技术领域Technical field
本发明属于石油开采技术领域，具体涉及一种耐高温改性瓜尔胶及其合成方法。The invention belongs to the technical field of petroleum extraction, and specifically relates to a high-temperature-resistant modified guar gum and a synthesis method thereof.
背景技术Background technique
瓜尔胶是从瓜尔胶豆种子中分离获得的一种天然高分子水溶性胶体，其化学组成主要是半乳甘露聚糖，具有良好的水溶性、増黏性、稳定性、耐热性，化学改性潜力大等特点，应用于石油钻采、建筑涂料、 纺织印染、食品医药、兵工炸药等行业。Guar gum is a natural polymer water-soluble colloid isolated from guar gum bean seeds. Its chemical composition is mainly galactomannan and has good water solubility, viscosity, stability, and heat resistance. , with the characteristics of great potential for chemical modification, it is used in industries such as oil drilling, architectural coatings, textile printing and dyeing, food and medicine, ordnance and explosives.
尽管瓜尔胶具有很好的水溶性和增稠性，但是原粉瓜尔胶往往具有下述缺点：不能快速溶胀和水合，溶解速度慢；水不溶物含量高；粘度不易控制；易被微生物分解而不能长期保存。这些缺点使瓜尔胶的应用受到很大限制，因此需要改变其理化特性，使其可广泛应用。Although guar gum has good water solubility and thickening properties, raw guar gum often has the following shortcomings: it cannot swell and hydrate quickly, and the dissolution rate is slow; the content of water-insoluble matter is high; the viscosity is difficult to control; and it is easily affected by microorganisms Decomposes and cannot be stored for long periods of time. These shortcomings greatly limit the application of guar gum, so it is necessary to change its physical and chemical properties so that it can be widely used.
油气田开采过程中，对低渗储层通过水力压裂的方式达到増产増效目的而使用的压裂液，就是以改性瓜尔胶为稠化剂配制的。压裂液的性能好坏对压裂施工的成败有着决定性的影响，直接关系着增产效果。近几年，从瓜胶分子结构进行机理分析，对瓜胶分子进行改性方面进行了大量的研究，得到的改性瓜尔胶的表观粘度、耐温、抗菌等性能都会进一步提升。In the process of oil and gas field exploitation, the fracturing fluid used to increase production and efficiency through hydraulic fracturing of low-permeability reservoirs is formulated with modified guar gum as a thickener. The performance of fracturing fluid has a decisive influence on the success or failure of fracturing construction and is directly related to the production increase effect. In recent years, a lot of research has been done on the modification of guar gum molecules based on the mechanism analysis of the guar gum molecular structure. The apparent viscosity, temperature resistance, antibacterial and other properties of the modified guar gum will be further improved.
《化工时刊》第21卷第2期发表的“羧甲基羟丙基瓜尔胶合成工艺的研究”，报道的方法中采用氯乙酸为羧甲基化醚化剂，氯乙酸毒性较大，接触或吸入其高浓度蒸汽，对身体造成极大伤害；另外，酸性较强，对设备腐蚀性大。"Research on the Synthesis Process of Carboxymethyl Hydroxypropyl Guar Gum" published in Volume 21, Issue 2 of "Chemical Engineering Times", the reported method uses chloroacetic acid as the carboxymethylation etherification agent, and chloroacetic acid is highly toxic. , contact or inhalation of its high concentration vapor will cause great harm to the body; in addition, it is highly acidic and highly corrosive to equipment.
CN102827300A公开了一种疏水改性瓜尔胶的制备方法及应用，包括如下步骤：将瓜尔胶悬浮在离子液体中，加入碱性催化剂，在10～40℃碱化；氮气保护下逐渐升温，慢慢滴加改性剂，将温度升至30～80℃进行改性反应；反应结束后加入有机酸调节pH为5～7，乙醇浸泡洗涤，过滤，滤饼真空烘干，得到疏水改性瓜尔胶。该发明在瓜尔胶羟基上引入疏水烷基长链，端基为羧酸基团，提高了瓜尔胶的水溶速度，最大限度保护了其大分子质量特性，赋予瓜尔胶疏水性能。和其他改性瓜尔胶相比，该疏水瓜尔胶分子质量大，和纤维素的相亲性好，增加了纤维素-瓜尔胶的分子结合力，从而提高纸页强度，可作为增强剂和表面施胶剂应用于造纸湿部化学过程。但是该发明的改性瓜尔胶因只有单一的疏水长链加入，其溶解性大为降低，不利于现场的快速配液。CN102827300A discloses a preparation method and application of hydrophobically modified guar gum, which includes the following steps: suspend guar gum in an ionic liquid, add an alkaline catalyst, and alkalize at 10 to 40°C; gradually heat up under nitrogen protection, Slowly add the modifier dropwise, and raise the temperature to 30-80°C to carry out the modification reaction; after the reaction, add organic acid to adjust the pH to 5-7, soak in ethanol and wash, filter, and vacuum dry the filter cake to obtain hydrophobic modification. Guar gum. This invention introduces a long chain of hydrophobic alkyl groups into the hydroxyl groups of guar gum, and the terminal groups are carboxylic acid groups, which increases the water-solubility speed of guar gum, protects its macromolecular mass characteristics to the maximum extent, and gives guar gum hydrophobic properties. Compared with other modified guar gums, this hydrophobic guar gum has a large molecular weight and good affinity with cellulose. It increases the molecular binding force between cellulose and guar gum, thereby improving the strength of the paper and can be used as a reinforcing agent. and surface sizing agents used in the papermaking wet-end chemical process. However, since only a single hydrophobic long chain is added to the modified guar gum of this invention, its solubility is greatly reduced, which is not conducive to rapid liquid preparation on site.
