CN115449074B - Polyasparagine derivative thickener with side chain containing straight-chain alkyl chain and lysine - Google Patents

Polyasparagine derivative thickener with side chain containing straight-chain alkyl chain and lysine Download PDF

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CN115449074B
CN115449074B CN202211071557.5A CN202211071557A CN115449074B CN 115449074 B CN115449074 B CN 115449074B CN 202211071557 A CN202211071557 A CN 202211071557A CN 115449074 B CN115449074 B CN 115449074B
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lysine
chain
linear alkyl
side chain
polyaspartic acid
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CN115449074A (en
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张光彦
武欣然
付开乔
杨虎平
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Guangzhou Keluode New Material Technology Co ltd
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1092—Polysuccinimides
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

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Abstract

The invention belongs to the technical field of new materials, and discloses a polyamide derivative thickener with a side chain containing a linear alkyl chain and lysine, wherein the polyamide derivative thickener with the side chain containing the linear alkyl chain and lysine comprises the following chemical structures:wherein R represents a compound of formula C 12 H 25 、C 14 H 29 、C 16 H 33 A linear alkyl chain of (a); n represents the polymerization degree of the polyaspartic acid derivative thickener with a side chain containing a linear alkyl chain and lysine, and n is an integer of 100-1000; x represents the grafting amount of the linear alkyl chain; n-x represents the grafting amount of lysine; q represents the grafting amount of an amido bond formed by the amino group at the position 2 in lysine and the main chain of polyaspartic acid, and q is more than or equal to 0 and less than or equal to n-x; n-x-q represents the grafting amount of the amino group at the 6-position in lysine and the polyaspartic acid main chain to form an amide bond. The polyaspartic acid derivative with the side chain containing the linear alkyl chain and lysine, which is provided by the invention, is a non-crosslinking thickener, is a safe and biodegradable polymer material, and provides a greener, safe and environment-friendly thickening scheme for an aqueous system.

Description

Polyasparagine derivative thickener with side chain containing straight-chain alkyl chain and lysine
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a polyasparagine derivative thickener with a side chain containing a straight-chain alkyl chain and lysine.
Background
The thickener is a substance capable of increasing the viscosity of a liquid system, is mainly used for increasing the viscosity of a product system, keeping a stable and balanced suspension state and the like, and has the characteristics of small dosage and obvious thickening. Common thickeners mainly include: two major classes, namely (1) crosslinked and (2) uncrosslinked. At present, the thickener has been widely applied to the fields of cosmetics, foods and the like. The common thickening agent mainly comprises high polymer, and the most widely used in the cosmetic field is a cross-linked polyacrylic acid series thickening agent (such as carbomer series).
Although polyacrylic acid-based thickeners are widely used in various industries (such as daily chemicals and medicines), they have problems such as difficult biodegradation of the main chain, and adverse effects on the environment and ecology. With the increasing awareness of environmental protection, there is an increasing demand for biodegradable products. Accordingly, biodegradable products based on natural sources have received a great deal of attention in recent years.
Polyaspartic Acid (PASP) takes 'aspartic acid' as a main chain structural unit, is biodegradable, and degradation products are nontoxic, and gradually starts to replace polyacrylic acid to enter an industrial application stage (such as scale inhibition and corrosion inhibition) in the field of water treatment. In the agricultural field, polyaspartic acid is used as a fertilizer synergistic additive, and is a raw material for producing polypeptide fertilizer and plant synergistic fertilizer. In the field of daily chemicals, sodium salts of polyaspartic acid are also listed in the catalog of names of raw materials for cosmetics that have been used (2015). In the biomedical field, a large number of polyaspartic acid derivatives taking aspartic acid as a main chain are widely studied, and a small number of derivatives (such as NC-6300) enter a clinical research stage and all show good human safety.
Through the above analysis, the problems and defects existing in the prior art are as follows: the existing polyacrylic acid series thickener is mainly cross-linked, has the problems that the carbon-carbon main chain is difficult to biodegrade and the like, and has adverse effects on the environment and ecology. In addition, polyacrylic acid series thickeners are generally weak in ionic resistance, and the thickening effect is significantly influenced by the pH value of the system (carboxyl groups are required to be deprotonated, and a negative charge repulsive effect is formed to stretch out molecular chains).
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a polyaspartic acid amide derivative thickener with a side chain containing a linear alkyl chain and lysine.
