# Patent

## Title
Amphiphilic macromolecule and the purpose of this amphiphilic macromolecule

## Abstract

Amphiphilic macromolecules having structural units to adjust molecular weight and molecular weight distribution and charging property effects, high stereo-hindrance structural units, and having amphiphilic structural units. The Amphiphilic macromolecules are suitable for fields such as oil field well drilling, well cementation fracturing, oil gathering and transfer, sewage treatment, sludge treatment and papermaking, etc., and can be used as an oil-displacing agent for enhanced oil production, a heavy oil viscosity reducer, a fracturing fluid, a clay stabilizing agent, a sewage treatment agent, a papermaking retention and drainage aid or a reinforcing agent, etc.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage entry of PCT/CN2011/001578 filed Sep. 16, 2011, which claims priority to Chinese Patent Application No. 201110210344.1, filed on Jul. 26, 2011, said applications are expressly incorporated herein in their entirety.
TECHNICAL FIELD
This invention relates to an amphiphilic macromolecule and uses thereof, and this amphiphilic macromolecule is applicable to oilfield drilling, well cementing, fracturing, crude oil gathering and transporting, sewage treating, sludge treating and papermaking, and it can be used as intensified oil producing agent and oil displacing agent, heavy oil viscosity reducer, fracturing fluid, clay stabilizer, sewage treating agent, retention aid and drainage aid and strengthening agent for papermaking.
BACKGROUND OF THE INVENTION
The main function of the polymer used for tertiary oil recovery is believed to increase solution viscosity and decrease water permeability in oil layer, so as to decrease mobility ratio and adjust water injection profile, and thus to enhance oil recovery by increasing the conformance factor. The solution viscosity and stability of the viscosity are important indicators for determining polymer displacement characteristics, and also are the key problem for determining recovery effect. With the continuous increase of oilfield comprehensive water content, it becomes increasingly difficult to extract oil and keep stable production, thus the requirements on the polymer used for tertiary oil recovery also increase constantly.
Heavy oil recovery is a common problem worldwide. The heavy oil has characteristics of high viscosity, high gum asphaltene content or high wax content; heavy oil gathers up about 70% sulfur and 90% nitrogen of the crude oil, the light component which accounts for about 70% of the total heavy oil is the convertible section by using the current technology, but it is still difficult to convert it efficiently. The heavy component which accounts for about 20% of the total heavy oil is difficult to be converted directly by using conventional technology. The rest of the heaviest is 10% of bottom residue of the heavy oil, which is rich in over 70% of metals and over 40% of sulfur and nitrogen, it can't be converted effectively into light product. The heavy oil does not easily flow in the formation, wellbore and oil pipeline. Furthermore, since the oil-water mobility ratio is big, heavy oil can easily cause many problems such as rapid water breakthrough, high water content of produced fluid, and easy formation sand production. The process for heavy oil recovery can be mainly divided into recovery of liquid flooding (e.g., hot water flooding, steam huff and puff, steam flood and so on) and recovery of yield enhancement (e.g., horizontal well, compositing branched well, electric heating and etc). A chemical viscosity reducer can disperse and emulsify the heavy oil effectively, reduce the viscosity of the heavy oil remarkably and decrease the flow resistance of heavy oil in the formation and wellbore, which is significantly important for reducing energy consumption in the process of recovery, decreasing discharging pollution and enhancing heavy oil recovery.
BRIEF DESCRIPTION OF THE INVENTION
In the following context of this invention, unless otherwise defined, the same variable group, and molecular and structural formula have the same definitions.
The instant invention relates to an amphiphilic macromolecule, this amphiphilic macromolecule has repeating units as described below: a structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics, a highly sterically hindered structural unit B and an amphiphilic structural unit C.
In an embodiment, the structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics comprises (meth)acrylamide monomer unit A1 and/or (meth)acrylic monomer unit A2. Preferably, the structural unit A includes (meth)acrylamide monomer unit A1 and/or (meth)acrylic monomer unit A2 simultaneously. In the art, the molecular weight of the amphiphilic macromolecule may be selected as needed, preferably, this molecular weight may be selected between 1000000-20000000.
Preferably, the (meth)acrylamide monomer unit A1 has a structure of formula (1):




