[75] Inventor: Roy F. House, Lafayette, La.
[75] 发明者罗伊-F.-豪斯，拉法叶市
[73] Assignee: Venture Innovations, Inc., Lafayette, La.
[73] Assignee：Venture Innovations, Inc.
[21] Appl. No.: 574,379 [21] 申请号：574,379
[22] Filed: Jan. 27, 1984
[22] 归档：1984年1月27日
[51] Int. Cl. 4 C07C 91/26; C09F 7/14
[51] Int.Cl.4 C07C 91/26; C09F 7/14
52] U.S. Cl 260/501.15; 260/501.11; 260/404.5
52]U.S. Cl 260/501.15；260/501.11；260/404.5
[58] Field of Search 260/501.15, 501.11 260/404.5 PA
[260/501.15, 501.11 260/404.5 PA

3,494,865 2/1970 Andrews, Jr. et al. ......... 252/8.5 M
3,671,427 6/1972 Andrews, Jr. et al. .......... 260/404.5
3,671,428 6/1972 Kim ............................... 252/8.5 M
3,775,447 11/1973 Andrews et al. .......... 260/404.5 PA
Primary Examiner-Glennon H. Hollrah Assistant Examiner-Raymond Covington
主审查员--格伦农-H-霍拉赫 助理审查员--雷蒙德-考文顿
[57]
ABSTRACT 摘要
The invention provides a novel process of preparing organophilic humate derivatives wherein: an aqueous solution of a humic acid-containing material is prepared with an alkali metal or ammonium base; an amine containing at least 16 carbon atoms and at least one functional group per molecule selected from the group consisting of primary amino, secondary amino, quaternary ammonium, and mixtures thereof, is mixed with the humate solution; an acid is mixed with the amine-containing humate solution in an amount at least sufficient to neutralize all of the alkali metal or ammonium base used to prepare the humate solution; and thereafter the organophilic substituted ammonium humate derivative is recovered.
本发明提供了一种制备亲有机腐植酸衍生物的新工艺，其中包括用碱金属或铵碱制备含腐植酸材料的水溶液；将至少含有 16 个碳原子且每个分子至少含有一个官能团的胺与腐植酸溶液混合，该官能团选自伯氨基、仲氨基、季铵及其混合物组成的组；将一种酸与含胺腐植酸盐溶液混合，其用量至少足以中和所有用于制备腐植酸盐溶液的碱金属或铵碱，然后回收亲有机取代的腐植酸铵衍生物。
9 Claims, No Drawings 9 项索赔，无图纸

The invention relates to methods for the manufacture of organophilic amine derivatives of complex phenolic compounds.
本发明涉及复杂酚类化合物的亲有机胺衍生物的制造方法。

