount of modifiable terminal group functional groups, and if proper dendritic macromolecule (the terminal group is mostly amino, hydroxyl and other groups which are easy to modify) is taken as a core molecule, monomers with flocculation effect are selected to carry out terminal group modification and branched chain growth reaction on the dendritic macromolecule, so that different types of dendritic macromolecule derivatives can be prepared. Compared with linear macromolecules, the derivatives have the following advantages when used as flocculating agents: (1) branched chains in the molecular structure are separated from each other due to steric hindrance effect, the twisting and tangling among molecular chains are not easy to occur, and the structure rigidity is extremely strong; (2) the end group density is extremely high, a large amount of required functional groups are easily introduced through addition reaction, and then the extremely high functional group density is realized in a limited molecular scale, and the flocculation performance of the polymer is ensured; (3) under the condition of equivalent molecular weight, the hydrodynamic size and the characteristic viscosity number of the dendrimer derivative are smaller, and the liquid phase is not easy to excessively thicken.

Disclosure of Invention

Based on the background technology, the invention provides a dendrimer derivative and preparation and application thereof. The dendrimer derivative can be used as a flocculant for treating the waste water-based drilling fluid, can realize high-efficiency flocculation of harmful solid phases in the waste water-based drilling fluid under a small addition amount, and still has good flocculation efficiency in a high-salinity environment. The dendrimer derivative is obtained by carrying out addition and condensation reactions in solution one by one, and the preparation method has the advantages of simple operation, mild conditions and high yield.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a dendrimer derivative having the following structural formula:

wherein R is independently:

x is a positive integer less than or equal to 24, and is less than or equal to 24 [ (m + n) × x + i (24-x) ] and less than or equal to 5000; at 24, the 24 amino groups in the structure are each added with a segment of only one ammonium salt.

The dendrimer derivative takes dendrimers as cores, terminal amine groups of the dendrimer derivative are modified by using quaternary ammonium monomers, so that the dendrimer derivative connected with a plurality of branched chains formed by repeated quaternary ammonium units is obtained, quaternary ammonium groups of the dendrimer derivative can show strong electropositivity after the dendrimer derivative is dissolved in waste liquid to be treated, hydration films coated outside harmful substances can be damaged, and the dendrimer derivative can adsorb and flocculate the hydration films, so that the harmful substances are settled and removed.

The second aspect of the present invention provides a method for preparing the above dendrimer derivative, comprising the steps of:

s100, carrying out Michael addition reaction on pentaerythritol tetraamine and methyl acrylate to obtain an intermediate product G0.5PATAM, wherein the structure is as follows:

s200, carrying out ester ammonolysis reaction on the intermediate product G0.5PATAM and pentaerythrityl tetramine to obtain an intermediate product G1.0PATAM, wherein the structure is as follows:

s300, carrying out Michael addition reaction on the intermediate product G1.0PATAM and dimethyl diallyl ammonium chloride, and carrying out alkene addition reaction on the residual dimethyl diallyl ammonium chloride and the dimethyl diallyl ammonium chloride connected with terminal amine groups to obtain a final product.

In a preferred embodiment of the invention, the pentaerythrityl tetramine is obtained by the following steps:

s110, oxidizing pentaerythritol to generate tetramethylaldehydic methane;

s120, carrying out a Liu Kate reaction on the tetramethylaldehyde methane to obtain pentanetetramine.

The invention simplifies the traditional conversion steps from four to five steps to two steps from pentaerythritol to pentamine, greatly simplifies the preparation process, and effectively controls the raw material loss and the reaction time.

Specifically, in S110, pentaerythritol is oxidized to tetramethylaldehydic methane using a PCC reagent (sarrette reagent).

The preparation of the PCC reagent can be obtained by adopting a mature method, and the specific method adopted in the invention is as follows: weighing a certain amount of hydrochloric acid, adding a certain amount of chromium trioxide under the stirring condition, cooling to a certain temperature after uniformly mixing, dropwise adding a certain amount of pyridine within a specified time, and reacting to obtain a PCC reagent crude product after a predetermined time;

and drying the crude product of the PCC reagent in a vacuum dryer, and then drying the crude product of the PCC reagent in a dryer filled with phosphorus pentoxide at normal temperature to obtain the pure PCC reagent.

