CN109777377B - Shale intercalation inhibitor prepared from ultra-low molecular weight branched tertiary amine polyamine - Google Patents

Shale intercalation inhibitor prepared from ultra-low molecular weight branched tertiary amine polyamine Download PDF

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CN109777377B
CN109777377B CN201910111800.3A CN201910111800A CN109777377B CN 109777377 B CN109777377 B CN 109777377B CN 201910111800 A CN201910111800 A CN 201910111800A CN 109777377 B CN109777377 B CN 109777377B
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谢刚
肖玉容
邓明毅
黄丹超
罗平亚
江林峰
聂梦圆
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Southwest Petroleum University
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Abstract

一种超低分子量支化叔胺型聚胺制成的页岩插层抑制剂，由超低分子量支化叔胺型聚胺与水按比例混合配制而成，所述超低分子量支化叔胺型聚胺由多胺类化合物与含有烯键的叔胺类化合物采用分步合成法或一锅合成法制得，其中，多胺类化合物为烷基二胺、多乙烯多胺和低分子量多胺中的一种。本发明提供的超低分子量支化叔胺型聚胺无毒无害，其合成方法简单、产率较高、原料简单易得，适合大规模工业化生产，配制而成的页岩插层抑制剂相对于同类产品的抑制效果有明显提升，能有效降低由于泥页岩水化分散发生井壁不稳定的发生概率，完全满足各种复杂井况的钻井需求。

Figure 201910111800

A shale intercalation inhibitor made of an ultra-low molecular weight branched tertiary amine type polyamine is prepared by mixing an ultra-low molecular weight branched tertiary amine type polyamine and water in proportion. Amine type polyamines are prepared from polyamine compounds and tertiary amine compounds containing ethylenic bonds by a step-by-step synthesis method or a one-pot synthesis method, wherein the polyamine compounds are alkyl diamines, polyethylene polyamines and low molecular weight polyamines. one of the amines. The ultra-low molecular weight branched tertiary amine type polyamine provided by the invention is non-toxic and harmless, the synthesis method is simple, the yield is high, the raw materials are simple and easy to obtain, and it is suitable for large-scale industrial production. The prepared shale intercalation inhibitor Compared with similar products, the inhibition effect is significantly improved, which can effectively reduce the probability of wellbore instability due to the hydration and dispersion of shale, and fully meet the drilling needs of various complex well conditions.

Figure 201910111800

Description

Shale intercalation inhibitor prepared from ultra-low molecular weight branched tertiary amine polyamine
Technical Field
The invention belongs to the technical field of oil and gas field drilling, and particularly relates to a shale intercalation inhibitor prepared from branched tertiary amine polyamine with ultralow molecular weight.
Background
The instability of the well wall often causes complex accidents under the well such as collapse, shrinkage, sticking and the like of the well wall, and the well drilling time and the well drilling cost are increased. 75% of borehole wall instability occurs primarily in shale formations, particularly water sensitive formations. The shale stratum has high clay mineral content, the horizontal section of the shale gas horizontal well is long, the contact time of the drilling fluid and the stratum is long, the shale hydration is more serious, and the instability of the well wall is more prominent. Although the oil-based drilling fluid has obvious advantages in the aspects of well wall stability, lubrication and anti-sticking, inhibition of shale hydration expansion, formation slurrying, rapid drilling and the like, due to serious environmental pollution and overhigh treatment cost, researchers at home and abroad are gradually focusing on the water-based drilling fluid, and therefore, the development and research of the water-based drilling fluid with the effect equivalent to that of the oil-based drilling fluid to replace the oil-based drilling fluid is a trend of the current drilling fluid technical development.
In order to replace oil-based drilling fluids with water-based drilling fluids, it is necessary to first achieve a water-based drilling fluid that completely inhibits hydration of clay minerals like oil-based drilling fluids. The polyamine high-performance drilling fluid system is a novel environment-friendly drilling fluid which meets the requirements of various aspects of the drilling process and is considered to replace oil-based drilling fluid, and domestic and foreign researches show that the polyamine inhibitor taking an amine monomer as a main 7 raw material is widely applied to a water-based drilling fluid system and obtains a better inhibition effect, but the polyamine inhibitors researched and applied at present are mostly of linear structures. The linear polyamine inhibitor with high molecular weight is usually in a random coil configuration after being dissolved in water, so that the winding and coating on the clay are uneven when the linear polyamine inhibitor is acted with the shale clay, and repeated adsorption or no adsorption is easily caused. Meanwhile, the acting groups are generally present at two ends of a molecular chain, so that one molecular chain generally only contains two acting groups, and the acting effect of the linear polyamine inhibitor in the case also has certain limitation. And the polyamine compound having a high molecular weight is difficult to enter between clay layers, so that its inhibiting property is limited.
