CN114990927B - Imidazoline quaternary ammonium salt cationic paper softener and preparation method thereof - Google Patents
Imidazoline quaternary ammonium salt cationic paper softener and preparation method thereof Download PDFInfo
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- CN114990927B CN114990927B CN202210602831.0A CN202210602831A CN114990927B CN 114990927 B CN114990927 B CN 114990927B CN 202210602831 A CN202210602831 A CN 202210602831A CN 114990927 B CN114990927 B CN 114990927B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/22—Agents rendering paper porous, absorbent or bulky
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
- C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
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Abstract
The invention belongs to the field of paper softeners, and discloses an imidazoline quaternary ammonium salt cationic paper softener and a preparation method thereof, wherein the preparation method comprises the following steps: step 1: preparing vegetable oleic acid cyclic imidazoline; step 2: carrying out quaternization reaction on the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt; step 3: mixing and emulsifying the vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener. The softening agent takes mixed vegetable oleic acid containing saturated acid and unsaturated acid as a hydrophobic group, so that the softening effect and the smoothness effect of paper are remarkably improved.
Description
Technical Field
The invention relates to the field of paper softeners, in particular to an imidazoline quaternary ammonium salt cationic paper softener and a preparation method thereof.
Background
Softeners are a class of compounds in which one end of the molecular structure contains a long chain hydrocarbon group and the other end contains a polar or reactive group that can bind to the fiber. The softener molecules can form hydrophobic groups on the surface of the fiber to be adsorbed outwards, so that the dynamic friction factor and the static friction factor of the fiber material are reduced, and smooth and soft hand feeling is obtained. The softener is divided into an anionic softener, a cationic softener and a nonionic softener, wherein the cationic softener has better antistatic property, better softening smoothness and capability of reducing the static friction factor among fibers.
Studies in this respect can be referred to cn201811122209.X and CN202010038062.7.
CN200810025673.7 discloses a process for preparing a dialkylamide imidazoline quaternary ammonium salt type paper softener, which comprises preparing dialkylamide imidazoline intermediate from stearic acid and diethylenetriamine, and adding isopropanol and dimethyl sulfate into the dialkylamide imidazoline intermediate to obtain the dialkylamide imidazoline quaternary ammonium salt type paper softener.
CN202010038062.7 discloses a preparation method of amide imidazoline dimethyl sulfate fabric softener, which comprises the steps of heating stearic acid to melt, adding diethylenetriamine, introducing nitrogen to obtain imidazoline, mixing the obtained imidazoline with isopropanol solvent, heating to 85 ℃, and adding dimethyl sulfate to obtain active cationic imidazoline.
Problems with the above solution are: there is some benign improvement in softness and smoothness of the paper, but the effect is slightly worse.
The problem that this scheme needs to solve: further improving the softness and smoothness of the paper.
Disclosure of Invention
The invention aims to provide an imidazoline quaternary ammonium salt cationic paper softener and a preparation method thereof, and the scheme can effectively improve the softness and smoothness of paper under the condition that other parameters of the paper such as the fluffiness, the whiteness of paper pulp, the electrolyte resistance, the alkali resistance and the like are not damaged.
The invention is not specifically described: nM represents nanomole/liter, μM represents micromoles/liter, mM represents millimoles/liter, and M represents moles/liter.
A preparation method of an imidazoline quaternary ammonium salt cationic paper softener, which comprises the following steps:
step 1: preparing vegetable oleic acid cyclic imidazoline;
step 2: carrying out quaternization reaction on the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt;
step 3: mixing and emulsifying the vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener.
Preferably, the vegetable oil acid is selected from at least one of the following: cotton seed oleic acid, lauric acid, palmitoleic acid, soybean oleic acid, linoleic acid, and eleostearic acid.
Preferably, the vegetable oil acid is composed of at least two of palmitoleic acid, soybean oleic acid and linoleic acid;
the weight ratio of the palmitoleic acid to the soybean oleic acid to the linoleic acid is 1:0.8 to 1.2:0 to 1.2.