The invention is realized by the following steps that a polyaspartic acid derivative thickener with a side chain containing a linear alkyl chain and lysine comprises the following chemical structures:
wherein R represents a compound of formula C 12 H 25 、C 14 H 29 、C 16 H 33 A linear alkyl chain of (a); n represents the polymerization degree of the polyaspartic acid derivative thickener with a side chain containing a linear alkyl chain and lysine, and n is an integer of 100-1000; x represents the grafting amount of the linear alkyl chain; n-x represents the grafting amount of lysine; q represents the grafting amount of an amido bond formed by the amino group at the position 2 in lysine and the main chain of polyaspartic acid, and q is more than or equal to 0 and less than or equal to n-x; n-x-q represents the grafting amount of the amino group at the 6-position in lysine and the polyaspartic acid main chain to form an amide bond.
Further, in the polyaspartic acid derivative thickener having a side chain containing a linear alkyl chain and lysine, the main chain is preferably polyaspartic acid, and the side chain is preferably a linear aliphatic amine and lysine which can be derived from plants.
Further, the side chain of the polyaspartic acid derivative thickener containing a linear alkyl chain and lysine is bonded to the main chain by an amide bond.
Further, the chemical structure of the side chain corresponding to the polyaspartic acid derivative thickener with the side chain containing the linear alkyl chain and lysine is a linear alkyl amine group and a lysine group (called LL for short).
Further, the linear alkyl amine group of the side chain is-NHR, wherein R represents a compound of formula C 12 H 25 、C 14 H 29 、C 16 H 33 Is a linear alkyl chain of (a).
Further, the side chain chemical structure corresponding to the lysine group LL of the side chain is-NHC 5 H 9 NH 2 COOH。
Further, the optimal mass percentage concentration of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine is 1-8% and above.
Another object of the present invention is to provide a method for preparing a polyamide derivative thickener having a side chain containing a linear alkyl chain and lysine, comprising the steps of:
step one, dissolving polysuccinimide PSI in a solvent, and adding a specified amount of linear aliphatic amine R-NH 2 Carrying out the reaction at room temperature or a designated temperature;
step two, after the reaction is finished, removing the solvent and unreacted linear fatty amine by a dialysis and precipitation method, and purifying to obtain a polyaspartic acid derivative PASP-C12 or PASP-C14 or PASP-C16 with an intermediate product side chain containing a linear alkyl chain;
dispersing an intermediate product PASP-C12 or PASP-C14 or PASP-C16 in a solvent, adding excessive lysine, and reacting at room temperature or a designated temperature;
and step four, after the reaction is finished, removing the solvent and unreacted lysine by a dialysis and precipitation method to obtain the polyaspartic acid derivative PASP-C12-LL or PASP-C14-LL or PASP-C16-LL with the side chain containing the linear alkyl chain and the lysine.
Further, the solvent in the first step is any one of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO, and the solvent in the third step is water.
Further, the preparation method of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine comprises the following reaction processes:
wherein 12, 14, 16 in PASP-C12, PASP-C14, PASP-C16, PASP-C12-LL, PASP-C14-LL and PASP-C16-LL represent the carbon number of the side chain alkyl chain R.
In combination with the technical scheme and the technical problems to be solved, the technical scheme to be protected has the following advantages and positive effects:
first, aiming at the technical problems in the prior art and the difficulty in solving the problems, the technical problems solved by the technical proposal of the invention are analyzed in detail and deeply by tightly combining the technical proposal to be protected, the results and data in the research and development process, and the like, and some technical effects brought after the problems are solved have creative technical effects. The specific description is as follows:
in order to obtain the biodegradable and high-safety friendly thickener, the invention particularly preferably adopts linear fatty amine and lysine which can be obtained from natural sources as side chains, adopts aspartic acid as a main chain structural unit, and adopts amide bond combination between the main chains, so as to design the biodegradable polyaspartic acid derivative with the side chains containing linear alkyl chains and lysine for thickening an aqueous system.
Firstly, the polyaspartic acid derivative with the side chain containing the linear alkyl chain and lysine is non-crosslinked, so that the polyaspartic acid derivative can be swelled and dissolved at a higher speed in the process of adding and using, is easier to add and operate, and is superior to a crosslinked product in application. Secondly, thickening is mainly realized by virtue of a hydrophilic-hydrophobic repulsive effect, and charge repulsive force is not the main acting force of the polyaspartic acid derivative for generating the thickening effect, so that the linear alkyl chain of the side chain is insensitive to the ionic strength and pH of the system. Finally, the side chain LL is formed by the ring opening reaction of 1 amino group in the raw material lysine (basic amino acid: 2 amino groups, 1 carboxyl group) with the structural unit of PSI (because of the difference in activity of the 2,6 amino groups, mainly the 6 amino groups participate in the reaction), and the side chain LL is of a zwitterionic chemical structure and is wholly neutral (1 amino group and 1 carboxyl group). Therefore, when the pH of the system changes, no matter the pH is higher than the isoelectric point or lower than the isoelectric point, the charge repulsion effect can be generated, the molecular chain can be stretched, and the thickening of the system is beneficial. Thus, it has better tolerance to pH changes than polyacrylic acid series thickeners (single carboxyl groups).