Preferably, the step of oxidizing pentaerythritol to tetramethylaldehydic methane using a PCC reagent comprises:

and (3) dissolving a PCC reagent in a first solvent, dropwise adding a pentaerythritol solution into the PCC reagent under the condition of stirring at room temperature for reaction, and performing post-treatment after the reaction is finished to obtain the tetramethylaldehyde methane.

Preferably, the molar ratio of hydroxyl in the pentaerythritol to the PCC reagent is 1 (1-2); for example 1:1.5 in the preferred embodiment, to provide an excess of PCC reagent.

Preferably, the post-processing comprises: separating out the upper layer solution in the reaction system, and washing the lower layer solid matter by using a second solvent; combining the upper solution and the washing solution, and using saturated NaHCO to combine the combined solution₃Washing with aqueous solution, separating organic phase and using anhydrous Na₂SO₄Drying, filtering, and distilling under reduced pressure to remove solvent to obtain tetramethylaldehyde methane.

Preferably, the solvent in the first solvent, the second solvent and the solution of pentaerythritol are all Dichloromethane (DCM). More preferably, the dichloromethane is dichloromethane after water is redistilled.

In a preferred embodiment of the invention, the reaction of the liucate in S120 comprises:

adding ammonium formate and formic acid into an excessive third solvent, heating to a first preset temperature, then dropwise adding a solution of tetramethylaldehyde methane, continuing heating to a second preset temperature after dropwise adding is finished, reacting, and obtaining black tarry liquid which is mixed liquid containing pentaerythrityl tetramine after the reaction is finished; and carrying out post-treatment on the mixed solution to obtain the pentaerythrite.

Preferably, the molar ratio of ammonium formate to formic acid is 1: (1-2). Such as 1:2 in the preferred embodiment of the invention.

Preferably, the molar ratio of the ammonium formate to the tetramethylaldehyde methane is (6-8): 1.

preferably, the solvent of the third solvent and the solution of tetramethylaldehydic methane is toluene.

Preferably, the first predetermined temperature is 80 ℃ and the second predetermined temperature is 160 ℃.

Preferably, the post-processing comprises: vacuum filtering the mixed solution to remove black coke impurities, and sequentially using saturated NaHCO for the obtained filtrate₃Washing with saturated aqueous NaCl solution, separating the organic phase and using anhydrous Na₂SO₄Drying, filtering, and distilling the filtrate under reduced pressure to obtain white needle crystal, namely pentanetetramine.

Specifically, the step of carrying out Michael addition reaction on S100 pentaerythritol tetramine and methyl acrylate to obtain an intermediate product G0.5PATAM comprises the following steps:

dissolving pentaenetetramine in methanol, stirring at a third preset temperature, dropwise adding methyl acrylate for reaction, and performing post-treatment after the reaction is finished to obtain an intermediate product G0.5PATAM.

The intermediate G0.5PATAM is 0.5 generation dendrimer with pentanetetramine as core, so this dendrimer is named G0.5PATAM in the present invention.

Preferably, the molar ratio of the pentaerythritol tetraamine to the methyl acrylate is 1 (8-12).

Preferably, said third predetermined temperature is room temperature, for example 25 ℃.

Preferably, the post-processing comprises: and after the reaction is finished, carrying out reduced pressure distillation on the system, and carrying out silica gel column chromatography purification on the residue to obtain an intermediate product G0.5PATAM.

Preferably, the reduced pressure distillation conditions are 25 ℃ and 133 Pa.

Wherein, the solvent methanol and the excessive raw material methyl acrylate are removed by reduced pressure distillation, and the obtained light yellow viscous solid is the crude product of the intermediate product G0.5PATAM; column chromatography purification is carried out to obtain light yellow crystals, namely the purified G0.5PATAM finished product.

Specifically, the step of carrying out ester ammonolysis reaction on the S200 intermediate product G0.5PATAM and pentaerythrityl tetramine to obtain an intermediate product G1.0PATAM comprises:

and dissolving the intermediate product G0.5PATAM in methanol, stirring and dropwise adding pentaerythrite at a fourth preset temperature, and performing post-treatment after the reaction to obtain an intermediate product G1.0PATAM.

The intermediate G1.0PATAM is a 1.0 generation dendrimer crude product with pentanetetramine as a core, and the invention names the dendrimer G1.0PATAM.