Preferably, the step 1 specifically includes: adding vegetable oleic acid and diethylenetriamine into a reaction bottle, continuously stirring, and raising the temperature to 100 ℃ under the protection of nitrogen to mix reactants; gradually heating the reactant to 200-240 ℃ under the low pressure of 0.09kPa, and keeping the temperature for reaction for about 2.5-3 hours; stopping heating to naturally cool the intermediate product to about 100-120 ℃, pouring the product into a container while the product is hot, and continuously cooling to obtain an imidazoline intermediate product condensed into light yellow solid;
the weight ratio of the vegetable oleic acid to the diethylenetriamine is 10:1 to 2.1.
Preferably, the step 2 specifically includes: placing the imidazoline intermediate product into a flask, and adding a first organic solvent; dropwise adding dimethyl sulfate into a flask for reaction for 5-6 h after heating and stirring, and distilling the resultant under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt;
the weight ratio of the imidazoline intermediate product to the first organic solvent to the dimethyl sulfate is 10:4 to 5:5.
preferably, the step 3 specifically includes: transferring the vegetable oleic acid cyclic imidazoline quaternary ammonium salt into an emulsifier, adding an emulsifier, deionized water and a second organic solvent, emulsifying at 45-60 ℃, and cooling the product to a finished product;
the weight ratio of the vegetable oleic acid cyclic imidazoline quaternary ammonium salt, the emulsifier, the deionized water and the second organic solvent is 16-20: 5 to 6: 3-4: 9 to 12.
Preferably, the second organic solvent is any one or more of dipropylene glycol, triethylene glycol monobutyraldehyde, diethylene glycol, isopropanol and glycerin.
Preferably, the emulsifier is any one or more of ammonium perdodecyl chloride, cetyltrimethylammonium chloride and cetyltrimethyl pyridine bromide.
Preferably, the first organic solvent is any one or more of dipropylene glycol, triethylene glycol monobutyraldehyde, diethylene glycol, isopropanol and glycerin.
The imidazoline quaternary ammonium salt cationic paper softener is prepared by the method.
The beneficial effects of the invention are as follows:
according to the invention, vegetable oleic acid is used as a hydrophobic group in the softener, after the softener is added into paper pulp, hydrophilic groups are adsorbed on fibers, the hydrophobic groups are arranged outwards, the fibers are coated by the vegetable oleic acid groups, and a plump and smooth hand feeling is obtained; the softener is used as a cationic softener, has positive charges, and has extremely high affinity to fibers, so that the softener is more easily adsorbed; the vegetable oleic acid contains saturated acid and unsaturated acid, so that the softener provides smooth hand feeling for paper and simultaneously gives the paper rich in elasticity and warm hand feeling.
Drawings
FIG. 1 is a graph showing the performance test process of examples 1 to 13 and comparative example 1
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the attached tables in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Description of reagents
The vegetable oil in the invention is domestic industrial grade vegetable oleic acid.
In the description of the present invention, it is to be noted that the specific conditions are not specified in the examples, and the description is performed under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
(1) Preparation of vegetable oleic acid cyclic imidazoline: weighing 170 parts of cottonseed oleic acid and 36 parts of diethylenetriamine according to parts by weight, adding into a reaction bottle, continuously stirring, and raising the temperature to 100 ℃ under the protection of nitrogen to mix reactants; starting a vacuum pump to keep the pressure at 0.09kPa, gradually heating the reactant to 220 ℃, keeping the temperature for reaction for about 3 hours, stopping heating to naturally cool the intermediate product to about 120 ℃, pouring the product into a container while the intermediate product is hot, and continuously cooling to obtain the imidazoline intermediate product condensed into light yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: taking 100 parts of the imidazoline intermediate product obtained in the step (1), putting the imidazoline intermediate product into a flask, and adding 40 parts of a mixture of diethylene glycol and glycerol; heating and stirring according to the following steps: dimethyl sulfate = 2: and (3) dropwise adding dimethyl sulfate into the imidazoline in a mass ratio of 1, reacting for 5.5 hours, and distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 80 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of a dodecyl ammonium chloride emulsifier, 20 parts of deionized water and 45 parts of a mixture of diethylene glycol and glycerol to emulsify at 50 ℃, and cooling the product to a finished product.