发明内容Contents of the invention
本发明针对上述现有技术存在的不足而提供一种耐高温改性瓜尔胶及其合成方法。本发明的瓜尔胶具有原料来源广泛，合成简单，表观粘度高，水不溶物少，耐温和抗菌能力强等优点。In view of the deficiencies in the above-mentioned prior art, the present invention provides a high-temperature-resistant modified guar gum and a synthesis method thereof. The guar gum of the present invention has the advantages of wide source of raw materials, simple synthesis, high apparent viscosity, less water-insoluble matter, and strong temperature resistance and antibacterial ability.
因此，为了实现上述目的，一方面，本发明公开了一种耐高温改性瓜尔胶，所述的耐高温改性瓜尔胶的分子结构式如下：。Therefore, in order to achieve the above object, on the one hand, the present invention discloses a high temperature resistant modified guar gum, the molecular structural formula of the high temperature resistant modified guar gum is as follows: .
另一个方面，本发明公开了一种耐高温改性瓜尔胶的合成方法，所述合成方法包括：在催化剂盐酸作用下，在溶剂乙醇存在的条件下，N,N,N’,N’-四甲基-1,8-萘二胺与环氧氯丙烷发生季铵化反应；其次，季铵化反应产物与瓜尔胶在碱性条件下发生改性反应。In another aspect, the present invention discloses a synthesis method of high temperature-resistant modified guar gum. The synthesis method includes: under the action of catalyst hydrochloric acid and in the presence of solvent ethanol, N, N, N', N' -Tetramethyl-1,8-naphthalenediamine undergoes a quaternization reaction with epichlorohydrin; secondly, a modification reaction occurs between the quaternization reaction product and guar gum under alkaline conditions.
本发明的耐高温改性瓜尔胶分子是普通瓜尔胶进行改造得到。瓜尔胶分子通过季铵化过的N,N,N’,N’-四甲基-1,8-萘二胺连在一起，分子量得到大幅度升高，从而增加了表观粘度；分子中引入了两个季铵盐，使得瓜尔胶由非离子型转化为离子型，更加容易溶于水；分子中引入季铵盐，使得瓜尔胶具有杀菌型，因此可以提前配置瓜尔胶而不会遭到细菌攻击而变性；分子中引入萘环结构，可以增加分子的稳定性，提高分子的耐温性；分子中季铵盐中和粘土表面负电荷，使得粘土之间斥力减少，从而起到防膨作用。The high-temperature-resistant modified guar gum molecule of the present invention is obtained by modifying ordinary guar gum. Guar gum molecules are connected together through quaternized N,N,N',N'-tetramethyl-1,8-naphthalenediamine, and the molecular weight is greatly increased, thereby increasing the apparent viscosity; the molecule Two quaternary ammonium salts are introduced into the molecule, which converts guar gum from non-ionic to ionic, making it more soluble in water; the introduction of quaternary ammonium salts into the molecule makes guar gum bactericidal, so guar gum can be prepared in advance It will not be attacked by bacteria and denatured; the introduction of a naphthalene ring structure into the molecule can increase the stability of the molecule and improve the temperature resistance of the molecule; the quaternary ammonium salt in the molecule neutralizes the negative charges on the surface of the clay, reducing the repulsion between the clays. This plays a role in preventing swelling.
本发明与现有技术相比具有如下优点和有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
（1）本发明的耐高温改性瓜尔胶原料来源广泛，合成及制备工艺简单；(1) The high-temperature-resistant modified guar gum of the present invention has a wide range of raw materials and simple synthesis and preparation processes;
（2）本发明的耐高温改性瓜尔胶具有高表观粘度的特点，表观粘度大于420mPa•s；(2) The high temperature resistant modified guar gum of the present invention has the characteristics of high apparent viscosity, and the apparent viscosity is greater than 420mPa·s;
（3）本发明的耐高温改性瓜尔胶具有较高的耐温性，耐温大于80℃；(3) The high-temperature-resistant modified guar gum of the present invention has high temperature resistance, and the temperature resistance is greater than 80°C;
（4）本发明的耐高温改性瓜尔胶水不溶物含量低，小于2.8%；(4) The high-temperature-resistant modified guar glue of the present invention has a low content of water-insoluble matter, less than 2.8%;
（5）本发明的耐高温改性瓜尔胶具有较强的抗菌性能，粘度保持率大于92%。(5) The high-temperature-resistant modified guar gum of the present invention has strong antibacterial properties and a viscosity retention rate of greater than 92%.
附图说明Description of the drawings
图1为本发明耐高温改性瓜尔胶的粘温曲线。Figure 1 is the viscosity-temperature curve of the high-temperature-resistant modified guar gum of the present invention.