Preferably, the molar ratio of intermediate G0.5PATAM to pentaenetetramine is 1: (8-12).

Preferably, said fourth predetermined temperature is room temperature, for example 25 ℃.

Preferably, the post-processing comprises: and after the reaction is finished, carrying out reduced pressure distillation on the system, and carrying out silica gel column chromatography purification on the residue to obtain an intermediate product G1.0PATAM.

Wherein, the solvent methanol and the excessive raw material pentaerythritol tetraamine are removed by reduced pressure distillation, and the obtained pale yellow viscous solid is the crude product of the intermediate product G1.0PATAM; column chromatography purification is carried out to obtain light yellow crystals, namely the purified G1.0PATAM finished product.

Preferably, the reduced pressure distillation conditions are 72 ℃ and 266 Pa.

Specifically, the step of performing michael addition reaction on the S300 intermediate product G1.0PATAM and dimethyldiallylammonium chloride, and simultaneously performing polymerization reaction between the dimethyldiallylammonium chloride to obtain the final product comprises:

intermediate G1.0PATAM was dissolved in water and the pH of the system was adjusted to 7 at N₂Heating to a fifth preset temperature in the atmosphere, then dropwise adding a dimethyl diallyl ammonium chloride aqueous solution for reaction, and performing post-treatment after the reaction is finished to obtain the productTo the final product.

The final product is an ammonium salt type dendrimer derivative which is named G1.0PAT-D in the invention.

Preferably, the molar ratio of intermediate G1.0PATAM to dimethyldiallylammonium chloride is 1: (2000-5000).

Preferably, the pH of the aqueous solution of dimethyldiallylammonium chloride is also adjusted to 7.

Preferably, NaHCO is used₃The pH is adjusted.

Preferably, the fifth predetermined temperature is 50-70 ℃.

Preferably, the post-processing comprises: after the reaction is finished, carrying out reduced pressure distillation on the system, and precipitating and purifying the remainder by using absolute ethyl alcohol to obtain a crude product;

and (3) putting the crude product into distilled water, dialyzing by using an ultrafiltration membrane to remove oligomers and unreacted dimethyl diallyl ammonium chloride monomers in the product, and finally drying the product to obtain a purified final product.

Wherein the solvent was removed by distillation under reduced pressure. Preferably, the drying is vacuum drying at 60 ℃ for 48 h. Drying to obtain light yellow viscous solid which is the pure final product.

The dendrimer derivative is a copolymer generated by Michael addition of G1.0PATAM dendrimers and an alkenyl ammonium chloride monomer and alkene addition reaction between alkene monomers. The dendrimer derivative is abbreviated as G1.0PAT-D flocculant.

In a third aspect, the present invention provides the use of the dendrimer derivative G1.0PAT-D above as a flocculant for treating waste water-based drilling fluids.

The invention has the beneficial effects that:

(1) the traditional conversion step from pentaerythritol to pentamine is simplified from four to five steps to two steps, so that the preparation process is greatly simplified, and the raw material loss and the reaction time are effectively controlled.

(2) Simplifies the preparation process of obtaining the dendrimer with the similar terminal amine base number. The synthesis process for preparing the PAMAM dendrimer by using ethylenediamine and methyl acrylate as raw materials through successive iterative reaction is complex, G4.0PAMAM dendrimer with 32 terminal amino groups needs to undergo multiple iterative reactions, the raw materials are greatly lost due to the fact that purification and impurity removal are needed in each iterative reaction, the yield is low, pentaerythrine and methyl acrylate are used as the raw materials, the prepared G1.0PATAM has 24 terminal amino groups, the number of required iterative reaction steps is only one fourth of the number of G4.0PAMAM steps, the raw material loss, the reaction time and the cost are greatly reduced, and the large-scale production and industrial application of the G1.0PATAM dendrimer are facilitated.

(3) Compared with linear macromolecules with the same molecular weight, the G1.0PAT-D dendrimer derivative prepared by performing end group quaternization modification on G1.0PATAM has the advantages of large rigidity of molecular structure, difficulty in molecular entanglement in a high-salinity environment, difficulty in excessive thickening of a liquid phase and the like, can form good compatibility with a traditional flocculant, and is added with a small amount of G1.0PAT-D composite flocculant system, so that the flocculation-sedimentation efficiency of harmful substances in waste drilling fluid is greatly improved compared with that before the flocculant is added.

