Amphiphilic macromolecule and use thereof

Abstract

Amphiphilic macromolecules having repeating structural units: structural units to adjust molecular weight and molecular weight distribution and charging property effects, high stereo-hindrance structural units, and amphiphilic structural units, which 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.

Claims

1. An amphiphilic macromolecule comprising: as repeating units, 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, the highly sterically hindered structural unit B comprises a structure G and a structure of formula (4), 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): ##STR00031## wherein in formula (3), R.sub.5 is H or a methyl group; R.sub.6 is a radical selected from the group consisting of the structures of formula (5) and formula (6): ##STR00032## in formula (5), a is an integer from 1 to 11; in formula (4), R.sub.7 is H; R.sub.8 is selected from the group consisting of H, —SO.sub.3H and salts thereof, —(CH.sub.2).sub.2CH.sub.3Cl, —CH.sub.2N.sup.+(CH.sub.3).sub.2(CH.sub.2).sub.ξCH.sub.3Cl.sup.−, and —CH.sub.2N.sup.+(CH.sub.3).sub.2(CH.sub.2).sub.2 N.sup.+(CH.sub.3).sub.2(CH.sub.2).sub.σCH.sub.32Cl.sup.−; ξ and σ are respectively integers from 1 to 15; and the amphiphilic structural unit C has a structure of formula (8): ##STR00033## in formula (8), R.sub.9 is H or a methyl group; R.sub.10 is —N.sup.+(CH.sub.3).sub.2(CH.sub.2).sub.rCH.sub.3X.sup.−, —N.sup.+((CH.sub.2)sCH.sub.3).sub.3X.sup.− or —N.sup.+(CH.sub.3)((CH.sub.2).sub.tCH.sub.3).sub.2X.sup.−; r is an integer from 3 to 21; s is an integer from 2 to 9; t is an integer from 3 to 15; and X.sup.− is Cl.sup.− or Br.sup.−.

2. The amphiphilic macromolecule as claimed in claim 1, wherein the structural unit A for adjusting the molecular weight, molecular weight distribution and charge characteristics comprises a (meth)acrylamide monomer unit A.sub.1 and/or a (meth)acrylic monomer unit A.sub.2.

3. The amphiphilic macromolecule as claimed in claim 2, wherein based on 100 mol % of the entire amphiphilic macromolecule repeating units, the molar percentage of the (meth)acrylamide monomer unit A.sub.1 is 70-99 mol %; and the molar percentage of the (meth)acrylic monomer unit A.sub.2 is 1-30 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 G is 0.02-2 mol %; and the molar percentage of the structure of formula (4) is 0.05-5 mol %.

5. 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 %.

6. The amphiphilic macromolecule as claimed in claim 1, wherein the structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics has a structure of formula (2): ##STR00034## wherein in formula (2), R.sub.1 is H or a methyl group; R.sub.2 and R.sub.3 are independently selected from the group consisting of H and a C.sub.1-C.sub.3 alkyl group; R.sub.4 is selected from the group consisting of H and a methyl group; Gr is —OH or —O.sup.−Na.sup.+; 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 %.

7. 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: ##STR00035##

8. The amphiphilic macromolecule as claimed in claim 1, wherein the highly sterically hindered structural unit B has a structure of formula (7): ##STR00036## wherein in formula (7), the definition on G is as described in claim 1; the definitions of R.sub.7 and R.sub.8 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 %.

9. The amphiphilic macromolecule as claimed in claim 8, wherein the amphiphilic macromolecule has a structure of formula (9): ##STR00037## wherein in formula (9), R.sub.4 is selected from the group consisting of H and a methyl group; 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 %; the definitions of G, R.sub.7, R.sub.8, x and y are as described in formula (7); the definitions of R.sub.9 and R.sub.10 are as described in formula (8); z represents the molar percentage of this structural unit in the entire amphiphilic macromolecule, and z is from 0.05 to 10 mol %.

10. The amphiphilic macromolecule as claimed in claim 1, which is a compound of formulas (I)-(X): ##STR00038## ##STR00039## ##STR00040##

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

12. The amphiphilic macromolecule as claimed in claim 1 for use in at least one of oilfield drilling, well cementing, fracturing, crude oil gathering and transporting, sewage treating, sludge treating and papermaking as an intensified oil producing agent, oil displacing agent, heavy oil viscosity reducer, fracturing fluid, clay stabilizer, sewage treating agent, retention aid and drainage aid and strengthening agent for papermaking.

13. The amphiphilic macromolecule as claimed in claim 1, wherein R.sub.5 is H.

Description

DESCRIPTION OF FIGURES

(1) 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 1×10.sup.4 mg/L at a temperature of 60° C.

(2) 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 1×10.sup.4 mg/L at the concentration of 1750 mg/L.

DETAILED DESCRIPTION OF THE INVENTION

(3) The present invention is further illustrated below by combining specific examples; however, this invention is not limited to the following examples.

Example 1

(4) This example synthesized the amphiphilic macromolecule of formula (I):

(5) ##STR00013##

(6) The synthesis of the amphiphilic macromolecule of this example was as follows:

(7) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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%, 0.25%, 0.5%, 1.25% 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 18° 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 970×10.sup.4.

Example 2

(8) This example synthesized the amphiphilic macromolecule of formula (II):

(9) ##STR00014##

(10) The synthesis route of the monomer

(11) ##STR00015##
was as follows:

(12) ##STR00016##

(13) The synthesis of the amphiphilic macromolecule of this example was as follows:

(14) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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 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 22° 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 1030×10.sup.4.