In the drilling of wells for oil and gas by the rotary method, it is common to use a circulating fluid which is pumped down to the bottom of the well through a drill pipe, where the fluid emerges through ports in the drilling bit. The fluid rises to the surface in the annular space between the drill pipe and the walls of the hole, and at the surface it is treated to remove cuttings and the like and to prepare it for recirculation into the drill pipe. The circulation is substantially continuous while the drill pipe is rotated.
在用旋转法钻探石油和天然气井时，通常使用循环流体，通过钻杆将流体泵送到井底，流体从钻头的孔口流出。流体在钻杆和井壁之间的环形空间内上升到地面，在地面经过处理，除去切屑等，准备再循环到钻杆中。当钻杆旋转时，循环基本上是连续的。
An important feature of oil base well working fluids of the class described is their ability to resist filtration. In most instances when they are in actual use, whether as drilling fluids, packer fluids, fracturing or completion fluids, the well working fluid is in contact with a more or less permeable formation, such as, for example, sandstone, sandy shale and the like, with an effective balance of pressure such that the fluid tends to be forced into the permeable formation. When a well working fluid is deficient in its ability to resist filtration, then the solids in the fluid are held back by the permeable formation and build up as a filter cake or sludge on its surfaces, while the liquid per se of the well working fluid filters into the permeable formation. The filter cake or sludge thus formed is generally very undesirable. Moreover, the loss of oil to the formation is very expensive, not only because of the cost of the oil itself, but also due to the cost of maintaining the properties and composition of the fluid.
所述类别的油基油井工作液的一个重要特点是具有抗过滤能力。在实际使用中，无论是作为钻井液、封隔器液、压裂液还是完井液，在大多数情况下，油井工作液都会与或多或少具有渗透性的地层接触，例如砂岩、砂页岩等，压力的有效平衡使得油井工作液倾向于被迫进入渗透性地层。当油井工作流体的抗过滤能力不足时，流体中的固体就会被渗透地层阻挡，并在其表面形成滤饼或淤泥，而油井工作流体中的液体本身则会过滤到渗透地层中。这样形成的滤饼或淤泥通常是非常不理想的。此外，地层中石油的损失是非常昂贵的，这不仅是因为石油本身的成本，还因为维持液体特性和成分的成本。
Various additives have been used or suggested for use as fluid loss additives to prevent or decrease this loss of fluid by filtration from oil base muds. Some of the first materials used for this purpose were asphalt and various modified asphaltic materials. The following U.S. patents all disclose various amine derivatives of various polyphenolic compounds for use as fluid loss additives (hereinafter sometimes referred to as FLA) for oil base muds: Jordan et al. U.S. Pat. No. 3,168,475; Jordan et al. U.S. Pat. No. 3,281,458; Beasley et al. U.S. Pat. No 3,379,650; Cowan et al. U.S. Pat. No. 3,232,870; Cowan et al. U.S. Pat. No. 3,425,953; Andrews et al. U.S. Pat. No. 3,494,865; Andrews et al. U.S. Pat. No. 3,671,427; Andrews et al. U.S. Pat. No. 3,775,447; Kim U.S. Pat. No. 3,538,071; and Kim U.S. Pat. No. 3,671,428. These patents are incorporated herein by reference for all purposes.
人们使用或建议使用各种添加剂作为流体损失添加剂，以防止或减少油基泥浆中流体的过滤损失。最早用于此目的的一些材料是沥青和各种改性沥青材料。以下美国专利都公开了各种多酚化合物的各种胺衍生物，可用作油基泥浆的流体流失添加剂（以下有时称为 FLA）：Jordan et al.No. 3,168,475; Jordan et al.No. 3,281,458; Beasley et al.No 3,379,650; Cowan et al.No. 3,232,870; Cowan et al.3,425,953; Andrews et al.No. 3,494,865; Andrews et al.No. 3,671,427; Andrews et al.No. 3,775,447; Kim U.S. Pat.No. 3,538,071；以及 Kim U.S. Pat.第 3,671,428 号。为所有目的，这些专利通过引用并入本文。
Jordan et al. U.S. Pat. No. and U.S. Pat No. disclose certain substituted ammonium salts of humic acid. Compounds useful in the practice of their invention can be represented by the formula
Jordan et al. 号和美国专利 号公开了腐植酸的某些取代铵盐。在其发明实践中有用的化合物可由式表示

