CN1003592B - 含有水溶性共聚物分散剂的固体分散体 - Google Patents
含有水溶性共聚物分散剂的固体分散体 Download PDFInfo
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Abstract
固体分散体,特别是含有共聚物作为分散剂的钻探泥浆和水泥浆。该共聚物是下述单体的共聚物:(a)甲基丙烯酸或甲基丙烯酸的衍生物,(b)乙烯基磺酸、甲代烯丙基磺酸或丙烯酰胺丙烯基亚甲基磺酸,和(c)N-乙烯基羧酸酰胺。
Description
本发明涉及固体分散体,特别是在含有共聚物作为分散剂的水溶液中的固体分散体。固体的性质可能差别很大,其在液相中的浓度会变化非常显著。因此,共聚物分散每升几个毫克浓度的固体和分散高固体含量体系是同样有效的,例如钻探泥浆,象水泥浆、石膏浆和高岭土那样的无机粘合剂,碳浆以及碳酸钙浆等,有时溶剂含量很低。在高浓度固体分散体的情况下,本发明之共聚物能使水含量减至最少,使粘度降低,有利于工业上使用。
采用各种不同的分散助剂,可使差别很大的各种分散体系,如钻探泥浆,水泥浆、碳浆以及农药和颜料的分散体系,获得最佳的分散性。
用于钻探泥浆的分散剂有,例如联邦德国专利申请展出说明书第1,183,874号中介绍的,比如多磷酸盐、雀木,特别是木素磺酸盐和褐煤。美国专利第3,730,900号介绍的苯乙烯磺酸盐与马来酸酐的共聚物最近已作为高温稀释剂用于钻探泥浆领域中。
通过盐层钻探或在露天海钻探时,如果盐水必须用于钻探泥浆,如淀粉及淀粉衍生物、羧甲基羟乙基-羧基-甲基纤维素、生物聚合物及部分水解的丙烯酰胺等保护胶体对于稳定这些分散体系是必要的。在固体含量很高的情况下,优先选用低分子量离子型聚合物。关于在钻探泥浆中添加剂的应用,在乔治·R·格雷等的著作:“油井钻井液的组成及性质中已详细介绍(George R·Giay.,WalterF.R-ogers Composition and Properties of Oil Well Drilling Fluids,Fourth Edition,Gulf Publishing Company Houston/Texas1980)。
当用于含盐钻探泥浆时,最近已经证实,按照联邦德国专利申请公开说明书第2,931,897号和联邦德国专利申请展出说明书第2,444,108号中介绍的乙烯基磺酸盐和乙烯基酰胺的共聚物,对于在很深的热钻孔中预先构成稳定的性质是特别适用的。
对于用泵输送的水泥浆,分散剂降低其粘度。这便于泵送操作并使水含量减少,从而改善硬化后混凝土的力学性质。在水泥浆中使用的分散剂有美国专利第3,465,825号中介绍的木素磺酸盐、聚丙烯酸和单萘磺酸盐与甲醛的缩合物,以及美国专利第4,053,323号中介绍的N-磺烷基代丙烯酰胺。根据应用领域,水泥浆中应加入减少失水量的添加剂、沉降阻滞剂或沉降加速剂,而这些添加剂必须与特有的分散剂相容。这就限制了这些类型分散剂的实用性。例如,当钙盐用作沉降加速剂时,聚丙烯酸便不能用作分散剂。
在氯化钙存在的情况下,部分水解的聚丙烯酰胺作为减少失水量的添加剂的效果也大为降低。凡分散体容易受到特别高的应力之处,例如在很热的热孔中,基于盐水的水泥浆和钻探泥浆的情况下,便难以确定最佳性质。
性质上差别很大的非离子型、阴离子型以及阳离子型表面活性剂也都用作分散剂。
本发明与含有共聚物作为分散剂的固体分散体有关,该共聚物由通式Ⅰ的基团按重量计5-95%,通式Ⅱ、Ⅲ或Ⅳ的基团按重量计5-95%以及通式Ⅴ的基团按重量计0-5%组成,
式中:R1代表氢或甲基,
R2代表酰胺基,甲氧甲酰基,氰基或较好的基团-羧基,
式中:R3代表氢、C1-C6烷基或苯基,
R4代表氢或甲基,
R5代表C1-C10亚烷基,
K+代表铵、锂、钠或钾。
式中:R6代表氢,甲基或乙基,
R7代表甲基或乙基,或者
优先选用的共聚物由通式Ⅰ的单体20-90%和通式Ⅱ和(或)Ⅲ5-50%或通式Ⅳ20-70%组成。通式Ⅴ的单体可共聚到共聚物中,这种共聚物可用于粒度较粗的悬浮体。共聚物的分子量为2千至6百万,较好的分子量为1万至50万。当悬浮体存在于极端的条件下,比如高温、含盐以及低析出水量的情况下,使用较高分子量的共聚物是必要的。
所用的共聚物可通过已知的方法制备:在适当聚合催化剂存在下反应上述单体,反应温度为-10℃至+80℃,较好的温度范围为20℃至60℃。如果象甲醇、乙醇、特丁醇、四氢呋喃或二甲基甲酰胺那样的水溶性有机溶剂的适当水溶液也可用作聚合介质,聚合反应在水相中进行是有利的。可用的聚合催化剂特别包括过氧化物,比如过氧化苯甲酰、过氧化乙酰、特丁基过氧化氢或过硫酸硷金属盐或过硫酸铵,或氧化还原体系,比如N-对-甲苯磺酰基甲基氨基甲酸甲酯/过硫酸铵。
如果适当的话,加入如二丁基铵盐酸盐或微量铜盐那样的助催化剂也可能是有利的。如偶氮二异丁腈之类的化合物也可加入作为聚合引发剂。
按本发明,基于通式Ⅰ、Ⅱ、Ⅲ、Ⅳ和Ⅴ,使用下列单体进行共聚较好:
1、丙烯酸
2、乙烯基磺酸
3、甲代烯丙基磺酸
4、丙烯酰胺基丙烯基亚甲基磺酸
5、N-乙烯基-N-甲基乙酰胺