Example 2
(1) Preparation of vegetable oleic acid cyclic imidazoline: 120 parts of palmitoleic acid and 25 parts of diethylenetriamine are weighed according to parts by weight and added into a reaction bottle, the mixture is continuously stirred, and the temperature is increased to 100 ℃ under the protection of nitrogen, so that reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 200 c and maintained at the temperature for about 3 hours. Stopping heating to naturally cool the intermediate product to about 120 ℃, pouring the product into a container while the product is hot, and continuously cooling to obtain the imidazoline intermediate product condensed into light yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of the imidazoline intermediate product obtained in the step (1) are put into a flask, and 25 parts of diethylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 5h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 28 parts of a dodecyl ammonium chloride emulsifier, 15 parts of deionized water and 55 parts of a mixture of diethylene glycol and glycerol to emulsify at 60 ℃, and cooling the product to a finished product.
Example 3
(1) Preparation of vegetable oleic acid cyclic imidazoline: 150 parts of lauric acid and 15 parts of diethylenetriamine are weighed according to parts by weight and added into a reaction bottle, the mixture is continuously stirred, and the temperature is increased to 100 ℃ under the protection of nitrogen, so that the reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 235 c and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 120 ℃, pouring the product into a container while the product is hot, and continuously cooling to obtain the imidazoline intermediate product condensed into light yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 100 parts of the imidazoline intermediate obtained in the step (1) is put into a flask, and 50 parts of isopropanol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 5.5h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 85 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 60 parts of isopropanol to emulsify at 60 ℃, and cooling the product to a finished product.
Example 4
(1) Preparation of vegetable oleic acid cyclic imidazoline: 180 parts of linoleic acid and 37 parts of diethylenetriamine are weighed according to parts by weight and added into a reaction bottle, and the mixture is stirred continuously, and the temperature is increased to 100 ℃ under the protection of nitrogen, so that the reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 240 ℃ and maintained at temperature for about 3 hours. Stopping heating to naturally cool the intermediate product to about 110deg.C, pouring the product into a container while it is hot, and continuously cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of the imidazoline intermediate product obtained in the step (1) are put into a flask, and 25 parts of triethylene glycol monobutyraldehyde in proper amount is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 5h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 30 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 60 parts of triethylene glycol monobutyraldehyde to emulsify at 45 ℃, and cooling the product to a finished product.
Example 5
(1) Preparation of vegetable oleic acid cyclic imidazoline: 200 parts of eleostearic acid and 40 parts of diethylenetriamine are weighed according to parts by weight and added into a reaction bottle, the mixture is continuously stirred, and the temperature is increased to 100 ℃ under the protection of nitrogen, so that reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 230 c and maintained at temperature for about 3 hours. Stopping heating to naturally cool the intermediate product to about 120 ℃, pouring the product into a container while the product is hot, and continuously cooling to obtain the imidazoline intermediate product condensed into light yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 100 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 50 parts of glycerin are added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 90 parts of the sample obtained in the step (2) into an emulsifier, adding 28 parts of cetyl pyridine bromide emulsifier, 17 parts of deionized water and 45 parts of triethylene glycol monobutyraldehyde to emulsify at 50 ℃, and cooling the product to a finished product.
Example 6
(1) Preparation of vegetable oleic acid cyclic imidazoline: weighing 100 parts by weight of soybean oleic acid and 20 parts by weight of diethylenetriamine, adding into a reaction bottle, continuously stirring, and raising the temperature to 100 ℃ under the protection of nitrogen to mix reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 213 ℃ and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 110deg.C, pouring the product into a container while it is hot, and continuously cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 100 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 50 parts of dipropylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 30 parts of cetyl pyridine bromide emulsifier, 20 parts of deionized water and 60 parts of triethylene glycol monobutyraldehyde to emulsify at 55 ℃, and cooling the product to a finished product.
Example 7
(1) Preparation of vegetable oleic acid cyclic imidazoline: weighing the palmitoleic acid and the linolenic acid according to the mass parts, wherein the mass ratio of the palmitoleic acid to the linolenic acid is 1:1 and 25 parts of diethylenetriamine are added into a reaction bottle, the mixture is stirred continuously, and the temperature is increased to 100 ℃ under the protection of nitrogen, so that reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 c and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 100deg.C, pouring the product into a container while it is hot, and cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 100 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 50 parts of dipropylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 30 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 50 parts of isopropanol to emulsify at 55 ℃, and cooling the product to a finished product.