Disclosure of Invention
The invention aims to provide a shale intercalation inhibitor prepared from branched tertiary amine polyamine with ultralow molecular weight aiming at the defects and shortcomings in the prior art, and the shale intercalation inhibitor has the characteristics of no toxicity, no harm, high yield, better effect compared with like products and the like.
The technical scheme provided by the invention for solving the technical problems is as follows: a shale intercalation inhibitor made of ultra-low molecular weight branched tertiary amine polyamine is prepared by mixing ultra-low molecular weight branched tertiary amine polyamine and water, wherein the mass percentage of the ultra-low molecular weight branched tertiary amine polyamine in the shale intercalation inhibitor is 0.5-10%, the ultra-low molecular weight branched tertiary amine polyamine is synthesized by a step-by-step synthesis method or a one-pot method by taking polyamine compounds and tertiary amine compounds containing olefinic bonds as raw materials, and the ideal and completely branched structural formula is one of the following:
Figure GDA0002761821030000021
wherein R is1、R2Are respectively C1-C4An alkyl group; n is1Is 1 to 10; n is2Is 1 to 5; n is 1 to 5; m is 1 to 4.
Further, the stepwise synthesis method of the ultra-low molecular weight branched tertiary amine polyamine comprises the following steps:
s1, respectively dissolving 0.1 mol of polyamine compound and 0.1 mol of tertiary amine compound containing olefinic bond in 80-110mL of equivalent solvent, dropwise adding the solution of the tertiary amine compound containing olefinic bond into the solution of the polyamine compound at 10-40 ℃, heating to 90-100 ℃ after dropwise adding, carrying out heating reflux reaction for 4-12h, and carrying out rotary evaporation to dryness after the reaction is finished, thus obtaining the G1 ultra-low molecular weight tertiary amine type polyamine compound;
s2, respectively dissolving the G1 ultra-low molecular weight branched tertiary amine polyamine prepared in the step S1 and 1 molar part of a tertiary amine compound containing an olefinic bond in 80-110mL of equivalent solvent, dropwise adding the solution of the tertiary amine compound containing the olefinic bond into the solution of the G1 ultra-low molecular weight branched tertiary amine polyamine at 10-40 ℃, heating to 90-100 ℃, carrying out heating reflux reaction for 4-16h, and carrying out rotary evaporation to dryness after the reaction is finished to obtain the G2 ultra-low molecular weight branched tertiary amine polyamine;
s3, taking the G2 ultra-low molecular weight branched tertiary amine polyamine prepared in the previous step, operating according to the step S2, wherein the maximum number of the reaction steps is the same as the number M of hydrogen atoms of amino groups in the polyamine compound, and obtaining the G1-GM ultra-low molecular weight branched tertiary amine polyamine after the reaction of each step is completed.
Further, the one-pot synthesis method is specifically operated as follows: respectively dissolving 0.1 mole of polyamine compound (the number of hydrogen atoms of amino group is M) and 0.1M mole of tertiary amine compound containing olefinic bond in 80-120mL of equivalent solvent, dropwise adding the solution of the tertiary amine compound containing olefinic bond into the solution of the polyamine compound at 10-40 ℃, heating to 90-100 ℃ after dropwise adding, heating for reflux reaction for 4-12h, and after the reaction is finished, performing rotary evaporation to dryness to obtain the GM ultra-low molecular weight branched tertiary amine polyamine.
Further, the alkyl diamine is one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine or decylenediamine, N-methylethylenediamine, and 1, 2-diaminobutane; the polyethylene polyamine is one of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, tri (2-aminoethyl) amine, tri (3-aminopropyl) amine and tri (1-propylamino) amine.
Further, the tertiary amine compound containing the olefinic bond has the following structural formula:
Figure GDA0002761821030000031
wherein n is 1-5; r1、R2Are respectively C1-C4An alkyl group.
Further, the organic solvent is one of absolute methanol, absolute ethanol, acetone and isopropyl ether.
Further, the rotary evaporation temperature is 105 ℃, and the absolute vacuum degree is less than 3000 Pa.
The invention has the following beneficial effects:
1. the preparation method of the branched tertiary amine polyamine with ultralow molecular weight has stable and reliable technology, higher yield, easily obtained raw materials required by the synthesized product, and the step-by-step synthesis method and the one-pot synthesis method have the advantages that: the stepwise synthesis method can synthesize different branched tertiary amine polyamines with ultralow molecular weight according to actual needs; the one-pot synthesis method has the advantages of high total synthesis yield, few reaction steps, short reaction time, simplicity and easy use of both synthesis methods, and suitability for industrial production.
2. The ultra-low molecular weight branched tertiary amine polyamine synthesized by the method provided by the invention is nontoxic and harmless, has good water solubility, and the inhibition performance of the prepared shale intercalation inhibitor is obviously improved compared with the inhibition agents such as primary amine inhibitors, and the like, so that the drilling requirements of various complex well conditions can be completely met, and the occurrence probability of unstable well wall caused by shale hydration and dispersion is effectively reduced.