wherein at least one of the R's is an alkyl radical having from 12 to 22 carbon atoms in a straight chain, and in which those R's which do not have from 12 to 22 carbon atoms in a straight chain are chosen from the group consisting of hydrogen, alkyl radicals having fewer than
其中至少有一个 R 是直链上有 12 至 22 个碳原子的烷基，而直链上没有 12 至 22 个碳原子的 R 选自以下组别：氢、直链上的碳原子数少于 12 的烷基、直链上的碳原子数少于 22 的烷基、直链上的碳原子数少于 12 的烷基、直链上的碳原子数少于 22 的烷基、直链上的碳原子数少于 12 的烷基。
12 carbon atoms, phenyl, and benzyl; wherein Hu - is the anion of humic acid; wherein the term "alkyl" includes unsaturated alkyl chains, such as, for example, oleyl as well as stearyl; and wherein at least one of the
其中 Hu - 是腐植酸的阴离子；其中术语 "烷基 "包括不饱和烷基链，例如油基和硬脂基；其中至少一个 "烷基 "是腐植酸的阴离子。
5 alkyl radicals having from 12 to 22 carbon atoms may be attached to the nitrogen atom indirectly through an intermediate linkage, most generally a heterocylic carbon-nitrogen ring
5 个具有 12 至 22 个碳原子的烷基可通过中间连接间接连接到氮原子，最常见的是杂环碳氮环
Beasley et al. U.S. Pat. No. 3,379,650 discloses vari10 ous additives (dispersants) which facilitate the dispersion of long chain alkyl ammonium humates in organic liquids. Such humates are more readily dispersible in some organic liquids than in others. The dispersibility of these humates is also dependent to some extent on their long chain alkyl ammonium humates decreases their dispersibility.
Beasley et al.第 3,379,650 号专利公开了 10 种不同的添加剂（分散剂），它们有助于长链烷基腐植酸铵在有机液体中的分散。这些腐植酸盐在某些有机液体中比在其他有机液体中更容易分散。这些腐植酸盐的分散性在一定程度上还取决于它们的长链烷基腐植酸铵是否会降低其分散性。
Andrews et al. U.S. Pat. No. 3,494,865 discloses an adduct prepared by reacting humic acid with from about to about of its base-combining capacity, with certain fatty acid partial amides of a polyalkylene polyamine. As stated therein at column 3, lines 10-12. "The adduct as described and wherein the partial amide is present to the extent of about of the base-combining capacity of the humic acid probably represents salt formation for , the remaining being adsorption, although in view of the complicated nature of the constituents, exact structural analysis is difficult and somewhat undertain. Also, depending on the drying temperature, where heat is used for such a step, the adduct may undergo a certain extent of amidification where the amine groups of the polyamines are combined with the carboxyl groups of the humic acid." well working fluids and further discloses certain dispersants which are desirable to expedite the dispersion of the adducts without depending on down-hole circulation of the well working fluids.
Andrews et al.3,494,865号专利公开了一种加合物，该加合物是由腐植酸（其碱结合能力约为 至 ）与聚亚烷基多胺的某些脂肪酸部分酰胺反应制备而成。如其中第 3 栏第 10-12 行所述。"如上所述的加合物，其中部分酰胺的含量约为腐植酸碱结合能力的 ，可能代表 的盐形成，其余的 为吸附，但鉴于成分的复杂性，精确的结构分析很难，而且有些不充分。此外，根据干燥温度的不同（如果在这一步骤中使用了热量），加合物可能会发生一定程度的酰胺化，此时多胺的胺基团与腐植酸的羧基结合。

Andrews et al. U.S. Pat. No. 3,671,427 discloses certain adducts of humic acid and a fatty acyl partial amide of a polyalkylene polyamine wherein the partial amide is linked to the humic acid by an amide linkage.
Andrews et al.第 3,671,427 号专利公开了腐植酸与聚烯多胺的脂肪酰部分酰胺的某些加合物，其中部分酰胺通过酰胺连接与腐植酸相连。
Beasley et al. U.S. Pat. No. 3,325,537 discloses certain zation of at least by weight and at the same time obtain a resulting pH within the limits of 5.2 to 7.5 . Such lignite solutions are disclosed to be useful in preparing long chain alkyl ammonium humates.
Beasley et al.3,325,537号公开了按重量计至少 的某些zation，同时得到的pH值在5.2至7.5的范围内。这种褐煤溶液可用于制备长链烷基腐植酸铵。