The polyaspartic acid is preferably used as a main chain structure, so that the main structure is ensured to have good safety and degradability; preferably, the linear alkyl chain containing 12-16 carbons and lysine are used as side chain structural units, and the side chain is connected to the polyaspartic acid main chain in an amide bond mode, so that the thickener is safe and biodegradable, and has obvious thickening effect on water at a lower concentration (1% -8% of concentration by mass).
The invention has the beneficial effects that:
(1) Polyaspartic acid, which is listed in the catalog of names of raw materials for cosmetics (2015 edition), is preferable as a main chain structure to ensure good safety and degradability of the main structure of the designed thickener.
(2) The thickener side chain is prepared from (a) straight-chain fatty amine which can be derived from plants and (b) lysine, and both side chain raw materials have good biological safety.
(3) The main chain and the side chain are connected by an amide bond, and the formed amide bond has good degradability.
(4) The polyaspartic acid derivative thickener has good thickening performance, and can obviously improve the viscosity of an aqueous system under the condition of lower addition (the mass percentage concentration is not lower than 1% -8%).
Secondly, the technical scheme is regarded as a whole or from the perspective of products, and the technical scheme to be protected has the following technical effects and advantages:
the polyaspartic acid derivative with the side chain containing the linear alkyl chain and lysine, which is provided by the invention, is a non-crosslinking thickener, is a safe and biodegradable polymer material, and provides a greener, safe and environment-friendly thickening scheme for an aqueous system.
The polyaspartic acid derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the invention has a simple preparation method, and the prepared polyaspartic acid derivative thickener can obviously improve the viscosity of an aqueous system under the condition that the addition amount is not less than 1-8% (mass percentage concentration), and has an obvious thickening effect.
Thirdly, as inventive supplementary evidence of the claims of the present invention, the following important aspects are also presented:
(1) The expected benefits and commercial values after the technical scheme of the invention is converted are as follows: in view of the increasing level of awareness of people of the direction and safety of a good living environment, consumers are increasingly looking for products that are biodegradable and are composed of natural molecules. The main body of the polyaspartic acid derivative thickener is amino acid (aspartic acid and lysine) and fatty amine, and is formed by connecting degradable amide bonds, so that the thickener meets the requirements of times of development and consumers on environmental protection and safety. Meanwhile, the polyaspartic acid derivative thickener with the side chain containing the linear alkyl chain and lysine is simple in preparation method, is hopeful to replace the existing commercial polyacrylic acid series thickener quickly and partially after the technical scheme is converted, and has good commercial value (note: in the field of water treatment, in view of the excellent biodegradability of polyaspartic acid and the non-toxic property of degradation products, the commercial polyaspartic acid partially replaces polyacrylic acid for scale inhibition, corrosion inhibition, chelation of hard water calcium ions and the like, and the polyaspartic acid is a main chain structure of the thickener, and has the advantages of biodegradability and non-toxic property of main chain degradation products compared with the polyacrylic acid series thickener.
(2) The technical scheme of the invention fills the technical blank in the domestic and foreign industries: at present, no report of a non-crosslinked polyaspartic acid derivative thickener which takes polyaspartic acid as a main chain and has a side chain containing a linear alkyl chain and lysine is seen at home and abroad.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a preparation method of a polyasparagine derivative thickener with a side chain containing a linear alkyl chain and lysine, which is provided by the embodiment of the invention;
FIG. 2 is an infrared spectrum of an intermediate product PASP-C12 provided by an embodiment of the invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the intermediate PASP-C12 provided by the embodiment of the invention;
FIG. 4 is an infrared spectrum of PASP-C12-LL, a polyaspartic acid derivative with a side chain containing a linear alkyl chain and lysine, provided by the embodiment of the invention;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of a PASP-C12-LL derivative with a side chain containing a linear alkyl chain and lysine provided by the embodiment of the invention;
fig. 6 is a photograph showing the thickening effect of the polyaspartic acid derivative PASP-C12-LL having a linear alkyl chain and lysine in the side chain, according to the embodiment of the present invention, wherein (a) is a thickening effect graph of 1% by mass concentration, and (b) is a thickening effect graph of 5% by mass concentration.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In view of the problems of the prior art, the present invention provides a thickener of a polyaspartic acid derivative having a side chain comprising a linear alkyl chain and lysine, which is described in detail below with reference to the accompanying drawings.
The polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following chemical structures:
wherein R represents a compound of formula C 12 H 25 、C 14 H 29 、C 16 H 33 A linear alkyl chain of (a); n represents the polymerization degree of the polyaspartic acid derivative thickener with a side chain containing a linear alkyl chain and lysine, and n is an integer of 100-1000; x represents a grafting amount of a linear alkyl chain, and x is an integer of 15% ×n to 61% ×n; n-x represents the grafting amount of lysine, and n-x is an integer of 39%. Times.n-85%. Times.n; q represents the grafting amount of an amido bond formed by the amino group at the position 2 in lysine and the main chain of polyaspartic acid, and q is more than or equal to 0 and less than or equal to n-x;n-x-q represents the grafting amount of the amino group at the 6-position in lysine and the polyaspartic acid main chain to form an amide bond.
The main chain of the polyaspartic acid derivative thickener with the side chain containing the linear alkyl chain and the lysine provided by the embodiment of the invention is composed of polyaspartic acid, the side chain is composed of the linear alkyl chain (specifically comprising n-dodecyl amine, n-dodecyl amine and n-hexadecyl amine) and the lysine, and the side chain and the main chain are combined through an amide bond.
The polyaspartic acid derivative thickener provided by the embodiment of the invention, the side chain of which contains a linear alkyl chain and lysine, is biodegradable and safe in consideration of the following properties: the main chain is preferably polyaspartic acid in the name catalog of used cosmetic raw materials (2015 edition); the side chain is preferably (a) a linear aliphatic amine of vegetable origin, the chemical structure of the corresponding side chain being a linear alkylamino group (-NHR), wherein R represents a C 12 H 25 、C 14 H 29 、C 16 H 33 Linear alkyl chain) and (b) lysine, the corresponding side chain chemical structure being-NHC 5 H 9 NH 2 COOH. The side chains are bonded to the main chain by amide bonds.
The polyaspartic acid derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention can obviously improve the viscosity of an aqueous system and has obvious thickening effect under the condition that the addition amount is not less than 1-8% (mass percentage concentration).
As shown in FIG. 1, the preparation method of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following steps:
s101, dissolving polysuccinimide PSI in a solvent, and adding a specified amount of linear aliphatic amine R-NH 2 Carrying out the reaction at room temperature or a designated temperature;
s102, after the reaction is finished, removing the solvent and unreacted linear fatty amine by a dialysis and precipitation method, and purifying to obtain a polyaspartic acid derivative PASP-C12 or PASP-C14 or PASP-C16 with an intermediate product side chain containing a linear alkyl chain;
s103, dispersing an intermediate product PASP-C12 or PASP-C14 or PASP-C16 in a solvent, adding excessive lysine, and reacting at room temperature or a designated temperature;
s104, after the reaction is finished, removing the solvent and unreacted lysine by a dialysis and precipitation method to obtain the polyaspartic acid derivative PASP-C12-LL or PASP-C14-LL or PASP-C16-LL with the side chain containing the linear alkyl chain and the lysine.
The solvent in the step S101 provided by the embodiment of the invention is any one of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO, and the solvent in the step S103 is water.
The preparation method of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following reaction processes:
wherein 12, 14, 16 in PASP-C12, PASP-C14, PASP-C16, PASP-C12-LL, PASP-C14-LL and PASP-C16-LL represent the carbon number of the side chain alkyl chain R.
The thickener is a substance capable of increasing the viscosity of a liquid system, and is mainly used for increasing the viscosity of a product system, keeping a stable and balanced suspension state and the like. In the application example, pure water is used as a matrix, and the polyasparagine derivative with the side chain containing the linear alkyl chain and lysine is added to prepare aqueous solutions with different concentrations. The thickening effect of the polyasparagine derivatives according to the invention was evaluated on the basis of the viscosity of the aqueous solutions at different concentrations.
The polymerization degree of the raw material PSI used for preparing the polyaspartic acid derivative thickener containing a linear alkyl chain and lysine in a side chain provided in the embodiment of the invention is usually in the range of 50 to 1500, and particularly preferably 100 and more and 1000 and less. When the polymerization degree of PSI is less than 100, the addition amount required for thickening is too high (> 10%) due to the low molecular weight, so that the use is not preferable; when the polymerization degree of PSI is more than 1000, it is easy to cause "polyaspartic acid derivative having a linear alkyl chain and lysine in its side chain" to be too low in solubility in a water-based system, and it is difficult for the molecular chain to be fully extended, resulting in failure to obtain a good thickening effect. The polymerization degree of PSI was calibrated using Agilent EasiVial polystyrene standards and obtained by GPC testing with DMF (containing 10mM lithium bromide) as the mobile phase.