制得的共聚物为粘性溶液,以含水溶液为好。这种形式的共聚物是可以应用的。如欲制备固体共聚物,可将上述聚合物溶液进行蒸发或干燥,例如喷雾干燥或鼓式干燥。使用时,共聚物中的磺酸基团变为铵盐或硷金属盐的形式是恰当的。
对于很低的固体含量,例如工业冷却循环介质中的碳酸钙(比如含量仅为10ppm),或对于直到80%高固体含量的水泥浆,本发明的共聚物均具有非常有效的分散作用。冷却水中使用的最低浓度为5ppm,而水泥浆中最低浓度可达20%。水泥浆的高浓度明显地改进硬化水泥的力学性能。只有本发明共聚物的很好的分散效果才能使这些聚合物涉及到的高浓度能够均匀地分布在水泥浆中。
实例1、碳酸钙分散体
使用在水中新沉淀的碳酸钙浆(100毫克/升)。由甲代烯丙基磺酸10%和丙烯酸(K值约30)90%组成的共聚物25ppm、100ppm以及500ppm分别加入到量筒中的500毫升上述碳酸钙浆中。摇振此混合物,静置2小时,然后滗出上层水(250毫升)并测定其固体含量。实验结果在表1中列出。
用 量 在滗出的水中分散的碳酸钙 (在起始浓度中的百分含量%) | |
0ppm 0 25ppm 22 100ppm 47 500ppm 77 |
实例2、钻探泥浆
基本的泥浆:1升水,200克地层粘土,40克膨润土。
共聚物A:丙烯酸90%
甲代烯丙基磺酸钠10%
共聚物B:丙烯酸65%
丙烯酰胺丙烯基亚甲基磺酸盐 35%
在20℃测定钻井泥浆,然后在200℃陈化15小时后再测定。聚合物的K值约为60(Fikentscher,Cellulose-Chemie13,1932,page58)。用35SAFANN粘度计测定表观粘度和液性极限。按照美国石油学会(API)的失水量是按照“API code29”用7公斤/厘米2的标准压滤器在30分钟的过滤速度。实验结果在表2中列出。
实例3、水泥浆
a、组成:水349克
G级水泥792克
在每一实验中使用的共聚物含量为0.75%。用35 SAFANN粘度计测定表观粘度和液性极限。
b组成:水349克
D级水泥792克
实例4、基于硫酸钡、石膏,碳酸钙和碳的固体悬浮体。
a、硫酸钡
固体含量按重量计为80%,
分散剂浓度按重量计为0.25%
b、石膏:CaSO4·2H2O
固体含量按重量计为55%
分散剂浓度按重量计为1.0%
c、碳酸钙
固体含量按重量计为55%
分散剂浓度按重量计为0.25%
d、碳
固体含量按重量计为70%
分散剂浓度按重量计为0.25%
进行上述全部实验时,加入分散剂,所用分散剂K值约为60,组成如下(按重量计):
丙烯酸 65%
丙烯酰胺亚甲基丙烯基磺酸 30%
甲基磺酸 5%
全部单体均以其钠盐形式存在。
用Fann VG-35旋转粘度计,6转/分,测定粘度。由此测得的粘度值在下表中列出。
上述实例表明,本发明的共聚物十分有效地分散水溶液中很少量的固体以及象钻探泥浆和水泥浆角那样高浓度的固体。在钻探泥浆中应用时,特别突出的是其对热的稳定性以及二价离子对聚丙烯酸酯的相容性。
由中性范围内的应用效果来看,本发明之共聚物优于分散剂木素磺酸铬和褐煤铬,后两种铬化物是目前仍广泛用于钻井泥浆并且仅在高pH值条件下才能正常操作的分散剂。这是因为由于泥浆中的泥质成分与硷反应而在钻孔中产生的高温下,不可能保持高pH值。另外,由于环境保护方面的原因,人们越来越限制含铬钻探泥浆。
本发明之化合物降低水泥浆的粘度,显著地改进了其泵送的流畅性。由于良好的分散效果,水泥浆的水含量能够保持低含量值,这意味着硬化水泥的强度增加。此外,凝固水泥的力学性能也由于聚合物含量增加而改进。由硫酸钡,石膏,白垩以及碳悬浮体的实验结果表明,本发明的化合物如何有效地分散各种不同的固体悬浮体。通过改变本发明之化合物单体浓度及分子量,各种固体可以获得最佳分散效果。
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CN85101102.0A CN1003592B (zh) | 1983-10-22 | 1985-04-01 | 含有水溶性共聚物分散剂的固体分散体 |
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DE19833338431 DE3338431A1 (de) | 1983-10-22 | 1983-10-22 | Wasserloesliche mischpolymerisate und deren verwendung als dispergatoren fuer feststoffe |
CN85101102.0A CN1003592B (zh) | 1983-10-22 | 1985-04-01 | 含有水溶性共聚物分散剂的固体分散体 |
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CN85101102A CN85101102A (zh) | 1987-01-24 |
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EP (1) | EP0141327B2 (zh) |