Drawings
FIG. 1 is a mass spectrum of a G1 ultra-low molecular weight branched tertiary amine polyamine synthesized by the stepwise method in example 1;
FIG. 2 is a mass spectrum of an ultra-low molecular weight branched tertiary amine polyamine G2 synthesized by the stepwise method in example 1;
FIG. 3 is a mass spectrum of an ultra-low molecular weight branched tertiary amine polyamine G3 synthesized by the stepwise method in example 1;
FIG. 4 is a mass spectrum of an ultra-low molecular weight branched tertiary amine polyamine of G4 synthesized by the stepwise method in example 1;
FIG. 5 is a mass spectrum of an ultra-low molecular weight branched tertiary amine polyamine of G5 synthesized by the stepwise method in example 1;
FIG. 6, mass spectrum of one-pot synthesized G5 ultra-low molecular weight branched tertiary amine polyamine in example 2;
FIG. 7 is a mass spectrum of an ultra-low molecular weight branched tertiary amine polyamine of G1 synthesized by a stepwise method in example 3;
FIG. 8 is a mass spectrum of an ultra-low molecular weight branched tertiary amine polyamine of G2 synthesized by the stepwise method in example 3;
FIG. 9 is a mass spectrum of an ultra-low molecular weight branched tertiary amine polyamine of G3 synthesized by the stepwise method in example 3;
FIG. 10 is a mass spectrum of an ultra-low molecular weight branched tertiary amine polyamine of G4 synthesized by a stepwise method in example 3;
FIG. 11, mass spectrum of one-pot synthesized G4 ultra-low molecular weight branched tertiary amine polyamine in example 4.
Detailed Description
The present invention will be further described with reference to the accompanying fig. 1-11, and the preferred embodiments, it being understood that the preferred embodiments described herein are merely illustrative and explanatory of the invention and are not restrictive thereof. The percentages in the examples are given by mass unless otherwise indicated. Unless otherwise specified, the chemical articles referred to in the examples are all technical grade articles and may be obtained by conventional means.
Example 1
The preparation method is characterized in that diethylenetriamine and dimethyl allyl amine are used as raw materials, and a step-by-step synthesis method is adopted to prepare the branched tertiary amine polyamine with ultralow molecular weight, and the preparation method comprises the following specific steps:
(1) synthesis of G1 ultra low molecular weight branched tertiary amine type polyamines: accurately weighing 0.1 mole of diethylenetriamine and 0.1 mole of dimethylallylamine, respectively dissolving in 80mL of anhydrous methanol, transferring the methanol solution of diethylenetriamine into a round-bottom flask, slowly adding the methanol solution of dimethylallylamine into the round-bottom flask by using a constant-pressure separating funnel at 25 ℃, stirring, after dropwise adding, heating to 95 ℃, heating for reflux reaction for 8 hours, and after the reaction is finished, evaporating the solvent by using a rotary evaporator under the conditions of 105 ℃ and less than 3000Pa of absolute vacuum degree to obtain the G1 ultra-low molecular weight branched tertiary amine polyamine. The molecular formula of the G1 ultra-low molecular weight branched tertiary amine polyamine is: c9H24N4The precise molecular weight: 188.201, molar mass: 188.207, mass to charge ratio: 188.207 (100%), 189.203 (11.9%). Elemental analysis: c, 57.40; h, 12.85; n, 29.75. As shown in fig. 1, the mass to charge ratio by LC-MS was 189.207, since G1, an ultra-low molecular weight branched tertiary amine-type polyamine gave one proton with a molecular weight of 188.207 consistent with the theoretical exact molecular weight of 188.201, at a yield of 96.3%. The molecular structural formula of the G1 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000051
(2) synthesis of G2 ultra low molecular weight branched tertiary amine type polyamines: respectively dissolving 0.1 mol of G1 and 0.1 mol of dimethylallylamine in 80mL of anhydrous methanol, transferring a methanol solution of G1 into a round-bottom flask, slowly adding the methanol solution of the dimethylallylamine into the round-bottom flask by using a constant-pressure separating funnel at 25 ℃, stirring, after dropwise adding, heating to 95 ℃, heating and refluxing for 8 hours, and after the reaction is finished, heating to reflux for reaction for 8 hours at 105 ℃ under the condition that the absolute vacuum degree is less than 3000PaThe solvent was distilled off using a rotary evaporator to give G2, an ultra-low molecular weight branched tertiary amine polyamine. The molecular formula of the G2 ultra-low molecular weight branched tertiary amine polyamine is: c14H35N5The precise molecular weight: 273.289, molar mass: 273.461, mass to charge ratio: 273.289 (100%), 274.293 (15.6%), 275.296 (1.1%). Elemental analysis: c, 61.49; h, 12.90; n, 25.61. As shown in fig. 2, the mass to charge ratio by LC-MS was 274.297, since G2, an ultra-low molecular weight branched tertiary amine-type polyamine gave one proton with a molecular weight of 273.297 consistent with the theoretical exact molecular weight of 273.289, at a yield of 96.1%. The molecular structural formula of the G2 ultra-low molecular weight tertiary amine type polyamine compound is as follows:
