Biodegradable cationic galactomannan

Abstract

The present invention relates generally to biodegradable cationic galactomannans.

Description

[0001] This application claims priority to U.S. Provisional Patent Application 63 / 592,312, filed October 23, 2023, the entire contents of which are hereby incorporated herein by reference for all purposes. Technical Field

[0002] This invention generally relates to biodegradable cationic galactomannans. More specifically, this invention relates to those having a specific degree of cationic substitution (DS). 阳离子 The present invention relates to biodegradable cationic galactomannans with an average molecular weight (Mw) and a specific molecular weight. The invention also relates to methods for preparing biodegradable cationic galactomannans, and compositions having biodegradable cationic galactomannans. Background Technology

[0003] Galactomannans are a class of natural polymers formed from specific sugar residues. More specifically, galactomannans are polysaccharides with β-(1,4)-linked D-mannopyranosyl residues forming the polymer backbone (also known as the skeleton), and α-(1,6)-linked D-galactopyranosyl residues as side chains along the backbone with varying degrees of substitution. The mannose to galactose ratio not only determines the physical properties of galactomannans but also their type. For example, the galactomannan fenugreek has a mannose to galactose ratio of approximately 1:1. Other galactomannans have different mannose to galactose ratios. Tara, locust bean, and cassia have mannose to galactose ratios of approximately 3:1, 4:1, and 5:1, respectively. Meanwhile, native guar beans or guar gum typically have a mannose to galactose ratio of approximately 2:1.

[0004] Naturally occurring galactomannans can be extracted from the endosperm of the corresponding seeds. While naturally occurring galactomannans can be used in their native form for certain applications without any functionalization or chemical modification, functionalized galactomannans can offer improved performance properties in many applications through chemical modification. For example, depending on the application, cationic galactomannans can be used as conditioning agents, stabilizers, thickeners, emulsifiers, deposition aids, rheology modifiers, and flocculants. It is noteworthy that each galactose and mannose unit in native galactomannans has hydroxyl groups that can be chemically modified to functionalize the galactomannan. In this regard, a variety of reactants can be used to functionalize galactomannans. For example, to add cationic groups to galactomannans, one or more cationic reactants (also known as cationizing agents) can be used. By adding cationic functional groups, cationic galactomannans can not only have better performance properties, but also offer significant advantages over petroleum-based or synthetic polymers because galactomannans are extracted from natural and renewable sources.

[0005] However, while cationic galactomannans can be used in a variety of applications and unmodified galactomannans are of natural origin, they may not possess the desired biodegradability in the environment, especially based on newer and more stringent biodegradability guidelines and requirements. That is, cationic galactomannans may not be considered inherently biodegradable, particularly under more stringent biodegradability standards. In this regard, the art still needs cationic galactomannans that are not only sufficiently cationized to achieve the desired performance but also sufficiently biodegradable. In short, the art needs biodegradable cationic galactomannans.

[0006] Furthermore, there remains a need in the art for methods for preparing biodegradable cationic galactomannan, and for compositions having biodegradable cationic galactomannan. Summary of the Invention

[0007] This invention generally relates to biodegradable cationic galactomannans. In this regard, embodiments of the invention relate to biodegradable cationic galactomannans comprising a galactose unit to mannose unit ratio of approximately 1:1, wherein the cationic galactomannan has:

[0008] (a) DS of less than 0.17, preferably 0.16 or less, more preferably 0.15 or less 阳离子 ;as well as

[0009] (b) Average molecular weight (Mw) below 3,500,000 g / mol.

[0010] Embodiments of the present invention also relate to biodegradable cationic galactomannan comprising a galactose unit to mannose unit ratio of approximately 1:1, wherein the cationic galactomannan has:

[0011] (a) DS of less than 0.17, preferably 0.16 or less, more preferably 0.15 or less 阳离子 ;as well as

[0012] (b) Average molecular weight (Mw) below 3,500,000 g / mol.

[0013] According to OECD 302B, cationic galactomannan has a biodegradability of 60% or higher within 28 days, and in another embodiment, according to OECD 302B, cationic galactomannan has a biodegradability of 60% or higher within 60 days.

[0014] Another embodiment of the invention relates to a biodegradable cationic galactomannan comprising a ratio of galactose units to mannose units of about 1:3 to about 1:5, preferably about 1:3 to about 1:4, wherein the cationic galactomannan has:

[0015] (a) DS less than 0.20, preferably 0.18 or lower, more preferably less than 0.18 阳离子 ;as well as

[0016] (b) Average molecular weight (Mw) below 2,500,000 g / mol.

[0017] Embodiments of the present invention also relate to biodegradable cationic galactomannans comprising a ratio of galactose units to mannose units of about 1:3 to about 1:5, preferably about 1:3 to about 1:4, wherein the cationic galactomannan has:

[0018] (a) DS less than 0.20, preferably 0.18 or lower, more preferably less than 0.18 阳离子 ;as well as

[0019] (b) Average molecular weight (Mw) below 2,500,000 g / mol.

[0020] According to OECD 302B, cationic galactomannan has a biodegradability of 60% or higher within 28 days, and in another embodiment, according to OECD 302B, cationic galactomannan has a biodegradability of 60% or higher within 60 days.

[0021] In another embodiment, the present invention relates to a biodegradable cationic galactomannan comprising a galactose unit to mannose unit ratio of about 1:5, the cationic galactomannan having:

[0022] (a) DS below 0.24 阳离子 ;as well as

[0023] (b) Average molecular weight (Mw) below 1,000,000 g / mol.

[0024] Embodiments of the present invention also relate to biodegradable cationic galactomannan comprising a galactose unit to mannose unit ratio of approximately 1:5, wherein the cationic galactomannan has:

[0025] (a) DS below 0.24 阳离子 ;as well as

[0026] (b) Average molecular weight (Mw) below 1,000,000 g / mol.

[0027] According to OECD 302B, cationic galactomannan has a biodegradability of 60% or higher within 28 days, and in another embodiment, according to OECD 302B, cationic galactomannan has a biodegradability of 60% or higher within 60 days.

[0028] In other embodiments, the cationic galactomannan comprises a cationic group selected from: primary, secondary, or tertiary amino groups; quaternary ammonium groups; sulfonium groups; phosphonium groups; and combinations thereof, and preferably, the cationic group is selected from trialkylammonium groups, such as trimethylammonium groups, triethylammonium groups, or tributylammonium groups; aryldialkylammonium groups, such as benzyldimethylammonium groups; ammonium groups wherein the nitrogen atom is a member of a ring structure, such as pyridinium groups and imidazoline groups; and combinations thereof. Embodiments of the invention also include biodegradable cationic galactomannans, wherein the galactomannan is cationized by at least one cationizing agent selected from 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and mixtures thereof.

[0029] In yet another embodiment, the present invention relates to compositions having biodegradable cationic galactomannan. The invention also relates to a method for preparing biodegradable cationic galactomannan, comprising an embodiment of reacting a non-cationic galactomannan with at least one cationic agent. Detailed Implementation

[0030] The terms and phrases “invention,” “present invention,” and similar terms and phrases used herein are non-limiting and are not intended to limit the subject matter of the invention to any single embodiment, but rather to cover all possible embodiments as described.

[0031] Throughout this specification, including the claims, unless otherwise specified, the term "a" and the phrase "at least one" are synonymous, and similarly, the phrase "comprising one (or comprising a)" should be understood to be synonymous with the term "comprising at least one." Additionally, "between" should be understood to include the limiting term. Furthermore, throughout this specification, including the claims, the terms "comprising" and "having" are used interchangeably and should be understood to be synonymous.

[0032] It should be noted that when specifying any range of concentration, weight ratio, or amount, any specific upper limit concentration, weight ratio, or amount can be associated with any specific lower limit concentration, weight ratio, or amount.

[0033] Biodegradable cationic galactomannan

[0034] Various galactomannans can be used in this invention. As discussed above, galactomannans are natural polymers formed from mannose and galactose units, wherein the mannose units form the main chain or backbone of the polymer, while the galactose units are substituted along the main chain or backbone. In this regard, galactomannans having a mannose to galactose ratio of about 1:1 to about 5:1 can be used.

[0035] In some embodiments, the galactomannan may have a mannose to galactose ratio of about 1:1. Galactomannan with a mannose to galactose ratio of about 1:1 is commonly referred to as fenugreek, but it is also known as *Trigonella foenum-graecum*. In other embodiments, the galactomannan may have a mannose to galactose ratio of about 3:1 to about 5:1. Such galactomannans are commonly referred to as tara (also known as Tara spinosa), locust bean, or carob (also known as Parkia biglobosa) and cassia (also known as Cassia obtusifolia and Cassiatora). Cassia may also be referred to as Senna obtusifolia and Senna tora.