Drawings

FIG. 1 is an infrared spectrum of pentanetetramine in the examples of the present invention.

FIG. 2 is an infrared spectrum of G1.0PATAM in example of the present invention.

FIG. 3 is an IR spectrum of G1.0PAT-D in example of the present invention.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

Example 1:

preparation of pentaenetetramine

1. Preparation of PCC reagent

Adding 100g of chromium trioxide (added while stirring) into 184m L hydrochloric acid (containing 1.1mol of HCl) with the concentration of 6 mol/L quickly, cooling the homogeneous solution to 0 ℃ after 5min to obtain a reddish brown liquid, filtering at normal pressure to remove insoluble substances, adding 79.1g of pyridine into the mixture within 10min, gradually precipitating yellow solid along with the addition of the pyridine, dropwise adding the pyridine, cooling to 0 ℃ again to obtain orange solid, filtering and collecting the product by using a sand core funnel, drying the product in a vacuum drier for 1h, then drying the product in a drier containing phosphorus pentoxide for 48h at normal temperature to obtain 180g of a constant weight product, wherein the yield is 84%, and the reaction formula is as follows:

2. preparation of pentaerythrite aldehyde

Dichloromethane (DCM) was passed over anhydrous CaCl₂Drying, redistilling, dissolving a PCC reagent in DCM after redistilling water, stirring, pouring into a three-neck flask with the diameter of 500m L after the PCC reagent is completely dissolved, dropwise adding a DCM solution of pentaerythritol into the three-neck flask under the condition of stirring at room temperature, ensuring that the molar ratio of hydroxyl of the pentaerythritol to the PCC reagent is 1:1.5, continuing to react for 4 hours after dropwise adding is finished, stopping the reaction, pouring out an upper layer solution, washing a lower layer solid substance for 3 times by DCM, combining the upper layer solution and a washing solution, and sequentially using saturated NaHCO to sequentially combine the combined solutions₃Washing with aqueous solution, and adding anhydrous Na₂SO₄Drying, filtering to remove the solvent, and then distilling the residual liquid under reduced pressure to obtain the pentaerythrite aldehyde, wherein the reaction formula is as follows:

3. preparation of pentaenetetramine

Preparing ammonium formate and formic acid into a solution with a molar ratio of 1:2, uniformly stirring, pouring into excessive toluene, uniformly stirring, pouring into a three-neck flask with a condensation reflux pipe, carrying out oil bath, heating to 80 ℃, dropwise adding a toluene solution of pentaerythrityl tetraldehyde, slowly heating to 160 ℃ after dropwise adding, continuing to react for 6 hours, stopping the reaction to obtain black tar-like liquid, carrying out vacuum filtration to remove black coke impurities, and sequentially using the obtained filtrateSaturated NaHCO₃Washing with saturated NaCl aqueous solution, separating the separated liquid with separating funnel, and adding anhydrous Na₂SO₄Drying the upper layer mother liquor, and finally carrying out reduced pressure distillation on the residual liquor to obtain white acicular crystals, namely the pentaerythrite, wherein the yield of the pentaerythrite reaches 83.41 percent by taking the raw material pentaerythritol as an evaluation standard. The reaction route is as follows:

4. structural characterization of pentaenetetramine

Chloroform (CDCl) dissolved in deuterium bands using a Bruker A400 nuclear magnetic resonance spectrometer₃) Pentamine in (1) is subjected to¹HNMR, results are as follows:

¹HNMR(500MHz,CDCl₃),d(TMS,ppm):1.17(s,8H,4-NH₂),2.57(s,8H,4-CH₂-) are respectively the characteristic peaks of methylene between the terminal amine group and the branched chain of the pentaerythritol tetramine.

The pentaerythrine is subjected to infrared spectrum analysis by using a WQF-520 infrared spectrometer, the result is shown in figure 1, figure 1 is an infrared spectrum diagram of the pentaerythrine, and the characteristic absorption peak of the diagram is analyzed as follows: 3368cm^-1Is of the formula-NH₃Characteristic absorption peak of (a); 2926cm^-1Is represented by-CH₂-a stretching vibration absorption peak; 2864cm^-1Is of the formula-CH₂-an asymmetric stretching vibration absorption peak; 1597cm^-1is-CH₂Characteristic peak of-middle C-H bond, 1461cm^-1A bending vibration absorption peak at methylene; 1306cm^-1And 1096cm^-1Is independently-NH₃And the bending vibration and deformation vibration absorption peak of the medium N-H bond.