Figure GDA0002761821030000052
(3) synthesis of G3 ultra-low molecular weight tertiary amine type polyamine compounds: respectively dissolving 0.1 mole of G2 and 0.1 mole of dimethylallylamine in 100mL of anhydrous methanol, transferring a methanol solution of G2 into a round-bottom flask, slowly adding the methanol solution of the dimethylallylamine into the round-bottom flask by using a constant-pressure separating funnel at 25 ℃, stirring, after dropwise adding, heating to 95 ℃, heating and refluxing for 8 hours, and after the reaction is finished, evaporating the solvent by using a rotary evaporator under the conditions of 105 ℃ and an absolute vacuum degree of less than 3000Pa to obtain the G3 ultra-low molecular weight branched tertiary amine type polyamine. G3 molecular formula of ultra-low molecular weight branched tertiary amine type polyamines: c19H46N6The precise molecular weight: 358.378, molar mass: 358.609, mass to charge ratio: 358.378 (100%), 359.382 (21.1%), 360.385 (2.1%). Elemental analysis: c, 63.64; h, 12.93; n, 23.44. As shown in fig. 3, the mass to charge ratio was 359.386 by LC-MS, since G3, an ultra-low molecular weight branched tertiary amine-type polyamine gave one proton with a molecular weight of 358.386 consistent with the theoretical exact molecular weight of 358.378, at a yield of 95.8%. The molecular structural formula of the G3 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000061
(4) synthesis of G4 ultra low molecular weight branched tertiary amine type polyamines: respectively dissolving 0.1 mole of G3 and 0.1 mole of dimethylallylamine in 100mL of anhydrous methanol, transferring a methanol solution of G3 into a round-bottom flask, slowly adding the methanol solution of the dimethylallylamine into the round-bottom flask by using a constant-pressure separating funnel at 25 ℃, stirring, after dropwise adding, heating to 95 ℃, heating and refluxing for 8 hours, and after the reaction is finished, evaporating the solvent by using a rotary evaporator under the conditions of 105 ℃ and an absolute vacuum degree of less than 3000Pa to obtain the G4 ultra-low molecular weight branched tertiary amine type polyamine. G4 molecular formula of ultra-low molecular weight branched tertiary amine type polyamines: c24H57N7The precise molecular weight: 443.468, molar mass: 443.756, mass to charge ratio: 443.468 (100.0%), 444.471 (26.7%), 445.474 (2.6%). Elemental analysis: c, 64.96; h, 12.95; n, 22.09. As shown in FIG. 4, since the G4 ultra-low molecular weight tertiary amine type polyamine compound gave a proton with a mass-to-charge ratio of 444.475 as measured by LC-MS, its molecular weight of 443.475 coincided with the theoretically exact molecular weight of 443.468, with a yield of 96.1%. The molecular structural formula of the G4 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000071
(5) synthesis of G5 ultra-low molecular weight tertiary amine type polyamine compounds: respectively dissolving 0.1 mole of G4 and 0.1 mole of dimethylallylamine in 110mL of anhydrous methanol, transferring a methanol solution of G4 into a round-bottom flask, slowly adding the methanol solution of dimethylallyl into the round-bottom flask by using a constant-pressure separating funnel at 25 ℃, stirring, after dropwise addition, heating to 95 ℃, heating and refluxing for 8 hours, and after the reaction is finished, evaporating the solvent by using a rotary evaporator under the conditions of 105 ℃ and an absolute vacuum degree of less than 3000Pa to obtain the G5 ultra-low molecular weight branched tertiary amine type polyamine. G5 molecular formula of ultra-low molecular weight branched tertiary amine type polyamines: c29H68N8The precise molecular weight: 528.557, molar mass: 528.904, mass to charge ratio:528.557 (100.0%), 529.560 (32.3%), 529.554 (3.0%). Elemental analysis: c, 65.86; h, 12.96; n, 21.19. As shown in fig. 5, the mass to charge ratio was 529.564 by LC-MS, since G5, the ultra-low molecular weight branched tertiary amine polyamine, yielded one proton with a molecular weight of 528.564 consistent with the theoretical exact molecular weight of 528.557, in a 96.1% yield. The molecular structural formula of the G5 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000072
example 2
The preparation method of the ultra-low molecular weight branched tertiary amine polyamine by taking diethylenetriamine and dimethyl allyl amine as raw materials and adopting a one-pot method comprises the following specific steps
