• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A hydrophobe associative composition of an ethylenically unsaturated, water-soluble monomer such as acrylamide and an ethylenically unsaturated amphiphilic monomer such as dodecyl poly(oxyethylene)10 methacrylate which is particularly effective for increasing the viscosity of brines or other aqueous media contaning salts or other electrolytes. Such copolymers are therefor useful in mobility control fluids and fracturing fluids for enhanced oil recovery and as drag reduction agents.
    公开号:SU1588285A3
    申请号:SU853966245
    申请日:1985-10-01
    公开日:1990-08-23
    发明作者:Эвани Сиамаларао；Фунг К.Ван
    申请人:Дзе Дау Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to hydrophobic compositions that increase the viscosity of aqueous media containing water-soluble electrolytes.
    The purpose of the invention is to increase the viscosity of the composition.
    Example 1. A. Preparation of dodecylpoly (oxyethylene) methacrylate.
    Into a 100 ml reaction flask equipped with inlet and outlet openings for the supply and discharge of nitrogen with a column (30 cm) filled with glass balls, a condenser and a receiver, is charged with 20 wt. Hours. (32 mmol) dodecylpoly (oxyethylene); 0.03 May. h. Phenothiazine, 30 ma.ch. (0.3 mol) of methyl methacrylate and 0.4 wt.h. titanium (IV) isopropoxide. Nitrogen is slowly passed through the reaction mixture and heated to within 6 hours. Unreacted metal methacrylate is removed at 40 ° C and pressure of 5 to mm Hg. Amphiphilic monomer is 92% pure as determined by nuclear magnetic resonance.
    B. Preparation of dodecylpoly (hydroxyethyl) ethacrylate.
    From 20 ma.ch. Dodecyl (oxyethylene), which is a solid at 50 room temperature, is prepared with a 50% solution in toluene. . The solution is placed in a reaction flask,
    cl
    00 00
    one
    00 | SL
    s
    31588285
    from 0.03 math. fenokak described in (A) thiazine, 35 ma.ch.h. methyl methacrylate and About 5 ma.ch. titanium (IV) isopropoxide, and heated at 103 ° C for 7 hours. The frequency of removal of unreacted methyl methacrylate by extraction with toluene is determined by frequency using a magnetic magnetic resonance, which is 90%.
    Example 2. The polymers and composition are prepared as follows. In reactionary capacity 1
    300 ml of 25 ml of polymer water concentration about 0.5%. Reet
    ten
    the thief is kept at 23 ° C for 3-4 hours until equilibrium is reached.
    The viscosity of the composition solution is measured using Haake rotary dosimeters or LVT or RVT Brookfield viscometers with an appropriate spindle and rotational speed, which has already been established. if y .- - I «ooa containing dodecyl sulfate is sodium-j thief polymer and then incubated with pa ...., ,, -. Oh - t. TTTnKui GTRG TWUTi
    OUpcij „,, 1,.
    ri, a water-soluble monomer (.s} and an amphiphilic monomer of alkylpoly (oxystylen) methacrylate, in amounts specified in Table 1. The mixture is stirred until a clear solution is obtained. 20 Then, 1.5 ml of 2% pentanate are added successively - howl salt (carboxymethylamine (bis) - ethylene nitrile). tetraacetic acid (V-80) in water and 2.4 g of a 1% solution of 25 az azobisisobutylonitrile (AZO) in t-butyl alcohol per autoclave and for a few minutes agitated. If necessary, isopropyl alcohol (IPA) is then added as a chain transfer agent. the autoclave is then brought to a certain rate by adding deionized water and degassed several times alternately (5-10 cycles) by creating a vacuum and purging with nitrogen.The autoclave is then closed and heated in a water bath for 16 hours for copolymerization, by copolymerizing monomers in this way. After copolymerization, the contents of the autoclave are cooled to room temperature and the polymer is removed as a thick aqueous solution (polymeric
    gel) .45
    For comparison, water-soluble polymers of water-soluble monomers that do not contain alkyl (poly) oxyethylene-methacrylate are obtained.