[0036] For example, the galactomannan of the present invention may include those having repeating residues (i.e., units) as shown in formula (I):

[0037] (I)

[0038] Where n can be 0 to 5, preferably 0 to 4; m can be 0 to 5, preferably 0 to 4; provided that n+m is not greater than about 5, preferably n+m is not greater than about 4. The value p in formula (I) is based on the total molecular weight (Mw) of galactomannan, as further described below. In some preferred embodiments, n+m can be equal to about 0, 2, 3, 4, or 5, preferably n+m can be equal to about 0, 2, 3, or 4. Furthermore, in some embodiments, p can be up to about 35,000, up to about 30,000, up to about 25,000, and further up to about 20,000, and p can be at least about 10, at least about 100, and at least about 500. In alternative embodiments, p can be less than about 10, including at least about 5 (when n+m is not greater than about 5, preferably when n+m is not greater than about 4), and in some preferred alternative embodiments, p can be at least about 5 when n+m is equal to about 0, 2, 3, 4, or 5 (preferably about 0, 2, 3, or 4). For example, in some embodiments, p can range from about 10 to about 35,000, including about 100 to about 30,000. In some embodiments, p can be from about 500 to about 10,000, especially when n+m is about 0; when n+m is about 2 to 4, and especially about 2 to 3, p can be from about 2,500 to about 5,000; and when n+m is about 5, and especially about 4, p can be from about 100 to about 1,200.

[0039] Galactomannans can be functionalized by chemical modification using various cationic reactants (also known as cationizing agents). The cationizing agent can react with available hydroxyl groups of the galactomannan. Specifically, depending on the galactomannan and the hydroxyl groups available for chemical modification, the cationizing agent can react with available hydroxyl groups of the mannose backbone or skeleton, available hydroxyl groups of galactose units substituted along the mannose backbone or skeleton, or both. Various cationizing agents can be used in this regard. Furthermore, cationic galactomannans can be formed by reacting at least one galactomannan according to the invention with at least one cationizing agent.

[0040] As used herein, the terms “cationic” and “cationizing” mean at least partially cationic. Thus, the terms “cationizing agent,” “cationic group,” “cationic moiety,” or the plural thereof may include, for example, ammonium having a positive charge, and primary, secondary, and tertiary amines and their precursors that can cause or produce positively charged compounds.

[0041] Because the cationic agent can react with available hydroxyl groups of galactomannan to produce cationic galactomannan, the cationic agent can have at least one functional group (or portion) that can react with these available hydroxyl groups. Such functional groups include, but are not limited to, at least one epoxy group, halogroup, ester group, anhydride group, olefinic unsaturated group, or combinations thereof, as well as their salts and free radicals. In one embodiment, the cationic agent can have a divalent linking group, such as an alkylene group or oxyalkylene group, between or connecting one or more cationic groups (or portions) of the cationic agent and one or more functional groups or reactive groups (or portions). For example, the cationic group or portion can include, but is not limited to, amino groups (such as primary amino, secondary amino, and / or tertiary amino), quaternary ammonium groups, sulfonium groups, phosphonium groups, and combinations thereof.

[0042] In one embodiment, the cationic agent may have a cationic group or portion comprising a cationic nitrogen group, more typically a quaternary ammonium group. Typical quaternary ammonium groups include, but are not limited to, trialkylammonium groups (such as trimethylammonium, triethylammonium, and tributylammonium), aryldialkylammonium groups (such as benzyldimethylammonium), and ammonium groups in which the nitrogen atom is a member of a ring structure (such as pyridinium and imidazoline groups), each group being combined with a counterion (typically chloride, bromide, iodide, or acetate counterions). In one embodiment, the cationic substituent is connected to the reactive functional group of the cationic agent via an alkylene or oxyalkylene linking group.

[0043] In some embodiments, the cationic group or portion may have formula (II):

[0044] -N + R 2 R 3 R 4 X - (II)

[0045] For amine salt groups, R 2 R 3 and R 4 Each is an organic group or H, where R is an amine salt group. 2 R 3 and R 4 At least one of them is H; for quaternary ammonium groups, R2 R 3 and R 4 Each is an organic group, or R. 2 R 3 and R 4 Any two of them can fused together to form a heterocyclic group with the nitrogen atom to which they are attached, and X - It is an anion.

[0046] In other embodiments, the cationizing agent may be a cationic epoxide (such as an epoxy-functionalized cationic nitrogen compound) and a chlorohydrin-functionalized cationic nitrogen compound, a cationic olefinically unsaturated monomer or its precursor, or a combination thereof. For example, the cationic epoxide of the present invention may include, but is not limited to, 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium bromide, 2,3-epoxypropyltrimethylammonium iodide, and mixtures thereof; the chlorohydrin-functionalized cationic nitrogen compound may include, but is not limited to, 3-halo-2-hydroxypropyltrimethylammonium chloride, including, for example, 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyldodecyl dimethylammonium chloride, 3-chloro-2-hydroxypropyllauryl dimethylammonium chloride, 3-chloro-2-hydroxypropylcocoyl dimethylammonium chloride, 3-chloro-2- Hydroxypropylstearyldimethylammonium chloride, and mixtures thereof; and cationic olefinic unsaturated monomers or their precursors may include, but are not limited to, trimethylammonium propylmethacrylamide chloride, methacrylamide propyltrimethylammonium chloride (MAPTAC), trimethylammonium propylmethacrylamide methyl sulfate, diallyl dimethylammonium chloride, vinylbenzyltrimethylammonium chloride, cationic monomers of dimethylaminopropylmethacrylamide (tertiary amine) precursors such as N-vinylformamide and N-vinylacetamide (which may be hydrolyzed after polymerization or grafted onto vinylamine units), and combinations thereof.

[0047] In some preferred embodiments, the cationic agent may be selected from 2,3-epoxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium bromide, 2,3-epoxypropyltrimethylammonium iodide, 3-halo-2-hydroxypropyltrimethylammonium chloride (including, for example, 3-chloro-2-hydroxypropyltrimethylammonium chloride), and combinations thereof.

[0048] For example, the cationic galactomannan of the present invention may include those having repeating residues (i.e., units) as shown in formula (III):

[0049] (III)

[0050] in:

[0051] R 1 It can have the following formula:

[0052] R 5 N + R 2 R 3 R 4 X - (IV);

[0053] For amine salt groups, R 2 R 3 and R 4 Each is an organic group or H, preferably each is a C1-C group. 32 Alkyl or H, more preferably each independently is C1-C 18 Alkyl or H, and in some preferred embodiments, R 2 R 3 and R 4 Each is independently C1-C 10 Alkyl or H, including each being independently C1-C5 alkyl or H, and wherein for amine salt groups, R 2 R 3 and R 4 At least one of them is H; for quaternary ammonium groups, R 2 R 3 and R 4 Each is an organic group, and preferably each is a C1-C group. 32 Alkyl groups, more preferably each independently of the other, are C1-C. 18 Alkyl groups, and in some preferred embodiments, R 2 R 3 and R 4 Each is independently C1-C 10 Alkyl groups, including those that are individually C1-C5 alkyl groups, or R 2 R 3 and R 4 Any two atoms in X can fuse to form heterocyclic groups with the nitrogen atoms to which they are attached; and X - It is an anion, preferably Cl-, Br-, I, or a mixture thereof, more preferably Cl-;

[0054] R 5 It is a C1-C5 hydrocarbon group, which is optionally substituted by at least one group selected from (-OH), (=O), (-NH3), or a mixture thereof, preferably a C1-C5 alkyl group, which is optionally substituted by at least one group selected from (-OH), (=O), (-NH3), or a mixture thereof;

[0055] R 10 It can be selected from -OH, alkoxy quaternary ammonium groups, or combinations thereof, preferably R 10 Can be selected from -OH, -OR 1or a combination thereof, provided that at least one R 10 It is an alkoxy quaternary ammonium group, preferably -OR 1 ;and

[0056] n can be 0 to 5, preferably 0 to 4; m can be 0 to 5, preferably 0 to 4; provided that n+m is not greater than about 5, preferably not greater than about 4, and preferably n+m can be equal to about 0, 2, 3, 4, or 5, preferably n+m can be equal to about 0, 2, 3, or 4. The value p in formula (III) is based on the total molecular weight (Mw) of galactomannan, as further described below. In addition, in some embodiments, p can be up to about 35,000, up to about 30,000, up to about 25,000, and further up to about 20,000, and p can be at least about 10, at least about 100, and at least about 500. In alternative embodiments, p can be less than about 10, including at least about 5 (when n+m is not greater than about 5, preferably when n+m is not greater than about 4), and in some preferred alternative embodiments, p can be at least about 5 when n+m is equal to about 0, 2, 3, 4, or 5 (preferably about 0, 2, 3, or 4). In some embodiments, p can range from about 10 to about 35,000, including from about 100 to about 30,000. In some embodiments, p can be from about 500 to about 10,000, especially when n+m is about 0; when n+m is about 2 to 4, and especially about 2 to 3, p can be from about 2,500 to about 5,000; and when n+m is about 5, and especially about 4, p can be from about 100 to about 1,200.