Accurately weighing diethylenetriamine and dimethylallyl with a molar ratio of 1:5, respectively dissolving the diethylenetriamine and the dimethylallyl in 100mL of anhydrous methanol, wherein the molar ratio of diethylenetriamine is 0.1 mol, dropwise adding the methanol solution of dimethylallylamine into the methanol solution of diethylenetriamine at 25 ℃, heating to 100 ℃ after dropwise adding, carrying out heating reflux reaction for 12h, carrying out reduced pressure distillation at 105 ℃ under the absolute vacuum degree of less than 3000Pa after the reaction is finished, and evaporating the solvent to dryness to obtain the G5 ultra-low molecular weight branched tertiary amine type polyamine. G5 molecular formula of ultra-low molecular weight branched tertiary amine type polyamines: g5 molecular formula of ultra-low molecular weight branched tertiary amine type polyamines: c29H68N8The precise molecular weight: 528.557, molar mass: 528.904, mass to charge ratio: 528.557 (100.0%), 529.560 (32.3%), 529.554 (3.0%). Elemental analysis: c65.86; h12.96; and (3) N21.19. As shown in fig. 6, the mass to charge ratio by LC-MS was 529.564, since G5, an ultra-low molecular weight branched tertiary amine-type polyamine gave one proton with a molecular weight of 528.564 consistent with the theoretical exact molecular weight of 528.557, in 90.6% yield. The molecular structural formula of the G5 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000081
example 3
Ethylenediamine and dimethyl allyl amine are used as raw materials, and a step-by-step synthesis method is adopted to prepare the branched tertiary amine polyamine with ultralow molecular weight, and the specific steps are as follows:
(1) synthesis of G1 ultra low molecular weight branched tertiary amine type polyamines: respectively dissolving 0.1 mole of ethylenediamine and 0.1 mole of dimethylallylamine in 80mL of anhydrous methanol, transferring a methanol solution of ethylenediamine into a round-bottom flask, slowly adding the methanol solution of dimethylallylamine into the round-bottom flask by using a constant-pressure separating funnel at 25 ℃, stirring, after dropwise adding, heating to 95 ℃, heating and refluxing for 8 hours, and after the reaction is finished, evaporating the solvent by using a rotary evaporator under the conditions of 105 ℃ and an absolute vacuum degree of less than 3000pa to obtain the G1 ultra-low molecular weight branched tertiary amine polyamine. The molecular formula of the G1 ultra-low molecular weight branched tertiary amine polyamine is: c7H19N3The precise molecular weight: 145.158, molar mass: 145.246, mass to charge ratio: 145.158 (100.0%), 146.161 (7.8%), 146.155 (1.1%). Elemental analysis: c, 57.88; h, 13.19; n, 28.93. As shown in fig. 7, the mass to charge ratio by LC-MS was 146.165, since G1, an ultra-low molecular weight branched tertiary amine-type polyamine gave one proton with a molecular weight of 145.165 consistent with the theoretical exact molecular weight of 145.158, at a yield of 95.8%. The molecular structural formula of the G1 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000091
(2) synthesis of G2 ultra low molecular weight branched tertiary amine type polyamines: respectively dissolving 0.1 mole of G1 and 0.1 mole of dimethylallylamine in 80mL of anhydrous methanol, transferring G1 into a round-bottom flask, slowly adding a constant-pressure separating funnel of the dimethylallylamine into the round-bottom flask at 25 ℃, stirring, after dropwise adding, heating to 95 ℃, heating to reflux for 8 hours, and after the reaction is finished, evaporating the solvent by using a rotary evaporator under the conditions of 105 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G2 ultra-low molecular weight branched tertiary amine type polyamine. G2 ultra-low molecular weight branched tertiaryAmine-type polyamines have the formula: c12H30N4The precise molecular weight: 230.247, molar mass: 230.393, mass to charge ratio: 230.247 (100.0%), 231.250 (13.3%), 231.244 (1.5%). Elemental analysis: c, 62.56; h, 13.12; n, 24.32. As shown in fig. 8, the mass to charge ratio by LC-MS was 231.254, since G2, an ultra-low molecular weight branched tertiary amine-type polyamine gave one proton with a molecular weight of 230.254 consistent with the theoretical exact molecular weight of 230.247, at a yield of 96.0%. The molecular structural formula of the G2 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000092
(3) synthesis of G3 ultra low molecular weight branched tertiary amine type polyamines: respectively dissolving 0.1 mole of G2 and 0.1 mole of dimethylallylamine in 100mL of anhydrous methanol, transferring G2 into a round-bottom flask, slowly adding a methanol solution of the dimethylallylamine into the round-bottom flask at 25 ℃ by using a constant-pressure separating funnel, stirring, after dropwise adding, heating to 95 ℃, heating and refluxing for 8 hours, and after the reaction is finished, evaporating the solvent by using a rotary evaporator under the conditions of 105 ℃ and absolute vacuum degree of less than 3000Pa to obtain the G3 ultra-low molecular weight branched tertiary amine type polyamine. The molecular formula of the G3 ultra-low molecular weight branched tertiary amine polyamine is: c17H41N5The precise molecular weight: 315.336, molar mass: 315.541, mass to charge ratio: 315.336 (100.0%), 316.340 (18.9%), 317.343 (1.7%). Elemental analysis: c, 64.71; h, 13.10; n, 22.19. As shown in fig. 9, the mass to charge ratio by LC-MS was 316.349, since G3, an ultra-low molecular weight branched tertiary amine-type polyamine gave one proton with a molecular weight of 315.349 consistent with the theoretical exact molecular weight of 315.336, at a yield of 95.2%. The molecular structural formula of the G3 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000101