    Example 3. Preparation of the composition.
    The polymers are diluted with deionized water to obtain a solution which can be stirred and stirred for 24 hours to obtain a homogeneous solution. The solution is then made to pH 7.5 with 2% sodium hydroxide solution and then diluted with deionized water to a solution for 2 to 3 hours to achieve equilibrium. The viscosity of the resulting solution is measured as determined using a Brunfield or Gaack viscometer. The compositions are given in table. 2 and 3.
    As can be seen from the data table. 2, the viscosity of solutions of hydrophobic associative polymers (samples 1–4) is significantly higher than the viscosity of the solution of the control polymer (sample C), which is similar to hydrophobic polymers, except when it does not contain poly (oxyethylene) methacrylate. This difference in viscosity increases as shown in Table. 2 as polymer concentrations increased.
    The data table. 3 show that the addition of electrolyte (NaCl) to control aqueous solutions (samples C and
    C a) either does not affect viscosity at all, as in sample C, which contains an acrylamide homopolymer, or reduces viscosity, as in sample Cj, which contains an acrylamide / acrylic acid copolymer. On the contrary, the viscosities of aqueous solutions containing a hydrophobic copolymer are increased by the addition of electrolyte.
    As can be seen from the data table. 4. aqueous solutions of hydrophobic polymers (samples 9–12) retain a larger percentage of their initial viscosity when exposed to higher temperatures than aqueous solutions containing control polymers (image
    tsy G, and
    With c).
    Formula
    acquisitions
    Polymer composition for thickening aqueous media comprising a water-soluble copolymer, sodium chloride
    polymer concentration of about 0.5%. Reet
    the thief is kept at 23 ° C for 3-4 hours until equilibrium is reached.
    The viscosity of the composition solution is measured using Haake rotary dosimeters or LVT or RVT Brookfield viscometers with an appropriate spindle and rotational speed that has already been established. The solution of each copolymer and water soluble electrolyte is obtained by dissolving the calculated amount of electrolyte in the polymer solution and then incubating ,, -. Oh - t. TTTnKui GTRG TWUTi
    target within 2-3 hours to achieve balance. The viscosity of the resulting solution is measured as determined using a Brunfield or Gaack viscometer. The compositions are given in table. 2 and 3.
    As can be seen from the data table. 2, the viscosity of solutions of hydrophobic associative polymers (samples 1–4) is significantly higher than the viscosity of the solution of the control polymer (sample C), which is similar to hydrophobic polymers, except when it does not contain poly (oxyethylene) methacrylate. This difference in viscosity increases as shown in Table. 2 as polymer concentrations increased.
    The data table. 3 show that the addition of electrolyte (NaCl) to control aqueous solutions (samples C and
    C a) either does not affect viscosity at all, as in sample C, which contains an acrylamide homopolymer, or reduces viscosity, as in sample Cj, which contains an acrylamide / acrylic acid copolymer. Conversely, the viscosities of aqueous solutions containing a hydrophobic copolymer are increased by the addition of electrolyte.
    As can be seen from the data table. 4. aqueous solutions of hydrophobic polymers (samples 9-12) retain a large percentage of their initial viscosity when exposed to higher temperatures than aqueous solutions containing control polymers (samples G, and
    With c).