图2为本发明耐高温改性瓜尔胶G7的红外光谱图。Figure 2 is an infrared spectrum of the high temperature resistant modified guar gum G7 of the present invention.
实施方式Implementation
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints of ranges and any values disclosed herein are not limited to the precise range or value, but these ranges or values are to be understood to include values approaching such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges. These values The scope shall be deemed to be specifically disclosed herein.
根据本发明的第一方面，本发明公开了一种耐高温改性瓜尔胶，所述的耐高温改性瓜尔胶的分子结构式如下：。According to a first aspect of the present invention, the present invention discloses a high-temperature-resistant modified guar gum. The molecular structural formula of the high-temperature-resistant modified guar gum is as follows: .
第二个方面，本发明公开了一种耐高温改性瓜尔胶的合成方法，所述合成方法包括：在催化剂盐酸作用下，在溶剂乙醇存在的条件下，N,N,N’,N’-四甲基-1,8-萘二胺与环氧氯丙烷发生季铵化反应；其次，季铵化反应产物与瓜尔胶在碱性条件下发生改性反应。In a second aspect, the present invention discloses a synthesis method of high temperature resistant modified guar gum. The synthesis method includes: under the action of catalyst hydrochloric acid and in the presence of solvent ethanol, N, N, N', N '-Tetramethyl-1,8-naphthalenediamine undergoes a quaternization reaction with epichlorohydrin; secondly, a modification reaction occurs between the quaternization reaction product and guar gum under alkaline conditions.
在本发明中，优选地，所述的环氧氯丙烷与N,N,N’,N’-四甲基-1,8-萘二胺的摩尔比为1.8-2.5：1，更优选为2.2-2.5：1。In the present invention, preferably, the molar ratio of epichlorohydrin and N,N,N',N'-tetramethyl-1,8-naphthalenediamine is 1.8-2.5:1, more preferably 2.2-2.5:1.
在本发明中，优选地，所述的催化剂盐酸的用量为将N,N,N’,N’-四甲基-1,8-萘二胺和环氧氯丙烷的乙醇溶液调pH至2-2.5所需要的量。In the present invention, preferably, the amount of catalyst hydrochloric acid used is to adjust the pH of the ethanol solution of N,N,N',N'-tetramethyl-1,8-naphthalenediamine and epichlorohydrin to 2 -2.5 required amount.
在本发明中，优选地，所述的溶剂乙醇与N,N,N’,N’-四甲基-1,8-萘二胺的重量比为15-20：1。In the present invention, preferably, the weight ratio of the solvent ethanol to N,N,N’,N’-tetramethyl-1,8-naphthalenediamine is 15-20:1.
在本发明中，优选地，所述的季铵化反应的时间为24-48h，更优选为32-40h。In the present invention, preferably, the quaternization reaction time is 24-48h, more preferably 32-40h.
在本发明中，优选地，所述的瓜尔胶与 N,N,N’,N’-四甲基-1,8-萘二胺的质量比为3-5：1，更优选为3-4：1。In the present invention, preferably, the mass ratio of the guar gum to N,N,N',N'-tetramethyl-1,8-naphthalenediamine is 3-5:1, more preferably 3 -4:1.
在本发明中，优选地，所述的碱性条件为pH 12-13。In the present invention, preferably, the alkaline condition is pH 12-13.
在本发明中，优选地，所述的改性反应时间为30-60min，温度为60-65℃；更优选地，所述的改性反应时间为40-50min，温度为60-62℃。In the present invention, preferably, the modification reaction time is 30-60 min and the temperature is 60-65°C; more preferably, the modification reaction time is 40-50 min and the temperature is 60-62°C.
按照一种更具体的优选实施方式，所述耐高温改性瓜尔胶合成方法具体包括以下步骤：According to a more specific preferred embodiment, the high temperature resistant modified guar gum synthesis method specifically includes the following steps:
（1）在四口烧瓶中加入 N,N,N’,N’-四甲基-1,8-萘二胺和溶剂乙醇，开启搅拌，用滴液漏斗滴加环氧氯丙烷，滴加完毕后，用催化剂盐酸调节pH到2-2.5，加热回流反应24-48h；反应完毕，将混合液减压蒸馏，得到淡黄色粘稠固体；用乙酸乙酯进行重结晶，得到白色固体；(1) Add N,N,N',N'-tetramethyl-1,8-naphthylenediamine and solvent ethanol to a four-necked flask, start stirring, and add epichlorohydrin dropwise with a dropping funnel. After completion, use catalyst hydrochloric acid to adjust the pH to 2-2.5, heat and reflux for 24-48 hours; after the reaction is completed, distill the mixture under reduced pressure to obtain a light yellow viscous solid; use ethyl acetate to recrystallize to obtain a white solid;
（2）在烧杯中加入瓜尔胶和蒸馏水，调节pH 12-13，加入步骤（1）中的白色固体，升温到60-65℃，保温反应；(2) Add guar gum and distilled water to the beaker, adjust the pH to 12-13, add the white solid in step (1), raise the temperature to 60-65°C, and keep the reaction warm;
（3）调节pH 7-7.5，加入乙醇，降温到10℃以下，析出固体，过滤，烘干，得到产品耐高温改性瓜尔胶。(3) Adjust the pH to 7-7.5, add ethanol, lower the temperature to below 10°C, precipitate the solid, filter and dry to obtain the product high temperature resistant modified guar gum.