Example 8
(1) Preparation of vegetable oleic acid cyclic imidazoline: weighing the mass ratio of palmitoleic acid to soybean oleic acid according to the mass parts as 1:1 and 25 parts of diethylenetriamine are added into a reaction bottle, the mixture is stirred continuously, and the temperature is increased to 100 ℃ under the protection of nitrogen, so that reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 c and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 100deg.C, pouring the product into a container while it is hot, and cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol to emulsify at 55 ℃, and cooling the product to a finished product.
Example 9
(1) Preparation of vegetable oleic acid cyclic imidazoline: the mass ratio of the soybean oleic acid to the linoleic acid is 1:1 and 25 parts of diethylenetriamine are added into a reaction bottle, the mixture is stirred continuously, and the temperature is increased to 100 ℃ under the protection of nitrogen, so that reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 c and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 100deg.C, pouring the product into a container while it is hot, and cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol to emulsify at 55 ℃, and cooling the product to a finished product.
Example 10
(1) Preparation of vegetable oleic acid cyclic imidazoline: weighing palmitoleic acid, soybean oleic acid and linoleic acid according to the mass parts, wherein the mass ratio of the palmitoleic acid to the soybean oleic acid to the linoleic acid is 1:1:1 and 25 parts of diethylenetriamine are added into a reaction bottle, the mixture is stirred continuously, and the temperature is increased to 100 ℃ under the protection of nitrogen, so that reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 c and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 100deg.C, pouring the product into a container while it is hot, and cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol to emulsify at 55 ℃, and cooling the product to a finished product.
Example 11
(1) Preparation of vegetable oleic acid cyclic imidazoline: weighing palmitoleic acid, soybean oleic acid and linoleic acid according to the mass parts, wherein the mass ratio of the palmitoleic acid to the soybean oleic acid to the linoleic acid is 1:0.8:1.2 mixing vegetable oleic acid 120 parts and 25 parts diethylenetriamine were added to a reaction flask, stirred continuously, and the temperature was raised to 100℃under nitrogen protection to mix the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 c and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 100deg.C, pouring the product into a container while it is hot, and cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol to emulsify at 55 ℃, and cooling the product to a finished product.
Example 12
(1) Preparation of vegetable oleic acid cyclic imidazoline: weighing palmitoleic acid, soybean oleic acid and linoleic acid according to the mass parts, wherein the mass ratio of the palmitoleic acid to the soybean oleic acid to the linoleic acid is 1:1.2:1.2 mixing vegetable oleic acid 120 parts and 25 parts diethylenetriamine were added to a reaction flask, stirred continuously, and the temperature was raised to 100℃under nitrogen protection to mix the reactants. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 c and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 100deg.C, pouring the product into a container while it is hot, and cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol to emulsify at 55 ℃, and cooling the product to a finished product.
Example 13
(1) Preparation of vegetable oleic acid cyclic imidazoline: weighing palmitoleic acid and soybean oleic acid according to the mass parts, wherein the mass ratio of the palmitoleic acid to the soybean oleic acid is 1:0.8 part of mixed vegetable oleic acid 120 parts and 25 parts of diethylenetriamine are added into a reaction bottle, stirred continuously, and the temperature is raised to 100 ℃ under the protection of nitrogen, so that reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 c and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 100deg.C, pouring the product into a container while it is hot, and cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol to emulsify at 55 ℃, and cooling the product to a finished product.
Comparative example 1
(1) Preparation of oleic acid cyclic imidazoline: 120 parts of stearic acid and 25 parts of diethylenetriamine are weighed according to parts by weight and added into a reaction bottle, the mixture is continuously stirred, and the temperature is increased to 100 ℃ under the protection of nitrogen, so that the reactants are mixed. The vacuum pump was started to maintain the pressure at 0.09kPa while the reactants were gradually warmed to 220 c and maintained at temperature for about 2.5 hours. Stopping heating to naturally cool the intermediate product to about 100deg.C, pouring the product into a container while it is hot, and cooling to obtain imidazoline intermediate product condensed into pale yellow solid.