[0057] In some embodiments, the cationic galactomannan of the present invention may include those having repeating residues (i.e., units) as shown in the following formula (V):

[0058] (V)

[0059] in:

[0060] R 1 It can have the following formula:

[0061] R 5 N + R 2 R 3 R 4 X - (VI);

[0062] For amine salt groups, R 2 R 3 and R 4Each is an organic group or H, preferably each is a C1-C group. 32 Alkyl or H, more preferably each independently is C1-C 18 Alkyl or H, and in some preferred embodiments, R 2 R 3 and R 4 Each is independently C1-C 10 Alkyl or H, including each being independently C1-C5 alkyl or H, and wherein for amine salt groups, R 2 R 3 and R 4 At least one of them is H; for quaternary ammonium groups, R 2 R 3 and R 4 Each is an organic group, and preferably each is a C1-C group. 32 Alkyl groups, more preferably each independently of the other, are C1-C. 18 Alkyl groups, and in some preferred embodiments, R 2 R 3 and R 4 Each is independently C1-C 10 Alkyl groups, including those that are individually C1-C5 alkyl groups, or R 2 R 3 and R 4 Any two atoms in X can fuse to form heterocyclic groups with the nitrogen atoms to which they are attached; and X - It is an anion, preferably Cl-, Br-, I, or a mixture thereof, more preferably Cl-;

[0063] R 5 It is a C1-C5 hydrocarbon group, which is optionally substituted by at least one group selected from (-OH), (=O), (-NH3), or a mixture thereof, preferably a C1-C5 alkyl group, which is optionally substituted by at least one group selected from (-OH), (=O), (-NH3), or a mixture thereof;

[0064] R 10 It can be selected from -OH, alkoxy quaternary ammonium groups, or combinations thereof, preferably R 10 Can be selected from -OH, -OR 1 or a combination thereof; and

[0065] n can be 0 to 5, preferably 0 to 4; m can be 0 to 5, preferably 0 to 4; provided that n+m is not greater than about 5, preferably not greater than about 4, and preferably n+m can be equal to about 0, 2, 3, 4, or 5, preferably n+m can be equal to about 0, 2, 3, or 4. The value p in formula (V) is based on the total molecular weight (Mw) of galactomannan, as further described below. In addition, in some embodiments, p can be up to about 35,000, up to about 30,000, up to about 25,000, and further up to about 20,000, and p can be at least about 10, at least about 100, and at least about 500. In alternative embodiments, p can be less than about 10, including at least about 5 (when n+m is not greater than about 5, preferably when n+m is not greater than about 4), and in some preferred alternative embodiments, p can be at least about 5 when n+m is equal to about 0, 2, 3, 4, or 5 (preferably about 0, 2, 3, or 4). In some embodiments, p can range from about 10 to about 35,000, including from about 100 to about 30,000. In some embodiments, p can be from about 500 to about 10,000, especially when n+m is about 0; when n+m is about 2 to 4, and especially about 2 to 3, p can be from about 2,500 to about 5,000; and when n+m is about 5, and especially about 4, p can be from about 100 to about 1,200.

[0066] Once galactomannan reacts with at least one cationic agent to form the cationic galactomannan of the present invention, these cationic galactomannans have a certain degree of substitution (DS) for the cationic groups attached to the galactomannan. 阳离子 In particular, DS 阳离子 This refers to the average number of cationic groups or portions attached to each galactomannan monomer unit (i.e., each sugar unit). For clarity, the cationic galactomannans of the present invention have some degree of cationic substitution. That is, the cationic galactomannans of the present invention cannot have zero cationic substitution or no cationic substitution. In this regard, for DS where only the upper limit is specified... 阳离子Ranges, such as below 0.24, below 0.23, below 0.22, below 0.21, below 0.20, below 0.19, below 0.18, below 0.17, and below 0.16, and below 0.15, and similarly 0.24 or lower, 0.23 or lower, 0.22 or lower, 0.21 or lower, 0.20 or lower, 0.19 or lower, 0.18 or lower, 0.17 or lower, 0.16 or lower, 0.15 or lower, and similar ranges, with the lower limit of the range being greater than zero (> 0). In such embodiments, the lower limit of the range can be 0.000001, 0.00001, 0.0001, 0.001, 0.01, or 0.10.

[0067] Depending on the type and average molecular weight (Mw) of the galactomannan, in some embodiments, the cationic galactomannan of the present invention can typically have a DS of up to about 0.30. 阳离子 However, in one aspect of the invention, it has been unexpectedly and surprisingly discovered that while cationic galactomannans with lower average molecular weights can potentially have higher cationic substitution degrees while still maintaining sufficient biodegradability, cationic galactomannans with higher molecular weights generally have lower cationic substitution degrees in order to have sufficient biodegradability. In another aspect of the invention, it has been unexpectedly and surprisingly discovered that the type of galactomannan (i.e., the ratio of galactose units to mannose units) along with DS... 阳离子 The average molecular weight (Mw) can also affect biodegradability.

[0068] Therefore, in some embodiments where the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:1 (which is commonly referred to as fenugreek), the cationic galactomannan can typically have a DS of less than 0.17, including 0.16 or lower, and 0.15 or lower. 阳离子 For example, in some embodiments where the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:1, the cationic galactomannan can typically have a DS of less than 0.17. 阳离子 In another embodiment, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:1, the cationic galactomannan may have a DS of 0.15 or less, preferably 0.14 or less. 阳离子 In this regard, DS 阳离子The DS can range from 0.001 to 0.16, 0.01 to 0.16, and 0.10 to 0.16, as well as 0.001 to 0.15, 0.01 to 0.15, and 0.10 to 0.15, and further, 0.001 to 0.14, 0.01 to 0.14, and 0.10 to 0.14. In a further embodiment, a cationic galactomannan having a galactose unit to mannose unit ratio of about 1:1, wherein the cationic galactomannan may have a DS ranging from 0.05 to 0.16, preferably 0.08 to 0.16, more preferably 0.10 to 0.16. 阳离子 Similarly, in other embodiments, cationic galactomannans having a galactose-to-mannose unit ratio of approximately 1:1 may have a DS ranging from 0.05 to less than 0.17, preferably from 0.08 to less than 0.17, and more preferably from 0.10 to less than 0.17. 阳离子 Furthermore, cationic galactomannan having a galactose unit to mannose unit ratio of approximately 1:1 can further have a DS ratio ranging from 0.10 to 0.16, preferably 0.12 to 0.16, and more preferably 0.14 to 0.16. 阳离子 In some embodiments, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:1, the cationic galactomannan may have a DS of 0.16 or lower. 阳离子 Furthermore, according to OECD 302B as modified and discussed below, cationic galactomannan can have a biodegradability of 60% or higher within 60 days, preferably within 28 days.