优选情况下，步骤（2）中所述蒸馏水与瓜尔胶的重量比为5-6：1。Preferably, the weight ratio of distilled water to guar gum in step (2) is 5-6:1.
优选情况下，步骤（3）中所述乙醇与N,N,N’,N’-四甲基-1,8-萘二胺的重量比为4-6：1。Preferably, the weight ratio of ethanol and N,N,N’,N’-tetramethyl-1,8-naphthalenediamine described in step (3) is 4-6:1.
本发明耐高温改性瓜尔胶的合成反应方程式如下：The synthesis reaction equation of the high temperature resistant modified guar gum of the present invention is as follows:
。 .
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that each of the specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner without conflict. In order to avoid unnecessary repetition, the present invention combines various possible combinations. The combination method will not be further explained.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, any combination of various embodiments of the present invention can also be carried out. As long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.
下面将结合具体实施例对本发明作进一步的说明。The present invention will be further described below in conjunction with specific embodiments.
实施例Example
（1）在四口烧瓶中加入0.1mol N,N,N’,N’-四甲基-1,8-萘二胺和321g溶剂乙醇，开启搅拌，用滴液漏斗滴加0.18mol环氧氯丙烷，滴加完毕后，用2mol/L的催化剂盐酸调节pH到2，加热回流反应24h；反应完毕，将混合液减压蒸馏，得到淡黄色粘稠固体；用乙酸乙酯进行重结晶，得到白色固体；(1) Add 0.1mol N,N,N',N'-tetramethyl-1,8-naphthylenediamine and 321g solvent ethanol into a four-necked flask, start stirring, and add 0.18mol epoxy dropwise with a dropping funnel After the dropwise addition of propane chloride, adjust the pH to 2 with 2 mol/L catalyst hydrochloric acid, and heat to reflux for 24 hours; after the reaction is completed, distill the mixture under reduced pressure to obtain a light yellow viscous solid; use ethyl acetate for recrystallization. A white solid was obtained;
（2）在烧杯中加入64.2g瓜尔胶和385g蒸馏水，用1mol/L的氢氧化钠调节pH 12，加入（1）中的白色固体，升温到63℃，保温反应30min；(2) Add 64.2g guar gum and 385g distilled water to the beaker, adjust the pH to 12 with 1 mol/L sodium hydroxide, add the white solid in (1), raise the temperature to 63°C, and keep the reaction for 30 minutes;
（3）用2mol/L的盐酸调节pH 7，加入100g乙醇，降温到10℃以下，析出固体，过滤，烘干，得到产品耐高温改性瓜尔胶G1。(3) Adjust the pH to 7 with 2 mol/L hydrochloric acid, add 100g of ethanol, cool down to below 10°C, precipitate the solid, filter and dry to obtain the product high temperature resistant modified guar gum G1 .
实施例Example
（1）在四口烧瓶中加入0.1mol N,N,N’,N’-四甲基-1,8-萘二胺和368g溶剂乙醇，开启搅拌，用滴液漏斗滴加0.19mol环氧氯丙烷，滴加完毕后，用2mol/L的催化剂盐酸调节pH到2，加热回流反应28h；反应完毕，将混合液减压蒸馏，得到淡黄色粘稠固体；用乙酸乙酯进行重结晶，得到白色固体；(1) Add 0.1mol N,N,N',N'-tetramethyl-1,8-naphthylenediamine and 368g solvent ethanol into a four-necked flask, start stirring, and add 0.19mol epoxy dropwise with a dropping funnel After the dropwise addition of propane chloride, adjust the pH to 2 with 2 mol/L catalyst hydrochloric acid, heat and reflux for 28 hours; after the reaction is completed, distill the mixture under reduced pressure to obtain a light yellow viscous solid; use ethyl acetate for recrystallization. A white solid was obtained;
（2）在烧杯中加入77.8g瓜尔胶和428g蒸馏水，用1mol/L的氢氧化钠调节pH 13，加入（1）中的白色固体，升温到62℃，保温反应40min；(2) Add 77.8g guar gum and 428g distilled water to the beaker, adjust the pH to 13 with 1 mol/L sodium hydroxide, add the white solid in (1), raise the temperature to 62°C, and keep the reaction for 40 minutes;
（3）用2mol/L的盐酸调节pH 7，加入88g乙醇，降温到10℃以下，析出固体，过滤，烘干，得到产品耐高温改性瓜尔胶G2。(3) Adjust the pH to 7 with 2 mol/L hydrochloric acid, add 88g of ethanol, cool down to below 10°C, precipitate the solid, filter and dry to obtain the product high temperature resistant modified guar gum G2 .