Example 1
The preparation method of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following steps:
the reaction step I: 1.0 g of polysuccinimide (polymerization degree 200, 10.3 mmol) was weighed into a flask, and 10 ml of DMF was added to dissolve to homogeneity; then, 0.85 g of n-dodecylamine (4.6 mmol) was added to the flask, and the mixture was stirred at 60℃for 1 day; after the reaction, the reactants are dripped into ethanol to precipitate an intermediate product containing C in the side chain 12 H 25 Polyaspartic acid derivative PASP-C12) of straight chain alkyl chain.
The PASP-C12 is obtained by infrared spectrum (FTIR, see figure 2) and nuclear magnetic hydrogen spectrum 1 H-NMR, see FIG. 3). As can be seen from FIG. 2, PASP-C12 is at 2927cm -1 And 2854cm -1 The vicinity of which shows distinct peaks of alkyl chain (methyl and methylene) characteristic absorption; 1723cm -1 Is the carbonyl absorption peak on the un-ring-opened succinimide building block in PASP-C12; 1657cm -1 Characteristic absorption peak of carbonyl group on amide bond formed by n-dodecylamine ring-opening PSI, 3352cm -1 And 1539cm -1 The stretching vibration and bending vibration absorption peak of-NH-on amide bond formed by n-dodecylamine ring-opening PSI.
From FIG. 3PASP-C12 1 H-NMR (test solvent: DMSO-d) 6 ) It can be seen that the cyclic building blocks of PSI have been partially opened by n-dodecylamine. After ring opening, the H signal on the tertiary carbon in the succinimide building block was shifted from 5.3ppm (peak a) to 4.6ppm (peak a). The molar grafting ratio of n-dodecyl amine to PSI structural units was calculated as the integrated area ratio of peak a (5.3 ppm) and peak a (4.6 ppm) and was 41%.
And a reaction step II: 1.0 g of intermediate PASP-C12 was weighed into a flask, and 50 ml of water was added thereto for stirring and dispersion. Then, add into the flaskAdding excessive lysine, and stirring at 60 ℃ to react until the pH value of the system is not reduced; after the reaction is finished, ethanol is added into the flask, and the side chain C can be precipitated 12 H 25 Polyaspartic acid derivative thickener PASP-C12-LL of straight chain alkyl chain and lysine.
The PASP-C12-LL is obtained by infrared spectroscopy (FTIR, see figure 4) and nuclear magnetic resonance hydrogen spectroscopy 1 H-NMR, see FIG. 5). As can be seen by comparing the IR spectrum of PASP-C12-LL (see FIG. 4) with the IR spectrum of PASP-C12 (see FIG. 2), the absorption peak (1723 cm) corresponding to the carbonyl group on the "non-open-loop succinimide building block" in PASP-C12 -1 ) Complete disappearance, indicating that the succinimide building block in PASP-C12 has reacted completely with the amine group of lysine. From PASP-C12-LL 1 As can be seen by H-NMR (see FIG. 5), the peak at 5.3ppm completely disappeared (corresponding to peak a of the succinimide building block in PASP-C12 in FIG. 3), also indicating that the succinimide building block in PASP-C12 has been totally ring opened by lysine.
The thickening effect of the resulting product PASP-C12-LL in pure water is shown in FIG. 6. When the mass percentage of PASP-C12-LL in the aqueous solution is 1%, the system still has obvious fluidity although having a certain viscosity in sense, so that the aqueous solution can smoothly flow from the pointed bottom of the centrifuge tube to the lower half part of the centrifuge tube after the centrifuge tube is inverted (figure 6 a); when the mass percentage of PASP-C12-LL in the aqueous solution is increased to 5%, the thickening effect is obvious, the viscosity of the system is obviously increased, the fluidity is lost, and even if the centrifuge tube is inverted, the aqueous solution still stays in the upper half part of the centrifuge tube and cannot flow from the pointed bottom (upper part) of the centrifuge tube to the lower half part of the centrifuge tube. Meanwhile, bubbles generated in the configuration process are suspended in the system because the viscosity of the system is increased and cannot float to the top (FIG. 6b, at the pointed bottom of the centrifuge tube)
Example 2
The preparation method of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following steps:
the reaction step I: 1.0 g of polysuccinimide (degree of polymerization 5) was weighed out00 10.3 mmol) was added to the flask, and 10 ml DMSO was added to dissolve to homogeneity; then, 1.30 g of n-dodecylamine (7.0 mmol) was added to the flask, and the mixture was stirred at 60℃for 1 day; after the reaction, the reactants are dripped into ethanol to precipitate an intermediate product containing C in the side chain 12 H 25 Polyaspartic acid derivative PASP-C12) of straight chain alkyl chain. The molar grafting ratio of n-dodecyl amine to PSI structural units was calculated to be 61% by integrating area ratio of 5.3ppm and 4.6ppm of nuclear magnetic hydrogen spectrum.