Generally speaking, the substituted ammonium humates disclosed in these prior art patents may be produced by bringing together humic acid and the substituted ammonium compound in its base form. The base and the acid neturalize each other with salt formation to produce the desired humate derivative. Another general method of preparation disclosed is to convert the humic acid to a simple salt by reaction with an alkali, so as to produce sodium humate, potassium humate, ammonium humate, and the like, by reaction with alkali metal or ammonium bases, respectively. The substituted ammonium compound is caused to be present in the form of a simple salt or in quaternary ammonium form. Thus the free amine groups may be reacted with a simple acid such as hydrochloric, acetic, and the like to 5 give the corresponding substituted ammonium chloride or acetate, respectively. This method of procedure is stated to have the advantage that the substituted ammonium salts and quaternary ammonium salts, and the
一般来说，这些现有技术专利中公开的取代铵腐植酸盐可以通过将腐植酸和取代铵化合物以碱的形式结合在一起来生产。碱和酸通过盐的形成相互净化，生成所需的腐植酸衍生物。公开的另一种一般制备方法是通过与碱反应将腐植酸转化为简单的盐，从而通过与碱金属或铵碱反应分别生成腐植酸钠、腐植酸钾、腐植酸铵等。取代的铵化合物会以单盐或季铵的形式存在。因此，游离胺基团可与盐酸、醋酸等单酸反应，分别生成相应的取代氯化铵或醋酸铵。据说这种方法的优点是取代铵盐和季铵盐，以及
simple humates as described are both water soluble, so that solutions of each reactant may be made, and the reaction completed by mixing solutions thereof together. Mixtures of water with methanol, ethanol, isopropanol, acetone, and the like may be needed for some substituted ammonium salts and quaternary ammonium salts.
所述的简单腐殖酸盐均可溶于水，因此可以配制每种反应物的溶液，并通过将其溶液混合在一起完成反应。某些取代铵盐和季铵盐可能需要水与甲醇、乙醇、异丙醇、丙酮等的混合物。
I have found that the prior art method for preparing organophilic humate derivatives wherein the humic acid containing material and the substituted ammonium compound in base form are reacted together produces organophilic humate derivatives which are inefficient high temperature fluid loss control additives for oil base drilling fluids. The amount of substituted ammonium compound which can be reacted with the humic acid under these conditions is insufficient to react with all of the acidic functional groups of the humic acid.
我发现，现有技术中制备嗜有机腐植酸衍生物的方法是将含腐植酸的材料和碱形式的取代铵化合物反应在一起，生成的嗜有机腐植酸衍生物是一种低效的油基钻井液高温流体损失控制添加剂。在这些条件下能与腐植酸反应的取代铵化合物的量不足以与腐植酸的所有酸性官能团反应。
I have further found that the prior art method for preparing organophilic humate derivatives wherein the humic acid containing material is converted to a water soluble or colloidally dispersible humate salt and subsequently reacted with a substituted ammonium compound in the form of an acid salt or quaternary ammonium salt suffers from several disadvantages, i.e., (a) many substituted ammonium salts are not water soluble and a polar organic solvent such as an alcohol, ketone, and the like must be added to the salt in order for the substituted ammonium salt to properly react with the humate salt. The use of such solvents is expensive and creates disposal problems when it is removed from the product, as by filtration, drying, and the like; (b) as noted in Beasley et al. U.S. Pat. No. 3,325,537, an excessive amount of substituted ammonium salt must be used to precipitate the humate salt when the pH of the humate solution is greater than 7.5 ; (c) the humate salt and the substituted ammonium salt commence reaction as soon as the substituted ammonium salt is mixed with the humate solution. As the precipitation of the organophilic humate derivative proceeds, some of the reactive sites on the humate become unavailable for reaction resulting in a sorption of the substituted ammonium salt onto the reacted ammonium humate derivative; and (d) filtration of the precipitated organophilic humate derivative is poor when utilizing as the substituted ammonium salt an amino-amide compound of the types disclosed in Andrews et al. U.S. Pat. Nos. 3,494,865; ; and .
我还发现，现有技术中用于制备亲有机腐植酸衍生物的方法存在几个缺点，即先将含腐植酸的材料转化为水溶性或胶体分散性腐植酸盐，然后再与酸盐或季铵盐形式的取代铵化合物反应、(a) 许多取代铵盐不溶于水，必须在盐中加入极性有机溶剂，如醇、酮等，才能使取代铵盐与腐植酸盐正常反应。使用这类溶剂价格昂贵，而且在通过过滤、干燥等方法从产品中去除时会产生处理问题；（b）如 Beasley et al.3,325,537 号中指出，当腐植酸盐溶液的 pH 值大于 7.5 时，必须使用过量的取代铵盐来沉淀腐植酸盐；(c) 当取代铵盐与腐植酸盐溶液混合后，腐植酸盐和取代铵盐立即开始反应。随着亲有机腐植酸盐衍生物沉淀的进行，腐植酸盐上的一些反应位点无法进行反应，导致取代铵盐吸附在反应后的腐植酸铵衍生物上；以及 (d) 当使用 Andrews et al. U.S. Pat.Nos.3,494,865； ；和 。

I have now found a process for the preparation of organophilic humate derivatives which overcomes the disadvantages of the prior art processes and which produces efficient fluid loss control additives in oil base drilling fluids. These additives impart excellent high temperature filtration control characteristics to oil base drilling fluids.
我现在已经找到了一种制备亲有机腐殖酸衍生物的工艺，它克服了现有工艺的缺点，并能在油基钻井液中生产出高效的流体流失控制添加剂。这些添加剂可为油基钻井液提供出色的高温过滤控制特性。