    Formula
    acquisitions
    Polymer composition for thickening aqueous media, including water soluble copolymer, sodium chloride
    .one
    and water, characterized in that, in order to viscosity as a water-soluble copolymer, it contains a copolymer of 99.90- 99.975 mol.% acrylamide and 0.025- 0.1 mol.% dodecyl poly (oxyethyleneK, - methacrylate with viscosity O , 2% solution of copolymer with Brookfield 6.8-1075 cP or copolymer 74.8
    / L Q lg, t V. “,
    882856
    The endoly is poly (oxyethylene) "methacrylate and 25 mol.% of acrylic acid in zrg2 ° g r ° copolymer at 2.: with Brookfield 1000-1300 cP,
    where n is the number of oxyethylene units 10 or 20, with the following content of components, oil: Water-soluble
    Copolymer
    75.0 o
    25
    PR and “e ha and„ „e. DAM - acre“ la ““ in the water solution of the protruding government of the region
    ;; PCT - - - ° oks „e;„ l / ir fb,. l ° alkyl group, (a) m 20, n form 487 “og ° 2-AA - acrylic acid is added”; at
    .. ™ rLr: - -rb,. :: r.%, L;. I -: i7:, L-z-, f; - ;,. .Table 2
    a ni
    Brookfield viscosity at 25 s determined using a Brookfishche LVT viscometer operating at rpm. At viscosities of up to 100 cP, an adapter VL was used, at viscosities from 100 to 5000 SP, spindle No. 2 was used, at viscosities above 5000 cP, spindle No. 3. Concentration of the copolymer in solution tested for viscosity was used.
    25.0
    36.65 13.15 O
    2, i
    250
    0.2 6.8
    (izveY)
    7
    eight
    (ivej
    In S.
    1 C.
    0.2 0.2
    10.0 5.9
    0.2 1000.0
    0.1 0.2
    1330.0 500.0
    7.0
    10.1
    Undefined 9900.0
    4100.0 23.1
    t
    I C C.
    0.2 0.2 0.2
    86.2 86.2 86.2
    Table 3


    13.1
    Undefined 3700.0
    2600.0 14.0
    Lena
    3100.0
    5700.0 Not defined
    18.6 5.9
    Undefined 5100.0 12.0

    8.8 Not defined - 79.5
    Lena
    43.6 Undetermined 34.5
    Lena .6,6 Not defined 4.8
    Lena
    81.2 40.0 3.5
    权利要求:
    Claims (1)
    [1]
    Claim
    A polymer composition for thickening aqueous media, including a water-soluble copolymer, sodium chloride and water, characterized in that, in order to increase viscosity, it contains a copolymer as a water-soluble copolymer. 99.90- |
    99.975 mol.% Acrylamide and 0.0250.1 mol.% Dodecyl poly (oxyethylene methacrylate with a viscosity of 0.2% copolymer solution at 25 ° C Brookfield 6.8-1075 cP or copolymer 74.8-
    74.9 mol% acrylamide, 0.05-0.2 mol% dodecyl poly (oxyethylene) p methacrylate and 25 mol% acrylic acid with a viscosity of .0.2% copolymer solution at 25 ° C according to Brookfield 1000- 1300 cP, where η is the number of oxyethylene units of 10 or 20, with the following components, wt.%:
    Water soluble
    copolymer 0.2-0.5 Sodium chloride 1-4 Water Rest
    Table 1 l
    Copolymer Monomers, mol. 2 Active weight, g The total weight of the solution, g ADM | E h C „MA Hell! NaDS ADM AA | e „< ma ΑΖ0 A 99.95 0.05 (a) 0 23.64 47.28 0 0.189 2,4 236.4 IN 99.90 0.10 (a) 0 23.64 47.28 0 0.378 2,4 236.4 99,975 0.025 (b) 0 23.64 46.36 0 0.058 2,4 236.4 E 99,925 0.075 (b) 0 23.64 46.36 0 0.174 2,4 236.4 F 99.95 0.05 (b) 0 23.64 46.36 0 0.116 2,4 236.4 G 99.90 0.10 (b) 0 23.64 46.36 0 0.231 2,4 236.4 N 74.80 0.2 (a) 25 25.0 35.48 12.77 0, 772 2,4 250 I 74.90 0.10 (a) 25 25.0 36.05 12.96 0.392 2,4 250 J 74.95 0.05 (a). 25 25.0 36.47 13.08 0.198 2,4 250 TO 74.95 0.05 (b) 25 25.0 36.45 13.10 0.130 .2.4 250 74.90 0.10 (b) 25 25.0 36.27 13.04 0.260 2,4 250 C, (known 100 0 0 25.0 47.28 0 0 2,4 250 ny) C g (known 75.0 0 25 25.0 36.65 13.15 0 2,4 250
    ny)
    Note. DAM is acrylamide in an aqueous solution at a concentration of 502. E n C m MA t alkyl ^ poly (hydroxyethylene) to methacrylate, where m is the number of hydroxyethylene groups and η is the number of carbons in the alkyl group, (a) w = 20, η = = 12, (b) tn - 10, η = 12, AA is acrylic acid added as a 482-solution in water, adjusted to pH = 4.3 with NaOH. NaDS - sodium dodecyl sulfate, added as a 102% solution in water. AZO - azobisieobutyronitril added as a j-12 solution in t-butanol.