In formula (1), R1 is H or a methyl group; R2 and R3 are independently selected from the group consisting of H and a C1-C3 alkyl group; R2 and R3 are preferably H.
Preferably, the (meth)acrylic monomer unit A2 is (meth)acrylic acid and/or (meth)acrylate. Preferably the (meth)acrylate is sodium methacrylate.
Preferably, the molar percentage of (meth)acrylamide monomer unit A1 in the entire amphiphilic macromolecule repeating units is 70-99 mol %; preferably 70-90 mol %, more preferably 72.85-78 mol %.
Preferably, the molar percentage of (meth)acrylic monomer unit A2 in the entire amphiphilic polymer repeat units is 1-30 mol %; preferably 1-25 mol %, and more preferably 20-25 mol %.
In another embodiment, the structural unit A for the regulation of molecular weight, molecular weight distribution and charge characteristics has a structure of formula (2):




wherein, R1 is H or a methyl group; R2 and R3 are independently selected from the group consisting of H and a C1-C3 alkyl group; R2 and R3 are preferably H; R4 is selected from H or a methyl group; Gr is —OH or —O−Na+; m and n represent the molar percentages of the structural units in the entire amphiphilic macromolecule repeating units, and m is 70-99 mol %, preferably 70-90 mol %, more preferably 72.85-78 mol %; n is 1-30 mol %, preferably 1-25 mol %, more preferably 20-25 mol %.
In another embodiment, in formula (2), R1-R3 are preferably H, and Gr is preferably —O−Na+.
In another embodiment, the highly sterically hindered structural unit B contains at least a structure G, wherein the structure G is a cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain, or is selected from a structure of formula (3), and the highly sterically hindered structural unit B optionally contains a structure of formula (4):




In formula (3), R5 is H or a methyl group; preferably H; R6 is a radical selected from the group consisting of the structures of formulas (5) and (6).




In formula (5), a is an integer from 1 to 11; preferably 1-7;
In formula (4), R7 is H or a methyl group; R8 is selected from the group consisting of —NHPhOH, —OCH2Ph, —OPhOH, —OPhCOOH and salts thereof, —NHC(CH3)2CH2SO3H and salts thereof, —OC(CH3)2(CH2)bCH3, —NHC(CH3)2(CH2)cCH3, —OC(CH3)2CH2C(CH3)2(CH2)dCH3, —NHC(CH3)2CH2C(CH3)2(CH2)eCH3, —O(CH2)fN+(CH3)2CH2PhX−,




wherein b and c are respectively integers from 0 to 21, preferably from 1 to 11; d and e are respectively integers from 0 to 17, preferably from 1 to 7; f is an integer from 2 to 8, preferably from 2 to 4; and X− is CP or Br−.
Preferably, the highly sterically hindered structural unit B comprises a structure G and a structure of formula (4).
In another embodiment, the cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain is selected from the group consisting of:




Preferably, the molar percentage of structure G of the highly sterically hindered structural unit B in the entire amphiphilic macromolecule repeating units is 0.02-2 mol %; preferably 0.02-1.0 mol %, more preferably 0.05-0.5 mol %.
Preferably, the molar percentage of the structure of formula (4) of the highly sterically hindered structural unit B in the entire amphiphilic macromolecule repeating units is 0.05-5 mol %; preferably 0.1-2.5 mol %, more preferably 0.1-1.0 mol %.
In another embodiment, the highly sterically hindered structural unit B has a structure of formula (7):




In formula (7), the definition on G is as described above, preferably the structure of formula (3),




the definitions on R7 and R8 are as described in formula (4). x and y represent the molar percentages of the structure units in the entire amphiphilic macromolecule repeating units, and x is 0.02-2 mol %, preferably 0.02-1.0 mol %, more preferably 0.05-0.5 mol %; y is 0.05-5 mol %, preferably 0.1-2.5 mol %, and more preferably 0.1-1.0 mol %.