In combination with penta-tetramine¹The HNMR and the infrared spectrum can know that the molecular structure of the product has the expected molecular groups, so that the product is deduced to be consistent with the structure of the target product.

Example 2:

preparation of dendrimer G1.0PATAM

1. G0.5PATAM preparation

Adding pentaerythritylamine and methanol into a three-neck flask with a magnetic stirrer, a reflux condenser and a thermometer according to a molar ratio of 1:12, stirring at 25 ℃, dropwise adding methyl acrylate with a molar quantity 10 times that of the pentaerythritylamine by using a dropping tube, carrying out reduced pressure distillation at 25 ℃ and 133Pa after reacting for a period of time, and removing solvent methanol and excessive raw material methyl acrylate to obtain light yellow viscous solid which is G0.5PATAM crude finished products, wherein the reaction route is as follows:

2. G1.0PATAM preparation

G0.5PATAM and methanol are added into a three-neck flask with a magnetic stirrer, a reflux condenser tube and a thermometer according to the molar ratio of 1:12, stirred at 25 ℃, dripped by a dropping tube and dissolved in excessive methanol, pentanetetramine with the molar quantity of G0.5PATAM10 times is reacted for a fixed time, reduced pressure distillation is carried out at 72 ℃ and 266Pa pressure, the solvent methanol and excessive raw material ethylenediamine are removed, and the obtained pale yellow viscous solid is a G1.0PATAM crude product, and the reaction formula is as follows:

3. G1.0PATAM structural characterization

Chloroform (CDCl) dissolved in deuterium bands using a Bruker A400 nuclear magnetic resonance spectrometer₃) G1.0PATAM in¹HNMR, results are as follows:

¹HNMR(500MHz,CDCl3),d(TMS,ppm):1.47(s,48h,24-NH₂),2.22(s,8H,4C-CH₂-N),2.49(s,16H,8C-CH₂CO),3.61(s,16H,8N-CH₂-CH₂),3.76(s,8H,8NCH₂CH₂),8.01(s,8H,8-NH-)。

G1.0PATAM was subjected to IR spectroscopy using a WQF-520 IR spectrometer, the results of which are shown in FIG. 2, FIG. 2 is an IR spectrum G1.0PATAM, and the characteristic absorption peaks of the spectrum were analyzed as follows: 3257cm^-1Is of tertiaryN-H stretching vibration absorption peaks in amine groups; 3080cm^-1An out-of-plane bending vibration absorption peak at N-H; 2942cm^-1Asymmetric stretching vibration absorption peak of methylene is shown; 1735cm^-1And 1498cm^-1Is a characteristic absorption peak of an amide bond; 1436cm^-1、1384cm^-1The positions are respectively the bending vibration and deformation vibration absorption peaks of C-H in methylene; 12011cm^-1And 114cm^-1The position is the stretching vibration absorption peak of the tertiary amine.

Combined with G1.0PATAM¹The HNMR and the infrared spectrum can know that the molecular structure of the product has the expected molecular groups, so that the product is deduced to be consistent with the structure of the target product.

Example 3:

preparation of flocculant G1.0PAT-D

1. Preparation of flocculant G1.0PAT-D

1.622g G1.0PATAM dendrimer was dissolved in deionized water and NaHCO₃The pH of the system was adjusted to 7 and the mixture was charged into a 1000m L three-necked flask with an addition funnel and a reflux condenser under N₂After warming to a predetermined temperature in the atmosphere, 323g of DMDAAC in water (pH likewise NaHCO) are slowly added dropwise₃Adjusting to 7), taking out after reacting for a specified time, removing the solvent through reduced pressure rotary evaporation, precipitating and purifying the obtained product with absolute ethyl alcohol to obtain a crude product, then putting the crude product into distilled water for 96 hours through an ultrafiltration membrane to remove oligomers and unreacted monomers in the product, finally putting the product into a vacuum drying oven, and performing vacuum drying for 48 hours at 60 ℃ to obtain a milky viscous solid, namely a purified final product, which is named G1.0PAT-D, and has the following reaction formula:

in this preparation DMDAAC was used in an amount of 2000 equivalents to G1.0PATAM.