    table 2
    Sample Copolymer The viscosity of the solution, SP, at the indicated concentrations of the copolymer,% 0.2 j 0.3 ί 0.4 ;0.5 1 D 8.6 4.2 76.0 125.0 2 F 24.0 300,0 575.0 8.920.0 3 E 325,0 640,0 2900.0 11.000.0 4 G 1075,0 3750.0 5500,0 9.000.0 Ci with < 5.8 9.0 14.0 23,4 Note Viscosity GBrookfield at 25 ° C, op
    determined using a Brookfield LVT viscometer operating at 6 rpm. For viscosities up to 100 cP, the VL adapter was used, for viscosities from 100 to 5000 cP, a spindle of $ 2 was used, for viscosities above 5000 cP, spindle No. 3 was used. The concentration of the copolymer in the solution tested for viscosity.
    Ί
    1588285 ’
    Copolymer
    Table 3
    Sample
    The viscosity of the solution, SP, at a concentration of NaCl,%
    I.J ... ....... _____ A type Concentration, Z 0 1 2.0 3.0 3,5 4.0 . 5 A 0.2 6.8 7.0 8.3 9.2 Do not identify 10.9 6 IN 0.2 10.0 10.1 11.7 13, G Lena 18.6 C 2 (knownC 1 0.2 .5.9 Not defined - 5.9 Not defined - 5.9 stny)7 L 0.2 1000,0 divided9900.0 7700.0 . divided. 3700.0 3100.0 Not defined 8 I 0.1 1330.0 4100.0 4100.0 2600.0 5700.0 divided5100.0 C 3 (known FROM 2 0.2 500,0 23.1 15,2 14.0 Not defined 12.0 stny divided
    I
    Table 4 i
    I
    Sample Copolymer NaCl concentration, 7. Shear speed, s Viscosity25 | solution, cP, at temperature, A type Concentration% 40 FROM| 50 j 60 9 F 0.5 0 172.5 50,5 52.3 Not determined 54.0 len . 46.8 10 IN 0.5 0 172.5 84.1 92.1 90.1 91.1 60.6 C 4 (famous)C 1 0.5 0 172.5 14.2 11.1 9.8 8.2. '5.5 . eleven I 0.2 2 ' 86.2 83.8 8.8 Not identified 79.5 Lena 81.2 12 to 0.2 2 86.2 53.7 43.6 Not identified 34.5 Lena 40,0 C 5 (known H 0.2 3 86.2 8.9 6.6 Not defined 4.8 3,5
    Lena
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    同族专利:
    公开号 | 公开日
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    IT1186180B|1987-11-18|
    EP0171429A4|1986-07-23|
    NO166947B|1991-06-10|
    WO1985003510A1|1985-08-15|
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    ZA85808B|1986-10-29|
    MY103010A|1993-04-30|
    AU3995085A|1985-08-27|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/576,250|US4921902A|1984-02-02|1984-02-02|Hydrophobie associative composition containing a polymer of a water-soluble monomer and an amphiphilic monomer|
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