Comb polymer, method of preparing the same, and use thereof

Abstract

The present disclosure discloses a comb polymer or a salt thereof, wherein the structural formula of the comb polymer containing the following constitutional units. ##STR00001##
When the comb polymer provided in the present disclosure is used in a water-based drilling fluid as a filtration control agent, it can eliminate the defects of conventional filtration control agents which would be subject to ineffectiveness under high temperature and high salinity conditions. The comb polymer has high temperature and salt resistance, and can be produced through simple processes at comparatively low costs. When the comb polymer provided by the present disclosure is used as a filtration control agent, even being added into the drilling fluid at a comparatively low amount, it can still present rather good effects in lowering the amount of filter loss.

Claims

1. A comb polymer or a salt thereof for reducing filter loss of an oil drilling fluid, wherein the structural formula of the comb polymer contains the following constitutional units: ##STR00004## wherein the molar ratio of a to b to c is in the range of (20 to 50):(9 to 49):(1 to 60); wherein R.sub.1-R.sub.6 are identical to or different from one another and are independently selected from a group consisting of hydrogen and C.sub.1-C.sub.22 hydrocarbyls; wherein R.sub.7 is selected from a group consisting of hydrogen and alkyl sulfonic acids containing 1 to 22 carbon atoms; wherein R.sub.8 is selected from a group consisting of hydrogen, a carboxylic acid containing 1 carbon atom, and COO[(CH.sub.2).sub.2O].sub.mCH.sub.3; wherein R.sub.9 and R.sub.10 are hydrogen; wherein R.sub.11 is selected from a group consisting of [(CH.sub.2).sub.2O].sub.mCH.sub.3; wherein m is an integer in the range from 5 to 120; and wherein constitutional unit c is polyethylene glycol monomethyl ether acrylate or polyethylene glycol monomethyl ether maleate.

2. The comb polymer according to claim 1, wherein the viscosity average molecular weight of the comb polymer is in the range from 10,000 to 500,000.

3. The comb polymer according to claim 2, wherein the viscosity average molecular weight of the comb polymer is in the range from 10,000 to 200,000.

4. The comb polymer according to claim 1, wherein R.sub.1-R.sub.6 and R.sub.9-R.sub.10, identical to or different from one another respectively, can be independently selected from a group consisting of hydrogen and C.sub.1-C.sub.4 alkyls; wherein R.sub.7 is selected from a group consisting of hydrogen and alkyl sulfonic acids each containing 1 to 4 carbon atoms; and wherein R.sub.8 is selected from a group consisting of hydrogen, C.sub.1-C.sub.4 alkyls, and carboxylic acids each containing 1 to 4 carbon atoms, with m being an integer in the range from 10 to 110.

5. The comb polymer according to claim 4, wherein R.sub.2, R.sub.3, R.sub.5, R.sub.6, R.sub.9, and R.sub.10 are all hydrogen, wherein R.sub.1 and R.sub.4 are identical or different from one another and are selected from the group consisting of hydrogen and methyl, wherein R.sub.8 is hydrogen, and wherein R.sub.7 is selected from the group consisting of hydrogen and methylpropane sulfonic acid.

6. The comb polymer according to claim 1 prepared by mixing an aqueous solution of a first reactant, a second reactant, and a third reactant with an emulsifier and a nonpolar dispersion medium; and performing inverse emulsion polymerization in the presence of an initiator and an optional catalyst, wherein the first reactant, the second reactant, and the third reactant are respectively an unsaturated acid, an unsaturated amide or a derivative thereof, and an unsaturated acid ester.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows infra-red spectrum according to one example of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms a, an and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms comprises and/or comprising, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, group of elements, components, and/or groups thereof.

(3) Language such as including, comprising, having, containing, or involving, and variations thereof, is intended to be broad and encompass the subject matter listed thereafter, as well as equivalents, and additional subject matter not recited. Further, whenever a composition, a group of elements, process or method steps, or any other expression is preceded by the transitional phrase comprising, including or containing, it is understood that it is also contemplated herein the same composition, group of elements, process or method steps or any other expression with transitional phrases consisting essentially of, consisting of, or selected from the group of consisting of, preceding the recitation of the composition, the group of elements, process or method steps or any other expression.