And a reaction step II: 1.0 g of PASP-C12 with 61% grafting ratio of n-dodecylamine was weighed, added into a flask, and 50 ml of water was added for stirring and dispersion. Then, adding excessive lysine into the flask, and stirring at 60 ℃ to react until the pH value of the system is not reduced; after the reaction is finished, ethanol is added into the flask, and the side chain C can be precipitated 12 H 25 Polyaspartic acid derivative thickener PASP-C12-LL of straight chain alkyl chain and lysine. The complete disappearance of the peak at 5.3ppm was detected by nuclear magnetic hydrogen spectroscopy, indicating that the succinimide structural unit in "PASP-C12 with 61% n-dodecylamine grafting" had been totally ring opened by lysine.
The resulting product, PASP-C12-LL with 61% n-dodecylamine grafting, had the following thickening effect in pure water: when the mass percentage of PASP-C12-LL in the aqueous solution is 0.5%, the viscosity of the system is lower, and the system has good fluidity; when the mass percentage of PASP-C12-LL in the aqueous solution is 1%, the system has obvious viscosity, but still has fluidity; when the mass percentage of PASP-C12-LL in the aqueous solution is increased to 2%, the system loses fluidity.
Example 3
The preparation method of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following steps:
the reaction step I: 1.0 g of polysuccinimide (polymerization degree 1000, 10.3 mmol) was weighed into a flask, and 10 ml of DMSO was added to dissolve to homogeneity; then, 0.64 g of n-tetradecylamine (3.0 mmol) was added to the flask, and the mixture was stirred at 60℃for 1 day; after the reaction, the reactants are dripped into ethanolThe intermediate product "side chain contains C 14 H 29 Polyaspartic acid derivative PASP-C14 "of straight chain alkyl chain. The molar grafting ratio of n-tetramine to PSI structural units is calculated to be 25% by the integral area ratio of 5.3ppm and 4.6ppm of the nuclear magnetic hydrogen spectrum.
And a reaction step II: 1.0 g of PASP-C14 was weighed into a flask, and 50 ml of water was added thereto to perform stirring dispersion. Then, adding excessive lysine into the flask, and stirring at 60 ℃ to react until the pH value of the system is not reduced; after the reaction is finished, ethanol is added into the flask, and the side chain C can be precipitated 14 H 29 Polyaspartic acid derivative thickener PASP-C14-LL of straight chain alkyl chain and lysine. By complete disappearance of the peak at 5.3ppm of the nuclear magnetic hydrogen spectrum, it can be shown that the succinimide building block in PASP-C14 has been fully opened by lysine.
The thickening effect of the product PASP-C14-LL in pure water is as follows: when the mass percentage of PASP-C14-LL in the aqueous solution is 0.5%, the viscosity of the system is lower, and the system has good fluidity; when the mass percentage of PASP-C14-LL in the aqueous solution is 1%, the fluidity of the system is basically lost; when the mass percentage of PASP-C14-LL in the aqueous solution was increased to 2%, the system lost fluidity completely.
Example 4
The preparation method of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following steps:
the reaction step I: 1.0 g of polysuccinimide (polymerization degree 500, 10.3 mmol) was weighed into a flask, and 10 ml of DMSO was added to dissolve to homogeneity; then, 0.64 g of n-tetradecylamine (3.0 mmol) was added to the flask, and the mixture was stirred at 60℃for 1 day; after the reaction, the reactants are dripped into ethanol to precipitate an intermediate product containing C in the side chain 14 H 29 Polyaspartic acid derivative PASP-C14 "of straight chain alkyl chain. The molar grafting ratio of n-tetramine to PSI structural units is calculated to be 27% by the integral area ratio of 5.3ppm and 4.6ppm of the nuclear magnetic hydrogen spectrum.
And a reaction step II: 1.0 g of n-tetradecylamine is weighed to be grafted as27% PASP-C14 was added to the flask, and 50 ml of water was added thereto to disperse the mixture under stirring. Then, adding excessive lysine into the flask, and stirring at 60 ℃ to react until the pH value of the system is not reduced; after the reaction is finished, ethanol is added into the flask, and the side chain C can be precipitated 14 H 29 Polyaspartic acid derivative thickener PASP-C14-LL of straight chain alkyl chain and lysine. By complete disappearance of the peak at 5.3ppm of the nuclear magnetic hydrogen spectrum, it was demonstrated that PASP-C14 with a grafting ratio of n-tetradecylamine of 27% had all of its remaining succinimide structural units opened by lysine.