(4) synthesis of G4 ultra-low molecular weight branched tertiary amine-type polyaminesThe composition is as follows: respectively dissolving 0.1 mole of G3 and 0.1 mole of dimethylallylamine in 100mL of anhydrous methanol, transferring G3 into a round-bottom flask, slowly adding a methanol solution of the dimethylallylamine into the round-bottom flask at 25 ℃ by using a constant-pressure separating funnel, stirring, after dropwise adding, heating to 95 ℃, heating and refluxing for 8 hours, and after the reaction is finished, evaporating the solvent by using a rotary evaporator under the conditions of 105 ℃ and the absolute vacuum degree of less than 3000Pa to obtain the G4 ultra-low molecular weight branched tertiary amine type polyamine. The molecular formula of the G4 ultra-low molecular weight branched tertiary amine polyamine is: c22H52N6The precise molecular weight: 400.425, molar mass: 400.688, mass to charge ratio: 400.425 (100.0%), 401.432 (24.5%), 402.432 (2.9%), 401.422 (2.2%). Elemental analysis: c, 65.95; h, 13.08; and N, 20.97. As shown in fig. 10, the mass to charge ratio by LC-MS was 401.433, since G4, an ultra-low molecular weight branched tertiary amine-type polyamine gave one proton with a molecular weight of 400.433 consistent with the theoretical exact molecular weight of 400.425, at a yield of 95.8%. The molecular structural formula of the G4 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000111
example 4
The preparation method of the ultra-low molecular weight branched tertiary amine polyamine by using ethylenediamine and dimethylallylamine as raw materials and adopting a one-pot synthesis method comprises the following specific steps:
accurately weighing ethylenediamine and dimethylallyl with a molar ratio of 1:4, respectively dissolving the ethylenediamine and the dimethylallyl in 120mL of anhydrous methanol, wherein the ethylenediamine is 0.1 mol, transferring the ethylenediamine into a round-bottom flask, slowly adding a methanol solution of dimethylallyl amine into the round-bottom flask through a constant-pressure separating funnel at 25 ℃, stirring, after dropwise adding, heating to 95 ℃, heating for reflux reaction for 12 hours, and after the reaction is finished, evaporating the solvent by using a rotary evaporator under the conditions of 105 ℃ and an absolute vacuum degree of less than 3000Pa to obtain the G4 ultra-low molecular weight branched tertiary amine polyamine. The molecular formula of the G4 ultra-low molecular weight branched tertiary amine polyamine is: c22H52N6The precise molecular weight: 400.425, molar mass: 400.688, mass to charge ratio: 400.425 (100.0%), 401.432 (24.5%), 402.432 (2.9%), 401.422 (2.2%). Elemental analysis: c, 65.95; h, 13.08; and N, 20.97. As shown in fig. 11, the mass to charge ratio by LC-MS was 401.433, since G4, an ultra-low molecular weight branched tertiary amine-type polyamine gave one proton with a molecular weight of 400.433 consistent with the theoretical exact molecular weight of 400.425, in 90.6% yield. The molecular structural formula of the G4 ultra-low molecular weight branched tertiary amine polyamine is as follows:
Figure GDA0002761821030000112
second, performance test
The inhibitor prepared from the ultra-low molecular weight branched tertiary amine polyamine prepared in the examples 1-4 and clear water is compared with a conventional shale intercalation inhibitor (ethylenediamine inhibitor and polyamine inhibitor are selected) for experiment, the performance of the inhibitor prepared in the above examples is evaluated by linear expansion rate, and the specific operation steps refer to SY-T5613-2000 shale physical and chemical property test method and SY/T5971-1994 clay stabilizer performance evaluation method for water injection. The lower the linear expansion ratio, the better the inhibition performance of the inhibitor. The data measured after the test are shown in tables 1-2.
TABLE 1 Linear expansion Rate
Figure GDA0002761821030000121
TABLE 2 Effect of inhibitor addition on Linear expansion Rate
Figure GDA0002761821030000122
Figure GDA0002761821030000131
As can be seen from the linear expansion rate results shown in Table 1, under the same addition amount, different types of the branched tertiary amine polyamines with ultralow molecular weight all show excellent inhibition performance, and have better inhibition performance than the similar products of ethylenediamine and polyamines; ultra-low molecular weight branched tertiary amine-type polyamines having multiple tertiary amine groups have better inhibition performance than ethylenediamine having 2 primary amine groups. The inhibition performance of the G5 ultra-low molecular weight branched tertiary amine polyamine synthesized by the one-pot method is equivalent to that of the G5 ultra-low molecular weight branched tertiary amine polyamine synthesized by the step method.