(2) Quaternizing the oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt: 50 parts of the imidazoline intermediate obtained in the step (1) are put into a flask, and 25 parts of dipropylene glycol is added. Heating and stirring according to the imidazoline intermediate product: dimethyl sulfate = 2:1, dropwise adding dimethyl sulfate into the imidazoline intermediate product in parts by mass for reaction for 6h. And distilling under reduced pressure to remove redundant water and unreacted dimethyl sulfate, thereby obtaining the vegetable oleic acid cyclic imidazoline quaternary ammonium salt.
(3) Mixing and emulsifying the oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain the imidazoline quaternary ammonium salt cationic paper softener: and (3) transferring 100 parts of the sample obtained in the step (2) into an emulsifier, adding 25 parts of cetyl trimethyl ammonium chloride emulsifier, 20 parts of deionized water and 55 parts of isopropanol to emulsify at 55 ℃, and cooling the product to a finished product.
Performance testing
The test process is as shown in fig. 1, the pulp concentration is 30%, and the pulp is proportioned into northern pine: goldfish short fiber = 28%:72%. The paper softening agents of examples 1 to 13 and comparative examples were added in an amount of 0.25 kg/ton of pulp, and the pH of white water was 8.23.
Softness test: the standard is to measure the softness of paper according to a PY-H613 softness tester, and in the test, when a test head presses a sample into a gap to a certain depth (refer to standard group test standard), the sum of the bending resistance of the sample and the maximum vector of the friction force between the sample and the gap is called softness, and the softness value is smaller, so that the sample is softer.
Smoothness test: smoothness test the smoothness was measured according to paper and board smoothness measurement (allopatric) GB/T456-2002idt ISO 5627:1995.
Degree of fluffiness: effect of softening agent on finishing pulp the bulk of the pulp after sheeting was evaluated by measuring the thickness of the paper, with a standard thickness of 1.05-1.15 mm/double layer.
The softener stability was tested as follows:
electrolyte resistance: 3g of the sample was weighed and placed in a 150mL beaker, and 2% MgCl was added 2 ·6H 2 97mL of O solution, stirred uniformly, then stood for 24 hours, and the emulsion stability in the beaker was observed.
Alkali resistance: 3g of the sample was weighed and placed in a 100mL beaker, 97mL of sodium carbonate solution with pH=11 was added, and after stirring uniformly, the mixture was allowed to stand for 4 hours, and the emulsion stability in the beaker was observed.
The test results are shown in table 1:
table 1: performance test results for different softeners
As can be seen from table 1, the vegetable oleic acid hydrophobic type softener has higher softening effect, smoothing effect, bulk and pulp whiteness than the stearic acid hydrophobic type softener. When the vegetable oleic acid hydrophobic group is the mixed vegetable oleic acid hydrophobic group, the softening effect and the smoothing effect are further improved.
The following conclusions can be drawn from the above experiments:
1. it can be demonstrated by examples 1 to 13: when the vegetable oleic acid is mixed oleic acid of soybean oleic acid, palmitoleic acid and linoleic acid, the softener has more excellent performance.
2. It can be demonstrated by examples 1-13 and comparative example 1: when the vegetable oleic acid hydrophobic softener has better modifying effect on paper than the stearic acid hydrophobic softener.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the imidazoline quaternary ammonium salt cationic paper softener is characterized by comprising the following steps of:
step 1: preparing vegetable oleic acid cyclic imidazoline;
step 2: carrying out quaternization reaction on the vegetable oleic acid cyclic imidazoline to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt;
step 3: mixing and emulsifying vegetable oleic acid cyclic imidazoline quaternary ammonium salt, an emulsifier, deionized water and an organic solvent to obtain an imidazoline quaternary ammonium salt cationic paper softener;
the vegetable oil acid is composed of at least two of palmitoleic acid, soybean oleic acid and linoleic acid;
the weight ratio of the palmitoleic acid to the soybean oleic acid to the linoleic acid is 1:0.8 to 1.2:0 to 1.2.
2. The method for preparing the imidazoline quaternary ammonium salt cationic paper softener according to claim 1, wherein the step 1 is specifically: adding vegetable oleic acid and diethylenetriamine into a reaction bottle, continuously stirring, and raising the temperature to 100 ℃ under the protection of nitrogen to mix reactants; gradually heating the reactant to 200-240 ℃ under the low pressure of 0.09kPa, and keeping the temperature for reaction for 2.5-3 hours; stopping heating to naturally cool the intermediate product to 100-120 ℃, pouring the product into a container while the product is hot, and continuously cooling to condense the imidazoline intermediate product into light yellow solid;
the weight ratio of the vegetable oleic acid to the diethylenetriamine is 10:1 to 2.1.