JP (1) | JPS60104109A (zh) |
CN (1) | CN1003592B (zh) |
AT (1) | ATE42757T1 (zh) |
AU (1) | AU583481B2 (zh) |
BR (1) | BR8405319A (zh) |
CA (1) | CA1258947A (zh) |
DE (2) | DE3338431A1 (zh) |
ES (1) | ES536902A0 (zh) |
NO (1) | NO844203L (zh) |
ZA (1) | ZA848178B (zh) |
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US4652623A (en) * | 1984-11-23 | 1987-03-24 | Calgon Corporation | Polymers for use as filtration control aids in drilling muds |
JPH0625317B2 (ja) * | 1986-08-26 | 1994-04-06 | 日本ペイント株式会社 | 防汚塗料用球形崩壊型ビニル樹脂粒子 |
JPH01226757A (ja) * | 1988-03-04 | 1989-09-11 | Takemoto Oil & Fat Co Ltd | セメント用分散剤 |
US5221489A (en) * | 1990-04-26 | 1993-06-22 | Atlantic Richfield Company | Sulfonated polymeric dispersant compositions for subterranean well drilling, completion, and cementing |
DE69120947T2 (de) * | 1990-04-26 | 1996-11-28 | Atlantic Richfield Co | Dispergiermittel-zusammensetzungen für bohrung und abdichtung untererdischer quellen |
DE4320220A1 (de) * | 1993-06-18 | 1994-12-22 | Basf Ag | Verwendung von Polymerisaten I, die spezielle monoethylenisch ungesättigte Sulfonsäuren einpolymerisiert enthalten, als Hilfsmittel bei der Sprühtrocknung wäßriger Dispersionen von Polymerisaten II |
FR2732009B1 (fr) * | 1995-03-22 | 1997-06-06 | Schlumberger Cie Dowell | Composition de cimentation comportant un agent dispersant et son application a la cimentation de puits petroliers |
DE19909231C2 (de) | 1999-03-03 | 2001-04-19 | Clariant Gmbh | Wasserlösliche Copolymere auf AMPS-Basis und ihre Verwendung als Bohrhilfsmittel |
CN1093095C (zh) * | 2000-11-07 | 2002-10-23 | 复旦大学 | 羧酸类接枝型高效减水剂及其合成方法 |
US7247662B2 (en) | 2001-10-07 | 2007-07-24 | Nippon Shokubai Co., Ltd. | Cement dispersant, its production process, and cement composition using the cement dispersant |
JP2008208016A (ja) * | 2007-02-28 | 2008-09-11 | Nippon Shokubai Co Ltd | 粉体状セメント分散剤 |
WO2017158441A1 (en) * | 2016-03-17 | 2017-09-21 | Lubrizol Oilfield Solutions, Inc. | Carboxylic acid/acrylamidoalkane sulfonic acid/styrene sulfonate copolymers for ultrahigh temperature and pressure retardation of oil-well cement |