The process of my invention comprises: preparing an aqueous humate solution; mixing with the humate solution an amine containing at least one functional group per molecule selected from the group consisting of primary amino ( ), secondary amino ( ), quaternary ammonium
本发明的工艺包括：制备腐植酸水溶液；与腐植酸水溶液混合的胺，其每个分子至少含有一个官能团，该官能团选自由伯氨基（ ）、仲氨基（ ）、季铵组成的组。

5
or mixtures thereof; mixing with this amine containing humate solution an acid in an amount sufficient to at least neutralize all of the base used in preparing the 0 aqueous humate solution; and thereafter recovering an organophilic ammonium humate; wherein the temperature of the amine containing humate, solution is at least about . .).
或其混合物；与该含腐植酸胺溶液混合一种酸，其量至少足以中和制备0腐植酸水溶液时使用的所有碱；然后回收一种嗜有机腐植酸铵；其中含腐植酸胺溶液的温度至少约为 . )。

Accordingly, it is an object of this invention to pro15 vide an improved process for the preparation of organophilic humate derivatives which are useful as additives to control the fluid loss from oil base drilling fluids.
因此，本发明的目的是提供15 一种改进的亲有机腐殖酸衍生物的制备工艺，这种衍生物可用作添加剂来控制油基钻井液的流体损失。
It is another object of this invention to provide a process for the preparation of organophilic ammonium humate derivatives in which the humic acid and the ammonium compound are more uniformly reacted.
本发明的另一个目的是提供一种制备亲有机腐殖酸铵衍生物的工艺，其中腐殖酸和铵化合物的反应更加均匀。
It is yet another object of this invention to provide a process for the preparation of organophilic ammonium humates which requires no polar organic solvents.
本发明的另一个目的是提供一种无需极性有机溶剂的亲有机腐植酸铵制备工艺。

These and other objects of this invention will be apparent to one skilled in the art upon reading this specification and the appended claims.
本领域技术人员在阅读本说明书和所附权利要求书后，就会明白本发明的上述和其他目的。

While the invention is susceptible of various modifi30 cations and alternative forms, specific embodiments thereof will hereinafter be described in detail and shown by way of example. It should be understood, however, that it is not intended to limit the invention to the particular forms disclosed, but, on the contrary, the invention is to cover all modifications and alternatives falling within the spirit and scope of the invention as expressed in the appended claims.
虽然本发明可以有各种修改30 和替代形式，但下文将详细描述其具体实施例，并以举例的方式加以说明。然而，应当理解的是，本发明无意限制于所公开的特定形式，相反，本发明涵盖了在所附权利要求书所表达的本发明精神和范围内的所有修改和替代形式。
The compositions can comprise, consist essentially of, or consist of the stated materials. The method can comprise, consist essentially of, or consist of the stated steps with the stated materials.
组合物可以包括、主要包括或包括所述材料。该方法可以包括、主要包括或包括使用所述材料的所述步骤。

The novel process of my invention for preparing organophilic humate derivatives comprises: (a) dispersing a humic acid-containing material in water with an alkali metal or ammonium base to produce a humate solution; (b) mixing with the humate solution an amine containing at least sixteen carbon atoms and at least one functional group per molecule selected from the group consisting of primary amino, secondary amino, quater nary ammonium, or mixtures thereof; (c) mixing with said amine containing humate solution an acid in an amount sufficient to at least neutralize all of the alkali metal or ammonium base; and (d) thereafter recovering the organophilic ammonium humate; wherein the temperature of the amine containing humate solution is above about . ( .).
本发明制备亲有机腐植酸衍生物的新工艺包括(a) 将含腐植酸的材料与碱金属或铵盐分散在水中，生成腐植酸盐溶液； (b) 与腐植酸盐溶液混合一种胺，该胺至少含有 16 个碳原子，每个分子至少含有一个官能团，该官能团选自由伯氨基、仲氨基、季铵或它们的混合物组成的组；(c) 与所述含腐植酸胺溶液混合一种酸，其用量足以至少中和所有碱金属或铵碱；以及 (d) 随后回收嗜有机腐植酸铵；其中，含腐植酸胺溶液的温度高于约 。( 。)。
Humic acid is a material of wide distribution and is present in soils, peat, and coals, particularly lignite or brown coal, and most particularly in the soft brown coal known as a leonardite. Humic acids are complex organic molecules that are formed by the breakdown of organic matter. Their exact structures are unknown and they are extremely variable. The principal organic groups present are phenolic and carboxylic OH , aliphatic CH, carbonyl, conjugated carbonyl or aromatic
腐植酸是一种分布广泛的物质，存在于土壤、泥炭和煤炭中，特别是褐煤或褐煤，尤其是被称为褐铁矿的软褐煤中。腐植酸是有机物质分解后形成的复杂有机分子。它们的确切结构尚不清楚，而且极其易变。存在的主要有机基团是酚基和羧基 OH、脂肪族 CH、羰基、共轭羰基或芳香基。
or or ionic carboxyl, and possibly others. The average molecular weight of the humic acids is between 5,000 and 50,000 . They have no -ray or electron diffraction patterns and are therefore presumably amorphous.
或 或离子羧基，可能还有其他。腐植酸的平均分子量在 5,000 到 50,000 之间。它们没有 射线或电子衍射图，因此可能是无定形的。