Example 3

(15) This example synthesized the amphiphilic macromolecule of formula (III):

(16) ##STR00017##

(17) The synthesis route of the monomer

(18) ##STR00018##
was as follows:

(19) ##STR00019##

(20) The synthesis of the amphiphilic macromolecule of this example was as follows:

(21) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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%, 26%, 0.1%, 0.1%, 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 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 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 620×10.sup.4.

Example 4

(22) This example synthesized the amphiphilic macromolecule of formula (IV):

(23) ##STR00020##

(24) The synthesis route of the monomer

(25) ##STR00021##
was as follows:

(26) ##STR00022##

(27) The synthesis of the amphiphilic macromolecule of this example was as follows:

(28) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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%, 0.1%, 0.4%, 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 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 390×10.sup.4.

Example 5

(29) This example synthesized the amphiphilic macromolecule of formula (V):

(30) ##STR00023##

(31) The synthesis route of the monomer

(32) ##STR00024##
was as follows:

(33) ##STR00025##

(34) The synthesis of the amphiphilic macromolecule of this example was as follows:

(35) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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%, 21%, 0.1%, 0.1%, 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 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 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 390×10.sup.4.

Example 6

(36) This example synthesized the amphiphilic macromolecule of formula (VI):

(37) ##STR00026##

(38) The synthesis of the amphiphilic macromolecule of this example was as follows:

(39) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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 73.5%, 25%, 0.5%, 0.5%, 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 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 45° 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 680×10.sup.4.

Example 7

(40) This example synthesized the amphiphilic macromolecule of formula (VII):

(41) ##STR00027##

(42) The synthesis of the amphiphilic macromolecule of this example was as follows:

(43) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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 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 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 690×10.sup.4.

Example 8

(44) This example synthesized the amphiphilic macromolecule of formula (VIII):

(45) ##STR00028##

(46) The synthesis of the amphiphilic macromolecule of this example was as follows:

(47) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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 70%, 28%, 0.15%, 0.75%, 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 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 390×10.sup.4.

Example 9

(48) This example synthesized the amphiphilic macromolecule of formula (IX):

(49) ##STR00029##

(50) The synthesis of the amphiphilic macromolecule of this example was as follows:

(51) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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%, 23.5%, 0.5%, 0.5%, 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 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 430×10.sup.4.

Example 10

(52) This example synthesized the amphiphilic macromolecule of formula (X):

(53) ##STR00030##

(54) The synthesis of the amphiphilic macromolecule of this example was as follows:

(55) Firstly, water, accounting for ¾ of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for ¼ 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 74%, 23%, 0.5%, 1.5%, 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 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 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 560×10.sup.4.

MEASUREMENT EXAMPLES

Measurement Example 1

(56) Saline having a mineralization degree of 1×10.sup.4 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.

(57) 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

(58) 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:

(59) $\mathrm{Viscosity}\mathrm{reduction}\mathrm{rate}\left(\%\right)=\frac{\begin{array}{c}\mathrm{viscosity}\mathrm{of}\mathrm{crude}\mathrm{oil}\mathrm{sample}-\\ \mathrm{viscosity}\mathrm{after}\mathrm{mixing}\end{array}}{\mathrm{viscosity}\mathrm{of}\mathrm{crude}\mathrm{oil}\mathrm{sample}}\times 100$

(60) Table 1 Experimental results of the heavy oil viscosity reduction of the amphiphilic macromolecule obtained from the example 6-example 10. (oil-water ratio 1:1, 25° C.)

(61) TABLE-US-00001 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 .Math. s) 1800 — 6700 — 18000 — Example 6 400 mg/L 850 52.78 2300 65.67 4700 73.89 600 mg/L 550 69.44 1475 77.99 2350 86.94 800 mg/L 340 81.11 975 85.45 1250 93.06 1000 mg/L  280 84.44 750 88.81 950 94.72 1200 mg/L  220 87.78 650 90.30 825 95.42 Example 7 400 mg/L 910 49.44 2400 64.18 4450 75.28 600 mg/L 590 67.22 1600 76.12 2100 88.33 800 mg/L 450 75.00 1175 82.46 1050 94.17 1000 mg/L  340 81.11 830 87.61 890 95.06 1200 mg/L  260 85.56 680 89.85 780 95.67 Example 8 400 mg/L 820 54.44 2050 69.40 4250 76.39 600 mg/L 470 73.89 1370 79.55 1975 89.03 800 mg/L 315 82.50 850 87.31 1325 92.64 1000 mg/L  230 87.22 675 89.93 930 94.83 1200 mg/L  200 88.89 590 91.19 850 95.28 Example 9 400 mg/L 925 48.61 2270 66.12 4700 73.89 600 mg/L 630 65.00 1420 78.81 2550 85.83 800 mg/L 450 75.00 940 85.97 1480 91.78 1000 mg/L  380 78.89 680 89.85 1050 94.17 1200 mg/L  340 81.11 530 92.09 880 95.11 Example 10 400 mg/L 820 54.44 1900 71.64 5100 71.67 600 mg/L 530 70.56 1250 81.34 2900 83.89 800 mg/L 390 78.33 825 87.69 1890 89.50 1000 mg/L  305 83.06 650 90.30 1400 92.22 1200 mg/L  260 85.56 575 91.42 1175 93.47

(62) 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

(63) 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.

(64) 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.