(4) The present disclosure will be explained in further details with reference to examples, which, however, will not limit the present disclosure in any manner.

(5) Testing Methods

(6) Test of polymers: infrared spectrometer VERTEX-70 produced by Germany's Elemeraor company, KBr disc technique, and a nuclear magnetic resonance spectrometer Bruker Avance 400 MHz with deuterated dimethyl sulfoxide as a solvent were used.

(7) Test of viscosity: Viscosity was tested by a drilling-fluid six-speed viscometer at room temperature. Apparent viscosity equals 600 times reading of rotation divided by 2.

(8) Test of API filter loss: an API medium-pressure filtration device was used to measure the amount of filter loss at room temperature. API filter loss equals twice of the filter loss in 7.5 min.

(9) FIG. 1 shows spectrum according to one example of the present disclosure by means of FT-IR. In FIG. 1, 3438.11 cm.sup.1 represents a characteristic absorption peak of an NH bond in an amide group; 2874.16 cm.sup.1 represents an antisymmetric stretching vibration peak of a methyl group at a branch end; 1732.04 cm.sup.1 and 1677.28 cm.sup.1 are respectively in representation of a stretching vibration peak of a CO bond in an ester and a stretching vibration peak of a CO bond in an amide group; 1112.37 cm.sup.1 indicates a characteristic absorption peak of an ether in the structure of the polymer; and 1040.35 cm.sup.1 shows a stretching vibration peak of a CO bond.

EXAMPLES OF SYNTHESIS

Example 1

(10) 20 g of caustic soda was added into 80 mL of fresh water, which preceded slow dropwise addition of 30 g of acrylic acid. 25 g of acrylamide was then gradually added. The resulting mixture was stirred for homogeneous mixing to prepare an aqueous solution I for use. 2.28 g of peroxosulfuric acid and 1.04 g of sodium bisulfite were weighed and dissolved into 100 mL of water to prepare an initiator solution II. After that, 20 g of polyethylene glycol monomethyl ether acrylate (the molecular weight of which is about 5,000) was weighed, placed into a reactor, and completely liquefied at 90 C. 0.1 g of aminobenzenesulfonic acid and 0.1 g of p-toluenesulfonic acid were then respectively added, followed by dropwise addition of 0.4 ml of acrylic acid. After reaction was kept for 2 h at 95 C. in the reactor, the temperature was lowered down to 40 C. Subsequently, 100 mL of 5# white oil, 8 mL of OP-10, 6 mL of Tween60, and the aqueous solution I were added into the reactor in succession. The resulting mixture was stirred to generate a swirl and was homogeneously mixed. 8 mL of the initiator solution II was then dropwise added into the reactor. The resulting mixture was stirred for 1 h at 40 C. and this temperature was maintained for 4 h after the stirring. After routine purification treatment, a comb polymer salt I was obtained, the infrared spectrum of which is shown in FIG. 1.

Example 2

(11) The steps of Example 1 were repeated except the following differences. The aqueous solution I contained 25 g of caustic soda, 35 g of acrylic acid, and 30 g of acrylamide; 25 g of polyethylene glycol monomethyl ether acrylate (the molecular weight of which is about 2,400) was weighed, placed into a reactor, and completely liquefied at 90 C., followed by addition of 0.15 g of p-toluenesulfonic acid and dropwise addition of 0.5 ml of acrylic acid; 60 mL of 5# white oil, 60 mL of 7# white oil, 10 mL of OP-10, 7 mL of Tween60, and the aqueous solution I were successively added into the reactor; and 9 mL of the initiator solution II was dropwise added into the reactor. A comb polymer salt II was finally obtained.

