JP5948486B2 - 低粘度合成セメント - Google Patents
低粘度合成セメント Download PDFInfo
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- JP5948486B2 JP5948486B2 JP2015503238A JP2015503238A JP5948486B2 JP 5948486 B2 JP5948486 B2 JP 5948486B2 JP 2015503238 A JP2015503238 A JP 2015503238A JP 2015503238 A JP2015503238 A JP 2015503238A JP 5948486 B2 JP5948486 B2 JP 5948486B2
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- Prior art keywords
- cement
- weight
- viscosity
- compressive strength
- synthetic cement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/142—Polyethers
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
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- C04B2103/0046—Polymers chosen for their physico-chemical characteristics added as monomers or as oligomers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0061—Block (co-)polymers
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Description
i)低粘度単官能基モノマーと、
ii)アクリレート、メタクリレート、ビニル、オレフィン、アリルもしくはアミドのペンダントフリーラジカル反応種を有するジシクロペンタジエニル部の二官能基モノマーおよび/または1,3−グリコールジメタクリレート(BGDM)と、
iii)不飽和スチレンブロックコポリマーと、
iv)フリーラジカル開始剤と
を含む。
合成セメントの組成はそれぞれ、
1)Kraton D0243ポリマーとして知られる高ジブロック、高ビニル、スチレン−ブタジエン−スチレンブロックコポリマーを7.5重量%と、
2)ビニルエステルの単官能基モノマー(VeoVa(商標)10モノマー)を0から92.5重量%と、
3)さまざまな比のDCPDとBGDMのブレンドである二官能基モノマーと
を含む。
表3に示す本発明の実施例12は、圧縮強さと70°Fでの平均粘度のバランスが良好な合成セメントの組成である。実施例12では、過酸化物フリーラジカル開始剤としてLuperox DC40P−SP2を0.36重量%用いた。
実施例1から17の配合物について、平均粘度に対し、圧縮強さを試験した。14ポンド/ガロンのメキシコ湾(GOM)セメントスラリー(比較例、表9)は、70°Fで平均粘度は267cP、250°Fで24時間硬化させたとき、圧縮強さは2,000psiであった。本発明の実施例では、少なくとも1000psiの圧縮強さを有していた。最良の性能の実施例では、2000psiを超える圧縮強さを有していた。
図3中の約240cPの太い横線は、油性さく井泥水の70°Fでの平均粘度を表し、縦線は、メキシコ湾セメントの圧縮強さ(約2000psi)を表す。本発明においては、合成セメントが、さく井泥水の粘度を有するように、合成セメントが約50から300cP−横線付近から下の溶液粘度を有することが最も好ましい。しかし本発明においては、平均溶液粘度は約1000cP以下(ただし、50cP以上)にすることができて、この一方で1000psi以上の圧縮強さ(縦線のすぐ左側および上側から縦線のすぐ右側)を有する。本発明では、組成物の多くが300cPよりも低い平均溶液粘度および2000psiよりも大きい圧縮強さを有する。表4を参照のこと。ヤング率は、組成物の剛性をpsiの単位で測定する。実施例16および17では、約800psiを下回る、低すぎるヤング率を示している。剛性が低すぎる場合、組成物は容易に変形し、シーリング材として不十分である。ヤング率が高すぎる場合(約150,000psi以上)、組成物は剛性が高すぎて、わずか5%の変形で破壊する。さらに比較例16および17が本発明に不適当であることを示すものとして、硬さに注目する。ショア硬さOOは、軟らかい組成物用であり、実施例16および17は凝結時に軟らかい組成物となる。媒体の硬さはショアAスケールで試験する。実施例12、13および15では、このような硬さを有する。最も硬い組成物はショアD硬さで測定する。実施例14は、この硬度に適合する。
本発明が(さく井泥水としてではなく)合成セメントとしてのみ用いられるとき、油性泥水(OBM)がセメントの一部を汚染している場合であっても、シールする能力があることが重要である。実施例12について、0重量%、10重量%、20重量%および30重量%のOBM汚染において、GOMセメントと比較した。それぞれの場合において、平均粘度、圧縮強さおよび鋼に対する付着性(パイプに対する付着性)を試験した。結果は、表12にて報告した。これらの結果に対して、同じ試験を比較例16および17について繰り返し行い、結果を表13にて報告している。
濃縮時間:セメントスラリーが液体から固体に変化できる能力を稠度計にて測定する。この装置では、溶液の粘稠度を、時間、温度および圧力に応じて測定する。この試験の単位は、Bearden粘稠度(Bc)単位で、スケールは0から100Bcである。セメントは、70Bc(以上)で「ポンプでの送り出し不可(unpumpable)」と見なされ、70Bcに達するまでの時間が報告される濃縮時間である。また、重要なのは曲線の形状である。理想的には、材料が凝結するにつれて、粘稠度は急激に増加し、粘稠度対時間の曲線は直角の上昇を示すであろうが、これは、液体状態からゲル化/凝結状態への急速な変化を示している。実施例12(ポリマーF参照)は、1)高ジブロック、高ビニル、スチレン−ブタジエン−スチレンブロックコポリマー(Kraton D0243)を7.5重量%と、2)ビニルエステルの単官能基モノマーであるVeoVa 10 モノマーを70重量%と、3)DCPD(5重量%)とBGDM(17.5重量%)のブレンドで、DCPD:BGDMの重量比が22:78であった二官能基モノマーとを含んでいた。これらの成分は合計で100重量%である。この重量に基づいて、開始剤−Luperox DC40P−SP2を0.36重量%用いて、3時間25分で凝結させた。図5は、稠度計にて試験した結果であり、直角凝結を示している。稠度計は最大値に達し、20,000psiの粘稠度(100Bcに対応)が達成されたとき、スイッチを切ったことに留意されたい。示してはいないが、ある程度の量の過酸化物開始剤を用いることで、ほぼあらゆる所望の凝結時間も実現できる。
Claims (2)
- 井戸のセメンチングのための、油性泥水と親和性のある合成セメントであって、
i)ジシクロペンタジエニル部を除く低粘度単官能基モノマーと、
ii)アクリレート、メタクリレート、ビニル、オレフィン、アリルもしくはアミドを含むフリーラジカル反応を受けやすい1つの結合部を有するジシクロペンタジエニル部および/または1,3−ブチレングリコールジメタクリレートと、
iii)不飽和スチレンブロックコポリマーと、
iv)フリーラジカル開始剤と
を含む合成セメント。 - 井戸のセメンチングのための、油性泥水と親和性のある合成セメントであって、
i)10から80重量%のビニルエステルと、
ii)アクリレート、メタクリレート、ビニル、オレフィン、アリルもしくはアミドを含むフリーラジカル反応を受けやすいペンダント化学種を有するジシクロペンタジエニル部および/または1,3−ブチレングリコールジメタクリレートと、
iii)5から45重量%の不飽和スチレンブロックコポリマーと、
iv)成分iからivの全重量に基づいて、0.1から1.0重量%の過酸化物硬化剤と
を含む合成セメント。