As can be seen from the results of the effect of the amount of the inhibitor added on the linear expansion ratio shown in Table 2, the linear expansion ratio decreased and the inhibition performance was better as the amount of the inhibitor added was increased, and the inhibition performance was improved as the number of the tertiary amine groups was increased.
In conclusion, the preparation method of the branched tertiary amine polyamine with ultralow molecular weight has stable and reliable technology, higher yield and low price of raw materials required by synthetic products, and is suitable for industrial production; and provides two synthetic methods, namely a step-by-step synthetic method and a one-pot synthetic method, and each has the advantages; the synthesized ultra-low molecular weight branched tertiary amine polyamine product is non-toxic and harmless, has good water solubility, obviously improves the inhibition performance of the prepared shale intercalation inhibitor compared with similar products, can completely meet the drilling requirements of various complex well conditions, and effectively reduces the problem of unstable well wall caused by the hydration and dispersion of the shale.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (7)

1.一种超低分子量支化叔胺型聚胺制成的页岩插层抑制剂，其特征在于，所述页岩插层抑制剂由超低分子量支化叔胺型聚胺和水混合配置而成，超低分子量支化叔胺型聚胺在页岩插层抑制剂中的质量百分比为0.5-10％，所述超低分子量支化叔胺型聚胺以多胺类化合物和含有烯键的叔胺类化合物为原料、用分步法或一锅法合成，其理想的、完全支化的结构式为如下之一：1. a shale intercalation inhibitor made of ultra-low molecular weight branched tertiary amine type polyamine, is characterized in that, described shale intercalation inhibitor is mixed by ultra-low molecular weight branched tertiary amine type polyamine and water It is configured so that the mass percentage of the ultra-low molecular weight branched tertiary amine type polyamine in the shale intercalation inhibitor is 0.5-10%, and the ultra-low molecular weight branched tertiary amine type polyamine is composed of polyamine compounds and containing The tertiary amine compound of ethylenic bond is a raw material, and is synthesized by a step-by-step method or a one-pot method, and its ideal, fully branched structural formula is one of the following:
Figure FDA0002761821020000011
Figure FDA0002761821020000011
 其中，R1、R2分别为C1-C4烷基；n1为1-10；n2为1-5；n为1-5；m为1-4。Wherein, R 1 and R 2 are C 1 -C 4 alkyl groups respectively; n 1 is 1-10; n 2 is 1-5; n is 1-5; m is 1-4. 2.根据权利要求1所述的一种超低分子量支化叔胺型聚胺制成的页岩插层抑制剂，其特征在于，所述超低分子量支化叔胺型聚胺的分步合成法为以下步骤：2. the shale intercalation inhibitor that a kind of ultra-low molecular weight branched tertiary amine type polyamine according to claim 1 is made, it is characterized in that, the step by step of described ultra-low molecular weight branched tertiary amine type polyamine The synthesis method is the following steps: S1、将0.1摩尔的多胺类化合物与0.1摩尔含有烯键的叔胺类化合物分别溶解在80-110mL的等量溶剂中，且在10-40℃条件下将含有烯键的叔胺类化合物的溶液逐滴加入多胺类化合物的溶液中，滴加完后，再升温至90-100℃回流反应4-12h，反应完毕后，旋蒸至干得到G1超低分子量叔胺型聚胺化合物；S1. Dissolve 0.1 moles of polyamine compounds and 0.1 moles of tertiary amine compounds containing ethylenic bonds in 80-110 mL of an equal amount of solvent respectively, and dissolve the tertiary amine compounds containing ethylenic bonds at 10-40 °C. The solution was added dropwise to the solution of polyamine compounds. After the dropwise addition, the temperature was raised to 90-100 °C and refluxed for 4-12 h. After the reaction was completed, rotary evaporated to dryness to obtain G1 ultra-low molecular weight tertiary amine polyamine compound. ; S2、将上一步制备的G1超低分子量支化叔胺型聚胺与0.1摩尔含有烯键的叔胺类化合物分别溶解在80-110mL等量溶剂中，在10-40℃条件下将含有烯键的叔胺类化合物的溶液逐滴加入G1超低分子量支化叔胺型聚胺的溶液中，滴加完后，再升温至90-100℃，加热回流反应4-12h，反应完毕后，旋蒸至干得到G2超低分子量支化叔胺型聚胺；S2. Dissolve the G1 ultra-low molecular weight branched tertiary amine polyamine prepared in the previous step and 0.1 mole of the tertiary amine compound containing an ethylenic bond in 80-110 mL of an equal amount of solvent, respectively, at 10-40 ° C. The solution of the tertiary amine compound of the bond is added dropwise to the solution of the G1 ultra-low molecular weight branched tertiary amine type polyamine. Rotary evaporation to dryness to obtain G2 ultra-low molecular weight branched tertiary amine polyamine; S3、取上一步制得的G2超低分子量支化叔胺型聚胺，按照步骤S2所述进行操作，反应步骤的最大步数与多胺类化合物中胺基基团的氢原子的个数M相同，各步骤反应完成后，得到G1-GM超低分子量支化叔胺型聚胺。