Example 3

(12) The steps of Example 1 were repeated except the following differences. The aqueous solution I contained 25 g of caustic soda, 20 g of acrylic acid, 15 g of methacrylic acid, and 35 g of acrylamide; 25 g of polyethylene glycol monomethyl ether maleate (the molecular weight of which is about 500) was weighed, placed into a reactor, and completely liquefied at 90 C., followed by addition of 0.15 g of alkyl benzene sulfonic acid and dropwise addition of 0.5 ml of acrylic acid; 120 mL of 7# white oil, 10 mL of OP-10, 8 mL of Tween80, and the aqueous solution I were successively added into the reactor; and 9 mL of the initiator solution II was dropwise added into the reactor. A comb polymer salt III was finally obtained.

(13) The salts of the polymers in Examples 1 to 3 were tested by the infrared spectrometer and the nuclear magnetic resonance spectrometer, and the data thereof showed that the molar ratio among the three structure units was substantially the same as the molar ratio among the corresponding reactants added in the reactions.

EXAMPLES OF USE

Comparative Example 1

(14) 25 g of bentonite for slurry formulation was weighed and dissolved into 500 mL of water. The resulting mixture was stirred for 20 min, and stood for 24 h to obtain a bentonite slurry. The apparent viscosity and the API filter loss of the bentonite slurry were tested to be 18 mPa.Math.s, and 24 mL, respectively.

Example 4

(15) 2.5 g of the comb polymer salt I was weighed and added into the bentonite slurry obtained in Comparative Example 1. The resulting mixture was stirred for 20 min to obtain a mud slurry. The apparent viscosity of the mud slurry was tested to be 37 mPa.Math.s, and the API filter loss thereof was tested to be 10 mL by a drilling-fluid API medium-pressure filtration device.

Example 5

(16) 2.5 g of the comb polymer salt II was weighed and added into the bentonite slurry obtained in Comparative Example 1. The resulting mixture was stirred for 20 min to obtain a mud slurry. The apparent viscosity of the mud slurry and the API filter loss thereof were tested to be 40 mPa.Math.s and 8 mL, respectively. The mud slurry was hot rolled for 16 h at 180 C., and then taken out to be cooled down to room temperature. The apparent viscosity of the mud slurry and the API filter loss thereof were then tested to be 27 mPa.Math.s and 8.4 mL, respectively.

Example 6

(17) 2.5 g of the comb polymer salt III was weighed and added into the bentonite slurry obtained in Comparative Example 1. The resulting mixture was stirred for 20 min to obtain a mud slurry. The apparent viscosity of the mud slurry and the API filter loss thereof were tested to be 45 mPa.Math.s and 6 mL, respectively. 50 g of sodium chloride was further added. And the apparent viscosity of the mud slurry and the API filter loss thereof were further tested to be 44 mPa.Math.s and 7 mL, respectively. The mud slurry was hot rolled for 16 h at 180 C., and then taken out to be cooled down to room temperature. The apparent viscosity of the mud slurry and the API filter loss thereof were then tested to be 24 mPa.Math.s and 7.2 mL, respectively.

(18) TABLE-US-00001 TABLE 1 Apparent viscosity API filter loss Testing conditions (mPa .Math. s) (mL) Comparative Room temperature 18 24 Example 1 Example 4 Room temperature 37 10 Example 5 Room temperature 40 8 180 C./16 h 27 8.4 Example 6 Room temperature 45 6 Addition of NaCl 44 7 180 C./16 h 24 7.2

(19) The data in Table 1 indicate that when the comb polymer or the salt thereof according to the present disclosure was used as a filtration control agent, it can effectively reduce the amount of filter loss and improve the apparent viscosity. Moreover, the comb polymer can still lead to a comparatively low amount of filter loss after being treated at a high temperature, which shows rather good temperature resistance of the comb polymer as a filtration control agent. After sodium chloride (10%) was further added, the comb polymer obtained, as a filtration control agent, can still effectively lower the amount of filter loss and improve the apparent viscosity, which shows rather good salt resistance of the comb polymer. Therefore, the comb polymer provided by the present disclosure, as a filtration control agent, possesses excellent temperature and salt resistance, favorable chemical stability, and superior comprehensive performance. The polymer can reduce the amount of filter loss and enhance the apparent viscosity with effect, and thus has rather broad application prospects.