The humic acids have a large cation exchange capacity which varies from 200 to 500 milliequivalents per 100 grams at pH 7 depending on the humus source. Humic acids are colloids. When the cation exchange sites on the humic molecule are filled predominantly with other than hydrogen, the material is called humate. The humates of monovalent inorganic and ammonium ions are soluble in water, but the humates of multivalent cations are insoluble.
腐殖酸具有很大的阳离子交换容量，根据腐殖质来源的不同，在 pH 值为 7 时，每 100 克腐殖酸的阳离子交换容量从 200 毫当量到 500 毫当量不等。腐殖酸是胶体。当腐殖酸分子上的阳离子交换位点主要由氢以外的元素填充时，这种物质就被称为腐殖酸盐。单价无机离子和铵离子的腐殖酸盐可溶于水，但多价阳离子的腐殖酸盐则不溶于水。
The term humic acid is used herein to include all of the colloidal acids derived from humus, including humic acid, ulmic acid and fulvic acid. Humic acid is soluble in alkali but insoluble in acid, methyl ethyl ketone, and methyl alcohol. Ulmic acid is soluble in alkali and methyl etyl ketone but insoluble in methyl alcohol. Fulvic acid is soluble in alkali, methyl ethyl ketone and methyl alcohol. The term humic acid is also intended to mean humic acids which have been further oxidized to increase their carboxyl content. See for example, "Chemistry of Brown Coals. IV. Action of Oxygen in Presence of Alkali", R. A. Durie and S. Sternhill, Australian Journal of Applied Science, 9, No. 4, 360-369, 1958.
这里所说的腐植酸包括从腐殖质中提取的所有胶体酸，包括腐植酸、溃疡酸和富勒酸。腐植酸可溶于碱，但不溶于酸、甲乙酮和甲醇。腐植酸可溶于碱和甲乙酮，但不溶于甲醇。富里酸可溶于碱、甲乙酮和甲醇。腐植酸一词也指经过进一步氧化以增加其羧基含量的腐植酸。例如，参见 "褐煤的化学"。IV.IV. 氧气在碱存在下的作用"，R. A. Durie 和 S. Sternhill，《澳大利亚应用科学杂志》，9，第 4 期，360-369，1958 年。

While humic acid is present in soils and peat, and may be extracted from them, for example, with dilute aqueous alkali, it is preferred to obtain humic acid for the purposes of this invention in the form of lignite of high alkali solubility, of which vast deposits are found throughout the world, including particularly, the United States, for example, in North Dakota, Montana, Texas, New Mexico, and California. While I do not mean to be limited thereby, I prefer a humic acid source having a solubility in dilute, aqueous sodium hydroxide of at least by dry weight, preferably at least as this provides a reasonable compromise between cost and efficacy in the final product.
虽然腐植酸存在于土壤和泥炭中，并且可以从它们中提取，例如用稀碱水溶液提取，但为了本发明的目的，最好以高碱溶解度的褐煤的形式获得腐植酸，全世界都有大量的褐煤矿藏，特别是美国，例如在北达科他州、蒙大拿州、得克萨斯州、新墨西哥州和加利福尼亚州。虽然我无意因此而受到限制，但我更倾向于使用在稀氢氧化钠水溶液中的溶解度至少为 （以干重计），最好至少为 的腐植酸源，因为这样可以在最终产品的成本和功效之间达成合理的折衷。