The thickening effect of PASP-C14-LL with 27% grafting rate of the obtained n-tetradecylamine in pure water is as follows: when the mass percentage of PASP-C14-LL in the aqueous solution is 0.5%, the viscosity of the system is lower, and the system has good fluidity; when the mass percentage of PASP-C14-LL in the aqueous solution is 1%, the system shows a certain viscosity, but still has better fluidity; when the mass percentage of PASP-C14-LL in the aqueous solution is increased to 2%, the viscosity of the system is obviously increased, and the fluidity is obviously reduced; when the mass percentage of PASP-C14-LL in the aqueous solution was increased to 4%, the fluidity of the system had been substantially lost.
Example 5
The preparation method of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following steps:
the reaction step I: 1.0 g of polysuccinimide (polymerization degree 100, 10.3 mmol) was weighed into a flask, and 10 ml of DMSO was added to dissolve to homogeneity; then, 0.48 g of n-hexadecylamine (2.0 mmol) was added to the flask, and the mixture was stirred at 60℃for 1 day; after the reaction, the reactants are dripped into ethanol to precipitate an intermediate product containing C in the side chain 16 H 33 Polyaspartic acid derivative PASP-C16 "of straight chain alkyl chain. The molar grafting ratio of n-hexadecylamine to PSI structural unit was calculated to be 15% by integrating area ratio of 5.3ppm and 4.6ppm of nuclear magnetic hydrogen spectrum.
And a reaction step II: 1.0 g of PASP-C16 was weighed into a flask, and 50 ml of water was added thereto to perform stirring dispersion. Then, excess rice was added to the flaskThe ammonia acid is stirred at 60 ℃ to react until the pH value of the system is not reduced any more; after the reaction is finished, ethanol is added into the flask, and the side chain C can be precipitated 16 H 33 Polyaspartic acid derivative thickener PASP-C16-LL of straight chain alkyl chain and lysine. By complete disappearance of the peak at 5.3ppm of the nuclear magnetic hydrogen spectrum, it can be shown that the succinimide building block in PASP-C16 has been fully opened by lysine.
The thickening effect of the product PASP-C16-LL in pure water is as follows: when the mass percentage of PASP-C16-LL in the aqueous solution is 1%, the viscosity of the system is lower, and the system has good fluidity; when the mass percentage of PASP-C16-LL in the aqueous solution is 4%, the system has obvious viscosity, but still has fluidity; when the mass percent of PASP-C16-LL in the aqueous solution is increased to 8%, the system essentially loses fluidity.
Comparative example 1
The preparation method of the polyasparagine derivative with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following steps:
the reaction step I: 1.0 g of polysuccinimide (polymerization degree 500, 10.3 mmol) was weighed into a flask, and 10 ml of DMF was added to dissolve to homogeneity; then, 1.48 g of n-dodecylamine (8.0 mmol) was added to the flask, and the mixture was stirred at 60℃for 1 day; after the reaction was completed, a large amount of viscous solid was precipitated from DMF.
And a reaction step II: after the product of the first step is washed and dried by ethanol, 1.0 g of the product is weighed and put into a flask, and 50 ml of water is added for stirring and dispersion. Then, an excessive amount of lysine was added to the flask, and the reaction was stirred at 60 ℃. After 48 hours of reaction, the mixture remained solid and was not dissolved in water. It is therefore believed that there is no thickening effect on the water-based system.
Comparative example 2
The preparation method of the polyasparagine derivative with the side chain containing the linear alkyl chain and lysine provided by the embodiment of the invention comprises the following steps:
the reaction step I: 1.0 g of polysuccinimide (polymerization degree 500, 10.3 mmol) was weighed out, added into a flask, and 10 ml of DMF was added to dissolve until homogeneousA phase; then, 0.39 g of n-hexadecylamine (1.6 mmol) was added to the flask, and the mixture was stirred at 60℃for 1 day; after the reaction, the reactants are dripped into ethanol to precipitate an intermediate product containing C in the side chain 16 H 33 Polyaspartic acid derivative PASP-C16 "of straight chain alkyl chain. The molar grafting ratio of n-hexadecylamine to PSI structural unit was calculated to be 12% by integrating area ratio of 5.3ppm and 4.6ppm of nuclear magnetic hydrogen spectrum.
And a reaction step II: 1.0 g of PASP-C16 with 12% grafting rate of n-hexadecylamine is weighed into a flask, and 50 ml of water is added for stirring and dispersion. Then, adding excessive lysine into the flask, and stirring at 60 ℃ to react until the pH value of the system is not reduced; after the reaction is finished, adding ethanol into the flask to precipitate out the side chain C 16 H 33 Polyaspartic acid derivative thickener PASP-C16-LL of straight chain alkyl chain and lysine. The complete disappearance of the peak at 5.3ppm was detected by nuclear magnetic hydrogen spectroscopy, indicating that the succinimide structural unit in "PASP-C16 with 12% grafting of n-hexadecylamine" had been fully ring opened by lysine.