Comparative Example 2

(20) 12 g of bentonite and 0.9 g of sodium carbonate were weighed and added into 300 mL of deionized water. The resulting mixture was stirred at a high speed for 20 min, stood, and hydrated for 24 h to obtain a fresh-water-base slurry (4%). The data tested are shown in Table 2. The fresh-water-base slurry was then hot rolled for 16 h at 180 C. and the data are shown in Table 2.

Comparative Example 3

(21) Based on the volume of the fresh-water-base slurry obtained in Comparative Example 2, 1 wt/v % of DriscalD was added. The resulting mixture was stirred for 20 min. The data tested are shown in Table 2. 16 hours of hot rolling was then performed at 180 C. and the data are shown in Table 2.

Example 7

(22) Based on the volume of the fresh-water-base slurry obtained in Comparative Example 2, 0.2 wt/v % of the comb polymer salt I was added. The resulting mixture was stirred for 20 min. The data tested are shown in Table 2. 16 hours of hot rolling was performed at 180 C. and the data are shown in Table 2.

(23) TABLE-US-00002 TABLE 2 API Apparent Plastic Yield filter Testing viscosity viscosity point loss conditions (mPa .Math. s) (mPa .Math. s) (Pa) (mL) pH Comparative Room 7.2 2.5 4.7 27 8.00 Example 2 temperature 180 C./16 h 6.5 5.5 1 33 7.50 Example 7 Room 20 14 6 9 8.86 temperature 180 C./16 h 9 8 1 18 9.08 Comparative Room 66.5 21 45.5 11 8.00 Example 3 temperature 180 C./16 h 36.5 24.5 12 18.2 7.50

(24) The data in the table were tested and calculated according to the API standard.

(25) It can be seen from Table 2 that, the filtration-reducing effect of a fresh-water drilling fluid with an addition of 0.2% of the comb polymer salt would be equal to the filtration-reducing effect thereof with an addition of 1% of DriscalD. After being aged at a high temperature of 180 C., the slurry added with the comb polymer salt can still maintain the performance thereof.

Comparative Example 4

(26) 24 g of sodium chloride was weighed and added to 300 mL of the drilling fluid of Comparative example 2. The resulting mixture was stirred for 20 min at a high speed and then stood for 24 h to obtain a salt-water-base slurry (8%). The data tested are shown in Table 3. 16 hours of hot rolling was performed at 180 C. and the data are shown in Table 3.

Comparative Example 5

(27) Based on the volume of the salt-water-base slurry obtained in Comparative Example 4, 1 wt/v % of DriscalD was added. The resulting mixture was stirred for 20 min. The data tested are shown in Table 3. 16 hours of hot rolling was performed at 180 C. and the data are shown in Table 3.

Example 8

(28) Based on the volume of the salt-water-base slurry obtained in Comparative Example 4, 1 wt/v % of the comb polymer salt I was added. The resulting mixture was stirred for 20 min. The data tested are shown in Table 3. 16 hours of hot rolling was performed at 180 C. and the data are shown in Table 3. The data in the table were tested and calculated according to the API standard.

(29) TABLE-US-00003 TABLE 3 Apparent Plastic Yield Filter Testing viscosity viscosity point loss conditions (mPa .Math. s) (mPa .Math. s) (Pa) (ml) pH Comparative Room 4.5 3 1.5 53 8.00 Example 4 temperature 180 C./16 h 2.5 2 0.5 120 7.50 Example 8 Room 23 13 10 12 8.50 temperature 180 C./16 h 10 8 2 20 8.59 Comparative Room 45 21 24 7 9.00 Example 5 temperature 180 C./16 h 12.5 11 1.5 19 7.00

(30) Table 3 shows that when the same amount of a different filtration control agent (1 wt/v %) was added into a salt-water-base slurry, different results would be obtained after an aging treatment at a high temperature of 180 C. For example, when the comb polymer salt of the present disclosure was added, a high retention rate of viscosity of the base slurry can be obtained, and the apparent viscosity thereof was reduced by 55%; while addition of DriscalD would result in a reduction of apparent viscosity of the base slurry by 72%.