实施例Example
（1）在四口烧瓶中加入0.1mol N,N,N’,N’-四甲基-1,8-萘二胺和354g溶剂乙醇，开启搅拌，用滴液漏斗滴加0.2mol环氧氯丙烷，滴加完毕后，用2mol/L的催化剂盐酸调节pH到2.5，加热回流反应30h；反应完毕，将混合液减压蒸馏，得到淡黄色粘稠固体；用乙酸乙酯进行重结晶，得到白色固体；(1) Add 0.1mol N,N,N',N'-tetramethyl-1,8-naphthylenediamine and 354g solvent ethanol into a four-necked flask, start stirring, and add 0.2mol epoxy dropwise with a dropping funnel After the dropwise addition of propane chloride, adjust the pH to 2.5 with 2 mol/L catalyst hydrochloric acid, heat and reflux for 30 hours; after the reaction is completed, distill the mixture under reduced pressure to obtain a light yellow viscous solid; use ethyl acetate for recrystallization. A white solid was obtained;
（2）在烧杯中加入107g瓜尔胶和585g蒸馏水，用1mol/L的氢氧化钠调节pH 12，加入（1）中的白色固体，升温到64℃，保温反应50min；(2) Add 107g guar gum and 585g distilled water to the beaker, adjust the pH to 12 with 1mol/L sodium hydroxide, add the white solid in (1), raise the temperature to 64°C, and keep the reaction for 50 minutes;
（3）用2mol/L的盐酸调节pH 7，加入88g乙醇，降温到10℃以下，析出固体，过滤，烘干，得到产品耐高温改性瓜尔胶G3。(3) Adjust the pH to 7 with 2 mol/L hydrochloric acid, add 88g of ethanol, cool down to below 10°C, precipitate the solid, filter and dry to obtain the product high temperature resistant modified guar gum G3 .
实施例Example
（1）在四口烧瓶中加入0.1mol N,N,N’,N’-四甲基-1,8-萘二胺和392g溶剂乙醇，开启搅拌，用滴液漏斗滴加0.21mol环氧氯丙烷，滴加完毕后，用2mol/L的催化剂盐酸调节pH到2.1，加热回流反应36h；反应完毕，将混合液减压蒸馏，得到淡黄色粘稠固体；用乙酸乙酯进行重结晶，得到白色固体；(1) Add 0.1mol N,N,N',N'-tetramethyl-1,8-naphthylenediamine and 392g solvent ethanol into a four-necked flask, start stirring, and add 0.21mol epoxy dropwise with a dropping funnel After the dropwise addition of propane chloride, adjust the pH to 2.1 with 2 mol/L catalyst hydrochloric acid, heat and reflux for 36 hours; after the reaction is completed, distill the mixture under reduced pressure to obtain a light yellow viscous solid; use ethyl acetate for recrystallization. A white solid was obtained;
（2）在烧杯中加入102g瓜尔胶和510g蒸馏水，用1mol/L的氢氧化钠调节pH 12.5，加入（1）中的白色固体，升温到63℃，保温反应35min；(2) Add 102g guar gum and 510g distilled water to the beaker, adjust the pH to 12.5 with 1 mol/L sodium hydroxide, add the white solid in (1), raise the temperature to 63°C, and keep the reaction for 35 minutes;
（3）用2mol/L的盐酸调节pH 7.5，加入86g乙醇，降温到10℃以下，析出固体，过滤，烘干，得到产品耐高温改性瓜尔胶G4。(3) Adjust the pH to 7.5 with 2 mol/L hydrochloric acid, add 86g of ethanol, cool down to below 10°C, precipitate the solid, filter and dry to obtain the product high temperature resistant modified guar gum G4 .
实施例Example
（1）在四口烧瓶中加入0.1mol N,N,N’,N’-四甲基-1,8-萘二胺和400g溶剂乙醇，开启搅拌，用滴液漏斗滴加0.22mol环氧氯丙烷，滴加完毕后，用2mol/L的催化剂盐酸调节pH到2.2，加热回流反应40h；反应完毕，将混合液减压蒸馏，得到淡黄色粘稠固体；用乙酸乙酯进行重结晶，得到白色固体；(1) Add 0.1mol N,N,N',N'-tetramethyl-1,8-naphthylenediamine and 400g solvent ethanol into a four-necked flask, start stirring, and add 0.22mol epoxy dropwise with a dropping funnel After the dropwise addition of propane chloride, adjust the pH to 2.2 with 2 mol/L catalyst hydrochloric acid, heat and reflux for 40 hours; after the reaction is completed, distill the mixture under reduced pressure to obtain a light yellow viscous solid; use ethyl acetate for recrystallization. A white solid was obtained;
（2）在烧杯中加入86.3g瓜尔胶和518g蒸馏水，用1mol/L的氢氧化钠调节pH 13，加入（1）中的白色固体，升温到61℃，保温反应45min；(2) Add 86.3g guar gum and 518g distilled water to the beaker, adjust the pH to 13 with 1 mol/L sodium hydroxide, add the white solid in (1), raise the temperature to 61°C, and keep the reaction for 45 minutes;
（3）用2mol/L的盐酸调节pH 7.5，加入104g乙醇，降温到10℃以下，析出固体，过滤，烘干，得到产品耐高温改性瓜尔胶G5。(3) Adjust the pH to 7.5 with 2 mol/L hydrochloric acid, add 104g of ethanol, cool down to below 10°C, precipitate the solid, filter and dry to obtain the product high temperature resistant modified guar gum G5 .