S3, take the G2 ultra-low molecular weight branched tertiary amine type polyamine obtained in the previous step, and operate as described in step S2, the maximum number of steps in the reaction steps and the number of hydrogen atoms of the amine group in the polyamine compound M is the same, and after the reaction of each step is completed, G1-GM ultra-low molecular weight branched tertiary amine polyamine is obtained. 3.根据权利要求1所述的一种超低分子量支化叔胺型聚胺制成的页岩插层抑制剂，其特征在于，所述一锅合成法具体操作为：将0.1摩尔的多胺类化合物与0.1M摩尔份含有烯键的叔胺类化合物分别溶解在80-120mL等量溶剂中，其中M为多胺类化合物中氨基基团的氢原子数目，在10-40℃条件下将含有烯键的叔胺类化合物的溶液逐滴加入多胺类化合物的溶液中，滴加完后，再升温至90-100℃，加热回流反应4-12h，反应完毕后，旋蒸至干即可得到GM超低分子量支化叔胺型聚胺。3. the shale intercalation inhibitor that a kind of ultra-low molecular weight branched tertiary amine type polyamine according to claim 1 is made, it is characterized in that, the concrete operation of described one-pot synthesis method is: The amine compound and 0.1M molar portion of the tertiary amine compound containing an olefinic bond are dissolved in 80-120mL of an equal amount of solvent, wherein M is the number of hydrogen atoms of the amino group in the polyamine compound, and the temperature is 10-40 ℃. Add the solution of the tertiary amine compound containing ethylenic bond dropwise to the solution of the polyamine compound. After the dropwise addition, the temperature is raised to 90-100°C, and the reaction is heated and refluxed for 4-12h. After the reaction is completed, it is evaporated to dryness. The GM ultra-low molecular weight branched tertiary amine polyamine can be obtained. 4.根据权利要求1-3任一所述的一种超低分子量支化叔胺型聚胺制成的页岩插层抑制剂，其特征在于，所述的多胺类化合物为烷基二胺、多乙烯多胺或低分子量多胺中的一种，所述烷基二胺为乙二胺、丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛二胺、壬二胺或癸二胺、N-甲基乙二胺、1,2-二氨基丁烷中的一种；所述多乙烯多胺为二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺中的一种，所述低分子量多胺为三(2-胺乙基)胺、三(3-氨基丙基)胺、三(1-丙基氨基)胺中的一种。4. the shale intercalation inhibitor that a kind of ultra-low molecular weight branched tertiary amine type polyamine according to any one of claims 1-3 is made, it is characterized in that, described polyamine compound is alkyl two A kind of amine, polyethylene polyamine or low molecular weight polyamine, the alkyl diamine is ethylene diamine, propylene diamine, butane diamine, pentamethylene diamine, hexamethylene diamine, heptane diamine, octanediamine , a kind of in nonanediamine or decanediamine, N-methylethylenediamine, 1,2-diaminobutane; the polyethylene polyamine is diethylenetriamine, triethylenetetramine, tetraethylenepentane A kind of amine, pentaethylene hexamine, the low molecular weight polyamine is a tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, tris (1-propylamino) amine kind. 5.根据权利要求1-3任一所述的一种超低分子量支化叔胺型聚胺制成的页岩插层抑制剂，其特征在于，所述含烯键的叔胺类化合物结构式如下：5. the shale intercalation inhibitor made of a kind of ultra-low molecular weight branched tertiary amine type polyamine according to any one of claims 1-3, is characterized in that, the described ethylenic bond-containing tertiary amine compound structural formula as follows:
Figure FDA0002761821020000021
Figure FDA0002761821020000021
 其中，n为1-5；R1、R2分别为C1-C4烷基。Wherein, n is 1-5; R 1 and R 2 are respectively C 1 -C 4 alkyl groups. 6.权利要求2或3所述一种超低分子量支化叔胺型聚胺制成的页岩插层抑制剂，其特征在于，所述有机溶剂为无水甲醇、无水乙醇、丙酮、异丙醚中的一种。6. the shale intercalation inhibitor that a kind of ultra-low molecular weight branched tertiary amine type polyamine of claim 2 or 3 is made, it is characterized in that, described organic solvent is anhydrous methanol, dehydrated alcohol, acetone, A kind of isopropyl ether. 7.权利要求2或3所述一种超低分子量支化叔胺型聚胺制成的页岩插层抑制剂，其特征在于，所述旋蒸温度为105℃，绝对真空度小于3000Pa。7. The shale intercalation inhibitor made of an ultra-low molecular weight branched tertiary amine type polyamine according to claim 2 or 3, characterized in that the rotary steaming temperature is 105°C, and the absolute vacuum degree is less than 3000Pa.
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