Comparative Example 6

(31) 180 g of sodium chloride was weighed and added into the bentonite slurry of Comparative example 1. The resulting mixture was stirred for 20 min and then stood for 24 h to obtain a saturated salt water slurry, and the data tested thereof are shown in Table 4. 16 hours of hot rolling was performed at 180 C. and the data are shown in Table 4.

Comparative Example 7

(32) 7.5 g of DriscalD was weighed and added into the saturated salt water slurry of Comparative Example 6. The resulting mixture was stirred for 20 min, and the performance thereof was tested and listed in Table 4.

Example 9

(33) 7.5 g of comb polymer I was weighed and added into the above saturated salt water slurry. The resulting mixture was stirred for 20 min, and the performance thereof was tested and listed in Table 4.

(34) TABLE-US-00004 TABLE 4 Apparent Plastic Yield Testing viscosity viscosity point Filter loss conditions (mPa .Math. s) (mPa .Math. s) (Pa) (ml) Comparative Room 4 2.5 1.5 120 Example 6 temperature 180 C./16 h 2 1.5 0.5 280 Comparative Room 33 18 15 20 Example 7 temperature 180 C./16 h 9.2 7 2.2 38 Example 9 Room 18 13 5 13 temperature 180 C./16 h 9 7 2 22

(35) Table 4 shows that in saturated salt water slurry, the comb polymer according to the present disclosure can effectively lower filter loss and improve apparent viscosity. After high-temperature treatment, a relatively low filter loss can still be maintained. Hence, the comb polymer, as a filtration control agent, has high temperature and salt resistance.

Comparative Example 8

(36) 15 g of calcium chloride was weighed and added into the bentonite slurry of Comparative example 1. The resulting mixture was stirred for 20 min and then stood for 24 h to obtain a 3 wt/v % calcium chloride-containing slurry, and the data tested thereof are shown in Table 5. 16 hours of hot rolling was performed at 180 C. and the data are shown in Table 5.

Comparative Example 9

(37) 7.5 g of DriscalD was weighed and added into the slurry of Comparative Example 8. The resulting mixture was stirred for 20 min, and the performance thereof was tested and listed in Table 5.

Example 10

(38) 7.5 g of comb polymer I was weighed and added into the slurry of Comparative Example 8. The resulting mixture was stirred for 20 min, and the performance thereof was tested and listed in Table 5.

(39) TABLE-US-00005 TABLE 5 Apparent Plastic Filter Testing viscosity viscosity Yield loss conditions (mPa .Math. s) (mPa .Math. s) point (Pa) (ml) Comparative Room 3 2 1 96 Example 8 temperature 180 C./16 h 2 1.5 0.5 192 Comparative Room 4 3 1 35 Example 9 temperature 180 C./16 h 5.5 4.5 1 56 Example 10 Room 4 3 1 22 temperature 180 C./16 h 5 4 1 32

(40) Table 5 shows that addition of the comb polymer according to the present disclosure in 3 wt/v % calcium chloride-containing slurry can effectively low filter loss and improve apparent viscosity. After high-temperature treatment, a relatively low filter loss can still be maintained. Hence, the comb polymer, as a filtration control agent, has high temperature and calcium resistance.

(41) The data in Tables 2 to 5 indicate that compared with the prior art (e.g. DriscalD), when the comb polymer according to the present disclosure is used as a filtration control agent, it will lead to rather good filtration-reducing effect when being added at an extremely small amount. Furthermore, the comb polymer of the present disclosure has good high-temperature stability with high retention rate of viscosity, and better temperature, salt, and calcium resistance. The data relating to parameters of yield point and the like also show that the comb polymer provided by the present disclosure can be used in a drilling fluid as a filtration control agent.

(42) It should be noted that the above examples are only used to explain, rather than to limit the present disclosure in any manner. Although the present disclosure has been discussed with reference to preferable examples, it should be understood that the terms and expressions adopted are for describing and explaining instead of limiting the present disclosure. The present disclosure can be modified within the scope of the claims, or can be amended without departing from the scope or spirits of the present disclosure. Although the present disclosure is described with specific methods, materials, and examples, the scope of the present disclosure herein disclosed should not be limited by the particularly disclosed examples as described above, but can be extended to other methods and uses having the same functions.