3. The method for preparing the imidazoline quaternary ammonium salt cationic paper softener according to claim 2, wherein the step 2 is specifically: placing the imidazoline intermediate product into a flask, and adding a first organic solvent; dropwise adding dimethyl sulfate into a flask for reaction for 5-6 h after heating and stirring, and distilling the resultant under reduced pressure to remove redundant water and unreacted dimethyl sulfate to obtain vegetable oleic acid cyclic imidazoline quaternary ammonium salt;
the weight ratio of the imidazoline intermediate product to the first organic solvent to the dimethyl sulfate is 10:4 to 5:5.
4. the method for preparing the imidazoline quaternary ammonium salt cationic paper softener according to claim 3, wherein the step 3 is specifically: transferring the vegetable oleic acid cyclic imidazoline quaternary ammonium salt into an emulsifier, adding an emulsifier, deionized water and a second organic solvent, emulsifying at 45-60 ℃, and cooling the product to a finished product;
the weight ratio of the vegetable oleic acid cyclic imidazoline quaternary ammonium salt, the emulsifier, the deionized water and the second organic solvent is 16-20: 5 to 6: 3-4: 9 to 12.
5. The method for preparing an imidazoline quaternary ammonium salt cationic paper softener according to claim 4, wherein the second organic solvent is any one or more of dipropylene glycol, triethylene glycol monobutyraldehyde, diethylene glycol, isopropanol and glycerin.
6. The method for preparing an imidazoline quaternary ammonium salt cationic paper softener according to claim 4, wherein the emulsifier is any one or more of ammonium perdodecyl chloride, cetyltrimethylammonium bromide and cetyltrimethyl pyridinium bromide.
7. The method for preparing an imidazoline quaternary ammonium salt cationic paper softener according to claim 3, wherein the first organic solvent is any one or more of dipropylene glycol, triethylene glycol monobutyraldehyde, diethylene glycol, isopropanol and glycerin.
8. An imidazoline quaternary ammonium salt cationic paper softener, which is prepared by the method of any one of claims 1-7.
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| US4844823A (en) * | 1985-01-30 | 1989-07-04 | Colgate-Palmolive Company | Fabric softener composition containing di-esterified long chain fatty acid quaternary ammonium salt |
| CN104379836A (en) * | 2012-07-25 | 2015-02-25 | 星光Pmc株式会社 | Softening agent for paper, paper, and method for producing sanitary paper |
| JP2018145583A (en) * | 2017-03-07 | 2018-09-20 | 三洋化成工業株式会社 | Softener base and softener |
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| JP3235928B2 (en) * | 1993-12-28 | 2001-12-04 | 花王株式会社 | Paper softener |
| JP5347480B2 (en) * | 2008-12-17 | 2013-11-20 | 星光Ｐｍｃ株式会社 | Softener for paper |
| CN101885706B (en) * | 2010-01-13 | 2013-06-26 | 广东省造纸研究所 | High-yield preparation method for imidazoline-ammonium-salt paper softener |
| CA2991414C (en) * | 2015-07-10 | 2021-01-26 | The Procter & Gamble Company | Fabric care composition comprising metathesized unsaturated polyol esters |
| CN105254566A (en) * | 2015-09-11 | 2016-01-20 | 陕西科技大学 | Imidazoline quaternary ammonium salt compound and preparation method therefor |
| CN108948068B (en) * | 2018-07-23 | 2020-03-10 | 皖西学院 | Preparation method of alkyl imidazoline organosilicon quaternary ammonium salt |
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| US4844823A (en) * | 1985-01-30 | 1989-07-04 | Colgate-Palmolive Company | Fabric softener composition containing di-esterified long chain fatty acid quaternary ammonium salt |
| CN104379836A (en) * | 2012-07-25 | 2015-02-25 | 星光Pmc株式会社 | Softening agent for paper, paper, and method for producing sanitary paper |
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