In another embodiment, the amphiphilic structural unit C has a structure of formula (8):




In formula (8), R9 is H or a methyl group; R10 is —N+(CH3)2(CH2)ξCH3X−, —N+((CH2)σCH3)3X− or —N+(CH3)((CH2)τCH3)2X−; ξ is an integer from 3 to 21; σ is an integer from 2 to 9; τ is an integer from 3 to 15; X− is Cl− or Br−. Preferably, ξ is from 3 to 17, σ is from 2 to 5, τ is from 3 to 11.
Preferably, the molar percentage of amphiphilic structural unit C in the entire amphiphilic macromolecule repeating units is 0.05-10 mol %; preferably 0.1-5.0 mol %, more preferably 0.5-1.8 mol %.
In another embodiment, the amphiphilic macromolecule has a structure of formula (9):




In formula (9), the definitions on R4, m and n are as described in formula (2); the definitions on R7, R8, G, x and y are as described in formula (7); the definitions on R9 and R10 are as described in formula (8); z represents the molar percentage of this structural unit in the entire amphiphilic macromolecule repeat units, and z is 0.05-10 mol %, preferably 0.1-5.0 mol %, more preferably 0.5-1.8 mol %.
Specifically, this present invention provides a high molecular compound having a structure of formulas (I)-(X):










The molecular weight of the amphiphilic macromolecule described above is between 1000000 and 20000000; preferably between 3000000 and 13000000.
The measurement of the molecular weight M is as follows: The intrinsic viscosity [η] is measured by Ubbelohde viscometer as known in the art, then the obtained intrinsic viscosity [η] value is used in the following equation to obtain the desired molecular weight M:

M=802[η]1.25 

The amphiphilic macromolecule according to this present invention can be prepared by known methods in the art, for example, by polymerizing the structural unit for adjusting molecular weight, molecular weight distribution and charge characteristics, the highly sterically hindered structural unit and the amphiphilic structural unit in the presence of an initiator. The polymerization process can be any type well known in the art, such as, suspension polymerization, emulsion polymerization, solution polymerization, precipitation polymerization, and etc.
A typical preparation method is as follows: the above monomers are each dispersed or dissolved in an aqueous system under stirring, the monomer mixture is polymerized by the aid of an initiator under nitrogen atmosphere to form the amphiphilic macromolecule. The so far existing relevant technologies for preparing an amphiphilic macromolecule can all be used to prepare the amphiphilic macromolecule of this invention.
All the monomers for preparing the amphiphilic macromolecule can be commercially available, or can be prepared on the basis of prior art technology directly, and some monomers' synthesis are described in details in specific examples.



DESCRIPTION OF FIGURES
FIG. 1 depicts the relationship of viscosity vs. concentration of the amphiphilic macromolecules obtained from examples 1-5 of the invention in saline having a degree of mineralization of 3×104 mg/L at a temperature of 85° C.
FIG. 2 depicts the relationship of viscosity vs. temperature of the amphiphilic macromolecules obtained from the examples 1-5 of the invention in saline having a degree of mineralization of 3×104 mg/L at the concentration of 1750 mg/L.



DETAILED DESCRIPTION OF THE INVENTION
The present invention is further illustrated below by combining specific examples; however, this invention is not limited to the following examples.
Example 1
This example synthesized the amphiphilic macromolecule of formula (I):




The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.15%, 0.65%, 1.2% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 28° C.; after 5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 1160×104.
Example 2
This example synthesized the amphiphilic macromolecule of formula (II).




The synthesis route of the monomer




was as follows:





The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 24%, 0.15%, 0.1%, 0.75% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 40 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 25° C.; after 5.5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 730×104.
Example 3
This example synthesized the amphiphilic macromolecule of formula (III):




The synthesis route of the monomer




was as follows:





The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 77%, 21%, 0.25%, 0.25%, 1.5% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 23° C.; after 5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 720×104.
Example 4
This example synthesized the amphiphilic macromolecule of formula (IV):




The synthesis route of the monomer





was as follows:





The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.05%, 0.15%, 1.8% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 28° C.; after 5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 460×104.
Example 5
This example synthesized the amphiphilic macromolecule of formula (V):




The synthesis route of the monomer




was as follows





The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 78%, 20%, 0.2%, 1%, 0.8% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 10, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 25° C.; after 6 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 580×104.
Example 6
This example synthesized the amphiphilic macromolecule of formula (VI):




The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 73%, 24%, 0.5%, 1%, 1.5% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 55° C.; after 3 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 770×104.
Example 7
This example synthesized the amphiphilic macromolecule of formula (VII):