[0069] In other embodiments where the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:3 to about 1:5 (which are commonly referred to as tara, locust bean, carob, and cassia seed) and an average molecular weight of less than 2,500,000 g / mol, the cationic galactomannan may typically have a DS of less than 0.20, preferably 0.18 or lower, more preferably less than 0.18. 阳离子 In some preferred embodiments, the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:3 to about 1:4, preferably about 1:3 or about 1:4. In other embodiments, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:3 to about 1:5, preferably about 1:3 to about 1:4, more preferably about 1:3 or about 1:4 and an average molecular weight below 2,500,000 g / mol, the cationic galactomannan may have a DS of 0.19 or less, preferably 0.18 or less. 阳离子In other embodiments, when the cationic galactomannan has a ratio of galactose units to mannose units of about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4) and an average molecular weight of less than 2,500,000 g / mol, the cationic galactomannan may have a DS of less than 0.20, preferably 0.18 or lower, more preferably less than 0.18. 阳离子 In other embodiments, the cationic galactomannan may have a DS of 0.17 or lower, preferably lower than 0.17, more preferably 0.16 or lower. 阳离子 In this regard, DS 阳离子 The range can be from 0.001 to less than 0.20 (inclusive of 0.001 to 0.18), 0.01 to less than 0.20 (inclusive of 0.01 to 0.18), and 0.10 to less than 0.20 (inclusive of 0.10 to 0.18), as well as 0.001 to less than 0.18, 0.01 to less than 0.18, and 0.10 to less than 0.18, and further, 0.001 to 0.17 or less, 0.01 to 0.17 or less, and 0.10 to 0.17 or less. When the cationic galactomannan has a ratio of galactose units to mannose units of about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (inclusive of about 1:3 or about 1:4), DS 阳离子 The range can also be from 0.001 to 0.16, 0.01 to 0.16, and 0.10 to 0.16. In a further embodiment, a cationic galactomannan having a ratio of galactose units to mannose units of about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4) and an average molecular weight of less than 2,500,000 g / mol is used. This cationic galactomannan may have a DS of 0.05 to 0.20, preferably 0.08 to 0.20, more preferably 0.10 to 0.20. 阳离子 Furthermore, in some embodiments, the cationic galactomannan may have a DS in the range of 0.10 to 0.20, preferably 0.12 to 0.20, and more preferably 0.14 to 0.20. 阳离子 In other embodiments, cationic galactomannans are used, having a ratio of galactose units to mannose units of about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4), and an average molecular weight of less than 2,500,000 g / mol. These cationic galactomannans may have a DS of preferably 0.05 to 0.18, preferably 0.08 to 0.18, and more preferably 0.10 to 0.18. 阳离子In other embodiments, cationic galactomannans are used, having a galactose-to-mannose unit ratio of about 1:3 to about 1:5, preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4), and an average molecular weight of less than 2,500,000 g / mol. These cationic galactomannans may have a DS of 0.05 to 0.16, preferably 0.08 to 0.16, more preferably 0.10 to 0.16. 阳离子 In some embodiments, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:3 to about 1:5, and preferably about 1:3 to about 1:4 (including about 1:3 or about 1:4), the cationic galactomannan may have a DS of less than 0.20, preferably 0.18 or lower (including less than 0.18), and more preferably less than 0.16. 阳离子 Furthermore, according to OECD 302B as modified and discussed below, cationic galactomannan can have a biodegradability of 60% or higher within 60 days, preferably within 28 days.

[0070] Additionally, in some embodiments, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:3, the cationic galactomannan may have a DS of less than 0.20, preferably 0.18 or lower (including less than 0.18), more preferably 0.17 or lower. 阳离子 Furthermore, in some embodiments, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:4, the cationic galactomannan may have a DS of less than 0.20, preferably 0.18 or lower (including less than 0.18), preferably 0.17 or lower. 阳离子 .

[0071] In another embodiment, in which the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:5 (which is commonly referred to as cassia seed) and an average molecular weight of less than 1,000,000 g / mol, the cationic galactomannan may typically have a DS of less than 0.24, preferably 0.22 or lower. 阳离子 In another embodiment, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol, the cationic galactomannan may have a DS of 0.21 or less, preferably 0.20 or less. 阳离子In some embodiments, cationic galactomannans having a galactose-to-mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol are used. These cationic galactomannans may typically have a DS of 0.18 or less (including less than 0.18) and a DS of 0.17 or less. 阳离子 In this regard, DS 阳离子 The range can be 0.001 to less than 0.24, 0.01 to less than 0.24, and 0.10 to less than 0.24, as well as 0.001 to 0.22, 0.01 to 0.22, and 0.10 to 0.22, and further, 0.001 to 0.21, 0.01 to 0.21, and 0.10 to 0.21, and also includes 0.001 to 0.20, 0.01 to 0.20, and 0.10 to 0.20. In other embodiments, DS 阳离子 The DS can range from 0.001 to 0.18, 0.01 to 0.18, and 0.10 to 0.18, and further, from 0.001 to 0.16, 0.01 to 0.16, and 0.10 to 0.16. In yet another embodiment, a cationic galactomannan having a galactose unit to mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol may have a DS ranging from 0.05 to 0.16 (inclusive to less than 0.16), preferably 0.08 to 0.16 (inclusive to less than 0.16), and more preferably 0.10 to 0.16 (inclusive to less than 0.16). 阳离子 When cationic galactomannan has a galactose unit to mannose unit ratio of approximately 1:5, DS 阳离子 The range can also be from 0.10 to less than 0.18, preferably from 0.12 to less than 0.18. In a further embodiment, a cationic galactomannan having a galactose unit to mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol may have a DS ranging from 0.05 to less than 0.24, preferably from 0.08 to 0.22, and more preferably from 0.10 to 0.20. 阳离子 In other embodiments, cationic galactomannans having a galactose-to-mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol are used. These cationic galactomannans may have a DS ranging from 0.10 to less than 0.24, preferably 0.14 to 0.22, and more preferably 0.14 to 0.20. 阳离子 .

[0072] In other embodiments where the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:5 (which is commonly referred to as cassia seed) and an average molecular weight of less than 1,000,000 g / mol, the cationic galactomannan may typically have a DS of 0.18 or less (including less than 0.18), preferably 0.16 or less. 阳离子 In another embodiment, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol, the cationic galactomannan may have a DS of 0.15 or less and 0.14 or less. 阳离子 In some embodiments, cationic galactomannans having a galactose-to-mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol are used. These cationic galactomannans may typically have a DS of less than 0.18, including 0.17 or lower. 阳离子 In this regard, DS 阳离子 The range can be 0.001 to below 0.18, 0.01 to below 0.18, and 0.10 to below 0.18, as well as 0.001 to 0.17 or lower, 0.01 to 0.17 or lower, and 0.10 to 0.17 or lower, and further, 0.001 to 0.16 or lower, 0.01 to 0.16 or lower, and 0.10 to 0.16 or lower, and also includes 0.001 to 0.15 or lower, 0.01 to 0.15 or lower, and 0.10 to 0.15 or lower. In other embodiments, DS 阳离子 The DS can range from 0.001 to 0.18, 0.01 to 0.18, and 0.10 to 0.18, and further, from 0.001 to 0.16, 0.01 to 0.16, and 0.10 to 0.16. In yet another embodiment, a cationic galactomannan having a galactose unit to mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol may have a DS ranging from 0.05 to 0.16 (inclusive to less than 0.16), preferably 0.08 to 0.16 (inclusive to less than 0.16), and more preferably 0.10 to 0.16 (inclusive to less than 0.16). 阳离子 When cationic galactomannan has a galactose unit to mannose unit ratio of approximately 1:5, DS 阳离子The range can also be from 0.10 to less than 0.18, preferably from 0.12 to less than 0.18. In a further embodiment, a cationic galactomannan having a galactose unit to mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol may have a DS ranging from 0.05 to less than 0.24, preferably from 0.08 to 0.22, and more preferably from 0.10 to 0.20. 阳离子 In other embodiments, cationic galactomannans having a galactose-to-mannose unit ratio of about 1:5 and an average molecular weight of less than 1,000,000 g / mol are used. These cationic galactomannans may have a DS ranging from 0.10 to less than 0.24, preferably 0.14 to 0.22, and more preferably 0.14 to 0.20. 阳离子 In some embodiments, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:5, the cationic galactomannan can have a DS of less than 0.24. 阳离子 Furthermore, according to OECD 302B as modified and discussed below, cationic galactomannan can have a biodegradability of 60% or higher within 60 days, preferably within 28 days.

[0073] Generally, the degree of cationic substitution of the cationic galactomannan of the present invention can be determined before or after the extraction step. In some embodiments, the extraction step is performed by an acidic methanol extraction step. The ratio of methanol to acid, preferably concentrated HCl having about 37% acid v / v, can be from about 25:1 to 100:1, preferably about 50:1. Furthermore, in some embodiments, the acidic methanol extraction step can be considered a washing step, which can remove other quaternary ammonium compounds that may be present at the end of the cationization reaction, including but not limited to one or more residual cationizing agents, byproducts of one or more unreacted cationizing agents, or mixtures thereof.

[0074] As used herein, the terms "degree of cationic substitution" and "DS" are used interchangeably. 阳离子 "Interchangeable and synonymous, and refers to the degree of cationic substitution measured after the acidic methanol extraction step. Additionally, DS..." 阳离子 This refers to the average molar number of cationic groups or portions per molar sugar unit, which can be determined by... 1 Measurements were performed using ¹H-NMR (solvent: D₂O). Once obtained... 1The H NMR spectrum was normalized by integrating the multiplets (typically between approximately 3.5 and 5.5 ppm) corresponding to anodic protons on all galactomannan units. The target peak (the peak corresponding to the methyl proton of the quaternary ammonium group on the galactomannan unit) was centered at approximately 3–3.5 ppm. Given the presence of three methyl groups on the ammonium functional group, the peak was integrated for all nine protons. Therefore, as an example, in the case of the cationic agent 2,3-epoxypropyltrimethylammonium chloride, (DS... 阳离子 The calculation is as follows:

[0075]

[0076] The presence of any one or more residual cationizing agents, one or more byproducts of any unreacted cationizing agents, or mixtures thereof, can be used to... 1 This is evidenced by a smaller peak at a lower field than the target peak (centered at approximately 3–3.5 ppm) in the H-NMR spectrum.