Wherein 24 is less than or equal to [ (m + n) × x + i (24-x) ] < 2000.

2. Characterization of flocculant G1.0PAT-D

G1.0PAT-D was infrared analyzed using a WQF-520 infrared spectrometerThe results of the spectral analysis are shown in FIG. 3, and FIG. 3 is an infrared spectrogram of G1.0PAT-D, and the characteristic absorption peaks of the spectrogram are analyzed as follows: 3352cm^-1The position is a characteristic peak of a C-C bond in a polymer molecular chain; 2929cm^-1、1494cm^-1Is the stretching vibration peak of the C-N bond in DMDAAC; 2124cm^-1Is represented by-N-CH in DMDAAC junction₃Absorption peak of (4); 1722cm^-1、1635cm^-1Is a characteristic peak of quaternary ammonium group; 1407cm^-1The absorption peak is the methine in the five-membered ring formed by DMDAAC. The result of infrared spectroscopic analysis shows that the product contains the characteristic peak of the molecular chain of the DMDAAC polymer, and the structure of the prepared product is in accordance with the expected result of the subject.

The infrared spectrum of G1.0PAT-D shows that the molecular structure has the predicted molecular groups, and the structure is deduced to be consistent with the structure of the target product.

Example 4:

flocculation performance of dendrimer derivative on waste water-based drilling fluid

According to the method described below, the physical and chemical performance indexes of the waste drilling fluid before and after the treatment agents are added are respectively measured.

(1) Determination of oil content

The determination of the oil content is carried out according to the standard SY/T0530-1993 spectrophotometry for determining the oil content in oil field sewage of the oil and gas industry of the people's republic of China, firstly, reference oil is prepared according to the standard method, the absorbance of the reference oil with different concentrations is determined, a standard curve is drawn, the absorption coefficient K is calculated, then, the oil content in the waste drilling fluid is determined, the waste drilling fluid diluted by n times is placed in a test tube with the 100m L scale, the waste drilling fluid is placed for 30min, an upper water sample is placed in a separating funnel, a proper amount of 1:1 (the volume ratio of the hydrochloric acid to the water is 1:1) hydrochloric acid is added, the pH value is adjusted to be about 2, a proper amount of gasoline is added for extraction, the gasoline extract is placed in a 50m L volumetric flask for constant volume, an ultraviolet spectrophotometer is used for determining the absorbance at the wavelength.

In the formula C₀Oil content of the test Water sample, mg L^-1(ii) a E, absorbance of the detected water sample; v₀Total volume of extract, m L;. V_wThe volume of the sample to be tested, m L, K-absorption coefficient, L. mg^-1(ii) a n-dilution factor.

(2) Determination of solid phase content

① soaking the filter membrane in deionized water for 30min, flushing with deionized water for 3-4 times, ② placing the filter membrane in a culture dish and placing in an oven, drying at 70 deg.C for 3min, taking out, placing in a dryer, cooling to room temperature, weighing ③, repeating the operation ② for many times until the mass of the filter membrane is kept unchanged, and recording the mass m of the filter membrane₁④ setting the mass m₀⑤ opening a valve to filter the waste drilling fluid, taking out the filter membrane from the suspended solids tester by tweezers, drying to constant weight, recording the mass of the filter membrane at the moment, and recording the mass as m₂And simultaneously collecting filtered water for later use. The suspended solids content was calculated as follows:

SC-suspended solids content,%; m is₁-mass of filter membrane before test, g; m is₂-mass of filter membrane after test, g; m is₀-mass of waste drilling fluid, g, charged into suspended solids meter.