The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 77%, 22%, 0.25%, 0.25%, 0.5% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 55° C.; after 2 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 920×104.
Example 8
This example synthesized the amphiphilic macromolecule of formula (VIII):




The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 72.85%, 25%, 0.15%, 1%, 1% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 10, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 55° C.; after 3 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 430×104.
Example 9
This example synthesized the amphiphilic macromolecule of formula (IX):




The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.25%, 0.25%, 1.5% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 50° C.; after 2.5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 690×104.
Example 10
This example synthesized the amphiphilic macromolecule of formula (X):




The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3⁄4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1⁄4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.25%, 0.25%, 1.5% in succession. The mixture was stirred until complete dissolution, and a pH adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 50° C.; after 4 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 830×104.
MEASUREMENT EXAMPLES
Measurement Example 1
Saline having a mineralization degree of 3×104 mg/L was used to prepare amphiphilic macromolecule solutions with different concentrations, and the relationship between the concentration, temperature and the viscosity of the solution was determined. The results were shown in FIG. 1 and FIG. 2.
The figures showed that the amphiphilic macromolecule solutions of examples 1-5 still have favorable viscosifying capacity under the condition of high temperature and high degree of mineralization. The highly sterically hindered unit in the amphiphilic macromolecule reduced the rotational degree of freedom in the main chain and increased the rigidity of the macromolecule chain, which made the macromolecule chain difficult to curl and tend to stretch out, thus enlarging the hydrodynamic radius of the macromolecule; in the meantime, the amphiphilic structural unit associated each other to form the microdomain by intramolecular- or intermolecular-interaction, thus enhancing the viscosifying capacity of the solution remarkably under the conditions of high temperature and high salinity.
Measurement Example 2
Testing method: Under a testing temperature of 25° C., 25 ml electric dehydration crude oil samples from three types of oilfields were added in a 50 ml test tube with a plug, then 25 ml aqueous solutions of amphiphilic macromolecule with different concentrations formulated with distilled water were added in. The plug of the test tube was tightened, then the test tube was shaken manually or by using an oscillating box for 80-100 times in horizontal direction, and the shaking amplitude should be greater than 20 cm. After sufficient mixing, the plug of the test tube was loosed. Viscosity reduction rate for crude oil was calculated according to the following equation:




  
    Viscosity
    ⁢
    
      
    
    ⁢
    reduction
    ⁢
    
      
    
    ⁢
    
      rate
      ⁡
      
        (
        %
        )
      
    
  
  =
  
    
      
        
          viscosity
          ⁢
          
            
          
          ⁢
          of
          ⁢
          
            
          
          ⁢
          crude
          ⁢
          
            
          
          ⁢
          oil
          ⁢
          
            
          
          ⁢
          sample
        
        -
        
          viscosity
          ⁢
          
            
          
          ⁢
          after
          ⁢
          
            
          
          ⁢
          mixing
        
      
      
        viscosity
        ⁢
        
          
        
        ⁢
        of
        ⁢
        
          
        
        ⁢
        crude
        ⁢
        
          
        
        ⁢
        oil
        ⁢
        
          
        
        ⁢
        sample
      
    
    ×
    100
  











TABLE 1







Experimental results of the heavy oil viscosity reduction of the amphiphilic macromolecule


obtained from the example 6 to example 10 (oil-water ratio 1:1, 25)













oil-water volume ratio








(1:1)
oil
viscosity
oil
viscosity
oil
viscosity


test temperature
sample
reduction
sample
reduction
sample
reduction


(25° C.)
1
rate(%)
2
rate(%)
3
rate(%)
