[0077] The extraction step can be performed in a variety of ways. As mentioned above, in some embodiments, the extraction step can be performed by acidifying methanol (50:1, MeOH / HCl). 浓37% The extraction is performed (v / v). Alternatively, cationic galactomannan can be added to acidic methanol at a concentration of approximately 1% under stirring. After adding acidic methanol to the cationic galactomannan, the mixture is brought to reflux temperature and maintained at reflux temperature for approximately 45 minutes. At the end of this extraction step, the acidic methanol can be decanted and the process can be repeated. In some embodiments, the extraction step comprises one to three, preferably three, consecutive steps: adding acidic methanol to the cationic galactomannan and refluxing the mixture for a specified period of time, wherein after each intermediate step, the acidic methanol is removed and replaced with fresh acidic methanol. After the extraction step is completely completed, the cationic galactomannan can be filtered and washed with pure methanol, ethanol, or another suitable solvent. The so-called purified non-cellulose polysaccharide derivative is then dried and ground, followed by... 1 H-NMR analysis.

[0078] In other embodiments, the cationization of galactomannan can also be expressed as charge density. As used herein, the term "charge density" refers to the ratio of the positive charge on the monomer unit constituting the galactomannan to the molecular weight of the monomer unit. The product of charge density and polymer molecular weight determines the number of positively charged sites on a given polymer chain. The degree of cationic substitution can be converted to charge density using several methods. In specific embodiments, the method for calculating the charge density of cationic galactomannan employs a method that specifically quantifies the equivalent of cationic groups or portions, preferably quaternary ammonium groups, on the galactomannan. In a non-limiting example, for cationic galactomannan obtained by reacting galactomannan with 3-chloro-2-hydroxypropyltrimethylammonium chloride or 2,3-epoxypropyltrimethylammonium chloride, the cationic charge density can be calculated from the degree of cationic substitution using the following formula:

[0079] Cation charge density in milliequivalents per gram (meq / g) =

[0080] Generally, the above formula depends on the groups grafted onto the galactomannan.

[0081] In some embodiments, the galactomannan has a charge density of about 1.0 to about 2 meq / g, preferably about 1.1 to about 1.8 meq / g, and more preferably 1.2 to 1.5 meq / g after an acidic methanol extraction step.

[0082] Regarding the average molecular weight (Mw) of the cationic galactomannan of the present invention, generally, the cationic galactomannan can have an average molecular weight (Mw) of at least about 3,500 g / mol, including at least about 5,000 g / mol, and in some embodiments at least about 10,000 g / mol. The cationic galactomannan of the present invention can also typically have an average molecular weight (Mw) of up to about 10,000,000 g / mol, up to about 7,500,000 g / mol, including up to about 5,000,000 g / mol. In some embodiments, the cationic galactomannan can typically have an average molecular weight (Mw) ranging from 20,000 g / mol to 10,000,000 g / mol, preferably from 50,000 g / mol to 7,500,000 g / mol, and more preferably from 100,000 g / mol to 5,000,000 g / mol. In some embodiments where the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:1 (which is commonly referred to as fenugreek), the cationic galactomannan can typically have an average molecular weight (Mw) of less than 3,500,000 g / mol, including 3,000,000 g / mol or lower. In other embodiments, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:1, the cationic galactomannan can have an average molecular weight (Mw) ranging from 200,000 g / mol to 3,000,000 g / mol, more preferably from 250,000 g / mol to 2,500,000 g / mol, and even more preferably from 500,000 g / mol to 2,500,000 g / mol.

[0083] In further embodiments, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:3 to about 1:5 (which is commonly referred to as tara, locust bean, or carob and cassia), the cationic galactomannan can typically have an average molecular weight (Mw) of less than 2,500,000 g / mol. In some preferred embodiments, the cationic galactomannan can have a galactose unit to mannose unit ratio of about 1:3 to about 1:4 (including about 1:3 or about 1:4), wherein the average molecular weight (Mw) is less than 2,500,000 g / mol. In other embodiments in which the cationic galactomannan has a ratio of galactose units to mannose units of about 1:3 to about 1:5, the cationic galactomannan may have an average molecular weight (Mw) ranging from 200,000 g / mol to 2,000,000 g / mol, more preferably from 250,000 g / mol to 2,000,000 g / mol, and even more preferably from 300,000 g / mol to 2,000,000 g / mol.

[0084] In another embodiment, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:5 (which is commonly referred to as cassia seed as described above), the cationic galactomannan can typically have an average molecular weight (Mw) of less than 1,000,000 g / mol. Furthermore, when the cationic galactomannan has a galactose unit to mannose unit ratio of about 1:5, the cationic galactomannan can typically have an average molecular weight (Mw) ranging from 900,000 g / mol or lower, preferably from about 100,000 g / mol to 900,000 g / mol, more preferably from about 150,000 g / mol to 800,000 g / mol, including more preferably from about 150,000 g / mol to 750,000 g / mol.

[0085] As used herein, the terms “average molecular weight,” “molecular weight,” and “(Mw)” are interchangeable and synonymous, and all these terms have the same meaning as weight-average molecular weight. Average molecular weight was measured using a Shodex Pack SB-806 M HQ column in SEC-MALS (size exclusion chromatography with detection by multi-angle light scattering). Molecular weight measurements were performed using a value of 0.140 for dn / dc. The Agilent refractive index detector and WYATT miniDawn were calibrated using 22.5 kDa polyethylene glycol standards. All calculations of molecular weight distribution were performed using Wyatt’s ASTRA software. Samples were prepared as 0.05% solutions in the mobile phase (100 mM Na₂NO₃, 200 ppm NaN₃, 20 ppm pDADMAC, 100 ppm sodium azide) and filtered through a 0.45 µm PVDF filter prior to analysis. Average molecular weight is expressed by weight.

[0086] As discussed above, the cationic galactomannan of the present invention is biodegradable. Furthermore, it has been unexpectedly discovered that it possesses certain DS (diethylsaturated hydrocarbons). 阳离子Cationic galactomannans with certain average molecular weights (Mw) can exhibit sufficient biodegradability. In this regard, the cationic galactomannans of the present invention are considered biodegradable under OECD 302, and particularly under OECD 302B as modified and discussed. Specifically, OECD 302B provides test criteria for determining whether a chemical substance is considered biodegradable (including inherently biodegradable). The test method in OECD 302B means, and as used herein, the method without any preconditioning of the inoculum (i.e., inherent final biodegradation of the inoculum without preconditioning), as modified in that: (i) regarding the percentage of biodegradation of the tested sample, the sample is considered biodegradable if at least 60% of the tested sample is biodegradable during the test period; and (ii) the biodegradation is determined using an OxiTop®-IDS sensor available from Xylem Analytics. Therefore, for example, according to the foregoing and as used herein, a material is considered biodegradable under OECD 302B if at least 60% of it is biodegradable within 60 days (the testing period). As used herein, the inoculum used in OECD 302B as modified and described above means that the inoculum is sampled from the environment and is not cultured specifically to enhance the biodegradability of cationic galactomannan (i.e., the inoculum is not pre-adapted). In some embodiments, according to OECD 302B, the cationic galactomannan has a biodegradability of 60% or higher, preferably 70% or higher, within 60 days, preferably within 28 days. In further embodiments, according to OECD 302B, the cationic galactomannan has a biodegradability of 75% or higher within 60 days, preferably within 28 days.

[0087] Cationic galactomannans can be prepared in a variety of ways. First, the unmodified native (or gum-like) galactomannan used to prepare chemically modified and functionalized cationic galactomannans can be derived from their respective seeds. For example, galactomannans can be extracted from the endosperm of seeds. Subsequently, galactomannans can be cationically functionalized by reacting them with at least one cationic agent.

[0088] Generally, the cationic galactomannans of the present invention can be prepared by reacting a non-cationic galactomannan with at least one cationizing agent. Non-cationic galactomannans include galactomannans in their respective native forms, as well as galactomannans that may have undergone chemical pretreatment steps. In some embodiments, the cationic galactomannans of the present invention can be prepared by reacting an unmodified galactomannan with at least one cationizing agent. In such embodiments, the galactomannans may be in their respective native forms (i.e., gel form). As a non-limiting example, galactomannans having repeating residues of formula (I) as shown above can be used to prepare cationic galactomannans having repeating residues of formulas (III), (V), or combinations thereof as shown above. In other embodiments, the cationic galactomannans can be prepared by reacting a non-cationic galactomannan with at least one cationizing agent, wherein the non-cationic galactomannans are optionally chemically modified prior to cationization.

[0089] Generally, the cationization process can be carried out in a reaction medium having an aqueous solution, at least one cationizing agent, galactomannan, and at least one base. Preferred bases include, but are not limited to, alkali metal hydroxides, such as sodium hydroxide, ammonium hydroxide, and combinations thereof. The base may be present in excess, which can catalyze the reaction. In some embodiments, the base may be present in amounts from about 0.01 to about 25 wt.%, more preferably from about 0.05 to about 20 wt.%, based on the amount of galactomannan in the reaction.