实施例Example
（1）在四口烧瓶中加入0.1mol N,N,N’,N’-四甲基-1,8-萘二胺和388g溶剂乙醇，开启搅拌，用滴液漏斗滴加0.23mol环氧氯丙烷，滴加完毕后，用2mol/L的催化剂盐酸调节pH到2.3，加热回流反应42h；反应完毕，将混合液减压蒸馏，得到淡黄色粘稠固体；用乙酸乙酯进行重结晶，得到白色固体；(1) Add 0.1mol N,N,N',N'-tetramethyl-1,8-naphthylenediamine and 388g solvent ethanol into a four-necked flask, start stirring, and add 0.23mol epoxy dropwise with a dropping funnel After the dropwise addition of propane chloride, adjust the pH to 2.3 with 2 mol/L catalyst hydrochloric acid, and heat to reflux for 42 hours; after the reaction is completed, distill the mixture under reduced pressure to obtain a light yellow viscous solid; use ethyl acetate for recrystallization. A white solid was obtained;
（2）在烧杯中加入98.8g瓜尔胶和500g蒸馏水，用1mol/L的氢氧化钠调节pH 12.5，加入（1）中的白色固体，升温到62℃，保温反应50min；(2) Add 98.8g guar gum and 500g distilled water to the beaker, adjust the pH to 12.5 with 1mol/L sodium hydroxide, add the white solid in (1), raise the temperature to 62°C, and keep the reaction for 50 minutes;
（3）用2mol/L的盐酸调节pH 7，加入95g乙醇，降温到10℃以下，析出固体，过滤，烘干，得到产品耐高温改性瓜尔胶G6。(3) Adjust the pH to 7 with 2 mol/L hydrochloric acid, add 95g of ethanol, cool down to below 10°C, precipitate the solid, filter and dry to obtain the product high temperature resistant modified guar gum G6 .
实施例Example
（1）在四口烧瓶中加入0.1mol N,N,N’,N’-四甲基-1,8-萘二胺和428g溶剂乙醇，开启搅拌，用滴液漏斗滴加0.24mol环氧氯丙烷，滴加完毕后，用2mol/L的催化剂盐酸调节pH到2.4，加热回流反应44h；反应完毕，将混合液减压蒸馏，得到淡黄色粘稠固体；用乙酸乙酯进行重结晶，得到白色固体；(1) Add 0.1mol N,N,N',N'-tetramethyl-1,8-naphthylenediamine and 428g solvent ethanol into a four-necked flask, start stirring, and add 0.24mol epoxy dropwise from a dropping funnel After the dropwise addition of propane chloride, adjust the pH to 2.4 with 2 mol/L catalyst hydrochloric acid, heat and reflux for 44 hours; after the reaction is completed, distill the mixture under reduced pressure to obtain a light yellow viscous solid; use ethyl acetate for recrystallization. A white solid was obtained;
（2）在烧杯中加入81.2g瓜尔胶和444g蒸馏水，用1mol/L的氢氧化钠调节pH 13，加入（1）中的白色固体，升温到65℃，保温反应60min；(2) Add 81.2g guar gum and 444g distilled water to the beaker, adjust the pH to 13 with 1 mol/L sodium hydroxide, add the white solid in (1), raise the temperature to 65°C, and keep the reaction for 60 minutes;
（3）用2mol/L的盐酸调节pH 7.2，加入128g乙醇，降温到10℃以下，析出固体，过滤，烘干，得到产品耐高温改性瓜尔胶G7。(3) Adjust the pH to 7.2 with 2 mol/L hydrochloric acid, add 128g of ethanol, cool down to below 10°C, precipitate the solid, filter and dry to obtain the product high temperature resistant modified guar gum G7 .
实施例Example
（1）在四口烧瓶中加入0.1mol N,N,N’,N’-四甲基-1,8-萘二胺和412g溶剂乙醇，开启搅拌，用滴液漏斗滴加0.25mol环氧氯丙烷，滴加完毕后，用2mol/L的催化剂盐酸调节pH到2.5，加热回流反应48h；反应完毕，将混合液减压蒸馏，得到淡黄色粘稠固体；用乙酸乙酯进行重结晶，得到白色固体；(1) Add 0.1mol N,N,N',N'-tetramethyl-1,8-naphthylenediamine and 412g solvent ethanol into a four-necked flask, start stirring, and add 0.25mol epoxy dropwise with a dropping funnel After the dropwise addition of propane chloride, adjust the pH to 2.5 with 2 mol/L catalyst hydrochloric acid, heat and reflux for 48 hours; after the reaction is completed, distill the mixture under reduced pressure to obtain a light yellow viscous solid; use ethyl acetate for recrystallization. A white solid was obtained;
（2）在烧杯中加入88.4g瓜尔胶和468g蒸馏水，用1mol/L的氢氧化钠调节pH 12.5，加入（1）中的白色固体，升温到60℃，保温反应55min；(2) Add 88.4g guar gum and 468g distilled water to the beaker, adjust the pH to 12.5 with 1 mol/L sodium hydroxide, add the white solid in (1), raise the temperature to 60°C, and keep the reaction for 55 minutes;
（3）用2mol/L的盐酸调节pH 7.3，加入116g乙醇，降温到10℃以下，析出固体，过滤，烘干，得到产品耐高温改性瓜尔胶G8。(3) Adjust the pH to 7.3 with 2 mol/L hydrochloric acid, add 116g of ethanol, cool down to below 10°C, precipitate the solid, filter and dry to obtain the product high temperature resistant modified guar gum G8 .