However, the PASP-C16-LL with the grafting rate of 12% of the n-hexadecylamine still has low system viscosity and good fluidity even when the mass percentage of the PASP-C16-LL in an aqueous solution reaches 10%. Therefore, it is not considered to have a good thickening effect.
Comparative example 3
The preparation method of the polyasparagine derivative with the side chain containing only lysine provided by the embodiment of the invention comprises the following steps:
the reaction step I: lysine (3.0 g, 20.5 mmol) was weighed into a flask and dissolved by stirring with 50 ml of water. Then, 1.0 g of polysuccinimide (polymerization degree 1000, 10.3 mmol) was added into the flask, and the reaction was stirred at 60℃until the pH of the system was no longer lowered, and the reaction system was transparent; after the reaction, ethanol was added to the flask to precipitate "Polyaspartame derivative PASP-LL having only lysine in the side chain". Complete disappearance of the peak of the succinimide ring at 5.3ppm was detected by nuclear magnetic hydrogen spectroscopy, demonstrating that the succinimide building block in PSI has been fully opened by lysine.
However, the PASP-LL product of comparative example 3 is not considered to have a thickening effect because it has a low system viscosity and good fluidity even when it is present in an aqueous solution at a mass percentage of 10%. The main reason for this may be that when the side chain has no hydrophobic linear alkyl chain, a strong hydrophilic-hydrophobic repellent effect cannot be produced, and thus a thickening effect cannot be produced.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.

Claims (2)

1. A polyaspartic acid derivative thickener having a side chain containing a linear alkyl chain and lysine, characterized in that the polyaspartic acid derivative thickener having a side chain containing a linear alkyl chain and lysine comprises the following chemical structure:
；
wherein R represents a compound of formula C 12 H 25 、C 14 H 29 、C 16 H 33 A linear alkyl chain of (a); n represents the polymerization degree of the polyaspartic acid derivative thickener with a side chain containing a linear alkyl chain and lysine, and n is an integer of 100-1000; x represents a grafting amount of a linear alkyl chain, and x is an integer of 15% ×n to 61% ×n; n-x represents the grafting amount of lysine, and n-x is an integer of 39%. Times.n-85%. Times.n; q represents the grafting amount of an amido bond formed by the amino group at the position 2 in lysine and the main chain of polyaspartic acid, and q is more than or equal to 0 and less than or equal to n-x; n-x-q represents the grafting amount of an amide bond formed by an amino group at the 6-position in lysine and a polyaspartic acid main chain;
in the polyaspartic acid derivative thickener with the side chain containing a linear alkyl chain and lysine, the main chain is polyaspartic acid, and the side chain is linear fatty amine and lysine which can be derived from plants;
the optimal mass percentage concentration of the polyasparagine derivative thickener with the side chain containing the linear alkyl chain and lysine is 1-8%.
2. The polyaspartic acid derivative thickener having a linear alkyl chain and lysine in a side chain according to claim 1, wherein the polyaspartic acid derivative thickener having a linear alkyl chain and lysine in a side chain has a chemical structure of-NHC 5 H 9 NH 2 COOH。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001354768A (en) * 2000-06-12 2001-12-25 Mitsui Chemicals Inc Polymer and its manufacturing method
JP2002069184A (en) * 2000-06-12 2002-03-08 Mitsui Chemicals Inc Polymer and method of producing the same
JP2005344061A (en) * 2004-06-04 2005-12-15 Mitsui Chemicals Inc Polyamino acid derivative composition having thickening, foaming or foam increasing action
KR20120009848A (en) * 2010-07-21 2012-02-02 유효경 Nanoemulsion containing polyaspartic acid derivative and personal care composition comprising the same
WO2013047923A1 (en) * 2011-09-28 2013-04-04 주식회사 코스메카코리아 Nanoemulsion containing a polyaspartic acid derivative and personal care composition containing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001354768A (en) * 2000-06-12 2001-12-25 Mitsui Chemicals Inc Polymer and its manufacturing method
JP2002069184A (en) * 2000-06-12 2002-03-08 Mitsui Chemicals Inc Polymer and method of producing the same
JP2005344061A (en) * 2004-06-04 2005-12-15 Mitsui Chemicals Inc Polyamino acid derivative composition having thickening, foaming or foam increasing action
KR20120009848A (en) * 2010-07-21 2012-02-02 유효경 Nanoemulsion containing polyaspartic acid derivative and personal care composition comprising the same
WO2013047923A1 (en) * 2011-09-28 2013-04-04 주식회사 코스메카코리아 Nanoemulsion containing a polyaspartic acid derivative and personal care composition containing same

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