[0090] The aqueous solution may have at least one solvent, including at least one organic water-miscible solvent. The organic water-miscible solvent may be selected from alkanols, glycols, cyclic and non-cyclic alkyl ethers, ketones, dialkylformamides, and mixtures thereof. Non-limiting organic water-miscible solvents include methanol, ethanol, propanol (including isopropanol), butanol, pentanol (including sec-pentanol), ethylene glycol, acetone, methyl ethyl ketone, diethyl ketone, tetrahydrofuran, dioxane, dimethylformamide, and mixtures thereof. In some embodiments, the amount of the organic water-miscible solvent may be from about 1 to about 20 wt.%, preferably from about 1 to about 10 wt.%. In other embodiments, the weight ratio of the organic water-miscible solvent to galactomannan is about 10 to 1, preferably about 5 to 1.

[0091] The cationization process can be carried out at temperatures ranging from about 10°C to about 100°C, preferably from about 20°C to about 80°C. The reaction time can range from about 1 to about 8 hours, and preferably from about 1 to about 6 hours. The cationization process can be carried out in a variety of devices and containers, including open or closed containers or reactors equipped with stirrers, operating intermittently or continuously.

[0092] Furthermore, after functionalizing galactomannan by reacting unmodified native galactomannan (i.e., galactomannan gum) with at least one cationic agent, the cationic galactomannan can undergo at least one chemical post-treatment step. In some embodiments, after the cationization process, the cationic galactomannan can be chemically post-treated to remove and / or neutralize any unreacted reactants (including any unreacted or partially reacted cationic agent) and to remove any water-miscible solvents. Non-limiting examples of chemical post-treatment include at least one washing step (with water), crosslinking with borate, at least one alkali treatment step, at least one acid addition step, and combinations thereof. For example, after functionalizing galactomannan by reacting unmodified native galactomannan with at least one cationic agent, the cationic galactomannan can be chemically post-treated with borate, washed with water, or both. In another embodiment, the cationic galactomannan can be chemically post-treated with an alkali treatment step, washed with water, or both. In embodiments using an alkaline treatment step, alkali metal hydroxides, such as sodium hydroxide, ammonium hydroxide, and combinations thereof, can be used. Furthermore, in embodiments using an alkaline treatment step, the pH can be adjusted to neutral or acidic pH using at least one acid (including at least one inorganic acid, at least one organic acid, and mixtures thereof) as needed. Non-limiting acids include, but are not limited to, hydrochloric acid, sulfuric acid, acetic acid, lactic acid, citric acid, carbon dioxide, fumaric acid, and mixtures thereof.

[0093] After obtaining cationic galactomannan from the cationization process (including any chemical post-processing steps), the cationic galactomannan can be dried and further mechanically processed, such as by milling.

[0094] The biodegradable cationic galactomannan of the present invention can be used in a variety of compositions and applications. For example, the biodegradable cationic galactomannan can be used as a conditioning agent, suspending agent, thickener or rheology modifier, film-forming agent, or a combination thereof. In some embodiments, the biodegradable cationic galactomannan can be used in household and personal care compositions, as well as in cleaning and disinfectant compositions. In some embodiments, the biodegradable cationic galactomannan can be used in hair care, skin care, and cosmetic compositions, such as, but not limited to, shampoos, hair conditioners, shower gels, soaps, facial cleansers, makeup products, lotions, skin creams, skin conditioning agents, ointments, hairsprays, sunscreen compositions, and similar compositions. In other embodiments, the biodegradable cationic galactomannan can be used in laundry or fabric detergents, softeners, and conditioning agents, as well as in hard surface cleaning compositions, such as sprays, wipes, aerosols, gels, sticks, and similar compositions.

[0095] Depending on the composition and application, the composition may contain a variety of other conventional components and additives known in the relevant field, in addition to biodegradable cationic galactomannan. For example, a composition having biodegradable cationic galactomannan may further contain at least one surfactant, emulsifier, emollient, moisturizer, hair conditioner, hair fixative, film-forming agent, skin protectant, binder, chelating agent, disinfectant, insecticide, fungicide, deodorant, pest repellent, fragrance material, antimicrobial agent, antifungal agent, antibiotic, antidandruff agent, abrasive, adhesive, absorbent, colorant, deodorant, antiperspirant, humectant, or oil (such as mineral oil, vegetable oil, or animal oil). Synthetic oils, silicone oils and mixtures thereof), opacifiers and pearlescent agents, antioxidants, preservatives, propellants, spreading agents, exfoliants, keratolytic agents, blood coagulants, vitamins, sunscreens, artificial tanning agents, ultraviolet absorbers, pH adjusters, plant-based ingredients, hair colorants, dyes, preservatives, inorganic particles, buffers, oxidants, reducing agents, rheology modifiers, skin bleaching agents, pigments, anti-inflammatory agents, thickeners, local anesthetics, fragrances, fragrance solubilizers, particulate matter, microabrasives and combinations thereof. Example

[0096] The following examples illustrate preferred embodiments of cationic galactomannan and their preparation methods, and are not intended to limit the scope thereof. Unless otherwise specified, all percentages are based on a total amount equal to 100% by weight.

[0097] Test methods

[0098] molecular weight

[0099] As described above, the average molecular weight of cationic galactomannan was measured using a Shodex Pack SB-806 M HQ column by SEC-MALS (size exclusion chromatography with multi-angle light scattering detection). Measurements were performed at ambient temperature with a run time of 50 minutes and a flow rate of 1.0 mL / min.

[0100] Degree of cation substitution

[0101] As mentioned above, the degree of cationic substitution of cationic galactomannan is determined by... 1 H-NMR (solvent: D2O) measurement.

[0102] Biodegradable

[0103] The biodegradability of cationic galactomannan was measured according to OECD 302B (modified as discussed above), a method modified for the percentage of biodegradation (i.e., at least 60%) of the tested sample and the sensor used to determine biodegradation. Biodegradability was assessed on a 28-day and 60-day basis. The OxiTop®-IDS sensor, available from Xylem Analytical Instruments, was used to determine biodegradation. The inoculum was not pre-adapted.

[0104] Example 1 - Biodegradable cationic fenugreek

[0105] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 280.0 g of isopropanol solvent, mixed with 110.0 g of deionized water, was introduced at room temperature. Then, 125.0 g of fenugreek powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 47.1 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the fenugreek dispersion at room temperature for 30 minutes, after which 18.0 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing process.

[0106] The reaction mixture obtained as described above was dispersed with 158.0 g of isopropanol (99%) and 44.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 1.4 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 356 g of isopropanol (99%) and 145 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0107] Degree of cation substitution (DS) 阳离子 The concentration was 0.12 and the average molecular weight (Mw) was 1,626,000 g / mol. The biodegradability of cationic fenugreek was tested and showed that it was inherently biodegradable within 28 days and 60 days (i.e., qualified).

[0108] Example 2 - Biodegradable cationic fenugreek

[0109] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 196.7 g of isopropanol solvent, mixed with 75.2 g of deionized water, was introduced at room temperature. Then, 87.5 g of fenugreek powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 45.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the fenugreek dispersion at room temperature for 30 minutes, after which 15.4 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing process.

[0110] The reaction mixture obtained as described above was dispersed with 112.0 g of isopropanol (99%) and 23.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 4.1 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0111] Degree of cation substitution (DS) 阳离子 The concentration was 0.13 and the average molecular weight (Mw) was 2,020,000 g / mol. The biodegradability of cationic fenugreek was tested and showed that it was inherently biodegradable within 60 days (i.e., qualified).

[0112] Example 3 - Biodegradable cationic fenugreek

[0113] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 195.5 g of isopropanol solvent, mixed with 74.8 g of deionized water, was introduced at room temperature. Then, 87.8 g of fenugreek powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 45.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the fenugreek dispersion at room temperature for 30 minutes, after which 15.4 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing process.

[0114] The reaction mixture obtained as described above was dispersed with 110.5 g of isopropanol (99%) and 22.9 g of water under stirring. The pH was adjusted to approximately 9–10 using 4.1 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0115] Degree of cation substitution (DS) 阳离子 The concentration was 0.15 and the average molecular weight (Mw) was 1,384,000 g / mol. The biodegradability of cationic fenugreek was tested and showed that it was inherently biodegradable within 60 days (i.e., qualified).

[0116] Comparative Example 1 - Non-biodegradable cationic fenugreek

[0117] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 195.5 g of isopropanol solvent, mixed with 74.8 g of deionized water, was introduced at room temperature. Then, 87.8 g of fenugreek powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 45.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the fenugreek dispersion at room temperature for 30 minutes, after which 17.0 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing process.