测试例1 表观粘度的测试Test Example 1 Test of apparent viscosity
评价方法参考SY/T 5764—2007《压裂用植物胶通用技术要求》，按照其中4.6的要求执行。The evaluation method refers to SY/T 5764-2007 "General Technical Requirements for Vegetable Glues for Fracturing" and is implemented in accordance with the requirements of 4.6.
表观粘度测试结果见表1。The apparent viscosity test results are shown in Table 1.
从表1可以看出：本发明的耐高温改性瓜尔胶G1、G2、G3、G4、G5、G6、G7、G8的表观粘度均大于420mPa•s，其中，G7最高达到了527mPa•s；而改性前瓜尔胶的表观粘度为205mPa•s，明显低于本发明改性后瓜尔胶的表观粘度。It can be seen from Table 1 that the apparent viscosity of the high temperature resistant modified guar gum G1 , G2 , G3 , G4 , G5 , G6 , G7 and G8 of the present invention is all greater than 420mPa·s. Among them, G7 reaches a maximum of 527 mPa·s; while the apparent viscosity of guar gum before modification is 205 mPa·s, which is significantly lower than the apparent viscosity of guar gum after modification in the present invention.
测试例2 耐温性的测定Test Example 2 Measurement of Temperature Resistance
将测试例1的样品测试耐温性，用哈克流变仪测试不同温度的粘度，从30℃开始，每增加5℃记录一次表观粘度，当粘度小于50mPa•s时，停止测试，对应的温度为改性瓜尔胶的耐温温度。Test the temperature resistance of the sample in Test Example 1, and use a Hacker rheometer to test the viscosity at different temperatures. Starting from 30°C, record the apparent viscosity every 5°C. When the viscosity is less than 50mPa·s, stop the test, corresponding to The temperature is the temperature resistance temperature of modified guar gum.
粘温曲线测试结果见图1，耐温温度测试结果见表1。The viscosity-temperature curve test results are shown in Figure 1, and the heat resistance temperature test results are shown in Table 1.
从表1可以看出：本发明的耐高温改性瓜尔胶G1、G2、G3、G4、G5、G6、G7、G8的耐温均大于80℃，其中，G7最高达到了87℃；而改性前瓜尔胶的耐温为65℃，明显低于本发明改性后瓜尔胶。It can be seen from Table 1 that the temperature resistance of the high temperature resistant modified guar gum G1 , G2 , G3 , G4 , G5 , G6 , G7 , and G8 of the present invention is all greater than 80°C, among which, G7 reaches a maximum of 87°C; while the temperature resistance of guar gum before modification is 65°C, which is significantly lower than the modified guar gum of the present invention.
测试例3 水不溶物的测定Test Example 3 Determination of water-insoluble matter
评价方法参考SY/T 5764—2007《压裂用植物胶通用技术要求》，按照其中4.8的要求执行。The evaluation method refers to SY/T 5764-2007 "General Technical Requirements for Vegetable Glues for Fracturing" and is implemented in accordance with the requirements of 4.8.
水不溶物含量测试结果见表1。The test results of water-insoluble matter content are shown in Table 1.
从表1可以看出：本发明的耐高温改性瓜尔胶G1、G2、G3、G4、G5、G6、G7、G8的水不溶物含量均低于2.8%，其中，G7最低为2.04%；而改性前瓜尔胶的水不溶物含量为5.68%，明显高于本发明改性后瓜尔胶。It can be seen from Table 1 that the water-insoluble matter content of the high-temperature-resistant modified guar gum G1 , G2 , G3 , G4 , G5 , G6 , G7 and G8 of the present invention is all less than 2.8%. , among which, the lowest G7 is 2.04%; and the water-insoluble content of guar gum before modification is 5.68%, which is significantly higher than the modified guar gum of the present invention.
测试例4 抗菌能力的测试Test Example 4 Test of antibacterial ability
评价方法参考Q/SH1025 0784—2011《压裂用杀菌剂技术条件》，按照其中5.3的要求执行。The evaluation method refers to Q/SH1025 0784-2011 "Technical Conditions for Fungicides for Fracturing" and is implemented in accordance with the requirements of 5.3.
基液制备：量取1000 ml自来水倒入无菌混调器中，调节无菌混调器转速至液体形成的漩涡可以见到混调器浆叶中轴顶端为止。然后缓慢加入5 g（精确至0.001 g）瓜尔胶，形成均匀的溶液，停止搅拌，30℃的电热恒温培养箱中静置恒温。Base liquid preparation: Measure 1000 ml of tap water and pour it into the sterile mixer. Adjust the speed of the sterile mixer until the vortex formed by the liquid can be seen at the top of the central axis of the mixer blades. Then slowly add 5 g (accurate to 0.001 g) guar gum to form a uniform solution, stop stirring, and let it stand at a constant temperature in a 30°C electric constant temperature incubator.