(3) Determination of the Metal ion content

Measuring the content of various metal ions in the waste drilling fluid by adopting an atomic absorption spectrophotometer, wherein the unit is mg-L^-1。

(4) Determination of organic content

By usingAnd (4) determining the total amount of the total organic matters in the waste drilling fluid by a gravimetric method. Accurately weighing mass m of spare crucible₁Putting the sample in the evaporating dish with the measured water content into a crucible, transferring the crucible into an oven to be dried at 105 ℃, then putting the crucible into a dryer to be cooled, weighing, and repeating for several times until the constant weight is m₂Then placing the crucible with the sample into a muffle furnace to heat at 550 +/-50 ℃ for 2h, then turning off a power supply, taking out the crucible when the temperature in the furnace is reduced to about 200 ℃, placing the crucible into a dryer to cool to room temperature, and weighing m₃And finally, calculating the content of organic matters in the waste drilling fluid according to the following formula:

wherein OC-organic matter content,%; m is₁-the mass of the crucible to be used, g; m is₂-total mass of sample after crucible drying, g; m is₃-total mass of sample after crucible firing, g.

(5) Determination of floc sedimentation Rate

The sedimentation rate of flocs was determined as follows: weighing a certain amount of waste drilling fluid in a beaker, adding a flocculating agent with the mass of 0.4% of the mass of the waste drilling fluid, uniformly stirring, quickly moving the waste drilling fluid into a cylindrical pipe with the millimeter scale and the diameter of 40mm and the height of 250mm, vertically placing the waste drilling fluid, gradually increasing the supernatant along with the extension of standing time, and recording the height of the supernatant every 1min, wherein the unit is mm.

(6) Determination of the degree of compactness of the flocs

The flocs are divided into more compact and looser according to the morphology of the flocs, and the compactness of the formed flocs is observed after the flocculation and sedimentation are finished.

(7) Determination of flocculation Properties

Four groups of flocculants with different formulas are selected, and the flocculation performance of the flocculants with different formulas on the selected waste drilling fluid is researched according to the method for measuring the physical and chemical properties.

The formula of the four groups of flocculating agents comprises the following components:

1#：3.0％AlCl₃+0.5％HPAM (300-500 ppm molecular weight) + 1.0% polyaluminium chloride;

2#：3.0％AlCl₃+ 0.5% of acrylamide-dimethyldiallylammonium chloride copolymer (PAT, 200-300 ten thousand molecular weight) + 1.0% of polyaluminium chloride;

3#：3.0％AlCl₃+ 0.2% G1.0PAT-D + 0.5% HPAM (300-500 ppm molecular weight) + 1.0% polyaluminium chloride;

4#：3.0％AlCl₃+ 0.2% G1.0PAT-D + 0.5% copolymer of acrylamide with dimethyldiallylammonium chloride (PAT) + 1.0% polyaluminium chloride.

The specific experimental results are shown in table 1.

TABLE 1 Effect of inhibitor dosage on anti-swelling Rate

The data in table 1 show that, in four groups of flocculants with different formulas, the 3# and 4# formulas with 0.2% of G1.0PAT-D are added to achieve approximately 95% removal rate of sedimentation of crude oil, solid phase, metal ions and organic matters in the waste drilling fluid, the removal rate of various harmful substances in waste liquid is greatly improved compared with the 1# and 2# formulas without G1.0PAT-D, the 3# and 4# formulas have higher sedimentation rate of the harmful substances, the compactness of formed flocs is also remarkably improved, the prepared dendrimer derivative G1.0PAT-D has good compatibility with common organic and inorganic flocculants, and after the composite flocculant is formed, the dendrimer derivative has good flocculation-sedimentation performance on the harmful substances in the waste drilling fluid.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims

1. A dendrimer derivative, characterized in that the structural formula is as follows:

wherein R is independently:

x is a positive integer less than or equal to 24, and 24 is less than or equal to [ (m + n) × x + i (24-x) ] and less than or equal to 5000.

2. A method for preparing the dendrimer derivative of claim 1, comprising the steps of:

3. The method according to claim 2, wherein the pentaerythrityl tetramine is obtained by:

s110, oxidizing pentaerythritol to generate tetramethylaldehydic methane;

4. The method according to claim 3, wherein the PCC reagent is used to oxidize pentaerythritol to form tetramethylaldehydic methane in S110.

5. The method of claim 4, wherein the step of oxidizing pentaerythritol to tetramethylaldehydic methane using a PCC reagent comprises:

6. The method according to claim 5, wherein the molar ratio of hydroxyl groups in the pentaerythritol to the PCC reagent is 1 (1-2).