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US3730900A (en) | 1972-09-25 | 1973-05-01 | Milchem Inc | Composition and process for drilling subterranean wells |
DE2444108C2 (de) | 1974-09-14 | 1978-01-19 | Hoechst Ag | Wasserbasische tonspuelung fuer tiefbohrungen und verwendung eines mischpolymerisats fuer solche spuelungen |
US4053323A (en) | 1976-11-11 | 1977-10-11 | Calgon Corporation | Method of using cementing composition having improved flow properties |
US4293427A (en) * | 1979-03-09 | 1981-10-06 | Milchem Incorporated | Drilling fluid containing a copolymer filtration control agent |
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1983
- 1983-10-22 DE DE19833338431 patent/DE3338431A1/de not_active Withdrawn
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1984
- 1984-10-13 EP EP84112373A patent/EP0141327B2/de not_active Expired - Lifetime
- 1984-10-13 DE DE8484112373T patent/DE3478028D1/de not_active Expired
- 1984-10-13 AT AT84112373T patent/ATE42757T1/de not_active IP Right Cessation
- 1984-10-19 CA CA000465864A patent/CA1258947A/en not_active Expired
- 1984-10-19 JP JP59218788A patent/JPS60104109A/ja active Pending
- 1984-10-19 ZA ZA848178A patent/ZA848178B/xx unknown
- 1984-10-19 BR BR8405319A patent/BR8405319A/pt unknown
- 1984-10-19 AU AU34528/84A patent/AU583481B2/en not_active Ceased
- 1984-10-19 ES ES536902A patent/ES536902A0/es active Granted
- 1984-10-19 NO NO844203A patent/NO844203L/no unknown
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1985
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Publication number | Publication date |
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DE3478028D1 (en) | 1989-06-08 |
EP0141327A1 (de) | 1985-05-15 |
ES8506331A1 (es) | 1985-07-01 |
ATE42757T1 (de) | 1989-05-15 |
ZA848178B (en) | 1985-06-26 |
BR8405319A (pt) | 1985-09-03 |
EP0141327B1 (de) | 1989-05-03 |
NO844203L (no) | 1985-04-23 |
ES536902A0 (es) | 1985-07-01 |
EP0141327B2 (de) | 1992-08-19 |
CN85101102A (zh) | 1987-01-24 |
AU3452884A (en) | 1985-04-26 |
CA1258947A (en) | 1989-08-29 |
JPS60104109A (ja) | 1985-06-08 |
DE3338431A1 (de) | 1985-05-02 |
AU583481B2 (en) | 1989-05-04 |
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