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US13/434,262 US9238770B2 (en) | 2012-03-29 | 2012-03-29 | Low viscosity synthetic cement |
US13/434,262 | 2012-03-29 | ||
PCT/US2013/029852 WO2013148116A2 (en) | 2012-03-29 | 2013-03-08 | Low viscosity synthetic cement |
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EP3044280A4 (en) | 2013-11-25 | 2017-04-12 | Halliburton Energy Services, Inc. | Cement with resilient latex polymer |
NO338018B1 (no) | 2013-12-04 | 2016-07-18 | Wellcem As | Fremgangsmåte for tetting av hydrokarbonbrønner. |
CN104808436B (zh) * | 2014-01-27 | 2017-11-24 | 太阳油墨(苏州)有限公司 | 碱显影型感光性树脂组合物、干膜和固化物、以及印刷电路板 |
US9657213B2 (en) * | 2014-10-20 | 2017-05-23 | Kraton Polymers U.S. Llc | Curable, resealable, swellable, reactive sealant composition for zonal isolation and well integrity |
CA2970976C (en) * | 2014-12-19 | 2020-12-29 | Dynasol Elastomeros, S.A. De C.V. | Sbs latex for use in concrete modification. |
FR3037073B1 (fr) * | 2015-06-03 | 2017-07-14 | Rhodia Operations | Polymeres amphiphiles pour le controle du filtrat |
US10781306B2 (en) * | 2018-02-13 | 2020-09-22 | Dairen Chemical Corporation | Mortar formulation comprising long chain acrylic ester modified vinyl ester polymers |
US11008498B2 (en) | 2018-08-16 | 2021-05-18 | Saudi Arabian Oil Company | Cement slurry responsive to hydrocarbon gas |
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GB1065053A (en) * | 1962-10-19 | 1967-04-12 | Cement Marketing Company Ltd | Inorganic polymer structures |
US4816503A (en) * | 1986-06-04 | 1989-03-28 | The Dow Chemical Company | Polymer concrete having high bond strength and long working time |
JPH0196204A (ja) * | 1987-10-08 | 1989-04-14 | Hitachi Chem Co Ltd | セメント用樹脂組成物 |
US5464060A (en) | 1989-12-27 | 1995-11-07 | Shell Oil Company | Universal fluids for drilling and cementing wells |
US5382290A (en) | 1991-04-26 | 1995-01-17 | Shell Oil Company | Conversion of oil-base mud to oil mud-cement |
US6082456A (en) | 1996-10-25 | 2000-07-04 | Wecem As | Means and method for the preparation of sealings in oil and gas wells |
US5886125A (en) | 1997-02-25 | 1999-03-23 | E. I. Du Pont De Nemours And Company | Crosslinkable copolymers comprising vinyl silane and vinyl esters of branched fatty acid |
US6311448B1 (en) | 1998-01-21 | 2001-11-06 | Rohm And Haas Company | Precast concrete plates |
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CA2277683A1 (en) * | 1998-07-22 | 2000-01-22 | Dainippon Ink And Chemicals, Inc. | Resin concrete composition and molded article thereof |
DE19858141A1 (de) * | 1998-12-16 | 2000-06-21 | Basf Ag | Thermoplasische Formmassen |
US7266587B2 (en) | 2002-05-15 | 2007-09-04 | Broadcom Corporation | System having interfaces, switch, and memory bridge for CC-NUMA operation |
EP1751396A2 (en) | 2004-06-03 | 2007-02-14 | Shell International Research Maatschappij B.V. | Method and apparatus for performing chemical treatments of exposed geological formations |
US7267174B2 (en) | 2005-01-24 | 2007-09-11 | Halliburton Energy Services, Inc. | Methods of plugging a permeable zone downhole using a sealant composition comprising a crosslinkable material and a reduced amount of cement |
US7696133B2 (en) | 2005-06-02 | 2010-04-13 | Shell Oil Company | Geosynthetic composite for borehole strengthening |
GB2427630B (en) * | 2005-06-30 | 2007-11-07 | Schlumberger Holdings | Methods and materials for zonal isolation |
FR2910012B1 (fr) * | 2006-12-15 | 2009-03-06 | Cray Valley S A Sa | Resines polyesters insatures fonctionnalises par imides cycloaliphatiques insaturees, pour revetements et compositions de moulage |
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