7. The method of manufacturing according to claim 5, wherein the post-treatment comprises: separating out the upper layer solution in the reaction system, and washing the lower layer solid matter by using a second solvent; combining the upper solution and the washing solution, and using saturated NaHCO to combine the combined solution₃Washing with aqueous solution, separating organic phase and using anhydrous Na₂SO₄Drying, filtering, and distilling under reduced pressure to remove solvent to obtain tetramethylaldehyde methane.

8. The method according to claim 7, wherein the first solvent, the second solvent and the solvent in the solution of pentaerythritol are all dichloromethane.

9. The method of claim 3, wherein the reaction of S120 with the Liougat comprises:

10. The method according to claim 9, wherein the molar ratio of ammonium formate to formic acid is from 1: (1-2).

11. The preparation method according to claim 9, wherein the molar ratio of ammonium formate to tetramethylaldehyde methane is (6-8): 1.

12. the method according to claim 9, wherein the solvent of the third solvent and the solution of tetramethylaldehydic methane is toluene.

13. The method of claim 9, wherein the first predetermined temperature is 80 ℃ and the second predetermined temperature is 160 ℃.

14. The method of manufacturing according to claim 9, wherein the post-treatment comprises: vacuum filtering the mixed solution to remove black coke impurities, and sequentially using saturated NaHCO for the obtained filtrate₃Washing with saturated aqueous NaCl solution, separating the organic phase and using anhydrous Na₂SO₄Drying, filtering, and distilling the filtrate under reduced pressure to obtain white needle crystal, namely pentanetetramine.

15. The method of claim 2, wherein the step of reacting S100 pentaerythrityl tetramine with methyl acrylate by michael addition to obtain intermediate G0.5PATAM comprises:

16. The preparation method of claim 15, wherein the molar ratio of the pentaerythritol tetraamine to the methyl acrylate is 1 (8-12).

17. The method of claim 15, wherein the third predetermined temperature is 25 ℃.

18. The method of manufacturing according to claim 15, wherein the post-treatment comprises: and after the reaction is finished, carrying out reduced pressure distillation on the system, and carrying out silica gel column chromatography purification on the residue to obtain an intermediate product G0.5PATAM.

19. The method according to claim 18, wherein the distillation under reduced pressure is carried out at 25 ℃ and 133 Pa.

20. The method of claim 2, wherein the step of performing ester ammonolysis reaction between S200 intermediate G0.5PATAM and pentaerythritol tetraamine to obtain intermediate G1.0PATAM comprises:

21. The method of claim 20, wherein the molar ratio of intermediate G0.5PATAM to pentaenetetramine is 1: (8-12).

22. The method of claim 20, wherein the fourth predetermined temperature is 25 ℃.

23. The method of manufacturing of claim 20, wherein the post-processing comprises: and after the reaction is finished, carrying out reduced pressure distillation on the system, and carrying out silica gel column chromatography purification on the residue to obtain an intermediate product G1.0PATAM.

24. The method according to claim 23, wherein the distillation under reduced pressure is carried out at 72 ℃ and 266 Pa.

25. The method of claim 2, wherein the step of reacting intermediate G1.0PATAM with dimethyldiallylammonium chloride by Michael addition and simultaneously polymerizing dimethyldiallylammonium chloride to obtain the final product comprises:

intermediate G1.0PATAM was dissolved in water and the pH of the system was adjusted to 7 at N₂And (4) after the temperature is raised to a fifth preset temperature in the atmosphere, dropwise adding a dimethyl diallyl ammonium chloride aqueous solution for reaction, and performing post-treatment after the reaction is finished to obtain a final product.

26. The method of claim 25, wherein the molar ratio of intermediate G1.0PATAM to dimethyldiallylammonium chloride is 1: (2000-5000).

27. The method of claim 25, wherein the pH of the aqueous solution of dimethyldiallylammonium chloride is also adjusted to 7.

28. The process of claim 27, wherein NaHCO is used₃The pH is adjusted.

29. The method of claim 25, wherein the fifth predetermined temperature is 50-70 ℃.

30. The method of manufacturing of claim 25, wherein the post-processing comprises: after the reaction is finished, carrying out reduced pressure distillation on the system, and precipitating and purifying the remainder by using absolute ethyl alcohol to obtain a crude product;

31. The method of claim 30, wherein the drying is vacuum drying at 60 ℃ for 48 hours.

32. Use of the dendrimer derivative of claim 1 as a flocculant for treating waste water-based drilling fluids.