冻胶制备：量取上述基液70 ml倒入100 ml烧杯中，在玻璃棒的搅拌下依次加入0.35 ml压裂用高温稳定剂和0.30 ml液体氢氧化钠，搅拌均匀，然后边搅拌边加入0.35 ml交联剂，直至形成能挑挂的均匀冻胶。Gel preparation: Measure 70 ml of the above base solution and pour it into a 100 ml beaker. Add 0.35 ml of high-temperature stabilizer for fracturing and 0.30 ml of liquid sodium hydroxide in sequence while stirring with a glass rod. Stir evenly and then add while stirring. 0.35 ml of cross-linking agent until a uniform gel that can be picked is formed.
粘度测定：分别将恒温4 h和120 h的基液制备冻胶，然后装入RT20型流变仪中，按SY/T 5107—2005《水基压裂液性能评价方法》中6.6进行压裂液耐温耐剪切能力测定。设定温度为120 ℃，设定转子在剪切速率为170s-1 下剪切90 min，取剪切最后10 min所对应表观粘度的平均值为冻胶表观粘度。Viscosity measurement: Prepare jelly from the base fluid at constant temperature for 4 h and 120 h respectively, then put it into the RT20 rheometer, and perform fracturing according to 6.6 in SY/T 5107-2005 "Water-based Fracturing Fluid Performance Evaluation Method" Determination of liquid temperature and shear resistance. Set the temperature to 120°C, set the rotor to shear for 90 minutes at a shear rate of 170 s-1 , and take the average value of the apparent viscosity corresponding to the last 10 minutes of shearing as the apparent viscosity of the gel.
式中：In the formula:
R —压裂液粘度保持率，%；R —Fracturing fluid viscosity retention rate, %;
h1—基液恒温4 h时的冻胶表观粘度，单位为毫帕秒（mPa•s）；h 1—apparent viscosity of the gel when the base fluid is kept at constant temperature for 4 h, in milliPascal seconds (mPa·s);
h2—基液恒温120 h时的冻胶表观粘度，单位为毫帕秒（mPa•s）。h 2—The apparent viscosity of the gel when the base fluid is kept at constant temperature for 120 h, in milliPascal seconds (mPa·s).
抗菌能力测试结果见表1。The results of the antibacterial ability test are shown in Table 1.
表1 改性瓜尔胶表观粘度、耐温性、水不溶物、抗菌能力测试结果Table 1 Test results of apparent viscosity, temperature resistance, water-insoluble matter, and antibacterial ability of modified guar gum
从表1可以看出：本发明的耐高温改性瓜尔胶G1、G2、G3、G4、G5、G6、G7、G8的抗菌能力均大于92%，其中，G8最高为94.8%；而改性前瓜尔胶的抗菌能力为31.2%，明显低于本发明改性后瓜尔胶。It can be seen from Table 1 that the antibacterial abilities of the high temperature resistant modified guar gum G1 , G2 , G3 , G4 , G5 , G6 , G7 and G8 of the present invention are all greater than 92%, among which, The highest G8 is 94.8%; and the antibacterial ability of guar gum before modification is 31.2%, which is significantly lower than the modified guar gum of the present invention.
测试例5 红外光谱表征Test Example 5 Infrared Spectral Characterization
采用红外光谱对本发明的产品耐高温改性瓜尔胶G7进行了表征，结果如图2所示。The high-temperature-resistant modified guar gum G7 , a product of the present invention, was characterized using infrared spectroscopy, and the results are shown in Figure 2.
图2中，3447cm-1是分子中O-H的伸缩振动吸收峰；2922cm-1是分子中C-H键伸缩振动吸收峰；1111cm-1是分子中胍胶醚C-O-C键伸缩振动吸收峰；949cm-1是分子中季铵盐C-N键伸缩振动吸收峰。In Figure 2, 3447cm-1 is the stretching vibration absorption peak of OH in the molecule; 2922cm-1 is the stretching vibration absorption peak of CH bond in the molecule; 1111cm-1 is the stretching vibration absorption peak of COC bond in guar gum ether in the molecule; 949cm-1 is The CN bond stretching vibration absorption peak of the quaternary ammonium salt in the molecule.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.
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| CN202310969653.XACN116693715B (en) | 2023-08-03 | 2023-08-03 | High-temperature-resistant modified guar gum and synthetic method thereof |
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| CN117164738B (en)* | 2023-09-27 | 2024-08-13 | 东营施普瑞石油工程技术有限公司 | Modified guar gum for fracturing and preparation method thereof |
| CN117088993B (en)* | 2023-10-18 | 2024-02-02 | 东营市宝泽能源科技有限公司 | Guar gum for oilfield fracturing and preparation method thereof |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right | Denomination of invention:A high-temperature resistant modified guar gum and its synthesis method Granted publication date:20231027 Pledgee:Shandong Guangrao Rural Commercial Bank Co.,Ltd. Pledgor:DONGYING BAOZE ENERGY TECHNOLOGY Co.,Ltd. Registration number:Y2025980005341 |