[0118] The reaction mixture obtained as described above was dispersed with 110.5 g of isopropanol (99%) and 22.7 g of water under stirring. The pH was adjusted to approximately 9–10 using 2.0 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0119] Degree of cation substitution (DS) 阳离子The value was 0.17 and the average molecular weight (Mw) was 1,696,000 g / mol. The biodegradability of cationic fenugreek was tested and it was shown that it was not inherently biodegradable within 60 days (i.e., failed).

[0120] Comparative Example 2 - Non-biodegradable cationic fenugreek

[0121] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 280.2 g of isopropanol solvent, mixed with 112.0 g of deionized water, was introduced at room temperature. Then, 125.2 g of fenugreek powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 74.2 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the fenugreek dispersion at room temperature for 30 minutes, after which 28.3 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the fenugreek dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing procedure.

[0122] The reaction mixture obtained as described above was dispersed with 158.5 g of isopropanol (99%) and 36.2 g of water under stirring. The pH was adjusted to approximately 9–10 using 2.0 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 357 g of isopropanol (99%) and 146 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0123] Degree of cation substitution (DS) 阳离子 The concentration was 0.20 and the average molecular weight (Mw) was 1,819,000 g / mol. The biodegradability of cationic fenugreek was tested and it was shown that it was not inherently biodegradable within 60 days (i.e., it failed).

[0124] The results of Examples 1-3 and Comparative Examples 1 and 2 are shown in Table 1 below.

[0125] Table 1: Cationic Fenugreek

[0126]

[0127] As shown in Table 1 above, cationic fenugreek with a cationic substitution degree of less than 0.17 exhibits superior biodegradability compared to cationic fenugreek with a cationic substitution degree of 0.17 or higher.

[0128] Example 4 - Biodegradable cationic tara

[0129] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 98.7 g of isopropanol solvent, mixed with 37.4 g of deionized water, was introduced at room temperature. Then, 43.8 g of tara gum powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 18.5 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the tara gum dispersion at room temperature for 30 minutes, after which 7.1 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing process.

[0130] The reaction mixture obtained as described above was dispersed with 55.2 g of isopropanol (99%) and 12.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 1.0 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 125 g of isopropanol (99%) and 50 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0131] Degree of cation substitution (DS) 阳离子 The concentration was 0.14 and the average molecular weight (Mw) was 1,167,000 g / mol. The biodegradability of cationic tara was tested and showed that it was inherently biodegradable within 28 days and 60 days (i.e., qualified).

[0132] Example 5 - Biodegradable cationic tara

[0133] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 195.9 g of isopropanol solvent, mixed with 74.8 g of deionized water, was introduced at room temperature. Then, 87.6 g of tara gum powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 45.3 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the tara gum dispersion at room temperature for 30 minutes, after which 16.2 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing process.

[0134] The reaction mixture obtained as described above was dispersed with 119.0 g of isopropanol (99%) and 23.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 4.1 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0135] Degree of cation substitution (DS) 阳离子 The concentration was 0.17 and the average molecular weight (Mw) was 1,057,000 g / mol. The biodegradability of cationic tara was tested and showed that it was inherently biodegradable within 60 days (i.e., qualified).

[0136] Example 6 - Biodegradable cationic tara

[0137] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 196.0 g of isopropanol solvent, mixed with 74.6 g of deionized water, was introduced at room temperature. Then, 87.8 g of tara gum powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 45.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the tara gum dispersion at room temperature for 30 minutes, after which 16.3 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing process.

[0138] The reaction mixture obtained as described above was dispersed with 113.0 g of isopropanol (99%) and 24.0 g of water under stirring. The pH was adjusted to approximately pH 9-10 using 1.6 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0139] Degree of cation substitution (DS) 阳离子 The concentration was 0.18 and the average molecular weight (Mw) was 1,387,000 g / mol. The biodegradability of cationic tara was tested and showed that it was inherently biodegradable within 60 days (i.e., qualified).

[0140] Comparative Example 3 - Non-biodegradable cationic tara

[0141] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 97.4 g of isopropanol solvent, mixed with 39.0 g of deionized water, was introduced at room temperature. Then, 43.8 g of tara gum powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 27.8 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the tara gum dispersion at room temperature for 30 minutes, after which 11.0 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing procedure.

[0142] The reaction mixture obtained as described above was dispersed with 110.0 g of isopropanol (99%) and 23.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 1.6 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0143] Degree of cation substitution (DS) 阳离子The concentration was 0.20 and the average molecular weight (Mw) was 1,020,000 g / mol. The biodegradability of cationic tara was tested and it was shown that it was not inherently biodegradable within 60 days (i.e., it failed).

[0144] Comparative Example 4 - Non-biodegradable cationic tara

[0145] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 140.1 g of isopropanol solvent, mixed with 55.2 g of deionized water, was introduced at room temperature. Then, 63.0 g of tara gum powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 32.5 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the tara gum dispersion at room temperature for 30 minutes, after which 12.5 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing procedure.

[0146] The reaction mixture obtained as described above was dispersed with 79.8 g of isopropanol (99%) and 16.8 g of water under stirring. The pH was adjusted to approximately 9–10 using 1.9 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 180 g of isopropanol (99%) and 72 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0147] Degree of cation substitution (DS) 阳离子 The concentration was 0.20 and the average molecular weight (Mw) was 1,368,000 g / mol. The biodegradability of cationic tara was tested and it was shown that it was not inherently biodegradable within 60 days (i.e., it failed).

[0148] Comparative Example 5 - Non-biodegradable cationic tara

[0149] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 195.9 g of isopropanol solvent, mixed with 74.8 g of deionized water, was introduced at room temperature. Then, 87.8 g of tara gum powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 65.8 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the tara gum dispersion at room temperature for 30 minutes, after which 23.5 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing procedure.

[0150] The reaction mixture obtained as described above was dispersed with 110.0 g of isopropanol (99%) and 23.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 2.5 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0151] Degree of cation substitution (DS) 阳离子 The concentration was 0.25 and the average molecular weight (Mw) was 1,195,000 g / mol. The biodegradability of cationic tara was tested and it was shown that it was not inherently biodegradable within 60 days (i.e., it failed).

[0152] Comparative Example 6 - Non-biodegradable cationic tara

[0153] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 97.8 g of isopropanol solvent, mixed with 37.3 g of deionized water, was introduced at room temperature. Then, 43.4 g of tara gum powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 45.1 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the tara gum dispersion at room temperature for 30 minutes, after which 11.1 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the tara gum dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing procedure.

[0154] The reaction mixture obtained as described above was dispersed with 110.0 g of isopropanol (99%) and 23.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 1.0 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0155] Degree of cation substitution (DS) 阳离子 The value was 0.29. The biodegradability of cationic tara was tested and it was shown that it was not inherently biodegradable within 60 days (i.e., it failed).

[0156] The results of Examples 4-6 and Comparative Examples 3-6 are shown in Table 2 below.

[0157] Table 2: Cation Tarra

[0158]

[0159] As shown in Table 2 above, cationic tara with a cationic substitution degree of less than 0.20 exhibits superior biodegradability compared to cationic fenugreek with a cationic substitution degree of 0.20 or higher.

[0160] Example 7 - Biodegradable cationic cassia seed

[0161] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 195.1 g of isopropanol solvent, mixed with 74.0 g of deionized water, was introduced at room temperature. Then, 87.6 g of cassia seed powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 28.1 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the cassia seed dispersion at room temperature for 30 minutes, after which 15.1 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the cassia seed dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing procedure.

[0162] The reaction mixture obtained as described above was dispersed with 110.0 g of isopropanol (99%) and 23.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 3.9 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0163] Degree of cation substitution (DS) 阳离子 The concentration was 0.13 and the average molecular weight (Mw) was 563,000 g / mol. The biodegradability of cationic cassia was tested and showed that it was inherently biodegradable within 28 days and 60 days (i.e., qualified).

[0164] Example 8 - Biodegradable cationic cassia seed

[0165] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 144.0 g of isopropanol solvent, mixed with 55.0 g of deionized water, was introduced at room temperature. Then, 62.5 g of cassia seed powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 32.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the cassia seed dispersion at room temperature for 30 minutes, after which 11.8 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the cassia seed dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing procedure.

[0166] The reaction mixture obtained as described above was dispersed with 90.0 g of isopropanol (99%) and 15.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 3.9 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 180 g of isopropanol (99%) and 70 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0167] Degree of cation substitution (DS) 阳离子The concentration was 0.18 and the average molecular weight (Mw) was 743,000 g / mol. The biodegradability of cationic cassia was tested and showed that it was inherently biodegradable within 28 days and 60 days (i.e., qualified).