The amino compounds which may be used in this invention include polyamines or polyamidoamines which contain at least one primary or secondary amine 45 group per molecule and at least 16 carbon atoms selected from the group consisting of (I), (II), (III), and mixtures thereof:
本发明中可使用的氨基化合物包括多胺或多氨基胺，它们每个分子至少含有一个伯胺或仲胺 45 基团，至少含有 16 个碳原子，这些碳原子选自由（I）、（II）、（III）及其混合物组成的组：

where is an aliphatic group containing from 12 to 30 carbon atoms; is selected from the group consisting of H and , and mix- 60 tures thereof; is an aliphatic group containing from 11 to 29 carbon atoms; and wherein at least one of the groups are H
其中 是含有 12 至 30 个碳原子的脂肪族基团； 选自 H 和 组成的组，以及它们的混合物； 是含有 11 至 29 个碳原子的脂肪族基团；其中 基团中至少有一个是 H

The amine compound may also be a quaternary am monium compound obtained by quaternizing the above 65 compounds such that the H atoms are replaced with an alkyl group containing 1 to 3 carbon atoms, a benzyl group, or mixtures thereof, and excess of the quaterniz- ing reagent is used sufficient to effect the quaternization of the amino group.
胺化合物也可以是一种季铵化合物，通过对上述 65 种化合物进行季铵化处理，使 H 原子被含有 1 至 3 个碳原子的烷基、苄基或它们的混合物所取代，并使用过量的季铵化试剂来实现氨基的季铵化。

Preferably in the compounds represented by formula and in the compounds represented by
优选式 代表的化合物中的 和式 代表的化合物中的 。
5 formulas II and III. Preferably is an alkyl group containing from 12 to 22 carbon atoms, and is an alkyl group containing from 11 to 21 carbon atoms. Most preferably at least of the aliphatic radicals represented by R contain 18 carbon atoms, and at least of the aliphatic groups represented by contain 17 carbon atoms. Still more preferably the R" group is derived from tall oil fatty acid.
5 式 II 和 III。最好 是含有 12 至 22 个碳原子的烷基， 是含有 11 至 21 个碳原子的烷基。最优选的是，由 R 代表的脂肪族基团中至少 含有 18 个碳原子，而由 代表的脂肪族基团中至少 含有 17 个碳原子。更优选的是，R "基团来自妥尔油脂肪酸。

The amino compound may also be a quaternary ammonium compound having the molecular formula (IV), and mixtures thereof with compounds (I), (II), and (III).
氨基化合物也可以是分子式为(IV)的季铵盐化合物及其与化合物(I)、(II)和(III)的混合物。

where , and are independently selected 20 from the group consisting of H , lower alkyl groups containing from one to three carbon atoms, and higher aliphatic groups containing from 12 to 30 carbon atoms; and where is a charge balancing anion of valence .
其中 和 分别独立地从 H、含有 1 至 3 个碳原子的低级烷基和含有 12 至 30 个碳原子的高级脂肪族基团组成的组中选出；且 是价数 的电荷平衡阴离子。
Preferably at least two of the , and
最好是 和 中的至少两个
5 groups contain at least 16 carbon atoms, and the anion is chloride.
5 个基团含有至少 16 个碳原子，阴离子为氯化物。
In the foregoing as well as elsewhere in this specification and the claims which follow, the term aliphatic is to be understood as including unsaturated as well as saturated (alkyl) straight carbon chain radicals, and straight carbon chain radicals which contain one or more hydroxyl or amino groups substituted therein.
在上文以及本说明书的其它地方和后面的权利要求中，术语脂肪族应理解为包括不饱和以及饱和（烷基）直碳链基，以及含有一个或多个羟基或氨基取代的直碳链基。
By way of further explanation of the nature and types of the amino compounds utilized in the present invention are some typical members of the series in the following table, although these are merely illustrative and not at all by way of limitation.
为了进一步说明本发明中使用的氨基化合物的性质和类型，下表中列出了该系列中的一些典型成员，但这些仅仅是说明性的，完全不是限制性的。

-

where is the imidazoline group
其中