initial viscosity (mPa · s)
1650
—
5100
—
16000
—














Example 6
400 mg/L
730
55.76
1750
65.69
7100
55.63



600 mg/L
470
71.52
1250
75.49
3250
79.69



800 mg/L
330
80.00
950
81.37
1850
88.44



1000 mg/L 
295
82.12
820
83.92
1500
90.63



1200 mg/L 
270
83.64
675
86.76
1225
92.34


Example 7
400 mg/L
780
52.73
1800
64.71
7700
51.88



600 mg/L
590
64.24
1350
73.53
4200
73.75



800 mg/L
460
72.12
1100
78.43
2850
82.19



1000 mg/L 
340
79.39
880
82.75
1900
88.13



1200 mg/L 
300
81.82
790
84.51
1500
90.63


Example 8
400 mg/L
820
50.30
1475
71.08
5650
64.69



600 mg/L
590
64.24
1200
76.47
3950
75.31



800 mg/L
450
72.73
850
83.33
2600
83.75



1000 mg/L 
375
77.27
670
86.86
1450
90.94



1200 mg/L 
330
80.00
620
87.84
1290
91.94


Example 9
400 mg/L
780
52.73
1450
71.57
5800
63.75



600 mg/L
450
72.73
1150
77.45
4100
74.38



800 mg/L
360
78.18
850
83.33
2500
84.38



1000 mg/L 
280
83.03
680
86.67
1570
90.19



1200 mg/L 
260
84.24
620
87.84
1390
91.31


Example 10
400 mg/L
710
56.97
1450
71.57
5270
67.06



600 mg/L
500
69.70
1050
79.41
3100
80.63



800 mg/L
410
75.15
830
83.73
1890
88.19



1000 mg/L 
320
80.61
675
86.76
1200
92.50



1200 mg/L 
270
83.64
650
87.25
950
94.06









Table 1 showed that the amphiphilic macromolecules of examples 6-10 had good effects for viscosity reduction as to all three oil samples. With the increase of the concentration of the amphiphilic macromolecule solution, the viscosity reduction rate increased. And, when the concentration of the amphiphilic macromolecule solution was the same, the viscosity reduction rate increased with the enhancing of the viscosity of the oil sample. It was believed that the amphiphilic macromolecule could reduce the viscosity of the crude oil remarkably via a synergetic effect between the highly sterically hindered structural unit and the amphiphilic structural unit, which could emulsify and disperse the crude oil effectively.
INDUSTRIAL APPLICATION
The amphiphilic macromolecule of this invention can be used in oilfield drilling, well cementing, fracturing, crude oil gathering and transporting, sewage treating, sludge treating and papermaking, and it can be used as intensified oil producing agent and oil displacing agent, heavy oil viscosity reducer, fracturing fluid, clay stabilizer, sewage treating agent, retention aid and drainage aid and strengthening agent for papermaking.
The amphiphilic macromolecule of this invention is especially suitable for crude oil exploitation, for instance, it can be used as an intensified oil displacement polymer and a viscosity reducer for heavy oil. When it is used as an oil displacement agent, it has remarkable viscosifying effect even under the condition of high temperature and high salinity, and can thus enhance the crude oil recovery. When it is used as a viscosity reducer for heavy oil, it can remarkably reduce the viscosity of the heavy oil and decrease the flow resistance thereof in the formation and wellbore by emulsifying and dispersing the heavy oil effectively.

## Claims

1. An amphiphilic macromolecule comprising: as repeating units, a structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics, a sterically hindered structural unit B and an amphiphilic structural unit C, wherein the amphiphilic structural unit C has a structure of formula (8):



wherein in formula (8), R9 is H or a methyl group; R10 is —N+(CH3)2(CH2)86CH3X−, —N+((CH2)σCH3)3X− or —N+(CH3)((CH2)τCH3)2X−; ξ is an integer from 3 to 21; σ is an integer from 2 to 9; τ is an integer from 3 to 15; and X− is Cl− or Br−; and
wherein the structural unit A for adjusting the molecular weight, molecular weight distribution and charge characteristics comprises a (meth)acrylamide monomer unit A1 and a (meth)acrylic monomer unit A2; and
wherein the sterically hindered structural unit B contains a structure G, the structure G is a cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain, or is selected from a structure of formula (3), and the sterically hindered structural unit B optionally contains a structure of formula (4):




wherein in formula (3), R5 is H or a methyl group; R6 is a radical selected from the structures of formula (5) and formula (6),




wherein in formula (5), a is an integer from 1 to 11, and
wherein in formula (4), R7 is H or a methyl group; R8 is selected from the group consisting of —NHPhOH, —OCH2Ph, —OPhOH, —OPhCOOH and salts thereof, —NHC(CH3)2CH2SO3H and salts thereof, —OC(CH3)2(CH2)bCH3, —NHC(CH3)2(CH2)cCH3, —OC(CH3)2CH2C(CH3)2(CH2)dCH3, —NHC(CH3)2CH2C(CH3)2(CH2)eCH3, —O(CH2)fN+(CH3)2CH2PhX−,




wherein b and c are integers from 0 to 21 respectively; d and e are integers from 0 to 17 respectively; f is an integer from 2 to 8; and X− is Cl− or Br.