[0168] Comparative Example 7 - Non-biodegradable cationic cassia seed

[0169] In a 1-liter stirred reactor, under inert nitrogen atmosphere, 195.6 g of isopropanol solvent, mixed with 74.9 g of deionized water, was introduced at room temperature. Then, 87.7 g of cassia seed powder was loaded at room temperature with vigorous stirring. After stirring for several minutes to allow homogenization, 65.0 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride (Quat188, 65% in water) was added. This reagent was allowed to mix with the cassia seed dispersion at room temperature for 30 minutes, after which 12.6 g of sodium hydroxide (50% in water) was slowly added. This reagent was allowed to mix with the cassia seed dispersion and cationic etherifying agent at room temperature for 15 minutes. The dispersion was then heated to 60°C and maintained at that temperature for 60 minutes, after which the temperature was lowered to at least 50°C to begin the washing process.

[0170] The reaction mixture obtained as described above was dispersed with 100.0 g of isopropanol (99%) and 25.0 g of water under stirring. The pH was adjusted to approximately 9–10 using 2.0 g of glacial acetic acid. The mixture was then allowed to stand with stirring for 30 minutes and then discharged from the reactor after settling. The dispersion was then filtered under vacuum through qualitative filter paper. This washing and filtration process was repeated once more with 250 g of isopropanol (99%) and 100 g of water for 30 minutes. The resulting solid was then dried overnight in an oven at 60°C for 6 hours.

[0171] Degree of cation substitution (DS) 阳离子 The concentration was 0.24 and the average molecular weight (Mw) was 757,000 g / mol. The biodegradability of cationic cassia was tested and it was shown that it was not inherently biodegradable within 60 days (i.e., it failed).

[0172] The results of Examples 7-8 and Comparative Example 7 are shown in Table 3 below.

[0173] Table 3: Cation-containing Cassia tora

[0174]

[0175] As shown in Table 3 above, cationic cassia seed with a cationic substitution degree of less than 0.24 exhibits superior biodegradability compared to cationic cassia seed with a cationic substitution degree of 0.24 or higher.

[0176] The subject matter of this invention has been described in this way, and it is obvious that it can be modified or altered in various ways. Such modifications and alterations are not considered to depart from the spirit and scope of the subject matter of this invention, and all such modifications and alterations are intended to be included within the scope of the following claims.

Claims

1. A biodegradable cationic galactomannan comprising a galactose unit to mannose unit ratio of about 1:1, wherein the cationic galactomannan has: (a) DS of less than 0.17, preferably 0.16 or less, more preferably 0.15 or less 阳离子 ;as well as (b) Average molecular weight (Mw) below 3,500,000 g / mol. in, According to OECD 302B, this cationic galactomannan has a biodegradability of 60% or higher within 60 days, preferably within 28 days.

2. The biodegradable cationic galactomannan as described in claim 1, wherein, This cationic galactomannan contains cationic fenugreek (fenugreek).

3. The biodegradable cationic galactomannan as described in any of the preceding claims, wherein, The DS 阳离子 The range is 0.10 to 0.16, preferably 0.12 to 0.16, and more preferably 0.14 to 0.

16.

4. The biodegradable cationic galactomannan as described in any of the preceding claims, wherein, The Mw is 3,000,000 g / mol or lower, preferably in the range of 200,000 g / mol to 3,000,000 g / mol, more preferably in the range of 250,000 g / mol to 2,500,000 g / mol, and even more preferably in the range of 500,000 g / mol to 2,500,000 g / mol.

5. A biodegradable cationic galactomannan comprising a ratio of galactose units to mannose units of about 1:3 to about 1:5, preferably about 1:3 to about 1:4, wherein the cationic galactomannan has: (a) DS less than 0.20, preferably 0.18 or lower, more preferably less than 0.18 阳离子 ;as well as (b) Average molecular weight (Mw) below 2,500,000 g / mol. in, According to OECD 302B, this cationic galactomannan has a biodegradability of 60% or higher within 60 days, preferably within 28 days.

6. The biodegradable cationic galactomannan as described in claim 5, wherein, This cationic galactomannan contains cationic tara (a type of citrus fruit), cationic locust bean (a type of African locust bean), or a combination thereof.

7. The biodegradable cationic galactomannan as described in claim 5, wherein, This cationic galactomannan contains a galactose unit to mannose unit ratio of about 1:4, and has a DS of 0.18 or less, preferably less than 0.18, more preferably 0.17 or less. 阳离子 .

8. The biodegradable cationic galactomannan as described in claim 5, wherein, This cationic galactomannan contains a galactose unit to mannose unit ratio of about 1:3, and has a DS of 0.18 or less, preferably less than 0.18, more preferably 0.17 or less. 阳离子 .

9. The biodegradable cationic galactomannan as described in claim 5 or 6, wherein, The DS 阳离子 The range is 0.10 to 0.20, preferably 0.12 to 0.20, and more preferably 0.14 to 0.

20.

10. The biodegradable cationic galactomannan as described in claims 5 to 9, wherein, The Mw is 2,000,000 g / mol or lower, preferably in the range of 200,000 g / mol to 2,000,000 g / mol, more preferably in the range of 250,000 g / mol to 2,000,000 g / mol, and even more preferably in the range of 300,000 g / mol to 2,000,000 g / mol.

11. A biodegradable cationic galactomannan comprising a galactose unit to mannose unit ratio of about 1:5, wherein the cationic galactomannan has: (a) DS below 0.24 阳离子 ;as well as (b) Average molecular weight (Mw) below 1,000,000 g / mol. in, According to OECD 302B, this cationic galactomannan has a biodegradability of 60% or higher within 60 days, preferably within 28 days.

12. The biodegradable cationic galactomannan as described in claim 11, wherein, This cationic galactomannan contains cationic cassia (Cassia obtusifolia / Cassia truncatula).

13. The biodegradable cationic galactomannan as described in claim 11 or 12, wherein, The DS 阳离子 The range is from 0.10 to less than 0.24, preferably from 0.14 to 0.22, and more preferably from 0.14 to 0.

20.

14. The biodegradable cationic galactomannan as described in claims 11 to 13, wherein, The cationic galactomannan has an Mw of 900,000 g / mol or less, preferably from about 100,000 g / mol to 900,000 g / mol, and more preferably from about 150,000 g / mol to 750,000 g / mol.

15. The biodegradable cationic galactomannan as described in any of the preceding claims, wherein, This cationic galactomannan is cationicized by at least one cationic agent selected from 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, and mixtures thereof.

16. The biodegradable cationic galactomannan as described in any of the preceding claims, wherein, This cationic galactomannan contains cationic groups selected from the following: amino groups selected from primary amino, secondary amino, tertiary amino and combinations thereof; quaternary ammonium groups; sulfonium groups; phosphonium groups; and combinations thereof.

17. The biodegradable cationic galactomannan as described in any of the preceding claims, wherein, The cationic group is selected from trialkylammonium groups, such as trimethylammonium, triethylammonium, or tributylammonium; aryldialkylammonium groups, such as benzyldimethylammonium; ammonium groups in which the nitrogen atom is a member of a ring structure, such as pyridinium and imidazoline; and combinations thereof.

18. The biodegradable cationic galactomannan as described in any of the preceding claims, wherein, According to OECD 302B, this cationic galactomannan has a biodegradability of 70% or higher within 28 days.

19. A composition comprising a biodegradable cationic galactomannan as described in any of the preceding claims.

20. The composition of claim 19, wherein, The composition further comprises at least one surfactant, emulsifier, emollient, humectant, hair conditioner, hair fixative, film-forming agent, skin protectant, binder, chelating agent, disinfectant, insecticide, fungicide, deodorant, pest repellent, fragrance material, antimicrobial agent, antifungal agent, antibiotic, antidandruff agent, abrasive, adhesive, absorbent, colorant, deodorant, antiperspirant, humectant, and oil (such as mineral oil, vegetable oil, animal oil, synthetic oil, silicone oil, and mixtures thereof). ), opacifiers and pearlescent agents, antioxidants, preservatives, propellants, spreading agents, exfoliants, keratolytic agents, blood coagulants, vitamins, sunscreens, artificial tanning agents, ultraviolet absorbers, pH adjusters, plant-based ingredients, hair coloring agents, dyes, preservatives, inorganic particles, buffers, preservatives, oxidizing agents, reducing agents, rheology modifiers, skin bleaching agents, pigments, anti-inflammatory agents, thickeners, local anesthetics, fragrances, fragrance solubilizers, particulate matter, microabrasives, abrasives and combinations thereof.

21. A method for preparing biodegradable cationic galactomannan as described in any of the preceding claims, wherein, The method involves reacting a non-cationic galactomannan with at least one cationic agent.

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