2. The amphiphilic macromolecule as claimed in claim 1, wherein based on 100 mol % of the entire amphiphilic macromolecule repeating units, the molar percentage of the (meth)acrylamide monomer unit A1 is 70-99 mol %; and the molar percentage of the (meth)acrylic monomer unit A2 is 1-30 mol %.

3. The amphiphilic macromolecule as claimed in claim 1, wherein based on 100 mol % of the entire amphiphilic macromolecule repeating units, the molar percentage of the structure G is 0.02-2 mol %; and the molar percentage of the structure of formula (4) is 0.05-5 mol %.

4. The amphiphilic macromolecule as claimed in claim 1, wherein based on 100 mol % of the entire amphiphilic macromolecule repeating units, the molar percentage of the structure of formula (8) is 0.05-10 mol %.

5. The amphiphilic macromolecule as claimed in claim 1, wherein the cyclic hydrocarbon structure formed on the basis of the two adjacent carbon atoms in the main chain is selected from the group consisting of:

6. The amphiphilic macromolecule as claimed in claim 1, wherein the sterically hindered structural unit B has a structure of formula (7):



wherein in formula (7) the definition on R7 and R8 are as described in formula (4); x and y respectively represent the molar percentages of the structural units in the entire amphiphilic macromolecule, and x is from 0.02 to 2 mol %, y is from 0.05 to 5 mol %.

7. The amphiphilic macromolecule as claimed in claim 1, wherein the amphiphilic macromolecule has a structure of formula (9):



in formula (9), the definitions on R4, m and n are as described in formula (2); the definitions on R7, R8, G, x and y are as described in formula (7); the definitions on R9 and R10 are as described in formula (8); z represents the molar percentage of this structural unit in the entire amphiphilic macromolecule repeating unit, and z is from 0.05 to 10 mol %.

8. The amphiphilic macromolecule as claimed in claim 1, which is a compound of formulas (I)-(X):









wherein m, n, x, y, and z in formulae (I) to (X) respectively represent the molar percentages of the structural units in the entire amphiphilic macromolecule, in which, m is from 70 to 99 mol %; n is from 1 to 30 mol %; x is from 0.02 to 2 mol %, y is from 0.05 to 5 mol %, and z is from 0.05 to 10 mol %.

9. The amphiphilic macromolecule as claimed in claim 1, wherein the amphiphilic macromolecule has a molecular weight of between 1000000-20000000.

10. A method comprising:
formulating the amphiphilic macromolecule as claimed in claim 1 into an aqueous solution; and
utilizing the aqueous solution in oilfield drilling, well cementing, fracturing, crude oil gathering and transporting, sewage treating, sludge treating and papermaking as intensified oil producing agent and oil displacing agent, or as a heavy oil viscosity reducer, fracturing fluid component, clay stabilizer, sewage treating agent, retention aid and drainage aid or strengthening agent for papermaking.

11. An amphiphilic macromolecule comprising: as repeating units, a structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics, a sterically hindered structural unit B and an amphiphilic structural unit C, wherein the amphiphilic structural unit C has a structure of formula (8):



wherein in formula (8), R9 is H or a methyl group; R10 is —N+(CH3)2(CH2)ξCH3X−, —N+((CH2)σCH3)3X− or —N+(CH3)((CH2)τCH3)2X−; ξ is an integer from 3 to 21; σ is an integer from 2 to 9; τ is an integer from 3 to 15; and X− is Cl− or Br−; and
wherein the structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics has a structure of formula (2);




wherein in formula (2), R1 is H or a methyl group; R2 and R3 are independently selected from the group consisting of H and a C1-C3 alkyl group; R4 is selected from the group consisting of H and a methyl group; Gr is —OH or —O−Na+; m and n represent the molar percentages of the structural units in the entire amphiphilic macromolecule, and m is from 70 to 99 mol %; n is from 1 to 30 mol %.